Analytical Chemistry最新文献

筛选
英文 中文
Ozonolysis Dissociation Kinetics for the Relative Quantification of Geometrical Phosphatidylcholine Isomers 臭氧分解解离动力学对几何磷脂酰胆碱异构体的相对定量
IF 7.4 1区 化学
Analytical Chemistry Pub Date : 2025-05-30 DOI: 10.1021/acs.analchem.5c00670
Troy R. Scoggins IV, Yingchan Guo, Paul Zerebinski, Boone M. Prentice
{"title":"Ozonolysis Dissociation Kinetics for the Relative Quantification of Geometrical Phosphatidylcholine Isomers","authors":"Troy R. Scoggins IV, Yingchan Guo, Paul Zerebinski, Boone M. Prentice","doi":"10.1021/acs.analchem.5c00670","DOIUrl":"https://doi.org/10.1021/acs.analchem.5c00670","url":null,"abstract":"The structural diversity of lipids presents significant challenges for accurate identification and characterization, necessitating advanced analytical tools. Among these challenges is the differentiation between cis and trans isomers of lipids, which differ only by the geometry of a carbon–carbon double bond. This study employs ozonolysis kinetics to distinguish these isomers based on the reactivity of their gas phase ions with ozone. To achieve precise differentiation, it is essential to use an ion adduct that enhances reactivity, thereby improving the sensitivity of the kinetic assays. We evaluated various ion types, including protonated lipids as well as lipids cationized with lithium, sodium, and potassium, using a modified quadrupole ion trap mass spectrometer. Our results demonstrate that lithium-adducted lipids exhibit the highest reaction efficiency and greatest sensitivity for distinguishing between cis and trans isomers. Subsequent analysis of cis and trans isomer mixtures of PC 18:1/18:1 (Δ9), PC 16:1/16:1 (Δ9), and PC 14:1/14:1 (Δ9) confirmed the method’s robustness.","PeriodicalId":27,"journal":{"name":"Analytical Chemistry","volume":"41 1","pages":""},"PeriodicalIF":7.4,"publicationDate":"2025-05-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144183810","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
One-Drop Serum Screening Test to Monitor Tissue Iron Accumulation 一滴血清筛选试验监测组织铁积累
IF 7.4 1区 化学
Analytical Chemistry Pub Date : 2025-05-30 DOI: 10.1021/acs.analchem.5c00778
Gabriely S. Folli, Anne Louise S. Torres, Matthews Martins, Luiz Ricardo Rodrigues Silva, Vinícius Bermond Marques, Maria Tereza Carneiro, Larissa Dias Roriz, Leonardo dos Santos, Wanderson Romão, Francis L. Martin, Paulo R. Filgueiras, Valério G. Barauna
{"title":"One-Drop Serum Screening Test to Monitor Tissue Iron Accumulation","authors":"Gabriely S. Folli, Anne Louise S. Torres, Matthews Martins, Luiz Ricardo Rodrigues Silva, Vinícius Bermond Marques, Maria Tereza Carneiro, Larissa Dias Roriz, Leonardo dos Santos, Wanderson Romão, Francis L. Martin, Paulo R. Filgueiras, Valério G. Barauna","doi":"10.1021/acs.analchem.5c00778","DOIUrl":"https://doi.org/10.1021/acs.analchem.5c00778","url":null,"abstract":"Although iron is an essential element for vital body functions, iron overload (IO) is accompanied by significant cellular damage due to its accumulation within organs. Thus, early diagnosis and accurate identification of the affected organs are critical for preventing irreversible damage and improving patient survival rates. Diagnosing tissue iron deposits relieves invasive biopsies with atomic absorption spectrometry (reserved for specific cases) or noninvasive but costly and time-consuming imaging techniques like computerized tomography and magnetic resonance, which provide limited analytical data and are unsuitable for routine screening. As an alternative, Fourier transform infrared spectroscopy combined with machine learning has emerged as a promising approach for supporting medical decision-making. In this study, we developed a minimally invasive method to identify IO and quantify iron