Methacrylamide Based Polymeric Cryogels for the Effective Removal of Neonicotinoid Insecticide, Clothianidin

Methacrylamide Based Polymeric Cryogels for the Effective Removal of Neonicotinoid Insecticide, Clothianidin | 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 Research Article Methacrylamide Based Polymeric Cryogels for the Effective Removal of Neonicotinoid Insecticide, Clothianidin Semiha Kundakcı, Mihrican Muti This is a preprint; it has not been peer reviewed by a journal. https://doi.org/ 10.21203/rs.3.rs-6536945/v1 This work is licensed under a CC BY 4.0 License Status: Published Journal Publication published 10 Dec, 2025 Read the published version in Polymer Bulletin → Version 1 posted 8 You are reading this latest preprint version Abstract In recent years, the increasing use of pesticides, particularly in agriculture, has become a significant concern due to their detrimental effects on aquatic ecosystems. Therefore, the effective removal of such pollutants from contaminated environments through appropriate treatment processes is of great importance. Clothianidin (CLT), a widely used neonicotinoid insecticide, has been reported to negatively impact human health, affecting the respiratory, nervous, and digestive systems. This study involves investigating the CLT removal performance of polymeric cryogels from aqueous solutions, based on the CLT reduction signal. To achieve this, crosslinked methacrylamide/2-hydroxyethyl methacrylate/poly(acrylic acid) (MAmHP) cryogels were fabricated using free-radical copolymerization under cryogenic conditions. The macroporous polymeric samples that were synthesized underwent characterization through swelling tests, Fourier Transform Infrared Spectroscopy (FT-IR/ATR), and Scanning Electron Microscopy-Energy Dispersive X-ray Spectroscopy (SEM-EDX). Swelling parameters, widely applied in polymeric gel characterization, were assessed through dynamic swelling experiments carried out at 25°C. The pesticide adsorption performance of the MAmHP sorbent gel systems was evaluated for the removal of Clothianidin (CLT) using the voltammetric method at room temperature. The dynamic swelling tests performed at 25°C were used to determine the swelling parameters, which are widely utilized for characterizing polymeric gels. Clothianidin Electrochemistry hydrogel/cryogel pesiticide swelling behaviour Figures Figure 1 Figure 2 Figure 3 Figure 4 Figure 5 Figure 6 Figure 7 Figure 8 1. Introduction Environmental factors are becoming increasingly significant in public health due to the emergence of new environmental impacts, while efforts to address existing issues continue. Pesticides are biologically active chemicals employed to prevent damage to agricultural products during production and storage, as well as to maintain product quality. Most pesticides also serve as plant protection products, safeguarding plants from weeds, fungi, or insects. Despite their effectiveness and widespread use in controlling various pests, the exposure to and residues of pesticides in food and water can present significant health risks [ 1 , 2 ]. Pesticides are classified into various categories, including insecticides, fungicides, herbicides, nematicides, and rodenticides, based on the species they target and their areas of application. Neonicotinoids are broad-spectrum systemic insecticides that have become widely used worldwide in recent years. At present, seven neonicotinoid insecticides exist, categorized into different types, including acetamiprid, imidacloprid, clothianidin, thiamethoxam, thiacloprid, dinotefuran and nitenpyram [ 1 – 5 ]. Clothianidin ((E)-1-(2-chloro-1,3-thiazol-5-ylmethyl)-3-methyl-2-nitroguanidine) is a neonicotinoid insecticide used as a pesticide. Insecticides, such as clothianidin, which exhibit specific activity on the insect nervous system, are effective compounds used to control the harmful effects of pests like aphids, thrips, whiteflies, adelgids, and leafhoppers. However, the residues left by such compounds after use pose a potential risk to agricultural products, human health, and beneficial insects such as bees. Therefore, it is crucial that these pesticides are removed from the environment [ 6 – 8 ]. Polymeric gels, also known as hydrogels, are unique structures that exhibit swelling behavior without dissolving when in contact with aqueous solutions. Cryogels are a type of polymeric material distinguished from hydrogels by the conditions under which they are prepared (at sub-zero temperatures). Cryogels are formed by freezing a reaction mixture that contains precursors facilitating gel formation at temperatures lower than the solvent’s crystallization threshold. Once the polymerization process is completed, void formation is achieved by melting the ice crystals that were frozen. These pores create a system of interconnected continuous macropores, and due to this porous structure, cryogels have numerous applications, including in bioseparation, chromatography, tissue engineering, and as adsorbents for environmental applications [ 9 – 14 ]. Investigating the adsorption and retention capabilities of polymeric gels in aqueous media is a crucial step in understanding their structure and potential properties. The swelling ratio, diffusion, and sorption mechanism parameters are determined by measuring the mass or volume of the gel in its hydrated (swollen) and unhydrated (dry) states. The resulting swelling profile of the newly synthesized polymeric gels provides valuable insight into their suitability for various specific applications [ 15 – 18 ]. In recent years, significant research efforts have focused on utilizing polymeric gel systems as adsorbents for the removal of harmful species that may be present as pollutants in aqueous environments. Due to its low cost and ease of application, the adsorption method has become a widely adopted approach [ 15 , 18 ]. Numerous studies in the literature have focused on the use of polymeric materials for the removal of pesticides. The removal of Imidacloprid from aqueous systems has been carried out using carboxymethyl cellulose-based bionanocomposite (CMC/Fe₃O₄-Zeolite) hydrogel beads [ 20 ], Cellulose acetate (CA) hydrogel beads designed for the elimination of Chlorpyrifos from aqueous environments [ 15 ], UiO-66-based alginate hydrogel for the controlled release of Clothianidin [ 21 ], β-cyclodextrin cross-linked cellulose/poly(vinyl alcohol) (β-CD/cellulose/PVA) hydrogel for Malathion removal [ 22 ], chitosan/clay nanocomposite hydrogels for Paraquat removal from water [ 23 ], nicotinamide-modified cryogels for the removal of Chlordane [ 24 ], and Chitosan-based organoclay hydrogels designed for the adsorption of Carbendazim [ 25 ]. This study is the first that investigated clothianidin removal from aqueous solution by polymeric cryogels. We aim to develop a novel methacrylamide-based polymeric sorbent and investigate its capability in removing the neonicotinoid insecticide Clothianidin (CLT) using the voltammetric method. For this purpose, MAm cryogels with diverse formulations were produced through free radical cryopolymerization in an aqueous environment. Additionally, HEMA and PAA were incorporated to enhance the functionality of the polymeric samples and to assess the properties imparted by these additives. Various analytical methods were employed to assess the structural, surface, and swelling features of the polymeric samples. Dynamic swelling tests were performed to calculate the swelling parameters, which are frequently utilized for characterizing synthesized polymeric gels, and the diffusion mechanism was analyzed. To assess the efficacy of these gels in mitigating environmental pollutants, their performance in the removal of CLT was evaluated. 2. Experimental 2.1. Chemicals Methacrylamide (MAm, monomer), 2-hydroxyethyl methacrylate (HEMA, co-monomer), and poly(acrylic acid) (PAA) were used for the formation of polymeric structures and were purchased from Sigma-Aldrich. To enable cross-linking, Bisacrylamide (BAm) (Sigma-Aldrich, Steinheim, Germany) was used as a crosslinking agent. Ammonium persulphate (APS) and N,N,N′,N′-tetramethylethylenediamine (TEMED) were functioned as a redox-initiator pair and sourced from Merck, Schuchardt, Germany. Phosphate-buffered saline (PBS, pH 7.2) and ethyl alcohol were obtained from Sigma-Aldrich, Steinheim, Germany. The acquisition of Clothianidin was also made through Sigma-Aldrich. 2.2. Equipment Electrochemical measurements were carried out by IVIUM Compact Stat Plus Module. Working, reference and counter electrodes are pencil graphite (HB in 0.5 mm diameter), Ag/AgCl (3 M KCl BAS, Model RE-5B, W. Lafayette, USA) and platinum wire, respectively. Characterization of cryogels was carried out using FT-IR spectroscopy (Thermo Scientific Nicolet is 10 SMARTt FT-IR/ATR, USA). The morphological characteristics of polymeric cryogels were examined by scanning electron microscope, SEM (Phillips XL-30S FEG, FEI Quanta 250 FEG). 2.3. Procedure Preparation of Polymeric Sorbents and Cryopolymerization of MAmHP cryogels Through free radical copolymerization, MAm and HEMA monomers were crosslinked with BAm under cryogenic conditions to synthesize polymeric samples. PAA, a synthetic polymer, was incorporated to impart additional functional properties to the polymeric structures. Ammonium persulfate (APS) functioned as an initiator, while N,N,N′,N′-tetramethylethylenediamine (TEMED) acted as an accelerator during the synthesis process. Initially, MAm (1.0 g) was solubilized in a 2.0 mL water-ethanol blend (1:1) at ambient temperature. Subsequently, HEMA (180 µL) and PAA (50 mg) were introduced into the solution and stirred until a uniform monomer blend was obtained. Following this, 0.5 mL of BAm (1% w/v), 0.5 mL of APS (5.0 g/100 mL water), and 1.0 mL of TEMED (1.0% v/v) were sequentially added. Following complete mixing, the solution was rapidly cooled in an ice bath, transferred into a 2.0 mL syringe, and subsequently frozen at − 20°C for 24 hours to induce crosslinking and cryopolymerization. After polymerization, the cryogels were thawed at ambient temperature and sectioned into cylindrical segments (3–4 mm in length). These pieces were then immersed in distilled water to eliminate any residual monomers, polymers, or other unreacted substances. The distilled water was replaced three times a day for four days to ensure thorough purification. The cryogels were then initially air-dried and then vacuum-dried for 24 hours at a temperature of 40°C. The dried samples were stored for further use. Synthesis of samples without HEMA or PAA was performed following the same procedure. The polymeric cryogels having different compositions were detailed MAmHP cryogels formulations are given in Table 1 . The synthesis and swelling phases of the polymeric samples are depicted in Fig. 1 . Table 1 Combinations of polymeric cryogels developed using various formulations Sample Code Abbreviation MAAm (mmol) HEMA (mmol) PAA (mg) MAm MAmH2 MAmH2P2 MAmP2 MAm MAm/180 HEMA MAm/180 HEMA/50 PAA MAm/50 PAA 11.75 11.75 11.75 11.75 - 1.48 