Pub Date : 2026-03-08Epub Date: 2026-01-22DOI: 10.1016/j.aca.2026.345141
Xin Zhang , Guangxing Gu , Jiajin Weng , Chenyang Wang , Zixuan Ma , Xiaojun Tang , Yanchuan Zhao
Background
Chiral pesticides are increasingly important in agrochemicals, with enantiomers differing significantly in bioactivity, toxicity, and environmental impact. Rapid and robust methods for resolving these enantiomers in complex matrices are essential for regulatory monitoring and mechanistic studies.
Results
We developed a separation-free 19F NMR chemosensing platform using dual-stereocenter 19F-labeled Pd probes. The method enables direct enantiodifferentiation of N-heterocyclic pesticides, including complex cases like difenoconazole where all four stereoisomers are fully resolved in a single 19F spectrum. Quantitative enantiomeric excess (ee values) determination shows excellent linearity, with deviations from the true ee values of less than 2 %. The platform also resolves six pesticides simultaneously in a mixture and, in soil extracts, monitors in situ stereoselective degradation, revealing significant degradation bias between enantiomers.
Significance
Dual-stereocenter 19F NMR probes deliver a practical alternative to chiral chromatography for pesticide residue analysis, combining operational simplicity, matrix tolerance, multicomponent capability, and quantitative rigor. The method enables direct, separation-free readout of stereochemistry and kinetics in complex samples and reveals in situ enantioselective degradation pathways. These attributes provide actionable insight for precision application, environmental risk assessment, and regulatory surveillance of chiral agrochemicals.
{"title":"Separation-free enantiodiscrimination of chiral pesticides via dual-stereocenter 19F NMR probes for multicomponent and environmental analysis","authors":"Xin Zhang , Guangxing Gu , Jiajin Weng , Chenyang Wang , Zixuan Ma , Xiaojun Tang , Yanchuan Zhao","doi":"10.1016/j.aca.2026.345141","DOIUrl":"10.1016/j.aca.2026.345141","url":null,"abstract":"<div><h3>Background</h3><div>Chiral pesticides are increasingly important in agrochemicals, with enantiomers differing significantly in bioactivity, toxicity, and environmental impact. Rapid and robust methods for resolving these enantiomers in complex matrices are essential for regulatory monitoring and mechanistic studies.</div></div><div><h3>Results</h3><div>We developed a separation-free <sup>19</sup>F NMR chemosensing platform using dual-stereocenter <sup>19</sup>F-labeled Pd probes. The method enables direct enantiodifferentiation of N-heterocyclic pesticides, including complex cases like difenoconazole where all four stereoisomers are fully resolved in a single <sup>19</sup>F spectrum. Quantitative enantiomeric excess (ee values) determination shows excellent linearity, with deviations from the true ee values of less than 2 %. The platform also resolves six pesticides simultaneously in a mixture and, in soil extracts, monitors in situ stereoselective degradation, revealing significant degradation bias between enantiomers.</div></div><div><h3>Significance</h3><div>Dual-stereocenter <sup>19</sup>F NMR probes deliver a practical alternative to chiral chromatography for pesticide residue analysis, combining operational simplicity, matrix tolerance, multicomponent capability, and quantitative rigor. The method enables direct, separation-free readout of stereochemistry and kinetics in complex samples and reveals in situ enantioselective degradation pathways. These attributes provide actionable insight for precision application, environmental risk assessment, and regulatory surveillance of chiral agrochemicals.</div></div>","PeriodicalId":240,"journal":{"name":"Analytica Chimica Acta","volume":"1390 ","pages":"Article 345141"},"PeriodicalIF":6.0,"publicationDate":"2026-03-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146014724","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
This study introduces a data-driven deep learning framework for optimizing the extraction of plant biomolecules, aiming to improve both efficiency and sustainability in analytical sample preparation. Conventional extraction methods such as maceration, Soxhlet, reflux, and liquid–liquid partition, often paired with solvents of varying profiles are frequently resource-intensive and environmentally demanding. To address these limitations, we developed the Deep Green Optimization (DeepGO) framework, a hybrid CNN-LSTM deep learning model trained on more than five thousand experimental data points that includes sustainability indicators such as solvent properties, energy demand, and toxicity.
Results
The DeepGO framework predicts multiple extraction outcomes including extraction yields, phenolic, flavonoid, and tannin contents, as well as antioxidant and metal chelating activities. Decision-making algorithms revealed that moderately toxic and polar solvents, particularly n-butanol and ethyl acetate, generated the highest extraction efficiencies (R2 reached 0.87). We demonstrate that hexane and water, as the two solvents of extreme polarity, showed limited compatibility with these conventional methods (0.44<R2<0.65).
Significance
Based on environmental impact and energy consumption, the DeepGO framework provides a valuable predictive tool to enhance plant-based extractions. This approach substantially reduces solvent consumption, lowers energy demand, and minimizes waste generation, which are key aspects of sustainable chemical practices.
