Small molecule near-infrared (NIR) fluorophores play a critical role in disease diagnosis and early detection of various markers in living organisms. To accelerate their development and design, a deep learning platform, NIRFluor, was established to rapidly screen small molecule NIR fluorophores with the desired optical properties. The core component of NIRFluor is a state-of-the-art deep learning model trained on 5179 experimental big data. First, novel hybrid fingerprints including Morgan fingerprints, physicochemical properties, and solvent properties were proposed. Then, a powerful deep learning model, multitask fingerprint-enhanced graph convolutional network (MT-FinGCN), was designed, which combines fingerprint information and molecule graph structure information to achieve accurate prediction of six properties (absorption wavelength, emission wavelength, Stokes shift, extinction coefficient, photoluminescence quantum yield, and lifetime) of different small molecule NIR fluorophores in different solvents. Furthermore, the “black-box” of the GCN model was opened through interpretability studies. Finally, the well-trained models were placed on the web platform NIRFluor for free use (https://nirfluor.aicbsc.com).
{"title":"NIRFluor: A Deep Learning Platform for Rapid Screening of Small Molecule Near-Infrared Fluorophores with Desired Optical Properties","authors":"Xiaozhi Wang, Hailong Wu, Tong Wang, Yao Chen, Baoshuo Jia, Huan Fang, Xiaoyue Yin, Yanping Zhao, Ruqin Yu","doi":"10.1021/acs.analchem.4c01953","DOIUrl":"https://doi.org/10.1021/acs.analchem.4c01953","url":null,"abstract":"Small molecule near-infrared (NIR) fluorophores play a critical role in disease diagnosis and early detection of various markers in living organisms. To accelerate their development and design, a deep learning platform, NIRFluor, was established to rapidly screen small molecule NIR fluorophores with the desired optical properties. The core component of NIRFluor is a state-of-the-art deep learning model trained on 5179 experimental big data. First, novel hybrid fingerprints including Morgan fingerprints, physicochemical properties, and solvent properties were proposed. Then, a powerful deep learning model, multitask fingerprint-enhanced graph convolutional network (MT-FinGCN), was designed, which combines fingerprint information and molecule graph structure information to achieve accurate prediction of six properties (absorption wavelength, emission wavelength, Stokes shift, extinction coefficient, photoluminescence quantum yield, and lifetime) of different small molecule NIR fluorophores in different solvents. Furthermore, the “black-box” of the GCN model was opened through interpretability studies. Finally, the well-trained models were placed on the web platform NIRFluor for free use (https://nirfluor.aicbsc.com).","PeriodicalId":27,"journal":{"name":"Analytical Chemistry","volume":"36 1","pages":""},"PeriodicalIF":7.4,"publicationDate":"2025-01-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142988050","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}
Pub Date : 2025-01-17DOI: 10.1021/acs.analchem.4c05197
Úna. E. Hogan, H. Ben Voss, Benjamin Lei, Rodney D. L. Smith
Research has shown microplastic particles to be pervasive pollutants in the natural environment, but labor-intensive sample preparation, data acquisition, and analysis protocols continue to be necessary to navigate their diverse chemistry. Machine learning (ML) classification models have shown promise for identifying microplastics from their Raman spectra, but all attempts to date have focused on the lower energy “fingerprint” region of the spectrum. We explore strategies to improve ML classification models based on the k-nearest-neighbor algorithm by including other regions of the Raman spectra. The information content inherent in C–H bonds, which occur in the higher frequency region of 2500–3600 cm–1, is found to be particularly powerful in improving classification model performance. Variations in the relative intensity of peaks arising from C–H vibrations improve identification capabilities for plastics that the fingerprint region alone struggles with, such as resolving acrylonitrile butadiene styrene from polystyrene and identifying poly(vinyl chloride), polyurethane, and polyoxymethylene. Testing of strategies to both acquire and analyze data across the two regions is explored for their efficacy and their compatibility with real-world sampling restrictions. We find that localized normalization of spectra, independently acquired in the two regions, provides the most direct and effective route to improving the ML classification performance.