1.48 - - - 50 50 BAm (0.0324 mmol) APS (0.1096 mmol) and TEMED (0.0671 mmol) were used in all polymeric systems Characterization FT-IR analysis was conducted to characterize the chemical structure of the synthesized polymeric cryogels. The chemical composition of MAm/HEMA/PAA (MAmHP) was examined within the spectral range of 4000–400 cm⁻¹ using an ATR apparatus. The microstructural composition of the polymeric cryogels was examined using scanning electron microscopy (SEM) to investigate their internal architecture and surface features. To enhance imaging quality, the dry polymeric specimens were first coated with a conductive gold layer using a deposition device (Emitech K550X) prior to SEM analysis. Additionally, energy dispersive X-ray spectroscopy (EDX) was utilized in conjunction with the SEM analysis to investigate the elemental distribution within the samples. Swelling studies The swelling capacity of a polymeric gel is a critical parameter used to characterize its structure and properties. Swelling values can be determined through simple measurements of the dry and swollen gel weights. Assessing the water retention capacity of polymeric gels through swelling studies is essential for understanding polymeric matrix diffusion. Based on the obtained data, key swelling parameters—including equilibrium swelling, equilibrium water content, diffusion exponent, diffusion constant, and diffusion coefficient—were calculated, as these parameters are commonly used for the swelling characterization of polymeric gels [ 16 , 26 – 28 ]. Pesticide sorption At this stage, the adsorption efficiency of the prepared polymeric cryogels for Clothianidin (CLT) was examined. Batch studies were carried out to examine the elimination of CLT from aqueous media, considering the composition of the polymeric sorbents (MAm, MAm/HEMA, MAm/HEMA/PAA, and MAm/PAA) and varying CLT concentrations (1.0 × 10⁻⁴ M, 2.5 × 10⁻⁴ M, and 5.0 × 10⁻⁴ M) under constant temperature conditions (25°C). Voltammetric transduction DPV measurements (Differential pulse voltammetric) were carried out across various CLT concentrations prepared in PBS. The measurements were conducted using cathodic scanning within the potential range of -0.7 V to -1.4 V vs. an Ag/AgCl reference electrode, with a pulse amplitude of 50 mV and a scan rate of 20 mV/s. 3. Result and Discussion 3.1. FT-IR analysis FT-IR analysis was conducted to characterize the structural properties of MAm/HEMA/PAA (MAmHP) using FT-IR spectroscopy (Fig. 2 ). As shown in Fig. 2 , a strong and broad absorption band between 3400–3100 cm⁻¹ was observed, attributed to the N–H stretching vibrations of MAm. The peak observed in the 3000–2700 cm⁻¹ range corresponds to the stretching vibrations of CH, CH₂, and CH₃ groups. The band at 1652 cm⁻¹ is associated with the stretching vibration of the carbonyl (C = O) group in the amide functional group. Characteristic peaks of HEMA were identified at 3432 cm⁻¹ and 1703 cm⁻¹, corresponding to O–H stretching and C = O stretching vibrations, respectively, which appeared as shoulder formations. Additionally, C–OH in-plane bending at 1447 cm⁻¹ and C–O–C (ester group) stretching at 1247 cm⁻¹ were detected. The presence of poly(acrylic acid) (PAA) was confirmed by the characteristic absorption bands at 3432 cm⁻¹ and 1025 cm⁻¹, which correspond to the O–H stretching and O–H deformation vibrations of carboxyl groups, respectively. Furthermore, the C = O stretching peak at 1703 cm⁻¹, along with the C–O stretching and bending vibrations at 1386 cm⁻¹ and 1200 cm⁻¹, were clearly identified [ 29 – 35 ]. 3.2. Microscopic Characterization The surface properties of the polymeric cryogels, as characterized by SEM, are presented in Fig. 3 . The changes in pore structure resulting from the incorporation of HEMA and PAA into MAm-based cryogels can be observed (Fig. 3 ). It was noted that samples without PAA exhibited a more porous morphology, whereas the addition of PAA led to polymer entanglement within the pore spaces, resulting in a denser structure. Furthermore, the elemental distribution within the polymeric samples was investigated using energy-dispersive X-ray spectroscopy (EDX), enabling compositional mapping of the identified elements. [ 16 , 36 ]. 3.3. Water swelling studies of the polymeric cryogels A key characteristic of hydrogels is their ability to absorb water. Dry polymeric gels undergo swelling upon contact with a suitable solvent. The swelling reaction is influenced by the intrinsic properties of both the polymer and the solvent. Swelling measurements were conducted in a water bath at specified time periods. Pre-weighed polymeric specimens with defined masses were introduced into a 40 mL volume of deionized water within a beaker. Periodically, the samples were withdrawn from the water, and any surface moisture was gently blotted using absorbent paper before weighing. The samples were reintroduced to the swelling medium, and the cycle continued until the mass remained unchanged. The equilibrium swelling value, expressed as the equilibrium percent swelling (PS%), was determined using Eq. ( 1 ) [ 26 , 28 , 37 , 38 ]. The percentage of equilibrium water content (PEWC) in polymeric gel systems defines the amount of water stabilized within the structure. PEWC values, determined via Eq. 2 , provide crucial information on permeability, mechanical integrity, surface attributes, and biocompatibility (17, 39, 40). $$\:\text{P}\text{S}\text{%}=\frac{{\text{m}}_{\text{t}}-{\text{m}}_{0}}{{\text{m}}_{0}}\text{x}100$$ 1 $$\:\text{P}\text{E}\text{W}\text{C}\text{%}=\frac{{\text{m}}_{t}-{\text{m}}_{0}}{{\text{m}}_{t}}\text{x}100$$ 2 In this equation, m t represents the gel’s mass after absorbing water at time t , with m o being its initial dry weight at t = 0 . The hydration behavior of MAm-based MAmHP cryogels crosslinked with BAm was observed, with swelling isotherms computed via Eq. 1 and illustrated in Fig. 4 . The Fickian diffusion model, formulated in Eq. 3 , was applied to evaluate water penetration into the polymer matrix. $$\:F=\frac{{M}_{t}}{{M}_{s}}={kt}^{n}$$ 3 F represents the ratio of solvent uptake by the gel at time t to equilibrium absorption and is defined as the swelling ratio. The diffusional exponent (n) and diffusion coefficient (k) were obtained using the linearized model (lnF = lnk + nln t) from Eq. 3 , to analyze the macromolecular structure, penetrant behavior, and transport mechanisms (Fig. 4 ). Water diffusion into the macromolecular matrix follows Fick’s diffusion equation, predominantly influencing the process in its initial 60% phase. A diffusion coefficient of (n = 0.5) corresponds to Fickian diffusion, where molecular mobility is restricted by a slower diffusion rate relative to relaxation kinetics. When (n) lies in the range (0.5 < n 1), the transport dynamics shift to Super Case II behavior, characterized by a dominant diffusion rate over relaxation effects. [ 17 , 41 – 43 ]. Table 2 reveals that the calculated nnn values, which elucidate the mechanism of water movement in the gel network, surpass 1.0 for MAm and MAmP2, indicating Super Case II transport behavior. In this mechanism, the diffusion time of water into the cryogels exceeds the polymer relaxation time. For the remaining polymeric samples, the nnn values range from 0.5 to 1.0, suggesting a non-Fickian diffusion process. Analyzing water transport phenomena in hydrogels is essential for comprehending polymer behavior. The calculation of diffusion coefficient values, fundamental for hydrogel characterization, was conducted using Eq. 4 for cylindrical-shaped hydrogels [ 43 , 44 ]. $$\:\text{D}=\pi\:{r}^{2}{\left(\frac{k}{4}\right)}^{\raisebox{1ex}{$1$}\!\left/\:\!\raisebox{-1ex}{$n$}\right.}$$ 4 In this formulation, D corresponds to the diffusion coefficient (cm 2 /min), describing the permeable area of the polymeric gel through which solvent species migrate per unit time. The parameter, r designates the radius of the cylindrical gel matrix, with k and n were defined earlier. When all of the synthesized polymeric structures are considered, the diffusion coefficients vary in the range of 31.97x10 − 5 cm 2 s − 1 -166.99x10 − 5 cm 2 s − 1 . The rise in HEMA unit concentration within the polymeric structure resulted in a decreased gel area for solvent diffusion per unit time. Among the polymeric gels, MAm cryogels exhibit the largest area allowing solvent molecules to pass per unit time. Figure 4 demonstrates that swelling gradually rises over time until reaching equilibrium, after which it stabilizes. This steady swelling value is referred as the equilibrium percentage swelling (PS eq %), with corresponding values provided in Table 2 for all polymeric matrices. Table 3 Experimentally obtained swelling and diffusion parameters of polymeric gels PS eq % PEWC% n kx10 3 Dx10 5 MAm MAmH2 MAmH2P2 MAmP2 180 271 260 205 64.28 73.01 72.18 67.17 1.6293 0.9945 0.9578 1.5776 0.39 3.95 3.69 0.31 166.99 51.90 31.97 124.70 3.4. CLT adsorption studies of the polymeric cryogels For the purpose of investigating the surface adsorption characteristics of the synthesized polymeric gels, an adsorption study of Clothianidin (CLT) was conducted at 25°C. A calibration curve was initially prepared by measuring the reduction signal of CLT at various concentrations ranging from 5.0 × 10⁻⁵ to 5.0 × 10⁻⁴ M (Fig. 5 ) to quantitatively evaluate CLT adsorption. Subsequently, aqueous CLT solutions were allowed to interact with the cross-linked copolymer-based polymeric gels until equilibrium was reached at varying concentrations between 1.5 × 10⁻⁵ M and 5.0 × 10⁻⁴ M. The effect of cryogels on CLT sorption was examined using aqueous solutions at a concentration of 2.5 × 10⁻⁴ M, which corresponds to the midpoint of the calibration curve. After the sorption process, 5 mL of the CLT solution was collected and transferred to an electrochemical cell. A three-electrode setup was subsequently submerged in the solution, and electrochemical analyses were performed at room temperature The change in the CLT reduction signal before and after adsorption is presented in Fig. 5 . 