levels in blood and tissues (heart, liver, spleen, and kidney) without biopsies. PLS-DA classification models and PLS regression models were constructed based on samples categorized into a control group (<i>n</i> = 10) and three iron-administered groups at 250 mg kg<sup>–1</sup> (<i>n</i> = 14), 500 mg·kg<sup>–1</sup> (<i>n</i> = 13), and 1000 mg·kg<sup>–1</sup> (<i>n</i> = 15). Iron levels were measured in blood samples and tissue biopsies (spleen, heart, liver, and kidney). The binary classification models (control vs iron-administered) and multiclass models (control, 250, 500, and 1000 mg·kg<sup>–1</sup>) demonstrated satisfactory performance into train and validation groups. PLS regression models for quantifying iron concentrations in blood and tissues exhibited excellent linearity and low associated errors across both calibration and test groups. Permutation tests confirmed that all models found a real class structure in the data, were not random, and were built using true chemical information. The chemical insights from the spectra may reflect adaptations associated with iron-induced dysregulation. Alterations in biomolecules could reflect systemic stress responses and may result from free radicals generated by the iron-induced Fenton reaction. Moreover, key spectral regions revealed functional interrelationships, particularly between spleen and liver, and heart and kidneys. In summary, the findings support the potential of this innovative for future research to identify IO and quantify iron levels in human blood and different human tissues using only a single drop of blood without tissue biopsies.","PeriodicalId":27,"journal":{"name":"Analytical Chemistry","volume":"81 1","pages":""},"PeriodicalIF":7.4,"publicationDate":"2025-05-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144184014","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
Revised Diffusion Law Permits Quantitative Nanoscale Characterization of Membrane Organization 修订扩散法允许定量纳米级表征膜组织
IF 7.4 1区 化学
Analytical Chemistry Pub Date : 2025-05-29 DOI: 10.1021/acs.analchem.5c00021
Barbora Svobodová, David Št’astný, Hans Blom, Ilya Mikhalyov, Natalia Gretskaya, Alena Balleková, Erdinc Sezgin, Martin Hof, Radek Šachl
{"title":"Revised Diffusion Law Permits Quantitative Nanoscale Characterization of Membrane Organization","authors":"Barbora Svobodová, David Št’astný, Hans Blom, Ilya Mikhalyov, Natalia Gretskaya, Alena Balleková, Erdinc Sezgin, Martin Hof, Radek Šachl","doi":"10.1021/acs.analchem.5c00021","DOIUrl":"https://doi.org/10.1021/acs.analchem.5c00021","url":null,"abstract":"The formation of functional nanoscopic domains is an inherent property of plasma membranes. Stimulated emission depletion combined with fluorescence correlation spectroscopy (STED-FCS) has been previously used to identify such domains; however, the information obtained by STED-FCS has been limited to the presence of such domains while crucial parameters have not been accessible, such as size (<i>R</i><sub>d</sub>), the fraction of occupied membrane surface (<i>f</i>), in-membrane lipid diffusion inside (<i>D</i><sub>in</sub>) and outside (<i>D</i><sub>out</sub>) the nanodomains as well as their self-diffusion (<i>D</i><sub>d</sub>). Here, we introduce a quantitative approach based on a revised interpretation of the diffusion law. By analyzing experimentally recorded STED-FCS diffusion law plots using a comprehensive library of simulated diffusion law plots, we extract these five parameters from STED-FCS data. That approach is verified on ganglioside nanodomains in giant unilamellar vesicles, validating the Saffman-Delbrück assumption for <i>D</i><sub>d</sub>. STED-FCS data in both plasma membranes of living PtK2 cells and giant plasma membrane vesicles are examined, and a quantitative framework for molecular diffusion modes in biological membranes is presented.","PeriodicalId":27,"journal":{"name":"Analytical Chemistry","volume":"49 1","pages":""},"PeriodicalIF":7.4,"publicationDate":"2025-05-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144165368","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
