Magnetic nanoparticle-decorated metal organic frameworks for chemiluminescence detection of glutathione

Magnetic nanoparticle-decorated metal organic frameworks for chemiluminescence detection of glutathione | 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 Magnetic nanoparticle-decorated metal organic frameworks for chemiluminescence detection of glutathione Xiaohu Ma, Peiyu Jiang, Jingbo Geng, Xinyi Li, Yan Jin, Baoxin Li, and 1 more This is a preprint; it has not been peer reviewed by a journal. https://doi.org/ 10.21203/rs.3.rs-4678477/v1 This work is licensed under a CC BY 4.0 License Status: Published Journal Publication published 24 Sep, 2024 Read the published version in Microchimica Acta → Version 1 posted 10 You are reading this latest preprint version Abstract In this study, a chemiluminescence (CL) method for determination of glutathione (GSH) was developed with magnetic nanoparticle-decorated metal organic frameworks (Fe 3 O 4 NPs@Cu-TATB). The composite material was synthesized via a hydrothermal method and glutathione (GSH) can be tested by both visual and chemiluminescence (CL) methods. The synthesized Fe 3 O 4 NPs@Cu-TATB exhibited excellent catalytic activity in the luminol-H 2 O 2 CL system. The mechanism revealed that three types of oxygen-containing radicals (ROS) was generated in this system. As GSH can reduce the catalytic effect of generated ROS radicals, the inhibiting CL signal was produced in the Fe 3 O 4 NPs@Cu-TATB-luminol-H 2 O 2 system. Based on the established CL system, the detection limits for GSH using CL and visual methods were found to be 0.3 µM and 0.7 µM, respectively. This low-cost and convenient detection method can be applied to the analysis of GSH content in human blood. Fe3O4 NPs@Cu-TATB Glutathione Chemiluminescence Visual Luminol Figures Figure 1 Figure 2 Figure 3 Figure 4 Figure 5 Figure 6 Figure 7 Introduction Glutathione (GSH), widely found in plants and animals, is a thiol-containing tripepti- de [ 1 ] which plays an important role for maintaining normal immune function in organisms with the biological processes [ 2 – 5 ]. As we all know, the abnormal levels of GSH were associated with certain diseases. Then, it was necessary to detect GSH in organisms. Currently, the main traditional methods for detecting GSH in human blood include liquid chromatography [ 6 , 7 ], electrochemical methods [ 8 , 9 ], fluorescence methods [ 10 , 11 ], and colorimetric methods [ 12 , 13 , 14 ], etc. However, the expensive instrumentation, complicated operation and high cost of liquid chromatography and fluorescence have limited their application. Also, electrodes should be coupled with the electrochemical method. High sensitivity cannot be achieved with colorimetric method. Therefore, it was important to develop a simple, sensitive and intuitive assay for the determination of GSH levels in human blood. Chemiluminescence (CL) is a common used detection method with simple operation, low cost and high sensitivity [ 15 ]. Different CL systems have been used for the detection of GSH. For example, using red fluorescent alkene as fluorophore, Khajvand's group investigated the CL behaviour of GSH, L-cysteine and L-methionine in bis(2,4,6-trichlorophenyl)oxalate (TCPO)-H 2 O 2 system [ 16 ]. In addition, Zuo's team constructed a CL resonance energy transfer (CRET) method in Na 2 SO 3 -Ce(IV) system for the detection of GSH with a detection limit of 0.065 nmol/L [ 17 ]. And the reports on the detection of GSH using the luminol-H 2 O 2 system were also general [ 18 – 22 ]. Although the reported luminol CL systems had good linear ranges and low detection limits, none of these reports had achieved the CL visual detection of GSH. If the CL visual detection could be taken by a common mobile without higher luminol concentration, the application will be further broadened for CL detection field. To achieve the above goal, the best way is to find excellent catalysts in luminol system. In recent years, metal-organic frameworks (MOFs), which have large specific surface area, high active sites, easy modification and adjustable structure, have been favoured by researchers in the field of catalysis [ 23 – 25 ]. MOFs were self-assembly formed by connecting inorganic metal center (metal ions or metal clusters) and bridging organic ligands [ 26 ], which have good catalytic activity for CL systems [ 27 ]. As their metal centers have good catalytic activity, the CL intensity can be greatly enhanced to obtain higher sensitivity. In recent years, some MOFs with CL catalytic properties have been reported, such as Cu-MOF [ 28 ], MIL-53(Fe) MOF [ 29 ], etc. Huang's group found that MIL-53(Fe) MOFs could significantly enhance the CL of the luminol system under alkaline conditions, and its intensity was about 20 times than that of the luminescent system without MOFs [ 29 ]. Our group designed a Cu-TATB paper-based sensor by in situ growth method and found that Cu-TATB had peroxidase-like activity. The synthesized Cu-TATB could catalyze the luminol-H 2 O 2 CL system and used for the volatile sulfur compounds detection in exhaled breath [ 30 ]. Nowadays, nanoparticles had also been doped with MOFs to furtherly enhance the catalytic effect in CL system [ 31 ]. Due to MOFs have a permanent porous structure, nanoparticles could be incorporated into MOFs to form a composite material with highlighted catalytic character [ 32 ]. Fe 3 O 4 nanoparticles (Fe 3 O 4 NPs) have peroxide activity and could be recycled and reused by magnets as a biocompatibility magnetic material [ 33 , 34 ]. There have also been reports of Fe 3 O 4 NPs combined with MOFs to form composites [ 35 – 38 ]. Zhang’s group used the synthesized composite Cu-BTC@Fe 3 O 4 to catalyze the Suzuki-Miyaura reaction under mild conditions with good catalytic activity [ 35 ]. Liu's group used Fe 3 O 4 @Au/Cu-MOF to construct an electrochemical sensor with enhanced peroxide-like properties for efficient real-time monitoring of p-aminophenol [ 37 ]. For CL detection, Li's team found that Fe 3 O 4 NPs and MOF-MIL-101(Fe) composites have good catalytic properties, which could directly catalyse the luminescence of luminol without even the need of additional oxidants [ 38 ]. Therefore, in order to further obtain materials with excellent catalytic properties, Fe 3 O 4 NPs and Cu-TATB composites (Fe 3 O 4 NPs@Cu-TATB) was applied to the luminol CL system for the detection of GSH. In this work, Fe 3 O 4 NPs@Cu-TATB composite material was synthesized via a hydrothermal method, achieving the excellent catalytic effect for luminol-H 2 O 2 CL system. By utilizing the chemical interaction between the sulfhydryl group of GSH and Cu 2+ in the composite material, the CL intensity of the system was inhibited, enabling sensitive detection of GSH (Scheme 1 ). This study proposed means for CL-based and CL visual detection methods for GSH, with the expectation that this method holds promising application prospects for detecting GSH in actual human blood samples. Experimental section The chemicals, materials, synthesis of Fe 3 O 4 NPs and Fe 3 O 4 NPs@Cu-TATB, the details of pre-treatment of blood samples were detailed in the Supporting Information (Section 1, Section 2, Section 3 and Section 4). CL detection of GSH by Fe 3 O 4 NPs@Cu-TATB Firstly, 50 µL of Fe 3 O 4 NPs@Cu-TATB suspension and different concentrations of GSH solution were added sequentially to the transparent 96-well plate. Then, the 96-well plate was placed in a dark box to block the light inside and the mobile phone was fixed above the 96-well plate in the dark box. Then, 1.0 mM luminol (25 µL) and 1.0 M H 2 O 2 (25 µL) were mixed. 50µL of the mixture was dropwised to the 96-well plate, and the CL photos at different concentrations of GSH were recorded using the mobile phone. The photos were taken at the 3rd second immediately after the mixture was added on the 96-well plate. The CL images at different GSH concentrations was calculated by the grayscale values with Photoshop software. For the CL assay, a 96-well plate containing Fe 3 O 4 NPs@Cu-TATB suspension and GSH solution was placed in the dark box of the CL instrument. After closing the dark box, the CL signal was detected and recorded by injecting a mixture of luminol (25 µL) and H 2 O 2 (25 µL) into the 96-well plate. Detection of GSH levels in actual blood samples Blood samples were taken from three healthy volunteers at Shaanxi Normal University Hospital. Prior to blood collection, the volunteers were required to sit still for 30 minutes. The collected blood samples were pre-treated as the procedure in Supporting Information (Section 4) and stored in a refrigerator at 4 ℃ until use. For CL detection, 96-well plates containing Fe 3 O 4 NPs@Cu-TATB suspension and serum samples from different volunteers were placed in the dark box of the CL instrument. After closing the dark box, a mixture of luminol (25 µL) and H 2 O 2 (25 µL) was injected into the 96-well plate. The CL signal was detected and recorded by the CL instrument. Results and discussion Investigation of catalytic CL performance of Fe 3 O 4 NPs@Cu-TATB According to the literature [ 39 , 40 ], metal ions such as Co 2+ and horseradish peroxidase (HRP) could serve as excellent catalysts for the luminol-H 2 O 2 CL system. In this study, Fe 3 O 4 NPs@Cu-TATB composite material was used as the catalyst for the luminol-H 2 O 2 CL system. We evaluated the catalytic effects (Fig. 1 A) of these substances under the same conditions and found that the catalytic effect of Fe 3 O 4 NPs@Cu-TATB (4×10 − 2 mg/mL) was approximately 7 times higher than that of HRP (4×10 − 2 mg/mL), and its catalytic effect was close to the signal strength of Co 2+ (4×10 − 2 mg/mL). To investigate whether the catalytic ability of Fe 3 O 4 NPs@Cu-TATB was stronger than that of Cu-TATB, Fe 3 O 4 NPs, and Fe NPs@Cu-TATB individually, their catalytic effects were verified under the same conditions. Specifically, the catalytic ability of Fe 3 O 4 NPs@Cu-TATB was found to be 6.5 times higher than that of Cu-TATB, 3.4 times that of Fe 3 O 4 NPs, and 10.4 times that of Fe