3.5. Comparison of cryogels in terms of CLT adsorption To investigate the effect of HEMA and PAA added to the MAm structure during the synthesis of cryogels on CLT adsorption, MAm, MAmH2, MAmH2P2, and MAmP2 cryogels were incubated in a 2.5x10 − 4 M CLT solution for 1 hour. Upon completion of the designed time interval, the cryogels were extracted, and the filtrate was transferred to an electrochemical cell. The reduction signal of CLT was measured using a three-electrode system, and the CLT removal was compared with the reduction signal of CLT before treatment with the cryogels. The obtained results are presented in Fig. 6 . The CLT reduction current values before and after adsorption, along with the adsorption percentages of the cryogels, are presented as histograms in Fig. 7 . In equilibrium sorption analysis, the CLT uptake capacity (Q), expressed as the amount of sorbed CLT in moles per unit mass of adsorbent in grams, adsorption percentage (A%), and partition constant (PC) were evaluated. The CLT uptake capacity (Q) of the polymeric cryogels was calculated according to the following equation: $$\:\text{Q}=\frac{\left({C}_{0}-C\right)v}{m}$$ 4 Where Q denotes the CLT uptake capacity of the polymeric cryogels (mol g⁻¹), and C₀ and C correspond to the initial and post-treatment CLT concentrations in the liquid phase after a stated measurement duration, respectively (mol L⁻¹). Additionally, v corresponds to the liquid phase volume (L), with m indicating the mass of the polymeric cryogels (g) [ 17 , 45 , 46 ]. The adsorption efficiency (A%) of polymeric cryogels was calculated according to the following mathematical expression: $$\:A\%=\frac{{C}_{0}-C}{{C}_{0}}x100$$ 5 C o and C were defined earlier. The partitioning of dissolved compounds between the liquid phase and adsorbing materials in aquatic systems is typically expressed through an empirical partition coefficient (PC), which correlates overall concentration of the dissolved species with that the adsorbed species. $$\:PC=\frac{{C}_{0}-C}{C}$$ 6 Here, PC represents the equilibrium partition coefficient based on empirical data. Definitions of C₀ and C were provided earlier. The distribution ratios of CLT between the CLT-containing solution and the polymeric matrices were computed and summarized in Table 4 . The Q values ​​in the Table 4 are given in mg/g. Table 4 Some adsorption values ​​of polymeric cryogels with different compositions Sample Code 1.0x10 − 4 M 2.5x10 − 4 M 5.0x10 − 4 M Q (mg/g) MAm MAmH2 MAmH2P2 MAmP2 3.50 3.16 1.97 3.04 7.08 7.25 4.15 5.98 9.24 10.41 6.81 11.95 ADS% MAm MAmH2 MAmH2P2 MAmP2 50.08 50.00 38.81 44.49 39.28 50.01 34.84 36.45 29.27 37.55 28.57 36.99 K d MAm MAmH2 MAmH2P2 MAmP2 1.00 1.00 0.63 0.80 0.65 1.00 0.53 0.57 0.41 0.60 0.41 0.59 Considering the CLT sorption parameters of the polymeric gel systems (Table 4 ), it can be observed that the Q value (moles of CLT sorbed per unit dry mass) increases with increasing concentration (Fig. 8 ). For MAmH₂ gels, this value rises from 3.16 mg to 10.41 mg. It was determined that the sorption capacity increased with the incorporation of HEMA into the structure for all systems, while it decreased with the addition of PAA. The increased sorption can be linked to the hydrophilic groups in the HEMA structure, while the PAA polymer restricts available spaces for CLT diffusion. Voltammetric measurements revealed that the MAmH2 formulation exhibited the highest adsorption capacity for clothianidin (CLT). This enhancement can be attributed to the incorporation of 2-hydroxyethyl methacrylate (HEMA) into the polymeric matrix, which increased porosity and promoted a more open network structure, thus improving the accessibility to binding sites and facilitating greater diffusion of the analyte. The voltammetric data provided critical information regarding the adsorption dynamics, highlighting the effective uptake of Clothianidin by the cryogel. A significant increase in current intensity correlated with higher adsorption capacity, suggesting that the cryogels efficiently adsorb the pesticide. The adsorption process likely involves both electrostatic and hydrophobic interactions. 4. Conclusion In this study, a novel polymeric gel was synthesized for the effective Clothianidin removal for the first time in the literature. Using methacrylamide (MAm) as the primary monomer, and its structure was functionalized by incorporating 2-hydroxyethyl methacrylate (HEMA) and poly(acrylic acid) (PAA) in varying compositions. The potential application of these gels in the removal of Clothianidin (CLT) from aqueous media was systematically investigated. In MAm and MAmP2 gels, water transport followed super Case II diffusion (n > 1.0), indicating that the diffusion rate exceeded the polymer relaxation rate. In gels containing HEMA, a non-Fickian diffusion mechanism was observed (0.5 < n < 1.0), where water diffusion and polymer relaxation occurred simultaneously. iv. The adsorption behavior of the cryogels was examined with respect to MAm, HEMA, PAA, and CLT concentrations. The results demonstrated a clear enhancement in adsorption capacity (Q, mg/g) with increasing CLT concentration. In conclusion, the synthesized MAmHP cryogels exhibit strong potential as environmentally friendly and efficient adsorbent materials for the removal of pollutants from aqueous solutions. Their demonstrated effectiveness in eliminating pesticides such as CLT highlights their broader applicability for addressing various organic and inorganic contaminants, including dyes and heavy metals. These findings suggest that MAmHP-based systems could serve as versatile platforms for water purification and pollution control in diverse environmental settings. Declarations Declaration of competing interest The authors declare no competing interests. Research funding This study was supported by Aydın Adnan Menderes University Scientific Research Projects (FEF 22022). 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J Turkısh Chem Soc 5(2):941–952. http://dx.doi.org/10.18596/jotcsa.394592 Baigorria E, Fraceto LF (2022b) Novel nanostructured materials based on polymer/organic-clay composite networks for the removal of carbendazim from waters. J Clean Prod 331:129867. https://doi.org/10.1016/j.jclepro.2021.129867 Peppas NA, Franson NM (1983) The swelling interface number as a criterion for prediction of dif fusional solute release mechanisms in swellable polymers. J Polym Sci 2:983–997 Protsak I, Morozov YM (2024) Fundamentals and advances in stimuli-responsive hydrogels and their aplications: A review. Gels. https://doi.org/10.3390/gels11010030 . 11;30 Karadağ E, Nalbantoglu A, Kundakcı S, Üzüm ÖB (2018) Uranyl ion sorption characteristics of novel polymer/montmorillonite/carboxymethyl cellulose composite biosorbents-based AAm/AMPS hydrogels and semi IPNs. Adv Polym Technol 37:575–585 Şahiner N, Demirci S (2016) Conducting semi-interpenetrating polymeric composites via the preparation of poly(aniline), poly(thiophene), and poly(pyrrole) polymers within superporous poly (acrylic acid) cryogels. React Funct Polym 105:60–65. http://dx.doi.org/10.1016/j.reactfunctpolym.2016.05.017 Sun Y, Ma Y, Fang G, Ren S, Fu Y (2016) Controlled pesticide release from porous composite hydrogels based on lignin and polyacrylic acid. BioResources 11(1):2361–2371. http://dx.doi.org/10.1016/j.reactfunctpolym.2016.05.017 Jing Z, Xu A, Liang TQ, Zhang Z, Yu C, Hong P, Li Y (2019) Biodegradable poly(acrylic acid- co -acrylamide)/poly(vinyl alcohol) double network hydrogels with tunable mechanics and high self-healing performance. Polymers 11:952. 10.3390/polym11060952 Barati A, Asgari M, Miri T, Eskandari Z (2013) Removal and recovery of copper and nickel ions from aqueous solution by poly(methacrylamide-co-acrylic acid)/montmorillonite nanocomposites. Environ Sci Pollut Res 20:6242–6255 Kousar F, Malana MA, Chughtai AH, Khan MS (2018) Synthesis and characterization of methacrylamide-acrylic acid-N-isopropylacrylamide polymeric hydrogel: degradation kinetics and rheological studies. Polym Bull 75:1275–1298 Şahiner N, Demirci Ş (2017) The use of grapheme oxide-embedded superporous poly(2-hydroxyethylmethacrylate) cryogels for p(aniline) conductive polymer synthesis and their use in sensor applications. Mater Des 120:47–55. http://dx.doi.org/10.1016/j.matdes.2017.02.004 Elgueta E, Rivas BL, Mancisidor A, Nunez D, Dahrouch M (2019) Hydrogels derived from 2-hydroxyethyl-methacrylate and 2-acrylamido-2-methyl-2-1-propanesulfonic acid, with ability to remove metal cations from wastewater. Polym Bull 76:6503–6528. https://doi.org/10.1007/s00289-019-02697-z Dinu IA, Ghimici L, Raschip IE (2022) Macroporous 3D chitosan cryogels for fastac 10EC pesticide adsorption and anti,bacterial applications. Polymers 14:3145. https://doi.org/10.3390/polym14153145 Kundakci S, Üzüm ÖB, Karadağ E (2008) Swelling and dye sorption studies of acrylamide/2-acrylamido-2-1-propanesulfonic acid/bentonite highly swollen composite hydrogels. React Functl Polym 68:458–473 Pal K, Banthia AK, Majumdar DK (2009) Polymeric hydrogels: Characterization and biomedical applications-A mini review. Des Monomers Polym 12:197–220 Pedley DG, Skelly PJ, Tighe BJ (1980) Hydrogels in Biomedical Applications. Brit Polym J 12:99–110 Lee SJ, Kim SS, Lee YM (2000) Interpenetrating polymer network hydrogels based on poly(ethylene glycol) macromer and chitosan. Carbohyd Polym 41:197–205 Mandal M, Lodhi RS, Chourasia S, Das S, Das P (2025) A review on sustainable slow-release N, P, K fertilizer hydrogels for smart apriculture. ChemPlusChem. org/10.1002/cplu.202400643 Ritger PL, Peppas NA (1987) Transport of penetrants in the macromolecular structure of coals. 7. Transport in thin coal sections. Fuel 66:1379–1388 Dengre R, Bajpai M, Bajpai SK (2000) Release of vitamin B-12 from poly(N-vinyl-2-pyrrolidone)-crosslinked polyacrylamide hydrogels: a kinetic study. J Appl Polym Sci 76:1706–1714 Saraydin D, Karadağ E, Işıkver Y, Şahiner N, Güven O (2004) The influence of preparation methods on the swelling and network properties of acrylamide hydrogels with crosslinkers. J Macromol Sci A A41(4):421–433 Şahiner N, Saraydın D, Karadağ E, Güven O (1998) Swelling and dye adsorption properties of radiation induced N -vinyl-2- purrolidone /acrylonitrile hydrogels. Polym Bull 41:371–378 Kyzas GZ, Lazaridis NK (2009) Reactive and basic dyes removal by sorption onto chitosan derivatives. J Colloid Interf Sci 331:32–39. 10.1016/j.jcis.2008.11.003 Additional Declarations No competing interests reported. Cite Share Download PDF Status: Published Journal Publication published 10 Dec, 2025 Read the published version in Polymer Bulletin → Version 1 posted Editorial decision: Revision requested 04 Jul, 2025 Reviews received at journal 25 Jun, 2025 Reviewers agreed at journal 16 Jun, 2025 Reviewers agreed at journal 13 Jun, 2025 Reviewers invited by journal 13 Jun, 2025 Editor assigned by journal 28 Apr, 2025 Submission checks completed at journal 27 Apr, 2025 First submitted to journal 26 Apr, 2025 You are reading this latest preprint version Research Square lets you share your work early, gain feedback from the community, and start making changes to your manuscript prior to peer review in a journal. As a division of Research Square Company, we’re committed to making research communication faster, fairer, and more useful. We do this by developing innovative software and high quality services for the global research community. 