{"title":"Integrating C–H Information to Improve Machine Learning Classification Models for Microplastic Identification from Raman Spectra","authors":"Úna. E. Hogan, H. Ben Voss, Benjamin Lei, Rodney D. L. Smith","doi":"10.1021/acs.analchem.4c05197","DOIUrl":"https://doi.org/10.1021/acs.analchem.4c05197","url":null,"abstract":"Research has shown microplastic particles to be pervasive pollutants in the natural environment, but labor-intensive sample preparation, data acquisition, and analysis protocols continue to be necessary to navigate their diverse chemistry. Machine learning (ML) classification models have shown promise for identifying microplastics from their Raman spectra, but all attempts to date have focused on the lower energy “fingerprint” region of the spectrum. We explore strategies to improve ML classification models based on the <i>k</i>-nearest-neighbor algorithm by including other regions of the Raman spectra. The information content inherent in C–H bonds, which occur in the higher frequency region of 2500–3600 cm<sup>–1</sup>, is found to be particularly powerful in improving classification model performance. Variations in the relative intensity of peaks arising from C–H vibrations improve identification capabilities for plastics that the fingerprint region alone struggles with, such as resolving acrylonitrile butadiene styrene from polystyrene and identifying poly(vinyl chloride), polyurethane, and polyoxymethylene. Testing of strategies to both acquire and analyze data across the two regions is explored for their efficacy and their compatibility with real-world sampling restrictions. We find that localized normalization of spectra, independently acquired in the two regions, provides the most direct and effective route to improving the ML classification performance.","PeriodicalId":27,"journal":{"name":"Analytical Chemistry","volume":"34 1","pages":""},"PeriodicalIF":7.4,"publicationDate":"2025-01-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142988052","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}
Pub Date : 2025-01-17DOI: 10.1021/acs.analchem.4c04591
Filip Stefanovic, Lauren G. Brown, James MacDonald, Theo Bammler, Darawan Rinchai, Serena Nguyen, Yuting Zeng, Victoria Shinkawa, Karen Adams, Damien Chaussabel, Erwin Berthier, Amanda J. Haack, Ashleigh B. Theberge
Remote research studies are an invaluable tool for reaching populations with limited access to large medical centers or universities. To expand the remote study toolkit, we previously developed homeRNA, which allows for at-home self-collection and stabilization of blood and demonstrated the feasibility of using homeRNA in high temperature climates. Here, we expand upon this work through a systematic study exploring the effects of high temperature on RNA integrity (represented as RNA Integrity Number, RIN) through in-lab and field experiments. Compared to the frozen controls (overall mean RIN of 8.2, n = 8), samples kept at 37 °C for 2, 4, and 8 days had mean RINs of 7.6, 5.9, and 5.2 (n = 3), respectively, indicating that typical shipping conditions (∼2 days) yield samples suitable for downstream RNA sequencing. Shorter time intervals (6 h) resulted in minimal RNA degradation (median RIN of 6.4, n = 3) even at higher temperatures (50 °C) compared to the frozen control (mean RIN of 7.8, n = 3). Additionally, we shipped homeRNA-stabilized blood from a single donor to 14 states and back during the summer with continuous temperature probes (7.1 median RIN, n = 42). Samples from all locations were analyzed with 3′ mRNA-seq to assess differences in gene counts, with the data suggesting that there was no preferential degradation of transcripts as a result of different shipping times, temperatures, and regions. Overall, our data support that homeRNA can be used in elevated temperature conditions, enabling decentralized sample collection for telemedicine, global health, and clinical research.