{"title":"AI-driven optimization of sustainable solvent-based extraction: A deep learning approach for green sample preparation","authors":"Hedi Mighri , Noureddine Jarray , Naima Bennour , Nesrine Harboub , Hafedh Hajlaoui , Raoudha Abdellaoui","doi":"10.1016/j.aca.2026.345106","DOIUrl":"10.1016/j.aca.2026.345106","url":null,"abstract":"<div><h3>Background</h3><div>This study introduces a data-driven deep learning framework for optimizing the extraction of plant biomolecules, aiming to improve both efficiency and sustainability in analytical sample preparation. Conventional extraction methods such as maceration, Soxhlet, reflux, and liquid–liquid partition, often paired with solvents of varying profiles are frequently resource-intensive and environmentally demanding. To address these limitations, we developed the Deep Green Optimization (DeepGO) framework, a hybrid CNN-LSTM deep learning model trained on more than five thousand experimental data points that includes sustainability indicators such as solvent properties, energy demand, and toxicity.</div></div><div><h3>Results</h3><div>The DeepGO framework predicts multiple extraction outcomes including extraction yields, phenolic, flavonoid, and tannin contents, as well as antioxidant and metal chelating activities. Decision-making algorithms revealed that moderately toxic and polar solvents, particularly n-butanol and ethyl acetate, generated the highest extraction efficiencies (<em>R</em><sup><em>2</em></sup> reached 0.87). We demonstrate that hexane and water, as the two solvents of extreme polarity, showed limited compatibility with these conventional methods (0.44<<em>R</em><sup><em>2</em></sup><0.65).</div></div><div><h3>Significance</h3><div>Based on environmental impact and energy consumption, the DeepGO framework provides a valuable predictive tool to enhance plant-based extractions. This approach substantially reduces solvent consumption, lowers energy demand, and minimizes waste generation, which are key aspects of sustainable chemical practices.</div></div>","PeriodicalId":240,"journal":{"name":"Analytica Chimica Acta","volume":"1390 ","pages":"Article 345106"},"PeriodicalIF":6.0,"publicationDate":"2026-03-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146014728","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-03-08Epub Date: 2026-01-16DOI: 10.1016/j.aca.2026.345109
Siqi Gao , Jinhui Zhao , Yue Guan , Liyan Liu
Background
Dried blood spot (DBS) technology, as a method of blood collection and preservation, has the advantages of small blood collection, convenient transportation and avoiding the degradation of metabolites. In particular, it has broad clinical application prospects in newborn screening and therapeutic drug monitoring. Desorption electrospray mass spectrometry (DESI-MS) is a simple, rapid and in situ spatial metabolomics detection technique, but its throughput, accuracy and coverage for DBS remain to be investigated compared with traditional methods.
Results
In the UPLC-MS/MS platform, the optimal extraction solvent, extraction solvent volume and extraction method were ACN: H2O (v:v/3:1), 300 μL and ultrasonic extraction, respectively. Based on the DESI-MS/MS platform, the best spray solvent was MeOH: H2O (v:v/3:1), the spray velocity was set at 2 μL/min, the spray needle angle was set at 55°, and the capillary voltage was set at 4.5 kv (DESI+), respectively. The approach delivered consistent data assurance, broad metabolite coverage, and acceptable reproducibility. Finally, these methods were applied to detect the metabolic profiles of subjects before and after drinking sugar-sweetened soy milk, and the metabolic map was well isolated, and the difference metabolites were successfully found.
Significance
Two protocols of metabolic profiles for DBS were constructed and optimized. The good performance of DESI-MS/MS was obtained when comparing to the UPLC-MS/MS. The application of sweetened soy milk showed that the two protocols developed have the practicability of detecting differential changes in metabolic profiles of DBS.
{"title":"A high-throughput detection platform for dried blood spots constructed with DESI-MS/MS","authors":"Siqi Gao , Jinhui Zhao , Yue Guan , Liyan Liu","doi":"10.1016/j.aca.2026.345109","DOIUrl":"10.1016/j.aca.2026.345109","url":null,"abstract":"<div><h3>Background</h3><div>Dried blood spot (DBS) technology, as a method of blood collection and preservation, has the advantages of small blood collection, convenient transportation and avoiding the degradation of metabolites. In particular, it has broad clinical application prospects in newborn screening and therapeutic drug monitoring. Desorption electrospray mass spectrometry (DESI-MS) is a simple, rapid and in situ spatial metabolomics detection technique, but its throughput, accuracy and coverage for DBS remain to be investigated compared with traditional methods.</div></div><div><h3>Results</h3><div>In the UPLC-MS/MS platform, the optimal extraction solvent, extraction solvent volume and extraction method were ACN: H<sub>2</sub>O (v:v/3:1), 300 μL and ultrasonic extraction, respectively. Based on the DESI-MS/MS platform, the best spray solvent was MeOH: H<sub>2</sub>O (v:v/3:1), the spray velocity was set at 2 μL/min, the spray needle angle was set at 55°, and the capillary voltage was set at 4.5 kv (DESI<sup>+</sup>), respectively. The approach delivered consistent data assurance, broad metabolite coverage, and acceptable reproducibility. Finally, these methods were applied to detect the metabolic profiles of subjects before and after drinking sugar-sweetened soy milk, and the metabolic map was well isolated, and the difference metabolites were successfully found.</div></div><div><h3>Significance</h3><div>Two protocols of metabolic profiles for DBS were constructed and optimized. The good performance of DESI-MS/MS was obtained when comparing to the UPLC-MS/MS. The application of sweetened soy milk showed that the two protocols developed have the practicability of detecting differential changes in metabolic profiles of DBS.</div></div>","PeriodicalId":240,"journal":{"name":"Analytica Chimica Acta","volume":"1390 ","pages":"Article 345109"},"PeriodicalIF":6.0,"publicationDate":"2026-03-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145995957","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-03-08Epub Date: 2026-01-19DOI: 10.1016/j.aca.2026.345121
Tong He, Gelin Liu, Yanwen Zhao, Jianzhong Shen, Zhanhui Wang, Wen Kai
Background
The introduction of nanoparticles (NPs) has led to substantial improvements in the performance of immunoassays. However, the further development of NP-based immunoassays is hampered by the lack of precise conjugation strategies and a systematic investigation of how antibody valency affects assay performance.
