The sensitive detection of hydrogen peroxide is important for many applications, including biomedical diagnostics and environmental monitoring. In this work, we report a simple turn-on fluorescent platform based on conjugated polyelectrolytes (CPEs), specifically poly[5-methoxy-2-(3-sulfopropoxy)-1,4-phenylenevinylene] (MPS-PPV), complexed with polyvinylpyrrolidone (PVP) for the detection of hydrogen peroxide (H2O2). MPS-PPV alone exhibits weak fluorescence enhancement in response to the incremental addition of H2O2. However, when PVP is added, a sixfold increase in fluorescence is observed. Mechanistically, this enhancement is attributed to the dual role of PVP: (1) its complexation with hydrogen peroxide increases the local oxidant concentration, promoting oxidative attack on the CPE backbone, and (2) it stabilizes the resulting oxidized polymers, thus reducing aggregation and enhancing their emission. Changes in the ionic strength further confirm that the CPE conformation and its complexation with PVP are key to the observed fluorescence enhancement. Time-resolved fluorescence measurements in the presence of ascorbic acid, a radical scavenger, demonstrate that hydroxyl radicals are the active species responsible for the sensing response. Finally, as a proof of concept, the sensor was successfully applied to the enzymatic detection of glucose, enabling quantitative detection over a physiologically relevant range (3.5-10.5 mM). This work demonstrates how microenvironmental control of conjugated polyelectrolytes can play a critical role in developing CPE-based fluorescent sensors and enhancing their sensitivity.
{"title":"Microenvironment-mediated oxidative enhancement of conjugated polyelectrolytes for the detection of hydrogen peroxide.","authors":"Kareem Alhafi,Pierre Karam","doi":"10.1039/d5an01257k","DOIUrl":"https://doi.org/10.1039/d5an01257k","url":null,"abstract":"The sensitive detection of hydrogen peroxide is important for many applications, including biomedical diagnostics and environmental monitoring. In this work, we report a simple turn-on fluorescent platform based on conjugated polyelectrolytes (CPEs), specifically poly[5-methoxy-2-(3-sulfopropoxy)-1,4-phenylenevinylene] (MPS-PPV), complexed with polyvinylpyrrolidone (PVP) for the detection of hydrogen peroxide (H2O2). MPS-PPV alone exhibits weak fluorescence enhancement in response to the incremental addition of H2O2. However, when PVP is added, a sixfold increase in fluorescence is observed. Mechanistically, this enhancement is attributed to the dual role of PVP: (1) its complexation with hydrogen peroxide increases the local oxidant concentration, promoting oxidative attack on the CPE backbone, and (2) it stabilizes the resulting oxidized polymers, thus reducing aggregation and enhancing their emission. Changes in the ionic strength further confirm that the CPE conformation and its complexation with PVP are key to the observed fluorescence enhancement. Time-resolved fluorescence measurements in the presence of ascorbic acid, a radical scavenger, demonstrate that hydroxyl radicals are the active species responsible for the sensing response. Finally, as a proof of concept, the sensor was successfully applied to the enzymatic detection of glucose, enabling quantitative detection over a physiologically relevant range (3.5-10.5 mM). This work demonstrates how microenvironmental control of conjugated polyelectrolytes can play a critical role in developing CPE-based fluorescent sensors and enhancing their sensitivity.","PeriodicalId":63,"journal":{"name":"Analyst","volume":"53 1","pages":""},"PeriodicalIF":4.2,"publicationDate":"2026-03-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147350604","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Olaparib (Lynparza®) is a highly selective poly(ADP-ribose) polymerase (PARP) inhibitor used in the advanced treatment of ovarian, breast, and prostate cancers. An effective, environmentally friendly, rapid, and reliable UPLC-MS/MS method was established to quantify OLA in human liver microsomes (HLMs) and was used to evaluate the in vitro metabolic stability of OLA. The UPLC-MS/MS method was validated in accordance with the US-FDA bioanalytical method validation standards. The current UPLC-MS/MS method showed a high degree of greenness, as evidenced by a ComplexMoGAPI value of 66.0 and an AGREEprep tool value of 0.63. The StarDrop software package (WhichP450 and DEREK modules) was used to assess metabolic lability and characterize in silico alerts regarding the OLA chemical structure. The current UPLC-MS/MS method showed a linearity range of 1 to 4000 ng mL-1, ultra-fast separation in 1 min, and exhibited precision and accuracy unaffected by HLMs. Chromatographic separation of OLA and dasatinib (internal standard) was performed using a reversed-phase Eclipse Plus 1.8 µm C8 column (50 mm × 2.1 mm), with the mobile phase consisting of 0.1% HCOOH in water (pH 3.2) at 60% and 0.1% HCOOH in ACN (40%). The intra- and inter-day evaluations of the accuracy and precision of the UPLC-MS/MS approach ranged from 0.79% to 11.67% and -0.86% to 10.33%, respectively. The in vitro half-life (t1/2) of OLA was 43.7 min, and its intrinsic clearance (Clint) was 18.55 mL min-1 kg-1, confirming the low metabolic clearance (high metabolic stability). In silico studies suggest that minor structural modifications of the phthalazin-1-one (52%) and piperazine (24%) moieties during drug design may improve the safety profile and metabolic stability of new derivatives compared with OLA; however, experimental confirmation is needed.