NPs@Cu-TATB, as shown in Fig. 1 B. Also, the CL signal was recorded with the composite in different conditions. In Fig. 1 C and Fig. 1 D, CL intensity of Fe 3 O 4 NPs@Cu-TATB was shown on paper and in solution under the same conditions. We found that the CL intensity in the solution was much higher than the CL intensity on paper [ 41 ]. Fe 3 O 4 NPs@Cu-TATB may accumulate on the paper and greatly decrease the catalytic function for luminol-H 2 O 2 CL system. This also suggests that the Fe 3 O 4 NPs@Cu-TATB-luminol-H 2 O 2 CL system performed better in solution. Characterization of Fe 3 O 4 NPs@Cu-TATB In this work, Fe 3 O 4 NPs@Cu-TATB composite was synthesized. Then, the composite was charactered by the next methods. Firstly, the morphology of Fe 3 O 4 NPs@Cu-TATB was observed using scanning electron microscopy (SEM). From Fig. 2 A and Fig. 2 B, it could be seen that Cu-TATB appears as regular octahedrons with micropores on the surface. From Fig. 2 C we could see that a large number of Fe 3 O 4 NPs could be observed in the composite material, indicating that Cu-TATB was heavily enveloped by Fe 3 O 4 NPs. To confirm the successful synthesis of Fe 3 O 4 NPs@Cu-TATB, the crystalline structure and functional groups of the samples were analyzed using X-ray diffraction data (XRD) and fourier transform infrared (FTIR) spectroscopy, respectively. As shown in Fig. 2 D, the characteristic diffraction peaks of Fe 3 O 4 NPs were observed at 2θ = 30.1°, 35.5°, and 43.1° [ 42 ], and those of Cu-TATB are observed at 2θ = 5.5°, 6.7°, 7.7°, 10.8°, 12.7°, 16.4°, and 19.5° [ 43 ]. The characteristic diffraction peaks of Fe 3 O 4 NPs@Cu-TATB coincided well with those of individual Fe 3 O 4 NPs and Cu-TATB, confirming that Fe 3 O 4 NPs@Cu-TATB was successfully prepared. Subsequently, the functional groups of Fe 3 O 4 NPs@Cu-TATB were investigated using FTIR spectroscopy (Fig. 2 E). For Fe 3 O 4 NPs@Cu-TATB, the absorption peak at 624 cm − 1 represented the stretching vibration peak of Fe-O [ 44 ]. What's more, peaks observed at 1246 cm − 1 , 1354 cm − 1 , and 1708 cm − 1 represented the stretching vibration peaks of C-O, C-N, and C = O groups, respectively. This confirmed the presence of H 3 TATB. Additionally, the peak at 748 cm − 1 proved the stretching vibration peak of Cu-O [ 45 ], indicating the coordination between Cu 2+ and the ligand of H 3 TATB. The main FTIR absorption peaks of Fe 3 O 4 NPs@Cu-TATB coincided with those of Fe 3 O 4 NPs and Cu-TATB. This furtherly indicated the successful preparation of Fe 3 O 4 NPs@Cu-TATB. Furthermore, the stability of Fe 3 O 4 NPs@Cu-TATB was investigated. From the CL results in Fig. S1 A, Fe 3 O 4 NPs@Cu-TATB could maintain its catalytic performance steadily over 14 days. Utilizing the same batch of Fe 3 O 4 NPs@Cu-TATB, CL signals remained stable after repeated the measurements for 30 times just in a single day (Fig. S1 B). (the details of stability and reproducibility were provided in Supplementary Information, Section 5). The catalytic mechanism of Fe 3 O 4 NPs@Cu-TATB in the Luminol-H 2 O 2 system As Fe 3 O 4 NPs@Cu-TATB could greatly enhance the CL intensity of luminol-H 2 O 2 system, the luminescence mechanism should be investigated. To confirm the emitting species in the Fe 3 O 4 NPs@Cu-TATB-Luminol-H 2 O 2 CL system, CL spectra (Fig. S2A) were utilized for validation. It could be observed that with the involvement of Fe 3 O 4 NPs@Cu-TATB, the maximum emission peak of the CL spectrum in this system was located around 425 nm. The position of the maximum emission peak in the CL spectrum was the same to Luminol-H 2 O 2 CL system. This indicates that the emitting species in this system was the excited-state 3-aminophthalate anion (3-APA*). Furthermore, UV-visible spectrophotometry was investigated by Fe 3 O 4 NPs@Cu-TATB. As shown in Fig. S2B, the position of the maximum absorption peak remained unchanged before and after the addition of Fe 3 O 4 NPs@Cu-TATB in the Luminol-H 2 O 2 CL system. This results showed that there was no new subtance's formation in this system. This confirms that Fe 3 O 4 NPs@Cu-TATB was the catalyst in this system. The utilization of free radical scavengers (Fig. S2C-F) and electron spin resonance (ESR) (Fig. S2G-I) confirmed the presence of OH · , O 2 . − and 1 O 2 in the system. The three free radicals' confirmation could be found in the Supporting Information, Section 6. Based on the experimental exploration of the mechanism described above, we could speculate the mechanism of Fe 3 O 4 NPs@Cu-TATB in luminol-H 2 O 2 CL system. Firstly, H 2 O 2 decomposed under alkaline conditions to produce HO 2 − . Also, luminol can form the luminol anion (L − ) in the system. Then, in the presence of Fe and Cu dual active sites of Fe 3 O 4 NPs@Cu-TATB, the generated OH · from the decomposition of H 2 O 2 reacted with L − and HO 2 − to produce luminol radicals (L. − ) and O 2 . − . The generated O 2 . − can be transfered to 1 O 2 . Finally, due to the synergistic effect of the Fe and Cu dual active sites in Fe 3 O 4 NPs@Cu-TATB, L. − was oxidized by a large amount of O 2 . − to the excited-state 3-aminophthalate anion (3-APA*). When it returns to the ground state, it emits intense blue CL. The specific principle is illustrated in Fig. 3 . The sulfhydryl group in GSH reacts with Cu 2+ to generate CuS, resulting in a decrease in the CL intensity of the system. The extent of the decrease in CL signal could be used to determine the concentration of GSH. This was the principle for Fe 3 O 4 NPs@Cu-TATB-Luminol-H 2 O 2 system to detect GSH (the details of principle was provided in Supplementary Information, Section 7 (Fig. S3)). In addition, optimization of the detection conditions for GSH revealed that the strongest CL signal was achieved with 0.5 g of Fe 3 O 4 NPs, 1.0 mM of luminol, 6.5 mM of of H 2 O 2 and the best pH value of 12.5 (the details for the optimization of the detection conditions were provided in Supplementary Information, Section 8 (Fig. S4)). The sensitivity of GSH detection Under the optimized experimental conditions, GSH was visually detected using the Fe 3 O 4 NPs@Cu-TATB-Luminol-H 2 O 2 system. Figure 4 shown the variation in CL intensity of the solution system at different concentrations (0-200 µM) of GSH. In a dark background, CL photos were captured at different GSH concentrations using a mobile phone. It could be observed that the CL intensity of the solution system gradually decreased with the increased GSH concentration. With luminol of 1.0 mM, H 2 O 2 of 1.0 M, Fe 3 O 4 NPs@Cu-TATB of 3.0 mg/mL, the blue luminescence dimed with the addition of 50 µL GSH in 2 minutes. During the visual detection, changes in luminescence intensity from 0 to 200 µM GSH concentrations could be clearly observed by the naked eye. To quantitatively express the visual results, photos were taken with a mobile phone. Then, Photoshop software was used to convert brightness into grayscale images. The CL intensity at each concentration of GSH was quantitatively expressed using grayscale values. As shown in Fig. 5 A, a standard curve was plotted for GSH concentrations ranging from 0 to 10 µM. The grayscale values showed a negative correlation with GSH concentration. The linear regression equation was determined as G = -3.98 C + 62.07 (R 2 = 0.9776), where G represents the grayscale value and C represents the concentration of GSH. In Fig. 5 B, a standard curve was plotted for GSH concentrations ranging from 20 to 200 µM. The linear regression equation was calculated as G = -0.05 C + 17.57 (R 2 = 0.9999), where G represents the grayscale value at the respective GSH concentration and C represents the concentration of GSH. According to the 3σ rule, the detection limit of GSH with the visual method was determined to be 0.7 µM, indicating good sensitivity for GSH detection. The Fe 3 O 4 NPs@Cu-TATB-Luminol-H 2 O 2 system was employed for CL detection of GSH. As shown in Fig. 6 A, the CL curves of the Fe 3 O 4 NPs@Cu-TATB-Luminol-H 2 O 2 system at different GSH concentrations indicate a decreasing trend in CL intensity with the increasing GSH concentration. In Fig. 6 B, when the GSH concentration ranged from 1 to 20 µM, the relative CL intensity was proportional to the GSH concentration, with a linear regression equation of I R = 41.004 C + 160.933 (R 2 = 0.9993), where I R represents the relative CL intensity and C represents the concentration of GSH. In Fig. 6 C, when the GSH concentration ranged from 20 to 200 µM, the relative CL intensity was also proportional to the GSH concentration, with a linear regression equation of I R = 4.152 C + 895.988 (R 2 = 0.9970), where I R represents the relative CL intensity at the respective GSH concentration and C represents the concentration of GSH. According to the 3σ rule, the detection limit of GSH was determined to be 0.3 µM, indicating good sensitivity for detecting GSH using CL. The interference determination during detection of GSH In order to assess the selectivity of this method for detecting GSH, we investigated the effects of coexisting ions (K + , Na + , Ca 2+ , Fe 3+ ), glucose, amino acids (glycine (Gly), serine (Ser), histidine (His), cysteine (Cys)), and vitamin C (Vc) in human blood [ 46 , 47 ]. Typically, human blood contains approximately 4 mM K + , 140 mM Na + , 2 mM Ca 2+ , and 10 µM Fe 3+ , as well as 200 µM Gly, 128 µM Ser, 32–107 µM His, 5 µM Cys, and 5.7 µM Vc. As shown in Fig. 7 , when 100 µM GSH was mixed with interfering substances at 10-fold or 0.1-fold concentrations, using the Fe 3 O 4 NPs@Cu-TATB-Luminol-H 2 O 2 system for CL detection, it was found that the CL signal was not significantly affected. Although Cys and Vc could cause a decrease in the CL intensity of the system, their concentrations in human blood (µmol/L) were much lower than the concentration of GSH (mmol/L) [ 47 , 48 ]. In summary, these interfering substances do not interfere with the detection of GSH, indicating that the Fe 3 O 4 NPs@Cu-TATB-Luminol-H 2 O 2 system had good selectivity for detecting GSH in human blood. The detection of GSH in actual blood samples To evaluate