Analytical Chemistry最新文献_第7页

Amplified Intracellular Imaging of Polynucleotide Kinase via a Self-Stacking Autocatalytic DNA Circuit. 通过自堆叠自催化DNA电路放大多核苷酸激酶的细胞内成像。

IF 7.4 1区化学

Analytical Chemistry Pub Date : 2025-10-08 DOI: 10.1021/acs.analchem.5c03752

Zhaolin Wang,Sini Li,Ying Deng,Ruomeng Li,Xiaoqing Liu,Fuan Wang

{"title":"Amplified Intracellular Imaging of Polynucleotide Kinase via a Self-Stacking Autocatalytic DNA Circuit.","authors":"Zhaolin Wang,Sini Li,Ying Deng,Ruomeng Li,Xiaoqing Liu,Fuan Wang","doi":"10.1021/acs.analchem.5c03752","DOIUrl":"https://doi.org/10.1021/acs.analchem.5c03752","url":null,"abstract":"Polynucleotide kinase (PNK) plays a pivotal role in nucleic acid metabolism and is closely associated with genome instability and disease progression. However, current PNK detection methods are constrained by the low sensitivity and complex probe composition. Herein, we report a self-stacking autocatalytic assembly circuit (AAC) for the sensitive and specific detection of PNK activity in live cells. In this system, PNK phosphorylates a 5'-hydroxylated hairpin substrate, enabling its selective degradation by λ-exonuclease to release a single-stranded DNA trigger. This DNA trigger further initiates a catalytic hairpin assembly reaction among three rationally designed probes, generating Y-shaped DNA junctions that expose new recombinational trigger sequences. The regenerated triggers drive a self-sustaining amplification cycle, enabling the rapid signal generation with low background. The AAC system, requiring minimal DNA components, enables the sensitive and robust detection of PNK both in vitro and in living cells and supports intracellular PNK activity monitoring and inhibitor screening. This strategy provides a robust and efficient tool for low-abundance biomarker analysis and holds broad potential in biomedical research and diagnostic applications.","PeriodicalId":27,"journal":{"name":"Analytical Chemistry","volume":"114 1","pages":""},"PeriodicalIF":7.4,"publicationDate":"2025-10-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145246536","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

"Repaired and Activated" DNAzyme-RCA Circuit Enables One-Pot and Label-Free Detection of O6-Methylguanine DNA Methyltransferase in Clinical Tissues. “修复和激活”DNAzyme-RCA电路使临床组织中o6 -甲基鸟嘌呤DNA甲基转移酶的一锅和无标记检测成为可能。

IF 7.4 1区化学

Analytical Chemistry Pub Date : 2025-10-08 DOI: 10.1021/acs.analchem.5c05231

Wen-Jing Liu,Jun-Zhi Liu,Li-Juan Wang,Chun-Yang Zhang,Wei Gao

{"title":"\"Repaired and Activated\" DNAzyme-RCA Circuit Enables One-Pot and Label-Free Detection of O6-Methylguanine DNA Methyltransferase in Clinical Tissues.","authors":"Wen-Jing Liu,Jun-Zhi Liu,Li-Juan Wang,Chun-Yang Zhang,Wei Gao","doi":"10.1021/acs.analchem.5c05231","DOIUrl":"https://doi.org/10.1021/acs.analchem.5c05231","url":null,"abstract":"O6-Methylguanine-DNA methyltransferase (MGMT) is a DNA repair enzyme that catalyzes the reversal of O6-alkylguanine lesions, with an essential role in tumor resistance to alkylating chemotherapeutic agents. Herein, we develop a \"repaired and activated\" DNAzyme-RCA circuit for label-free and one-pot detection of MGMT in cells and tissues. The presence of MGMT can catalyze the demethylation of O6MeG-caged circular DNAzyme probe (O6MeG-cDZ), restoring its catalytic activity to specifically cleave adenine ribonucleotide (rA)-bearing substrate probe to produce a trigger sequence with a 2',3'-cyclic phosphate at its 3'-end. Subsequently, the resulting trigger can serve as a primer to initiate rolling circle amplification (RCA) upon healing its 3'-end by T4 polynucleotide kinase (T4 PNK), generating a large number of long G-quadruplex sequences. The G-quadruplex sequences can incorporate with thioflavin T (ThT) to produce a dramatically amplified fluorescence signal. Notably, O6MeG-cDZ integrates both a DNAzyme sequence and an RCA template sequence to achieve cleavage-and-amplification detection, efficiently eliminating nonspecific amplification. This method enables one-pot, isothermal, and label-free detection of MGMT down to 8.17 × 10-9 ng/μL and even quantification of MGMT at the single-cell level. Moreover, it can be employed for screening of MGMT inhibitors and precise discrimination of MGMT expression in breast cancer tissues and healthy counterparts, providing a novel paradigm for DNA repair enzyme-related clinical diagnosis and drug discovery.","PeriodicalId":27,"journal":{"name":"Analytical Chemistry","volume":"9 1","pages":""},"PeriodicalIF":7.4,"publicationDate":"2025-10-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145246673","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Rational Design of Bismuth-Based Metal-Organic Framework Electrochemiluminescence Sensing Platform: A Proactive Approach for Early Warning of Mycotoxin Contaminants. 铋基金属-有机骨架电化学发光传感平台的合理设计：真菌毒素污染预警的主动途径。