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Also discoverable on Platform About Our Team In Review Editorial Policies Advisory Board Help Center Resources Author Services Accessibility API Access RSS feed Manage Cookie Preferences © Research Square 2026 | ISSN 2693-5015 (online) Privacy Policy Terms of Service Do Not Sell My Personal Information {"props":{"pageProps":{"initialData":{"identity":"rs-6536945","acceptedTermsAndConditions":true,"allowDirectSubmit":false,"archivedVersions":[],"articleType":"Research Article","associatedPublications":[],"authors":[{"id":471996296,"identity":"b9b2f88e-acd6-4ab4-9b46-18c18ab2cb99","order_by":0,"name":"Semiha Kundakcı","email":"data:image/png;base64,iVBORw0KGgoAAAANSUhEUgAAAZAAAAAyAQMAAABI0h/eAAAABlBMVEX///8AAABVwtN+AAAACXBIWXMAAA7EAAAOxAGVKw4bAAAA10lEQVRIiWNgGAWjYDACHjBOYGBjb2CQALIZG4jXwnMApoWZSC0MEglEapHvOWP24E1Nmjyf5OOHt3kYbGQ3HOA/9gGfFoOzPeaGc47lGLZJpxlb8zCkGW84wMw8A68Wfh4zaR62igQ26QQgg+FwIkgLfof1g7T8A2qRPP4NqOU/YS0MZ3vMpHnbchLYJEB6GQ4Q1mJw5liZ5Ny+NMM2npxiyzkGycYzDzMb43dYT/I2iTffkuXl249vvPGmwk6273jjY/wOQ7MUiAnF5CgYBaNgFIwCwgAA/Oc/gAaaiwQAAAAASUVORK5CYII=","orcid":"","institution":"Adnan Menderes University","correspondingAuthor":true,"prefix":"","firstName":"Semiha","middleName":"","lastName":"Kundakcı","suffix":""},{"id":471996297,"identity":"d0699bb6-00ca-4b34-aba7-84d478c76880","order_by":1,"name":"Mihrican Muti","email":"","orcid":"","institution":"Adnan Menderes University","correspondingAuthor":false,"prefix":"","firstName":"Mihrican","middleName":"","lastName":"Muti","suffix":""}],"badges":[],"createdAt":"2025-04-26 21:23:05","currentVersionCode":1,"declarations":"","doi":"10.21203/rs.3.rs-6536945/v1","doiUrl":"https://doi.org/10.21203/rs.3.rs-6536945/v1","draftVersion":[],"editorialEvents":[{"content":"https://doi.org/10.1007/s00289-025-06198-0","type":"published","date":"2025-12-10T15:59:18+00:00"}],"editorialNote":"","failedWorkflow":false,"files":[{"id":84780945,"identity":"b7088028-60d4-4713-8b83-112ed5cf076d","added_by":"auto","created_at":"2025-06-17 09:30:15","extension":"jpeg","order_by":1,"title":"Figure 1","display":"","copyAsset":false,"role":"figure","size":130639,"visible":true,"origin":"","legend":"\u003cp\u003eChemical structure of polymer and monomers in MAmH2P2 cryogels (a), some of preparation steps of polymeric samples (b) and their dry and water swollen appearance (c).\u003c/p\u003e","description":"","filename":"image1.jpeg","url":"https://assets-eu.researchsquare.com/files/rs-6536945/v1/84a765ffd32ed4dc737ab147.jpeg"},{"id":84779440,"identity":"d7b59631-2265-4fd7-b400-39be57f18df7","added_by":"auto","created_at":"2025-06-17 09:22:15","extension":"jpeg","order_by":2,"title":"Figure 2","display":"","copyAsset":false,"role":"figure","size":96054,"visible":true,"origin":"","legend":"\u003cp\u003eFTIR spectra of MAmH2P2 polimeric cryogels\u003c/p\u003e","description":"","filename":"image2.jpeg","url":"https://assets-eu.researchsquare.com/files/rs-6536945/v1/2aac4391368277e1ccd140e3.jpeg"},{"id":84779444,"identity":"12b1c959-1378-4ba7-a5dc-a6f3df4da09d","added_by":"auto","created_at":"2025-06-17 09:22:15","extension":"jpeg","order_by":3,"title":"Figure 3","display":"","copyAsset":false,"role":"figure","size":227736,"visible":true,"origin":"","legend":"\u003cp\u003eSEM micrographs and EDX spectrum of MAm (a), MAmH2 (b) and MAmH2P2 (c)\u003c/p\u003e","description":"","filename":"image3.jpeg","url":"https://assets-eu.researchsquare.com/files/rs-6536945/v1/a9b6e7feb629ebd6c555c21c.jpeg"},{"id":84779443,"identity":"a550c94b-0117-44e3-863f-373947987ee0","added_by":"auto","created_at":"2025-06-17 09:22:15","extension":"jpeg","order_by":4,"title":"Figure 4","display":"","copyAsset":false,"role":"figure","size":77362,"visible":true,"origin":"","legend":"\u003cp\u003eSwelling isotherms of polymeric gels\u003c/p\u003e","description":"","filename":"image4.jpeg","url":"https://assets-eu.researchsquare.com/files/rs-6536945/v1/003723648a02077b5d1bb4c5.jpeg"},{"id":84779446,"identity":"78c6f627-7628-4531-b807-de61ce8ddb34","added_by":"auto","created_at":"2025-06-17 09:22:15","extension":"jpeg","order_by":5,"title":"Figure 5","display":"","copyAsset":false,"role":"figure","size":83700,"visible":true,"origin":"","legend":"\u003cp\u003eDifferential Pulse Voltammograms (A) and calibration graph (B) of CLT solutions in PBS at concentrations of (a) 5.0 × 10⁻⁵ M, (b) 1.0 × 10⁻⁴ M, (c) 1.5 × 10⁻⁴ M, (d) 2.0 × 10⁻⁴ M, (e) 2.5 × 10⁻⁴ M, (f) 3.5 × 10⁻⁴ M, (g) 4.5 × 10⁻⁴ M, and (h) 5.0 × 10⁻⁴ M are shown.\u003c/p\u003e","description":"","filename":"image5.jpeg","url":"https://assets-eu.researchsquare.com/files/rs-6536945/v1/b6b9f6df174df30194d3c1cd.jpeg"},{"id":84779460,"identity":"c74ff93d-ebaa-4e71-bab8-4de7efa73785","added_by":"auto","created_at":"2025-06-17 09:22:16","extension":"jpeg","order_by":6,"title":"Figure 6","display":"","copyAsset":false,"role":"figure","size":130266,"visible":true,"origin":"","legend":"\u003cp\u003eThe voltammograms represent the reduction signal of 2.5 × 10⁻⁴ M CLT (a) before and after adsorption, (b) with MAm, (c) with MAmH2, (d) with MAmH2P2, and (e) with MAmP2.\u003c/p\u003e","description":"","filename":"image6.jpeg","url":"https://assets-eu.researchsquare.com/files/rs-6536945/v1/234f167ac92d500608512f18.jpeg"},{"id":84779450,"identity":"0e7a6639-004e-4ad5-82c7-69ac7fb35e09","added_by":"auto","created_at":"2025-06-17 09:22:15","extension":"jpeg","order_by":7,"title":"Figure 7","display":"","copyAsset":false,"role":"figure","size":78057,"visible":true,"origin":"","legend":"\u003cp\u003eHistograms show A) CLT reduction current values before (C\u003csub\u003einitial\u003c/sub\u003e) and after adsorption (C\u003csub\u003eLast\u003c/sub\u003e) and B) adsorption percentage of different cryogels.\u003c/p\u003e","description":"","filename":"image7.jpeg","url":"https://assets-eu.researchsquare.com/files/rs-6536945/v1/5138e33f855154a9f616505a.jpeg"},{"id":84779454,"identity":"878cb784-264f-479a-a394-25da3f4422e8","added_by":"auto","created_at":"2025-06-17 09:22:16","extension":"jpeg","order_by":8,"title":"Figure 8","display":"","copyAsset":false,"role":"figure","size":55249,"visible":true,"origin":"","legend":"\u003cp\u003eEquilibrium adsorption isotherms of polymeric gels in aqueous solutions of CLT at different concentrations.\u003c/p\u003e","description":"","filename":"image8.jpeg","url":"https://assets-eu.researchsquare.com/files/rs-6536945/v1/7de0f0c119feebab69494d0a.jpeg"},{"id":98244805,"identity":"66d54929-f8d6-435f-9be4-4aec06a3f835","added_by":"auto","created_at":"2025-12-15 16:15:18","extension":"pdf","order_by":0,"title":"","display":"","copyAsset":false,"role":"manuscript-pdf","size":1654774,"visible":true,"origin":"","legend":"","description":"","filename":"manuscript.pdf","url":"https://assets-eu.researchsquare.com/files/rs-6536945/v1/37cda999-d02e-4c5a-b7fe-b200f3b4cf1d.pdf"}],"financialInterests":"No competing interests reported.","formattedTitle":"Methacrylamide Based Polymeric Cryogels for the Effective Removal of Neonicotinoid Insecticide, Clothianidin","fulltext":[{"header":"1. Introduction","content":"\u003cp\u003eEnvironmental factors are becoming increasingly significant in public health due to the emergence of new environmental impacts, while efforts to address existing issues continue. Pesticides are biologically active chemicals employed to prevent damage to agricultural products during production and storage, as well as to maintain product quality. Most pesticides also serve as plant protection products, safeguarding plants from weeds, fungi, or insects. Despite their effectiveness and widespread use in controlling various pests, the exposure to and residues of pesticides in food and water can present significant health risks [\u003cspan citationid=\"CR1\" class=\"CitationRef\"\u003e1\u003c/span\u003e, \u003cspan citationid=\"CR2\" class=\"CitationRef\"\u003e2\u003c/span\u003e].\u003c/p\u003e \u003cp\u003ePesticides are classified into various categories, including insecticides, fungicides, herbicides, nematicides, and rodenticides, based on the species they target and their areas of application. Neonicotinoids are broad-spectrum systemic insecticides that have become widely used worldwide in recent years. At present, seven neonicotinoid insecticides exist, categorized into different types, including acetamiprid, imidacloprid, clothianidin, thiamethoxam, thiacloprid, dinotefuran and nitenpyram [\u003cspan additionalcitationids=\"CR2 CR3 CR4\" citationid=\"CR1\" class=\"CitationRef\"\u003e1\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR5\" class=\"CitationRef\"\u003e5\u003c/span\u003e].\u003c/p\u003e \u003cp\u003eClothianidin ((E)-1-(2-chloro-1,3-thiazol-5-ylmethyl)-3-methyl-2-nitroguanidine) is a neonicotinoid insecticide used as a pesticide. Insecticides, such as clothianidin, which exhibit specific activity on the insect nervous system, are effective compounds used to control the harmful effects of pests like aphids, thrips, whiteflies, adelgids, and leafhoppers. However, the residues left by such compounds after use pose a potential risk to agricultural products, human health, and beneficial insects such as bees. Therefore, it is crucial that these pesticides are removed from the environment [\u003cspan additionalcitationids=\"CR7\" citationid=\"CR6\" class=\"CitationRef\"\u003e6\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR8\" class=\"CitationRef\"\u003e8\u003c/span\u003e].\u003c/p\u003e \u003cp\u003ePolymeric gels, also known as hydrogels, are unique structures that exhibit swelling behavior without dissolving when in contact with aqueous solutions. Cryogels are a type of polymeric material distinguished from hydrogels by the conditions under which they are prepared (at sub-zero temperatures). Cryogels are formed by freezing a reaction mixture that contains precursors facilitating gel formation at temperatures lower than the solvent\u0026rsquo;s crystallization threshold. Once the polymerization process is completed, void formation is achieved by melting the ice crystals that were frozen. These pores create a system of interconnected continuous macropores, and due to this porous structure, cryogels have numerous applications, including in bioseparation, chromatography, tissue engineering, and as adsorbents for environmental applications [\u003cspan additionalcitationids=\"CR10 CR11 CR12 CR13\" citationid=\"CR9\" class=\"CitationRef\"\u003e9\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR14\" class=\"CitationRef\"\u003e14\u003c/span\u003e].\u003c/p\u003e \u003cp\u003eInvestigating the adsorption and retention capabilities of polymeric gels in aqueous media is a crucial step in understanding their structure and potential properties. The swelling ratio, diffusion, and sorption mechanism parameters are determined by measuring the mass or volume of the gel in its hydrated (swollen) and unhydrated (dry) states. The resulting swelling profile of the newly synthesized polymeric gels provides valuable insight into their suitability for various specific applications [\u003cspan additionalcitationids=\"CR16 CR17\" citationid=\"CR15\" class=\"CitationRef\"\u003e15\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR18\" class=\"CitationRef\"\u003e18\u003c/span\u003e].