Eliminating or decreasing matrix effect in skin moisturizers employing a magnetic adsorbent in the analysis of primary aliphatic amines

Eliminating or decreasing matrix effect in skin moisturizers employing a magnetic adsorbent in the analysis of primary aliphatic amines | Research Square window.SnipcartSettings = { analytics: { enabled: false } }; (function() { var accessVector = localStorage.getItem('access_vector') || ''; window.dataLayer = window.dataLayer || []; if (accessVector) { window.dataLayer.push({ user: { profile: { profileInfo: { snid: accessVector } } } }); } })(); (function(w,d,s,l,i){w[l]=w[l]||[];w[l].push({'gtm.start':new Date().getTime(),event:'gtm.js'});var f=d.getElementsByTagName(s)[0],j=d.createElement(s),dl=l!='dataLayer'?'&l='+l:'';j.async=true;j.src='https://www.googletagmanager.com/gtm.js?id='+i+dl;f.parentNode.insertBefore(j,f);})(window,document,'script','dataLayer','GTM-K279D39R'); Browse Preprints In Review Journals COVID-19 Preprints AJE Video Bytes Research Tools Research Promotion AJE Professional Editing AJE Rubriq About Preprint Platform In Review Editorial Policies Our Team Advisory Board Help Center Sign In Submit a Preprint Cite Share Download PDF Article Eliminating or decreasing matrix effect in skin moisturizers employing a magnetic adsorbent in the analysis of primary aliphatic amines Mir Ali Farajzadeh, Sina Mohammad Mehri, Mohammad Reza Afshar Mogaddam This is a preprint; it has not been peer reviewed by a journal. https://doi.org/ 10.21203/rs.3.rs-5836920/v1 This work is licensed under a CC BY 4.0 License Status: Published Journal Publication published 17 Mar, 2025 Read the published version in Scientific Reports → Version 1 posted 12 You are reading this latest preprint version Abstract In this study, a combining method using dispersive micro solid phase extraction and vortex-assisted liquid-liquid microextraction was presented for the first time as a pioneering methodology capable of concurrently cleaning up and derivatizing/ extracting existing primary aliphatic amines in aqueous solutions after eliminating or decreasing matrix effect posed by skin moisturizers. A magnetic adsorbent (iron oxide modified by mercapto acetic acid, MAA@Fe 3 O 4 ) has been employed to facilitate the matrix removal. To corroborate the authenticity of the synthesized adsorbent, various identification methods were employed, including X-ray diffraction, Brunauer-Emmett-Teller, scanning electron microscopy, Fourier transform infrared spectrometry, energy dispersive X-ray spectroscopy, and vibrating sample magnetometry analyses. All effective parameters were optimized in passivation of the adsorbent for the analytes and their concurrent derivatization and extraction. A gas chromatograph equipped with a flame ionization detector was utilized to identify and quantify the derivatives of amines. Eco-friendly characteristics, short extraction duration, high matrix removal efficiency, high unadsorbed percentage of amines by the adsorbent, simplicity, high precision, lack of requirement for specialized equipment, adsorbent reusability up to five cycles, exceptional proficiency in the extraction and derivatization of amines, and a comprehensive or relative superiority in analytical parameters, including extraction recovery, enrichment factor, relative standard deviation, coefficient of determination, limit of quantification and detection, and relative recovery, underscoring the merits and advantages of the proposed method. Physical sciences/Chemistry Physical sciences/Materials science Physical sciences/Nanoscience and technology Primary aliphatic amines Dispersive micro solid phase extraction Skin moisturizer Magnetic adsorbent Vortex-assisted liquid-liquid microextraction Gas chromatography Figures Figure 1 Figure 2 Figure 3 Figure 4 Figure 5 Figure 6 1. Introduction Primary aliphatic amines (PAAs) are the organic compounds with a -NH 2 group and a saturated carbon chain 1,2 . They are crucial in various chemical reactions and are used as building blocks in synthesizing pharmaceuticals, agrochemicals, and other important organic materials 3 . PAAs are widely used in the chemical, pharmaceutical, petrochemical, and textile industries. However, improper wastewater treatment in these industries can introduce PAAs into the environment, which negatively affects the quality of water and soil and are known as toxic pollutants for the ecosystem 4–8 . Also, long-term exposure to these amines can cause serious damage to human health, including neurological and pulmonary diseases 9,10 . Therefore, the identification and measurement of PAAs is necessary to assess environmental pollution and human health threats 11 . To accurately measure these compounds, various analytical methods are utilized such as gas chromatography (GC) 12–14 , high-performance liquid chromatography 11,15,16 , and spectrofluorimetry 17 . However, due to the complexity of the matrix and low concentration of PAAs, the measurement of these compounds in aqueous samples is challenging. The employment of extraction and preconcentration techniques is correlated with enhanced sensitivity and reduced matrix effects. Among these techniques, liquid-liquid extraction 18 and solid phase extraction (SPE) 19 are widely used, but they have limitations, including high use of organic solvents, time-consuming, and high costs. In addition, SPE can encounter issues such as cartridge blockage and memory effects 20 . Microextraction methods have been introduced to overcome these limitations. In single drop microextraction method, a single drop is accomplished to extract analytes, but this method faces issues such as disturbance in the stability of the organic drop during rapid stirring and long extraction times 20 . In hollow fiber-liquid phase microextraction method, an extractant droplet is placed inside a hollow fiber, but this method is usually faced with low efficiency and a long extraction time 21 . Solid phase microextraction method is a solvent-free technique, but it is usually associated with high costs and limited efficiency 22–24 . In dispersive liquid-liquid microextraction, the extraction is done quickly and efficiently because the extractant is completely dispersed into an aqueous solution 25,26 . As the name of the technique suggests, this technique is based on the use of a disperser solvent, which has turned it into one of the limitations of this method, because this solvent, due to its semi-polar nature, reduces the polarity of the aqueous phase, which causes the analytes to be more dissolved in this phase and do not tend to be extracted into the organic phase. Moreover, it leads to the loss of certain analytes, particularly volatile ones, during injection of the mixture of disperser and extractant into the aqueous phase 27 . Vortex-assisted liquid-liquid microextraction (VALLME) obviates the necessity for a disperser solvent by employing vortex to facilitate dispersion of the extraction solvent within the sample solution. Furthermore, it not only diminishes costs but also mitigates the issues associated with the loss of volatile analytes 28,29 . Extraction of PAAs from aqueous phase is challenging due to high polarity of these compounds. Also, another problem appeared especially in GC because amines can have unexpected interactions with the stationary phase, which causes peak tailing. To solve these limitations, these compounds can be derivatized 30 . Different derivation agents for the derivatization of PAAs are utilized, including silylating agents 31 , acylating agents 32 , alkylating agents 33 , and carbamates 34 . Each of them offers distinct advantages in terms of efficiency, specificity, and nature of the resulting derivatives. Alkyl chloroformate is a suitable derivation agent for amines due to formation of stable derivatives with amines (alkyl carbamates) and improved chromatographic properties 35 . In alkaline conditions, the rate of derivatization rises, contributing to the formation of more stable and efficient derivatives 34 . To accurately monitor and measure PAAs in complex real samples, it is essential to eliminate or reduce matrix effects. Dispersive micro solid phase extraction (DµSPE) methodology represents a new approach wherein adsorbent particulates are uniformly dispersed within the sample solution, facilitating comprehensive interaction with the target analytes and enhancing the overall extraction efficacy 36 . This technique, contingent upon the specific adsorbent employed, can selectively adsorb various chemical compounds. Based on the structure of PAAs and their pH sensitivity, an adsorbent capable of fulfilling this role within a specific pH range should be employed to remove the matrix while selectively retaining the amines. This study was carried out in two parts: passivation of adsorbent in elimination of PAAs, and simultaneous extraction and derivatization of PAAs during VALLME. In the first part, the attempt was to optimize the conditions in the DµSPE method using iron oxide modified by mercapto acetic acid (MAA@Fe 3 O 4 ) adsorbent to eliminate or decrease sample matrix effect while maintaining PAAs in the solution. In the second part, VALLME was used for concurrent extraction and derivatization of PAAs. In this process, butyl chloroformate (BCF) was used as a derivatization agent to convert amines into carbamate derivatives and successfully extraction of them. This method has a great potential in PAAs analysis due to utilization of µL-scale extractant and derivatization agent, eco-friendliness of the adsorbent used, and its effective efficiency. 2. Experimental 2.1 Chemicals and solutions Utilized PAAs included propylamine (PrA), butylamine (BuA) [purchased from Fluka, Bosch, Switzerland], pentylamine (PeA), benzylamine (BeA), and sec -butylamine ( sec -BuA) [obtained from Merck, Darmstadt, Germany]. A standard solution of PAAs with a concentration of 500 mg L − 1 (of each analyte) was prepared in methanol. To prepare the daily standard solution, it was diluted using deionized water [obtained from Ghazi Company, Tabriz, Iran]. For adsorbent synthesis process, iron sulfate heptahydrate (FeSO 4 .7H 2 O) 99.5%, mercaptoacetic acid (MAA) 98%, concentrated ammonia (25%, w/w ), ethanol 99.8%, and iron chloride hexahydrate (FeCl 3 .6H 2 O) 98.5% [all purchased from Merck] were used. To optimize the ionic strength, sodium sulfate 99%, potassium chloride 99.9%, sodium chloride 99% [purchased from Merck], to adjust pH of the aqueous phase, sodium hydroxide 99% and hydrochloric acid (37%, w/w ) [purchased from Fluka], and to prevent precipitation in alkaline media disodium ethylenediaminetetraacetic acid (EDTA) [obtained from Merck] were utilized. In this work extraction solvents including 1,1,1-trichloroethane (1,1,1-TCE) 99.7%, 1,2-dibromoethane (1,2-DBE) 98%, chloroform (CHCl 3 ) 99%, and 1,1,2-trichloroethane(1,1,2-TCE) 99.5% [obtained from Johnson, Beerse, Belgium] were utilized. 2.2 Samples Three skin moisturizers were purchased from a cosmetic store (Tabriz, Iran). All samples were placed in contact with the adsorbent according to the DµSPE method to eliminate or decrease the matrix effect (without dilution). Then, the supernatant was subjected to the simultaneous derivatization and extraction of PAAs in VALLME method. It should be noted that before adjusting pH at 10, EDTA (10 mg) was added to 5 mL of each sample. 2.3 Apparatus A GC equipped with flame ionization detector (FID) model 2014 (manufactured by Shimadzu, Kyoto, Japan) was used to study the matrix of real samples before and after contact with the adsorbent, and to separate, identify, and quantify the derived PAAs. The instrument was equipped with a split/splitless injector that was set in a splitless/split mode (split time 1 min and split ratio 1:10) thermostated at 300°C. The FID temperature was set at 300°C. A capillary column (dimethyl: diphenylpolysiloxane 95:5) with a length of 30 m, inner diameter of 0.25 mm, and a stationary phase film thickness of 0.25 µm (Restex, Center, PA, USA) was used for the separation and detection of PAAs. The initial temperature of column oven was adjusted to 60°C and maintained at this level for 2 min. Then it was increased to 200°C with a ramp of 10°C min − 1 and maintained at this temperature for 2 min. The carrier gas utilized was helium (99.999%, Crewe Bay, Dubai, United Arab Emirates) which was introduced into the GC at a linear velocity of 30 cm s − 1 . The fuel used in the FID was hydrogen supplied by a hydrogen generator (OPGU 1500S, Shimadzu, Kyoto, Japan) with a flow rate of 30 mL min − 1 . Also, the oxidant used in FID was air, which entered the FID chamber with an airflow rate of 300 mL min − 1 . Drying of the synthesized MAA@Fe 3 O 4 was done using an oven (Heraeus UT 12, Hanau, Germany). A vortex (Labinco L46 vortex mixer, Breda, the Netherlands) was utilized to establish sufficient contact between the analytes and adsorbent, and analytes, derivatization agent, and extraction solvent. After derivatization and extraction, a centrifuge (Hettich D7200, Kitchener, Germany) was used to facilitate separation of organic and aqueous phases. pH of samples was adjusted before the contact of the analytes with the adsorbent and before derivatization and extraction by employing a pH meter (Metrohm 654, Herisau, Switzerland). To identify the adsorbent morphology and assess its composition, scanning electron microscopy (SEM) and energy diffraction X-ray (EDX) analyses were performed using a Mira 3 microscope (Tescan Mira 3, Brno, Czech Republic). Fourier transform infrared (FTIR) (Bruker, Billerica, MA, USA) and X-ray diffraction (XRD) (Siemens D500 diffractometer AG, Karlsruhe, Germany) analyses were performed to authenticate the synthesis and formation of the desired bonds. To verify the magnetic characteristics of the adsorbent, vibrating sample magnetometry (VSM) (MDKB, Magnetic DaneshPajoh Kashan Co. Kashan, Iran) was conducted, and for assessing the surface area and pore size, Brunauer-Emmett-Teller (BET) analysis was performed using a BELSORP-mini-instrument (MicrotracBEL Corp, Osaka, Japan). 2.4 Synthesis of MAA@Fe3O4 Synthesis of magnetic adsorbent functionalized with MAA included two steps. The first step was the synthesis of Fe 3 O 4 particles as described in our previous work 37 . The second step was functionalizing MAA on Fe 3 O 4 particles 38 . For this purpose, 2.9 mmol of MAA was dissolved in 100 mL of ethanol and then 0.5 g of Fe 3 O 4 particles were added into it. The resulting mixture was stirred on a stirrer for 24 h, and then MAA@Fe 3 O 4 particles were collected from the reaction mixture using an external magnetic field and washed with a 1:1 mixture of ethanol and water (several times). Finally, MAA@Fe 3 O 4 microspheres were dried in an oven at 50°C for 3 h under vacuum conditions. 2.5 Clean up and derivatization/ extraction Procedures 2.5.1 DµSPE step Five milliliters of real sample or deionized water (spiked with the analytes at 500 mg L − 1 of each amine) was poured into a 10-mL conical bottom glass test tube, and pH of solution was adjusted at 10 using 0.1 M NaOH solution. Sodium chloride (0.375 g) was added to adjust the ionic strength along with 10 mg of EDTA to prevent unexpected precipitate formation. Finally, 20 mg of MAA@Fe 3 O 4 was added to the solution and then vortexed for 3 min to establish adequate contact between the analytes and MAA@Fe 3 O 4 particles. It should be noted that to prevent the escape of PAAs, everything that was added to the glass test tube immediately and the cap was put on it. An external magnetic field was used to easily separate the adsorbent particles from the solution in a short time. Then the supernatant was transferred into another glass test tube. 2.5.2 VALLME step Due to the acidity of the adsorbent, after the contact of the aqueous solution with the adsorbent, its pH decreased. As mentioned in the introduction section, the suitable pH for the derivatization of PAAs is an alkaline medium. Therefore, first, the pH of the supernatant (obtained from the DµSPE step) was checked and re-adjusted at pH 10. Then 5 µL of BCF was mixed with 15 µL of 1,1,2-TCE inside a 1-mL conical bottom vial, and then slowly introduced into the aqueous solution by a 50-µL syringe. The cap was immediately placed and vortexed for 5 min to perform derivatization and extraction. To separate the phases and settle down the extractive phase, it was centrifuged for 3 min with a speed of 4000 rpm. Finally, 1 µL of the settled phase (10 ± 0.5 µL) was injected into GC-FID. The schematic of whole process is shown in Fig. 1 . Figure 1 2.6 Calculations Enrichment factor (EF) is an indication of the extent of analytes preconcentration (Eq. 1). Extraction recovery (ER) serves as an indicator of how effectively analytes are extracted from an aqueous phase into the organic phase (Eq. 2). Unadsorbed percent (UP) of the analyte indicates the percentage of analyte that is not adsorbed by the adsorbent (Eq. 3). This equation is used exclusively in the DµSPE stage. The high value of this parameter is favorite in this study. Relative recovery (RR) is a criterion for evaluating the effectiveness of the proposed method, indicating whether complex matrices can diminish the method's efficiency (Eq. 4). $$\:EF=\frac{{C}_{sed}}{{C}_{₀}}\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\left(1\right)$$ $$\:ER=\frac{{n}_{sed}}{{n}_{₀}}\times\:100=\frac{{C}_{sed}\times\:\:{V}_{sed}}{{C}_{₀}\:\times\:\:{V}_{₀}}\times\:100=EF\times\:\frac{{V}_{sed}}{{V}_{₀}}\times\:100\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\left(2\right)$$ In these equations, \(\:{C}_{sed}\) represents concentration of analyte in organic phase, \(\:{C}_{₀}\) indicates the initial concentration of analyte in aqueous solution, \(\:{n}_{sed}\) denotes the number of moles of analyte in the organic phase, \(\:{n}_{₀}\) signifies the number of moles of analyte in aqueous phase, \(\:{V}_{sed}\:\) refers to the volume of the sedimented organic phase, and \(\:{V}_{₀}\) represents the volume of the aqueous phase. $$\:UP=100-\left[\left(\frac{{C}_{{sed}_{1}}-{C}_{{sed}_{2}}}{{C}_{{sed}_{1}}}\right)*100\right]\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:$$ In this equation, \(\:{C}_{{sed}_{1}}\) represents the concentration of analyte extracted directly from the aqueous solution without contacting with the adsorbent, while \(\:{C}_{{sed}_{2}}\) denotes the concentration of analyte extracted from the supernatant solution after contacting with the adsorbent. In this equation, if PAAs are entirely adsorbed, no PAAs will be present in the supernatant solution, making the value of \(\:{C}_{{sed}_{2}}\) equal to 0, resulting in UP being 0. If PAAs are not adsorbed at all, PAAs will be found in the supernatant solution and \(\:{C}_{{sed}_{2}}\) will be equal to \(\:{C}_{{sed}_{1}}\) , making UP = 100. Therefore, in the intermediate states, the value of UP varies from 0 to 100. $$\:RR=\frac{{C}_{total}-{C}_{real}}{{C}_{added}}\:\times\:100\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\:\left(4\right)$$ In this equation, \(\:{C}_{real}\) is concentration of the analyte in real sample, \(\:{C}_{added}\) is the spiked concentration of the analyte to the real sample, and \(\:{C}_{total}\) is total concentration of the analyte in the real sample after spiking. 