Olaparib （Lynparza®）是一种高选择性聚（adp -核糖）聚合酶（PARP）抑制剂，用于卵巢癌、乳腺癌和前列腺癌的晚期治疗。建立了一种高效、环保、快速、可靠的hplc -MS/MS定量人肝微粒体（HLMs）中OLA的方法，并用于评价OLA的体外代谢稳定性。UPLC-MS/MS方法按照美国fda生物分析方法验证标准进行验证。目前UPLC-MS/MS方法的ComplexMoGAPI值为66.0，AGREEprep工具值为0.63，绿色度较高。StarDrop软件包（其中p450和DEREK模块）用于评估代谢不稳定性和表征有关OLA化学结构的硅警报。该方法线性范围为1 ~ 4000 ng mL-1，在1 min内实现超快速分离，精密度和准确度不受HLMs的影响。OLA和达沙替尼（内标）采用反相Eclipse Plus 1.8µm C8色谱柱（50 mm × 2.1 mm）进行色谱分离，流动相为0.1% HCOOH在60%的水（pH 3.2）和0.1% HCOOH在ACN（40%）中。UPLC-MS/MS方法的日内、日间准确度和精密度评价范围分别为0.79% ~ 11.67%和-0.86% ~ 10.33%。体外半衰期（t1/2）为43.7 min，内在清除率（Clint）为18.55 mL min-1 kg-1，具有低代谢清除率（高代谢稳定性）。硅研究表明，与OLA相比，在药物设计过程中对酞菁-1- 1（52%）和哌嗪（24%）部分进行轻微的结构修饰可能会提高新衍生物的安全性和代谢稳定性；然而，还需要实验证实。
{"title":"Quantification of olaparib in human liver microsomes using an ultra-fast UPLC-MS/MS quantitative approach: in vitro and in silico metabolic stability assessment.","authors":"Mohamed W Attwa,Haitham AlRabiah,Adnan A Kadi","doi":"10.1039/d6an00077k","DOIUrl":"https://doi.org/10.1039/d6an00077k","url":null,"abstract":"Olaparib (Lynparza®) is a highly selective poly(ADP-ribose) polymerase (PARP) inhibitor used in the advanced treatment of ovarian, breast, and prostate cancers. An effective, environmentally friendly, rapid, and reliable UPLC-MS/MS method was established to quantify OLA in human liver microsomes (HLMs) and was used to evaluate the in vitro metabolic stability of OLA. The UPLC-MS/MS method was validated in accordance with the US-FDA bioanalytical method validation standards. The current UPLC-MS/MS method showed a high degree of greenness, as evidenced by a ComplexMoGAPI value of 66.0 and an AGREEprep tool value of 0.63. The StarDrop software package (WhichP450 and DEREK modules) was used to assess metabolic lability and characterize in silico alerts regarding the OLA chemical structure. The current UPLC-MS/MS method showed a linearity range of 1 to 4000 ng mL-1, ultra-fast separation in 1 min, and exhibited precision and accuracy unaffected by HLMs. Chromatographic separation of OLA and dasatinib (internal standard) was performed using a reversed-phase Eclipse Plus 1.8 µm C8 column (50 mm × 2.1 mm), with the mobile phase consisting of 0.1% HCOOH in water (pH 3.2) at 60% and 0.1% HCOOH in ACN (40%). The intra- and inter-day evaluations of the accuracy and precision of the UPLC-MS/MS approach ranged from 0.79% to 11.67% and -0.86% to 10.33%, respectively. The in vitro half-life (t1/2) of OLA was 43.7 min, and its intrinsic clearance (Clint) was 18.55 mL min-1 kg-1, confirming the low metabolic clearance (high metabolic stability). In silico studies suggest that minor structural modifications of the phthalazin-1-one (52%) and piperazine (24%) moieties during drug design may improve the safety profile and metabolic stability of new derivatives compared with OLA; however, experimental confirmation is needed.","PeriodicalId":63,"journal":{"name":"Analyst","volume":"245 1","pages":""},"PeriodicalIF":4.2,"publicationDate":"2026-03-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147350813","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
There is a growing demand for the continuous monitoring of residual chlorine for water-circulating cooling facilities to remotely maintain concentrations within an appropriate range. This study aims to develop a lightweight, low-cost, and wireless water quality monitor. We further propose a highly simplified and miniaturized configuration based on a wet chemical analysis method, which combines a liquid delivery mechanism driven by water head pressure rather than a highprecision pump with a low-power latch valve. Furthermore, to prevent fluctuations in flow path resistance, we adopted a glass-made mixing and reaction flow path device fabricated using imprint processing, which offers excellent surface smoothness and high rigidity. The evaluation results demonstrated that this monitor's flow system achieves highly stable flow behaviour while reducing reagent consumption to less than 1/10 (a few μL per measurement). Under this stable flow condition, we confirmed sufficient analytical performance for residual chlorine rate of cooling water. Furthermore, in a demonstration test using a small-scale circulating cooling unit, we confirmed that the signal response of the monitor was perfectly synchronized with changes in chlorine concentration following periodic additions at 60-min intervals. Consequently, a super-lightweight, extremely low-cost, and fully wireless water quality monitor is ready to use.