the feasibility of detecting GSH in human blood using the Fe 3 O 4 NPs@Cu-TATB-Luminol-H 2 O 2 system, blood samples were collected from three healthy volunteers at Shaanxi Normal University. After pretreatment, gradient concentrations of reduced GSH were added to the blood samples. The spiked blood samples were then detected, and the results were compared with those obtained using standard electrochemiluminescence (ECL). It was found that there were no significant differences between the two methods. The analysis results, as shown in Table 1 , indicated that the GSH content in the blood of the three volunteers was approximately 1.1 mM. Using the standard addition method to determine the recovery rate, it was observed that the recovery rate was ranging from 90–110% (n = 3). These results demonstrated the feasibility of this detection method for measuring GSH in human blood. Table 1 Detection of GSH in Human Serum Samples by CL Method (n = 3) Sample Found in sample(mM) Add(mM) Total found(mM) Recovery(%) ECL CL 1.0 2.0 ± 0.1 95.2 1 1.1 ± 0.2 1.1 ± 0.1 3.0 4.1 ± 0.3 100.0 5.0 5.9 ± 0.1 96.7 1.0 2.1 ± 0.1 105.0 2 1.1 ± 0.1 1.0 ± 0.1 3.0 3.9 ± 0.1 97.5 5.0 6.2 ± 0.2 103.3 1.0 2.1 ± 0.3 105.0 3 1.1 ± 0.2 1.0 ± 0.3 3.0 4.1 ± 0.2 102.5 5.0 6.1 ± 0.2 101.7 Conclusions This study synthesized Fe 3 O 4 NPs@Cu-TATB composite material via a hydrothermal method, and developed a CL and CL visual detection method for GSH in human blood samples. Fe 3 O 4 NPs@Cu-TATB exhibited excellent catalytic effects in the luminol-H 2 O 2 CL system. Fe 3 O 4 NPs@Cu-TATB can interact with GSH and the CL intensity decreased. The detection limits with visual and CL methods were 0.7 µM and 0.3 µM, respectively. When applied to actual human blood samples, this method offers advantages such as simplicity and good selectivity. This low-cost and convenient detection method is expected to be applied in future analyses of GSH levels in human blood. Declarations Ethics approval and consent to participate This study received approval from the Committee on Ethics at Shaanxi Normal University, and all volunteers provided informed consent prior to their participation. Conflict of interest The authors declare no competing interests. Funding We are very thankful to Natural Science Foundation of Shaanxi Province (No. 2024JC-YBMS-116) for supporting this work. The authors also thank the Fundamental Research Funds for the Central Universities (GK201902009 and GK201701002) and Program for Innovative Research Team in Shaanxi Province (2014KCT-28) for supporting this work. Author Contribution Xiaohu Ma: Conceptualization, Methodology, Software, Formal analysis, Writing –Review&Editing, Investigation, Data curation, Writing-Original Draft, Visualization. Peiyu Jiang: Validation. Jingbo Geng: Data curation. 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Additional Declarations No competing interests reported. Supplementary Files SI0702.doc floatimage2.jpeg Scheme 1 Schematic Representation of Synthetic Fe 3 O 4 NPs@Cu-TATB and CL Detection of GSH Cite Share Download PDF Status: Published Journal Publication published 24 Sep, 2024 Read the published version in Microchimica Acta → Version 1 posted Editorial decision: Revision requested 21 Aug, 2024 Reviews received at journal 21 Aug, 2024 Reviewers agreed at journal 21 Aug, 2024 Reviewers agreed at journal 01 Aug, 2024 Reviews received at journal 24 Jul, 2024 Reviewers agreed at journal 14 Jul, 2024 Reviewers invited by journal 05 Jul, 2024 Editor assigned by journal 04 Jul, 2024 Submission checks completed at journal 04 Jul, 2024 First submitted to journal 03 Jul, 2024 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. 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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-4678477","acceptedTermsAndConditions":true,"allowDirectSubmit":false,"archivedVersions":[],"articleType":"Research Article","associatedPublications":[],"authors":[{"id":331514699,"identity":"2f57ffdb-2617-46ed-8549-979dab42c309","order_by":0,"name":"Xiaohu Ma","email":"","orcid":"","institution":"Shaanxi Normal University","correspondingAuthor":false,"prefix":"","firstName":"Xiaohu","middleName":"","lastName":"Ma","suffix":""},{"id":331514700,"identity":"fe7f8dc7-9835-4a89-af3d-ebd83b8a0a8d","order_by":1,"name":"Peiyu Jiang","email":"","orcid":"","institution":"Shaanxi Normal University","correspondingAuthor":false,"prefix":"","firstName":"Peiyu","middleName":"","lastName":"Jiang","suffix":""},{"id":331514701,"identity":"7060df32-11d3-4483-97e1-d07292f98f80","order_by":2,"name":"Jingbo Geng","email":"","orcid":"","institution":"Shaanxi Normal University","correspondingAuthor":false,"prefix":"","firstName":"Jingbo","middleName":"","lastName":"Geng","suffix":""},{"id":331514702,"identity":"4b926853-864e-4839-b751-69d35ab6fa85","order_by":3,"name":"Xinyi Li","email":"","orcid":"","institution":"Shaanxi Normal University","correspondingAuthor":false,"prefix":"","firstName":"Xinyi","middleName":"","lastName":"Li","suffix":""},{"id":331514703,"identity":"bafd23d3-e275-42c5-afe4-703e6ec6dfb3","order_by":4,"name":"Yan Jin","email":"","orcid":"","institution":"Shaanxi Normal University","correspondingAuthor":false,"prefix":"","firstName":"Yan","middleName":"","lastName":"Jin","suffix":""},{"id":331514704,"identity":"1fd76d6a-7963-4888-ac16-33987b15e2cb","order_by":5,"name":"Baoxin Li","email":"","orcid":"","institution":"Shaanxi Normal University","correspondingAuthor":false,"prefix":"","firstName":"Baoxin","middleName":"","lastName":"Li","suffix":""},{"id":331514705,"identity":"039d4ac8-4086-48e2-bde6-bf17cb7bd2ae","order_by":6,"name":"Wei Liu","email":"data:image/png;base64,iVBORw0KGgoAAAANSUhEUgAAAZAAAAAyAQMAAABI0h/eAAAABlBMVEX///8AAABVwtN+AAAACXBIWXMAAA7EAAAOxAGVKw4bAAAAqklEQVRIiWNgGAWjYFACxsYDCQw2PPzsDcRraQBqSZOR7DlAgj1AtYdtDG44EKnc4Hhzw4GHbed5GG4wMH74mEOMljMHGw4ktt3mYZzdwCw5cxsRWsxuJEK0MMscYGPmJUrL/YcgLed42CQSiNVygxGk5QAPD9Fa7M8AHZZwLplHgudgM3F+kWw//vDhjzI7e/vjzQc/fCRGCxJgbCBN/SgYBaNgFIwC3AAABa87zs8gE94AAAAASUVORK5CYII=","orcid":"","institution":"Shaanxi Normal University","correspondingAuthor":true,"prefix":"","firstName":"Wei","middleName":"","lastName":"Liu","suffix":""}],"badges":[],"createdAt":"2024-07-03 07:38:11","currentVersionCode":1,"declarations":"","doi":"10.21203/rs.3.rs-4678477/v1","doiUrl":"https://doi.org/10.21203/rs.3.rs-4678477/v1","draftVersion":[],"editorialEvents":[{"content":"https://doi.org/10.1007/s00604-024-06686-6","type":"published","date":"2024-09-24T15:57:08+00:00"}],"editorialNote":"","failedWorkflow":false,"files":[{"id":61314198,"identity":"f3778051-a7c3-4d5b-81b7-beee816c1a00","added_by":"auto","created_at":"2024-07-29 11:40:55","extension":"jpeg","order_by":1,"title":"Figure 1","display":"","copyAsset":false,"role":"figure","size":433073,"visible":true,"origin":"","legend":"\u003cp\u003e(A) CL profiles of different substances in luminol-H\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e2\u003c/sub\u003e CL system; (HRP\u0026nbsp; 4×10\u003csup\u003e-2 \u003c/sup\u003emg/mL, Co\u003csup\u003e2+ \u003c/sup\u003e4×10\u003csup\u003e-2 \u003c/sup\u003emg/mL; Fe\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4 \u003c/sub\u003eNPs@Cu-TATB 4×10\u003csup\u003e-2 \u003c/sup\u003emg/mL) (B) CL profiles with different substances in luminol-H\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e2\u003c/sub\u003e CL system; (a: 4×10\u003csup\u003e-4 \u003c/sup\u003emg/mL Cu-TATB; b: 4×10\u003csup\u003e-4 \u003c/sup\u003emg/mL Fe\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4 \u003c/sub\u003eNPs; c: 4×10\u003csup\u003e-4 \u003c/sup\u003emg/mL Fe\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4 \u003c/sub\u003eNPs@Cu-TATB; d: 4×10\u003csup\u003e-4 \u003c/sup\u003emg/mL Fe NPs@Cu-TATB) (C) CL profiles of Fe\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e NPs@Cu-TATB (4×10\u003csup\u003e-2 \u003c/sup\u003emg/mL) in luminol-H\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e2 \u003c/sub\u003eCL system on paper surface; (D) CL profiles of Fe\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e NPs@Cu-TATB (4×10\u003csup\u003e-2 \u003c/sup\u003emg/mL) in Cu-TATB-luminol-H\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e2 \u003c/sub\u003eCL system in solution.\u003c/p\u003e\n\u003cp\u003e\u0026nbsp;\u003c/p\u003e","description":"","filename":"floatimage3.jpeg","url":"https://assets-eu.researchsquare.com/files/rs-4678477/v1/7a4fd6d48310fa0b0879ebad.jpeg"},{"id":61314745,"identity":"f1471774-8e8b-4f72-876e-e5926d94cb9a","added_by":"auto","created_at":"2024-07-29 11:48:55","extension":"jpeg","order_by":2,"title":"Figure 2","display":"","copyAsset":false,"role":"figure","size":588984,"visible":true,"origin":"","legend":"\u003cp\u003eThe characterization results of Fe\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e NPs@Cu-TATB. (A,B) SEM image of Cu-TATB, (C) SEM image of Fe\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e NPs@Cu-TATB, (D) XRD pattern of Fe\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e NPs@Cu-TATB, (E) FTIR spectra of Fe\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e NPs@Cu-TATB.\u003c/p\u003e\n\u003cp\u003e\u0026nbsp;\u003c/p\u003e","description":"","filename":"floatimage4.jpeg","url":"https://assets-eu.researchsquare.com/files/rs-4678477/v1/b2c3ade78b181aeab76b6670.jpeg"},{"id":61314194,"identity":"cc471e08-06da-43d2-a3d6-02a524bfaf70","added_by":"auto","created_at":"2024-07-29 11:40:55","extension":"jpeg","order_by":3,"title":"Figure 3","display":"","copyAsset":false,"role":"figure","size":202514,"visible":true,"origin":"","legend":"\u003cp\u003eSchematic diagram of mechanism for Luminol-H\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e2 \u003c/sub\u003eCL system catalyzed by Fe\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4 \u003c/sub\u003eNPs@Cu-TATB.