Results
Using homogeneous chemiluminescence immunoassays (HCLIA) as a model system, we present a novel site-specific coupling strategy. This strategy integrates cysteine-engineered single-chain variable fragment (scFv), click chemistry, and biotin-streptavidin interactions to precisely control scFv loading density on NPs. Compared to the traditional chemical conjugation and secondary antibody capture methods, this strategy shown significantly higher conjugates structural uniformity, superior antibody functionality retention, and enhanced assay sensitivity and reproducibility. Then, we present a quantitative study elucidating how antibody valency governs the sensitivity and robustness of HCLIA. Results show that low valency (coupling proportion <10 %) compromised sensitivity and robustness, medium antibody valency (10 % < coupling proportion <50 %) maximized sensitivity, while high valency (coupling proportion >50 %) significantly enhanced robustness at the expense of sensitivity. These insights enabled development of an optimized HCLIA for detecting 17 quinolones (QNs) in milk, which exhibited exceptional sensitivity with limits of detection ranging from 0.010 to 0.131 μg/L.
Significance
This study presents a precisely controllable antibody conjugation strategy and advances our understanding of the effect of antibody valency, offering key guidelines for the rational design of future NP-based immunoassays. The established HCLIA method can be used as a practical tool for the detection of QNs residues in milk.
{"title":"Engineering antibody conjugation and valency for optimized nanoparticle-based immunoassays","authors":"Tong He, Gelin Liu, Yanwen Zhao, Jianzhong Shen, Zhanhui Wang, Wen Kai","doi":"10.1016/j.aca.2026.345121","DOIUrl":"10.1016/j.aca.2026.345121","url":null,"abstract":"<div><h3>Background</h3><div>The introduction of nanoparticles (NPs) has led to substantial improvements in the performance of immunoassays. However, the further development of NP-based immunoassays is hampered by the lack of precise conjugation strategies and a systematic investigation of how antibody valency affects assay performance.</div></div><div><h3>Results</h3><div>Using homogeneous chemiluminescence immunoassays (HCLIA) as a model system, we present a novel site-specific coupling strategy. This strategy integrates cysteine-engineered single-chain variable fragment (scFv), click chemistry, and biotin-streptavidin interactions to precisely control scFv loading density on NPs. Compared to the traditional chemical conjugation and secondary antibody capture methods, this strategy shown significantly higher conjugates structural uniformity, superior antibody functionality retention, and enhanced assay sensitivity and reproducibility. Then, we present a quantitative study elucidating how antibody valency governs the sensitivity and robustness of HCLIA. Results show that low valency (coupling proportion <10 %) compromised sensitivity and robustness, medium antibody valency (10 % < coupling proportion <50 %) maximized sensitivity, while high valency (coupling proportion >50 %) significantly enhanced robustness at the expense of sensitivity. These insights enabled development of an optimized HCLIA for detecting 17 quinolones (QNs) in milk, which exhibited exceptional sensitivity with limits of detection ranging from 0.010 to 0.131 μg/L.</div></div><div><h3>Significance</h3><div>This study presents a precisely controllable antibody conjugation strategy and advances our understanding of the effect of antibody valency, offering key guidelines for the rational design of future NP-based immunoassays. The established HCLIA method can be used as a practical tool for the detection of QNs residues in milk.</div></div>","PeriodicalId":240,"journal":{"name":"Analytica Chimica Acta","volume":"1390 ","pages":"Article 345121"},"PeriodicalIF":6.0,"publicationDate":"2026-03-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146001600","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-03-08Epub Date: 2026-01-20DOI: 10.1016/j.aca.2026.345133
Xingyu Shi , Xuan Liang , Shuilin Xie , Ting Zhou , Wei Xiong
Background
Fatty acids (FAs) are essential metabolites involved in energy storage, signaling, and inflammation regulation, and their biological functions are closely linked to the position and geometric configuration of carbon–carbon double bonds (CC). However, the isomer-resolved characterization and highly sensitive detection of FAs in complex biological matrices remain challenging due to their co-elution, similar fragmentation, and low ionization efficiency. Therefore, there remains a critical need for an efficient approach that can simultaneously enhance chromatographic separation, enable unambiguous CC characterization, and improve detection sensitivity for FA isomers in biological samples.
Results
In this study, we developed a double derivatization strategy combining magnesium monoperoxyphthalate hexahydrate (MMPP) epoxidation with N,N-diethyl-1,2-ethanediamine (DEEA) amidation, coupled with LC–MS/MS, for isomer-resolved FA analysis. The double derivatization enhanced the chromatographic resolution of positional and cis/trans isomers, enabled reliable localization of CC positions via Δ16 Da diagnostic ion pairs, and improved detection sensitivity by 16–32 fold relative to epoxidation alone. Cis-trans configurations were further supported by parallel linear relationships between retention time and CC position under identical LC conditions, providing a standards-sparing criterion for structural assignment. Applied to mouse plasma, the strategy identified 69 FAs, including 55 unsaturated species, representing an increase of 46 over the underivatized approach. Quantitative analyses and differential analyses showed most FAs were elevated in hepatitis B virus (HBV) mice, with altered isomer ratios pointing to disrupted desaturase activity and oxidative stress.