{"title":"Super-lightweight, Low-cost and Wireless Water Quality Monitor for Remote Chlorine-rate Management in Water-circulating Cooling Facilities","authors":"Masayuki Kawakami, Toshihiro Kasama, TOMOMI SATO, Hidekatsu Tazawa, Daisaku Yano, Madoka Takai, Ryo Miyake","doi":"10.1039/d6an00029k","DOIUrl":"https://doi.org/10.1039/d6an00029k","url":null,"abstract":"There is a growing demand for the continuous monitoring of residual chlorine for water-circulating cooling facilities to remotely maintain concentrations within an appropriate range. This study aims to develop a lightweight, low-cost, and wireless water quality monitor. We further propose a highly simplified and miniaturized configuration based on a wet chemical analysis method, which combines a liquid delivery mechanism driven by water head pressure rather than a highprecision pump with a low-power latch valve. Furthermore, to prevent fluctuations in flow path resistance, we adopted a glass-made mixing and reaction flow path device fabricated using imprint processing, which offers excellent surface smoothness and high rigidity. The evaluation results demonstrated that this monitor's flow system achieves highly stable flow behaviour while reducing reagent consumption to less than 1/10 (a few μL per measurement). Under this stable flow condition, we confirmed sufficient analytical performance for residual chlorine rate of cooling water. Furthermore, in a demonstration test using a small-scale circulating cooling unit, we confirmed that the signal response of the monitor was perfectly synchronized with changes in chlorine concentration following periodic additions at 60-min intervals. Consequently, a super-lightweight, extremely low-cost, and fully wireless water quality monitor is ready to use.","PeriodicalId":63,"journal":{"name":"Analyst","volume":"68 1","pages":""},"PeriodicalIF":4.2,"publicationDate":"2026-03-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147358933","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Afef Dhaffouli, Pedro Ángel Salazar Carballo, Soledad Carinelli, Livia Florio Sgobbi, Adam Slabon, Bruno V.M. Rodrigues
We report a green and scalable strategy to engineer a next-generation dopamine (DA) sensor using copper-based nanoparticles (NPs) on activated carbon derived from juniper seeds and functionalized with ethylenediamine (Cu@AC-CONH-CH2CH2-NH2). The carbon matrix, enriched with uniformly dispersed Cu-based NPs and surface-anchored amine groups, delivers abundant catalytic sites, accelerated electron transfer, and exceptional sensitivity. Differential pulse voltammetry revealed three broad linear ranges for DA (0.0015–1 µM, R2 ≥ 0.991), an ultralow limit of detection (LOD) of 1.4 nM, a limit of quantification (LOQ) of 4.7 nM, and a high sensitivity of 92.3 µA·µM-1. The electrode exhibited remarkable anti-interference performance against uric acid, ascorbic acid, and urea, ensuring reliable DA quantification even in complex biological environments. Real-sample analysis yielded recoveries of 90.08–106.80%, demonstrating its clinical relevance. This environmentally friendly, low-cost, and high-performance Cu@AC-CONH-CH2CH2-NH2 composite provides a powerful platform for non-enzymatic dopamine sensing, offering a sustainable route toward practical diagnostics and environmental monitoring.