3. Results and discussion 3.1 Characterization of MAA@Fe3O4 SEM is a powerful tool for studying the surface of materials with very high magnification. Through SEM images, surface morphology, particle size, size distribution, and other surface characteristics of materials can be examined. Figures 2 a and 2 b show the particles have an irregular and sometimes granular morphology. Their size is in the range of 30–50 nm, and the distribution of particles size is relatively uniform. EDX is the technique used to determine the elemental composition of solid samples. The spectrum reported in Fig. 2 c confirms the presence of iron, carbon, oxygen, and sulfur in the adsorbent composition. The presence of iron and carbon, respectively, indicates the magnetic phase and the presence of organic substance in the absorbent structure. The peak related to sulfur confirms the presence of MAA in the absorbent structure. It should be noted that there is a specific peak at around 2.3 Kev, which is related to the gold coating used to increase the electrical conductivity of the sample. VSM is an appropriate technique for assessing the magnetic characteristics of materials. As illustrated in Fig. 2 d, the hysteresis curve of MAA@Fe 3 O 4 demonstrates its ferromagnetic or superparamagnetic characteristics. At 300 K, the saturation magnetization of Fe 3 O 4 is measured at 14.82 emu g − 1 , while that of MAA@Fe 3 O 4 is 9.52 emu g − 1 . Consequently, it can be inferred that the coating MAA on Fe 3 O 4 nanoparticles decreases their magnetization, and this alteration arises from the interactions between Fe 3 O 4 nanoparticles and MAA, leading to magnetic anisotropy. FTIR is an effective method for identifying functional groups and chemical bonds in different substances. In this study, FTIR spectra of Fe 3 O 4 and MAA@Fe 3 O 4 (Fig. 2 e), were examined to assess the influence of the coating on the sorbent structure and composition. The main peak occurring around 625 cm − 1 corresponds to the stretching vibration of the Fe-O bond within Fe 3 O 4 structure. This peak verifies the existence of Fe 3 O 4 phase in the sample. Wide peaks at approximately 3395 cm − 1 and a faint peak near 1643 cm − 1 correspond to water molecules that are adsorbed on the surface of Fe 3 O 4 nanoparticles. To examine the spectrum of MAA@Fe 3 O 4 in greater details, we needed to identify the alterations that took place in comparison to the spectrum of Fe 3 O 4 . These alterations may signify the existence of functional groups of MAA on the nanoparticle surface. The wide peak associated with the stretching vibration of O-H bond at 3395 cm − 1 is more intense in the MAA@Fe 3 O 4 spectrum compared to the Fe 3 O 4 spectrum. This is attributed to the existence of carboxyl groups (-COOH) in MAA. The peak associated with the stretching vibration of the carbonyl bond (C = O) within the carboxyl group is seen in the range of 1559 cm − 1 . The peak related to the stretching vibration of the C-S bond is seen at around 587 cm − 1 . The peak associated with the stretching vibration of sulfhydryl bond (S-H) can be detected in the region of 2919 cm − 1 . Based on the observations recorded, it can be inferred that the functionalization procedure has been effectively achieved and the MAA is bonded onto the Fe 3 O 4 nanoparticle surface. XRD is one of the suitable tools for identifying crystalline phases and structural changes in materials. To confirm the success of the MAA@Fe 3 O 4 synthesis and investigate the binding of MAA, XRD patterns for Fe 3 O 4 and MAA@Fe 3 O 4 were prepared and are shown in Fig. 2 f. These patterns were recorded in the angular range of 2θ between 10 and 80 ⸰ . In the spectrum of Fe 3 O 4 , the specific peaks of the spinel structure in the crystal planes of (111), (220), (311), (400), (422), (511), and (440) at 2θ values ​​equal to 18, 30.1, 35.5, 43.1, 53.4, 57.3, and 62.5 are observed. These peaks are still present in the spectrum of MAA@Fe 3 O 4 , but a significant decrease in their intensity is seen, especially at 35.5 and 62.5. This decrease in intensity indicates the surface coating of particles by MAA. Also, the slight increase in baseline at low 2θ values ​​confirms the presence of organic groups. The changes observed in the XRD spectrum confirm that MAA is successfully functionalized on the surface of Fe 3 O 4 particles. BET analysis determines the specific surface area, cumulative pore volume, and pore size distribution of porous materials by measuring the amount of nitrogen adsorption at a constant temperature of liquid nitrogen. Figure 2 g shows the nitrogen adsorption isotherm of the adsorbent based on the BET method. The results of this analysis show that the specific surface area of ​​the absorbent is equal to 64.275 m 2 g − 1 , its cumulative pore volume is 0.3527 cm 3 g − 1 , and the average diameter of its pores is 21.949 nm. The high values ​​of the specific surface area and cumulative pore volume indicate the presence of active surface and high porosity in the absorbent structure, which are very favorable for adsorption and catalytic applications. Also, the average pore diameter obtained shows that the adsorbent has the pores in the mesoporous range. Figure 2 3.2 Optimization of parameters in DµSPE-VALLME 3.2.1 Aqueous solution pH in DµSPE stage Considering that MAA has a carboxylic acid group, it can be expected that the pKa of the MMA attaches to Fe 3 O 4 to be in the range of pKa of common carboxylic acids (between 4 and 5). The adsorbent at pH lower and higher than this range is in the forms of R-COOH and R-COO − , respectively. In addition, considering that the pKa of PAAs is in the range 9.3–10.7, these compounds are in the forms of R-NH 3 + and R-NH 2 at the pHs lower and higher than this range, respectively. At pH below 4, both adsorbent and PAAs are in the protonated forms and have not electrostatic attraction. At pH above 9, the adsorbent and PAAs are in R-COO − and R-NH 2 forms, respectively, so electrostatic attraction between the adsorbent and the PAAs does not occur. In the pHs between 4 and 9, the adsorbent and PAAs are in the forms of -COO − and R-NH 3 + , respectively, and the PAAs are electrostatically adsorbed by the adsorbent. To examine the influence of pH on PAAs adsorption, the pH values of 1, 3, 7, 10, and 13 were investigated and assessed according to the UP criteria (Fig. 3 ). As expected, the lowest UP value or highest adsorbed value is related to neutral pH, which indicates the electrostatic attraction between the adsorbent and PAAs. At pH 3, the level of PAAs adsorption is lower than that of pH 7. This is likely because, at this pH, some parts of the adsorbent exist as R-COOH and another part as R-COO − , allowing it to adsorb some PAAs electrostatically. At pH 1, the quantity of UP is risen, due to decreasing R-COO − form in this pH. At pHs 10 and 13, all analytes show the highest UP values (lowest adsorbed values). Likely, PAAs exist mainly in their R-NH 2 forms at these pHs, which prevent them from interacting electrostatically with the adsorbent. Therefore, pH 10 was selected for the further studies. Figure 3 3.2.2 MAA@Fe 3 O 4 weight In this section, several factors should be considered to select the optimal adsorbent weight: the method's efficiency and cost-effectiveness, the elimination or decreasing matrix effect, and the prevention of PAAs adsorption by the sorbent. The values ​​of 3, 5, 10, 15, 20, 25, and 30 mg adsorbent were examined and evaluated based on the UP criteria to optimize the adsorbent weight. According to the reported findings (Fig. 4 ), the UP values remain constant in the weights ≤ 20 mg. Increasing the adsorbent weight beyond 20 mg has led to a reduction in UP. The objective of this study is to eliminate or reduce the sample matrix effect while preserving the presence of PAAs in the samples; consequently, it is imperative to determine the maximum adsorbent weight that does not eliminate PAAs. Accordingly, 20 mg of the adsorbent was selected as the ideal weight that suits the aims of this study for the future optimizations. Figure 4 3.2.3 Ionic strength study The modification of the ionic strength of an aqueous solution is accomplished through addition of a salt. The process of salt addition can have two distinct outcomes. The introduction of salt into the aqueous solution decreases the solubility of PAAs, which enhances their adsorption (thereby reducing UP values), a phenomenon referred to "salting-out" effect. Conversely, the addition of salt may lead to an increase in viscosity of the aqueous solution, a reduction in the adsorption of PAAs (increasing UP values), known as the "salting-in" effect. According to the procedure stated in section 2.5, the aqueous solution containing PAAs, after contact with the adsorbent, was subjected to simultaneous extraction and derivatization conditions. Therefore, the effect of salt addition can be effective in both DµSPE and VALLME steps. To investigate this parameter, three salts consisting of sodium chloride, sodium sulfate, and potassium chloride with a concentration of 1 M as well as without salt addition were utilized. It should be noted that the UP and ER% criteria during the DµSPE and VALLME stages, respectively, were employed to assess the effect of salt addition. As reported in Fig. 5 a, in the DµSPE stage, sodium chloride and sodium sulfate have the highest and lowest UP values, respectively. Sodium sulfate increases the adsorption of PAAs because it induces higher ionic strength than other salts. On the other hand, sodium chloride reduces the adsorption of PAAs due to its higher viscosity than saltless case. As reported in Fig. 5 b, sodium chloride has the highest ER in the VALLME stage. Therefore, NaCl was selected as the optimal salt in both stages. Figure 5 Afterward, it is necessary to optimize the concentration of sodium chloride salt. Different concentrations from 5 to 30% (w/v ) were evaluated using the proposed method. According to Fig. S1 a, it is observed that with the increase of sodium chloride concentration up to 7.5% (w/v) , the viscosity of the solution increases and the adsorption of PAAs decreases, after that, it has no effect on the adsorption. Figure S1 b also shows that in the concentrations less than 7.5% (w/v) , "salting-out" effect doesn't work well, and in the concentrations higher than 7.5% (w/v) , the ERs decrease gradually due to the increase in viscosity of solution. Therefore, sodium chloride 7.5% (w/v) was used as the optimal salt in the next optimization steps. 3.2.4 Vortexing time in DµSPE stage Vortex operation is another key parameter in the adsorption process. Therefore, it is necessary to optimize the vortexing time. To accurately adjust the duration of vortexing, 3, 5, 7, and 9 min were selected, and UPs of the analytes were evaluated. The findings show that the UP values ​​in the examined times are not significantly different (Fig. S2), and 3 min vortexing was chosen for the further tests. 3.2.5 Derivatization agent volume BCF serves as an appropriate derivatization agent for PAAs in basic conditions. It was determined that optimizing BCF volume is essential for achieving the best derivatization. Therefore, volumes of 3, 5, 7, 9, and 11 of BCF were examined and compared based on ER values. As shown in Fig. S3, BCF volumes below and above 5 µL result in reduced derivatization and decreased ERs. It is clear that derivatization is not fully achieved in the volumes under 5 µL. In the volumes exceeding 5 µL, BCF is hydrolyzed and pH of solution decreases. It leads to incomplete derivatization of amines. Thus, 5 µL of BCF was utilized as the ideal volume for the subsequent optimization steps. 3.2.6 Study of pH in VALLME stage Derivatization of PAAs is only possible in alkaline environments because PAAs in acidic environments are as R-NH3 + form, which cannot be derivatized. As mentioned in the DµSPE section, pH 10 was chosen as the optimal pH in the aqueous phase. It has been observed that after adding adsorbent and EDTA, pH of the aqueous solution decreased from 10 to 8.5-9.0, which reduced the possibility of PAAs derivatization. For these reasons, it is necessary to re-optimize the pH of the aqueous phase. In this regard, pH 8, 9, 10, and 11 were compared based on ER criteria. Based on the reported findings (Fig. S4), low ERs are achieved at pH 8, likely because some PAAs exist in R-NH 3 + form, rendering their derivatization unfeasible. According to the pKa values ​​of PAAs, at pH 10, most PAAs are in R-NH 2 form, so derivatization and ER values are increased. At pH 11, due to the hydrolysis of BCF, ER values ​​are decreased. Therefore, pH 10 was chosen as the optimal pH in this step. 3.2.7 Type and volume of extraction solvent How to extract the derivatized PAAs depends on choosing a suitable extraction solvent. This extractant should have the following characteristics: immiscibility and higher density than deionized water, no reaction with BCF, and high ability to dissolve the derivatized PAAs. To determine the appropriate extraction solvent, ER values ​​were compared for 1,1,2-TCE, 1,1,1-TCE, 1,2-DBE, and CHCl 3 solvents. Respectively 15, 16, 15, and 26 µL of the mentioned solvents were utilized to achieve a specific organic phase volume (10 ± 0.5 µL). Figure 6 shows that 1,1,2-TCE has the highest ER values ​​for PAAs. The reason for this is high ability of 1,1,2-TCE to dissolve analytes compared to the other solvents, which led to more PAA derivatives being extracted. Figure 6 In the next step, the volume optimization of 1,1,2-TCE was done. At this stage, the volumes of 15, 20, 25, and 30 µL were evaluated using EF values. The volumes of the sedimented phase when using the mentioned volumes of the solvent were 10, 15, 21, and 27 µL, respectively. According to the results reported in Fig. S5, increasing the extractant volume leads to a decrease in EFs, which is attributed to the dilution phenomenon. Therefore, 15 µL of 1,1,2-TCE solvent was selected for PAAs extraction. 3.2.8 Vortexing time in VALLME step To complete the extraction process, after adding BCF and 1,1,2-TCE, the mixture must be vortexed. The duration of this process is one of the most important parameters of extraction. To optimize the vortexing time, 1, 3, 5, 7, and 9 min were evaluated and compared based on ER values. As reported in Fig. S6, the duration of 5 min has the highest ER values. At low vortexing times, sufficient opportunity for the simultaneous extraction and derivatization of PAAs is not provided, therefore ER values ​​are low. At high vortexing times, due to the disruption of the balance between derivatization and providing sufficient time for back extraction, the amount of ERs decreases. Therefore, a duration of 5 min was chosen as the optimal vortexing time for the next optimizations. 3.2.9 Centrifugation operation Centrifugation operation is one of the necessary steps in the extraction process, which is utilized for phases separation. Figures S7a, and S7b show the effect of time (3, 5, 7, and 9 min) and centrifugation rate (4000, 5000, 6000, and 7000 rpm) in the extraction process. As can be seen from Fig. S7a, with the increase in centrifugation time, there is a noticeable decrease in ER values, which can be attributed to the heat generated in the centrifuge, which leads to the back extraction of the derivatized PAAs. As reported in Fig. S7b, centrifugation rate has no significant effect on ER values. Therefore, in the operation of the centrifugation, the duration of 3 min and the rate of 4000 rpm were chosen as optimal values. 3.3 Reusability of adsorbent The ability of the adsorbent to eliminate or decrease matrix effect in skin moisturizers while maintaining PAAs in solution was assessed, revealing the absence of a memory effect. Following the adsorption of the matrix, the adsorbent was rinsed with a mixture of iso -propanol and deionized water (1:3, v/v) to desorb the adsorbed compounds onto the sorbent surface. The method's efficiency for matrix effect elimination was validated over 5 successive cycles using the same adsorbent, with RSD ≤ 8%. 3.4 Method validation In this section, various analytical parameters have been assessed and presented in Table 1 to validate the approach under study. UP is an important parameter in the DµSPE section that evaluates the efficiency of the adsorbent. The UP values ​​obtained for PAAs were in the range of 92–97%. ER and EF are two effective parameters to evaluate the extraction method, which were in the ranges of 84–105% and 420–525, respectively. The calibration curves in wide concentration ranges were linear with the coefficient of determination (r 2 ) greater than 0.99. Limits of detection (LOD) and quantification (LOQ) define the concentration of analytes in those signal-to-noise ratios are equal to 3 and 10, respectively. The range of LOD values ​​for PAAs was 0.50–0.82 µg L − 1 and LOQ values ​​also ranged from 1.6–2.5 µg L − 1 . To evaluate precision of the proposed method, repeatability of the results of both intra- and inter-day experiments should be assessed. Relative standard deviation (RSD) was calculated at the concentrations of approximately 5, 25, and 125 times of LOQ. Intra-day precisions (n = 6) were less than or equal to 1.1, 1.4, and 2.7% at the concentrations of 200, 40, and 10 µg L − 1 , respectively. Also, inter-day precisions (n = 4) in the concentrations mentioned above were less than or equal to 2.5, 3.7, and 5.1%. Table 1 Quantitative features of the developed DµSPE-VALLME-GC-FID method. RSD % e at the concentrations of Analyte LOD a LOQ b LR c r 2 d 10 µg L − 1 40 µg L − 1 µg L − 1 200 EF ± SD f ER ± SD g UP ± SD h Intra-day Inter-day Intra-day Inter-day Intra-day Inter-day PrA 0.50 1.6 1.6-10000 0.9991 1.6 2.4 0.95 2.0 0.9 1.9 420 ± 5 84 ± 1 96 ± 2 sec -BuA 0.65 2.1 2.1-10000 0.9989 1.9 3.0 1.0 2.1 1.0 2.0 495 ± 10 99 ± 2 96 ± 2 BuA 0.51 1.6 1.6-10000 0.9993 1.4 2.9 0.91 1.8 0.8 1.8 485 ± 5 97 ± 1 92 ± 1 PeA 0.74 2.4 2.4-10000 0.9995 2.0 3.8 1.1 2.3 1.0 2.1 510 ± 10 102 ± 2 92 ± 2 BeA 0.82 2.5 2.5-10000 0.9995 2.7 5.1 1.4 3.7 1.1 2.5 525 ± 15 105 ± 3 97 ± 3 a Limit of detection (S/N = 3) (µg L − 1 ) b Limit of quantification (S/N = 10) (µg L − 1 ) c Linear range (µg L − 1 ) d Coefficient of determination e Relative standard deviation for intra- (n = 6) and inter-day (n = 4) precisions f Enrichment factor ± standard deviation (n = 3) g Extraction recovery ± standard deviation (n = 3) h Unadsorbed percentage ± standard deviation (n = 3) Table 1 3.5 Real samples analysis This section aimed to examine the impact of eliminating the real sample matrix on relative recovery (RR) values. In this context, following spiking 10, 50, and 250 µg L − 1 of each amine to real samples and deionized water, clean up and the simultaneous extraction and derivatization processes were executed by the established method. For the second time, all the previously mentioned steps were followed, with the exception that both the real samples and deionized water were exposed to the adsorbent. The RR% values were computed based on Eq. 4 and presented in Table 2 . The RR values obtained from skin moisturizer samples (#1, #2, and #3), after matrix elimination or decrease, were 101–110, 95–112, and 100–105%, respectively. It should be noted that, without using clean up step, these figures were 100–128, 110–130, and 95–128%, respectively. Thus, it can be inferred that eliminating or decreasing the matrix of real samples has successfully diminished the major impacts of the matrix on the extraction and derivatization processes, making this method as a reliable approach for analyzing the studied compounds. The chromatograms obtained from