Gabriela Castro, Pablo Pereiro, Ysabel Santos, Mauricio Perín, Isaac Rodriguez
{"title":"Hindered amine light stabilizers in indoor dust: method development and occurrence.","authors":"Gabriela Castro, Pablo Pereiro, Ysabel Santos, Mauricio Perín, Isaac Rodriguez","doi":"10.1007/s00216-026-06541-y","DOIUrl":"https://doi.org/10.1007/s00216-026-06541-y","url":null,"abstract":"<p><p>Hindered amine light stabilizers (HALS) are polymer additives extensively used to improve the durability of plastic materials by inhibiting degradation induced by ultraviolet radiation. Due to their effectiveness, HALS are incorporated into a wide variety of polymeric products intended for both indoor and outdoor applications. However, because these compounds are not chemically bound to the polymer, they can be released into the environment through processes such as volatilization, abrasion, and dissolution. As a result, HALS may accumulate in dust and other environmental matrices. Their occurrence in indoor and outdoor dust raises concerns regarding environmental persistence and potential human exposure, underscoring the need for robust and sensitive analytical methods for their determination. In this study, a new analytical methodology for the determination of HALS in dust samples was developed and optimized. Different sample preparation techniques, including matrix solid-phase dispersion (MSPD), pressurized liquid extraction (PLE), and ultrasound-assisted extraction (UAE), were evaluated with the aim of improving extraction efficiency while minimizing matrix effects. Quantitative analysis was performed using liquid chromatography coupled to tandem mass spectrometry (LC-MS/MS) equipped with a triple quadrupole (QqQ) mass analyzer, providing high sensitivity and selectivity. The optimized procedure was subsequently applied to dust samples collected from various indoor environments to investigate the occurrence and distribution of HALS. These findings contribute to a better understanding of HALS contamination in dust and associated human exposure pathways.</p>","PeriodicalId":462,"journal":{"name":"Analytical and Bioanalytical Chemistry","volume":" ","pages":""},"PeriodicalIF":3.8,"publicationDate":"2026-05-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147832169","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}
{"title":"Poly(bromocresol green) and poly(bromocresol purple) films by electropolymerization in ternary deep eutectic solvent on gold nanoparticle/graphene quantum dot modified electrodes for the biosensing of glucose.","authors":"Joseany M S Almeida, Christopher M A Brett","doi":"10.1007/s00216-026-06524-z","DOIUrl":"https://doi.org/10.1007/s00216-026-06524-z","url":null,"abstract":"<p><p>The triarylmethane dyes brilliant cresyl green (BCG) and brilliant cresyl purple (BCP) have been electropolymerized on glassy carbon electrodes (GCE) modified with gold nanoparticles (AuNP) and graphene quantum dots (GQD) dispersed in chitosan (AuNP+GQD)<sub>chitosan</sub> by potential cycling in a novel ternary deep eutectic solvent (tDES). The tDES was composed of choline chloride (ChCl) as the hydrogen bond acceptor plus acetic acid and ethylene glycol as hydrogen bond donors, with perchloric acid as a tDES acid dopant. GQD<sub>chitosan</sub> was synthesized by a simple and eco-friendly procedure using citric acid as the carbon source in chitosan solution with 1% v/v acetic acid. AuNP dispersed in citrate buffer were mixed with GQD<sub>chitosan</sub> in the proportion (70/30% v/v). The PBCG/(AuNP+GQD)<sub>chitosan</sub>/GCE and PBCP/(AuNP+GQD)<sub>chitosan</sub>/GCE modified electrodes were compared and characterized by cyclic voltammetry and electrochemical impedance spectroscopy. The morphology of the synthesized polymer films was examined by scanning electron microscopy. After immobilization of glucose oxidase (GOx), GOx/PBCG/(AuNP+GQD)<sub>chitosan</sub>/GCE and GOx/PBCP/(AuNP+GQD)<sub>chitosan</sub>/GCE biosensors were employed for the determination of glucose by amperometry at a potential of -0.2 V vs. Ag/AgCl. Linear concentration ranges were 10-200 µM for GOx/PBCG/(AuNP+GQD)<sub>chitosan</sub>/GCE and 10-140 µM for GOx/PBCP/(AuNP+GQD)<sub>chitosan</sub>/GCE, with corresponding limits of detection of 2.3 µM and 3.1 µM. The biosensor with PBCG film showed slightly better analytical parameters. The biosensors demonstrated good repeatability, reproducibility, stability, and selectivity and were successfully applied to wine samples with very good recoveries.</p>","PeriodicalId":462,"journal":{"name":"Analytical and Bioanalytical Chemistry","volume":" ","pages":""},"PeriodicalIF":3.8,"publicationDate":"2026-05-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147809346","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}