\u003c/p\u003e\n\u003cp\u003e\u0026nbsp;\u003c/p\u003e","description":"","filename":"floatimage5.jpeg","url":"https://assets-eu.researchsquare.com/files/rs-4678477/v1/e8778186c4e1e3bfe9467117.jpeg"},{"id":61314191,"identity":"db352aa9-27ed-4123-a1bb-5a02c164c03e","added_by":"auto","created_at":"2024-07-29 11:40:55","extension":"jpeg","order_by":4,"title":"Figure 4","display":"","copyAsset":false,"role":"figure","size":79777,"visible":true,"origin":"","legend":"\u003cp\u003eCL photographs of Fe\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e NPs@Cu-TATB-Luminol-H\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e2\u003c/sub\u003e system at different concentrations of GSH.\u003c/p\u003e","description":"","filename":"floatimage6.jpeg","url":"https://assets-eu.researchsquare.com/files/rs-4678477/v1/880dcebb46d77ab55e8de0d4.jpeg"},{"id":61314747,"identity":"d293feed-36e3-42d3-b2c7-fa4c648989d7","added_by":"auto","created_at":"2024-07-29 11:48:55","extension":"jpeg","order_by":5,"title":"Figure 5","display":"","copyAsset":false,"role":"figure","size":166924,"visible":true,"origin":"","legend":"\u003cp\u003eSensitivity results for the detection of GSH. (A) Standard graphs of GSH at concentrations of 0-10 mM with greyscale values, (B) Standard graphs of GSH at 20-200 mM with greyscale values.\u003c/p\u003e","description":"","filename":"floatimage7.jpeg","url":"https://assets-eu.researchsquare.com/files/rs-4678477/v1/e53278237187afceabafb4c0.jpeg"},{"id":61315726,"identity":"08228b55-7f9c-48ea-a03e-1bf8e134ce9e","added_by":"auto","created_at":"2024-07-29 11:56:55","extension":"jpeg","order_by":6,"title":"Figure 6","display":"","copyAsset":false,"role":"figure","size":398579,"visible":true,"origin":"","legend":"\u003cp\u003eSensitivity of the Fe\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e NPs@Cu-TATB-Luminol-H\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e2\u003c/sub\u003e CL system for the detection of GSH. (A) CL profiles of Fe\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e NPs@Cu-TATB-Luminol-H\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e2\u003c/sub\u003e system for different concentrations of GSH, (B) Standard graphs of GSH at concentrations of 0-20 mM with relative CL intensity, (C) Standard graphs of GSH at 20-200 mM with relative CL intensity.\u003c/p\u003e","description":"","filename":"floatimage8.jpeg","url":"https://assets-eu.researchsquare.com/files/rs-4678477/v1/380f7982018e262ac10f1275.jpeg"},{"id":61314197,"identity":"611055b0-95fd-4a8f-b524-f42f8bed0151","added_by":"auto","created_at":"2024-07-29 11:40:55","extension":"png","order_by":7,"title":"Figure 7","display":"","copyAsset":false,"role":"figure","size":30043,"visible":true,"origin":"","legend":"\u003cp\u003eEffect of different interfering substances on the detection of GSH by Fe\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e NPs@Cu-TATB-Luminol-H\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e2\u003c/sub\u003e CL system.\u003c/p\u003e\n\u003cp\u003e\u0026nbsp;\u003c/p\u003e","description":"","filename":"7.png","url":"https://assets-eu.researchsquare.com/files/rs-4678477/v1/e4f26f787c62606cf9d9783c.png"},{"id":65627159,"identity":"1371cc53-52c2-447f-8c18-70a1e7af1006","added_by":"auto","created_at":"2024-09-30 16:12:40","extension":"pdf","order_by":0,"title":"","display":"","copyAsset":false,"role":"manuscript-pdf","size":2567131,"visible":true,"origin":"","legend":"","description":"","filename":"manuscript.pdf","url":"https://assets-eu.researchsquare.com/files/rs-4678477/v1/1400915d-16c2-4d6a-bb7a-94343b4b9b81.pdf"},{"id":61314199,"identity":"e59dd01d-fb21-4e0b-b9c8-0663eae591ed","added_by":"auto","created_at":"2024-07-29 11:40:56","extension":"doc","order_by":1,"title":"","display":"","copyAsset":false,"role":"supplement","size":2434344,"visible":true,"origin":"","legend":"","description":"","filename":"SI0702.doc","url":"https://assets-eu.researchsquare.com/files/rs-4678477/v1/5819299e135266a51f3c0eee.doc"},{"id":61314195,"identity":"b77d4d98-2826-4a10-8f9f-d57330624646","added_by":"auto","created_at":"2024-07-29 11:40:55","extension":"jpeg","order_by":2,"title":"","display":"","copyAsset":false,"role":"supplement","size":300928,"visible":true,"origin":"","legend":"\u003cp\u003e\u003cstrong\u003eScheme 1\u003c/strong\u003e Schematic Representation of Synthetic Fe\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e NPs@Cu-TATB and CL Detection of GSH\u003c/p\u003e","description":"","filename":"floatimage2.jpeg","url":"https://assets-eu.researchsquare.com/files/rs-4678477/v1/404251e6ae40ca7f9f2fb630.jpeg"}],"financialInterests":"No competing interests reported.","formattedTitle":"Magnetic nanoparticle-decorated metal organic frameworks for chemiluminescence detection of glutathione","fulltext":[{"header":"Introduction","content":"\u003cp\u003eGlutathione (GSH), widely found in plants and animals, is a thiol-containing tripepti-\u003c/p\u003e \u003cp\u003ede [\u003cspan citationid=\"CR1\" class=\"CitationRef\"\u003e1\u003c/span\u003e] which plays an important role for maintaining normal immune function in organisms with the biological processes [\u003cspan additionalcitationids=\"CR3 CR4\" citationid=\"CR2\" class=\"CitationRef\"\u003e2\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR5\" class=\"CitationRef\"\u003e5\u003c/span\u003e]. As we all know, the abnormal levels of GSH were associated with certain diseases. Then, it was necessary to detect GSH in organisms. Currently, the main traditional methods for detecting GSH in human blood include liquid chromatography [\u003cspan citationid=\"CR6\" class=\"CitationRef\"\u003e6\u003c/span\u003e, \u003cspan citationid=\"CR7\" class=\"CitationRef\"\u003e7\u003c/span\u003e], electrochemical methods [\u003cspan citationid=\"CR8\" class=\"CitationRef\"\u003e8\u003c/span\u003e, \u003cspan citationid=\"CR9\" class=\"CitationRef\"\u003e9\u003c/span\u003e], fluorescence methods [\u003cspan citationid=\"CR10\" class=\"CitationRef\"\u003e10\u003c/span\u003e, \u003cspan citationid=\"CR11\" class=\"CitationRef\"\u003e11\u003c/span\u003e], and colorimetric methods [\u003cspan citationid=\"CR12\" class=\"CitationRef\"\u003e12\u003c/span\u003e, \u003cspan citationid=\"CR13\" class=\"CitationRef\"\u003e13\u003c/span\u003e, \u003cspan citationid=\"CR14\" class=\"CitationRef\"\u003e14\u003c/span\u003e], etc. However, the expensive instrumentation, complicated operation and high cost of liquid chromatography and fluorescence have limited their application. Also, electrodes should be coupled with the electrochemical method. High sensitivity cannot be achieved with colorimetric method. Therefore, it was important to develop a simple, sensitive and intuitive assay for the determination of GSH levels in human blood.\u003c/p\u003e \u003cp\u003eChemiluminescence (CL) is a common used detection method with simple operation, low cost and high sensitivity [\u003cspan citationid=\"CR15\" class=\"CitationRef\"\u003e15\u003c/span\u003e]. Different CL systems have been used for the detection of GSH. For example, using red fluorescent alkene as fluorophore, Khajvand's group investigated the CL behaviour of GSH, L-cysteine and L-methionine in bis(2,4,6-trichlorophenyl)oxalate (TCPO)-H\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e2\u003c/sub\u003e system [\u003cspan citationid=\"CR16\" class=\"CitationRef\"\u003e16\u003c/span\u003e]. In addition, Zuo's team constructed a CL resonance energy transfer (CRET) method in Na\u003csub\u003e2\u003c/sub\u003eSO\u003csub\u003e3\u003c/sub\u003e-Ce(IV) system for the detection of GSH with a detection limit of 0.065 nmol/L [\u003cspan citationid=\"CR17\" class=\"CitationRef\"\u003e17\u003c/span\u003e]. And the reports on the detection of GSH using the luminol-H\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e2\u003c/sub\u003e system were also general [\u003cspan additionalcitationids=\"CR19 CR20 CR21\" citationid=\"CR18\" class=\"CitationRef\"\u003e18\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR22\" class=\"CitationRef\"\u003e22\u003c/span\u003e]. Although the reported luminol CL systems had good linear ranges and low detection limits, none of these reports had achieved the CL visual detection of GSH. If the CL visual detection could be taken by a common mobile without higher luminol concentration, the application will be further broadened for CL detection field.\u003c/p\u003e \u003cp\u003eTo achieve the above goal, the best way is to find excellent catalysts in luminol system. In recent years, metal-organic frameworks (MOFs), which have large specific surface area, high active sites, easy modification and adjustable structure, have been favoured by researchers in the field of catalysis [\u003cspan additionalcitationids=\"CR24\" citationid=\"CR23\" class=\"CitationRef\"\u003e23\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR25\" class=\"CitationRef\"\u003e25\u003c/span\u003e]. MOFs were self-assembly formed by connecting inorganic metal center (metal ions or metal clusters) and bridging organic ligands [\u003cspan citationid=\"CR26\" class=\"CitationRef\"\u003e26\u003c/span\u003e], which have good catalytic activity for CL systems [\u003cspan citationid=\"CR27\" class=\"CitationRef\"\u003e27\u003c/span\u003e]. As their metal centers have good catalytic activity, the CL intensity can be greatly enhanced to obtain higher sensitivity. In recent years, some MOFs with CL catalytic properties have been reported, such as Cu-MOF [\u003cspan citationid=\"CR28\" class=\"CitationRef\"\u003e28\u003c/span\u003e], MIL-53(Fe) MOF [\u003cspan citationid=\"CR29\" class=\"CitationRef\"\u003e29\u003c/span\u003e], etc. Huang's group found that MIL-53(Fe) MOFs could significantly enhance the CL of the luminol system under alkaline conditions, and its intensity was about 20 times than that of the luminescent system without MOFs [\u003cspan citationid=\"CR29\" class=\"CitationRef\"\u003e29\u003c/span\u003e]. Our group designed a Cu-TATB paper-based sensor by in situ growth method and found that Cu-TATB had peroxidase-like activity. The synthesized Cu-TATB could catalyze the luminol-H\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e2\u003c/sub\u003e CL system and used for the volatile sulfur compounds detection in exhaled breath [\u003cspan citationid=\"CR30\" class=\"CitationRef\"\u003e30\u003c/span\u003e]. Nowadays, nanoparticles