Dual-Mode Photoelectrochemical/ColoriMetric Biosensor with a Broad Linear Range for the Sensitive Detection of Enrofloxacin in Aquatic Products 宽线性范围双模光电电化学/比色生物传感器灵敏检测水产品中恩诺沙星
IF 7.4 1区 化学
Analytical Chemistry Pub Date : 2025-05-29 DOI: 10.1021/acs.analchem.5c00991
Yu-shuang Jin, Li Chen, Yi-Fei Chen, Ruo Yuan, Ya-Qin Chai, Jia-li Liu
{"title":"Dual-Mode Photoelectrochemical/ColoriMetric Biosensor with a Broad Linear Range for the Sensitive Detection of Enrofloxacin in Aquatic Products","authors":"Yu-shuang Jin, Li Chen, Yi-Fei Chen, Ruo Yuan, Ya-Qin Chai, Jia-li Liu","doi":"10.1021/acs.analchem.5c00991","DOIUrl":"https://doi.org/10.1021/acs.analchem.5c00991","url":null,"abstract":"In this study, an integrated dual-mode biosensor combining photoelectrochemical (PEC) and colorimetric (CL) methods was proposed to broaden the linear detection range of enrofloxacin (ENR), thus enabling sensitive detection of ENR in aquatic products. Compared to traditional PEC/CL dual-mode biosensors that rely on the same sensitizer for both PEC and CL signals, this biosensor expanded the linear range and enhanced sensitivity by separating the sensitizer of PEC and the signal label of CL. Specifically, the PEC detection platform employed a Z-type heterojunction of iron indium sulfide (FeIn<sub>2</sub>S<sub>4</sub>) and cadmium sulfide (CdS) to significantly improve the photoelectric conversion efficiency for the sensitivity of PEC detection. Furthermore, based on an entropy-driven catalytic nucleic acid circuit (ETSD) strategy mediated by aptamers, ENR was converted into a mass of output DNA. Subsequently, the output DNA triggered a strand displacement reaction mediated by a palindrome-catalyzed DNA assembly (NEPA) to form a three-dimensional gold nanoparticle-DNA nanocomposite for the adsorption of methylene blue (3D Au-DNA NC-MB). The resulting 3D Au-DNA NC-MB biomolecular nanocarrier was then used in PEC detection for trace ENR with a linear detection range of 10<sup>–5</sup>–10<sup>2</sup> ng·mL<sup>–1</sup>. Concurrently, the unadsorbed MB solution was used in CL detection for a high level of ENR with a linear detection range from 10<sup>–1</sup> to 10<sup>4</sup> ng·mL<sup>–1</sup>. Finally, the method was successfully applied to detect ENR in aquatic products with higher sensitivity and a wider linear range than most reported detection methods, which is anticipated for use in food safety and environmental surveillance.","PeriodicalId":27,"journal":{"name":"Analytical Chemistry","volume":"148 1","pages":""},"PeriodicalIF":7.4,"publicationDate":"2025-05-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144165372","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
High-Efficient and Controllable Purification of Protein by Cyclic Injection in an Orthogonal Micro-Free-Flow Electrophoresis 正交微自由流动电泳循环注射纯化蛋白质的高效可控方法
IF 7.4 1区 化学
Analytical Chemistry Pub Date : 2025-05-29 DOI: 10.1021/acs.analchem.5c00436
Xin Xu, Dan Wang, Cailin Zhou, Yuhang Xing, Tianpei Cai, Xinlei Yang, Ruilin Yang, Peijie Xie, Fei Liu, Zeyang Jia, Xueli Zhai, Lu Liu, Donghao Li