\u003c/p\u003e \u003cp\u003eIn recent years, significant research efforts have focused on utilizing polymeric gel systems as adsorbents for the removal of harmful species that may be present as pollutants in aqueous environments. Due to its low cost and ease of application, the adsorption method has become a widely adopted approach [\u003cspan citationid=\"CR15\" class=\"CitationRef\"\u003e15\u003c/span\u003e, \u003cspan citationid=\"CR18\" class=\"CitationRef\"\u003e18\u003c/span\u003e]. Numerous studies in the literature have focused on the use of polymeric materials for the removal of pesticides. The removal of Imidacloprid from aqueous systems has been carried out using carboxymethyl cellulose-based bionanocomposite (CMC/Fe₃O₄-Zeolite) hydrogel beads [\u003cspan citationid=\"CR20\" class=\"CitationRef\"\u003e20\u003c/span\u003e], Cellulose acetate (CA) hydrogel beads designed for the elimination of Chlorpyrifos from aqueous environments [\u003cspan citationid=\"CR15\" class=\"CitationRef\"\u003e15\u003c/span\u003e], UiO-66-based alginate hydrogel for the controlled release of Clothianidin [\u003cspan citationid=\"CR21\" class=\"CitationRef\"\u003e21\u003c/span\u003e], β-cyclodextrin cross-linked cellulose/poly(vinyl alcohol) (β-CD/cellulose/PVA) hydrogel for Malathion removal [\u003cspan citationid=\"CR22\" class=\"CitationRef\"\u003e22\u003c/span\u003e], chitosan/clay nanocomposite hydrogels for Paraquat removal from water [\u003cspan citationid=\"CR23\" class=\"CitationRef\"\u003e23\u003c/span\u003e], nicotinamide-modified cryogels for the removal of Chlordane [\u003cspan citationid=\"CR24\" class=\"CitationRef\"\u003e24\u003c/span\u003e], and Chitosan-based organoclay hydrogels designed for the adsorption of Carbendazim [\u003cspan citationid=\"CR25\" class=\"CitationRef\"\u003e25\u003c/span\u003e].\u003c/p\u003e \u003cp\u003eThis study is the first that investigated clothianidin removal from aqueous solution by polymeric cryogels. We aim to develop a novel methacrylamide-based polymeric sorbent and investigate its capability in removing the neonicotinoid insecticide Clothianidin (CLT) using the voltammetric method. For this purpose, MAm cryogels with diverse formulations were produced through free radical cryopolymerization in an aqueous environment. Additionally, HEMA and PAA were incorporated to enhance the functionality of the polymeric samples and to assess the properties imparted by these additives. Various analytical methods were employed to assess the structural, surface, and swelling features of the polymeric samples. Dynamic swelling tests were performed to calculate the swelling parameters, which are frequently utilized for characterizing synthesized polymeric gels, and the diffusion mechanism was analyzed. To assess the efficacy of these gels in mitigating environmental pollutants, their performance in the removal of CLT was evaluated.\u003c/p\u003e"},{"header":"2. Experimental","content":"\u003cdiv id=\"Sec3\" class=\"Section2\"\u003e \u003ch2\u003e2.1. Chemicals\u003c/h2\u003e \u003cp\u003eMethacrylamide (MAm, monomer), 2-hydroxyethyl methacrylate (HEMA, co-monomer), and poly(acrylic acid) (PAA) were used for the formation of polymeric structures and were purchased from Sigma-Aldrich. To enable cross-linking, Bisacrylamide (BAm) (Sigma-Aldrich, Steinheim, Germany) was used as a crosslinking agent. Ammonium persulphate (APS) and N,N,N\u0026prime;,N\u0026prime;-tetramethylethylenediamine (TEMED) were functioned as a redox-initiator pair and sourced from Merck, Schuchardt, Germany. Phosphate-buffered saline (PBS, pH 7.2) and ethyl alcohol were obtained from Sigma-Aldrich, Steinheim, Germany. The acquisition of Clothianidin was also made through Sigma-Aldrich.\u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec4\" class=\"Section2\"\u003e \u003ch2\u003e2.2. Equipment\u003c/h2\u003e \u003cp\u003eElectrochemical measurements were carried out by IVIUM Compact Stat Plus Module. Working, reference and counter electrodes are pencil graphite (HB in 0.5 mm diameter), Ag/AgCl (3 M KCl BAS, Model RE-5B, W. Lafayette, USA) and platinum wire, respectively. Characterization of cryogels was carried out using FT-IR spectroscopy (Thermo Scientific Nicolet is 10 SMARTt FT-IR/ATR, USA). The morphological characteristics of polymeric cryogels were examined by scanning electron microscope, SEM (Phillips XL-30S FEG, FEI Quanta 250 FEG).\u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec5\" class=\"Section2\"\u003e \u003ch2\u003e2.3. Procedure\u003c/h2\u003e \u003cp\u003e \u003cb\u003ePreparation of Polymeric Sorbents and Cryopolymerization of MAmHP cryogels\u003c/b\u003e \u003c/p\u003e \u003cp\u003eThrough free radical copolymerization, MAm and HEMA monomers were crosslinked with BAm under cryogenic conditions to synthesize polymeric samples. PAA, a synthetic polymer, was incorporated to impart additional functional properties to the polymeric structures. Ammonium persulfate (APS) functioned as an initiator, while N,N,N\u0026prime;,N\u0026prime;-tetramethylethylenediamine (TEMED) acted as an accelerator during the synthesis process.\u003c/p\u003e \u003cp\u003eInitially, MAm (1.0 g) was solubilized in a 2.0 mL water-ethanol blend (1:1) at ambient temperature. Subsequently, HEMA (180 \u0026micro;L) and PAA (50 mg) were introduced into the solution and stirred until a uniform monomer blend was obtained. Following this, 0.5 mL of BAm (1% w/v), 0.5 mL of APS (5.0 g/100 mL water), and 1.0 mL of TEMED (1.0% v/v) were sequentially added. Following complete mixing, the solution was rapidly cooled in an ice bath, transferred into a 2.0 mL syringe, and subsequently frozen at \u0026minus;\u0026thinsp;20\u0026deg;C for 24 hours to induce crosslinking and cryopolymerization.\u003c/p\u003e \u003cp\u003eAfter polymerization, the cryogels were thawed at ambient temperature and sectioned into cylindrical segments (3\u0026ndash;4 mm in length). These pieces were then immersed in distilled water to eliminate any residual monomers, polymers, or other unreacted substances. The distilled water was replaced three times a day for four days to ensure thorough purification. The cryogels were then initially air-dried and then vacuum-dried for 24 hours at a temperature of 40\u0026deg;C. The dried samples were stored for further use.\u003c/p\u003e \u003cp\u003eSynthesis of samples without HEMA or PAA was performed following the same procedure. The polymeric cryogels having different compositions were detailed MAmHP cryogels formulations are given in Table\u0026nbsp;\u003cspan refid=\"Tab1\" class=\"InternalRef\"\u003e1\u003c/span\u003e. The synthesis and swelling phases of the polymeric samples are depicted in Fig.\u0026nbsp;\u003cspan refid=\"Fig1\" class=\"InternalRef\"\u003e1\u003c/span\u003e.\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\u003eCombinations of polymeric cryogels developed using various formulations\u003c/p\u003e \u003c/div\u003e \u003c/caption\u003e \u003ccolgroup cols=\"5\"\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 \u003cthead\u003e \u003ctr\u003e \u003cth align=\"left\" colname=\"c1\"\u003e \u003cp\u003eSample Code\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c2\"\u003e \u003cp\u003eAbbreviation\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c3\"\u003e \u003cp\u003eMAAm\u003c/p\u003e \u003cp\u003e(mmol)\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c4\"\u003e \u003cp\u003eHEMA\u003c/p\u003e \u003cp\u003e(mmol)\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c5\"\u003e \u003cp\u003ePAA\u003c/p\u003e \u003cp\u003e(mg)\u003c/p\u003e \u003c/th\u003e \u003c/tr\u003e \u003c/thead\u003e \u003ctbody\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eMAm\u003c/p\u003e \u003cp\u003eMAmH2\u003c/p\u003e \u003cp\u003eMAmH2P2\u003c/p\u003e \u003cp\u003eMAmP2\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003eMAm\u003c/p\u003e \u003cp\u003eMAm/180 HEMA\u003c/p\u003e \u003cp\u003eMAm/180 HEMA/50 PAA\u003c/p\u003e \u003cp\u003eMAm/50 PAA\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e11.75\u003c/p\u003e \u003cp\u003e11.75\u003c/p\u003e \u003cp\u003e11.75\u003c/p\u003e \u003cp\u003e11.75\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e-\u003c/p\u003e \u003cp\u003e1.48\u003c/p\u003e \u003cp\u003e1.48\u003c/p\u003e \u003cp\u003e-\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e-\u003c/p\u003e \u003cp\u003e-\u003c/p\u003e \u003cp\u003e50\u003c/p\u003e \u003cp\u003e50\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\u003eBAm (0.0324 mmol) APS (0.1096 mmol) and TEMED (0.0671 mmol) were used in all polymeric systems\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003e \u003cb\u003eCharacterization\u003c/b\u003e \u003c/p\u003e \u003cp\u003eFT-IR analysis was conducted to characterize the chemical structure of the synthesized polymeric cryogels. The chemical composition of MAm/HEMA/PAA (MAmHP) was examined within the spectral range of 4000\u0026ndash;400 cm⁻\u0026sup1; using an ATR apparatus.\u003c/p\u003e \u003cp\u003eThe microstructural composition of the polymeric cryogels was examined using scanning electron microscopy (SEM) to investigate their internal architecture and surface features. To enhance imaging quality, the dry polymeric specimens were first coated with a conductive gold layer using a deposition device (Emitech K550X) prior to SEM analysis. Additionally, energy dispersive X-ray spectroscopy (EDX) was utilized in conjunction with the SEM analysis to investigate the elemental distribution within the samples.\u003c/p\u003e \u003cp\u003e \u003cb\u003eSwelling studies\u003c/b\u003e \u003c/p\u003e \u003cp\u003eThe swelling capacity of a polymeric gel is a critical parameter used to characterize its structure and properties. Swelling values can be determined through simple measurements of the dry and swollen gel weights. Assessing the water retention capacity of polymeric gels through swelling studies is essential for understanding polymeric matrix diffusion. Based on the obtained data, key swelling parameters\u0026mdash;including equilibrium swelling, equilibrium water content, diffusion exponent, diffusion constant, and diffusion coefficient\u0026mdash;were calculated, as these parameters are commonly used for the swelling characterization of polymeric gels [\u003cspan citationid=\"CR16\" class=\"CitationRef\"\u003e16\u003c/span\u003e, \u003cspan additionalcitationids=\"CR27\" citationid=\"CR26\" class=\"CitationRef\"\u003e26\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR28\" class=\"CitationRef\"\u003e28\u003c/span\u003e].\u003c/p\u003e \u003cp\u003e \u003cb\u003ePesticide sorption\u003c/b\u003e \u003c/p\u003e \u003cp\u003eAt this stage, the adsorption efficiency of the prepared polymeric cryogels for Clothianidin (CLT) was examined. Batch studies were carried out to examine the elimination of CLT from aqueous media, considering the composition of the polymeric sorbents (MAm, MAm/HEMA, MAm/HEMA/PAA, and MAm/PAA) and varying CLT concentrations (1.0 \u0026times; 10⁻⁴ M, 2.5 \u0026times; 10⁻⁴ M, and 5.0 \u0026times; 10⁻⁴ M) under constant temperature conditions (25\u0026deg;C).\u003c/p\u003e \u003cp\u003e \u003cb\u003eVoltammetric transduction\u003c/b\u003e \u003c/p\u003e \u003cp\u003eDPV measurements (Differential pulse voltammetric) were carried out across various CLT concentrations prepared in PBS. The measurements were conducted using cathodic scanning within the potential range of -0.7 V to -1.4 V vs. an Ag/AgCl reference electrode, with a pulse amplitude of 50 mV and a scan rate of 20 mV/s.