had also been doped with MOFs to furtherly enhance the catalytic effect in CL system [\u003cspan citationid=\"CR31\" class=\"CitationRef\"\u003e31\u003c/span\u003e]. Due to MOFs have a permanent porous structure, nanoparticles could be incorporated into MOFs to form a composite material with highlighted catalytic character [\u003cspan citationid=\"CR32\" class=\"CitationRef\"\u003e32\u003c/span\u003e]. Fe\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e nanoparticles (Fe\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e NPs) have peroxide activity and could be recycled and reused by magnets as a biocompatibility magnetic material [\u003cspan citationid=\"CR33\" class=\"CitationRef\"\u003e33\u003c/span\u003e, \u003cspan citationid=\"CR34\" class=\"CitationRef\"\u003e34\u003c/span\u003e]. There have also been reports of Fe\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e NPs combined with MOFs to form composites [\u003cspan additionalcitationids=\"CR36 CR37\" citationid=\"CR35\" class=\"CitationRef\"\u003e35\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR38\" class=\"CitationRef\"\u003e38\u003c/span\u003e]. Zhang\u0026rsquo;s group used the synthesized composite Cu-BTC@Fe\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e to catalyze the Suzuki-Miyaura reaction under mild conditions with good catalytic activity [\u003cspan citationid=\"CR35\" class=\"CitationRef\"\u003e35\u003c/span\u003e]. Liu's group used Fe\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e@Au/Cu-MOF to construct an electrochemical sensor with enhanced peroxide-like properties for efficient real-time monitoring of p-aminophenol [\u003cspan citationid=\"CR37\" class=\"CitationRef\"\u003e37\u003c/span\u003e]. For CL detection, Li's team found that Fe\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e NPs and MOF-MIL-101(Fe) composites have good catalytic properties, which could directly catalyse the luminescence of luminol without even the need of additional oxidants [\u003cspan citationid=\"CR38\" class=\"CitationRef\"\u003e38\u003c/span\u003e]. Therefore, in order to further obtain materials with excellent catalytic properties, Fe\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e NPs and Cu-TATB composites (Fe\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e NPs@Cu-TATB) was applied to the luminol CL system for the detection of GSH.\u003c/p\u003e \u003cp\u003eIn this work, Fe\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e NPs@Cu-TATB composite material was synthesized via a hydrothermal method, achieving the excellent catalytic effect for luminol-H\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e2\u003c/sub\u003e CL system. By utilizing the chemical interaction between the sulfhydryl group of GSH and Cu\u003csup\u003e2+\u003c/sup\u003e in the composite material, the CL intensity of the system was inhibited, enabling sensitive detection of GSH (Scheme \u003cspan refid=\"Sch1\" class=\"InternalRef\"\u003e1\u003c/span\u003e). This study proposed means for CL-based and CL visual detection methods for GSH, with the expectation that this method holds promising application prospects for detecting GSH in actual human blood samples.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e"},{"header":"Experimental section","content":"\u003cp\u003eThe chemicals, materials, synthesis of Fe\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e NPs and Fe\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e NPs@Cu-TATB, the details of pre-treatment of blood samples were detailed in the Supporting Information (Section 1, Section 2, Section 3 and Section 4).\u003c/p\u003e \u003cdiv id=\"Sec3\" class=\"Section2\"\u003e \u003ch2\u003eCL detection of GSH by Fe\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e NPs@Cu-TATB\u003c/h2\u003e \u003cp\u003eFirstly, 50 \u0026micro;L of Fe\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e NPs@Cu-TATB suspension and different concentrations of GSH solution were added sequentially to the transparent 96-well plate. Then, the 96-well plate was placed in a dark box to block the light inside and the mobile phone was fixed above the 96-well plate in the dark box. Then, 1.0 mM luminol (25 \u0026micro;L) and 1.0 M H\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e2\u003c/sub\u003e (25 \u0026micro;L) were mixed. 50\u0026micro;L of the mixture was dropwised to the 96-well plate, and the CL photos at different concentrations of GSH were recorded using the mobile phone. The photos were taken at the 3rd second immediately after the mixture was added on the 96-well plate. The CL images at different GSH concentrations was calculated by the grayscale values with Photoshop software. For the CL assay, a 96-well plate containing Fe\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e NPs@Cu-TATB suspension and GSH solution was placed in the dark box of the CL instrument. After closing the dark box, the CL signal was detected and recorded by injecting a mixture of luminol (25 \u0026micro;L) and H\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e2\u003c/sub\u003e (25 \u0026micro;L) into the 96-well plate.\u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec4\" class=\"Section2\"\u003e \u003ch2\u003eDetection of GSH levels in actual blood samples\u003c/h2\u003e \u003cp\u003eBlood samples were taken from three healthy volunteers at Shaanxi Normal University Hospital. Prior to blood collection, the volunteers were required to sit still for 30 minutes. The collected blood samples were pre-treated as the procedure in Supporting Information (Section 4) and stored in a refrigerator at 4 ℃ until use. For CL detection, 96-well plates containing Fe\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e NPs@Cu-TATB suspension and serum samples from different volunteers were placed in the dark box of the CL instrument. After closing the dark box, a mixture of luminol (25 \u0026micro;L) and H\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e2\u003c/sub\u003e (25 \u0026micro;L) was injected into the 96-well plate. The CL signal was detected and recorded by the CL instrument.\u003c/p\u003e \u003c/div\u003e"},{"header":"Results and discussion","content":"\u003cdiv id=\"Sec6\" class=\"Section2\"\u003e \u003ch2\u003eInvestigation of catalytic CL performance of Fe\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e NPs@Cu-TATB\u003c/h2\u003e \u003cp\u003eAccording to the literature [\u003cspan citationid=\"CR39\" class=\"CitationRef\"\u003e39\u003c/span\u003e, \u003cspan citationid=\"CR40\" class=\"CitationRef\"\u003e40\u003c/span\u003e], metal ions such as Co\u003csup\u003e2+\u003c/sup\u003e and horseradish peroxidase (HRP) could serve as excellent catalysts for the luminol-H\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e2\u003c/sub\u003e CL system. In this study, Fe\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e NPs@Cu-TATB composite material was used as the catalyst for the luminol-H\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e2\u003c/sub\u003e CL system. We evaluated the catalytic effects (Fig.\u0026nbsp;\u003cspan refid=\"Fig1\" class=\"InternalRef\"\u003e1\u003c/span\u003eA) of these substances under the same conditions and found that the catalytic effect of Fe\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e NPs@Cu-TATB (4\u0026times;10\u003csup\u003e\u0026minus;\u0026thinsp;2\u003c/sup\u003e mg/mL) was approximately 7 times higher than that of HRP (4\u0026times;10\u003csup\u003e\u0026minus;\u0026thinsp;2\u003c/sup\u003e mg/mL), and its catalytic effect was close to the signal strength of Co\u003csup\u003e2+\u003c/sup\u003e (4\u0026times;10\u003csup\u003e\u0026minus;\u0026thinsp;2\u003c/sup\u003e mg/mL). To investigate whether the catalytic ability of Fe\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e NPs@Cu-TATB was stronger than that of Cu-TATB, Fe\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e NPs, and Fe NPs@Cu-TATB individually, their catalytic effects were verified under the same conditions. Specifically, the catalytic ability of Fe\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e NPs@Cu-TATB was found to be 6.5 times higher than that of Cu-TATB, 3.4 times that of Fe\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e NPs, and 10.4 times that of Fe NPs@Cu-TATB, as shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig1\" class=\"InternalRef\"\u003e1\u003c/span\u003eB. Also, the CL signal was recorded with the composite in different conditions. In Fig.\u0026nbsp;\u003cspan refid=\"Fig1\" class=\"InternalRef\"\u003e1\u003c/span\u003eC and Fig.\u0026nbsp;\u003cspan refid=\"Fig1\" class=\"InternalRef\"\u003e1\u003c/span\u003eD, CL intensity of Fe\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e NPs@Cu-TATB was shown on paper and in solution under the same conditions. We found that the CL intensity in the solution was much higher than the CL intensity on paper [\u003cspan citationid=\"CR41\" class=\"CitationRef\"\u003e41\u003c/span\u003e]. Fe\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e NPs@Cu-TATB may accumulate on the paper and greatly decrease the catalytic function for luminol-H\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e2\u003c/sub\u003e CL system. This also suggests that the Fe\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e NPs@Cu-TATB-luminol-H\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e2\u003c/sub\u003e CL system performed better in solution.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec7\" class=\"Section2\"\u003e \u003ch2\u003eCharacterization of Fe\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e NPs@Cu-TATB\u003c/h2\u003e \u003cp\u003eIn this work, Fe\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e NPs@Cu-TATB composite was synthesized. Then, the composite was charactered by the next methods. Firstly, the morphology of Fe\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e NPs@Cu-TATB was observed using scanning electron microscopy (SEM). From Fig.\u0026nbsp;\u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e2\u003c/span\u003eA and Fig.