{"title":"Juniper-Based Cu@Activated Carbon Functionalized with Ethylenediamine: A Green Platform for Non-Enzymatic Detection of Dopamine","authors":"Afef Dhaffouli, Pedro Ángel Salazar Carballo, Soledad Carinelli, Livia Florio Sgobbi, Adam Slabon, Bruno V.M. Rodrigues","doi":"10.1039/d5an01141h","DOIUrl":"https://doi.org/10.1039/d5an01141h","url":null,"abstract":"We report a green and scalable strategy to engineer a next-generation dopamine (DA) sensor using copper-based nanoparticles (NPs) on activated carbon derived from juniper seeds and functionalized with ethylenediamine (Cu@AC-CONH-CH2<small><sub></sub></small>CH2<small><sub></sub></small>-NH2<small><sub></sub></small>). The carbon matrix, enriched with uniformly dispersed Cu-based NPs and surface-anchored amine groups, delivers abundant catalytic sites, accelerated electron transfer, and exceptional sensitivity. Differential pulse voltammetry revealed three broad linear ranges for DA (0.0015–1 µM, R2<small><sup></sup></small> ≥ 0.991), an ultralow limit of detection (LOD) of 1.4 nM, a limit of quantification (LOQ) of 4.7 nM, and a high sensitivity of 92.3 µA·µM-1<small><sup></sup></small>. The electrode exhibited remarkable anti-interference performance against uric acid, ascorbic acid, and urea, ensuring reliable DA quantification even in complex biological environments. Real-sample analysis yielded recoveries of 90.08–106.80%, demonstrating its clinical relevance. This environmentally friendly, low-cost, and high-performance Cu@AC-CONH-CH2<small><sub></sub></small>CH2<small><sub></sub></small>-NH2<small><sub></sub></small> composite provides a powerful platform for non-enzymatic dopamine sensing, offering a sustainable route toward practical diagnostics and environmental monitoring.","PeriodicalId":63,"journal":{"name":"Analyst","volume":"36 1","pages":""},"PeriodicalIF":4.2,"publicationDate":"2026-03-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147329943","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Spontaneous hypertension (SH) is a prevalent chronic cardiovascular disorder characterized by the synergistic elevation of hydrogen peroxide (H2O2) levels and tyrosine hydroxylase (TH) activity in the brainstem nucleus tractus solitarius (NTS). Traditional detection techniques lack the specificity and spatiotemporal resolution to monitor the dynamic interplay of these two core pathological biomarkers, hindering the in-depth exploration of SH pathogenesis. Herein, a series of novel cascade-activated fluorescent probes (PPTHs) were rationally designed and synthesized based on a purine core, which achieve specific fluorescence responses only upon sequential activation by H2O2 and TH. In vitro assays demonstrated that the probes exhibited high sensitivity toward H2O2 in SH-SY5Y cell lysates, with a reliable limit of detection (LOD) and ideal anti-interference capability. Live-cell imaging further confirmed that purine-based molecules not only successfully mitigated probe adsorption on the cell membrane but also effectively improved the imaging signal-to-noise (S/N) ratio. Notably, PPTH-2-assisted confocal imaging clearly distinguished the differential fluorescence signals between normotensive control and SHR groups, which correlated with endogenous H2O2 level and TH activity in the NTS region. Our study presents a robust fluorescent probe platform for the synchronous detection of H2O2 and TH, offering a promising molecular tool for the early diagnosis and elucidation of the pathological mechanisms of SH.