Significance
In conclusion, this double derivatization LC-MS/MS platform provided improved structural resolution, higher detection sensitivity, and more reliable configurational assignment of FAs without requiring extensive standards. Its successful application to HBV mouse plasma demonstrated its suitability for complex biological matrices and highlighted its potential for biomarker discovery and mechanistic studies of lipid-related metabolic diseases.
{"title":"Double derivatization-enhanced LC-MS/MS for isomer-resolved identification and quantification of fatty acids","authors":"Xingyu Shi , Xuan Liang , Shuilin Xie , Ting Zhou , Wei Xiong","doi":"10.1016/j.aca.2026.345133","DOIUrl":"10.1016/j.aca.2026.345133","url":null,"abstract":"<div><h3>Background</h3><div>Fatty acids (FAs) are essential metabolites involved in energy storage, signaling, and inflammation regulation, and their biological functions are closely linked to the position and geometric configuration of carbon–carbon double bonds (C<img>C). However, the isomer-resolved characterization and highly sensitive detection of FAs in complex biological matrices remain challenging due to their co-elution, similar fragmentation, and low ionization efficiency. Therefore, there remains a critical need for an efficient approach that can simultaneously enhance chromatographic separation, enable unambiguous C<img>C characterization, and improve detection sensitivity for FA isomers in biological samples.</div></div><div><h3>Results</h3><div>In this study, we developed a double derivatization strategy combining magnesium monoperoxyphthalate hexahydrate (MMPP) epoxidation with N,N-diethyl-1,2-ethanediamine (DEEA) amidation, coupled with LC–MS/MS, for isomer-resolved FA analysis. The double derivatization enhanced the chromatographic resolution of positional and cis/trans isomers, enabled reliable localization of C<img>C positions via Δ16 Da diagnostic ion pairs, and improved detection sensitivity by 16–32 fold relative to epoxidation alone. <em>Cis</em>-trans configurations were further supported by parallel linear relationships between retention time and C<img>C position under identical LC conditions, providing a standards-sparing criterion for structural assignment. Applied to mouse plasma, the strategy identified 69 FAs, including 55 unsaturated species, representing an increase of 46 over the underivatized approach. Quantitative analyses and differential analyses showed most FAs were elevated in hepatitis B virus (HBV) mice, with altered isomer ratios pointing to disrupted desaturase activity and oxidative stress.</div></div><div><h3>Significance</h3><div>In conclusion, this double derivatization LC-MS/MS platform provided improved structural resolution, higher detection sensitivity, and more reliable configurational assignment of FAs without requiring extensive standards. Its successful application to HBV mouse plasma demonstrated its suitability for complex biological matrices and highlighted its potential for biomarker discovery and mechanistic studies of lipid-related metabolic diseases.</div></div>","PeriodicalId":240,"journal":{"name":"Analytica Chimica Acta","volume":"1390 ","pages":"Article 345133"},"PeriodicalIF":6.0,"publicationDate":"2026-03-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146014736","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-03-08Epub Date: 2026-01-17DOI: 10.1016/j.aca.2026.345113
Yu Zhang , Xueqing Zhao , Beth Crowell , Heinrich Lob , Sarah Hatsell , Aris N. Economides , Evangelos Pefanis , Jikang Wu , Haibo Qiu , Ning Li
Background
Wilson's disease (WD) is a genetic disorder caused by ATP7B gene mutations, impairing copper excretion and leading to toxic copper accumulation in vital organs. Inductively coupled plasma mass spectrometry (ICPMS)-based serum copper analysis has shown reliability in WD studies, with relative exchangeable copper (REC, proportion of exchangeable copper in the blood relative to the total copper) and accurate non-ceruloplasmin-bound copper (ANCC) emerging as promising biomarkers. However, challenges persist in applying these methods in live animal studies because of limited sample volumes and impractical copper specifications, necessitating alternative analytical approaches.
Results
This study comprehensively evaluated a size-exclusion chromatography coupled with ultraviolet (SEC-UV)-ICPMS method for precise copper speciation in mouse serum. This method effectively separated major copper-binding proteins while minimizing sample preparation and consumption. As a comparison, the direct injection-based ICPMS method was optimized to determine relative exchangeable copper (REC), and strong anion exchange (SAX)-ICPMS-based copper speciation approaches were investigated to validate the accuracy of the SEC-UV-ICPMS method, further confirming its robustness for live mouse studies. Further application to WD mouse models (ATP7Btx−J) revealed distinct copper distribution differences between diseased and healthy states. Relative non-ceruloplasmin-bound copper (RNCC) was newly identified as a promising potential biomarker, defining a diagnostic threshold of 52–58 %. By accurately quantifying copper species in mouse serum, this study established a reliable analytical framework that greatly improved our understanding of copper distribution in Wilson's disease research. Our approach demonstrated high specificity, reproducibility, and throughput, suitable for live mouse studies.
Significance
The SEC-UV-ICPMS platform offers a robust and efficient approach for serum copper speciation and quantification that addresses current limitations in live animal studies. By establishing RNCC as a reliable potential biomarker and enabling detailed copper profiling, this method enhances the precision of copper measurement and supports therapeutic monitoring. The applicability to WD research and capability of absolute quantification of copper species underscore its potential as a critical tool in clinical diagnostics and mechanistic studies, advancing the understanding and treatment of copper metabolism disorders.