IF 7.4 1区化学

Analytical Chemistry Pub Date : 2025-10-08 DOI: 10.1021/acs.analchem.5c04761

Yinmin Min,Kehui Wei,Tianshuo Wang,Lianxi Pu,Min Zhang,Deping Wang,Qian Liu,Kun Wang

{"title":"Rational Design of Bismuth-Based Metal-Organic Framework Electrochemiluminescence Sensing Platform: A Proactive Approach for Early Warning of Mycotoxin Contaminants.","authors":"Yinmin Min,Kehui Wei,Tianshuo Wang,Lianxi Pu,Min Zhang,Deping Wang,Qian Liu,Kun Wang","doi":"10.1021/acs.analchem.5c04761","DOIUrl":"https://doi.org/10.1021/acs.analchem.5c04761","url":null,"abstract":"Exploring a proactive control strategy for early assessment of toxigenic potential is of great significance in preventing health risks and economic losses. This study proposes an efficient electrochemiluminescence (ECL) protocol for ultrasensitive detection of the ochratoxin A (OTA) biosynthesis key gene, the halogenase gene (halA), enabling intervention before mass toxin production. An ECL system was developed using a bismuth-based metal-organic framework (Bi-TBAPy MOF) as an emitter. This material integrates low-toxicity, highly biocompatible Bi3+ ions with a 1,3,6,8-tetrakis(4-carboxyphenyl)pyrene (H4TBAPy) organic ligand exhibiting aggregation-induced emission enhancement characteristics. The rigid coordination network of the MOF effectively suppresses the ligand's aggregation-caused quenching effect, significantly enhancing ECL efficiency (2.4-fold higher luminescence intensity than H4TBAPy aggregates). The proposed biosensor achieved ultrasensitive detection of the halA gene fragment (detection limit: 0.84 fM; linear range: 1 fM to 100 nM), providing early warning of toxigenic fungal activity. This work not only provides a practical approach for developing high-performance ECL emitters but also establishes a key technical foundation for constructing proactive mycotoxin control systems in agricultural supply chains, demonstrating significant implications for safeguarding food safety and reducing economic losses.","PeriodicalId":27,"journal":{"name":"Analytical Chemistry","volume":"112 1","pages":""},"PeriodicalIF":7.4,"publicationDate":"2025-10-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145246675","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Microsensor Array for the Electrochemical Analysis of Hydroxyurea in Blood Samples of Children Affected by Sickle Cell Anemia 微传感器阵列用于镰状细胞性贫血患儿血液中羟基脲的电化学分析

IF 7.4 1区化学

Analytical Chemistry Pub Date : 2025-10-08 DOI: 10.1021/acs.analchem.5c03569

Rajendra P. Shukla, Matan Aroosh, Remi Cazelles, Russell E. Ware, Alexander A. Vinks, Hadar Ben-Yoav