\u0026nbsp;\u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e2\u003c/span\u003eB, it could be seen that Cu-TATB appears as regular octahedrons with micropores on the surface. From Fig.\u0026nbsp;\u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e2\u003c/span\u003eC we could see that a large number of Fe\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e NPs could be observed in the composite material, indicating that Cu-TATB was heavily enveloped by Fe\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e NPs. To confirm the successful synthesis of Fe\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e NPs@Cu-TATB, the crystalline structure and functional groups of the samples were analyzed using X-ray diffraction data (XRD) and fourier transform infrared (FTIR) spectroscopy, respectively. As shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e2\u003c/span\u003eD, the characteristic diffraction peaks of Fe\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e NPs were observed at 2θ\u0026thinsp;=\u0026thinsp;30.1\u0026deg;, 35.5\u0026deg;, and 43.1\u0026deg; [\u003cspan citationid=\"CR42\" class=\"CitationRef\"\u003e42\u003c/span\u003e], and those of Cu-TATB are observed at 2θ\u0026thinsp;=\u0026thinsp;5.5\u0026deg;, 6.7\u0026deg;, 7.7\u0026deg;, 10.8\u0026deg;, 12.7\u0026deg;, 16.4\u0026deg;, and 19.5\u0026deg; [\u003cspan citationid=\"CR43\" class=\"CitationRef\"\u003e43\u003c/span\u003e]. The characteristic diffraction peaks of Fe\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e NPs@Cu-TATB coincided well with those of individual Fe\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e NPs and Cu-TATB, confirming that Fe\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e NPs@Cu-TATB was successfully prepared. Subsequently, the functional groups of Fe\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e NPs@Cu-TATB were investigated using FTIR spectroscopy (Fig.\u0026nbsp;\u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e2\u003c/span\u003eE). For Fe\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e NPs@Cu-TATB, the absorption peak at 624 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e represented the stretching vibration peak of Fe-O [\u003cspan citationid=\"CR44\" class=\"CitationRef\"\u003e44\u003c/span\u003e]. What's more, peaks observed at 1246 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e, 1354 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e, and 1708 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e represented the stretching vibration peaks of C-O, C-N, and C\u0026thinsp;=\u0026thinsp;O groups, respectively. This confirmed the presence of H\u003csub\u003e3\u003c/sub\u003eTATB. Additionally, the peak at 748 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e proved the stretching vibration peak of Cu-O [\u003cspan citationid=\"CR45\" class=\"CitationRef\"\u003e45\u003c/span\u003e], indicating the coordination between Cu\u003csup\u003e2+\u003c/sup\u003e and the ligand of H\u003csub\u003e3\u003c/sub\u003eTATB. The main FTIR absorption peaks of Fe\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e NPs@Cu-TATB coincided with those of Fe\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e NPs and Cu-TATB. This furtherly indicated the successful preparation of Fe\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e NPs@Cu-TATB. Furthermore, the stability of Fe\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e NPs@Cu-TATB was investigated. From the CL results in Fig. \u003cspan refid=\"MOESM1\" class=\"InternalRef\"\u003eS1\u003c/span\u003eA, Fe\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e NPs@Cu-TATB could maintain its catalytic performance steadily over 14 days. Utilizing the same batch of Fe\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e NPs@Cu-TATB, CL signals remained stable after repeated the measurements for 30 times just in a single day (Fig. \u003cspan refid=\"MOESM1\" class=\"InternalRef\"\u003eS1\u003c/span\u003eB). (the details of stability and reproducibility were provided in Supplementary Information, Section 5).\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec8\" class=\"Section2\"\u003e \u003ch2\u003eThe catalytic mechanism of Fe\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e NPs@Cu-TATB in the Luminol-H\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e2\u003c/sub\u003e system\u003c/h2\u003e \u003cp\u003eAs Fe\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e NPs@Cu-TATB could greatly enhance the CL intensity of luminol-H\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e2\u003c/sub\u003e system, the luminescence mechanism should be investigated. To confirm the emitting species in the Fe\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e NPs@Cu-TATB-Luminol-H\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e2\u003c/sub\u003e CL system, CL spectra (Fig. S2A) were utilized for validation. It could be observed that with the involvement of Fe\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e NPs@Cu-TATB, the maximum emission peak of the CL spectrum in this system was located around 425 nm. The position of the maximum emission peak in the CL spectrum was the same to Luminol-H\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e2\u003c/sub\u003e CL system. This indicates that the emitting species in this system was the excited-state 3-aminophthalate anion (3-APA*). Furthermore, UV-visible spectrophotometry was investigated by Fe\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e NPs@Cu-TATB. As shown in Fig. S2B, the position of the maximum absorption peak remained unchanged before and after the addition of Fe\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e NPs@Cu-TATB in the Luminol-H\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e2\u003c/sub\u003e CL system. This results showed that there was no new subtance's formation in this system. This confirms that Fe\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e NPs@Cu-TATB was the catalyst in this system. The utilization of free radical scavengers (Fig. S2C-F) and electron spin resonance (ESR) (Fig. S2G-I) confirmed the presence of OH\u003csup\u003e\u003cb\u003e\u0026middot;\u003c/b\u003e\u003c/sup\u003e, O\u003csub\u003e2\u003c/sub\u003e.\u003csup\u003e\u0026minus;\u003c/sup\u003e and \u003csup\u003e1\u003c/sup\u003eO\u003csub\u003e2\u003c/sub\u003e in the system. The three free radicals' confirmation could be found in the Supporting Information, Section 6.\u003c/p\u003e \u003cp\u003eBased on the experimental exploration of the mechanism described above, we could speculate the mechanism of Fe\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e NPs@Cu-TATB in luminol-H\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e2\u003c/sub\u003e CL system. Firstly, H\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e2\u003c/sub\u003e decomposed under alkaline conditions to produce HO\u003csub\u003e2\u003c/sub\u003e\u003csup\u003e\u0026minus;\u003c/sup\u003e. Also, luminol can form the luminol anion (L\u003csup\u003e\u0026minus;\u003c/sup\u003e) in the system. Then, in the presence of Fe and Cu dual active sites of Fe\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e NPs@Cu-TATB, the generated OH\u003cb\u003e\u0026middot;\u003c/b\u003e from the decomposition of H\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e2\u003c/sub\u003e reacted with L\u003csup\u003e\u0026minus;\u003c/sup\u003e and HO\u003csub\u003e2\u003c/sub\u003e\u003csup\u003e\u0026minus;\u003c/sup\u003e to produce luminol radicals (L.\u003csup\u003e\u0026minus;\u003c/sup\u003e) and O\u003csub\u003e2\u003c/sub\u003e.\u003csup\u003e\u0026minus;\u003c/sup\u003e. The generated O\u003csub\u003e2\u003c/sub\u003e.\u003csup\u003e\u0026minus;\u003c/sup\u003e can be transfered to \u003csup\u003e1\u003c/sup\u003eO\u003csub\u003e2\u003c/sub\u003e. Finally, due to the synergistic effect of the Fe and Cu dual active sites in Fe\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e NPs@Cu-TATB, L.\u003csup\u003e\u0026minus;\u003c/sup\u003e was oxidized by a large amount of O\u003csub\u003e2\u003c/sub\u003e.\u003csup\u003e\u0026minus;\u003c/sup\u003e to the excited-state 3-aminophthalate anion (3-APA*). When it returns to the ground state, it emits intense blue CL. The specific principle is illustrated in Fig.\u0026nbsp;\u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e3\u003c/span\u003e.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003eThe sulfhydryl group in GSH reacts with Cu\u003csup\u003e2+\u003c/sup\u003e to generate CuS, resulting in a decrease in the CL intensity of the system. The extent of the decrease in CL signal could be used to determine the concentration of GSH. This was the principle for Fe\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e NPs@Cu-TATB-Luminol-H\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e2\u003c/sub\u003e system to detect GSH (the details of principle was provided in Supplementary Information, Section 7 (Fig. S3)). In addition, optimization of the detection conditions for GSH revealed that the strongest CL signal was achieved with 0.5 g of Fe\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e NPs, 1.0 mM of luminol, 6.5 mM of of H\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e2\u003c/sub\u003e and the best pH value of 12.5 (the details for the optimization of the detection conditions were provided in Supplementary Information, Section 8 (Fig. S4)).