the GC-FID analysis of skin moisturizer samples exhibited no doubtful peaks in the retention times of the analytes. This finding indicates that none of the examined PAAs was detected in skin moisturizers at the concentrations equal to or exceeding the LODs established by the analytical method. Table 2 Study of matrix effect in the samples spiked at different concentrations (without dilution). Analyte Mean relative recovery ± standard deviation (n = 3) The samples were spiked with each analyte at a concentration of 10 µg L − 1 Before eliminating the matrix After eliminating the matrix Skin moisturizer #1 Skin moisturizer #2 Skin moisturizer #3 Skin moisturizer #1 Skin moisturizer #2 Skin moisturizer #3 PrA 125 ± 2 130 ± 2 127 ± 2 102 ± 2 99 ± 2 101 ± 2 sec -BuA 128 ± 2 127 ± 2 128 ± 2 101 ± 2 95 ± 2 105 ± 2 BuA 128 ± 2 129 ± 2 123 ± 2 105 ± 1 104 ± 1 103 ± 1 PeA 123 ± 2 125 ± 2 128 ± 3 108 ± 2 110 ± 2 100 ± 2 BeA 126 ± 3 119 ± 3 128 ± 3 110 ± 3 110 ± 3 101 ± 3 The samples were spiked with each analyte at a concentration of 50 µg L − 1 Before eliminating the matrix After eliminating the matrix Skin moisturizer #1 Skin moisturizer #2 Skin moisturizer #3 Skin moisturizer #1 Skin moisturizer #2 Skin moisturizer #3 PrA 100 ± 2 110 ± 2 95 ± 2 106 ± 2 100 ± 2 100 ± 2 sec -BuA 119 ± 2 125 ± 2 124 ± 2 102 ± 2 98 ± 2 105 ± 2 BuA 125 ± 2 130 ± 2 126 ± 2 109 ± 2 110 ± 2 105 ± 1 PeA 125 ± 2 129 ± 3 128 ± 3 103 ± 2 112 ± 2 100 ± 2 BeA 128 ± 3 127 ± 3 128 ± 3 105 ± 3 112 ± 3 104 ± 3 The samples were spiked with each analyte at a concentration of 250 µg L − 1 Before eliminating the matrix After eliminating the matrix Skin moisturizer #1 Skin moisturizer #2 Skin moisturizer #3 Skin moisturizer #1 Skin moisturizer #2 Skin moisturizer #3 PrA 121 ± 2 125 ± 2 120 ± 2 107 ± 2 98 ± 2 105 ± 2 sec -BuA 128 ± 2 128 ± 2 126 ± 2 101 ± 2 100 ± 2 100 ± 2 BuA 122 ± 2 130 ± 2 123 ± 2 110 ± 2 106 ± 1 103 ± 1 PeA 126 ± 3 130 ± 3 128 ± 3 109 ± 2 112 ± 2 105 ± 2 BeA 125 ± 3 126 ± 3 128 ± 3 110 ± 3 110 ± 3 102 ± 3 Table 2 3.6 Comparison with other approaches Based on the findings shown in Table 3 , the proposed method exhibits high ERs and EFs, and wider linear range values along with notable linearity compared to the other methods. Based on RSD values, it can be asserted that this technique is highly consistent, repeatable, and fully competitive with alternative methods. Utilizing an external magnetic field to detach the MAA@Fe 3 O 4 from the aqueous solution has significantly reduced the analysis time for PAAs. The LOQ and LOD values are less than or at least equal to the majority of analytical methods. The application of BCF rendered this method less toxic, very effective, and exhibited advantageous chromatographic characteristics, indicating that this method is better than or equal to similar methods. Table 3 Comparison of the development method with similar approaches for derivatization, extraction, and determination of PAAs. Method Sample Analyte Derivatization reagent LOD a LOQ b RSD c LR d r 2 e EF f ER g Ref. HS-SDME-GC-MS h Wastewater PrA BuA PeA Pentafluoro benzaldehyde 0.9 0.7 0.8 - - - 7.6 5.3 9.8 - - - 0.992 0.995 0.997 - - - - - - 39 AALLME-GC-FID i Well, river, tap waters, and wastewater PrA sec -BuA BuA PeA Butyl chloroformate 1.1 1.7 0.4 0.3 3.7 5.7 1.4 1.0 2.7 2.1 3.6 3.7 3.7–5000 5.7–5000 1.4–5000 1.0-5000 0991 0.992 0.994 0.996 315 266 250 360 63 53 50 72 27 SPME-GC-FID j Lake water PrA BuA PeA N-succinimidylbenzoate 0.17 0.13 0.16 - - - 2.4 1.1 1.3 1-1000 1-1000 1-1000 0.9920 0.9938 0.9956 - - - - - - 40 HF-LPME-GC-MS k River water PrA BuA PeA Pentafluoro benzaldehyde 0.29 0.37 0.32 - - - 6.7 5.2 4.9 - - - 0.995 0.993 0.998 172 205 244 - - - 41 DLLME-SFO-HPLC-DAD l Well, river, and sea waters and wastewater BuA PeA Phenyl isothiocyanate 0.01 0.006 - - < 12.5 0.1–500 0.05–500 0.994 0.997 210 287 - - 30 SPME-GC-MS m Fountain, tap, and surface waters PrA Pentafluoro benzaldehyde 1 5 5 5–500 0.9989 - - 42 LLE-GC-MS n Surface water and wastewater PrA PeA Trichloroethylene chloroformate 0.15 0.04 - - 7.5 2.0 - - 0.9967 0.9998 - - - - 43 DµSPE-VALLME-GC-FID o Skin moisturizer PrA sec -BuA BuA PeA BeA Butyl chloroformate 0.50 0.65 0.51 0.74 0.82 1.6 2.1 1.6 2.4 2.5 1.6 1.9 1.4 2.0 2.7 1.6–10 4 2.1–10 4 1.6–10 4 2.4–10 4 2.5–10 4 0.9991 0.9989 0.9993 0.9995 0.9995 420 495 485 510 525 84 99 97 102 105 This work a Limit of detection (µg L − 1 ) b Limit of quantification (µg L − 1 ) c Relative standard deviation (%) d Linear Range (µg L − 1 ) e Coefficient of determination f Enrichment factor g Extraction recovery (%) h Head space-single drop microextraction-gas chromatography-mass spectrometry i Air-assisted liquid-liquid microextraction-gas chromatography-flame ionization detection j Solid phase microextraction-gas chromatography-flame ionization detection k Hollow fiber-liquid phase microextraction-gas chromatography-mass spectrometry l Dispersive liquid-liquid microextraction based on solidification of floating organic droplet-high performance liquid chromatography-diode array detection m Solid phase microextraction-gas chromatography-mass spectrometry n Liquid-liquid extraction-gas chromatography-mass spectrometry o Dispersive micro solid phase extraction - vortex-assisted liquid-liquid microextraction-gas chromatography-flame ionization detection Table 3 4. Conclusions In this study, an innovative DµSPE-VALLME methodology was presented for the first time, aimed to eliminate or decrease matrix effect associated with skin moisturizing samples, thereby facilitating the derivatization and concurrent extraction of PAAs without interference from matrix effects. In this context, MAA@Fe 3 O 4 adsorbent was employed for the first time in the clean up samples. BCF was utilized for the derivatization of PAAs in an alkaline environment. Application of the magnetic adsorbent enabled the facile collection of the adsorbent in the presence of an external magnetic field, obviating the necessity for centrifuge, which resulted in a reduction of the analysis duration. Throughout the analytical process, organic solvents were employed at µL-volumes, thereby characterizing this methodology as a green and environmentally sustainable approach. The analytical parameters associated with this technique, which include broad linear ranges (2.5-10000 µg L − 1 ), low LODs (0.50–0.82 µg L − 1 ) and LOQs (1.6–2.5 µg L − 1 ), high EFs (420–525), significant r 2 values (0.9989–0.9995), and excellent ERs (84–105%), contribute to the comprehensive or relative superiority of this method over existing methodologies. Moreover, the elimination or decreasing matrix effect of skin moisturizing samples has effectively mitigated both extraction and derivatization processes, rendering this methodology as a credible approach for the analysis of the selected compounds. Abbreviations PAA , Primary aliphatic amine; DµSPE , Dispersive micro solid phase extraction; VALLME , Vortex - assisted liquid-liquid microextraction; GC , Gas chromatography; FID , Flame ionization detector; EF , Enrichment factor; ER, Extraction recovery; RSD , Relative standard deviation; LR , Linear range; LOD , Limit of detection; LOQ , Limit of quantification; UP , Unadsorbed percent; RR , Relative recovery; PrA , Propylamine; sec -BuA , sec -Butylamine; BuA , Butylamine ; PeA , Pentylamine; BeA , Benzylamine Declarations Competing interests The authors declare no competing interests. Author Contribution M.A.F. performed the analytical methodology and edited the manuscript.S.M.M. performed adsorbent synthesis, methodology and characterization, analytical analysis and methodology, data analysis, software applications, and manuscript writing.M.R.A.M. edited the manuscript. Acknowledgement The authors are thankful to the University of Tabriz for financial support. 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VALLME conditions: aqueous phase, the supernatant separated from the previous step, without pH adjusting; extraction solvent, 1,1,2-TCE with a volume of 15 µL; derivatization agent, BCF with a volume of 5 μL; vortexing time, 5 min, and centrifugation rate and time, 5000 rpm and 5 min, respectively. Error bars depict the minimum and maximum values of three repeated determinations.\u003c/p\u003e","description":"","filename":"Fig.3.tif.jpg","url":"https://assets-eu.researchsquare.com/files/rs-5836920/v1/de77e564847a509b76a6c49a.jpg"},{"id":74225618,"identity":"c00d4113-1a83-4fa6-9b7b-dbce21ffc73b","added_by":"auto","created_at":"2025-01-20 07:22:03","extension":"jpg","order_by":4,"title":"Figure 4","display":"","copyAsset":false,"role":"figure","size":143898,"visible":true,"origin":"","legend":"\u003cp\u003eOptimization of adsorbent amount.\u003c/p\u003e\n\u003cp\u003eExperimental conditions were identical to those implemented in Fig. 3, except for adjusting pH in DµSPE step at 10.\u003c/p\u003e","description":"","filename":"Fig.4.tif.jpg","url":"https://assets-eu.researchsquare.com/files/rs-5836920/v1/7aecd66ef39c7009696e8c6d.jpg"},{"id":74225626,"identity":"b194fa3e-e5e5-4fad-b912-33f28ecf4d37","added_by":"auto","created_at":"2025-01-20 07:22:03","extension":"jpg","order_by":5,"title":"Figure 5","display":"","copyAsset":false,"role":"figure","size":127124,"visible":true,"origin":"","legend":"\u003cp\u003eInfluence of ionic strength on UP and ER values of the analytes in DµSPE (a) and VALLME (b) steps.\u003c/p\u003e\n\u003cp\u003eExperimental conditions were the same as those shown in Fig. 4, except that the adsorbent weight utilized was 20 mg.\u003c/p\u003e","description":"","filename":"Fig.5.tif.jpg","url":"https://assets-eu.researchsquare.com/files/rs-5836920/v1/72ee90ec390627ba788b759b.jpg"},{"id":74227298,"identity":"6f34fd4d-64b4-4050-87fc-83a7351f1056","added_by":"auto","created_at":"2025-01-20 07:30:03","extension":"jpg","order_by":6,"title":"Figure 6","display":"","copyAsset":false,"role":"figure","size":104905,"visible":true,"origin":"","legend":"\u003cp\u003eSelection of extraction solvent type.\u003c/p\u003e\n\u003cp\u003eExperimental conditions correspond to those shown in Fig. 5, except for adjusting pH in VALLME at 10, and the vortexing time at 3 min.\u003c/p\u003e","description":"","filename":"Fig.6.tif.jpg","url":"https://assets-eu.researchsquare.com/files/rs-5836920/v1/4f4813e27e353b85c35e71b7.jpg"},{"id":79120548,"identity":"fa772a27-6e27-4379-bb2a-ea4330d9a2b2","added_by":"auto","created_at":"2025-03-24 16:09:39","extension":"pdf","order_by":0,"title":"","display":"","copyAsset":false,"role":"manuscript-pdf","size":4852427,"visible":true,"origin":"","legend":"","description":"","filename":"manuscript.pdf","url":"https://assets-eu.researchsquare.com/files/rs-5836920/v1/8ab2d4f6-1087-411e-b3a9-cd03a186c72e.pdf"},{"id":74225615,"identity":"744e4a1e-3e19-4488-82a7-0f8808d76cfc","added_by":"auto","created_at":"2025-01-20 07:22:03","extension":"docx","order_by":1,"title":"","display":"","copyAsset":false,"role":"supplement","size":584321,"visible":true,"origin":"","legend":"","description":"","filename":"Supplementary.docx","url":"https://assets-eu.researchsquare.com/files/rs-5836920/v1/d8dd89b501d34bba83c68674.docx"}],"financialInterests":"No competing interests reported.","formattedTitle":"Eliminating or decreasing matrix effect in skin moisturizers employing a magnetic adsorbent in the analysis of primary aliphatic amines","fulltext":[{"header":"1. Introduction","content":"\u003cp\u003ePrimary aliphatic amines (PAAs) are the organic compounds with a -NH\u003csub\u003e2\u003c/sub\u003e group and a saturated carbon chain \u003csup\u003e1,2\u003c/sup\u003e. They are crucial in various chemical reactions and are used as building blocks in synthesizing pharmaceuticals, agrochemicals, and other important organic materials \u003csup\u003e3\u003c/sup\u003e. PAAs are widely used in the chemical, pharmaceutical, petrochemical, and textile industries. However, improper wastewater treatment in these industries can introduce PAAs into the environment, which negatively affects the quality of water and soil and are known as toxic pollutants for the ecosystem \u003csup\u003e4\u0026ndash;8\u003c/sup\u003e. Also, long-term exposure to these amines can cause serious damage to human health, including neurological and pulmonary diseases \u003csup\u003e9,10\u003c/sup\u003e. Therefore, the identification and measurement of PAAs is necessary to assess environmental pollution and human health threats \u003csup\u003e11\u003c/sup\u003e.\u003c/p\u003e \u003cp\u003eTo accurately measure these compounds, various analytical methods are utilized such as gas chromatography (GC) \u003csup\u003e12\u0026ndash;14\u003c/sup\u003e, high-performance liquid chromatography \u003csup\u003e11,15,16\u003c/sup\u003e, and spectrofluorimetry \u003csup\u003e17\u003c/sup\u003e. However, due to the complexity of the matrix and low concentration of PAAs, the measurement of these compounds in aqueous samples is challenging. The employment of extraction and preconcentration techniques is correlated with enhanced sensitivity and reduced matrix effects. Among these techniques, liquid-liquid extraction \u003csup\u003e18\u003c/sup\u003e and solid phase extraction (SPE) \u003csup\u003e19\u003c/sup\u003e are widely used, but they have limitations, including high use of organic solvents, time-consuming, and high costs. In addition, SPE can encounter issues such as cartridge blockage and memory effects \u003csup\u003e20\u003c/sup\u003e.\u003c/p\u003e \u003cp\u003eMicroextraction methods have been introduced to overcome these limitations. In single drop microextraction method, a single drop is accomplished to extract analytes, but this method faces issues such as disturbance in the stability of the organic drop during rapid stirring and long extraction times \u003csup\u003e20\u003c/sup\u003e. In hollow fiber-liquid phase microextraction method, an extractant droplet is placed inside a hollow fiber, but this method is usually faced with low efficiency and a long extraction time \u003csup\u003e21\u003c/sup\u003e. Solid phase microextraction method is a solvent-free technique, but it is usually associated with high costs and limited efficiency \u003csup\u003e22\u0026ndash;24\u003c/sup\u003e. In dispersive liquid-liquid microextraction, the extraction is done quickly and efficiently because the extractant is completely dispersed into an aqueous solution \u003csup\u003e25,26\u003c/sup\u003e. As the name of the technique suggests, this technique is based on the use of a disperser solvent, which has turned it into one of the limitations of this method, because this solvent, due to its semi-polar nature, reduces the polarity of the aqueous phase, which causes the analytes to be more dissolved in this phase and do not tend to be extracted into the organic phase. Moreover, it leads to the loss of certain analytes, particularly volatile ones, during injection of the mixture of disperser and extractant into the aqueous phase \u003csup\u003e27\u003c/sup\u003e. Vortex-assisted liquid-liquid microextraction (VALLME) obviates the necessity for a disperser solvent by employing vortex to facilitate dispersion of the extraction solvent within the sample solution. Furthermore, it not only diminishes costs but also mitigates the issues associated with the loss of volatile analytes \u003csup\u003e28,29\u003c/sup\u003e.\u003c/p\u003e \u003cp\u003eExtraction of PAAs from aqueous phase is challenging due to high polarity of these compounds. Also, another problem appeared especially in GC because amines can have unexpected interactions with the stationary phase, which causes peak tailing. To solve these limitations, these compounds can be derivatized \u003csup\u003e30\u003c/sup\u003e. Different derivation agents for the derivatization of PAAs are utilized, including silylating agents \u003csup\u003e31\u003c/sup\u003e, acylating agents \u003csup\u003e32\u003c/sup\u003e, alkylating agents \u003csup\u003e33\u003c/sup\u003e, and carbamates \u003csup\u003e34\u003c/sup\u003e. Each of them offers distinct advantages in terms of efficiency, specificity, and nature of the resulting derivatives. Alkyl chloroformate is a suitable derivation agent for amines due to formation of stable derivatives with amines (alkyl carbamates) and improved chromatographic properties \u003csup\u003e35\u003c/sup\u003e. In alkaline conditions, the rate of derivatization rises, contributing to the formation of more stable and efficient derivatives \u003csup\u003e34\u003c/sup\u003e.\u003c/p\u003e \u003cp\u003eTo accurately monitor and measure PAAs in complex real samples, it is essential to eliminate or reduce matrix effects. Dispersive micro solid phase extraction (D\u0026micro;SPE) methodology represents a new approach wherein adsorbent particulates are uniformly dispersed within the sample solution, facilitating comprehensive interaction with the target analytes and enhancing the overall extraction efficacy \u003csup\u003e36\u003c/sup\u003e. This technique, contingent upon the specific adsorbent employed, can selectively adsorb various chemical compounds. Based on the structure of PAAs and their pH sensitivity, an adsorbent capable of fulfilling this role within a specific pH range should be employed to remove the matrix while selectively retaining the amines.\u003c/p\u003e \u003cp\u003eThis study was carried out in two parts: passivation of adsorbent in elimination of PAAs, and simultaneous extraction and derivatization of PAAs during VALLME. In the first part, the attempt was to optimize the conditions in the D\u0026micro;SPE method using iron oxide modified by mercapto acetic acid (MAA@Fe\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e) adsorbent to eliminate or decrease sample matrix effect while maintaining PAAs in the solution. In the second part, VALLME was used for concurrent extraction and derivatization of PAAs. In this process, butyl chloroformate (BCF) was used as a derivatization agent to convert amines into carbamate derivatives and successfully extraction of them. This method has a great potential in PAAs analysis due to utilization of \u0026micro;L-scale extractant and derivatization agent, eco-friendliness of the adsorbent used, and its effective efficiency.\u003c/p\u003e"},{"header":"2. Experimental","content":"\u003cdiv id=\"Sec3\" class=\"Section2\"\u003e \u003ch2\u003e2.1 Chemicals and solutions\u003c/h2\u003e \u003cp\u003eUtilized PAAs included propylamine (PrA), butylamine (BuA) [purchased from Fluka, Bosch, Switzerland], pentylamine (PeA), benzylamine (BeA), and \u003cem\u003esec\u003c/em\u003e-butylamine (\u003cem\u003esec\u003c/em\u003e-BuA) [obtained from Merck, Darmstadt, Germany]. A standard solution of PAAs with a concentration of 500 mg L\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e (of each analyte) was prepared in methanol. To prepare the daily standard solution, it was diluted using deionized water [obtained from Ghazi Company, Tabriz, Iran]. For adsorbent synthesis process, iron sulfate heptahydrate (FeSO\u003csub\u003e4\u003c/sub\u003e.7H\u003csub\u003e2\u003c/sub\u003eO) 99.5%, mercaptoacetic acid (MAA) 98%, concentrated ammonia (25%, \u003cem\u003ew/w\u003c/em\u003e), ethanol 99.8%, and iron chloride hexahydrate (FeCl\u003csub\u003e3\u003c/sub\u003e.6H\u003csub\u003e2\u003c/sub\u003eO) 98.5% [all purchased from Merck] were used. To optimize the ionic strength, sodium sulfate 99%, potassium chloride 99.9%, sodium chloride 99% [purchased from Merck], to adjust pH of the aqueous phase, sodium hydroxide 99% and hydrochloric acid (37%, \u003cem\u003ew/w\u003c/em\u003e) [purchased from Fluka], and to prevent precipitation in alkaline media disodium ethylenediaminetetraacetic acid (EDTA) [obtained from Merck] were utilized. In this work extraction solvents including 1,1,1-trichloroethane (1,1,1-TCE) 99.7%, 1,2-dibromoethane (1,2-DBE) 98%, chloroform (CHCl\u003csub\u003e3\u003c/sub\u003e) 99%, and 1,1,2-trichloroethane(1,1,2-TCE) 99.5% [obtained from Johnson, Beerse, Belgium] were utilized.