Francesca Merlo, Matteo Invernizzi, Sofia Salerno, Enrica Calleri, Antonella Profumo, Andrea Speltini
{"title":"Quantification of gastric cancer biomarkers in the urine matrix by high internal phase emulsion polymer-based µsolid-phase extraction followed by HPLC-MS/MS.","authors":"Francesca Merlo, Matteo Invernizzi, Sofia Salerno, Enrica Calleri, Antonella Profumo, Andrea Speltini","doi":"10.1007/s00216-026-06535-w","DOIUrl":"https://doi.org/10.1007/s00216-026-06535-w","url":null,"abstract":"<p><p>This paper reports on the development of an analytical method for the simultaneous determination of 4-methyl phenol, 4-hydroxybenzoic acid and five bile acids, namely cholic acid, glycochenodeoxycholic acid, chenodeoxycholic acid, deoxycholic acid, and hyodeoxycholic acid (logP 1.6-4.9) in urine, exploring porous acrylic polymers as unconventional solid-phase extraction sorbents before HPLC-MS/MS analysis. These materials, obtained by polymerization of high internal phase emulsions with different composition, were used in a miniaturized setting (µSPE), preliminarily in synthetic urine samples enriched with 200 ng mL<sup>-1</sup> of each selected compound. It was found that the polyethylene glycol (PEG)-modified polymer combines good analytical performance, in terms of extraction efficiency (76-100% for most analytes), from 1 mL samples and single-fraction elution in pure ethanol. Recovery was assessed in untreated real urine (1 mL, pH ~ 3.5) at three quality control levels (50, 200, 500 ng mL<sup>-1</sup>) observing inter-day RSD below 20% (n = 3). The polymer exhibited a service life of at least ten sorption/desorption cycles, a further strength point of this sample treatment ascertained by greenness metrics. This streamlined procedure also provided satisfactory sample clean-up, with a negligible matrix-effect, as observed in HPLC-MS/MS. An ad hoc chromatographic method was developed to enable the simultaneous separation and quantification of all targets in a single run. Good linearity was observed in the range 10-600 ng mL<sup>-1</sup> (R<sup>2</sup> > 0.9919) with suitable sensitivity (a few ng mL<sup>-1</sup>) to future application for monitoring these endogenous compounds.</p>","PeriodicalId":462,"journal":{"name":"Analytical and Bioanalytical Chemistry","volume":" ","pages":""},"PeriodicalIF":3.8,"publicationDate":"2026-05-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147831827","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}
Bohao Zhang, Pengcheng Liu, Jiyao Zhang, Xi Chen, Zhenggang Chen, Qingyin Zheng, Peng Ma, Chen Wang, Xing-Hua Xia, Wen-Chao Hu
{"title":"Dual-mode electrochemical and colorimetric biosensing platform using MOF-stabilized iron nanoclusters for ultrasensitive detection of Pseudomonas aeruginosa.","authors":"Bohao Zhang, Pengcheng Liu, Jiyao Zhang, Xi Chen, Zhenggang Chen, Qingyin Zheng, Peng Ma, Chen Wang, Xing-Hua Xia, Wen-Chao Hu","doi":"10.1007/s00216-026-06523-0","DOIUrl":"https://doi.org/10.1007/s00216-026-06523-0","url":null,"abstract":"<p><p>Pseudomonas aeruginosa is a prevalent multidrug-resistant pathogen responsible for severe infections. Rapid, ultrasensitive, and selective detection of this bacterium is essential for effective clinical diagnostics and infection control. Here, we report a novel dual-mode biosensing platform based on two-dimensional metal-organic framework-stabilized iron nanoclusters (MOF-Fe NCs) for the simultaneous electrochemical and colorimetric detection of P. aeruginosa. The MOF-Fe NCs display synergistic properties, including exceptional electrocatalytic