{"title":"High-throughput copper speciation with SEC-UV-ICPMS: Insights from Wilson's disease mouse models","authors":"Yu Zhang , Xueqing Zhao , Beth Crowell , Heinrich Lob , Sarah Hatsell , Aris N. Economides , Evangelos Pefanis , Jikang Wu , Haibo Qiu , Ning Li","doi":"10.1016/j.aca.2026.345113","DOIUrl":"10.1016/j.aca.2026.345113","url":null,"abstract":"<div><h3>Background</h3><div>Wilson's disease (WD) is a genetic disorder caused by <em>ATP7B</em> gene mutations, impairing copper excretion and leading to toxic copper accumulation in vital organs. Inductively coupled plasma mass spectrometry (ICPMS)-based serum copper analysis has shown reliability in WD studies, with relative exchangeable copper (REC, proportion of exchangeable copper in the blood relative to the total copper) and accurate non-ceruloplasmin-bound copper (ANCC) emerging as promising biomarkers. However, challenges persist in applying these methods in live animal studies because of limited sample volumes and impractical copper specifications, necessitating alternative analytical approaches.</div></div><div><h3>Results</h3><div>This study comprehensively evaluated a size-exclusion chromatography coupled with ultraviolet (SEC-UV)-ICPMS method for precise copper speciation in mouse serum. This method effectively separated major copper-binding proteins while minimizing sample preparation and consumption. As a comparison, the direct injection-based ICPMS method was optimized to determine relative exchangeable copper (REC), and strong anion exchange (SAX)-ICPMS-based copper speciation approaches were investigated to validate the accuracy of the SEC-UV-ICPMS method, further confirming its robustness for live mouse studies. Further application to WD mouse models (ATP7B<sup>tx−J</sup>) revealed distinct copper distribution differences between diseased and healthy states. Relative non-ceruloplasmin-bound copper (RNCC) was newly identified as a promising potential biomarker, defining a diagnostic threshold of 52–58 %. By accurately quantifying copper species in mouse serum, this study established a reliable analytical framework that greatly improved our understanding of copper distribution in Wilson's disease research. Our approach demonstrated high specificity, reproducibility, and throughput, suitable for live mouse studies.</div></div><div><h3>Significance</h3><div>The SEC-UV-ICPMS platform offers a robust and efficient approach for serum copper speciation and quantification that addresses current limitations in live animal studies. By establishing RNCC as a reliable potential biomarker and enabling detailed copper profiling, this method enhances the precision of copper measurement and supports therapeutic monitoring. The applicability to WD research and capability of absolute quantification of copper species underscore its potential as a critical tool in clinical diagnostics and mechanistic studies, advancing the understanding and treatment of copper metabolism disorders.</div></div>","PeriodicalId":240,"journal":{"name":"Analytica Chimica Acta","volume":"1390 ","pages":"Article 345113"},"PeriodicalIF":6.0,"publicationDate":"2026-03-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145993301","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-03-08Epub Date: 2026-01-20DOI: 10.1016/j.aca.2026.345135
Chengyao Hou , Lijun Zhao , Runmin Kang , Qinyuan Chu , Liangkai Liu , Changwei Lei , Hongning Wang , Xin Yang
Background
Nanobodies (Nbs), single-domain antibodies derived from camelid heavy-chain antibodies, possess high stability, strong affinity, and cost-effective production, making them attractive recognition elements for bioanalytical applications. Conventional immunoassays for detecting porcine deltacoronavirus (PDCoV) antibodies often require purified antibodies, multiple reagents, and lengthy protocols, limiting their use in rapid serological surveillance. To address these challenges, a robust, simple, and sensitive assay that directly couples nanobody recognition with enzymatic signal generation is needed.
Results
We developed a nanobody-horseradish peroxidase (Nb-HRP) fusion-based competitive ELISA for rapid and sensitive detection of PDCoV antibodies. A phage display library from immunized alpacas identified five high-affinity Nbs targeting the PDCoV nucleocapsid (N) protein, with 94Nb exhibiting the highest binding activity. A stable HEK293T cell line was engineered to secrete Nb94-HRP continuously, enabling direct use in the assay without purification. The resulting ELISA achieved an operational detection limit of 1:640, defined as the highest serum dilution yielding a positive result based on the established PI cut-off value, along with high specificity against related porcine coronaviruses and excellent reproducibility (CV<10 %). Optimization of assay conditions allowed completion within 60 min. This approach eliminates the need for complex purification steps and provides a modular platform for nanobody-based antibody detection.
Significance
This Nb-enzyme fusion-based assay offers a low-cost, rapid, and highly sensitive tool for PDCoV serological surveillance, demonstrating the potential of nanobody-HRP fusions as versatile biointerfaces. Its simplicity, reproducibility, and minimal reagent requirements make it suitable for high-throughput or field-based antibody detection, providing a promising strategy for animal health diagnostics and broader bioanalytical applications.