{"title":"Sequentially activated fluorescent probes based on a purine scaffold: enabling precise spatiotemporal monitoring of H2O2 and tyrosine hydroxylase in the brainstem NTS during spontaneous hypertension.","authors":"Yang Yu,Jia-Yi Yao,Xiao-Qi Yu,Kun Li,Kang-Kang Yu","doi":"10.1039/d6an00124f","DOIUrl":"https://doi.org/10.1039/d6an00124f","url":null,"abstract":"Spontaneous hypertension (SH) is a prevalent chronic cardiovascular disorder characterized by the synergistic elevation of hydrogen peroxide (H2O2) levels and tyrosine hydroxylase (TH) activity in the brainstem nucleus tractus solitarius (NTS). Traditional detection techniques lack the specificity and spatiotemporal resolution to monitor the dynamic interplay of these two core pathological biomarkers, hindering the in-depth exploration of SH pathogenesis. Herein, a series of novel cascade-activated fluorescent probes (PPTHs) were rationally designed and synthesized based on a purine core, which achieve specific fluorescence responses only upon sequential activation by H2O2 and TH. In vitro assays demonstrated that the probes exhibited high sensitivity toward H2O2 in SH-SY5Y cell lysates, with a reliable limit of detection (LOD) and ideal anti-interference capability. Live-cell imaging further confirmed that purine-based molecules not only successfully mitigated probe adsorption on the cell membrane but also effectively improved the imaging signal-to-noise (S/N) ratio. Notably, PPTH-2-assisted confocal imaging clearly distinguished the differential fluorescence signals between normotensive control and SHR groups, which correlated with endogenous H2O2 level and TH activity in the NTS region. Our study presents a robust fluorescent probe platform for the synchronous detection of H2O2 and TH, offering a promising molecular tool for the early diagnosis and elucidation of the pathological mechanisms of SH.","PeriodicalId":63,"journal":{"name":"Analyst","volume":"37 1","pages":""},"PeriodicalIF":4.2,"publicationDate":"2026-03-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147329646","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
The inherently weak Raman signals from molecules with small scattering cross-sections pose a significant challenge for surface-enhanced Raman scattering (SERS), a technique that is further limited by its reliance on costly precious metal substrates and exogenous labeling strategies. To address these limitations, this study constructs a Ti3C2-CoFe2O4 heterostructure by anchoring oxidase (OXD)-like CoFe2O4 nanoparticles (NPs) on two-dimensional (2D) conductive Ti3C2 MXene nanosheets. The resulting interface forms a Mott-Schottky junction, which facilitates rapid charge transfer and synergistically enhances both catalytic and SERS performance. Structurally, the 2D Ti3C2 framework provides abundant anchoring sites for the uniform dispersion of CoFe2O4 NPs. This effectively prevents particle aggregation and maximizes the exposure of catalytic active sites, thereby enhancing both stability and catalytic activity. Additionally, the Ti3C2-CoFe2O4 heterojunction effectively suppresses the recombination of charge carriers and promotes the separation of photogenerated charges, generating abundant superoxide anion radicals that oxidize 3,3',5,5'-tetramethylbenzidine (TMB) for catalytic signal amplification. Therefore, the ingenious combination of nanozymes and SERS technology enables the generation of SERS-active reporters via nanozyme-catalyzed reactions, thus avoiding the need for external labeling modifications. The strategy simultaneously enhances Raman signals through the synergistic effect of photoinduced charge transfer and localized surface plasmon resonance. This Ti3C2-CoFe2O4 heterojunction exhibits integrated OXD-like activity and SERS enhancement, enabling sensitive glutathione (GSH) detection in human serum samples. Through catalytic oxidation of TMB to oxidized TMB, a distinct Raman peak emerges at 1615 cm-1, with its intensity reduction quantitatively correlating with GSH concentration via competitive reactive oxygen species scavenging. Quantitative analysis demonstrates a linear response range of 0.50-200 μmol L-1 and a detection limit of 0.073 μmol L-1, with serum sample recoveries ranging from 94.7%-115%. This study provides a paradigm for designing non-precious metal nanozyme materials with integrated catalytic and SERS capabilities, demonstrating significant potential for practical applications in clinical diagnostics and biosensing.
{"title":"Heterojunction-engineered two-dimensional Ti3C2-CoFe2O4 nanozyme with oxidase-like activity for SERS detection of glutathione in human serum.","authors":"Huiqi Zhu,Ying Chen,Weiqing Yang,Zunxiang Zeng,Yuling Hu,Ji Zhang","doi":"10.1039/d6an00055j","DOIUrl":"https://doi.org/10.1039/d6an00055j","url":null,"abstract":"The inherently weak Raman signals from molecules with small scattering cross-sections pose a significant challenge for surface-enhanced Raman scattering (SERS), a technique that is further limited by its reliance on costly precious metal substrates and exogenous labeling strategies. To address these limitations, this study constructs a Ti3C2-CoFe2O4 heterostructure by anchoring oxidase (OXD)-like CoFe2O4 nanoparticles (NPs) on two-dimensional (2D) conductive Ti3C2 MXene nanosheets. The resulting interface forms a Mott-Schottky junction, which facilitates rapid charge transfer