{"title":"Microsensor Array for the Electrochemical Analysis of Hydroxyurea in Blood Samples of Children Affected by Sickle Cell Anemia","authors":"Rajendra P. Shukla, Matan Aroosh, Remi Cazelles, Russell E. Ware, Alexander A. Vinks, Hadar Ben-Yoav","doi":"10.1021/acs.analchem.5c03569","DOIUrl":"https://doi.org/10.1021/acs.analchem.5c03569","url":null,"abstract":"Sickle cell anemia (SCA) is an inherited blood disorder that causes morbidity and early mortality. Hydroxyurea is an effective oral medication to treat SCA, and optimal dosing benefits from pharmacokinetic (PK)-based methods that require accurate analysis of hydroxyurea levels in timed patient blood samples. Current gold standard assay methods, such as liquid chromatography–mass spectrometry (LC-MS), require sophisticated instrumentation, trained personnel, and laborious sample pretreatment steps that may alter target molecule levels. Additionally, LC-MS is time-consuming and costly, leading to delays in treatment decisions and making it infeasible for use in low-resource settings. Herein, we report a novel approach for the chemical analysis of serum hydroxyurea levels by using an array of electrochemical microsensors modified with thin films of nanomaterials to record the electrochemical signature of blood samples from 50 children treated with hydroxyurea. To analyze this complex data set, multiple machine learning models were trained and optimized to predict hydroxyurea levels from microliter sample volumes. We evaluated three regression algorithms: elastic net, random forest (RF), and partial least-squares regression (PLSR) across 11 different electrochemical feature matrices. Among these, PLSR demonstrated the best performance, achieving a root-mean-square error of 41.85 μM (3.18 μg/mL) and an average prediction error of 7.24 μM (0.55 μg/mL), thereby enabling accurate analysis of hydroxyurea levels within the therapeutic range using microliter sample volumes from pediatric patients. With further miniaturization of such sensor arrays and integration into point-of-care testing devices, hydroxyurea PK-based dosing can be simplified for use in low-resource settings to improve SCA treatment outcomes worldwide.","PeriodicalId":27,"journal":{"name":"Analytical Chemistry","volume":"30 1","pages":""},"PeriodicalIF":7.4,"publicationDate":"2025-10-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145247518","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Ozone Fine-Bubble Oxidation of Water-Soluble Alcohols via Electron Transfer across the Gas-Liquid Interface, Quantified by Kinetic Studies. 臭氧细泡氧化水溶性醇通过气液界面的电子转移，通过动力学研究量化。

IF 7.4 1区化学

Analytical Chemistry Pub Date : 2025-10-07 DOI: 10.1021/acs.analchem.5c03923

Takuya Kurahashi,Natsuki Yokoyama,Yuka Nakao

{"title":"Ozone Fine-Bubble Oxidation of Water-Soluble Alcohols via Electron Transfer across the Gas-Liquid Interface, Quantified by Kinetic Studies.","authors":"Takuya Kurahashi,Natsuki Yokoyama,Yuka Nakao","doi":"10.1021/acs.analchem.5c03923","DOIUrl":"https://doi.org/10.1021/acs.analchem.5c03923","url":null,"abstract":"A novel fine-bubble reactor was developed to enable stable and quantitative kinetic studies of reactions at the gas-liquid interface, a process previously challenging to elucidate. Using this advanced analytical platform, we investigated ozone fine-bubble oxidation of a series of water-soluble alcohols, revealing fundamentally new insights into interfacial reactivity. Under single-substrate conditions, ozone fine bubbles exhibited comparable reactivity toward primary 1-butanol and secondary 2-butanol. However, under competitive conditions with a 1:1 mixture, ozone fine bubbles preferentially oxidized secondary 2-butanol over primary 1-butanol. This marked difference between single-substrate and competitive reactivity cannot be explained by single-substrate kinetics. For the reaction with methanol, a kinetic isotope effect of kH/kD = 1.5 was observed under competitive conditions, but no isotope effect was found in the single-substrate reaction. The most plausible explanation is that the oxidation sequence is initiated by an electron transfer from surface-bound OH- to O3, which generates reactive HO• radicals at the gas-liquid interface. The subsequent reaction of these HO• radicals with alcohols is not rate-determining, thus giving rise to the observed difference between single-substrate and competitive conditions. Overall, this study reveals a two-step mechanism governing ozone fine-bubble oxidation at the gas-liquid interface: (1) a rate-determining substrate uptake step, as evidenced by hydrophobicity-dependent reactivity for a series of alcohols and by observed bubble size reduction upon substrate uptake; (2) the electron-transfer initiated process described above. Our study established a powerful analytical framework for probing gas-liquid interfacial reactions.","PeriodicalId":27,"journal":{"name":"Analytical Chemistry","volume":"128 1","pages":""},"PeriodicalIF":7.4,"publicationDate":"2025-10-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145240982","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Formic Acid Pretreatment Enhances Untargeted Serum and Plasma Metabolomics 甲酸预处理增强非靶向血清和血浆代谢组学

IF 7.4 1区化学

Analytical Chemistry Pub Date : 2025-10-07 DOI: 10.1021/acs.analchem.5c03725

Tereza Kacerova, Elisabete Pires, Abigail Dixon, Rachel Williams, Isabelle Legge, Mia Hippisley, Abi G. Yates, A. David Smith, Daniel C. Anthony, Fay Probert, James S. O. McCullagh