{"title":"Nanobody-HRP fusion-based competitive immunoassay for rapid and sensitive serological detection of porcine deltacoronavirus","authors":"Chengyao Hou , Lijun Zhao , Runmin Kang , Qinyuan Chu , Liangkai Liu , Changwei Lei , Hongning Wang , Xin Yang","doi":"10.1016/j.aca.2026.345135","DOIUrl":"10.1016/j.aca.2026.345135","url":null,"abstract":"<div><h3>Background</h3><div>Nanobodies (Nbs), single-domain antibodies derived from camelid heavy-chain antibodies, possess high stability, strong affinity, and cost-effective production, making them attractive recognition elements for bioanalytical applications. Conventional immunoassays for detecting porcine deltacoronavirus (PDCoV) antibodies often require purified antibodies, multiple reagents, and lengthy protocols, limiting their use in rapid serological surveillance. To address these challenges, a robust, simple, and sensitive assay that directly couples nanobody recognition with enzymatic signal generation is needed.</div></div><div><h3>Results</h3><div>We developed a nanobody-horseradish peroxidase (Nb-HRP) fusion-based competitive ELISA for rapid and sensitive detection of PDCoV antibodies. A phage display library from immunized alpacas identified five high-affinity Nbs targeting the PDCoV nucleocapsid (N) protein, with 94Nb exhibiting the highest binding activity. A stable HEK293T cell line was engineered to secrete Nb94-HRP continuously, enabling direct use in the assay without purification. The resulting ELISA achieved an operational detection limit of 1:640, defined as the highest serum dilution yielding a positive result based on the established PI cut-off value, along with high specificity against related porcine coronaviruses and excellent reproducibility (CV<10 %). Optimization of assay conditions allowed completion within 60 min. This approach eliminates the need for complex purification steps and provides a modular platform for nanobody-based antibody detection.</div></div><div><h3>Significance</h3><div>This Nb-enzyme fusion-based assay offers a low-cost, rapid, and highly sensitive tool for PDCoV serological surveillance, demonstrating the potential of nanobody-HRP fusions as versatile biointerfaces. Its simplicity, reproducibility, and minimal reagent requirements make it suitable for high-throughput or field-based antibody detection, providing a promising strategy for animal health diagnostics and broader bioanalytical applications.</div></div>","PeriodicalId":240,"journal":{"name":"Analytica Chimica Acta","volume":"1390 ","pages":"Article 345135"},"PeriodicalIF":6.0,"publicationDate":"2026-03-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146005635","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-03-08Epub Date: 2026-01-21DOI: 10.1016/j.aca.2026.345137
Xueyong Qiao, Rongrong Yang, Zhonghui Han, Lei Lü, Xiaolei Zhao, Jinxing He
Background
The accurate, ultrasensitive, and on-site detection of pollutants is critical for public health. As a carcinogen, Sudan I is strictly forbidden from use in food products at any levels. However, the conventional method suffers from the high instrument cost and complex procedure, resulting in poor sensitivity, low portability, and long detection time. A ratiometric fluorescence sensor offers a promising prospect for the ultra-rapid, high sensitivity, visual detection, and “point-of-care” testing. The objective of this work was to address the insufficient selectivity of fluorescence probe and enhance the recognition capability and mass transfer rate while diversifying their signal output modes.
Results
In this study, a novel hollow metal-organic frameworks (MOFs) structural biomimetic nanosensor was developed for the specific recognition and rapid analysis of Sudan I. The sensor separately integrated CsPbCl1.5Br1.5 perovskite quantum dots and CdSe/ZnS quantum dots as dual-emission fluorophores into hollow MOFs-based molecularly imprinted polymers, acting as the recognition element and a signal carrier. The hollow architecture significantly improved mass transfer efficiency, reducing response time to 10 min. The developed nanosensor in instrumental analysis mode exhibited a linearity within the range of 2.00–200.00 μg L−1 at a method's detection limit of 1.00 μg L−1, indicating high accuracy with recoveries of 88.00–109.65 % in real samples. Furthermore, a smartphone-based portable platform was designed for on-site intelligence detection with a good linear range (0.15–5.00 μg mL−1), a method's detection limit of 0.05 μg mL−1, and recoveries ranging from 80.20 % to 109.00 %, allowing for real-time quantitative monitoring of Sudan I.
Significance
This study employs hollow MOFs as support materials for in-situ growth of the imprinting layer, ensuring high adsorption capability and rapid binding. The successful implementation of two detection modes provides a comprehensive solution from laboratory precision to field application. Particularly, the portable sensing system enables real-time and on-site quantitative monitoring. This work exhibits the significant potential for the high-performance chemical sensing and point-of-care detection of food contaminants.
{"title":"Hollow MOFs-based biomimetic encoded microspheres as versatile probes for dual-mode ratiometric fluorescence sensing platform coupling instrumental and smartphone-assisted analysis of Sudan I","authors":"Xueyong Qiao, Rongrong Yang, Zhonghui Han, Lei Lü, Xiaolei Zhao, Jinxing He","doi":"10.1016/j.aca.2026.345137","DOIUrl":"10.1016/j.aca.2026.345137","url":null,"abstract":"<div><h3>Background</h3><div>The accurate, ultrasensitive, and on-site detection of pollutants is critical for public health. As a carcinogen, Sudan I is strictly forbidden from use in food products at any levels. However, the conventional method suffers from the high instrument cost and complex procedure, resulting in poor sensitivity, low portability, and long detection time. A ratiometric fluorescence sensor offers a promising prospect for the ultra-rapid, high sensitivity, visual detection, and “point-of-care” testing. The objective of this work was to address the insufficient selectivity of fluorescence probe and enhance the recognition capability and mass transfer rate while diversifying their signal output modes.