and synergistically enhances both catalytic and SERS performance. Structurally, the 2D Ti3C2 framework provides abundant anchoring sites for the uniform dispersion of CoFe2O4 NPs. This effectively prevents particle aggregation and maximizes the exposure of catalytic active sites, thereby enhancing both stability and catalytic activity. Additionally, the Ti3C2-CoFe2O4 heterojunction effectively suppresses the recombination of charge carriers and promotes the separation of photogenerated charges, generating abundant superoxide anion radicals that oxidize 3,3',5,5'-tetramethylbenzidine (TMB) for catalytic signal amplification. Therefore, the ingenious combination of nanozymes and SERS technology enables the generation of SERS-active reporters via nanozyme-catalyzed reactions, thus avoiding the need for external labeling modifications. The strategy simultaneously enhances Raman signals through the synergistic effect of photoinduced charge transfer and localized surface plasmon resonance. This Ti3C2-CoFe2O4 heterojunction exhibits integrated OXD-like activity and SERS enhancement, enabling sensitive glutathione (GSH) detection in human serum samples. Through catalytic oxidation of TMB to oxidized TMB, a distinct Raman peak emerges at 1615 cm-1, with its intensity reduction quantitatively correlating with GSH concentration via competitive reactive oxygen species scavenging. Quantitative analysis demonstrates a linear response range of 0.50-200 μmol L-1 and a detection limit of 0.073 μmol L-1, with serum sample recoveries ranging from 94.7%-115%. This study provides a paradigm for designing non-precious metal nanozyme materials with integrated catalytic and SERS capabilities, demonstrating significant potential for practical applications in clinical diagnostics and biosensing.","PeriodicalId":63,"journal":{"name":"Analyst","volume":"19 1","pages":""},"PeriodicalIF":4.2,"publicationDate":"2026-03-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147329647","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Historical production of per- and polyfluoroalkyl substances (PFAS) via electrochemical fluorination has resulted in complex mixtures of linear (L) and branched (Br) isomers, yet most environmental studies still treat them as single compounds. Emerging research highlights that isomer-specific differences critically shape PFAS environmental fate, bioaccumulation, and toxicity. These distinctions are particularly critical for aquatic organisms, which experience continuous exposure to PFAS and serve as sentinels of ecosystem health. A comprehensive review of literature from January 2000 to December 2025 reveals that most studies on PFAS in aquatic species overlook isomer resolution, constraining insights into mixture behavior. The relatively few studies that report isomer profiles across fish, sharks, marine mammals, aquatic insects, seabirds, alligators, and polar bears primarily focus on PFOS (perfluorooctane sulfonic acid), leaving substantial knowledge gaps for other PFAS classes. Evidence also indicates that precursor compositions strongly influence isomer-specific bioaccumulation; several studies show that L-isomers tend to bioaccumulate more than their Br counterparts, suggesting potential differences in environmental stability and metabolism. Advancing knowledge on PFAS isomer distribution requires broader use of orthogonal separation techniques. Ion mobility spectrometry can resolve L- and Br-isomers based on differences in their collision cross-sections. Other techniques that can separate L- and Br-isomers include gas chromatography/mass spectrometry with derivatization, and supercritical fluid chromatography/mass spectrometry, capable of efficient separation of isomers based on differences in partition coefficients between two phases. Integrating these techniques into current conventional PFAS analytical methods is essential for uncovering the PFAS structure-environmental behavior and for enhancing future ecological risk assessments.
{"title":"PFAS isomers in aquatic biota: revealing differences in occurrence, bioaccumulation, and biotransformation through isomer-specific analysis.","authors":"Mindula K Wijayahena,Diana S Aga","doi":"10.1039/d5an01246e","DOIUrl":"https://doi.org/10.1039/d5an01246e","url":null,"abstract":"Historical production of per- and polyfluoroalkyl substances (PFAS) via electrochemical fluorination has resulted in complex mixtures of linear (L) and branched (Br) isomers, yet most environmental studies still treat them as single compounds. Emerging research highlights that isomer-specific differences critically shape PFAS environmental fate, bioaccumulation, and toxicity. These distinctions are particularly critical for aquatic organisms, which experience continuous exposure to PFAS and serve as sentinels of ecosystem health. A comprehensive review of literature from January 2000 to December 2025 reveals that most studies on PFAS in aquatic species overlook isomer resolution, constraining insights into mixture behavior. The relatively few studies that report isomer profiles across fish, sharks, marine mammals, aquatic insects, seabirds, alligators, and polar bears primarily focus on PFOS (perfluorooctane sulfonic acid), leaving substantial knowledge gaps for other PFAS classes. Evidence also indicates that precursor compositions strongly influence isomer-specific bioaccumulation; several