\u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec4\" class=\"Section2\"\u003e \u003ch2\u003e2.2 Samples\u003c/h2\u003e \u003cp\u003eThree skin moisturizers were purchased from a cosmetic store (Tabriz, Iran). All samples were placed in contact with the adsorbent according to the D\u0026micro;SPE method to eliminate or decrease the matrix effect (without dilution). Then, the supernatant was subjected to the simultaneous derivatization and extraction of PAAs in VALLME method. It should be noted that before adjusting pH at 10, EDTA (10 mg) was added to 5 mL of each sample.\u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec5\" class=\"Section2\"\u003e \u003ch2\u003e2.3 Apparatus\u003c/h2\u003e \u003cp\u003eA GC equipped with flame ionization detector (FID) model 2014 (manufactured by Shimadzu, Kyoto, Japan) was used to study the matrix of real samples before and after contact with the adsorbent, and to separate, identify, and quantify the derived PAAs. The instrument was equipped with a split/splitless injector that was set in a splitless/split mode (split time 1 min and split ratio 1:10) thermostated at 300\u0026deg;C. The FID temperature was set at 300\u0026deg;C. A capillary column (dimethyl: diphenylpolysiloxane 95:5) with a length of 30 m, inner diameter of 0.25 mm, and a stationary phase film thickness of 0.25 \u0026micro;m (Restex, Center, PA, USA) was used for the separation and detection of PAAs. The initial temperature of column oven was adjusted to 60\u0026deg;C and maintained at this level for 2 min. Then it was increased to 200\u0026deg;C with a ramp of 10\u0026deg;C min\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e and maintained at this temperature for 2 min. The carrier gas utilized was helium (99.999%, Crewe Bay, Dubai, United Arab Emirates) which was introduced into the GC at a linear velocity of 30 cm s\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e. The fuel used in the FID was hydrogen supplied by a hydrogen generator (OPGU 1500S, Shimadzu, Kyoto, Japan) with a flow rate of 30 mL min\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e. Also, the oxidant used in FID was air, which entered the FID chamber with an airflow rate of 300 mL min\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e. Drying of the synthesized MAA@Fe\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e was done using an oven (Heraeus UT 12, Hanau, Germany). A vortex (Labinco L46 vortex mixer, Breda, the Netherlands) was utilized to establish sufficient contact between the analytes and adsorbent, and analytes, derivatization agent, and extraction solvent. After derivatization and extraction, a centrifuge (Hettich D7200, Kitchener, Germany) was used to facilitate separation of organic and aqueous phases. pH of samples was adjusted before the contact of the analytes with the adsorbent and before derivatization and extraction by employing a pH meter (Metrohm 654, Herisau, Switzerland). To identify the adsorbent morphology and assess its composition, scanning electron microscopy (SEM) and energy diffraction X-ray (EDX) analyses were performed using a Mira 3 microscope (Tescan Mira 3, Brno, Czech Republic). Fourier transform infrared (FTIR) (Bruker, Billerica, MA, USA) and X-ray diffraction (XRD) (Siemens D500 diffractometer AG, Karlsruhe, Germany) analyses were performed to authenticate the synthesis and formation of the desired bonds. To verify the magnetic characteristics of the adsorbent, vibrating sample magnetometry (VSM) (MDKB, Magnetic DaneshPajoh Kashan Co. Kashan, Iran) was conducted, and for assessing the surface area and pore size, Brunauer-Emmett-Teller (BET) analysis was performed using a BELSORP-mini-instrument (MicrotracBEL Corp, Osaka, Japan).\u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec6\" class=\"Section2\"\u003e \u003ch2\u003e2.4 Synthesis of MAA@Fe3O4\u003c/h2\u003e \u003cp\u003eSynthesis of magnetic adsorbent functionalized with MAA included two steps. The first step was the synthesis of Fe\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e particles as described in our previous work \u003csup\u003e37\u003c/sup\u003e. The second step was functionalizing MAA on Fe\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e particles \u003csup\u003e38\u003c/sup\u003e. For this purpose, 2.9 mmol of MAA was dissolved in 100 mL of ethanol and then 0.5 g of Fe\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e particles were added into it. The resulting mixture was stirred on a stirrer for 24 h, and then MAA@Fe\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e particles were collected from the reaction mixture using an external magnetic field and washed with a 1:1 mixture of ethanol and water (several times). Finally, MAA@Fe\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e microspheres were dried in an oven at 50\u0026deg;C for 3 h under vacuum conditions.\u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec7\" class=\"Section2\"\u003e \u003ch2\u003e2.5 Clean up and derivatization/ extraction Procedures\u003c/h2\u003e \u003cdiv id=\"Sec8\" class=\"Section3\"\u003e \u003ch2\u003e2.5.1 D\u0026micro;SPE step\u003c/h2\u003e \u003cp\u003eFive milliliters of real sample or deionized water (spiked with the analytes at 500 mg L\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e of each amine) was poured into a 10-mL conical bottom glass test tube, and pH of solution was adjusted at 10 using 0.1 M NaOH solution. Sodium chloride (0.375 g) was added to adjust the ionic strength along with 10 mg of EDTA to prevent unexpected precipitate formation. Finally, 20 mg of MAA@Fe\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e was added to the solution and then vortexed for 3 min to establish adequate contact between the analytes and MAA@Fe\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e particles. It should be noted that to prevent the escape of PAAs, everything that was added to the glass test tube immediately and the cap was put on it. An external magnetic field was used to easily separate the adsorbent particles from the solution in a short time. Then the supernatant was transferred into another glass test tube.\u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec9\" class=\"Section3\"\u003e \u003ch2\u003e2.5.2 VALLME step\u003c/h2\u003e \u003cp\u003eDue to the acidity of the adsorbent, after the contact of the aqueous solution with the adsorbent, its pH decreased. As mentioned in the introduction section, the suitable pH for the derivatization of PAAs is an alkaline medium. Therefore, first, the pH of the supernatant (obtained from the D\u0026micro;SPE step) was checked and re-adjusted at pH 10. Then 5 \u0026micro;L of BCF was mixed with 15 \u0026micro;L of 1,1,2-TCE inside a 1-mL conical bottom vial, and then slowly introduced into the aqueous solution by a 50-\u0026micro;L syringe. The cap was immediately placed and vortexed for 5 min to perform derivatization and extraction. To separate the phases and settle down the extractive phase, it was centrifuged for 3 min with a speed of 4000 rpm. Finally, 1 \u0026micro;L of the settled phase (10\u0026thinsp;\u0026plusmn;\u0026thinsp;0.5 \u0026micro;L) was injected into GC-FID. The schematic of whole process is shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig1\" class=\"InternalRef\"\u003e1\u003c/span\u003e.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003eFigure\u0026nbsp;\u003cspan refid=\"Fig1\" class=\"InternalRef\"\u003e1\u003c/span\u003e\u003c/p\u003e \u003c/div\u003e \u003c/div\u003e \u003cdiv id=\"Sec10\" class=\"Section2\"\u003e \u003ch2\u003e2.6 Calculations\u003c/h2\u003e \u003cp\u003eEnrichment factor (EF) is an indication of the extent of analytes preconcentration (Eq.\u0026nbsp;1). Extraction recovery (ER) serves as an indicator of how effectively analytes are extracted from an aqueous phase into the organic phase (Eq.\u0026nbsp;2). Unadsorbed percent (UP) of the analyte indicates the percentage of analyte that is not adsorbed by the adsorbent (Eq.\u0026nbsp;3). This equation is used exclusively in the D\u0026micro;SPE stage. The high value of this parameter is favorite in this study. Relative recovery (RR) is a criterion for evaluating the effectiveness of the proposed method, indicating whether complex matrices can diminish the method's efficiency (Eq.\u0026nbsp;4).\u003cdiv id=\"Equa\" class=\"Equation\"\u003e\u003cdiv format=\"TEX\" class=\"mathdisplay\" id=\"FileID_Equa\" name=\"EquationSource\"\u003e\n$$\\:EF=\\frac{{C}_{sed}}{{C}_{₀}}\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\left(1\\right)$$\u003c/div\u003e\u003c/div\u003e\u003cdiv id=\"Equb\" class=\"Equation\"\u003e\u003cdiv format=\"TEX\" class=\"mathdisplay\" id=\"FileID_Equb\" name=\"EquationSource\"\u003e\n$$\\:ER=\\frac{{n}_{sed}}{{n}_{₀}}\\times\\:100=\\frac{{C}_{sed}\\times\\:\\:{V}_{sed}}{{C}_{₀}\\:\\times\\:\\:{V}_{₀}}\\times\\:100=EF\\times\\:\\frac{{V}_{sed}}{{V}_{₀}}\\times\\:100\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\left(2\\right)$$\u003c/div\u003e\u003c/div\u003e\u003c/p\u003e \u003cp\u003eIn these equations, \u003cspan class=\"InlineEquation\"\u003e\u003cspan class=\"mathinline\"\u003e\\(\\:{C}_{sed}\\)\u003c/span\u003e\u003c/span\u003e represents concentration of analyte in organic phase, \u003cspan class=\"InlineEquation\"\u003e\u003cspan class=\"mathinline\"\u003e\\(\\:{C}_{₀}\\)\u003c/span\u003e\u003c/span\u003e indicates the initial concentration of analyte in aqueous solution, \u003cspan class=\"InlineEquation\"\u003e\u003cspan class=\"mathinline\"\u003e\\(\\:{n}_{sed}\\)\u003c/span\u003e\u003c/span\u003e denotes the number of moles of analyte in the organic phase, \u003cspan class=\"InlineEquation\"\u003e\u003cspan class=\"mathinline\"\u003e\\(\\:{n}_{₀}\\)\u003c/span\u003e\u003c/span\u003e signifies the number of moles of analyte in aqueous phase, \u003cspan class=\"InlineEquation\"\u003e\u003cspan class=\"mathinline\"\u003e\\(\\:{V}_{sed}\\:\\)\u003c/span\u003e\u003c/span\u003erefers to the volume of the sedimented organic phase, and \u003cspan class=\"InlineEquation\"\u003e\u003cspan class=\"mathinline\"\u003e\\(\\:{V}_{₀}\\)\u003c/span\u003e\u003c/span\u003e represents the volume of the aqueous phase.\u003cdiv id=\"Equc\" class=\"Equation\"\u003e\u003cdiv format=\"TEX\" class=\"mathdisplay\" id=\"FileID_Equc\" name=\"EquationSource\"\u003e\n$$\\:UP=100-\\left[\\left(\\frac{{C}_{{sed}_{1}}-{C}_{{sed}_{2}}}{{C}_{{sed}_{1}}}\\right)*100\\right]\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:$$\u003c/div\u003e\u003c/div\u003e\u003c/p\u003e \u003cp\u003eIn this equation, \u003cspan class=\"InlineEquation\"\u003e\u003cspan class=\"mathinline\"\u003e\\(\\:{C}_{{sed}_{1}}\\)\u003c/span\u003e\u003c/span\u003e represents the concentration of analyte extracted directly from the aqueous solution without contacting with the adsorbent, while \u003cspan class=\"InlineEquation\"\u003e\u003cspan class=\"mathinline\"\u003e\\(\\:{C}_{{sed}_{2}}\\)\u003c/span\u003e\u003c/span\u003e denotes the concentration of analyte extracted from the supernatant solution after contacting with the adsorbent. In this equation, if PAAs are entirely adsorbed, no PAAs will be present in the supernatant solution, making the value of \u003cspan class=\"InlineEquation\"\u003e\u003cspan class=\"mathinline\"\u003e\\(\\:{C}_{{sed}_{2}}\\)\u003c/span\u003e\u003c/span\u003eequal to 0, resulting in UP being 0. If PAAs are not adsorbed at all, PAAs will be found in the supernatant solution and \u003cspan class=\"InlineEquation\"\u003e\u003cspan class=\"mathinline\"\u003e\\(\\:{C}_{{sed}_{2}}\\)\u003c/span\u003e\u003c/span\u003ewill be equal to \u003cspan class=\"InlineEquation\"\u003e\u003cspan class=\"mathinline\"\u003e\\(\\:{C}_{{sed}_{1}}\\)\u003c/span\u003e\u003c/span\u003e, making UP\u0026thinsp;=\u0026thinsp;100. Therefore, in the intermediate states, the value of UP varies from 0 to 100.\u003cdiv id=\"Equd\" class=\"Equation\"\u003e\u003cdiv format=\"TEX\" class=\"mathdisplay\" id=\"FileID_Equd\" name=\"EquationSource\"\u003e\n$$\\:RR=\\frac{{C}_{total}-{C}_{real}}{{C}_{added}}\\:\\times\\:100\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\left(4\\right)$$\u003c/div\u003e\u003c/div\u003e\u003c/p\u003e \u003cp\u003eIn this equation, \u003cspan class=\"InlineEquation\"\u003e\u003cspan class=\"mathinline\"\u003e\\(\\:{C}_{real}\\)\u003c/span\u003e\u003c/span\u003e is concentration of the analyte in real sample, \u003cspan class=\"InlineEquation\"\u003e\u003cspan class=\"mathinline\"\u003e\\(\\:{C}_{added}\\)\u003c/span\u003e\u003c/span\u003e is the spiked concentration of the analyte to the real sample, and \u003cspan class=\"InlineEquation\"\u003e\u003cspan class=\"mathinline\"\u003e\\(\\:{C}_{total}\\)\u003c/span\u003e\u003c/span\u003e is total concentration of the analyte in the real sample after spiking.\u003c/p\u003e \u003c/div\u003e"},{"header":"3. Results and discussion","content":"\u003cdiv id=\"Sec12\" class=\"Section2\"\u003e \u003ch2\u003e3.1 Characterization of MAA@Fe3O4\u003c/h2\u003e \u003cp\u003eSEM is a powerful tool for studying the surface of materials with very high magnification. Through SEM images, surface morphology, particle size, size distribution, and other surface characteristics of materials can be examined. Figures\u0026nbsp;\u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e2\u003c/span\u003ea and \u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e2\u003c/span\u003eb show the particles have an irregular and sometimes granular morphology. Their size is in the range of 30\u0026ndash;50 nm, and the distribution of particles size is relatively uniform.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003eEDX is the technique used to determine the elemental composition of solid samples. The spectrum reported in Fig.\u0026nbsp;\u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e2\u003c/span\u003ec confirms the presence of iron, carbon, oxygen, and sulfur in the adsorbent composition. The presence of iron and carbon, respectively, indicates the magnetic phase and the presence of organic substance in the absorbent structure. The peak related to sulfur confirms the presence of MAA in the absorbent structure. It should be noted that there is a specific peak at around 2.3 Kev, which is related to the gold coating used to increase the electrical conductivity of the sample.\u003c/p\u003e \u003cp\u003eVSM is an appropriate technique for assessing the magnetic characteristics of materials. As illustrated in Fig.\u0026nbsp;\u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e2\u003c/span\u003ed, the hysteresis curve of MAA@Fe\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e demonstrates its ferromagnetic or superparamagnetic characteristics. At 300 K, the saturation magnetization of Fe\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e is measured at 14.82 emu g\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e, while that of MAA@Fe\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e is 9.52 emu g\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e. Consequently, it can be inferred that the coating MAA on Fe\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e nanoparticles decreases their magnetization, and this alteration arises from the interactions between Fe\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e nanoparticles and MAA, leading to magnetic anisotropy.\u003c/p\u003e \u003cp\u003eFTIR is an effective method for identifying functional groups and chemical bonds in different substances. In this study, FTIR spectra of Fe\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e and MAA@Fe\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e (Fig.\u0026nbsp;\u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e2\u003c/span\u003ee), were examined to assess the influence of the coating on the sorbent structure and composition. The main peak occurring around 625 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e corresponds to the stretching vibration of the Fe-O bond within Fe\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e structure. This peak verifies the existence of Fe\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e phase in the sample. Wide peaks at approximately 3395 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e and a faint peak near 1643 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e correspond to water molecules that are adsorbed on the surface of Fe\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e nanoparticles. To examine the spectrum of MAA@Fe\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e in greater details, we needed to identify the alterations that took place in comparison to the spectrum of Fe\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e. These alterations may signify the existence of functional groups of MAA on the nanoparticle surface. The wide peak associated with the stretching vibration of O-H bond at 3395 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e is more intense in the MAA@Fe\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e spectrum compared to the Fe\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e spectrum. This is attributed to the existence of carboxyl groups (-COOH) in MAA. The peak associated with the stretching vibration of the carbonyl bond (C\u0026thinsp;=\u0026thinsp;O) within the carboxyl group is seen in the range of 1559 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e. The peak related to the stretching vibration of the C-S bond is seen at around 587 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e. The peak associated with the stretching vibration of sulfhydryl bond (S-H) can be detected in the region of 2919 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e. Based on the observations recorded, it can be inferred that the functionalization procedure has been effectively achieved and the MAA is bonded onto the Fe\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e nanoparticle surface.\u003c/p\u003e \u003cp\u003eXRD is one of the suitable tools for identifying crystalline phases and structural changes in materials. To confirm the success of the MAA@Fe\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e synthesis and investigate the binding of MAA, XRD patterns for Fe\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e and MAA@Fe\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e were prepared and are shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e2\u003c/span\u003ef. These patterns were recorded in the angular range of 2θ between 10 and 80\u003csup\u003e⸰\u003c/sup\u003e. In the spectrum of Fe\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e, the specific peaks of the spinel structure in the crystal planes of (111), (220), (311), (400), (422), (511), and (440) at 2θ values ​​equal to 18, 30.1, 35.5, 43.1, 53.4, 57.3, and 62.5 are observed. These peaks are still present in the spectrum of MAA@Fe\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e, but a significant decrease in their intensity is seen, especially at 35.5 and 62.5. This decrease in intensity indicates the surface coating of particles by MAA. Also, the slight increase in baseline at low 2θ values ​​confirms the presence of organic groups. The changes observed in the XRD spectrum confirm that MAA is successfully functionalized on the surface of Fe\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e particles.