\u003c/p\u003e \u003c/div\u003e"},{"header":"3. Result and Discussion","content":"\u003cdiv id=\"Sec7\" class=\"Section2\"\u003e \u003ch2\u003e3.1. FT-IR analysis\u003c/h2\u003e \u003cp\u003eFT-IR analysis was conducted to characterize the structural properties of MAm/HEMA/PAA (MAmHP) using FT-IR spectroscopy (Fig.\u0026nbsp;\u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e2\u003c/span\u003e). As shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e2\u003c/span\u003e, a strong and broad absorption band between 3400\u0026ndash;3100 cm⁻\u0026sup1; was observed, attributed to the N\u0026ndash;H stretching vibrations of MAm. The peak observed in the 3000\u0026ndash;2700 cm⁻\u0026sup1; range corresponds to the stretching vibrations of CH, CH₂, and CH₃ groups. The band at 1652 cm⁻\u0026sup1; is associated with the stretching vibration of the carbonyl (C\u0026thinsp;=\u0026thinsp;O) group in the amide functional group. Characteristic peaks of HEMA were identified at 3432 cm⁻\u0026sup1; and 1703 cm⁻\u0026sup1;, corresponding to O\u0026ndash;H stretching and C\u0026thinsp;=\u0026thinsp;O stretching vibrations, respectively, which appeared as shoulder formations. Additionally, C\u0026ndash;OH in-plane bending at 1447 cm⁻\u0026sup1; and C\u0026ndash;O\u0026ndash;C (ester group) stretching at 1247 cm⁻\u0026sup1; were detected. The presence of poly(acrylic acid) (PAA) was confirmed by the characteristic absorption bands at 3432 cm⁻\u0026sup1; and 1025 cm⁻\u0026sup1;, which correspond to the O\u0026ndash;H stretching and O\u0026ndash;H deformation vibrations of carboxyl groups, respectively. Furthermore, the C\u0026thinsp;=\u0026thinsp;O stretching peak at 1703 cm⁻\u0026sup1;, along with the C\u0026ndash;O stretching and bending vibrations at 1386 cm⁻\u0026sup1; and 1200 cm⁻\u0026sup1;, were clearly identified [\u003cspan additionalcitationids=\"CR30 CR31 CR32 CR33 CR34\" citationid=\"CR29\" class=\"CitationRef\"\u003e29\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR35\" class=\"CitationRef\"\u003e35\u003c/span\u003e].\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec8\" class=\"Section2\"\u003e \u003ch2\u003e3.2. Microscopic Characterization\u003c/h2\u003e \u003cp\u003eThe surface properties of the polymeric cryogels, as characterized by SEM, are presented in Fig.\u0026nbsp;\u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e3\u003c/span\u003e. The changes in pore structure resulting from the incorporation of HEMA and PAA into MAm-based cryogels can be observed (Fig.\u0026nbsp;\u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e3\u003c/span\u003e). It was noted that samples without PAA exhibited a more porous morphology, whereas the addition of PAA led to polymer entanglement within the pore spaces, resulting in a denser structure. Furthermore, the elemental distribution within the polymeric samples was investigated using energy-dispersive X-ray spectroscopy (EDX), enabling compositional mapping of the identified elements. [\u003cspan citationid=\"CR16\" class=\"CitationRef\"\u003e16\u003c/span\u003e, \u003cspan citationid=\"CR36\" class=\"CitationRef\"\u003e36\u003c/span\u003e].\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec9\" class=\"Section2\"\u003e \u003ch2\u003e3.3. Water swelling studies of the polymeric cryogels\u003c/h2\u003e \u003cp\u003eA key characteristic of hydrogels is their ability to absorb water. Dry polymeric gels undergo swelling upon contact with a suitable solvent. The swelling reaction is influenced by the intrinsic properties of both the polymer and the solvent. Swelling measurements were conducted in a water bath at specified time periods. Pre-weighed polymeric specimens with defined masses were introduced into a 40 mL volume of deionized water within a beaker. Periodically, the samples were withdrawn from the water, and any surface moisture was gently blotted using absorbent paper before weighing. The samples were reintroduced to the swelling medium, and the cycle continued until the mass remained unchanged.\u003c/p\u003e \u003cp\u003eThe equilibrium swelling value, expressed as the equilibrium percent swelling (PS%), was determined using Eq.\u0026nbsp;(\u003cspan refid=\"Equ1\" class=\"InternalRef\"\u003e1\u003c/span\u003e) [\u003cspan citationid=\"CR26\" class=\"CitationRef\"\u003e26\u003c/span\u003e, \u003cspan citationid=\"CR28\" class=\"CitationRef\"\u003e28\u003c/span\u003e, \u003cspan citationid=\"CR37\" class=\"CitationRef\"\u003e37\u003c/span\u003e, \u003cspan citationid=\"CR38\" class=\"CitationRef\"\u003e38\u003c/span\u003e]. The percentage of equilibrium water content (PEWC) in polymeric gel systems defines the amount of water stabilized within the structure. PEWC values, determined via Eq.\u0026nbsp;\u003cspan refid=\"Equ2\" class=\"InternalRef\"\u003e2\u003c/span\u003e, provide crucial information on permeability, mechanical integrity, surface attributes, and biocompatibility (17, 39, 40).\u003cdiv id=\"Equ1\" class=\"Equation\"\u003e\u003cdiv format=\"TEX\" class=\"mathdisplay\" id=\"FileID_Equ1\" name=\"EquationSource\"\u003e\n$$\\:\\text{P}\\text{S}\\text{%}=\\frac{{\\text{m}}_{\\text{t}}-{\\text{m}}_{0}}{{\\text{m}}_{0}}\\text{x}100$$\u003c/div\u003e\u003cdiv class=\"EquationNumber\"\u003e1\u003c/div\u003e\u003c/div\u003e\u003cdiv id=\"Equ2\" class=\"Equation\"\u003e\u003cdiv format=\"TEX\" class=\"mathdisplay\" id=\"FileID_Equ2\" name=\"EquationSource\"\u003e\n$$\\:\\text{P}\\text{E}\\text{W}\\text{C}\\text{%}=\\frac{{\\text{m}}_{t}-{\\text{m}}_{0}}{{\\text{m}}_{t}}\\text{x}100$$\u003c/div\u003e\u003cdiv class=\"EquationNumber\"\u003e2\u003c/div\u003e\u003c/div\u003e\u003c/p\u003e \u003cp\u003eIn this equation, \u003cem\u003em\u003c/em\u003e\u003csub\u003e\u003cem\u003et\u003c/em\u003e\u003c/sub\u003e represents the gel\u0026rsquo;s mass after absorbing water at time \u003cem\u003et\u003c/em\u003e, with \u003cem\u003em\u003c/em\u003e\u003csub\u003e\u003cem\u003eo\u003c/em\u003e\u003c/sub\u003e being its initial dry weight at \u003cem\u003et\u0026thinsp;=\u0026thinsp;0\u003c/em\u003e.\u003c/p\u003e \u003cp\u003eThe hydration behavior of MAm-based MAmHP cryogels crosslinked with BAm was observed, with swelling isotherms computed via Eq.\u0026nbsp;\u003cspan refid=\"Equ1\" class=\"InternalRef\"\u003e1\u003c/span\u003e and illustrated in Fig.\u0026nbsp;\u003cspan refid=\"Fig4\" class=\"InternalRef\"\u003e4\u003c/span\u003e.\u003c/p\u003e \u003cp\u003eThe Fickian diffusion model, formulated in Eq.\u0026nbsp;\u003cspan refid=\"Equ3\" class=\"InternalRef\"\u003e3\u003c/span\u003e, was applied to evaluate water penetration into the polymer matrix.\u003cdiv id=\"Equ3\" class=\"Equation\"\u003e\u003cdiv format=\"TEX\" class=\"mathdisplay\" id=\"FileID_Equ3\" name=\"EquationSource\"\u003e\n$$\\:F=\\frac{{M}_{t}}{{M}_{s}}={kt}^{n}$$\u003c/div\u003e\u003cdiv class=\"EquationNumber\"\u003e3\u003c/div\u003e\u003c/div\u003e\u003c/p\u003e \u003cp\u003eF represents the ratio of solvent uptake by the gel at time \u003cem\u003et\u003c/em\u003e to equilibrium absorption and is defined as the swelling ratio. The diffusional exponent (n) and diffusion coefficient (k) were obtained using the linearized model (lnF\u0026thinsp;=\u0026thinsp;lnk\u0026thinsp;+\u0026thinsp;nln t) from Eq.\u0026nbsp;\u003cspan refid=\"Equ3\" class=\"InternalRef\"\u003e3\u003c/span\u003e, to analyze the macromolecular structure, penetrant behavior, and transport mechanisms (Fig.\u0026nbsp;\u003cspan refid=\"Fig4\" class=\"InternalRef\"\u003e4\u003c/span\u003e).\u003c/p\u003e \u003cp\u003eWater diffusion into the macromolecular matrix follows Fick\u0026rsquo;s diffusion equation, predominantly influencing the process in its initial 60% phase. A diffusion coefficient of (n\u0026thinsp;=\u0026thinsp;0.5) corresponds to Fickian diffusion, where molecular mobility is restricted by a slower diffusion rate relative to relaxation kinetics. When (n) lies in the range (0.5\u0026thinsp;\u0026lt;\u0026thinsp;n\u0026thinsp;\u0026lt;\u0026thinsp;1.0), diffusion operates under a non-Fickian regime, with both diffusion and relaxation mechanisms contributing significantly. If (n\u0026thinsp;\u0026gt;\u0026thinsp;1), the transport dynamics shift to Super Case II behavior, characterized by a dominant diffusion rate over relaxation effects. [\u003cspan citationid=\"CR17\" class=\"CitationRef\"\u003e17\u003c/span\u003e, \u003cspan additionalcitationids=\"CR42\" citationid=\"CR41\" class=\"CitationRef\"\u003e41\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR43\" class=\"CitationRef\"\u003e43\u003c/span\u003e].\u003c/p\u003e \u003cp\u003eTable\u0026nbsp;2 reveals that the calculated nnn values, which elucidate the mechanism of water movement in the gel network, surpass 1.0 for MAm and MAmP2, indicating Super Case II transport behavior. In this mechanism, the diffusion time of water into the cryogels exceeds the polymer relaxation time. For the remaining polymeric samples, the nnn values range from 0.5 to 1.0, suggesting a non-Fickian diffusion process.\u003c/p\u003e \u003cp\u003eAnalyzing water transport phenomena in hydrogels is essential for comprehending polymer behavior. The calculation of diffusion coefficient values, fundamental for hydrogel characterization, was conducted using Eq.\u0026nbsp;\u003cspan refid=\"Equ5\" class=\"InternalRef\"\u003e4\u003c/span\u003e for cylindrical-shaped hydrogels [\u003cspan citationid=\"CR43\" class=\"CitationRef\"\u003e43\u003c/span\u003e, \u003cspan citationid=\"CR44\" class=\"CitationRef\"\u003e44\u003c/span\u003e].\u003cdiv id=\"Equ4\" class=\"Equation\"\u003e\u003cdiv format=\"TEX\" class=\"mathdisplay\" id=\"FileID_Equ4\" name=\"EquationSource\"\u003e\n$$\\:\\text{D}=\\pi\\:{r}^{2}{\\left(\\frac{k}{4}\\right)}^{\\raisebox{1ex}{$1$}\\!\\left/\\:\\!\\raisebox{-1ex}{$n$}\\right.}$$\u003c/div\u003e\u003cdiv class=\"EquationNumber\"\u003e4\u003c/div\u003e\u003c/div\u003e\u003c/p\u003e \u003cp\u003eIn this formulation, \u003cem\u003eD\u003c/em\u003e corresponds to the diffusion coefficient (cm\u003csup\u003e2\u003c/sup\u003e/min), describing the permeable area of the polymeric gel through which solvent species migrate per unit time. The parameter, \u003cem\u003er\u003c/em\u003e designates the radius of the cylindrical gel matrix, with \u003cem\u003ek\u003c/em\u003e and \u003cem\u003en\u003c/em\u003e were defined earlier.\u003c/p\u003e \u003cp\u003eWhen all of the synthesized polymeric structures are considered, the diffusion coefficients vary in the range of 31.97x10\u003csup\u003e\u0026minus;\u0026thinsp;5\u003c/sup\u003e cm\u003csup\u003e2\u003c/sup\u003es\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e-166.99x10\u003csup\u003e\u0026minus;\u0026thinsp;5\u003c/sup\u003e cm\u003csup\u003e2\u003c/sup\u003es\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e.\u003c/p\u003e \u003cp\u003eThe rise in HEMA unit concentration within the polymeric structure resulted in a decreased gel area for solvent diffusion per unit time. Among the polymeric gels, MAm cryogels exhibit the largest area allowing solvent molecules to pass per unit time.