{"title":"Formic Acid Pretreatment Enhances Untargeted Serum and Plasma Metabolomics","authors":"Tereza Kacerova, Elisabete Pires, Abigail Dixon, Rachel Williams, Isabelle Legge, Mia Hippisley, Abi G. Yates, A. David Smith, Daniel C. Anthony, Fay Probert, James S. O. McCullagh","doi":"10.1021/acs.analchem.5c03725","DOIUrl":"https://doi.org/10.1021/acs.analchem.5c03725","url":null,"abstract":"Untargeted metabolic profiling of plasma and serum by liquid chromatography–mass spectrometry (LC-MS) is becoming increasingly important in clinical and translational research; however, sample preparation protocols can have a significant impact on study outcomes, and there is currently a lack of standardized approaches. In this study we demonstrate that pretreatment of serum and plasma samples with 1% formic acid (FA, v/v) prior to acetonitrile (MeCN)-induced protein precipitation significantly enhances analytical performance in untargeted metabolomics using reversed-phase liquid chromatography (RPLC)-MS. We show an increase in sample preparation reproducibility and signal intensity across both positive and negative ionization modes. In two independent serum cohorts (OPTIMA and VITACOG), FA-based extraction improved multivariate modeling (orthogonal partial least-squares discriminant analysis, OPLS-DA), with consistently higher classification accuracy, sensitivity, and specificity, alongside reduced variability and increased fold-changes in discriminatory compound-features. We investigated factors potentially involved in the enhanced performance and observed outcomes consistent with the disruption of noncovalent protein–metabolite interactions and the stabilization of labile species. We found no correlation with either protein depletion or differential adduct formation. The results were also not attributable to lowering pH after metabolite extraction. In summary, we demonstrate that FA pretreatment of plasma and serum, prior to protein precipitation, significantly improves sample reproducibility and detection sensitivity in untargeted RPLC-MS metabolomics. This optimized sample preparation strategy offers clear advantages for clinical and translational metabolomics, with the potential to enhance biomarker discovery and metabolic phenotyping.","PeriodicalId":27,"journal":{"name":"Analytical Chemistry","volume":"14 1","pages":""},"PeriodicalIF":7.4,"publicationDate":"2025-10-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145234968","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Hierarchically Organized Particles with Chirality-Regulating Assembly Restrictions for Enhanced Electrochemiluminescence. 具有手性调节装配限制的分层组织粒子用于增强电化学发光。

IF 7.4 1区化学

Analytical Chemistry Pub Date : 2025-10-07 DOI: 10.1021/acs.analchem.5c04164

Wenqi Chu,Xueting Cao,Linlin Song,Lin Cheng,Wenjie Gao,Siyuan Liu,Qiuying Li,Guang-Lu Zhang,Lin Cui

{"title":"Hierarchically Organized Particles with Chirality-Regulating Assembly Restrictions for Enhanced Electrochemiluminescence.","authors":"Wenqi Chu,Xueting Cao,Linlin Song,Lin Cheng,Wenjie Gao,Siyuan Liu,Qiuying Li,Guang-Lu Zhang,Lin Cui","doi":"10.1021/acs.analchem.5c04164","DOIUrl":"https://doi.org/10.1021/acs.analchem.5c04164","url":null,"abstract":"Electrochemiluminescence (ECL) efficiency depends on charge transfer between emitters and coreactants, but random collisions often make this transfer uncontrolled. Herein, we demonstrate that chirality-directed assembly could modulate the morphology of hierarchically organized particles (Au-Cys HOPs), generating an intense local electric field that accelerates electron transfer and enhances ECL. Using L/d-cysteine (Cys) as chiral ligands, we synthesize Au-Cys HOPs from polydisperse gold thiolate nanoplatelets, yielding radially organized twisted spikes. These spiky architectures exhibit a stronger built-in electric field (BIEF) than spherical Au-TGA particles (synthesized with achiral thioglycolic acid), facilitating rapid electron transfer and significantly improved ECL. In contrast, kayak-shaped Au-dl-Cys HOPs synthesized with racemic dl-Cys exhibit a smooth morphology devoid of spiky features, whereas Au-TGA particles entirely lack hierarchical organization. Thus, the Au-Cys HOPs exhibit strong anodic ECL emission with high efficiency (25.52%) with on-electrode preoxidation of radical ions (using TPrA as a coreactant), surpassing Au-dl-Cys HOPs and Au-TGA particles by 3.6- and 170.1-fold, respectively. An efficient ECL sensing platform is constructed using Au-Cys HOPs for achieving enantioselective recognition of tryptophan (Trp) isomers (Id-Trp/Il-Trp = 2.29), with a detection limit of 0.16 nM for l-Trp. This work demonstrates chirality's critical role in nanostructure design for efficient ECL and chiral sensing applications.","PeriodicalId":27,"journal":{"name":"Analytical Chemistry","volume":"80 1","pages":""},"PeriodicalIF":7.4,"publicationDate":"2025-10-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145240979","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Expanding Aerosol Acidity Measurements to the Water-Limited Regime: A Coupled Condensational Growth and Colorimetric Approach 将气溶胶酸度测量扩展到水限制状态：冷凝生长和比色法的耦合方法

