Analytical Chemistry最新文献_第5页

Acoustic Streaming-Induced Vortex Chromatography in Micron-Scale Rectangular Open Tubular Channels. 微米尺度矩形开管通道中声流诱导涡旋色谱。

IF 7.4 1区化学

Analytical Chemistry Pub Date : 2025-10-08 DOI: 10.1021/acs.analchem.5c04830

Elahe Naghdi,Dariush Bahrami Eisaabadi,Wim De Malsche

{"title":"Acoustic Streaming-Induced Vortex Chromatography in Micron-Scale Rectangular Open Tubular Channels.","authors":"Elahe Naghdi,Dariush Bahrami Eisaabadi,Wim De Malsche","doi":"10.1021/acs.analchem.5c04830","DOIUrl":"https://doi.org/10.1021/acs.analchem.5c04830","url":null,"abstract":"The separation resolution in the most advanced pressure-driven separation devices is predominantly limited by the Taylor-Aris dispersion. The induction of lateral flow perpendicular to the axial flow has recently been proposed and validated as a strategy to improve separation resolution by reducing Taylor-Aris dispersion. In the present study, we introduce an acoustic-based lateral flow into a microfluidic channel, which is enabled by matching the applied acoustic wavelength with the channel depth. With this approach, a small micrometer-scale (critical) dimension is foreseen for chromatographic purposes, and a larger dimension is foreseen to attain acoustic resonance. It is experimentally observed (in a 10 μm × 75 μm channel) that the induced acoustic streaming reduces Taylor-Aris dispersion by a factor of 10, hence resulting in a chromatographic system that behaves as if it has a critical dimension of 1 μm. It is also shown numerically that this gain can be further improved and what the impact of inevitable imperfections in the microfabricated chips is. The first example of the implication of the improvement in the chromatographic separation efficiency is shown for a macromolecule separation operated under reverse-phase conditions.","PeriodicalId":27,"journal":{"name":"Analytical Chemistry","volume":"101 1","pages":""},"PeriodicalIF":7.4,"publicationDate":"2025-10-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145246538","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

Ratiometric Fluorescence Chiral Sensors for pH Monitoring and Its Applications in Indicator Paper and Bioimaging. 比率荧光手性传感器在pH监测中的应用及其在指示纸和生物成像中的应用。

IF 7.4 1区化学

Analytical Chemistry Pub Date : 2025-10-08 DOI: 10.1021/acs.analchem.5c04243

Foroozan Feizi,Fatemeh Molaabasi,Mohanna Ezati,Mojtaba Shamsipur,Farimah Mousavi,Afsaneh Roshanfekr,Reza Mahdavian,Behnam Hajipourverdom,Ali Barati,Hossien Naderimanesh

{"title":"Ratiometric Fluorescence Chiral Sensors for pH Monitoring and Its Applications in Indicator Paper and Bioimaging.","authors":"Foroozan Feizi,Fatemeh Molaabasi,Mohanna Ezati,Mojtaba Shamsipur,Farimah Mousavi,Afsaneh Roshanfekr,Reza Mahdavian,Behnam Hajipourverdom,Ali Barati,Hossien Naderimanesh","doi":"10.1021/acs.analchem.5c04243","DOIUrl":"https://doi.org/10.1021/acs.analchem.5c04243","url":null,"abstract":"Chirality is a prevalent phenomenon in nature and living organisms and plays a significant role in biological systems. The chirality of nanomaterials represents one of the most exciting and rapidly expanding fields of science. Comparing the pH response of enantiomers of a particular chiral species remains a challenge in the field of chemistry. In this work, chiral d/l-Cdots were prepared by post-modifying an achiral Cdots core with arginine enantiomers as chiral ligands for comparing the pH sensitivity of enantiomers. In this case, modified silicon quantum dots (SiQDs) were employed to harness a sensitive and accurate ratiometric method. The fluorescence response of chiral sensors is based on an \"on-off\" strategy, with different pH ranges for d- and l-probes. Surprisingly, the d- and l-probes show different sensitivities to pH, with a linear range of pH 4.0-8.0 for d-probes and 3.5-7.5 for l-probes. The response mechanism is based on aggregation caused quenching (ACQ) due to protonated-deprotonated d-Cdots/Ca-SiQDs and l-Cdots/Ca-SiQDs probes in acidic and basic environments. Quantum mechanical (QM) calculations were in excellent agreement with the experimental results, confirming the stronger binding affinity of d-Cdots to protonated and aggregation in acidic conditions compared to l-Cdots. Crucially, these chiral probes have been successfully utilized as indicator paper and accurately detect intracellular pH (pHi) in SK-BR-3 breast cancer cells.","PeriodicalId":27,"journal":{"name":"Analytical Chemistry","volume":"54 1","pages":""},"PeriodicalIF":7.4,"publicationDate":"2025-10-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145246716","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