</div></div><div><h3>Results</h3><div>In this study, a novel hollow metal-organic frameworks (MOFs) structural biomimetic nanosensor was developed for the specific recognition and rapid analysis of Sudan I. The sensor separately integrated CsPbCl<sub>1.5</sub>Br<sub>1.5</sub> perovskite quantum dots and CdSe/ZnS quantum dots as dual-emission fluorophores into hollow MOFs-based molecularly imprinted polymers, acting as the recognition element and a signal carrier. The hollow architecture significantly improved mass transfer efficiency, reducing response time to 10 min. The developed nanosensor in instrumental analysis mode exhibited a linearity within the range of 2.00–200.00 μg L<sup>−1</sup> at a method's detection limit of 1.00 μg L<sup>−1</sup>, indicating high accuracy with recoveries of 88.00–109.65 % in real samples. Furthermore, a smartphone-based portable platform was designed for on-site intelligence detection with a good linear range (0.15–5.00 μg mL<sup>−1</sup>), a method's detection limit of 0.05 μg mL<sup>−1</sup>, and recoveries ranging from 80.20 % to 109.00 %, allowing for real-time quantitative monitoring of Sudan I.</div></div><div><h3>Significance</h3><div>This study employs hollow MOFs as support materials for in-situ growth of the imprinting layer, ensuring high adsorption capability and rapid binding. The successful implementation of two detection modes provides a comprehensive solution from laboratory precision to field application. Particularly, the portable sensing system enables real-time and on-site quantitative monitoring. This work exhibits the significant potential for the high-performance chemical sensing and point-of-care detection of food contaminants.</div></div>","PeriodicalId":240,"journal":{"name":"Analytica Chimica Acta","volume":"1390 ","pages":"Article 345137"},"PeriodicalIF":6.0,"publicationDate":"2026-03-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146014761","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-03-08Epub Date: 2026-01-19DOI: 10.1016/j.aca.2026.345130
Nannan Ma , Qilin Liu , Nianyang Cai , Fangfang Zhu , Ning Gan , Zhenzhong Yu
Background
Laser-induced graphene (LIG) technology has demonstrated considerable promise for the fabrication of wearable electrochemical sensing devices. However, the pristine LIG typically exhibits suboptimal electrochemical performance, often necessitating heteroatom doping to enhance its functionality. Among these strategies, metal doping has proven particularly effective in significantly boosting sensing capabilities. Conventional doping approaches, however, are frequently hampered by cumbersome pretreatment procedures or weak metal-graphene interfacial interaction, thereby restricting their practical efficacy. Therefore, novel synthetic methodologies are urgently needed for efficient metal-doped LIG fabrication.
Results
This study developed an in-situ laser-induced metal-doped graphene (M-LIG, M = Fe, Co, Ni, Cu) fabrication method. It involved plasma-treating polyimide films to introduce hydrophilic groups for metal ion adsorption, followed by CO2 laser irradiation that achieved atomic-scale metal doping during graphene formation. A systematic investigation of preparation parameters and metal dopant types revealed their significant effects on the morphology, structure, and electrochemical performance of the resulting LIG. These materials were used to construct a portable electrochemical detection system for highly sensitive uric acid monitoring in sweat. Results showed that M-LIG sensors outperformed pristine LIG, with Ni-LIG exhibiting optimal performance of a 10.6-fold reduction in detection limit and a 5-fold enhancement in the upper linear detection range. Density functional theory calculations indicated that Ni active sites played a crucial role in enhancing sensing performance by facilitating analyte adsorption and electron transfer.
Significance
This study presents a universal fabrication strategy for M-LIG, which significantly streamlines the preparation process of LIG and enhances its sensing performance. Demonstrating broad application prospects in electrode surface engineering for wearable electrochemical biosensors, this approach paves a new avenue for the development of advanced devices aimed at precise personalized health monitoring.
激光诱导石墨烯（LIG）技术在制造可穿戴电化学传感器件方面已经显示出相当大的前景。然而，原始的LIG通常表现出不理想的电化学性能，通常需要杂原子掺杂来增强其功能。在这些策略中，金属掺杂已被证明在显著提高传感能力方面特别有效。然而，传统的掺杂方法经常受到繁琐的预处理程序或弱金属-石墨烯界面相互作用的阻碍，从而限制了它们的实际效果。因此，迫切需要新的合成方法来制备高效的金属掺杂LIG。结果本研究开发了一种原位激光诱导金属掺杂石墨烯（M- lig, M = Fe, Co, Ni, Cu）制备方法。它包括等离子体处理聚酰亚胺薄膜以引入亲水基团以吸附金属离子，然后通过CO2激光照射在石墨烯形成过程中实现原子尺度的金属掺杂。系统地研究了制备参数和金属掺杂类型，揭示了它们对所得LIG的形貌、结构和电化学性能的显著影响。利用这些材料构建了一种便携式电化学检测系统，用于汗液中尿酸的高灵敏度监测。结果表明，M-LIG传感器优于原始LIG传感器，其中Ni-LIG传感器表现出最佳性能，检测限降低10.6倍，线性检测范围提高5倍。密度泛函理论计算表明，Ni活性位点通过促进分析物的吸附和电子转移，在提高传感性能方面起着至关重要的作用。本研究提出了一种通用的M-LIG制备策略，大大简化了LIG的制备过程，提高了其传感性能。该方法在可穿戴电化学生物传感器的电极表面工程中具有广阔的应用前景，为开发以精确个性化健康监测为目标的先进设备开辟了新的途径。
{"title":"In-situ laser-induced metal (M = Fe, Co, Ni, Cu)-doped graphene electrode for sensitive uric acid sensing in sweat","authors":"Nannan Ma , Qilin Liu , Nianyang Cai , Fangfang Zhu , Ning Gan , Zhenzhong Yu","doi":"10.1016/j.aca.2026.345130","DOIUrl":"10.1016/j.aca.2026.345130","url":null,"abstract":"<div><h3>Background</h3><div>Laser-induced graphene (LIG) technology has demonstrated considerable promise for the fabrication of wearable electrochemical sensing devices. However, the pristine LIG typically exhibits suboptimal electrochemical performance, often necessitating heteroatom doping to enhance its functionality. Among these strategies, metal doping has proven particularly effective in significantly boosting sensing capabilities. Conventional doping approaches, however, are frequently hampered by cumbersome pretreatment procedures or weak metal-graphene interfacial interaction, thereby restricting their practical efficacy. Therefore, novel synthetic methodologies are urgently needed for efficient metal-doped LIG fabrication.