activity and robust peroxidase-like (POD-like) behavior. Specific capture of the target bacteria by a surface-immobilized F23 aptamer modulates electrochemical signaling and suppresses the POD-like activity for colorimetric readout. The dual-mode bioassay achieves a broad detection range from 10<sup>1</sup> to 10<sup>8</sup> CFU/mL, with detection limits of 1.7 CFU/mL (electrochemical) and 1.0 CFU/mL (colorimetric), and demonstrates high selectivity against other bacterial species. This work provides a robust, self-validating sensing strategy with significant potential for point-of-care diagnostics and real-time infection monitoring.</p>","PeriodicalId":462,"journal":{"name":"Analytical and Bioanalytical Chemistry","volume":" ","pages":""},"PeriodicalIF":3.8,"publicationDate":"2026-05-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147809235","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}
{"title":"Uncovering monitoring gaps and novel persistent and mobile substances (PMs) in groundwater using lyophilisation enrichment and SFC-HRMS smart screening.","authors":"Till Meier, Thorsten Reemtsma, Qiuguo Fu","doi":"10.1007/s00216-026-06494-2","DOIUrl":"https://doi.org/10.1007/s00216-026-06494-2","url":null,"abstract":"<p><p>Persistent and mobile chemicals (PMs) threaten groundwater quality and drinking water safety, yet many remain undetected because analytical methods insufficiently address highly polar and ionic substances, while regulatory frameworks lack monitoring requirements for these compound classes. Here, we developed a supercritical fluid chromatography-high-resolution mass spectrometry-based smart-screen approach that integrates three key prioritisation strategies: (i) sampling site prioritisation, (ii) suspect-level prioritisation through tiered suspect lists, and (iii) candidate prioritisation using stepwise scoring. Additionally, the method achieved the sensitive identification and reliable quantification of PMs in groundwater, with a median limit of quantification of 6.8 ng/L, stable recoveries (75%), and low matrix effects (-12%) across diverse groundwater types. Prioritisation reduced 599 groundwater wells to 10 representative sites, yielding an 8.6-fold reduction in analytical workload while maintaining chemical diversity. The tiered suspect lists and stepwise scoring strategies improved confirmation efficiency and facilitated the detection of substances of high environmental relevance. Collectively, 34 PMs were detected across six substance groups including polar per- and polyfluoroalkyl substances, polyfluorinated inorganic species, transformation products, and amide or ether solvents at concentrations of 0.1-22,300 ng/L. Among these, 16 substances were newly detected in ambient groundwater and four were reported for the first time in any environmental compartment. Several substances (e.g. 2-phenylpropane-2-sulphonic acid) are not classified as persistent under EU regulation on registration, evaluation, authorisation and restriction of chemicals (REACH) yet occur ubiquitously in groundwater, suggesting an underestimation of PMs under aquifer conditions. These findings advance monitoring of PMs, supporting their regulation for groundwater and drinking water protection.</p>","PeriodicalId":462,"journal":{"name":"Analytical and Bioanalytical Chemistry","volume":" ","pages":""},"PeriodicalIF":3.8,"publicationDate":"2026-05-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147809396","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}
Simone Trimmel, Alexander V Epov, Nadine Abu Zahra, Tobias Berger, Thomas Prohaska, Markus Puschenreiter, Antonia Siebenbrunner, Alice Tognacchini, Stefan Wagner, Johanna Irrgeher