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003eFigure \u003cspan refid=\"Fig4\" class=\"InternalRef\"\u003e4\u003c/span\u003e demonstrates that swelling gradually rises over time until reaching equilibrium, after which it stabilizes. This steady swelling value is referred as the equilibrium percentage swelling (PS\u003csub\u003eeq\u003c/sub\u003e%), with corresponding values provided in Table\u0026nbsp;2 for all polymeric matrices.\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 3\u003c/div\u003e \u003cdiv class=\"CaptionContent\"\u003e \u003cp\u003eExperimentally obtained swelling and diffusion parameters of polymeric gels\u003c/p\u003e \u003c/div\u003e \u003c/caption\u003e \u003ccolgroup cols=\"6\"\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 \u003cthead\u003e \u003ctr\u003e \u003cth align=\"left\" colname=\"c1\"\u003e\u0026nbsp;\u003c/th\u003e \u003cth align=\"left\" colname=\"c2\"\u003e \u003cp\u003ePS\u003csub\u003eeq\u003c/sub\u003e%\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c3\"\u003e \u003cp\u003ePEWC%\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c4\"\u003e \u003cp\u003en\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c5\"\u003e \u003cp\u003ekx10\u003csup\u003e3\u003c/sup\u003e\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c6\"\u003e \u003cp\u003eDx10\u003csup\u003e5\u003c/sup\u003e\u003c/p\u003e \u003c/th\u003e \u003c/tr\u003e \u003c/thead\u003e \u003ctbody\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eMAm\u003c/p\u003e \u003cp\u003eMAmH2\u003c/p\u003e \u003cp\u003eMAmH2P2\u003c/p\u003e \u003cp\u003eMAmP2\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e180\u003c/p\u003e \u003cp\u003e271\u003c/p\u003e \u003cp\u003e260\u003c/p\u003e \u003cp\u003e205\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e64.28\u003c/p\u003e \u003cp\u003e73.01\u003c/p\u003e \u003cp\u003e72.18\u003c/p\u003e \u003cp\u003e67.17\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e1.6293\u003c/p\u003e \u003cp\u003e0.9945\u003c/p\u003e \u003cp\u003e0.9578\u003c/p\u003e \u003cp\u003e1.5776\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e0.39\u003c/p\u003e \u003cp\u003e3.95\u003c/p\u003e \u003cp\u003e3.69\u003c/p\u003e \u003cp\u003e0.31\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e166.99\u003c/p\u003e \u003cp\u003e51.90\u003c/p\u003e \u003cp\u003e31.97\u003c/p\u003e \u003cp\u003e124.70\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003c/tbody\u003e \u003c/colgroup\u003e \u003c/table\u003e\u003c/div\u003e \u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec10\" class=\"Section2\"\u003e \u003ch2\u003e3.4. CLT adsorption studies of the polymeric cryogels\u003c/h2\u003e \u003cp\u003eFor the purpose of investigating the surface adsorption characteristics of the synthesized polymeric gels, an adsorption study of Clothianidin (CLT) was conducted at 25\u0026deg;C. A calibration curve was initially prepared by measuring the reduction signal of CLT at various concentrations ranging from 5.0 \u0026times; 10⁻⁵ to 5.0 \u0026times; 10⁻⁴ M (Fig.\u0026nbsp;\u003cspan refid=\"Fig5\" class=\"InternalRef\"\u003e5\u003c/span\u003e) to quantitatively evaluate CLT adsorption. Subsequently, aqueous CLT solutions were allowed to interact with the cross-linked copolymer-based polymeric gels until equilibrium was reached at varying concentrations between 1.5 \u0026times; 10⁻⁵ M and 5.0 \u0026times; 10⁻⁴ M. The effect of cryogels on CLT sorption was examined using aqueous solutions at a concentration of 2.5 \u0026times; 10⁻⁴ M, which corresponds to the midpoint of the calibration curve. After the sorption process, 5 mL of the CLT solution was collected and transferred to an electrochemical cell. A three-electrode setup was subsequently submerged in the solution, and electrochemical analyses were performed at room temperature The change in the CLT reduction signal before and after adsorption is presented in Fig.\u0026nbsp;\u003cspan refid=\"Fig5\" class=\"InternalRef\"\u003e5\u003c/span\u003e.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec11\" class=\"Section2\"\u003e \u003ch2\u003e3.5. Comparison of cryogels in terms of CLT adsorption\u003c/h2\u003e \u003cp\u003eTo investigate the effect of HEMA and PAA added to the MAm structure during the synthesis of cryogels on CLT adsorption, MAm, MAmH2, MAmH2P2, and MAmP2 cryogels were incubated in a 2.5x10\u003csup\u003e\u0026minus;\u0026thinsp;4\u003c/sup\u003e M CLT solution for 1 hour. Upon completion of the designed time interval, the cryogels were extracted, and the filtrate was transferred to an electrochemical cell. The reduction signal of CLT was measured using a three-electrode system, and the CLT removal was compared with the reduction signal of CLT before treatment with the cryogels. The obtained results are presented in Fig.\u0026nbsp;\u003cspan refid=\"Fig6\" class=\"InternalRef\"\u003e6\u003c/span\u003e.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003eThe CLT reduction current values before and after adsorption, along with the adsorption percentages of the cryogels, are presented as histograms in Fig.\u0026nbsp;\u003cspan refid=\"Fig7\" class=\"InternalRef\"\u003e7\u003c/span\u003e.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003eIn equilibrium sorption analysis, the CLT uptake capacity (Q), expressed as the amount of sorbed CLT in moles per unit mass of adsorbent in grams, adsorption percentage (A%), and partition constant (PC) were evaluated. The CLT uptake capacity (Q) of the polymeric cryogels was calculated according to the following equation:\u003cdiv id=\"Equ5\" class=\"Equation\"\u003e\u003cdiv format=\"TEX\" class=\"mathdisplay\" id=\"FileID_Equ5\" name=\"EquationSource\"\u003e\n$$\\:\\text{Q}=\\frac{\\left({C}_{0}-C\\right)v}{m}$$\u003c/div\u003e\u003cdiv class=\"EquationNumber\"\u003e4\u003c/div\u003e\u003c/div\u003e\u003c/p\u003e \u003cp\u003eWhere Q denotes the CLT uptake capacity of the polymeric cryogels (mol g⁻\u0026sup1;), and C₀ and C correspond to the initial and post-treatment CLT concentrations in the liquid phase after a stated measurement duration, respectively (mol L⁻\u0026sup1;). Additionally, v corresponds to the liquid phase volume (L), with m indicating the mass of the polymeric cryogels (g) [\u003cspan citationid=\"CR17\" class=\"CitationRef\"\u003e17\u003c/span\u003e, \u003cspan citationid=\"CR45\" class=\"CitationRef\"\u003e45\u003c/span\u003e, \u003cspan citationid=\"CR46\" class=\"CitationRef\"\u003e46\u003c/span\u003e].\u003c/p\u003e \u003cp\u003eThe adsorption efficiency \u003cem\u003e(A%)\u003c/em\u003e of polymeric cryogels was calculated according to the following mathematical expression:\u003cdiv id=\"Equ6\" class=\"Equation\"\u003e\u003cdiv format=\"TEX\" class=\"mathdisplay\" id=\"FileID_Equ6\" name=\"EquationSource\"\u003e\n$$\\:A\\%=\\frac{{C}_{0}-C}{{C}_{0}}x100$$\u003c/div\u003e\u003cdiv class=\"EquationNumber\"\u003e5\u003c/div\u003e\u003c/div\u003e\u003c/p\u003e \u003cp\u003e \u003cem\u003eC\u003c/em\u003e \u003csub\u003e \u003cem\u003eo\u003c/em\u003e \u003c/sub\u003e and \u003cem\u003eC\u003c/em\u003e were defined earlier.\u003c/p\u003e \u003cp\u003eThe partitioning of dissolved compounds between the liquid phase and adsorbing materials in aquatic systems is typically expressed through an empirical partition coefficient (PC), which correlates overall concentration of the dissolved species with that the adsorbed species.\u003cdiv id=\"Equ7\" class=\"Equation\"\u003e\u003cdiv format=\"TEX\" class=\"mathdisplay\" id=\"FileID_Equ7\" name=\"EquationSource\"\u003e\n$$\\:PC=\\frac{{C}_{0}-C}{C}$$\u003c/div\u003e\u003cdiv class=\"EquationNumber\"\u003e6\u003c/div\u003e\u003c/div\u003e\u003c/p\u003e \u003cp\u003eHere, PC represents the equilibrium partition coefficient based on empirical data. Definitions of C₀ and C were provided earlier. The distribution ratios of CLT between the CLT-containing solution and the polymeric matrices were computed and summarized in Table\u0026nbsp;\u003cspan refid=\"Tab3\" class=\"InternalRef\"\u003e4\u003c/span\u003e. The Q values ​​in the Table\u0026nbsp;\u003cspan refid=\"Tab3\" class=\"InternalRef\"\u003e4\u003c/span\u003e are given in mg/g.\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 4\u003c/div\u003e \u003cdiv class=\"CaptionContent\"\u003e \u003cp\u003eSome adsorption values ​​of polymeric cryogels with different compositions\u003c/p\u003e \u003c/div\u003e \u003c/caption\u003e \u003ccolgroup cols=\"4\"\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 \u003cthead\u003e \u003ctr\u003e \u003cth align=\"left\" colname=\"c1\"\u003e \u003cp\u003eSample Code\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c2\"\u003e \u003cp\u003e1.0x10\u003csup\u003e\u0026minus;\u0026thinsp;4\u003c/sup\u003e M\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c3\"\u003e \u003cp\u003e2.5x10\u003csup\u003e\u0026minus;\u0026thinsp;4\u003c/sup\u003e M\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c4\"\u003e \u003cp\u003e5.0x10\u003csup\u003e\u0026minus;\u0026thinsp;4\u003c/sup\u003e M\u003c/p\u003e \u003c/th\u003e \u003c/tr\u003e \u003c/thead\u003e \u003ctbody\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e\u0026nbsp;\u003c/td\u003e \u003ctd align=\"left\" colspan=\"3\" nameend=\"c4\" namest=\"c2\"\u003e \u003cp\u003eQ (mg/g)\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eMAm\u003c/p\u003e \u003cp\u003eMAmH2\u003c/p\u003e \u003cp\u003eMAmH2P2\u003c/p\u003e \u003cp\u003eMAmP2\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e3.50\u003c/p\u003e \u003cp\u003e3.16\u003c/p\u003e \u003cp\u003e1.97\u003c/p\u003e \u003cp\u003e3.04\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e7.08\u003c/p\u003e \u003cp\u003e7.25\u003c/p\u003e \u003cp\u003e4.15\u003c/p\u003e \u003cp\u003e5.98\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e9.24\u003c/p\u003e \u003cp\u003e10.41\u003c/p\u003e \u003cp\u003e6.81\u003c/p\u003e \u003cp\u003e11.95\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e\u0026nbsp;\u003c/td\u003e \u003ctd align=\"left\" colspan=\"3\" nameend=\"c4\" namest=\"c2\"\u003e \u003cp\u003eADS%\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eMAm\u003c/p\u003e \u003cp\u003eMAmH2\u003c/p\u003e \u003cp\u003eMAmH2P2\u003c/p\u003e \u003cp\u003eMAmP2\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e50.08\u003c/p\u003e \u003cp\u003e50.00\u003c/p\u003e \u003cp\u003e38.81\u003c/p\u003e \u003cp\u003e44.49\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e39.28\u003c/p\u003e \u003cp\u003e50.01\u003c/p\u003e \u003cp\u003e34.84\u003c/p\u003e \u003cp\u003e36.45\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e29.27\u003c/p\u003e \u003cp\u003e37.55\u003c/p\u003e \u003cp\u003e28.57\u003c/p\u003e \u003cp\u003e36.99\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e\u0026nbsp;\u003c/td\u003e \u003ctd align=\"left\" colspan=\"3\" nameend=\"c4\" namest=\"c2\"\u003e \u003cp\u003eK\u003csub\u003ed\u003c/sub\u003e\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eMAm\u003c/p\u003e \u003cp\u003eMAmH2\u003c/p\u003e \u003cp\u003eMAmH2P2\u003c/p\u003e \u003cp\u003eMAmP2\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e1.00\u003c/p\u003e \u003cp\u003e1.00\u003c/p\u003e \u003cp\u003e0.63\u003c/p\u003e \u003cp\u003e0.80\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e0.65\u003c/p\u003e \u003cp\u003e1.00\u003c/p\u003e \u003cp\u003e0.53\u003c/p\u003e \u003cp\u003e0.57\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e0.41\u003c/p\u003e \u003cp\u003e0.60\u003c/p\u003e \u003cp\u003e0.41\u003c/p\u003e \u003cp\u003e0.59\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\u003e \u003c/p\u003e \u003cp\u003eConsidering the CLT sorption parameters of the polymeric gel systems (Table\u0026nbsp;\u003cspan refid=\"Tab3\" class=\"InternalRef\"\u003e4\u003c/span\u003e), it can be observed that the Q value (moles of CLT sorbed per unit dry mass) increases with increasing concentration (Fig.