\u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec9\" class=\"Section2\"\u003e \u003ch2\u003eThe sensitivity of GSH detection\u003c/h2\u003e \u003cp\u003eUnder the optimized experimental conditions, GSH was visually detected using the Fe\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e NPs@Cu-TATB-Luminol-H\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e2\u003c/sub\u003e system. Figure\u0026nbsp;\u003cspan refid=\"Fig4\" class=\"InternalRef\"\u003e4\u003c/span\u003e shown the variation in CL intensity of the solution system at different concentrations (0-200 \u0026micro;M) of GSH. In a dark background, CL photos were captured at different GSH concentrations using a mobile phone. It could be observed that the CL intensity of the solution system gradually decreased with the increased GSH concentration. With luminol of 1.0 mM, H\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e2\u003c/sub\u003e of 1.0 M, Fe\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e NPs@Cu-TATB of 3.0 mg/mL, the blue luminescence dimed with the addition of 50 \u0026micro;L GSH in 2 minutes. During the visual detection, changes in luminescence intensity from 0 to 200 \u0026micro;M GSH concentrations could be clearly observed by the naked eye. To quantitatively express the visual results, photos were taken with a mobile phone. Then, Photoshop software was used to convert brightness into grayscale images. The CL intensity at each concentration of GSH was quantitatively expressed using grayscale values. As shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig5\" class=\"InternalRef\"\u003e5\u003c/span\u003eA, a standard curve was plotted for GSH concentrations ranging from 0 to 10 \u0026micro;M. The grayscale values showed a negative correlation with GSH concentration. The linear regression equation was determined as \u003cem\u003eG\u003c/em\u003e = -3.98\u003cem\u003eC\u003c/em\u003e\u0026thinsp;+\u0026thinsp;62.07 (R\u003csup\u003e2\u003c/sup\u003e\u0026thinsp;=\u0026thinsp;0.9776), where G represents the grayscale value and C represents the concentration of GSH. In Fig.\u0026nbsp;\u003cspan refid=\"Fig5\" class=\"InternalRef\"\u003e5\u003c/span\u003eB, a standard curve was plotted for GSH concentrations ranging from 20 to 200 \u0026micro;M. The linear regression equation was calculated as \u003cem\u003eG\u003c/em\u003e = -0.05\u003cem\u003eC\u003c/em\u003e\u0026thinsp;+\u0026thinsp;17.57 (R\u003csup\u003e2\u003c/sup\u003e\u0026thinsp;=\u0026thinsp;0.9999), where G represents the grayscale value at the respective GSH concentration and C represents the concentration of GSH. According to the 3σ rule, the detection limit of GSH with the visual method was determined to be 0.7 \u0026micro;M, indicating good sensitivity for GSH detection.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003eThe Fe\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e NPs@Cu-TATB-Luminol-H\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e2\u003c/sub\u003e system was employed for CL detection of GSH. As shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig6\" class=\"InternalRef\"\u003e6\u003c/span\u003eA, the CL curves of the Fe\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e NPs@Cu-TATB-Luminol-H\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e2\u003c/sub\u003e system at different GSH concentrations indicate a decreasing trend in CL intensity with the increasing GSH concentration. In Fig.\u0026nbsp;\u003cspan refid=\"Fig6\" class=\"InternalRef\"\u003e6\u003c/span\u003eB, when the GSH concentration ranged from 1 to 20 \u0026micro;M, the relative CL intensity was proportional to the GSH concentration, with a linear regression equation of \u003cem\u003eI\u003c/em\u003e\u003csub\u003e\u003cem\u003eR\u003c/em\u003e\u003c/sub\u003e = 41.004\u003cem\u003eC\u003c/em\u003e\u0026thinsp;+\u0026thinsp;160.933 (R\u003csup\u003e2\u003c/sup\u003e\u0026thinsp;=\u0026thinsp;0.9993), where I\u003csub\u003eR\u003c/sub\u003e represents the relative CL intensity and C represents the concentration of GSH. In Fig.\u0026nbsp;\u003cspan refid=\"Fig6\" class=\"InternalRef\"\u003e6\u003c/span\u003eC, when the GSH concentration ranged from 20 to 200 \u0026micro;M, the relative CL intensity was also proportional to the GSH concentration, with a linear regression equation of \u003cem\u003eI\u003c/em\u003e\u003csub\u003e\u003cem\u003eR\u003c/em\u003e\u003c/sub\u003e = 4.152\u003cem\u003eC\u003c/em\u003e\u0026thinsp;+\u0026thinsp;895.988 (R\u003csup\u003e2\u003c/sup\u003e\u0026thinsp;=\u0026thinsp;0.9970), where I\u003csub\u003eR\u003c/sub\u003e represents the relative CL intensity at the respective GSH concentration and C represents the concentration of GSH. According to the 3σ rule, the detection limit of GSH was determined to be 0.3 \u0026micro;M, indicating good sensitivity for detecting GSH using CL.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec10\" class=\"Section2\"\u003e \u003ch2\u003eThe interference determination during detection of GSH\u003c/h2\u003e \u003cp\u003eIn order to assess the selectivity of this method for detecting GSH, we investigated the effects of coexisting ions (K\u003csup\u003e+\u003c/sup\u003e, Na\u003csup\u003e+\u003c/sup\u003e, Ca\u003csup\u003e2+\u003c/sup\u003e, Fe\u003csup\u003e3+\u003c/sup\u003e), glucose, amino acids (glycine (Gly), serine (Ser), histidine (His), cysteine (Cys)), and vitamin C (Vc) in human blood [\u003cspan citationid=\"CR46\" class=\"CitationRef\"\u003e46\u003c/span\u003e, \u003cspan citationid=\"CR47\" class=\"CitationRef\"\u003e47\u003c/span\u003e]. Typically, human blood contains approximately 4 mM K\u003csup\u003e+\u003c/sup\u003e, 140 mM Na\u003csup\u003e+\u003c/sup\u003e, 2 mM Ca\u003csup\u003e2+\u003c/sup\u003e, and 10 \u0026micro;M Fe\u003csup\u003e3+\u003c/sup\u003e, as well as 200 \u0026micro;M Gly, 128 \u0026micro;M Ser, 32\u0026ndash;107 \u0026micro;M His, 5 \u0026micro;M Cys, and 5.7 \u0026micro;M Vc. As shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig7\" class=\"InternalRef\"\u003e7\u003c/span\u003e, when 100 \u0026micro;M GSH was mixed with interfering substances at 10-fold or 0.1-fold concentrations, using the Fe\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e NPs@Cu-TATB-Luminol-H\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e2\u003c/sub\u003e system for CL detection, it was found that the CL signal was not significantly affected. Although Cys and Vc could cause a decrease in the CL intensity of the system, their concentrations in human blood (\u0026micro;mol/L) were much lower than the concentration of GSH (mmol/L) [\u003cspan citationid=\"CR47\" class=\"CitationRef\"\u003e47\u003c/span\u003e, \u003cspan citationid=\"CR48\" class=\"CitationRef\"\u003e48\u003c/span\u003e]. In summary, these interfering substances do not interfere with the detection of GSH, indicating that the Fe\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e NPs@Cu-TATB-Luminol-H\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e2\u003c/sub\u003e system had good selectivity for detecting GSH in human blood.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec11\" class=\"Section2\"\u003e \u003ch2\u003eThe detection of GSH in actual blood samples\u003c/h2\u003e \u003cp\u003eTo evaluate the feasibility of detecting GSH in human blood using the Fe\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e NPs@Cu-TATB-Luminol-H\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e2\u003c/sub\u003e system, blood samples were collected from three healthy volunteers at Shaanxi Normal University. After pretreatment, gradient concentrations of reduced GSH were added to the blood samples. The spiked blood samples were then detected, and the results were compared with those obtained using standard electrochemiluminescence (ECL). It was found that there were no significant differences between the two methods. The analysis results, as shown in Table\u0026nbsp;\u003cspan refid=\"Tab1\" class=\"InternalRef\"\u003e1\u003c/span\u003e, indicated that the GSH content in the blood of the three volunteers was approximately 1.1 mM. Using the standard addition method to determine the recovery rate, it was observed that the recovery rate was ranging from 90\u0026ndash;110% (n\u0026thinsp;=\u0026thinsp;3). These results demonstrated the feasibility of this detection method for measuring GSH in human blood.\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\u003eDetection of GSH in Human Serum Samples by CL Method (n\u0026thinsp;=\u0026thinsp;3)\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\" morerows=\"1\" rowspan=\"2\"\u003e \u003cp\u003eSample\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colspan=\"2\" nameend=\"c3\" namest=\"c2\"\u003e \u003cp\u003eFound in sample(mM)\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c4\" morerows=\"1\" rowspan=\"2\"\u003e \u003cp\u003eAdd(mM)\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c5\" morerows=\"1\" rowspan=\"2\"\u003e \u003cp\u003eTotal found(mM)\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c6\" morerows=\"1\" rowspan=\"2\"\u003e \u003cp\u003eRecovery(%)\u003c/p\u003e \u003c/th\u003e \u003c/tr\u003e \u003ctr\u003e \u003cth align=\"left\" colname=\"c2\"\u003e \u003cp\u003eECL\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c3\"\u003e \u003cp\u003eCL\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=\"2\" nameend=\"c3\" namest=\"c2\"\u003e\u0026nbsp;\u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e1.0\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e2.0\u0026thinsp;\u0026plusmn;\u0026thinsp;0.1\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e95.2\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e1\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e1.1\u0026thinsp;\u0026plusmn;\u0026thinsp;0.2\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e1.1\u0026thinsp;\u0026plusmn;\u0026thinsp;0.1\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e3.0\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e4.1\u0026thinsp;\u0026plusmn;\u0026thinsp;0.3\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e100.0\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=\"2\" nameend=\"c3\" namest=\"c2\"\u003e\u0026nbsp;\u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e5.0\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e5.9\u0026thinsp;\u0026plusmn;\u0026thinsp;0.1\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e96.7\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=\"2\" nameend=\"c3\" namest=\"c2\"\u003e\u0026nbsp;\u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e1.0\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e2.1\u0026thinsp;\u0026plusmn;\u0026thinsp;0.1\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e105.0\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e2\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e1.1\u0026thinsp;\u0026plusmn;\u0026thinsp;0.1\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e1.0\u0026thinsp;\u0026plusmn;\u0026thinsp;0.1\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e3.0\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e3.9\u0026thinsp;\u0026plusmn;\u0026thinsp;0.1\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e97.5\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=\"2\" nameend=\"c3\" namest=\"c2\"\u003e\u0026nbsp;\u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e5.0\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e6.2\u0026thinsp;\u0026plusmn;\u0026thinsp;0.2\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e103.3\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=\"2\" nameend=\"c3\" namest=\"c2\"\u003e\u0026nbsp;\u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e1.0\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e2.1\u0026thinsp;\u0026plusmn;\u0026thinsp;0.3\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e105.0\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e3\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e1.1\u0026thinsp;\u0026plusmn;\u0026thinsp;0.2\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e1.0\u0026thinsp;\u0026plusmn;\u0026thinsp;0.3\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e3.0\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e4.1\u0026thinsp;\u0026plusmn;\u0026thinsp;0.2\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e102.5\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=\"2\" nameend=\"c3\" namest=\"c2\"\u003e\u0026nbsp;\u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e5.0\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e6.1\u0026thinsp;\u0026plusmn;\u0026thinsp;0.2\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e101.7\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"},{"header":"Conclusions","content":"\u003cp\u003eThis study synthesized Fe\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e NPs@Cu-TATB composite material via a hydrothermal method, and developed a CL and CL visual detection method for GSH in human blood samples. Fe\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e NPs@Cu-TATB exhibited excellent catalytic effects in the luminol-H\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e2\u003c/sub\u003e CL system. Fe\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e NPs@Cu-TATB can interact with GSH and the CL intensity decreased. The detection limits with visual and CL methods were 0.7 \u0026micro;M and 0.3 \u0026micro;M, respectively. When applied to actual human blood samples, this method offers advantages such as simplicity and good selectivity. This low-cost and convenient detection method is expected to be applied in future analyses of GSH levels in human blood.\u003c/p\u003e"},{"header":"Declarations","content":"\u003ch2\u003eEthics approval and consent to participate\u003c/h2\u003e\n\u003cp\u003eThis study received approval from the Committee on Ethics at Shaanxi Normal University, and all volunteers provided informed consent prior to their participation.\u003c/p\u003e\n\u003ch2\u003eConflict of interest\u003c/h2\u003e\n\u003cp\u003eThe authors declare no competing interests.\u003c/p\u003e\n\u003ch2\u003eFunding\u003c/h2\u003e\n\u003cp\u003eWe are very thankful to Natural Science Foundation of Shaanxi Province (No. 2024JC-YBMS-116) for supporting this work. The authors also thank the Fundamental Research Funds for the Central Universities (GK201902009 and GK201701002) and Program for Innovative Research Team in Shaanxi Province (2014KCT-28) for supporting this work.\u003c/p\u003e\n\u003ch2\u003eAuthor Contribution\u003c/h2\u003e\n\u003cp\u003eXiaohu Ma: Conceptualization, Methodology, Software, Formal analysis, Writing \u0026ndash;Review\u0026amp;Editing, Investigation, Data curation, Writing-Original Draft, Visualization. Peiyu Jiang: Validation. Jingbo Geng: Data curation. Xinyi Li: Validation. Yan Jin: Review. Baoxin Li: Review. Wei Liu: Review\u0026amp;Editing, Supervision, Funding acquisition. All authors reviewed the manuscript.\u003c/p\u003e\n\u003ch2\u003eData availability\u003c/h2\u003e\n\u003cp\u003eData will be made available on request.\u003c/p\u003e"},{"header":"References","content":"\u003col\u003e\u003cli\u003e\u003cspan\u003eIskusnykh IY, Zakharova AA, Pathak D (2022) Glutathione in brain disorders and aging. 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Biosens Bioelectron 72:31\u0026ndash;36\u003c/span\u003e\u003c/li\u003e\u003c/ol\u003e"},{"header":"Scheme","content":"\u003cp\u003eScheme 1 is available in the Supplementary Files section.\u003c/p\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":"microchimica-acta","isNatureJournal":false,"hasQc":true,"allowDirectSubmit":false,"externalIdentity":"miac","sideBox":"Learn more about [Microchimica Acta](https://link.springer.com/journal/604)","snPcode":"604","submissionUrl":"https://submission.springernature.com/new-submission/604/3","title":"Microchimica Acta","twitterHandle":"","acdcEnabled":true,"dfaEnabled":true,"editorialSystem":"stoa","reportingPortfolio":"Springer Hybrid","inReviewEnabled":true,"inReviewRevisionsEnabled":false},"keywords":"Fe3O4 NPs@Cu-TATB, Glutathione, Chemiluminescence, Visual,Luminol ","lastPublishedDoi":"10.21203/rs.3.rs-4678477/v1","lastPublishedDoiUrl":"https://doi.org/10.21203/rs.3.rs-4678477/v1","license":{"name":"CC BY 4.0","url":"https://creativecommons.org/licenses/by/4.0/"},"manuscriptAbstract":"\u003cp\u003eIn this study, a chemiluminescence (CL) method for determination of glutathione (GSH) was developed with magnetic\u0026ensp;nanoparticle-decorated\u0026ensp;metal\u0026ensp;organic frameworks (Fe\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e NPs@Cu-TATB). The composite material was synthesized via a hydrothermal method and glutathione (GSH) can be tested by both visual and chemiluminescence (CL) methods. The synthesized Fe\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e NPs@Cu-TATB exhibited excellent catalytic activity in the luminol-H\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e2\u003c/sub\u003e CL system. The mechanism revealed that three types of oxygen-containing radicals (ROS) was generated in this system. As GSH can reduce the catalytic effect of generated ROS radicals, the inhibiting CL signal was produced in the Fe\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e NPs@Cu-TATB-luminol-H\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e2\u003c/sub\u003e system. Based on the established CL system, the detection limits for GSH using CL and visual methods were found to be 0.3 \u0026micro;M and 0.7 \u0026micro;M, respectively. This low-cost and convenient detection method can be applied to the analysis of GSH content in human blood.\u003c/p\u003e","manuscriptTitle":"Magnetic nanoparticle-decorated metal organic frameworks for chemiluminescence detection of glutathione","msid":"","msnumber":"","nonDraftVersions":[{"code":1,"date":"2024-07-29 11:40:51","doi":"10.21203/rs.3.rs-4678477/v1","editorialEvents":[{"type":"communityComments","content":0},{"type":"decision","content":"Revision requested","date":"2024-08-21T15:28:47+00:00","index":"","fulltext":""},{"type":"editorInvitedReview","content":"","date":"2024-08-21T10:28:34+00:00","index":"hide","fulltext":""},{"type":"reviewerAgreed","content":"45411988715211872126017554683907878200","date":"2024-08-21T10:06:04+00:00","index":"hide","fulltext":""},{"type":"reviewerAgreed","content":"131561686139225151792770295813394018126","date":"2024-08-01T09:36:40+00:00","index":"hide","fulltext":""},{"type":"editorInvitedReview","content":"","date":"2024-07-24T12:34:41+00:00","index":"hide","fulltext":""},{"type":"reviewerAgreed","content":"160771871687981348343995371457576120424","date":"2024-07-14T05:40:41+00:00","index":"hide","fulltext":""},{"type":"reviewersInvited","content":"","date":"2024-07-05T16:23:17+00:00","index":"","fulltext":""},{"type":"editorAssigned","content":"","date":"2024-07-04T07:17:33+00:00","index":"","fulltext":""},{"type":"checksComplete","content":"","date":"2024-07-04T07:14:17+00:00","index":"","fulltext":""},{"type":"submitted","content":"Microchimica Acta","date":"2024-07-03T07:36:28+00:00","index":"","fulltext":""}],"status":"published","journal":{"display":true,"email":"[email protected]","identity":"microchimica-acta","isNatureJournal":false,"hasQc":true,"allowDirectSubmit":false,"externalIdentity":"miac","sideBox":"Learn more about [Microchimica Acta](https://link.springer.com/journal/604)","snPcode":"604","submissionUrl":"https://submission.springernature.com/new-submission/604/3","title":"Microchimica Acta","twitterHandle":"","acdcEnabled":true,"dfaEnabled":true,"editorialSystem":"stoa","reportingPortfolio":"Springer Hybrid","inReviewEnabled":true,"inReviewRevisionsEnabled":false}}],"origin":"","ownerIdentity":"7155ed81-b183-4c0c-9164-69f2519ef695","owner":[],"postedDate":"July 29th, 2024","published":true,"recentEditorialEvents":[],"rejectedJournal":[],"revision":"","amendment":"","status":"published-in-journal","subjectAreas":[],"tags":[],"updatedAt":"2024-09-30T16:00:35+00:00","versionOfRecord":{"articleIdentity":"rs-4678477","link":"https://doi.org/10.1007/s00604-024-06686-6","journal":{"identity":"microchimica-acta","isVorOnly":false,"title":"Microchimica Acta"},"publishedOn":"2024-09-24 15:57:08","publishedOnDateReadable":"September 24th, 2024"},"versionCreatedAt":"2024-07-29 11:40:51","video":"","vorDoi":"10.1007/s00604-024-06686-6","vorDoiUrl":"https://doi.org/10.1007/s00604-024-06686-6","workflowStages":[]},"version":"v1","identity":"rs-4678477","journalConfig":"researchsquare"},"__N_SSP":true},"page":"/article/[identity]/[[...version]]","query":{"redirect":"/article/rs-4678477","identity":"rs-4678477","version":["v1"]},"buildId":"qtupq5eGEP_6zYnWcrvyt","isFallback":false,"isExperimentalCompile":false,"dynamicIds":[84888],"gssp":true,"scriptLoader":[]}