{"title":"Tracking nickel uptake pathways in hyperaccumulator plants using a <sup>61</sup>Ni-enriched stable isotope tracer in soil.","authors":"Simone Trimmel, Alexander V Epov, Nadine Abu Zahra, Tobias Berger, Thomas Prohaska, Markus Puschenreiter, Antonia Siebenbrunner, Alice Tognacchini, Stefan Wagner, Johanna Irrgeher","doi":"10.1007/s00216-026-06539-6","DOIUrl":"https://doi.org/10.1007/s00216-026-06539-6","url":null,"abstract":"<p><p>Understanding the mechanisms of nickel (Ni) uptake by hyperaccumulator plants is essential for advancing sustainable phytomanagement. In this study, saponite materials containing either isotopically natural or <sup>61</sup>Ni-enriched Ni were synthesised and applied in RHIZOtest experiments with Odontarrhena chalcidica. The amendments were mixed with two ultramafic soils differing in Ni content, alongside a serpentinite control. Ni bioavailability and uptake were evaluated via elemental and isotopic analysis of plant digests and diffusive gradients in thin films (DGT). Stable isotope spiking with <sup>61</sup>Ni allowed tracing of amendment-derived Ni uptake into plant tissues, even though total Ni mass fractions in planted versus unplanted soils did not indicate significant mobilisation during the 14-day growth period. Isotope pattern deconvolution (IPD) revealed clear shifts in Ni isotopic composition in both plant and DGT samples. Tracer uptake was more pronounced in the low Ni soil, with amendment-derived Ni (x<sub>amendment</sub>) contributing 19.3 ± 5.0% of total Ni in shoots, compared to 7.7 ± 1.8% in the high-Ni soil. In standard solutions containing 50 ng g<sup>-1</sup> total Ni, isotope pattern shifts were still detectable at enrichment levels as low as 0.01% x<sub>spike</sub> (≈ 5 pg g<sup>-1 61</sup>Ni). The findings demonstrate the sensitivity of stable isotope spiking combined with IPD in the detection of subtle uptake processes, even in short-term experiments. This approach enables the differentiation of various Ni sources in soil-plant systems that would not be achievable with quantification alone, and can thereby provide new insights into how soil mineralogy influences uptake dynamics in metal-hyperaccumulating species.</p>","PeriodicalId":462,"journal":{"name":"Analytical and Bioanalytical Chemistry","volume":" ","pages":""},"PeriodicalIF":3.8,"publicationDate":"2026-05-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147809371","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}
Raphael Henrique de Moura Pereira, Vinícius Humberto da Silva Bezerra, Maria José de Filgueiras Gomes, Elvis Joacir de França
{"title":"Assessment of between-bottle homogeneity, particle size, and element content of candidate reference materials of black cricket (Gryllus assimilis) employing energy-dispersive X-ray fluorescence spectrometry.","authors":"Raphael Henrique de Moura Pereira, Vinícius Humberto da Silva Bezerra, Maria José de Filgueiras Gomes, Elvis Joacir de França","doi":"10.1007/s00216-026-06503-4","DOIUrl":"https://doi.org/10.1007/s00216-026-06503-4","url":null,"abstract":"<p><p>Crickets are widely consumed edible insects with high nutritional value, requiring reliable analytical methods for elemental characterization. Their complex matrix can cause matrix effects, making suitable reference materials essential for quality control. Because certified cricket reference materials are scarce, particularly in Brazil, this study aimed to prepare and characterize a national reference material candidate using black cricket (Gryllus assimilis). The production process was adapted to the matrix and included grinding, lyophilization, and packaging, yielding a batch of 25 bottles. The influence of particle size and between-bottle homogeneity was evaluated. Homogeneity was assessed by ANOVA, supported by Levene and Shapiro-Wilk tests, using five randomly selected bottles and three subsamples of 0.250 g per bottle. Elemental characterization was performed by energy-dispersive X-ray fluorescence. Expanded uncertainties were estimated with a coverage factor of k = 2 at approximately 95% confidence. Results showed satisfactory between-bottle homogeneity (p-value > 0.05) and indicated that particle sizes below 500 µm did not significantly affect concentrations. The candidate presented average mass fractions ± expanded uncertainty of Ca (1531.0 ± 176.5 mg kg⁻<sup>1</sup>), Cl (5559.4 ± 1381.2 mg kg⁻<sup>1</sup>), Cu (22.9 ± 1.7 mg kg⁻<sup>1</sup>), Mg (1083.1 ± 295.8 mg kg⁻<sup>1</sup>), P (10 397.0 ± 1084.6 mg kg⁻<sup>1</sup>), and S (7608.1 ± 398.0 mg kg⁻<sup>1</sup>). Coefficients of variation were below 11%, and expanded uncertainties remained under 30%. These results demonstrate adequate precision, reproducibility, and matrix suitability of the proposed material. The study supports continued evaluation of intra-bottle homogeneity, stability, and certification to enable its availability for laboratories performing elemental analysis of cricket-based foods, strengthening analytical reliability and food safety assessment in emerging insect protein chains worldwide. This contribution addresses national needs and supports sustainable nutrition research efforts.