{"title":"High-Efficient and Controllable Purification of Protein by Cyclic Injection in an Orthogonal Micro-Free-Flow Electrophoresis","authors":"Xin Xu, Dan Wang, Cailin Zhou, Yuhang Xing, Tianpei Cai, Xinlei Yang, Ruilin Yang, Peijie Xie, Fei Liu, Zeyang Jia, Xueli Zhai, Lu Liu, Donghao Li","doi":"10.1021/acs.analchem.5c00436","DOIUrl":"https://doi.org/10.1021/acs.analchem.5c00436","url":null,"abstract":"High-abundance proteins (HAPs) in plasma significantly interfere with the purification of low-abundance proteins (LAPs). This study proposed a unique orthogonality microfluidic free-flow electrophoresis (OMFFE) platform and then set up a self-made device that can perform cyclic injection for protein purification. The OMFFE device consists of a focusing channel, an orthogonal separation channel, and two sets of voltage-controlled electrodes. In the scan voltage mode, the voltage and deflection angle are positively correlated for proteins, allowing the determination of the separation voltage for the target protein. In the selective voltage mode, proteins with a specific mass-to-charge ratio could be deflected into a specific channel, enabling selective separation of proteins. When the 75 V voltage was applied, the optimal resolution of the device between HAPs (human serum albumin, HSA, and immunoglobulin IgG) and LAP (green fluorescent protein, GFP) was achieved with Rs = 0.37. The OMFFE device achieved a removal rate of 94.7 ± 4.1% for HSA and IgG and a recovery rate of 95.3 ± 3.7% for GFP. The purity of GFP has increased by approximately 32 times. Furthermore, in human plasma, the removal rates of HAPs (HSA and IgG) and the recovery rates of LAP (GFP) are as high as 83.2 ± 3.9 and 76.3 ± 7.5%, respectively. The OMFFE device can achieve the removal and purification of proteins, hence posing promising potential in proteomics, protein function analysis, and medical diagnostics.","PeriodicalId":27,"journal":{"name":"Analytical Chemistry","volume":"2 1","pages":""},"PeriodicalIF":7.4,"publicationDate":"2025-05-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144177239","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
Characterizing for Subcellular Physical Property Changes of Chemotherapy Drug-Resistant Malignant Cancer Cells 化疗耐药恶性癌细胞亚细胞物理特性变化的表征
IF 7.4 1区 化学
Analytical Chemistry Pub Date : 2025-05-29 DOI: 10.1021/acs.analchem.5c01597
Dong Wang, I Wayan Ardyan Sudharta Putra, Hiroko Oshima, Han Gia Nguyen, Ayhan Yurtsever, Alexis Borowiak, Linhao Sun, Masanobu Oshima, Shinji Watanabe
{"title":"Characterizing for Subcellular Physical Property Changes of Chemotherapy Drug-Resistant Malignant Cancer Cells","authors":"Dong Wang, I Wayan Ardyan Sudharta Putra, Hiroko Oshima, Han Gia Nguyen, Ayhan Yurtsever, Alexis Borowiak, Linhao Sun, Masanobu Oshima, Shinji Watanabe","doi":"10.1021/acs.analchem.5c01597","DOIUrl":"https://doi.org/10.1021/acs.analchem.5c01597","url":null,"abstract":"Recently, scanning ion conductance microscopy (SICM) as a noncontact nanoprobe tool has offered great advantages for applications in revealing biophysicochemical properties of soft biological samples, specifically for living cells. These physical properties, e.g., stiffness, of the cell surface provide an efficient label-free biomarker for differing tumor from normal cells, leading to gradually increasing interest in cancer biological studies. However, expanding potential application of SICM for cancer treatment, especially targeting chemotherapy facing a challenge in drug resistance, is still rarely explored. In addition, in biology, some clues indicate that the physical factors (matrix stiffness and stress) can contribute to tumor drug resistance. Meanwhile, fundamental studies to quantify these unique physical properties of drug-resistant cancer cells correlated with leverage for targeted therapy are less known. Here, we utilized chemotherapy drugs, 5-fluorouracil (5-FU) and oxaliplatin (OXA), to establish three drug-resistant cell lines from human colorectal cancer, including DLD1, SW620, and HT29 cells. High-speed SICM measurements were performed to visualize surface characteristics of