\u0026nbsp;\u003cspan refid=\"Fig8\" class=\"InternalRef\"\u003e8\u003c/span\u003e). For MAmH₂ gels, this value rises from 3.16 mg to 10.41 mg. It was determined that the sorption capacity increased with the incorporation of HEMA into the structure for all systems, while it decreased with the addition of PAA. The increased sorption can be linked to the hydrophilic groups in the HEMA structure, while the PAA polymer restricts available spaces for CLT diffusion.\u003c/p\u003e \u003cp\u003eVoltammetric measurements revealed that the MAmH2 formulation exhibited the highest adsorption capacity for clothianidin (CLT). This enhancement can be attributed to the incorporation of 2-hydroxyethyl methacrylate (HEMA) into the polymeric matrix, which increased porosity and promoted a more open network structure, thus improving the accessibility to binding sites and facilitating greater diffusion of the analyte.\u003c/p\u003e \u003cp\u003eThe voltammetric data provided critical information regarding the adsorption dynamics, highlighting the effective uptake of Clothianidin by the cryogel. A significant increase in current intensity correlated with higher adsorption capacity, suggesting that the cryogels efficiently adsorb the pesticide. The adsorption process likely involves both electrostatic and hydrophobic interactions.\u003c/p\u003e \u003c/div\u003e"},{"header":"4. Conclusion","content":"\u003cp\u003eIn this study, a novel polymeric gel was synthesized for the effective Clothianidin removal for the first time in the literature. Using methacrylamide (MAm) as the primary monomer, and its structure was functionalized by incorporating 2-hydroxyethyl methacrylate (HEMA) and poly(acrylic acid) (PAA) in varying compositions. The potential application of these gels in the removal of Clothianidin (CLT) from aqueous media was systematically investigated.\u003c/p\u003e \u003cp\u003eIn MAm and MAmP2 gels, water transport followed super Case II diffusion (n\u0026thinsp;\u0026gt;\u0026thinsp;1.0), indicating that the diffusion rate exceeded the polymer relaxation rate. In gels containing HEMA, a non-Fickian diffusion mechanism was observed (0.5\u0026thinsp;\u0026lt;\u0026thinsp;n\u0026thinsp;\u0026lt;\u0026thinsp;1.0), where water diffusion and polymer relaxation occurred simultaneously.\u003c/p\u003e \u003cp\u003eiv. The adsorption behavior of the cryogels was examined with respect to MAm, HEMA, PAA, and CLT concentrations. The results demonstrated a clear enhancement in adsorption capacity (Q, mg/g) with increasing CLT concentration.\u003c/p\u003e \u003cp\u003eIn conclusion, the synthesized MAmHP cryogels exhibit strong potential as environmentally friendly and efficient adsorbent materials for the removal of pollutants from aqueous solutions. Their demonstrated effectiveness in eliminating pesticides such as CLT highlights their broader applicability for addressing various organic and inorganic contaminants, including dyes and heavy metals. These findings suggest that MAmHP-based systems could serve as versatile platforms for water purification and pollution control in diverse environmental settings.\u003c/p\u003e"},{"header":"Declarations","content":"\u003cp\u003e \u003ch2\u003eDeclaration of competing interest\u003c/h2\u003e \u003cp\u003eThe authors declare no competing interests.\u003c/p\u003e \u003c/p\u003e \u003cp\u003e \u003cstrong\u003eResearch funding\u003c/strong\u003e \u003cp\u003eThis study was supported by Aydın Adnan Menderes University Scientific Research Projects (FEF 22022).\u003c/p\u003e \u003c/p\u003e\u003ch2\u003eAuthor Contribution\u003c/h2\u003e\u003cp\u003eAuthor A played a major role in developing the experimental design, literature review, synthesis, performing swelling and adsorption experiments, graphical presentation and interpretation.Author B was actively involved in performing electrochemical measurements, graphical presentation and interpretation of voltammograms.\u003c/p\u003e\u003ch2\u003eData availability:\u003c/h2\u003e \u003cp\u003eNot applicable\u003c/p\u003e"},{"header":"References","content":"\u003col\u003e\u003cli\u003e\u003cspan\u003eMishra A, Saini RK, Bajpai AK (2020) Polymer formulations for pesticide release. Controlled Release of Pesticides for Sustainable Agriculture. \u003cspan class=\"ExternalRef\"\u003e\u003cspan class=\"RefSource\"\u003ehttps://doi.org/10.1007/978-3-030-23396-9_8\u003c/span\u003e\u003cspan address=\"10.1007/978-3-030-23396-9_8\" targettype=\"DOI\" class=\"RefTarget\"\u003e\u003c/span\u003e\u003c/span\u003e\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eSerrano E, Munoz M, de Pedro ZM, Casas JA (2020) Fast oxidation of the neonicotinoid pesticides listed in the EU decision 2018/840 from aqueous solutions. 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J Colloid Interf Sci 331:32\u0026ndash;39. \u003cspan class=\"ExternalRef\"\u003e\u003cspan class=\"RefSource\"\u003e10.1016/j.jcis.2008.11.003\u003c/span\u003e\u003cspan address=\"10.1016/j.jcis.2008.11.003\" targettype=\"DOI\" class=\"RefTarget\"\u003e\u003c/span\u003e\u003c/span\u003e\u003c/span\u003e\u003c/li\u003e\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":"polymer-bulletin","isNatureJournal":false,"hasQc":true,"allowDirectSubmit":false,"externalIdentity":"pobu","sideBox":"Learn more about [Polymer Bulletin](http://link.springer.com/journal/289)","snPcode":"289","submissionUrl":"https://submission.nature.com/new-submission/289/3","title":"Polymer Bulletin","twitterHandle":"","acdcEnabled":true,"dfaEnabled":true,"editorialSystem":"stoa","reportingPortfolio":"Springer Hybrid","inReviewEnabled":true,"inReviewRevisionsEnabled":false},"keywords":"Clothianidin, Electrochemistry, hydrogel/cryogel, pesiticide, swelling behaviour","lastPublishedDoi":"10.21203/rs.3.rs-6536945/v1","lastPublishedDoiUrl":"https://doi.org/10.21203/rs.3.rs-6536945/v1","license":{"name":"CC BY 4.0","url":"https://creativecommons.org/licenses/by/4.0/"},"manuscriptAbstract":"\u003cp\u003eIn recent years, the increasing use of pesticides, particularly in agriculture, has become a significant concern due to their detrimental effects on aquatic ecosystems. Therefore, the effective removal of such pollutants from contaminated environments through appropriate treatment processes is of great importance. Clothianidin (CLT), a widely used neonicotinoid insecticide, has been reported to negatively impact human health, affecting the respiratory, nervous, and digestive systems. This study involves investigating the CLT removal performance of polymeric cryogels from aqueous solutions, based on the CLT reduction signal. To achieve this, crosslinked methacrylamide/2-hydroxyethyl methacrylate/poly(acrylic acid) (MAmHP) cryogels were fabricated using free-radical copolymerization under cryogenic conditions. The macroporous polymeric samples that were synthesized underwent characterization through swelling tests, Fourier Transform Infrared Spectroscopy (FT-IR/ATR), and Scanning Electron Microscopy-Energy Dispersive X-ray Spectroscopy (SEM-EDX). Swelling parameters, widely applied in polymeric gel characterization, were assessed through dynamic swelling experiments carried out at 25\u0026deg;C. The pesticide adsorption performance of the MAmHP sorbent gel systems was evaluated for the removal of Clothianidin (CLT) using the voltammetric method at room temperature. The dynamic swelling tests performed at 25\u0026deg;C were used to determine the swelling parameters, which are widely utilized for characterizing polymeric gels.\u003c/p\u003e","manuscriptTitle":"Methacrylamide Based Polymeric Cryogels for the Effective Removal of Neonicotinoid Insecticide, Clothianidin","msid":"","msnumber":"","nonDraftVersions":[{"code":1,"date":"2025-06-17 09:22:11","doi":"10.21203/rs.3.rs-6536945/v1","editorialEvents":[{"type":"communityComments","content":0},{"type":"decision","content":"Revision requested","date":"2025-07-04T08:50:24+00:00","index":"","fulltext":""},{"type":"editorInvitedReview","content":"","date":"2025-06-25T12:23:04+00:00","index":"hide","fulltext":""},{"type":"reviewerAgreed","content":"173261420090955754844853020035372836085","date":"2025-06-16T13:05:30+00:00","index":"hide","fulltext":""},{"type":"reviewerAgreed","content":"66447066224376816697125492050530820305","date":"2025-06-13T09:03:39+00:00","index":"hide","fulltext":""},{"type":"reviewersInvited","content":"","date":"2025-06-13T08:45:45+00:00","index":"","fulltext":""},{"type":"editorAssigned","content":"","date":"2025-04-28T09:40:00+00:00","index":"","fulltext":""},{"type":"checksComplete","content":"","date":"2025-04-28T01:01:31+00:00","index":"","fulltext":""},{"type":"submitted","content":"Polymer Bulletin","date":"2025-04-26T21:12:26+00:00","index":"","fulltext":""}],"status":"published","journal":{"display":true,"email":"[email protected]","identity":"polymer-bulletin","isNatureJournal":false,"hasQc":true,"allowDirectSubmit":false,"externalIdentity":"pobu","sideBox":"Learn more about [Polymer Bulletin](http://link.springer.com/journal/289)","snPcode":"289","submissionUrl":"https://submission.nature.com/new-submission/289/3","title":"Polymer Bulletin","twitterHandle":"","acdcEnabled":true,"dfaEnabled":true,"editorialSystem":"stoa","reportingPortfolio":"Springer Hybrid","inReviewEnabled":true,"inReviewRevisionsEnabled":false}}],"origin":"","ownerIdentity":"0252ee28-da8d-4e78-bdbd-ee3b7434c545","owner":[],"postedDate":"June 17th, 2025","published":true,"recentEditorialEvents":[],"rejectedJournal":[],"revision":"","amendment":"","status":"published-in-journal","subjectAreas":[],"tags":[],"updatedAt":"2025-12-15T16:09:28+00:00","versionOfRecord":{"articleIdentity":"rs-6536945","link":"https://doi.org/10.1007/s00289-025-06198-0","journal":{"identity":"polymer-bulletin","isVorOnly":false,"title":"Polymer Bulletin"},"publishedOn":"2025-12-10 15:59:18","publishedOnDateReadable":"December 10th, 2025"},"versionCreatedAt":"2025-06-17 09:22:11","video":"","vorDoi":"10.1007/s00289-025-06198-0","vorDoiUrl":"https://doi.org/10.1007/s00289-025-06198-0","workflowStages":[]},"version":"v1","identity":"rs-6536945","journalConfig":"researchsquare"},"__N_SSP":true},"page":"/article/[identity]/[[...version]]","query":{"redirect":"/article/rs-6536945","identity":"rs-6536945","version":["v1"]},"buildId":"8U1c8b4HqxoKbykW_rLl7","isFallback":false,"isExperimentalCompile":false,"dynamicIds":[84888],"gssp":true,"scriptLoader":[]}