</p>","PeriodicalId":462,"journal":{"name":"Analytical and Bioanalytical Chemistry","volume":" ","pages":""},"PeriodicalIF":3.8,"publicationDate":"2026-05-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147809264","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}
Claudia López-Sánchez, Mohammed Zougagh, Ángel Ríos, Fernando de Andrés
{"title":"Screening-confirmation approach for urinary alpelisib by silver-nanorod enabled portable SERS platform and LC-MS validation.","authors":"Claudia López-Sánchez, Mohammed Zougagh, Ángel Ríos, Fernando de Andrés","doi":"10.1007/s00216-026-06536-9","DOIUrl":"https://doi.org/10.1007/s00216-026-06536-9","url":null,"abstract":"<p><p>Alpelisib, a selective PI3Kα inhibitor, benefits from reliable quantitative measurements to support exposure assessment and dose individualization. Here, we report a portable surface-enhanced Raman spectroscopy (SERS) workflow for rapid urinary screening and quantification of alpelisib using shaped-controlled silver nanoparticles, with silver nanorods selected as the substrate providing the highest SERS response among spherical, cubic, and rod-like morphologies. Key substrate-preparation and instrumental parameters were systematically optimized using a portable 785-nm Raman device, and the analytical figures of merit were thoroughly assessed in urine following a sample clean-up by protein precipitation and liquid-liquid extraction. Under optimized conditions, the diagnostic band at 993 cm⁻<sup>1</sup> was adopted for quantification, and the method provided a linear response from 7.93 to 113.26 µM (R<sup>2</sup> = 0.9993), with limits of detection and quantification of 2.28 µM and 7.61 µM, respectively. Precision was suitable for a rapid SERS workflow (repeatability and reproducibility RSD ≤ 8.71% and ≤ 8.25%, respectively), with accuracy close to 100% across quality-control levels. A selectivity assessment was performed in urine using an equimolar alpelisib mixture with representative pharmaceutical interferents, and the method reliability was further supported by LC-MS benchmarking, with no statistically significant differences between SERS and LC-MS results for calibration and QC samples at the 95% confidence level (two-tailed t-test). An apparent enhancement factor up to 10<sup>3</sup> was estimated for the 993 cm⁻<sup>1</sup> band under the selected conditions, consistent with a predominantly electromagnetic enhancement mechanism with a plausible interfacial chemical contribution. Finally, method sustainability was discussed using the AGREE metric (overall score 0.74/1.00) as a diagnostic tool to identify improvement hotspots. Overall, this portable SERS approach provides a practical, low-instrumentation option for rapid urinary screening and quantification of alpelisib, complementary to LC-MS-based methods for comprehensive bioanalysis.</p>","PeriodicalId":462,"journal":{"name":"Analytical and Bioanalytical Chemistry","volume":" ","pages":""},"PeriodicalIF":3.8,"publicationDate":"2026-05-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147809343","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}
Lucian-Mihai Stănescu, Corina-Cristina Aramă, Gabriela N Chirițoiu, Andrei J Petrescu, Ștefana M Petrescu, Cristian V A Munteanu