subcellular physical properties (heights, roughness, and stiffness) on the control (ctrl) sample and drug-resistant samples derived from ctrl samples. Statistical analysis of stiffness showed a reduced change from drug-resistant samples, especially those resistant to 5-FU and OXA simultaneously, in comparison to ctrl samples. This work sheds light on subcellular physical properties of drug-resistant cell lines. The SICM technique as an important strategy would provide useful assistance in biomedicine in leveraging for targeted therapy.","PeriodicalId":27,"journal":{"name":"Analytical Chemistry","volume":"1 1","pages":""},"PeriodicalIF":7.4,"publicationDate":"2025-05-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144165376","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
TopLib: Building and Searching Top-Down Mass Spectral Libraries for Proteoform Identification TopLib:构建和搜索自顶向下的质谱库用于蛋白质形态鉴定
IF 7.4 1区 化学
Analytical Chemistry Pub Date : 2025-05-29 DOI: 10.1021/acs.analchem.4c06627
Kun Li, Haixu Tang, Xiaowen Liu
{"title":"TopLib: Building and Searching Top-Down Mass Spectral Libraries for Proteoform Identification","authors":"Kun Li, Haixu Tang, Xiaowen Liu","doi":"10.1021/acs.analchem.4c06627","DOIUrl":"https://doi.org/10.1021/acs.analchem.4c06627","url":null,"abstract":"Mass spectral library search is a widely used approach for spectral identification in mass spectrometry (MS)-based proteomics. While numerous methods exist for building and searching bottom-up mass spectral libraries, there is a lack of software tools for top-down mass spectral libraries. To fill the gap, we introduce TopLib, a new software package designed for building and searching top-down spectral libraries. TopLib utilizes an efficient spectral representation technique to reduce database size and improve query speed and performance. We systematically evaluated various spectral representation techniques and scoring functions for top-down spectral clustering and search. Our results demonstrate that TopLib is significantly faster and yields higher reproducibility in proteoform identification compared to conventional database search methods in top-down MS.","PeriodicalId":27,"journal":{"name":"Analytical Chemistry","volume":"6 1","pages":""},"PeriodicalIF":7.4,"publicationDate":"2025-05-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144177204","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 Paper Strip-Based Photoinduced Electrogenerated Chemiluminescence Platform with CTF/PMo12 Heterojunction-Sensitive Glutamic Acid Detection 基于CTF/PMo12异质结敏感谷氨酸检测的纸条光致电致化学发光平台
IF 7.4 1区 化学
Analytical Chemistry Pub Date : 2025-05-29 DOI: 10.1021/acs.analchem.4c06603
Reza Sedghi Mehrbani, Mehdi Mohhamadian, Kheibar Dashtian, Neda Naseri, Rouholah Zare-Dorabei, Meissam Noroozifar, Kagan Kerman, Mohammad Mahdavi
{"title":"A Paper Strip-Based Photoinduced Electrogenerated Chemiluminescence Platform with CTF/PMo12 Heterojunction-Sensitive Glutamic Acid Detection","authors":"Reza Sedghi Mehrbani, Mehdi Mohhamadian, Kheibar Dashtian, Neda Naseri, Rouholah Zare-Dorabei, Meissam Noroozifar, Kagan Kerman, Mohammad Mahdavi","doi":"10.1021/acs.analchem.4c06603","DOIUrl":"https://doi.org/10.1021/acs.analchem.4c06603","url":null,"abstract":"Glutamic acid (GA), a crucial neurotransmitter, plays a significant role in brain function, muscle health, and various neurological disorders. Elevated GA levels have been associated with conditions such as stroke, Parkinson’s disease, epilepsy, and Alzheimer’s disease. Accurate detection of GA levels is paramount for both diagnostic and research purposes. Herein, we develop a photoinduced electrogenerated chemiluminescence (PECL) test strip fiber paper coated with a covalent triazine framework (CTF)/H<sub>3</sub>PMo<sub>12</sub>O<sub>40</sub> polyoxometalate (PMo12) heterojunction. Under blue-light irradiation, photogenerated carriers were separated by an electric field, π-electron delocalization, and polarization, leaving holes on the surface of PMo12 to drive ECL reactions based on luminol oxidation, enabling the detection of GA. This detection resulted in a PECL signal, and fluorometry information, including RGB values, was captured by using a smartphone. The PECL platform enabled the sensitive detection of GA as a neurotransmitter within a linear range of 0.05–1.7 mM, with a low limit of detection (LOD) of 15 nM. The results validated the safety and feasibility of this approach to detect GA in biological samples with satisfactory selectivity against other molecules. The combination of PECL with a smartphone reader presents an exciting avenue for the development of test strips on-site for visual real-time monitoring. This integration offers a high-throughput approach suitable for applications in point-of-care testing and disease monitoring.","PeriodicalId":27,"journal":{"name":"Analytical Chemistry","volume":"167 1","pages":""},"PeriodicalIF":7.4,"publicationDate":"2025-05-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144165367","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
Response to “Comment on ‘Differential Diagnosis of Urinary Cancers by Surface-Enhanced Raman Spectroscopy and Machine Learning’” 对“用表面增强拉曼光谱和机器学习鉴别诊断泌尿系统癌”的评论”的回应
IF 7.4 1区 化学
Analytical Chemistry Pub Date : 2025-05-29 DOI: 10.1021/acs.analchem.5c02282
Li Song, Fei Xue, Tingmiao Li, Qian Zhang, Xuesong Xu, Chengyan He, Bing Zhao, Xiao Xia Han, Linjun Cai
{"title":"Response to “Comment on ‘Differential Diagnosis of Urinary Cancers by Surface-Enhanced Raman Spectroscopy and Machine Learning’”","authors":"Li Song, Fei Xue, Tingmiao Li, Qian Zhang, Xuesong Xu, Chengyan He, Bing Zhao, Xiao Xia Han, Linjun Cai","doi":"10.1021/acs.analchem.5c02282","DOIUrl":"https://doi.org/10.1021/acs.analchem.5c02282","url":null,"abstract":"For each capillary sample, three SERS spectra were obtained from different positions The three spectra from each sample were preprocessed (spike removal, baseline correction, normalization) These three spectra were averaged to create one representative spectrum per sample The samples (not individual spectra) were randomly divided into training (70%) and testing (30%) sets This procedure was repeated 10 times to ensure robust cross-validation Healthy control versus prostate cancer: 35 principal components (cumulative variance: 87.3%); Healthy control versus kidney cancer: 40 principal components (cumulative variance: 89.1%); Healthy control versus bladder cancer: 40 principal components (cumulative variance: 89.1%); Healthy control versus all cancers: 43 principal components (cumulative variance: 90.2%); Four-class classification of three cancers: 43 principal components (cumulative variance: 90.2%). The entire dataset was first divided into 10 equal folds at the sample level (not at the spectral level); For each iteration, 7 folds were used for training and 3 folds for validation; All spectra from a single sample were kept together in the same fold; This process was repeated 10 times, with each fold serving once as the validation set. The sample size for kidney cancer in the test set was smaller (<i>n</i> = 16 cases based on Figure 3 (f)), making the accuracy metric more susceptible to fluctuation. As demonstrated by Beleites et al. in their comprehensive study on sample size planning for spectroscopic classification models, performance metrics can show considerable variance with small test sets. (4) They specifically noted that “small sample sizes lead to large variance in the performance estimates”, and that “with small sample sizes, the