studies show that L-isomers tend to bioaccumulate more than their Br counterparts, suggesting potential differences in environmental stability and metabolism. Advancing knowledge on PFAS isomer distribution requires broader use of orthogonal separation techniques. Ion mobility spectrometry can resolve L- and Br-isomers based on differences in their collision cross-sections. Other techniques that can separate L- and Br-isomers include gas chromatography/mass spectrometry with derivatization, and supercritical fluid chromatography/mass spectrometry, capable of efficient separation of isomers based on differences in partition coefficients between two phases. Integrating these techniques into current conventional PFAS analytical methods is essential for uncovering the PFAS structure-environmental behavior and for enhancing future ecological risk assessments.","PeriodicalId":63,"journal":{"name":"Analyst","volume":"99 1","pages":""},"PeriodicalIF":4.2,"publicationDate":"2026-03-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147329648","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Snehadrinarayan Khatua, Bhaskar Sen, Jogat Gogoi, Kripamoy Aguan
Herein, we report the highly selective detection of the reactive oxygen species hypochlorous acid (HOCl) using a solvatochromic cyclometalated Ir(III) complex through a unique C(sp2)-H hydroxylation mechanism. The complex, Ir-1, exhibits pronounced solvatochromic behavior, showing a bathochromic luminescence shift from green to orange-red with increasing solvent polarity. Ir-1, constructed from a benzothiazole-substituted pyridyl-1,2,3-triazole ligand (L1), was synthesized and comprehensively characterized for the selective recognition of HOCl over other competing ROS, RNS, and anions. Detailed ESI-HRMS and 1H NMR titration studies reveal an unusual regio-and stereoselective syn-addition of HOCl across the triazole C=C bond, followed by β-elimination of HCl, resulting in selective C-H hydroxylation and enabling HOCl specific sensing. Theoretical calculations and electrochemical analyses indicate that triazole hydroxylation enhances the σ and π-donor strength of the L1 ligand in Ir-1-OH, modulating the energy gap between the 3LLCT and 3MLCT excited states and thereby inducing luminescence color switching. Furthermore, bioimaging studies in HEK-293T cells demonstrate that Ir-1 is capable of staining HOCl in the cell cytoplasm and nucleus, highlighting its potential for biological sensing applications.
{"title":"Lighting Up Hypochlorous Acid through C(sp2)-H Hydroxylation with a Solvatochromic Organoiridium(III) Complex-based Probe","authors":"Snehadrinarayan Khatua, Bhaskar Sen, Jogat Gogoi, Kripamoy Aguan","doi":"10.1039/d6an00002a","DOIUrl":"https://doi.org/10.1039/d6an00002a","url":null,"abstract":"Herein, we report the highly selective detection of the reactive oxygen species hypochlorous acid (HOCl) using a solvatochromic cyclometalated Ir(III) complex through a unique C(sp2)-H hydroxylation mechanism. The complex, Ir-1, exhibits pronounced solvatochromic behavior, showing a bathochromic luminescence shift from green to orange-red with increasing solvent polarity. Ir-1, constructed from a benzothiazole-substituted pyridyl-1,2,3-triazole ligand (L1), was synthesized and comprehensively characterized for the selective recognition of HOCl over other competing ROS, RNS, and anions. Detailed ESI-HRMS and 1H NMR titration studies reveal an unusual regio-and stereoselective syn-addition of HOCl across the triazole C=C bond, followed by β-elimination of HCl, resulting in selective C-H hydroxylation and enabling HOCl specific sensing. Theoretical calculations and electrochemical analyses indicate that triazole hydroxylation enhances the σ and π-donor strength of the L1 ligand in Ir-1-OH, modulating the energy gap between the 3LLCT and 3MLCT excited states and thereby inducing luminescence color switching. Furthermore, bioimaging studies in HEK-293T cells demonstrate that Ir-1 is capable of staining HOCl in the cell cytoplasm and nucleus, highlighting its potential for biological sensing applications.","PeriodicalId":63,"journal":{"name":"Analyst","volume":"14 1","pages":""},"PeriodicalIF":4.2,"publicationDate":"2026-03-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147358934","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Monitoring anti-seizure medications (ASMs) such as carbamazepine is important to ensure that the correct dosage is given to patients which provides the maximum therapeutic effect. However, therapeutic windows for carbamazepine are narrow and need to be highly tailored towards the patients. Therefore, there is a need for more precise analytical methods for the monitoring of ASMs. Here we report a new hybrid aptamer/nanoMIP optical nanosensor utilising fluorescence quenching for the detection of carbamazepine. The nanosensor relies on a co-operative based binding mechanism whereby when the aptamer binds to carbamazepine it undergoes structural switching to change its 3D conformation and binds to the nanoMIP.Using a solid-phase imprinting technique, we synthesized nanoMIPs which recognise and bind to the aptamer/carbamazepine Complexes. The resultant nanoMIPs can then selectively recognise and bind to the aptamer complex resulting in a switch-off signal. The sensor demonstrated a LOD of 12.7 nM, excellent sample recoveries in 50% human serum (around 95%).