Europium(III) Coordination-Mediated Self-Assembly of N-Doped Carbon Dot Nanoclusters for Ratiometric Detection of Tetracycline 铕（III）配位介导的n掺杂碳点纳米团簇自组装用于四环素的比例检测

IF 7.4 1区化学

Analytical Chemistry Pub Date : 2025-10-08 DOI: 10.1021/acs.analchem.5c03576

Ying Wang, Yujing Han, Wei Wang, Yali Qiao

{"title":"Europium(III) Coordination-Mediated Self-Assembly of N-Doped Carbon Dot Nanoclusters for Ratiometric Detection of Tetracycline","authors":"Ying Wang, Yujing Han, Wei Wang, Yali Qiao","doi":"10.1021/acs.analchem.5c03576","DOIUrl":"https://doi.org/10.1021/acs.analchem.5c03576","url":null,"abstract":"Effective control of carbon dot (CD) self-assembly into larger nanoclusters in the liquid state for ultrasensitive detection is challenging and still in its infancy. For the first time, a europium(III) coordination-mediated strategy for self-assembly of N-doped carbon dots into large nanoclusters (N, Eu3+-CD nanoclusters) in aqueous solution was developed. It was found that the sizes and photoluminescence (PL) properties of nanoclusters could be effectively tuned by adjusting the Eu3+ content. The larger clusters with relatively longer fluorescence lifetimes were obtained by increasing the Eu3+ content. The simultaneous coordination of multi-CD particles with a Eu3+ and a dot particle with multiple Eu3+ was the key to inducing the self-assembly of CDs and regulating their optical properties. Furthermore, a dual-emitting N, Eu3+-CD nanocluster-based probe was constructed for the fluorescence ratiometric detection of tetracycline (TC). Once introducing TC, the blue emission of CDs was quenched through an IFE effect, but red emission of Eu3+ was significantly sensitized through an AE effect. Taking advantage of aggregation of CDs in aqueous solution, the N, Eu3+-CD nanocluster possessed a high sensitivity for detection of TC due to the spatial proximity of a large number of sensing units in the aggregated nanocluster assembly. The detection limit for TC was low to 35 nM. This work will provide a new insight into tuning the self-assembly of CDs and to regulate the photoluminescence and sensing performance of CDs.","PeriodicalId":27,"journal":{"name":"Analytical Chemistry","volume":"77 1","pages":""},"PeriodicalIF":7.4,"publicationDate":"2025-10-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145241630","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

Electrochemiluminescence Monitoring of the Ligand Exchange Process of Gold Nanoclusters 金纳米团簇配体交换过程的电化学发光监测

IF 7.4 1区化学

Analytical Chemistry Pub Date : 2025-10-08 DOI: 10.1021/acs.analchem.5c04409

Jiyuan Su, Dengke Xiang, Wan Zhong, Yizhuo Fu, Ruiting Diao, Xueqian Chen, Chao Lu

{"title":"Electrochemiluminescence Monitoring of the Ligand Exchange Process of Gold Nanoclusters","authors":"Jiyuan Su, Dengke Xiang, Wan Zhong, Yizhuo Fu, Ruiting Diao, Xueqian Chen, Chao Lu","doi":"10.1021/acs.analchem.5c04409","DOIUrl":"https://doi.org/10.1021/acs.analchem.5c04409","url":null,"abstract":"Ligand exchange reaction (LER) plays an important role in the synthesis and postmodification of metal nanoclusters (MNCs). However, due to the challenges in the analysis of the metal–ligand interface, the approaches of revealing the ligand exchange process of MNCs still lag behind. In this work, a detailed ligand exchange process of MNCs was revealed by monitoring their electrochemiluminescence (ECL) signals. Taking tetrakis(hydroxymethyl) phosphonium chloride (THPC)–gold nanoclusters (AuNCs) as a model for the existing nanocluster and 8-mercaptooctanoic acid (MOA) as a model for the incoming ligand, the ECL intensities of THPC/MOA-AuNCs first increased and then decreased before ultimately reaching a stable plateau. Further investigation confirmed that the initial increase in ECL corresponded to ligand replacement on the surface of AuNCs, while the subsequent ECL decrease was attributed to ligand rearrangement. Both the ligand replacement and ligand shell reconstruction processes modulated interligand interactions and ligand-to-metal charge transfer (LMCT) properties, thereby altering the electronic band of AuNCs and ultimately tuning their ECL emission performances. The developed ECL-based approach for monitoring LER also exhibited universal applicability, which can successfully extend to the other AuNCs with different ligand pairs. This work not only provides deep insight into the correlation between the ECL intensity and surface dynamics of MNCs but also offers a convenient approach to monitor the ligand exchange process of MNCs.","PeriodicalId":27,"journal":{"name":"Analytical Chemistry","volume":"33 1","pages":""},"PeriodicalIF":7.4,"publicationDate":"2025-10-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145241631","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

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