difference between the true performance and its estimation can be substantial”. (4) In our case, each misclassified sample in the kidney cancer test set represents a 6.25% change in accuracy, which aligns with their findings regarding small sample size effects. The performance on unseen test data remains clinically valuable across all cancer types (75%–86% accuracy), demonstrating generalization ability. We performed robust cross-validation with 10 repeated independent train-test splits at the sample level, which provides a more reliable performance estimate. Table S4 on page S6 of the Supporting Information further demonstrates the comparison of different algorithms’ performance across various classification tasks, indicating the reliability of our results. This article references 4 other publications. This article has not yet been cited by other publications.","PeriodicalId":27,"journal":{"name":"Analytical Chemistry","volume":"36 1","pages":""},"PeriodicalIF":7.4,"publicationDate":"2025-05-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144165435","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
Accurate Identification of MDMB-Type Synthetic Cannabinoids through Design of Dual Excited-State Intramolecular Proton Transfer Site Probe and Deep-Learning 基于双激发态质子转移位点探针设计和深度学习的mdmb型合成大麻素的准确鉴定
IF 7.4 1区 化学
Analytical Chemistry Pub Date : 2025-05-29 DOI: 10.1021/acs.analchem.5c00700
Baoqing Chen, Yudong Li, Chuanfang Zhao, Yuan Liu, Yuwan Du, Na Wang, Ming Guan, Xincun Dou
{"title":"Accurate Identification of MDMB-Type Synthetic Cannabinoids through Design of Dual Excited-State Intramolecular Proton Transfer Site Probe and Deep-Learning","authors":"Baoqing Chen, Yudong Li, Chuanfang Zhao, Yuan Liu, Yuwan Du, Na Wang, Ming Guan, Xincun Dou","doi":"10.1021/acs.analchem.5c00700","DOIUrl":"https://doi.org/10.1021/acs.analchem.5c00700","url":null,"abstract":"Synthetic cannabinoids, a novel class of highly toxic psychoactive substances with various disguised forms, have posed significant risks to public safety, and their weak reactivity presents a substantial challenge for swift and accurate analysis. In this work, we develop an optical probe equipped with dual excited-state intramolecular proton transfer (ESIPT) sites that inhibit the intramolecular proton transfer through hydrogen bonding, facilitating the specific detection of MDMB-type synthetic cannabinoids. The probe can sensitively detect the MDMB-type synthetic cannabinoids at 1.8 × 10<sup>–3</sup> mg/mL, specifically recognizing them among 20 potential interferents with a rapid fluorescence response within 1.2 s, leading to the development of a portable, user-friendly sensor for a swift and precise analysis of these compounds in complex scenarios. Furthermore, this study combines a portable sensing chip with an advanced convolutional algorithm for image processing, enabling precise differentiation among six MDMB-type synthetic cannabinoid variants. This study successfully detected the target substance by creating a dual ESIPT optical probe, thereby offering a novel approach to detect psychoactive substances with limited reactivity.","PeriodicalId":27,"journal":{"name":"Analytical Chemistry","volume":"48 1","pages":""},"PeriodicalIF":7.4,"publicationDate":"2025-05-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144177215","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
0
×
引用
GB/T 7714-2015
复制
MLA
复制
APA
复制
导出至
BibTeX EndNote RefMan NoteFirst NoteExpress
×
提示
您的信息不完整,为了账户安全,请先补充。
现在去补充
×
提示
您因"违规操作"
具体请查看互助需知
我知道了
×
提示
确定
请完成安全验证×
相关产品
×
本文献相关产品
联系我们:info@booksci.cn Book学术提供免费学术资源搜索服务,方便国内外学者检索中英文文献。致力于提供最便捷和优质的服务体验。 Copyright © 2023 布克学术 All rights reserved.
京ICP备2023020795号-1
ghs 京公网安备 11010802042870号
Book学术文献互助
Book学术文献互助群
群 号:481959085
Book学术官方微信