{"title":"Molecular Imprinting of Aptamer/Carbamazepine Complexes for the Development of an Optical Nanosensor","authors":"Iqra Nosheen Salim, Ellie Richards, Jon Ashley","doi":"10.1039/d5an01268f","DOIUrl":"https://doi.org/10.1039/d5an01268f","url":null,"abstract":"Monitoring anti-seizure medications (ASMs) such as carbamazepine is important to ensure that the correct dosage is given to patients which provides the maximum therapeutic effect. However, therapeutic windows for carbamazepine are narrow and need to be highly tailored towards the patients. Therefore, there is a need for more precise analytical methods for the monitoring of ASMs. Here we report a new hybrid aptamer/nanoMIP optical nanosensor utilising fluorescence quenching for the detection of carbamazepine. The nanosensor relies on a co-operative based binding mechanism whereby when the aptamer binds to carbamazepine it undergoes structural switching to change its 3D conformation and binds to the nanoMIP.Using a solid-phase imprinting technique, we synthesized nanoMIPs which recognise and bind to the aptamer/carbamazepine Complexes. The resultant nanoMIPs can then selectively recognise and bind to the aptamer complex resulting in a switch-off signal. The sensor demonstrated a LOD of 12.7 nM, excellent sample recoveries in 50% human serum (around 95%).","PeriodicalId":63,"journal":{"name":"Analyst","volume":"99 1","pages":""},"PeriodicalIF":4.2,"publicationDate":"2026-03-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147329940","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
MXene-based conductive hydrogels (MCHs) have emerged as highly promising materials for next-generation wearable electrochemical sensors, owing to their exceptional electrical conductivity, mechanical flexibility, and biocompatibility. This review provides a comprehensive and up-to-date overview of recent advances in the development of wearable sensors that incorporate Ti3C2TX MXene hydrogels for the detection of a wide range of analytes in various biofluids. Diverse hydrogel matrices have been integrated with MXenes to fabricate highly sensitive platforms capable of monitoring key biomarkers such as glucose, dopamine, uric acid, lactate, norepinephrine, sodium, creatinine, and pH. These sensors have been successfully deployed at various locations in the body, including the forearm, chest, wrist, and head, using flexible formats such as skin patches, microfluidic devices, pantyliners, wearable caps, and attachable body accessories. Notably, several configurations demonstrate ultralow detection limits, reaching the nanomolar level, enabling real-time, noninvasive analysis of sweat, urine, and other physiological fluids. The wide range of functional additives and customizable design approaches underscores the modularity and tunability of MCH-based systems for specific applications. This review critically evaluates the design principles, sensing mechanisms, performance metrics, and practical limitations of current MCH-based wearable platforms, providing insights that can guide future innovations in smart wearable healthcare technologies.
{"title":"Recent Progress in Wearable Electrochemical Sensors Based on MXene-Conductive Hydrogels","authors":"Hanieh Golshahi, Kheibar Dashtian, Rouholah Zare-Dorabei, Kagan Kerman","doi":"10.1039/d5an01118c","DOIUrl":"https://doi.org/10.1039/d5an01118c","url":null,"abstract":"MXene-based conductive hydrogels (MCHs) have emerged as highly promising materials for next-generation wearable electrochemical sensors, owing to their exceptional electrical conductivity, mechanical flexibility, and biocompatibility. This review provides a comprehensive and up-to-date overview of recent advances in the development of wearable sensors that incorporate Ti3C2TX MXene hydrogels for the detection of a wide range of analytes in various biofluids. Diverse hydrogel matrices have been integrated with MXenes to fabricate highly sensitive platforms capable of monitoring key biomarkers such as glucose, dopamine, uric acid, lactate, norepinephrine, sodium, creatinine, and pH. These sensors have been successfully deployed at various locations in the body, including the forearm, chest, wrist, and head, using flexible formats such as skin patches, microfluidic devices, pantyliners, wearable caps, and attachable body accessories. Notably, several configurations demonstrate ultralow detection limits, reaching the nanomolar level, enabling real-time, noninvasive analysis of sweat, urine, and other physiological fluids. The wide range of functional additives and customizable design approaches underscores the modularity and tunability of MCH-based systems for specific applications. This review critically evaluates the design principles, sensing mechanisms, performance metrics, and practical limitations of current MCH-based wearable platforms, providing insights that can guide future innovations in smart wearable healthcare technologies.","PeriodicalId":63,"journal":{"name":"Analyst","volume":"11 1","pages":""},"PeriodicalIF":4.2,"publicationDate":"2026-02-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147319887","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"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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