\u003c/p\u003e \u003cp\u003eBET analysis determines the specific surface area, cumulative pore volume, and pore size distribution of porous materials by measuring the amount of nitrogen adsorption at a constant temperature of liquid nitrogen. Figure\u0026nbsp;\u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e2\u003c/span\u003eg shows the nitrogen adsorption isotherm of the adsorbent based on the BET method. The results of this analysis show that the specific surface area of ​​the absorbent is equal to 64.275 m\u003csup\u003e2\u003c/sup\u003e g\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e, its cumulative pore volume is 0.3527 cm\u003csup\u003e3\u003c/sup\u003e g\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e, and the average diameter of its pores is 21.949 nm. The high values ​​of the specific surface area and cumulative pore volume indicate the presence of active surface and high porosity in the absorbent structure, which are very favorable for adsorption and catalytic applications. Also, the average pore diameter obtained shows that the adsorbent has the pores in the mesoporous range.\u003c/p\u003e \u003cp\u003eFigure\u0026nbsp;\u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e2\u003c/span\u003e\u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec13\" class=\"Section2\"\u003e \u003ch2\u003e3.2 Optimization of parameters in D\u0026micro;SPE-VALLME\u003c/h2\u003e \u003cdiv id=\"Sec14\" class=\"Section3\"\u003e \u003ch2\u003e3.2.1 Aqueous solution pH in D\u0026micro;SPE stage\u003c/h2\u003e \u003cp\u003eConsidering that MAA has a carboxylic acid group, it can be expected that the pKa of the MMA attaches to Fe\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e to be in the range of pKa of common carboxylic acids (between 4 and 5). The adsorbent at pH lower and higher than this range is in the forms of R-COOH and R-COO\u003csup\u003e\u0026minus;\u003c/sup\u003e, respectively. In addition, considering that the pKa of PAAs is in the range 9.3\u0026ndash;10.7, these compounds are in the forms of R-NH\u003csub\u003e3\u003c/sub\u003e\u003csup\u003e+\u003c/sup\u003e and R-NH\u003csub\u003e2\u003c/sub\u003e at the pHs lower and higher than this range, respectively. At pH below 4, both adsorbent and PAAs are in the protonated forms and have not electrostatic attraction. At pH above 9, the adsorbent and PAAs are in R-COO\u003csup\u003e\u0026minus;\u003c/sup\u003e and R-NH\u003csub\u003e2\u003c/sub\u003e forms, respectively, so electrostatic attraction between the adsorbent and the PAAs does not occur. In the pHs between 4 and 9, the adsorbent and PAAs are in the forms of -COO\u003csup\u003e\u0026minus;\u003c/sup\u003e and R-NH\u003csub\u003e3\u003c/sub\u003e\u003csup\u003e+\u003c/sup\u003e, respectively, and the PAAs are electrostatically adsorbed by the adsorbent. To examine the influence of pH on PAAs adsorption, the pH values of 1, 3, 7, 10, and 13 were investigated and assessed according to the UP criteria (Fig.\u0026nbsp;\u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e3\u003c/span\u003e). As expected, the lowest UP value or highest adsorbed value is related to neutral pH, which indicates the electrostatic attraction between the adsorbent and PAAs. At pH 3, the level of PAAs adsorption is lower than that of pH 7. This is likely because, at this pH, some parts of the adsorbent exist as R-COOH and another part as R-COO\u003csup\u003e\u0026minus;\u003c/sup\u003e, allowing it to adsorb some PAAs electrostatically. At pH 1, the quantity of UP is risen, due to decreasing R-COO\u003csup\u003e\u0026minus;\u003c/sup\u003e form in this pH. At pHs 10 and 13, all analytes show the highest UP values (lowest adsorbed values). Likely, PAAs exist mainly in their R-NH\u003csub\u003e2\u003c/sub\u003e forms at these pHs, which prevent them from interacting electrostatically with the adsorbent. Therefore, pH 10 was selected for the further studies.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003eFigure\u0026nbsp;\u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e3\u003c/span\u003e\u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec15\" class=\"Section3\"\u003e \u003ch2\u003e3.2.2 MAA@Fe\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e weight\u003c/h2\u003e \u003cp\u003eIn this section, several factors should be considered to select the optimal adsorbent weight: the method's efficiency and cost-effectiveness, the elimination or decreasing matrix effect, and the prevention of PAAs adsorption by the sorbent. The values ​​of 3, 5, 10, 15, 20, 25, and 30 mg adsorbent were examined and evaluated based on the UP criteria to optimize the adsorbent weight. According to the reported findings (Fig.\u0026nbsp;\u003cspan refid=\"Fig4\" class=\"InternalRef\"\u003e4\u003c/span\u003e), the UP values remain constant in the weights\u0026thinsp;\u0026le;\u0026thinsp;20 mg. Increasing the adsorbent weight beyond 20 mg has led to a reduction in UP. The objective of this study is to eliminate or reduce the sample matrix effect while preserving the presence of PAAs in the samples; consequently, it is imperative to determine the maximum adsorbent weight that does not eliminate PAAs. Accordingly, 20 mg of the adsorbent was selected as the ideal weight that suits the aims of this study for the future optimizations.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003eFigure\u0026nbsp;\u003cspan refid=\"Fig4\" class=\"InternalRef\"\u003e4\u003c/span\u003e\u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec16\" class=\"Section3\"\u003e \u003ch2\u003e3.2.3 Ionic strength study\u003c/h2\u003e \u003cp\u003eThe modification of the ionic strength of an aqueous solution is accomplished through addition of a salt. The process of salt addition can have two distinct outcomes. The introduction of salt into the aqueous solution decreases the solubility of PAAs, which enhances their adsorption (thereby reducing UP values), a phenomenon referred to \"salting-out\" effect. Conversely, the addition of salt may lead to an increase in viscosity of the aqueous solution, a reduction in the adsorption of PAAs (increasing UP values), known as the \"salting-in\" effect. According to the procedure stated in section 2.5, the aqueous solution containing PAAs, after contact with the adsorbent, was subjected to simultaneous extraction and derivatization conditions. Therefore, the effect of salt addition can be effective in both D\u0026micro;SPE and VALLME steps. To investigate this parameter, three salts consisting of sodium chloride, sodium sulfate, and potassium chloride with a concentration of 1 M as well as without salt addition were utilized. It should be noted that the UP and ER% criteria during the D\u0026micro;SPE and VALLME stages, respectively, were employed to assess the effect of salt addition. As reported in Fig.\u0026nbsp;\u003cspan refid=\"Fig5\" class=\"InternalRef\"\u003e5\u003c/span\u003ea, in the D\u0026micro;SPE stage, sodium chloride and sodium sulfate have the highest and lowest UP values, respectively. Sodium sulfate increases the adsorption of PAAs because it induces higher ionic strength than other salts. On the other hand, sodium chloride reduces the adsorption of PAAs due to its higher viscosity than saltless case. As reported in Fig.\u0026nbsp;\u003cspan refid=\"Fig5\" class=\"InternalRef\"\u003e5\u003c/span\u003eb, sodium chloride has the highest ER in the VALLME stage. Therefore, NaCl was selected as the optimal salt in both stages.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003eFigure\u0026nbsp;\u003cspan refid=\"Fig5\" class=\"InternalRef\"\u003e5\u003c/span\u003e\u003c/p\u003e \u003cp\u003eAfterward, it is necessary to optimize the concentration of sodium chloride salt. Different concentrations from 5 to 30% \u003cem\u003e(w/v\u003c/em\u003e) were evaluated using the proposed method. According to Fig. \u003cspan refid=\"MOESM1\" class=\"InternalRef\"\u003eS1\u003c/span\u003ea, it is observed that with the increase of sodium chloride concentration up to 7.5% \u003cem\u003e(w/v)\u003c/em\u003e, the viscosity of the solution increases and the adsorption of PAAs decreases, after that, it has no effect on the adsorption. Figure \u003cspan refid=\"MOESM1\" class=\"InternalRef\"\u003eS1\u003c/span\u003eb also shows that in the concentrations less than 7.5% \u003cem\u003e(w/v)\u003c/em\u003e, \"salting-out\" effect doesn't work well, and in the concentrations higher than 7.5% \u003cem\u003e(w/v)\u003c/em\u003e, the ERs decrease gradually due to the increase in viscosity of solution. Therefore, sodium chloride 7.5% \u003cem\u003e(w/v)\u003c/em\u003e was used as the optimal salt in the next optimization steps.\u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec17\" class=\"Section3\"\u003e \u003ch2\u003e3.2.4 Vortexing time in D\u0026micro;SPE stage\u003c/h2\u003e \u003cp\u003eVortex operation is another key parameter in the adsorption process. Therefore, it is necessary to optimize the vortexing time. To accurately adjust the duration of vortexing, 3, 5, 7, and 9 min were selected, and UPs of the analytes were evaluated. The findings show that the UP values ​​in the examined times are not significantly different (Fig. S2), and 3 min vortexing was chosen for the further tests.\u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec18\" class=\"Section3\"\u003e \u003ch2\u003e3.2.5 Derivatization agent volume\u003c/h2\u003e \u003cp\u003eBCF serves as an appropriate derivatization agent for PAAs in basic conditions. It was determined that optimizing BCF volume is essential for achieving the best derivatization. Therefore, volumes of 3, 5, 7, 9, and 11 of BCF were examined and compared based on ER values. As shown in Fig. S3, BCF volumes below and above 5 \u0026micro;L result in reduced derivatization and decreased ERs. It is clear that derivatization is not fully achieved in the volumes under 5 \u0026micro;L. In the volumes exceeding 5 \u0026micro;L, BCF is hydrolyzed and pH of solution decreases. It leads to incomplete derivatization of amines. Thus, 5 \u0026micro;L of BCF was utilized as the ideal volume for the subsequent optimization steps.\u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec19\" class=\"Section3\"\u003e \u003ch2\u003e3.2.6 Study of pH in VALLME stage\u003c/h2\u003e \u003cp\u003eDerivatization of PAAs is only possible in alkaline environments because PAAs in acidic environments are as R-NH3\u003csup\u003e+\u003c/sup\u003e form, which cannot be derivatized. As mentioned in the D\u0026micro;SPE section, pH 10 was chosen as the optimal pH in the aqueous phase. It has been observed that after adding adsorbent and EDTA, pH of the aqueous solution decreased from 10 to 8.5-9.0, which reduced the possibility of PAAs derivatization. For these reasons, it is necessary to re-optimize the pH of the aqueous phase. In this regard, pH 8, 9, 10, and 11 were compared based on ER criteria. Based on the reported findings (Fig. S4), low ERs are achieved at pH 8, likely because some PAAs exist in R-NH\u003csub\u003e3\u003c/sub\u003e\u003csup\u003e+\u003c/sup\u003e form, rendering their derivatization unfeasible. According to the pKa values ​​of PAAs, at pH 10, most PAAs are in R-NH\u003csub\u003e2\u003c/sub\u003e form, so derivatization and ER values are increased. At pH 11, due to the hydrolysis of BCF, ER values ​​are decreased. Therefore, pH 10 was chosen as the optimal pH in this step.\u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec20\" class=\"Section3\"\u003e \u003ch2\u003e3.2.7 Type and volume of extraction solvent\u003c/h2\u003e \u003cp\u003eHow to extract the derivatized PAAs depends on choosing a suitable extraction solvent. This extractant should have the following characteristics: immiscibility and higher density than deionized water, no reaction with BCF, and high ability to dissolve the derivatized PAAs. To determine the appropriate extraction solvent, ER values ​​were compared for 1,1,2-TCE, 1,1,1-TCE, 1,2-DBE, and CHCl\u003csub\u003e3\u003c/sub\u003e solvents. Respectively 15, 16, 15, and 26 \u0026micro;L of the mentioned solvents were utilized to achieve a specific organic phase volume (10\u0026thinsp;\u0026plusmn;\u0026thinsp;0.5 \u0026micro;L). Figure\u0026nbsp;\u003cspan refid=\"Fig6\" class=\"InternalRef\"\u003e6\u003c/span\u003e shows that 1,1,2-TCE has the highest ER values ​​for PAAs. The reason for this is high ability of 1,1,2-TCE to dissolve analytes compared to the other solvents, which led to more PAA derivatives being extracted.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003eFigure\u0026nbsp;\u003cspan refid=\"Fig6\" class=\"InternalRef\"\u003e6\u003c/span\u003e\u003c/p\u003e \u003cp\u003eIn the next step, the volume optimization of 1,1,2-TCE was done. At this stage, the volumes of 15, 20, 25, and 30 \u0026micro;L were evaluated using EF values. The volumes of the sedimented phase when using the mentioned volumes of the solvent were 10, 15, 21, and 27 \u0026micro;L, respectively. According to the results reported in Fig. S5, increasing the extractant volume leads to a decrease in EFs, which is attributed to the dilution phenomenon. Therefore, 15 \u0026micro;L of 1,1,2-TCE solvent was selected for PAAs extraction.\u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec21\" class=\"Section3\"\u003e \u003ch2\u003e3.2.8 Vortexing time in VALLME step\u003c/h2\u003e \u003cp\u003eTo complete the extraction process, after adding BCF and 1,1,2-TCE, the mixture must be vortexed. The duration of this process is one of the most important parameters of extraction. To optimize the vortexing time, 1, 3, 5, 7, and 9 min were evaluated and compared based on ER values. As reported in Fig. S6, the duration of 5 min has the highest ER values. At low vortexing times, sufficient opportunity for the simultaneous extraction and derivatization of PAAs is not provided, therefore ER values ​​are low. At high vortexing times, due to the disruption of the balance between derivatization and providing sufficient time for back extraction, the amount of ERs decreases. Therefore, a duration of 5 min was chosen as the optimal vortexing time for the next optimizations.\u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec22\" class=\"Section3\"\u003e \u003ch2\u003e3.2.9 Centrifugation operation\u003c/h2\u003e \u003cp\u003eCentrifugation operation is one of the necessary steps in the extraction process, which is utilized for phases separation. Figures S7a, and S7b show the effect of time (3, 5, 7, and 9 min) and centrifugation rate (4000, 5000, 6000, and 7000 rpm) in the extraction process. As can be seen from Fig. S7a, with the increase in centrifugation time, there is a noticeable decrease in ER values, which can be attributed to the heat generated in the centrifuge, which leads to the back extraction of the derivatized PAAs. As reported in Fig. S7b, centrifugation rate has no significant effect on ER values. Therefore, in the operation of the centrifugation, the duration of 3 min and the rate of 4000 rpm were chosen as optimal values.\u003c/p\u003e \u003c/div\u003e \u003c/div\u003e \u003cdiv id=\"Sec23\" class=\"Section2\"\u003e \u003ch2\u003e3.3 Reusability of adsorbent\u003c/h2\u003e \u003cp\u003eThe ability of the adsorbent to eliminate or decrease matrix effect in skin moisturizers while maintaining PAAs in solution was assessed, revealing the absence of a memory effect. Following the adsorption of the matrix, the adsorbent was rinsed with a mixture of \u003cem\u003eiso\u003c/em\u003e-propanol and deionized water (1:3, v/v) to desorb the adsorbed compounds onto the sorbent surface. The method's efficiency for matrix effect elimination was validated over 5 successive cycles using the same adsorbent, with RSD\u0026thinsp;\u0026le;\u0026thinsp;8%.\u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec24\" class=\"Section2\"\u003e \u003ch2\u003e3.4 Method validation\u003c/h2\u003e \u003cp\u003eIn this section, various analytical parameters have been assessed and presented in Table\u0026nbsp;\u003cspan refid=\"Tab1\" class=\"InternalRef\"\u003e1\u003c/span\u003e to validate the approach under study. UP is an important parameter in the D\u0026micro;SPE section that evaluates the efficiency of the adsorbent. The UP values ​​obtained for PAAs were in the range of 92\u0026ndash;97%. ER and EF are two effective parameters to evaluate the extraction method, which were in the ranges of 84\u0026ndash;105% and 420\u0026ndash;525, respectively. The calibration curves in wide concentration ranges were linear with the coefficient of determination (r\u003csup\u003e2\u003c/sup\u003e) greater than 0.99. Limits of detection (LOD) and quantification (LOQ) define the concentration of analytes in those signal-to-noise ratios are equal to 3 and 10, respectively. The range of LOD values ​​for PAAs was 0.50\u0026ndash;0.82 \u0026micro;g L\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e and LOQ values ​​also ranged from 1.6\u0026ndash;2.5 \u0026micro;g L\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e. To evaluate precision of the proposed method, repeatability of the results of both intra- and inter-day experiments should be assessed. Relative standard deviation (RSD) was calculated at the concentrations of approximately 5, 25, and 125 times of LOQ. Intra-day precisions (n\u0026thinsp;=\u0026thinsp;6) were less than or equal to 1.1, 1.4, and 2.7% at the concentrations of 200, 40, and 10 \u0026micro;g L\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e, respectively. Also, inter-day precisions (n\u0026thinsp;=\u0026thinsp;4) in the concentrations mentioned above were less than or equal to 2.5, 3.7, and 5.1%.\u003c/p\u003e \u003cp\u003e \u003cdiv class=\"gridtable\"\u003e\u003ctable float=\"Yes\" id=\"Tab1\" border=\"1\"\u003e \u003ccaption language=\"En\"\u003e \u003cdiv class=\"CaptionNumber\"\u003eTable 1\u003c/div\u003e \u003cdiv class=\"CaptionContent\"\u003e \u003cp\u003eQuantitative features of the developed D\u0026micro;SPE-VALLME-GC-FID method.