IF 7.4 1区化学

Analytical Chemistry Pub Date : 2025-10-07 DOI: 10.1021/acs.analchem.5c03995

Cara M. Waters, Mia B. Kauffman, Madeline E. Cooke, Evan Z. Dalton, Andrew P. Ault

{"title":"Expanding Aerosol Acidity Measurements to the Water-Limited Regime: A Coupled Condensational Growth and Colorimetric Approach","authors":"Cara M. Waters, Mia B. Kauffman, Madeline E. Cooke, Evan Z. Dalton, Andrew P. Ault","doi":"10.1021/acs.analchem.5c03995","DOIUrl":"https://doi.org/10.1021/acs.analchem.5c03995","url":null,"abstract":"Exposure to elevated concentrations of atmospheric aerosols leads to millions of deaths globally per year from respiratory and cardiovascular diseases. Acid-catalyzed multiphase reactions involving semivolatile organic species are a key pathway for forming additional particle-phase mass, as atmospheric aerosols are highly acidic (−1 < pH < 5, average ≈ 2). However, direct aerosol pH measurements are extremely challenging due to small particle sizes (atmospheric mode ∼100 nm), low water content, and the nonconservative nature of the H+ ion. This is particularly true in aerosols with pH < 2 where ionic strengths >10 molal are common. Widely used thermodynamic models for predicting aerosol pH have limited measurement-based validation and struggle at low pH, necessitating new experimental approaches. Herein, we present a method for measuring aerosol pH across a wide pH range (−2 to 4), including the difficult-to-access regime where pH < 0. Suspended particles are grown in a precisely controlled, supersaturated environment to a uniform diameter (4.8 μm) prior to impaction on a colorimetric pH indicator, with acidified ammonium sulfate (AAS). This dilution introduces sufficient liquid water for the indicator and increases the pH into the colorimetrically-measurable range. Our results demonstrate that aerosols can be more acidic than the original solution by up to 3 pH units, with increasing deviations from solution at lower pH. Measured aerosols were also more acidic than thermodynamic model predictions. Initial results with this method will enable pH measurement in complex atmospheric chamber experiments and real-world locations where pH values remain highly uncertain and poorly constrained, addressing the critical need for accurate aerosol acidity values to predict secondary aerosol formation.","PeriodicalId":27,"journal":{"name":"Analytical Chemistry","volume":"103 1","pages":""},"PeriodicalIF":7.4,"publicationDate":"2025-10-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145235012","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

A Versatile Cytochemical Labeling Technique as a Forensic Decision-Support Tool for In Situ Detection of Cell-Derived Markers in Invisible Biological Traces. 一种多功能细胞化学标记技术作为一种法医决策支持工具，用于在不可见的生物痕迹中原位检测细胞衍生标记物。

IF 7.4 1区化学

Analytical Chemistry Pub Date : 2025-10-07 DOI: 10.1021/acs.analchem.5c02284

Mathilde Bastat,Mathilde Recipon,Séverine Nozownik,Sabrina Kellouche,Vincent Castella,Joséphine Gibert,Franck Carreiras,Rémy Agniel,Olivier Gallet,Sylvain Hubac,Francis Hermitte,Cédric R Picot,Johanne Leroy-Dudal