{"title":"A new strategy to separate peptide methionine sulfoxides stereoisomers for potential immunotherapy application.","authors":"Lucian-Mihai Stănescu, Corina-Cristina Aramă, Gabriela N Chirițoiu, Andrei J Petrescu, Ștefana M Petrescu, Cristian V A Munteanu","doi":"10.1007/s00216-026-06507-0","DOIUrl":"https://doi.org/10.1007/s00216-026-06507-0","url":null,"abstract":"<p><p>Peptide-based immunotherapy is a promising cancer treatment due to its scalability and patient-centered approach; therefore, there is an increasing focus on discovering neoantigens or modified peptides which could elicit a better immune response. We recently found that the methionine sulfoxide variant of YMDGTMSQV, an immunogenic tyrosinase derived epitope, elicits a stronger immune response compared to the native one. Here, we address the separation of six MHC I-restricted tyrosinase-derived peptides methionine sulfoxide stereoisomers (YMNGTMSQV, YMDGTMSQV, YMQGTMSQV, YMDGVMSQV, FMNGTMSQV, FMDGTMSQV) using offline two-dimensional high-performance liquid chromatography coupled with UV/Vis-Circular Dichroism detection. For all analyzed peptides, using our methodology, we observed that placing the sulfoxide on the methionine in sixth position results in no enantiodiscrimination, suggesting the net contribution of the N-terminus tyrosine or phenylalanine π electrons in separation. We show how modifying the amino acids in the vicinities of the methionine-sulfoxide residues results in the ablation of the chiral discrimination. We also render our methodology analytical to semi-preparative level. We describe the stereoisomers stability and capture differences regarding their propensity towards oxidation, our results suggesting that the substitution of the N-terminus tyrosine to phenylalanine could be involved in this process. We analyzed the tandem mass spectrometry fragmentation patterns of the separated optic isomers and search for clues about their discrimination. Moreover, we found that the stereoisomers are similar recognized by specific HLA compared with the racemic variant. Our methodology could be valuable for potential applications in an enantiomer-specific peptide-based immunotherapy selection.</p>","PeriodicalId":462,"journal":{"name":"Analytical and Bioanalytical Chemistry","volume":" ","pages":""},"PeriodicalIF":3.8,"publicationDate":"2026-05-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147809189","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}
Nancheng Lian, Gengneng Lai, Ran Ge, Xiuzhi Xu, Fang Ke, Changsheng Wang
{"title":"A label-free colorimetric strategy for acid phosphatase detection based on in-situ Pd nanozyme formation and smartphone analysis.","authors":"Nancheng Lian, Gengneng Lai, Ran Ge, Xiuzhi Xu, Fang Ke, Changsheng Wang","doi":"10.1007/s00216-026-06529-8","DOIUrl":"https://doi.org/10.1007/s00216-026-06529-8","url":null,"abstract":"<p><p>Acid phosphatase (ACP) is a critical biomarker for prostate cancer prognosis, but conventional detection methods often lack sensitivity and portability. We report a label-free colorimetric platform for ACP detection that integrates in-situ Pd nanozyme synthesis with smartphone-based analysis. ACP hydrolyzes L-ascorbic acid 2-phosphate sesquimagnesium (AAPS) to generate ascorbic acid (AA), which reduces Pd<sup>2+</sup> to form palladium nanoparticles (Pd NPs) exhibiting peroxidase-like activity. Polyvinylpyrrolidone (PVP) stabilizes the nanoparticles, ensuring consistent linear response even at ultra-low ACP levels. The in-situ formed Pd NPs catalyze hydrogen peroxide (H<sub>2</sub>O<sub>2)</sub> mediated 3,3',5,5'-tetramethylbenzidine (TMB) oxidation, producing a blue color readout. The catalytic mechanism was validated through steady-state kinetics and radical scavenging studies. The sensor achieves a wide linear range from 0.1 to 10 U/L, a low limit of detection (LOD) of 0.043 U/L, and strong anti-interference performance. Coupled with smartphone-based color analysis, this method enables rapid, portable ACP quantification in human plasma with relative standard deviation below 5%. This work establishes a sensitive point-of-care testing (POCT) strategy for ACP and provides a generalized framework for stabilized in-situ nanozyme synthesis, mechanistic investigation, and portable detection in next-generation biosensor design.</p>","PeriodicalId":462,"journal":{"name":"Analytical and Bioanalytical Chemistry","volume":" ","pages":""},"PeriodicalIF":3.8,"publicationDate":"2026-05-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147809179","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}