</div></div><div><h3>Results</h3><div>This study developed an <em>in-situ</em> laser-induced metal-doped graphene (M-LIG, M = Fe, Co, Ni, Cu) fabrication method. It involved plasma-treating polyimide films to introduce hydrophilic groups for metal ion adsorption, followed by CO<sub>2</sub> laser irradiation that achieved atomic-scale metal doping during graphene formation. A systematic investigation of preparation parameters and metal dopant types revealed their significant effects on the morphology, structure, and electrochemical performance of the resulting LIG. These materials were used to construct a portable electrochemical detection system for highly sensitive uric acid monitoring in sweat. Results showed that M-LIG sensors outperformed pristine LIG, with Ni-LIG exhibiting optimal performance of a 10.6-fold reduction in detection limit and a 5-fold enhancement in the upper linear detection range. Density functional theory calculations indicated that Ni active sites played a crucial role in enhancing sensing performance by facilitating analyte adsorption and electron transfer.</div></div><div><h3>Significance</h3><div>This study presents a universal fabrication strategy for M-LIG, which significantly streamlines the preparation process of LIG and enhances its sensing performance. Demonstrating broad application prospects in electrode surface engineering for wearable electrochemical biosensors, this approach paves a new avenue for the development of advanced devices aimed at precise personalized health monitoring.</div></div>","PeriodicalId":240,"journal":{"name":"Analytica Chimica Acta","volume":"1390 ","pages":"Article 345130"},"PeriodicalIF":6.0,"publicationDate":"2026-03-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146001444","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-03-08Epub Date: 2025-12-29DOI: 10.1016/j.aca.2025.345044
Lorenzo Sanjuan-Navarro , Juan Luís Benedé , Soledad Rubio , Carlos Moreno , Verónica Pino , Francisco Javier Pena-Pereira , Yolanda Moliner-Martínez
Background
The use of current metric tools for sample preparation has proven highly valuable in identifying the strengths and weaknesses of various analytical approaches. However, as Analytical Sciences increasingly move towards sustainability, it becomes evident that existing metrics may not fully cover all the dimensions required for a comprehensive assessment.
Results
An overview to encourage the evolution towards more advanced metric tools for sample preparation by reflecting on which parameters should be evaluated and on the principles that ought to guide their design. The tutorial highlights the need for new or improved metrics capable and identify the most relevant criteria and how they can be integrated.
The discussion is particularly focused in the context of miniaturization and the development of new extractive materials. Through case studies, solvents and sorbents are examined using analytical performance, green, and market-related criteria, emphasizing the importance of integrating these perspectives into future tools. Solid-phase (SPME) and liquid-phase microextraction (LPME) are evaluated using the metric tools currently available, pointing out the challenges associated with the application. The results reveal the need to advance towards more advanced metric tools contextualizing the outcomes within the complexity of the analytical problem.
Significance and novelty
This manuscript highlight the need to advance metric tools towards models capable of integrating environmental, analytical, and practical dimensions within a coherent sustainability-oriented framework. The tutorial offers guidance for researchers and developers aiming to create more effective tools for the design and evaluation of sample preparation methods, tools that not only address greenness but also deliver greater robustness, relevance, and applicability in real analytical scenarios.
{"title":"A tutorial on developing metric tools for sample preparation: from green towards sustainable","authors":"Lorenzo Sanjuan-Navarro , Juan Luís Benedé , Soledad Rubio , Carlos Moreno , Verónica Pino , Francisco Javier Pena-Pereira , Yolanda Moliner-Martínez","doi":"10.1016/j.aca.2025.345044","DOIUrl":"10.1016/j.aca.2025.345044","url":null,"abstract":"<div><h3>Background</h3><div>The use of current metric tools for sample preparation has proven highly valuable in identifying the strengths and weaknesses of various analytical approaches. However, as Analytical Sciences increasingly move towards sustainability, it becomes evident that existing metrics may not fully cover all the dimensions required for a comprehensive assessment.</div></div><div><h3>Results</h3><div>An overview to encourage the evolution towards more advanced metric tools for sample preparation by reflecting on which parameters should be evaluated and on the principles that ought to guide their design. The tutorial highlights the need for new or improved metrics capable and identify the most relevant criteria and how they can be integrated.</div><div>The discussion is particularly focused in the context of miniaturization and the development of new extractive materials. Through case studies, solvents and sorbents are examined using analytical performance, green, and market-related criteria, emphasizing the importance of integrating these perspectives into future tools. Solid-phase (SPME) and liquid-phase microextraction (LPME) are evaluated using the metric tools currently available, pointing out the challenges associated with the application. The results reveal the need to advance towards more advanced metric tools contextualizing the outcomes within the complexity of the analytical problem.</div></div><div><h3>Significance and novelty</h3><div>This manuscript highlight the need to advance metric tools towards models capable of integrating environmental, analytical, and practical dimensions within a coherent sustainability-oriented framework. The tutorial offers guidance for researchers and developers aiming to create more effective tools for the design and evaluation of sample preparation methods, tools that not only address greenness but also deliver greater robustness, relevance, and applicability in real analytical scenarios.</div></div>","PeriodicalId":240,"journal":{"name":"Analytica Chimica Acta","volume":"1390 ","pages":"Article 345044"},"PeriodicalIF":6.0,"publicationDate":"2026-03-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146123187","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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