{"title":"A Versatile Cytochemical Labeling Technique as a Forensic Decision-Support Tool for In Situ Detection of Cell-Derived Markers in Invisible Biological Traces.","authors":"Mathilde Bastat,Mathilde Recipon,Séverine Nozownik,Sabrina Kellouche,Vincent Castella,Joséphine Gibert,Franck Carreiras,Rémy Agniel,Olivier Gallet,Sylvain Hubac,Francis Hermitte,Cédric R Picot,Johanne Leroy-Dudal","doi":"10.1021/acs.analchem.5c02284","DOIUrl":"https://doi.org/10.1021/acs.analchem.5c02284","url":null,"abstract":"Forensic genetic analysis of biological traces collected at a crime scene can aid in the rapid identification of perpetrators. Touch DNA samples consist of invisible biological traces left on an object or person after skin contact. Although these samples represent a significant portion of DNA evidence, they often fail to yield usable DNA profiles due to challenges in detection and collection. A decision-support tool capable of highlighting such traces would optimize sampling strategies and improve forensic outcomes. We previously identified cell-derived markers that persist on shed corneocytes. Here, we propose an in situ cytochemistry-based tool using a dual labeling technique that combines chromogenic and fluorescent visualization to enhance the detection of otherwise invisible traces. Chromogenic labeling of cell-derived mannose residues and keratin 10 allows the visualization of up to 100 cells on surfaces and swabs and enables the acquisition of usable DNA profiles. A combination of FITC-conjugated primary probes and an HRP-conjugated anti-FITC antibody enables versatile visualization, allowing both chromogenic and fluorescent detection of otherwise invisible biological traces and offering adaptability across various substrates. Corneocytes from fingermarks were successfully detected on both light and opaque surfaces (ceramic and metal) using a single cytochemistry process. In addition, the presence of biological material after swabbing a fingermark was highlighted, notably by chromogenic labeling. This approach could improve on-field touch DNA sample detection, proving valuable both before and after sampling. It can highlight areas for collection or prioritize swabs likely to contain biological material, thereby increasing the chances of obtaining usable DNA profiles for criminal investigation.","PeriodicalId":27,"journal":{"name":"Analytical Chemistry","volume":"108 1","pages":""},"PeriodicalIF":7.4,"publicationDate":"2025-10-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145240980","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

19F NMR-Guided Chiral Analysis and Machine Learning for Absolute Configuration Prediction of Carboxylic Acids 19F核磁共振引导手性分析和机器学习的绝对构型预测羧酸

IF 7.4 1区化学

Analytical Chemistry Pub Date : 2025-10-07 DOI: 10.1021/acs.analchem.5c05583

Shuyi Lu, Qian Wu, Shanshan Wang, Dongru Sun, Yan Liu, Shaohua Huang, Biling Huang

{"title":"19F NMR-Guided Chiral Analysis and Machine Learning for Absolute Configuration Prediction of Carboxylic Acids","authors":"Shuyi Lu, Qian Wu, Shanshan Wang, Dongru Sun, Yan Liu, Shaohua Huang, Biling Huang","doi":"10.1021/acs.analchem.5c05583","DOIUrl":"https://doi.org/10.1021/acs.analchem.5c05583","url":null,"abstract":"19F-labeled molecular probes offer significant advantages in chiral analysis, with their stereostructures playing a critical role in enantiodiscrimination. Rapid and accurate assignment of absolute configurations is particularly important for the pharmaceutical field and asymmetric synthesis. This work presents a comparative evaluation of two 19F-labeled probes as CDAs: aromatic P1 ((S)-1-(2-fluorophenyl)ethylamine) and aliphatic P2 (trans-2-fluorocyclohexanamine), focusing on their enantiomeric recognition of chiral carboxylic acids. The results demonstrate that P1 outperformed P2, particularly in analyzing carboxylic acids with chiral centers positioned several carbons away from the carboxyl group or possessing multiple chiral centers. Density functional theory calculations elucidated the underlying mechanisms, revealing that P1’s great recognition efficiency arises from a larger energy difference between diastereomers and the formation of hydrogen bonds between its fluorine atom and the analytes’ protons. These findings emphasize the importance of probe–analyte interactions in CDA-based enantiorecognition systems for achieving high-resolution discrimination. Moreover, P1 exhibited practical applications in determining ee values and analyzing various brands of ibuprofen capsules and tablets, highlighting its potential for pharmaceutical quality control. Furthermore, we introduced a novel online platform combining a P1-guided 19F NMR approach with machine learning for automated prediction of absolute configurations. This work sheds light on the differences between aromatic and aliphatic probes in enantiorecognition, while introducing an online predictive tool, in favor of the design of 19F molecular probes and the rapid assignment of absolute configurations.","PeriodicalId":27,"journal":{"name":"Analytical Chemistry","volume":"26 1","pages":""},"PeriodicalIF":7.4,"publicationDate":"2025-10-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145235015","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0