\u003c/p\u003e \u003c/div\u003e \u003c/caption\u003e \u003ccolgroup cols=\"14\"\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c1\" colnum=\"1\"\u003e\u003c/div\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c2\" colnum=\"2\"\u003e\u003c/div\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c3\" colnum=\"3\"\u003e\u003c/div\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c4\" colnum=\"4\"\u003e\u003c/div\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c5\" colnum=\"5\"\u003e\u003c/div\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c6\" colnum=\"6\"\u003e\u003c/div\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c7\" colnum=\"7\"\u003e\u003c/div\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c8\" colnum=\"8\"\u003e\u003c/div\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c9\" colnum=\"9\"\u003e\u003c/div\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c10\" colnum=\"10\"\u003e\u003c/div\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c11\" colnum=\"11\"\u003e\u003c/div\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c12\" colnum=\"12\"\u003e\u003c/div\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c13\" colnum=\"13\"\u003e\u003c/div\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c14\" colnum=\"14\"\u003e\u003c/div\u003e \u003cthead\u003e \u003ctr\u003e \u003cth align=\"left\" colname=\"c1\"\u003e\u0026nbsp;\u003c/th\u003e \u003cth align=\"left\" colname=\"c2\"\u003e\u0026nbsp;\u003c/th\u003e \u003cth align=\"left\" colname=\"c3\"\u003e\u0026nbsp;\u003c/th\u003e \u003cth align=\"left\" colname=\"c4\"\u003e\u0026nbsp;\u003c/th\u003e \u003cth align=\"left\" colname=\"c5\"\u003e\u0026nbsp;\u003c/th\u003e \u003cth align=\"left\" colspan=\"6\" nameend=\"c11\" namest=\"c6\"\u003e \u003cp\u003eRSD % \u003csup\u003ee\u003c/sup\u003e at the concentrations of\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c12\"\u003e\u0026nbsp;\u003c/th\u003e \u003cth align=\"left\" colname=\"c13\"\u003e\u0026nbsp;\u003c/th\u003e \u003cth align=\"left\" colname=\"c14\"\u003e\u0026nbsp;\u003c/th\u003e \u003c/tr\u003e \u003c/thead\u003e \u003ctbody\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eAnalyte\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003eLOD \u003csup\u003ea\u003c/sup\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003eLOQ \u003csup\u003eb\u003c/sup\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003eLR \u003csup\u003ec\u003c/sup\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003er\u003csup\u003e2 d\u003c/sup\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"2\" nameend=\"c7\" namest=\"c6\"\u003e \u003cp\u003e10 \u0026micro;g L\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"2\" nameend=\"c9\" namest=\"c8\"\u003e \u003cp\u003e40 \u0026micro;g L\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"2\" nameend=\"c11\" namest=\"c10\"\u003e \u003cp\u003e\u0026micro;g L\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e 200\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c12\"\u003e \u003cp\u003eEF\u0026thinsp;\u0026plusmn;\u0026thinsp;SD \u003csup\u003ef\u003c/sup\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c13\"\u003e \u003cp\u003eER\u0026thinsp;\u0026plusmn;\u0026thinsp;SD \u003csup\u003eg\u003c/sup\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c14\"\u003e \u003cp\u003eUP\u0026thinsp;\u0026plusmn;\u0026thinsp;SD \u003csup\u003eh\u003c/sup\u003e\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e\u0026nbsp;\u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e\u0026nbsp;\u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e\u0026nbsp;\u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e\u0026nbsp;\u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e\u0026nbsp;\u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003eIntra-day\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c7\"\u003e \u003cp\u003eInter-day\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c8\"\u003e \u003cp\u003eIntra-day\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c9\"\u003e \u003cp\u003eInter-day\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c10\"\u003e \u003cp\u003eIntra-day\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c11\"\u003e \u003cp\u003eInter-day\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c12\"\u003e\u0026nbsp;\u003c/td\u003e \u003ctd align=\"left\" colname=\"c13\"\u003e\u0026nbsp;\u003c/td\u003e \u003ctd align=\"left\" colname=\"c14\"\u003e\u0026nbsp;\u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003ePrA\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e0.50\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e1.6\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e1.6-10000\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e0.9991\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e1.6\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c7\"\u003e \u003cp\u003e2.4\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c8\"\u003e \u003cp\u003e0.95\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c9\"\u003e \u003cp\u003e2.0\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c10\"\u003e \u003cp\u003e0.9\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c11\"\u003e \u003cp\u003e1.9\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c12\"\u003e \u003cp\u003e420\u0026thinsp;\u0026plusmn;\u0026thinsp;5\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c13\"\u003e \u003cp\u003e84\u0026thinsp;\u0026plusmn;\u0026thinsp;1\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c14\"\u003e \u003cp\u003e96\u0026thinsp;\u0026plusmn;\u0026thinsp;2\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e\u003cem\u003esec\u003c/em\u003e-BuA\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e0.65\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e2.1\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e2.1-10000\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e0.9989\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e1.9\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c7\"\u003e \u003cp\u003e3.0\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c8\"\u003e \u003cp\u003e1.0\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c9\"\u003e \u003cp\u003e2.1\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c10\"\u003e \u003cp\u003e1.0\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c11\"\u003e \u003cp\u003e2.0\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c12\"\u003e \u003cp\u003e495\u0026thinsp;\u0026plusmn;\u0026thinsp;10\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c13\"\u003e \u003cp\u003e99\u0026thinsp;\u0026plusmn;\u0026thinsp;2\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c14\"\u003e \u003cp\u003e96\u0026thinsp;\u0026plusmn;\u0026thinsp;2\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eBuA\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e0.51\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e1.6\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e1.6-10000\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e0.9993\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e1.4\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c7\"\u003e \u003cp\u003e2.9\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c8\"\u003e \u003cp\u003e0.91\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c9\"\u003e \u003cp\u003e1.8\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c10\"\u003e \u003cp\u003e0.8\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c11\"\u003e \u003cp\u003e1.8\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c12\"\u003e \u003cp\u003e485\u0026thinsp;\u0026plusmn;\u0026thinsp;5\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c13\"\u003e \u003cp\u003e97\u0026thinsp;\u0026plusmn;\u0026thinsp;1\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c14\"\u003e \u003cp\u003e92\u0026thinsp;\u0026plusmn;\u0026thinsp;1\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003ePeA\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e0.74\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e2.4\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e2.4-10000\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e0.9995\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e2.0\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c7\"\u003e \u003cp\u003e3.8\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c8\"\u003e \u003cp\u003e1.1\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c9\"\u003e \u003cp\u003e2.3\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c10\"\u003e \u003cp\u003e1.0\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c11\"\u003e \u003cp\u003e2.1\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c12\"\u003e \u003cp\u003e510\u0026thinsp;\u0026plusmn;\u0026thinsp;10\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c13\"\u003e \u003cp\u003e102\u0026thinsp;\u0026plusmn;\u0026thinsp;2\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c14\"\u003e \u003cp\u003e92\u0026thinsp;\u0026plusmn;\u0026thinsp;2\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eBeA\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e0.82\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e2.5\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e2.5-10000\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e0.9995\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e2.7\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c7\"\u003e \u003cp\u003e5.1\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c8\"\u003e \u003cp\u003e1.4\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c9\"\u003e \u003cp\u003e3.7\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c10\"\u003e \u003cp\u003e1.1\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c11\"\u003e \u003cp\u003e2.5\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c12\"\u003e \u003cp\u003e525\u0026thinsp;\u0026plusmn;\u0026thinsp;15\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c13\"\u003e \u003cp\u003e105\u0026thinsp;\u0026plusmn;\u0026thinsp;3\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c14\"\u003e \u003cp\u003e97\u0026thinsp;\u0026plusmn;\u0026thinsp;3\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003c/tbody\u003e \u003c/colgroup\u003e \u003ctfoot\u003e \u003ctr\u003e\u003ctd colspan=\"14\"\u003e\u003csup\u003ea\u003c/sup\u003e Limit of detection (S/N\u0026thinsp;=\u0026thinsp;3) (\u0026micro;g L\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e)\u003c/td\u003e\u003c/tr\u003e \u003ctr\u003e\u003ctd colspan=\"14\"\u003e\u003csup\u003eb\u003c/sup\u003e Limit of quantification (S/N\u0026thinsp;=\u0026thinsp;10) (\u0026micro;g L\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e)\u003c/td\u003e\u003c/tr\u003e \u003ctr\u003e\u003ctd colspan=\"14\"\u003e\u003csup\u003ec\u003c/sup\u003e Linear range (\u0026micro;g L\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e)\u003c/td\u003e\u003c/tr\u003e \u003ctr\u003e\u003ctd colspan=\"14\"\u003e\u003csup\u003ed\u003c/sup\u003e Coefficient of determination\u003c/td\u003e\u003c/tr\u003e \u003ctr\u003e\u003ctd colspan=\"14\"\u003e\u003csup\u003ee\u003c/sup\u003e Relative standard deviation for intra- (n\u0026thinsp;=\u0026thinsp;6) and inter-day (n\u0026thinsp;=\u0026thinsp;4) precisions\u003c/td\u003e\u003c/tr\u003e \u003ctr\u003e\u003ctd colspan=\"14\"\u003e\u003csup\u003ef\u003c/sup\u003e Enrichment factor\u0026thinsp;\u0026plusmn;\u0026thinsp;standard deviation (n\u0026thinsp;=\u0026thinsp;3)\u003c/td\u003e\u003c/tr\u003e \u003ctr\u003e\u003ctd colspan=\"14\"\u003e\u003csup\u003eg\u003c/sup\u003e Extraction recovery\u0026thinsp;\u0026plusmn;\u0026thinsp;standard deviation (n\u0026thinsp;=\u0026thinsp;3)\u003c/td\u003e\u003c/tr\u003e \u003ctr\u003e\u003ctd colspan=\"14\"\u003e\u003csup\u003eh\u003c/sup\u003e Unadsorbed percentage\u0026thinsp;\u0026plusmn;\u0026thinsp;standard deviation (n\u0026thinsp;=\u0026thinsp;3)\u003c/td\u003e\u003c/tr\u003e \u003c/tfoot\u003e \u003c/table\u003e\u003c/div\u003e \u003c/p\u003e \u003cp\u003eTable\u0026nbsp;\u003cspan refid=\"Tab1\" class=\"InternalRef\"\u003e1\u003c/span\u003e\u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec25\" class=\"Section2\"\u003e \u003ch2\u003e3.5 Real samples analysis\u003c/h2\u003e \u003cp\u003eThis section aimed to examine the impact of eliminating the real sample matrix on relative recovery (RR) values. In this context, following spiking 10, 50, and 250 \u0026micro;g L\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e of each amine to real samples and deionized water, clean up and the simultaneous extraction and derivatization processes were executed by the established method. For the second time, all the previously mentioned steps were followed, with the exception that both the real samples and deionized water were exposed to the adsorbent. The RR% values were computed based on Eq.\u0026nbsp;4 and presented in Table\u0026nbsp;\u003cspan refid=\"Tab2\" class=\"InternalRef\"\u003e2\u003c/span\u003e. The RR values obtained from skin moisturizer samples (#1, #2, and #3), after matrix elimination or decrease, were 101\u0026ndash;110, 95\u0026ndash;112, and 100\u0026ndash;105%, respectively. It should be noted that, without using clean up step, these figures were 100\u0026ndash;128, 110\u0026ndash;130, and 95\u0026ndash;128%, respectively. Thus, it can be inferred that eliminating or decreasing the matrix of real samples has successfully diminished the major impacts of the matrix on the extraction and derivatization processes, making this method as a reliable approach for analyzing the studied compounds. The chromatograms obtained from the GC-FID analysis of skin moisturizer samples exhibited no doubtful peaks in the retention times of the analytes. This finding indicates that none of the examined PAAs was detected in skin moisturizers at the concentrations equal to or exceeding the LODs established by the analytical method.\u003c/p\u003e \u003cp\u003e \u003cdiv class=\"gridtable\"\u003e\u003ctable float=\"Yes\" id=\"Tab2\" border=\"1\"\u003e \u003ccaption language=\"En\"\u003e \u003cdiv class=\"CaptionNumber\"\u003eTable 2\u003c/div\u003e \u003cdiv class=\"CaptionContent\"\u003e \u003cp\u003eStudy of matrix effect in the samples spiked at different concentrations (without dilution).\u003c/p\u003e \u003c/div\u003e \u003c/caption\u003e \u003ccolgroup cols=\"7\"\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c1\" colnum=\"1\"\u003e\u003c/div\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c2\" colnum=\"2\"\u003e\u003c/div\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c3\" colnum=\"3\"\u003e\u003c/div\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c4\" colnum=\"4\"\u003e\u003c/div\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c5\" colnum=\"5\"\u003e\u003c/div\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c6\" colnum=\"6\"\u003e\u003c/div\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c7\" colnum=\"7\"\u003e\u003c/div\u003e \u003cthead\u003e \u003ctr\u003e \u003cth align=\"left\" colname=\"c1\" morerows=\"3\" rowspan=\"4\"\u003e \u003cp\u003eAnalyte\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colspan=\"6\" nameend=\"c7\" namest=\"c2\"\u003e \u003cp\u003eMean relative recovery\u0026thinsp;\u0026plusmn;\u0026thinsp;standard deviation (n\u0026thinsp;=\u0026thinsp;3)\u003c/p\u003e \u003c/th\u003e \u003c/tr\u003e \u003ctr\u003e \u003cth align=\"left\" colspan=\"6\" nameend=\"c7\" namest=\"c2\"\u003e \u003cp\u003eThe samples were spiked with each analyte at a concentration of 10 \u0026micro;g L\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e\u003c/p\u003e \u003c/th\u003e \u003c/tr\u003e \u003ctr\u003e \u003cth align=\"left\" colspan=\"3\" nameend=\"c4\" namest=\"c2\"\u003e \u003cp\u003eBefore eliminating the matrix\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colspan=\"3\" nameend=\"c7\" namest=\"c5\"\u003e \u003cp\u003eAfter eliminating the matrix\u003c/p\u003e \u003c/th\u003e \u003c/tr\u003e \u003ctr\u003e \u003cth align=\"left\" colname=\"c2\"\u003e \u003cp\u003eSkin moisturizer #1\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c3\"\u003e \u003cp\u003eSkin moisturizer #2\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c4\"\u003e \u003cp\u003eSkin moisturizer #3\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c5\"\u003e \u003cp\u003eSkin moisturizer #1\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c6\"\u003e \u003cp\u003eSkin moisturizer #2\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c7\"\u003e \u003cp\u003eSkin moisturizer #3\u003c/p\u003e \u003c/th\u003e \u003c/tr\u003e \u003c/thead\u003e \u003ctbody\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003ePrA\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e125\u0026thinsp;\u0026plusmn;\u0026thinsp;2\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e130\u0026thinsp;\u0026plusmn;\u0026thinsp;2\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e127\u0026thinsp;\u0026plusmn;\u0026thinsp;2\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e102\u0026thinsp;\u0026plusmn;\u0026thinsp;2\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e99\u0026thinsp;\u0026plusmn;\u0026thinsp;2\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c7\"\u003e \u003cp\u003e101\u0026thinsp;\u0026plusmn;\u0026thinsp;2\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e\u003cem\u003esec\u003c/em\u003e-BuA\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e128\u0026thinsp;\u0026plusmn;\u0026thinsp;2\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e127\u0026thinsp;\u0026plusmn;\u0026thinsp;2\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e128\u0026thinsp;\u0026plusmn;\u0026thinsp;2\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e101\u0026thinsp;\u0026plusmn;\u0026thinsp;2\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e95\u0026thinsp;\u0026plusmn;\u0026thinsp;2\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c7\"\u003e \u003cp\u003e105\u0026thinsp;\u0026plusmn;\u0026thinsp;2\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eBuA\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e128\u0026thinsp;\u0026plusmn;\u0026thinsp;2\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e129\u0026thinsp;\u0026plusmn;\u0026thinsp;2\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e123\u0026thinsp;\u0026plusmn;\u0026thinsp;2\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e105\u0026thinsp;\u0026plusmn;\u0026thinsp;1\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e104\u0026thinsp;\u0026plusmn;\u0026thinsp;1\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c7\"\u003e \u003cp\u003e103\u0026thinsp;\u0026plusmn;\u0026thinsp;1\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003ePeA\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e123\u0026thinsp;\u0026plusmn;\u0026thinsp;2\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e125\u0026thinsp;\u0026plusmn;\u0026thinsp;2\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e128\u0026thinsp;\u0026plusmn;\u0026thinsp;3\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e108\u0026thinsp;\u0026plusmn;\u0026thinsp;2\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e110\u0026thinsp;\u0026plusmn;\u0026thinsp;2\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c7\"\u003e \u003cp\u003e100\u0026thinsp;\u0026plusmn;\u0026thinsp;2\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eBeA\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e126\u0026thinsp;\u0026plusmn;\u0026thinsp;3\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e119\u0026thinsp;\u0026plusmn;\u0026thinsp;3\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e128\u0026thinsp;\u0026plusmn;\u0026thinsp;3\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e110\u0026thinsp;\u0026plusmn;\u0026thinsp;3\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e110\u0026thinsp;\u0026plusmn;\u0026thinsp;3\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c7\"\u003e \u003cp\u003e101\u0026thinsp;\u0026plusmn;\u0026thinsp;3\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\" morerows=\"2\" rowspan=\"3\"\u003e\u0026nbsp;\u003c/td\u003e \u003ctd align=\"left\" colspan=\"6\" nameend=\"c7\" namest=\"c2\"\u003e \u003cp\u003eThe samples were spiked with each analyte at a concentration of 50 \u0026micro;g L\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colspan=\"3\" nameend=\"c4\" namest=\"c2\"\u003e \u003cp\u003eBefore eliminating the matrix\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"3\" nameend=\"c7\" namest=\"c5\"\u003e \u003cp\u003eAfter eliminating the matrix\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003eSkin moisturizer #1\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003eSkin moisturizer #2\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003eSkin moisturizer #3\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003eSkin moisturizer #1\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003eSkin moisturizer #2\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c7\"\u003e \u003cp\u003eSkin moisturizer #3\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003ePrA\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e100\u0026thinsp;\u0026plusmn;\u0026thinsp;2\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e110\u0026thinsp;\u0026plusmn;\u0026thinsp;2\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e95\u0026thinsp;\u0026plusmn;\u0026thinsp;2\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e106\u0026thinsp;\u0026plusmn;\u0026thinsp;2\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e100\u0026thinsp;\u0026plusmn;\u0026thinsp;2\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c7\"\u003e \u003cp\u003e100\u0026thinsp;\u0026plusmn;\u0026thinsp;2\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e\u003cem\u003esec\u003c/em\u003e-BuA\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e119\u0026thinsp;\u0026plusmn;\u0026thinsp;2\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e125\u0026thinsp;\u0026plusmn;\u0026thinsp;2\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e124\u0026thinsp;\u0026plusmn;\u0026thinsp;2\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e102\u0026thinsp;\u0026plusmn;\u0026thinsp;2\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e98\u0026thinsp;\u0026plusmn;\u0026thinsp;2\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c7\"\u003e \u003cp\u003e105\u0026thinsp;\u0026plusmn;\u0026thinsp;2\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eBuA\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e125\u0026thinsp;\u0026plusmn;\u0026thinsp;2\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e130\u0026thinsp;\u0026plusmn;\u0026thinsp;2\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e126\u0026thinsp;\u0026plusmn;\u0026thinsp;2\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e109\u0026thinsp;\u0026plusmn;\u0026thinsp;2\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e110\u0026thinsp;\u0026plusmn;\u0026thinsp;2\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c7\"\u003e \u003cp\u003e105\u0026thinsp;\u0026plusmn;\u0026thinsp;1\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003ePeA\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e125\u0026thinsp;\u0026plusmn;\u0026thinsp;2\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e129\u0026thinsp;\u0026plusmn;\u0026thinsp;3\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e128\u0026thinsp;\u0026plusmn;\u0026thinsp;3\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e103\u0026thinsp;\u0026plusmn;\u0026thinsp;2\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e112\u0026thinsp;\u0026plusmn;\u0026thinsp;2\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c7\"\u003e \u003cp\u003e100\u0026thinsp;\u0026plusmn;\u0026thinsp;2\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eBeA\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e128\u0026thinsp;\u0026plusmn;\u0026thinsp;3\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e127\u0026thinsp;\u0026plusmn;\u0026thinsp;3\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e128\u0026thinsp;\u0026plusmn;\u0026thinsp;3\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e105\u0026thinsp;\u0026plusmn;\u0026thinsp;3\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e112\u0026thinsp;\u0026plusmn;\u0026thinsp;3\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c7\"\u003e \u003cp\u003e104\u0026thinsp;\u0026plusmn;\u0026thinsp;3\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\" morerows=\"2\" rowspan=\"3\"\u003e\u0026nbsp;\u003c/td\u003e \u003ctd align=\"left\" colspan=\"6\" nameend=\"c7\" namest=\"c2\"\u003e \u003cp\u003eThe samples were spiked with each analyte at a concentration of 250 \u0026micro;g L\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colspan=\"3\" nameend=\"c4\" namest=\"c2\"\u003e \u003cp\u003eBefore eliminating the matrix\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"3\" nameend=\"c7\" namest=\"c5\"\u003e \u003cp\u003eAfter eliminating the matrix\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003eSkin moisturizer #1\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003eSkin moisturizer #2\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003eSkin moisturizer #3\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003eSkin moisturizer #1\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003eSkin moisturizer #2\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c7\"\u003e \u003cp\u003eSkin moisturizer #3\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003ePrA\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e121\u0026thinsp;\u0026plusmn;\u0026thinsp;2\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e125\u0026thinsp;\u0026plusmn;\u0026thinsp;2\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e120\u0026thinsp;\u0026plusmn;\u0026thinsp;2\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e107\u0026thinsp;\u0026plusmn;\u0026thinsp;2\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e98\u0026thinsp;\u0026plusmn;\u0026thinsp;2\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c7\"\u003e \u003cp\u003e105\u0026thinsp;\u0026plusmn;\u0026thinsp;2\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e\u003cem\u003esec\u003c/em\u003e-BuA\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e128\u0026thinsp;\u0026plusmn;\u0026thinsp;2\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e128\u0026thinsp;\u0026plusmn;\u0026thinsp;2\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e126\u0026thinsp;\u0026plusmn;\u0026thinsp;2\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e101\u0026thinsp;\u0026plusmn;\u0026thinsp;2\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e100\u0026thinsp;\u0026plusmn;\u0026thinsp;2\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c7\"\u003e \u003cp\u003e100\u0026thinsp;\u0026plusmn;\u0026thinsp;2\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eBuA\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e122\u0026thinsp;\u0026plusmn;\u0026thinsp;2\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e130\u0026thinsp;\u0026plusmn;\u0026thinsp;2\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e123\u0026thinsp;\u0026plusmn;\u0026thinsp;2\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e110\u0026thinsp;\u0026plusmn;\u0026thinsp;2\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e106\u0026thinsp;\u0026plusmn;\u0026thinsp;1\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c7\"\u003e \u003cp\u003e103\u0026thinsp;\u0026plusmn;\u0026thinsp;1\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003ePeA\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e126\u0026thinsp;\u0026plusmn;\u0026thinsp;3\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e130\u0026thinsp;\u0026plusmn;\u0026thinsp;3\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e128\u0026thinsp;\u0026plusmn;\u0026thinsp;3\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e109\u0026thinsp;\u0026plusmn;\u0026thinsp;2\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e112\u0026thinsp;\u0026plusmn;\u0026thinsp;2\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c7\"\u003e \u003cp\u003e105\u0026thinsp;\u0026plusmn;\u0026thinsp;2\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eBeA\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e125\u0026thinsp;\u0026plusmn;\u0026thinsp;3\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e126\u0026thinsp;\u0026plusmn;\u0026thinsp;3\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e128\u0026thinsp;\u0026plusmn;\u0026thinsp;3\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e110\u0026thinsp;\u0026plusmn;\u0026thinsp;3\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e110\u0026thinsp;\u0026plusmn;\u0026thinsp;3\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c7\"\u003e \u003cp\u003e102\u0026thinsp;\u0026plusmn;\u0026thinsp;3\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003c/tbody\u003e \u003c/colgroup\u003e \u003c/table\u003e\u003c/div\u003e \u003c/p\u003e \u003cp\u003eTable\u0026nbsp;\u003cspan refid=\"Tab2\" class=\"InternalRef\"\u003e2\u003c/span\u003e\u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec26\" class=\"Section2\"\u003e \u003ch2\u003e3.6 Comparison with other approaches\u003c/h2\u003e \u003cp\u003eBased on the findings shown in Table\u0026nbsp;\u003cspan refid=\"Tab3\" class=\"InternalRef\"\u003e3\u003c/span\u003e, the proposed method exhibits high ERs and EFs, and wider linear range values along with notable linearity compared to the other methods. Based on RSD values, it can be asserted that this technique is highly consistent, repeatable, and fully competitive with alternative methods. Utilizing an external magnetic field to detach the MAA@Fe\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e from the aqueous solution has significantly reduced the analysis time for PAAs. The LOQ and LOD values are less than or at least equal to the majority of analytical methods. The application of BCF rendered this method less toxic, very effective, and exhibited advantageous chromatographic characteristics, indicating that this method is better than or equal to similar methods.\u003c/p\u003e \u003cp\u003e \u003cdiv class=\"gridtable\"\u003e\u003ctable float=\"Yes\" id=\"Tab3\" border=\"1\"\u003e \u003ccaption language=\"En\"\u003e \u003cdiv class=\"CaptionNumber\"\u003eTable 3\u003c/div\u003e \u003cdiv class=\"CaptionContent\"\u003e \u003cp\u003eComparison of the development method with similar approaches for derivatization, extraction, and determination of PAAs.\u003c/p\u003e \u003c/div\u003e \u003c/caption\u003e \u003ccolgroup cols=\"12\"\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c1\" colnum=\"1\"\u003e\u003c/div\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c2\" colnum=\"2\"\u003e\u003c/div\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c3\" colnum=\"3\"\u003e\u003c/div\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c4\" colnum=\"4\"\u003e\u003c/div\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c5\" colnum=\"5\"\u003e\u003c/div\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c6\" colnum=\"6\"\u003e\u003c/div\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c7\" colnum=\"7\"\u003e\u003c/div\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c8\" colnum=\"8\"\u003e\u003c/div\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c9\" colnum=\"9\"\u003e\u003c/div\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c10\" colnum=\"10\"\u003e\u003c/div\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c11\" colnum=\"11\"\u003e\u003c/div\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c12\" colnum=\"12\"\u003e\u003c/div\u003e \u003cthead\u003e \u003ctr\u003e \u003cth align=\"left\" colname=\"c1\"\u003e \u003cp\u003eMethod\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c2\"\u003e \u003cp\u003eSample\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c3\"\u003e \u003cp\u003eAnalyte\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c4\"\u003e \u003cp\u003eDerivatization reagent\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c5\"\u003e \u003cp\u003eLOD \u003csup\u003ea\u003c/sup\u003e\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c6\"\u003e \u003cp\u003eLOQ \u003csup\u003eb\u003c/sup\u003e\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c7\"\u003e \u003cp\u003eRSD \u003csup\u003ec\u003c/sup\u003e\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c8\"\u003e \u003cp\u003eLR \u003csup\u003ed\u003c/sup\u003e\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c9\"\u003e \u003cp\u003er\u003csup\u003e2 e\u003c/sup\u003e\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c10\"\u003e \u003cp\u003eEF\u003csup\u003ef\u003c/sup\u003e\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c11\"\u003e \u003cp\u003eER\u003csup\u003eg\u003c/sup\u003e\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c12\"\u003e \u003cp\u003eRef.\u003c/p\u003e \u003c/th\u003e \u003c/tr\u003e \u003c/thead\u003e \u003ctbody\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eHS-SDME-GC-MS \u003csup\u003eh\u003c/sup\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003eWastewater\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003ePrA\u003c/p\u003e \u003cp\u003eBuA\u003c/p\u003e \u003cp\u003ePeA\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003ePentafluoro benzaldehyde\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e0.9\u003c/p\u003e \u003cp\u003e0.7\u003c/p\u003e \u003cp\u003e0.8\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e-\u003c/p\u003e \u003cp\u003e-\u003c/p\u003e \u003cp\u003e-\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c7\"\u003e \u003cp\u003e7.6\u003c/p\u003e \u003cp\u003e5.3\u003c/p\u003e \u003cp\u003e9.8\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c8\"\u003e \u003cp\u003e-\u003c/p\u003e \u003cp\u003e-\u003c/p\u003e \u003cp\u003e-\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c9\"\u003e \u003cp\u003e0.992\u003c/p\u003e \u003cp\u003e0.995\u003c/p\u003e \u003cp\u003e0.997\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c10\"\u003e \u003cp\u003e-\u003c/p\u003e \u003cp\u003e-\u003c/p\u003e \u003cp\u003e-\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c11\"\u003e \u003cp\u003e-\u003c/p\u003e \u003cp\u003e-\u003c/p\u003e \u003cp\u003e-\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c12\"\u003e \u003cp\u003e\u003csup\u003e39\u003c/sup\u003e\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eAALLME-GC-FID \u003csup\u003ei\u003c/sup\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003eWell, river, tap waters, and wastewater\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003ePrA\u003c/p\u003e \u003cp\u003e\u003cem\u003esec\u003c/em\u003e-BuA\u003c/p\u003e \u003cp\u003eBuA\u003c/p\u003e \u003cp\u003ePeA\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003eButyl chloroformate\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e1.1\u003c/p\u003e \u003cp\u003e1.7\u003c/p\u003e \u003cp\u003e0.4\u003c/p\u003e \u003cp\u003e0.3\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e3.7\u003c/p\u003e \u003cp\u003e5.7\u003c/p\u003e \u003cp\u003e1.4\u003c/p\u003e \u003cp\u003e1.0\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c7\"\u003e \u003cp\u003e2.7\u003c/p\u003e \u003cp\u003e2.1\u003c/p\u003e \u003cp\u003e3.6\u003c/p\u003e \u003cp\u003e3.7\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c8\"\u003e \u003cp\u003e3.7\u0026ndash;5000\u003c/p\u003e \u003cp\u003e5.7\u0026ndash;5000\u003c/p\u003e \u003cp\u003e1.4\u0026ndash;5000\u003c/p\u003e \u003cp\u003e1.0-5000\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c9\"\u003e \u003cp\u003e0991\u003c/p\u003e \u003cp\u003e0.992\u003c/p\u003e \u003cp\u003e0.994\u003c/p\u003e \u003cp\u003e0.996\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c10\"\u003e \u003cp\u003e315\u003c/p\u003e \u003cp\u003e266\u003c/p\u003e \u003cp\u003e250\u003c/p\u003e \u003cp\u003e360\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c11\"\u003e \u003cp\u003e63\u003c/p\u003e \u003cp\u003e53\u003c/p\u003e \u003cp\u003e50\u003c/p\u003e \u003cp\u003e72\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c12\"\u003e \u003cp\u003e\u003csup\u003e27\u003c/sup\u003e\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eSPME-GC-FID \u003csup\u003ej\u003c/sup\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003eLake water\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003ePrA\u003c/p\u003e \u003cp\u003eBuA\u003c/p\u003e \u003cp\u003ePeA\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003eN-succinimidylbenzoate\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e0.17\u003c/p\u003e \u003cp\u003e0.13\u003c/p\u003e \u003cp\u003e0.16\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e-\u003c/p\u003e \u003cp\u003e-\u003c/p\u003e \u003cp\u003e-\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c7\"\u003e \u003cp\u003e2.4\u003c/p\u003e \u003cp\u003e1.1\u003c/p\u003e \u003cp\u003e1.3\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c8\"\u003e \u003cp\u003e1-1000\u003c/p\u003e \u003cp\u003e1-1000\u003c/p\u003e \u003cp\u003e1-1000\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c9\"\u003e \u003cp\u003e0.9920\u003c/p\u003e \u003cp\u003e0.9938\u003c/p\u003e \u003cp\u003e0.9956\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c10\"\u003e \u003cp\u003e-\u003c/p\u003e \u003cp\u003e-\u003c/p\u003e \u003cp\u003e-\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c11\"\u003e \u003cp\u003e-\u003c/p\u003e \u003cp\u003e-\u003c/p\u003e \u003cp\u003e-\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c12\"\u003e \u003cp\u003e\u003csup\u003e40\u003c/sup\u003e\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eHF-LPME-GC-MS \u003csup\u003ek\u003c/sup\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003eRiver water\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003ePrA\u003c/p\u003e \u003cp\u003eBuA\u003c/p\u003e \u003cp\u003ePeA\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003ePentafluoro benzaldehyde\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e0.29\u003c/p\u003e \u003cp\u003e0.37\u003c/p\u003e \u003cp\u003e0.32\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e-\u003c/p\u003e \u003cp\u003e-\u003c/p\u003e \u003cp\u003e-\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c7\"\u003e \u003cp\u003e6.7\u003c/p\u003e \u003cp\u003e5.2\u003c/p\u003e \u003cp\u003e4.9\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c8\"\u003e \u003cp\u003e-\u003c/p\u003e \u003cp\u003e-\u003c/p\u003e \u003cp\u003e-\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c9\"\u003e \u003cp\u003e0.995\u003c/p\u003e \u003cp\u003e0.993\u003c/p\u003e \u003cp\u003e0.998\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c10\"\u003e \u003cp\u003e172\u003c/p\u003e \u003cp\u003e205\u003c/p\u003e \u003cp\u003e244\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c11\"\u003e \u003cp\u003e-\u003c/p\u003e \u003cp\u003e-\u003c/p\u003e \u003cp\u003e-\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c12\"\u003e \u003cp\u003e\u003csup\u003e41\u003c/sup\u003e\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eDLLME-SFO-HPLC-DAD \u003csup\u003el\u003c/sup\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003eWell, river, and sea waters and wastewater\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003eBuA\u003c/p\u003e \u003cp\u003ePeA\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003ePhenyl isothiocyanate\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e0.01\u003c/p\u003e \u003cp\u003e0.006\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e-\u003c/p\u003e \u003cp\u003e-\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c7\"\u003e \u003cp\u003e\u0026lt;\u0026thinsp;12.5\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c8\"\u003e \u003cp\u003e0.1\u0026ndash;500\u003c/p\u003e \u003cp\u003e0.05\u0026ndash;500\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c9\"\u003e \u003cp\u003e0.994\u003c/p\u003e \u003cp\u003e0.997\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c10\"\u003e \u003cp\u003e210\u003c/p\u003e \u003cp\u003e287\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c11\"\u003e \u003cp\u003e-\u003c/p\u003e \u003cp\u003e-\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c12\"\u003e \u003cp\u003e\u003csup\u003e30\u003c/sup\u003e\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eSPME-GC-MS \u003csup\u003em\u003c/sup\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003eFountain, tap, and surface waters\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003ePrA\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003ePentafluoro benzaldehyde\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e1\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e5\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c7\"\u003e \u003cp\u003e5\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c8\"\u003e \u003cp\u003e5\u0026ndash;500\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c9\"\u003e \u003cp\u003e0.9989\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c10\"\u003e \u003cp\u003e-\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c11\"\u003e \u003cp\u003e-\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c12\"\u003e \u003cp\u003e\u003csup\u003e42\u003c/sup\u003e\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eLLE-GC-MS \u003csup\u003en\u003c/sup\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003eSurface water and wastewater\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003ePrA\u003c/p\u003e \u003cp\u003ePeA\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003eTrichloroethylene chloroformate\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e0.15\u003c/p\u003e \u003cp\u003e0.04\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e-\u003c/p\u003e \u003cp\u003e-\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c7\"\u003e \u003cp\u003e7.5\u003c/p\u003e \u003cp\u003e2.0\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c8\"\u003e \u003cp\u003e-\u003c/p\u003e \u003cp\u003e-\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c9\"\u003e \u003cp\u003e0.9967\u003c/p\u003e \u003cp\u003e0.9998\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c10\"\u003e \u003cp\u003e-\u003c/p\u003e \u003cp\u003e-\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c11\"\u003e \u003cp\u003e-\u003c/p\u003e \u003cp\u003e-\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c12\"\u003e \u003cp\u003e\u003csup\u003e43\u003c/sup\u003e\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eD\u0026micro;SPE-VALLME-GC-FID \u003csup\u003eo\u003c/sup\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003eSkin moisturizer\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003ePrA\u003c/p\u003e \u003cp\u003e\u003cem\u003esec\u003c/em\u003e-BuA\u003c/p\u003e \u003cp\u003eBuA\u003c/p\u003e \u003cp\u003ePeA\u003c/p\u003e \u003cp\u003eBeA\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003eButyl chloroformate\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e0.50\u003c/p\u003e \u003cp\u003e0.65\u003c/p\u003e \u003cp\u003e0.51\u003c/p\u003e \u003cp\u003e0.74\u003c/p\u003e \u003cp\u003e0.82\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e1.6\u003c/p\u003e \u003cp\u003e2.1\u003c/p\u003e \u003cp\u003e1.6\u003c/p\u003e \u003cp\u003e2.4\u003c/p\u003e \u003cp\u003e2.5\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c7\"\u003e \u003cp\u003e1.6\u003c/p\u003e \u003cp\u003e1.9\u003c/p\u003e \u003cp\u003e1.4\u003c/p\u003e \u003cp\u003e2.0\u003c/p\u003e \u003cp\u003e2.7\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c8\"\u003e \u003cp\u003e1.6\u0026ndash;10\u003csup\u003e4\u003c/sup\u003e\u003c/p\u003e \u003cp\u003e2.1\u0026ndash;10\u003csup\u003e4\u003c/sup\u003e\u003c/p\u003e \u003cp\u003e1.6\u0026ndash;10\u003csup\u003e4\u003c/sup\u003e\u003c/p\u003e \u003cp\u003e2.4\u0026ndash;10\u003csup\u003e4\u003c/sup\u003e\u003c/p\u003e \u003cp\u003e2.5\u0026ndash;10\u003csup\u003e4\u003c/sup\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c9\"\u003e \u003cp\u003e0.9991\u003c/p\u003e \u003cp\u003e0.9989\u003c/p\u003e \u003cp\u003e0.9993\u003c/p\u003e \u003cp\u003e0.9995\u003c/p\u003e \u003cp\u003e0.9995\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c10\"\u003e \u003cp\u003e420\u003c/p\u003e \u003cp\u003e495\u003c/p\u003e \u003cp\u003e485\u003c/p\u003e \u003cp\u003e510\u003c/p\u003e \u003cp\u003e525\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c11\"\u003e \u003cp\u003e84 99\u003c/p\u003e \u003cp\u003e97\u003c/p\u003e \u003cp\u003e102\u003c/p\u003e \u003cp\u003e105\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c12\"\u003e \u003cp\u003eThis work\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003c/tbody\u003e \u003c/colgroup\u003e \u003ctfoot\u003e \u003ctr\u003e\u003ctd colspan=\"12\"\u003e\u003csup\u003ea\u003c/sup\u003e Limit of detection (\u0026micro;g L\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e)\u003c/td\u003e\u003c/tr\u003e \u003ctr\u003e\u003ctd colspan=\"12\"\u003e\u003csup\u003eb\u003c/sup\u003e Limit of quantification (\u0026micro;g L\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e)\u003c/td\u003e\u003c/tr\u003e \u003ctr\u003e\u003ctd colspan=\"12\"\u003e\u003csup\u003ec\u003c/sup\u003e Relative standard deviation (%)\u003c/td\u003e\u003c/tr\u003e \u003ctr\u003e\u003ctd colspan=\"12\"\u003e\u003csup\u003ed\u003c/sup\u003e Linear Range (\u0026micro;g L\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e)\u003c/td\u003e\u003c/tr\u003e \u003ctr\u003e\u003ctd colspan=\"12\"\u003e\u003csup\u003ee\u003c/sup\u003e Coefficient of determination\u003c/td\u003e\u003c/tr\u003e \u003ctr\u003e\u003ctd colspan=\"12\"\u003e\u003csup\u003ef\u003c/sup\u003e Enrichment factor\u003c/td\u003e\u003c/tr\u003e \u003ctr\u003e\u003ctd colspan=\"12\"\u003e\u003csup\u003eg\u003c/sup\u003e Extraction recovery (%)\u003c/td\u003e\u003c/tr\u003e \u003ctr\u003e\u003ctd colspan=\"12\"\u003e\u003csup\u003eh\u003c/sup\u003e Head space-single drop microextraction-gas chromatography-mass spectrometry\u003c/td\u003e\u003c/tr\u003e \u003ctr\u003e\u003ctd colspan=\"12\"\u003e\u003csup\u003ei\u003c/sup\u003e Air-assisted liquid-liquid microextraction-gas chromatography-flame ionization detection\u003c/td\u003e\u003c/tr\u003e \u003ctr\u003e\u003ctd colspan=\"12\"\u003e\u003csup\u003ej\u003c/sup\u003e Solid phase microextraction-gas chromatography-flame ionization detection\u003c/td\u003e\u003c/tr\u003e \u003ctr\u003e\u003ctd colspan=\"12\"\u003e\u003csup\u003ek\u003c/sup\u003e Hollow fiber-liquid phase microextraction-gas chromatography-mass spectrometry\u003c/td\u003e\u003c/tr\u003e \u003ctr\u003e\u003ctd colspan=\"12\"\u003e\u003csup\u003el\u003c/sup\u003e Dispersive liquid-liquid microextraction based on solidification of floating organic droplet-high performance liquid\u003c/td\u003e\u003c/tr\u003e \u003ctr\u003e\u003ctd colspan=\"12\"\u003echromatography-diode array detection\u003c/td\u003e\u003c/tr\u003e \u003ctr\u003e\u003ctd colspan=\"12\"\u003e\u003csup\u003em\u003c/sup\u003e Solid phase microextraction-gas chromatography-mass spectrometry\u003c/td\u003e\u003c/tr\u003e \u003ctr\u003e\u003ctd colspan=\"12\"\u003e\u003csup\u003en\u003c/sup\u003e Liquid-liquid extraction-gas chromatography-mass spectrometry\u003c/td\u003e\u003c/tr\u003e \u003ctr\u003e\u003ctd colspan=\"12\"\u003e\u003csup\u003eo\u003c/sup\u003e Dispersive micro solid phase extraction - vortex-assisted liquid-liquid microextraction-gas chromatography-flame ionization detection\u003c/td\u003e\u003c/tr\u003e \u003c/tfoot\u003e \u003c/table\u003e\u003c/div\u003e \u003c/p\u003e \u003cp\u003eTable\u0026nbsp;\u003cspan refid=\"Tab3\" class=\"InternalRef\"\u003e3\u003c/span\u003e\u003c/p\u003e \u003c/div\u003e"},{"header":"4. Conclusions","content":"\u003cp\u003eIn this study, an innovative D\u0026micro;SPE-VALLME methodology was presented for the first time, aimed to eliminate or decrease matrix effect associated with skin moisturizing samples, thereby facilitating the derivatization and concurrent extraction of PAAs without interference from matrix effects. In this context, MAA@Fe\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e adsorbent was employed for the first time in the clean up samples. BCF was utilized for the derivatization of PAAs in an alkaline environment. Application of the magnetic adsorbent enabled the facile collection of the adsorbent in the presence of an external magnetic field, obviating the necessity for centrifuge, which resulted in a reduction of the analysis duration. Throughout the analytical process, organic solvents were employed at \u0026micro;L-volumes, thereby characterizing this methodology as a green and environmentally sustainable approach. The analytical parameters associated with this technique, which include broad linear ranges (2.5-10000 \u0026micro;g L\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e), low LODs (0.50\u0026ndash;0.82 \u0026micro;g L\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e) and LOQs (1.6\u0026ndash;2.5 \u0026micro;g L\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e), high EFs (420\u0026ndash;525), significant r\u003csup\u003e2\u003c/sup\u003e values (0.9989\u0026ndash;0.9995), and excellent ERs (84\u0026ndash;105%), contribute to the comprehensive or relative superiority of this method over existing methodologies. Moreover, the elimination or decreasing matrix effect of skin moisturizing samples has effectively mitigated both extraction and derivatization processes, rendering this methodology as a credible approach for the analysis of the selected compounds.\u003c/p\u003e"},{"header":"Abbreviations","content":"\u003cp\u003e\u003cstrong\u003ePAA\u003c/strong\u003e, Primary aliphatic amine; \u003cstrong\u003eD\u0026micro;SPE\u003c/strong\u003e, Dispersive micro solid phase extraction; \u003cstrong\u003eVALLME\u003c/strong\u003e, Vortex\u003cspan dir=\"RTL\"\u003e-\u003c/span\u003eassisted liquid-liquid microextraction;\u003cstrong\u003e\u0026nbsp;GC\u003c/strong\u003e, Gas chromatography; \u003cstrong\u003eFID\u003c/strong\u003e, Flame ionization detector; \u003cstrong\u003eEF\u003c/strong\u003e, Enrichment factor; \u003cstrong\u003eER,\u0026nbsp;\u003c/strong\u003eExtraction recovery; \u003cstrong\u003eRSD\u003c/strong\u003e, Relative standard deviation; \u003cstrong\u003eLR\u003c/strong\u003e, Linear range; \u003cstrong\u003eLOD\u003c/strong\u003e, Limit of detection; \u003cstrong\u003eLOQ\u003c/strong\u003e, Limit of quantification; \u003cstrong\u003eUP\u003c/strong\u003e, Unadsorbed percent; \u003cstrong\u003eRR\u003c/strong\u003e, Relative recovery;\u003cspan dir=\"RTL\"\u003e\u0026nbsp;\u003c/span\u003e\u003cstrong\u003ePrA\u003c/strong\u003e, Propylamine; \u003cstrong\u003e\u003cem\u003esec\u003c/em\u003e-BuA\u003c/strong\u003e, \u003cem\u003esec\u003c/em\u003e-Butylamine; \u003cstrong\u003eBuA\u003c/strong\u003e, Butylamine\u003cstrong\u003e;\u003cspan dir=\"RTL\"\u003e\u0026nbsp;\u003c/span\u003ePeA\u003c/strong\u003e, Pentylamine; \u003cstrong\u003eBeA\u003c/strong\u003e, Benzylamine\u003c/p\u003e"},{"header":"Declarations","content":"\u003cp\u003e \u003ch2\u003eCompeting interests\u003c/h2\u003e \u003cp\u003eThe authors declare no competing interests.\u003c/p\u003e \u003c/p\u003e\u003ch2\u003eAuthor Contribution\u003c/h2\u003e\u003cp\u003eM.A.F. performed the analytical methodology and edited the manuscript.S.M.M. performed adsorbent synthesis, methodology and characterization, analytical analysis and methodology, data analysis, software applications, and manuscript writing.M.R.A.M. edited the manuscript.\u003c/p\u003e\u003ch2\u003eAcknowledgement\u003c/h2\u003e\u003cp\u003eThe authors are thankful to the University of Tabriz for financial support.\u003c/p\u003e\u003ch2\u003eData Availability\u003c/h2\u003e\u003cp\u003eAll data generated or analyzed during this study are included in this published article. This data is provided within the manuscript or supplementary information files.\u003c/p\u003e"},{"header":"References","content":"\u003col\u003e\n\u003cli\u003eFekete, A.; Malik, A.K.; Kumar, A.; Schmitt-Kopplin, P. Amines in the environment. \u003cem\u003eCritical Reviews in Analytical Chemistry.\u003c/em\u003e \u003cstrong\u003e40\u003c/strong\u003e, 102-121 (2010).\u003c/li\u003e\n\u003cli\u003eJang, J.-K. Amines as occupational hazards for visual disturbance. \u003cem\u003eIndustrial Health. \u003c/em\u003e\u003cstrong\u003e54\u003c/strong\u003e, 101-115 (2016).\u003c/li\u003e\n\u003cli\u003eCowell, A. An investigation into the synthesis, structural characterisation, thermal and polymorphic behaviour of organic crystalline materials. University of Birmingham (2011).\u003c/li\u003e\n\u003cli\u003eBhat, A.P.; Gogate, P.R. 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Determination of aliphatic and alicyclic amines in water by gas and liquid chromatography after derivatization by chloroformates. \u003cem\u003eFresenius\u0026apos; Journal of Analytical Chemistry.\u003c/em\u003e \u003cstrong\u003e355\u003c/strong\u003e, 164-173 (1996).\u003c/li\u003e\n\u003c/ol\u003e"}],"fulltextSource":"","fullText":"","funders":[],"hasAdminPriorityOnWorkflow":false,"hasManuscriptDocX":true,"hasOptedInToPreprint":true,"hasPassedJournalQc":"","hasAnyPriority":false,"hideJournal":false,"highlight":"","institution":"","isAcceptedByJournal":true,"isAuthorSuppliedPdf":false,"isDeskRejected":"","isHiddenFromSearch":false,"isInQc":false,"isInWorkflow":false,"isPdf":false,"isPdfUpToDate":true,"isWithdrawnOrRetracted":false,"journal":{"display":true,"email":"[email protected]","identity":"scientific-reports","isNatureJournal":false,"hasQc":true,"allowDirectSubmit":false,"externalIdentity":"scirep","sideBox":"Learn more about [Scientific Reports](http://www.nature.com/srep/)","snPcode":"","submissionUrl":"","title":"Scientific Reports","twitterHandle":"","acdcEnabled":true,"dfaEnabled":true,"editorialSystem":"stoa","reportingPortfolio":"Scientific Reports","inReviewEnabled":true,"inReviewRevisionsEnabled":true},"keywords":"Primary aliphatic amines, Dispersive micro solid phase extraction, Skin moisturizer, Magnetic adsorbent, Vortex-assisted liquid-liquid microextraction, Gas chromatography","lastPublishedDoi":"10.21203/rs.3.rs-5836920/v1","lastPublishedDoiUrl":"https://doi.org/10.21203/rs.3.rs-5836920/v1","license":{"name":"CC BY 4.0","url":"https://creativecommons.org/licenses/by/4.0/"},"manuscriptAbstract":"\u003cp\u003eIn this study, a combining method using dispersive micro solid phase extraction and vortex-assisted liquid-liquid microextraction was presented for the first time as a pioneering methodology capable of concurrently cleaning up and derivatizing/ extracting existing primary aliphatic amines in aqueous solutions after eliminating or decreasing matrix effect posed by skin moisturizers. A magnetic adsorbent (iron oxide modified by mercapto acetic acid, MAA@Fe\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e) has been employed to facilitate the matrix removal. To corroborate the authenticity of the synthesized adsorbent, various identification methods were employed, including X-ray diffraction, Brunauer-Emmett-Teller, scanning electron microscopy, Fourier transform infrared spectrometry, energy dispersive X-ray spectroscopy, and vibrating sample magnetometry analyses. All effective parameters were optimized in passivation of the adsorbent for the analytes and their concurrent derivatization and extraction. A gas chromatograph equipped with a flame ionization detector was utilized to identify and quantify the derivatives of amines. Eco-friendly characteristics, short extraction duration, high matrix removal efficiency, high unadsorbed percentage of amines by the adsorbent, simplicity, high precision, lack of requirement for specialized equipment, adsorbent reusability up to five cycles, exceptional proficiency in the extraction and derivatization of amines, and a comprehensive or relative superiority in analytical parameters, including extraction recovery, enrichment factor, relative standard deviation, coefficient of determination, limit of quantification and detection, and relative recovery, underscoring the merits and advantages of the proposed method.\u003c/p\u003e","manuscriptTitle":"Eliminating or decreasing matrix effect in skin moisturizers employing a magnetic adsorbent in the analysis of primary aliphatic amines","msid":"","msnumber":"","nonDraftVersions":[{"code":1,"date":"2025-01-20 07:21:58","doi":"10.21203/rs.3.rs-5836920/v1","editorialEvents":[{"type":"communityComments","content":0},{"type":"decision","content":"Revision requested","date":"2025-02-03T11:42:34+00:00","index":"","fulltext":""},{"type":"editorInvitedReview","content":"","date":"2025-02-03T05:59:21+00:00","index":"hide","fulltext":""},{"type":"editorInvitedReview","content":"","date":"2025-02-02T19:33:44+00:00","index":"hide","fulltext":""},{"type":"reviewerAgreed","content":"112271981944177082120527996164197111993","date":"2025-01-18T12:37:17+00:00","index":"hide","fulltext":""},{"type":"reviewerAgreed","content":"270485823476727462533842822639786797012","date":"2025-01-18T09:31:12+00:00","index":"hide","fulltext":""},{"type":"reviewerAgreed","content":"280219067416371272764078339596823369307","date":"2025-01-18T09:01:42+00:00","index":"hide","fulltext":""},{"type":"reviewerAgreed","content":"285136872635747519253664032559390759709","date":"2025-01-18T08:51:44+00:00","index":"hide","fulltext":""},{"type":"reviewersInvited","content":"","date":"2025-01-18T08:43:41+00:00","index":"","fulltext":""},{"type":"editorAssigned","content":"","date":"2025-01-18T08:25:34+00:00","index":"","fulltext":""},{"type":"editorInvited","content":"","date":"2025-01-17T15:52:25+00:00","index":"","fulltext":""},{"type":"checksComplete","content":"","date":"2025-01-16T11:22:21+00:00","index":"","fulltext":""},{"type":"submitted","content":"Scientific Reports","date":"2025-01-15T19:32:20+00:00","index":"","fulltext":""}],"status":"published","journal":{"display":true,"email":"[email protected]","identity":"scientific-reports","isNatureJournal":false,"hasQc":true,"allowDirectSubmit":false,"externalIdentity":"scirep","sideBox":"Learn more about [Scientific Reports](http://www.nature.com/srep/)","snPcode":"","submissionUrl":"","title":"Scientific Reports","twitterHandle":"","acdcEnabled":true,"dfaEnabled":true,"editorialSystem":"stoa","reportingPortfolio":"Scientific Reports","inReviewEnabled":true,"inReviewRevisionsEnabled":true}}],"origin":"","ownerIdentity":"3f94b1f7-8c4e-4b3e-8166-c976ff429993","owner":[],"postedDate":"January 20th, 2025","published":true,"recentEditorialEvents":[],"rejectedJournal":[],"revision":"","amendment":"","status":"published-in-journal","subjectAreas":[{"id":43063784,"name":"Physical sciences/Chemistry"},{"id":43063785,"name":"Physical sciences/Materials science"},{"id":43063786,"name":"Physical sciences/Nanoscience and technology"}],"tags":[],"updatedAt":"2025-03-24T16:04:07+00:00","versionOfRecord":{"articleIdentity":"rs-5836920","link":"https://doi.org/10.1038/s41598-025-92919-4","journal":{"identity":"scientific-reports","isVorOnly":false,"title":"Scientific Reports"},"publishedOn":"2025-03-17 15:58:15","publishedOnDateReadable":"March 17th, 2025"},"versionCreatedAt":"2025-01-20 07:21:58","video":"","vorDoi":"10.1038/s41598-025-92919-4","vorDoiUrl":"https://doi.org/10.1038/s41598-025-92919-4","workflowStages":[]},"version":"v1","identity":"rs-5836920","journalConfig":"researchsquare"},"__N_SSP":true},"page":"/article/[identity]/[[...version]]","query":{"redirect":"/article/rs-5836920","identity":"rs-5836920","version":["v1"]},"buildId":"8U1c8b4HqxoKbykW_rLl7","isFallback":false,"isExperimentalCompile":false,"dynamicIds":[84888],"gssp":true,"scriptLoader":[]}