{"title":"Your Blood is Out for Delivery: Considerations of Shipping Time and Temperature on Degradation of RNA from Stabilized Whole Blood","authors":"Filip Stefanovic, Lauren G. Brown, James MacDonald, Theo Bammler, Darawan Rinchai, Serena Nguyen, Yuting Zeng, Victoria Shinkawa, Karen Adams, Damien Chaussabel, Erwin Berthier, Amanda J. Haack, Ashleigh B. Theberge","doi":"10.1021/acs.analchem.4c04591","DOIUrl":"https://doi.org/10.1021/acs.analchem.4c04591","url":null,"abstract":"Remote research studies are an invaluable tool for reaching populations with limited access to large medical centers or universities. To expand the remote study toolkit, we previously developed homeRNA, which allows for at-home self-collection and stabilization of blood and demonstrated the feasibility of using homeRNA in high temperature climates. Here, we expand upon this work through a systematic study exploring the effects of high temperature on RNA integrity (represented as RNA Integrity Number, RIN) through in-lab and field experiments. Compared to the frozen controls (overall mean RIN of 8.2, <i>n</i> = 8), samples kept at 37 °C for 2, 4, and 8 days had mean RINs of 7.6, 5.9, and 5.2 (<i>n</i> = 3), respectively, indicating that typical shipping conditions (∼2 days) yield samples suitable for downstream RNA sequencing. Shorter time intervals (6 h) resulted in minimal RNA degradation (median RIN of 6.4, <i>n</i> = 3) even at higher temperatures (50 °C) compared to the frozen control (mean RIN of 7.8, <i>n</i> = 3). Additionally, we shipped homeRNA-stabilized blood from a single donor to 14 states and back during the summer with continuous temperature probes (7.1 median RIN, <i>n</i> = 42). Samples from all locations were analyzed with 3′ mRNA-seq to assess differences in gene counts, with the data suggesting that there was no preferential degradation of transcripts as a result of different shipping times, temperatures, and regions. Overall, our data support that homeRNA can be used in elevated temperature conditions, enabling decentralized sample collection for telemedicine, global health, and clinical research.","PeriodicalId":27,"journal":{"name":"Analytical Chemistry","volume":"50 1","pages":""},"PeriodicalIF":7.4,"publicationDate":"2025-01-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142988048","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}
Pub Date : 2025-01-17DOI: 10.1021/acs.analchem.4c04911
Cecilia Magnusson, Mahdi Rezayati Charan, Per Augustsson
Isolation and characterization of circulating tumor cells (CTCs) present a noninvasive alternative to monitor disease progression in individual patients. However, the heterogeneous lineage specificity of CTCs makes it difficult to isolate and identify possible CTCs by a liquid biopsy. Better label-free methods for the isolation of viable CTCs are needed. Our solution is a combined approach that is inherently epitope independent. Cells are separated by size-sensitive acoustophoresis using an ultrasonic standing wave field, followed by size-insensitive, acoustic barrier-medium focusing, which enables the enrichment of viable cancer cells in blood. With standard acoustophoresis in homogeneous medium, lymphocytes and monocytes were efficiently removed, while removal of granulocytes from the target MCF7 breast cancer cells was not possible due to overlapping acoustic migration velocities for viable cells. Remaining granulocytes were removed by a second separation step with an acoustic impedance barrier-medium selectively blocking the transport of MCF7 cells to generate a clean cancer cell fraction. For two series of 500 mL samples containing 5 × 105 white blood cells, spiked with 2 × 104 or 1 × 103 MCF7 cells, the recovery of MCF7 cells was 77.3% with a 99.9% depletion of white blood cells in the final cancer cell fraction. The most abundant contaminating cell type was granulocytes (85.9% of remaining cells). Nearly all lymphocytes (99.996%) and monocytes (99.995%) were depleted. A two-step acoustic cell separation based on cell size and acoustic impedance is well suited to generate a purified cancer cell fraction as a preparatory step for downstream single-cell analysis.
{"title":"Two-Step Acoustic Cell Separation Based on Cell Size and Acoustic Impedance─toward Isolation of Viable Circulating Tumor Cells","authors":"Cecilia Magnusson, Mahdi Rezayati Charan, Per Augustsson","doi":"10.1021/acs.analchem.4c04911","DOIUrl":"https://doi.org/10.1021/acs.analchem.4c04911","url":null,"abstract":"Isolation and characterization of circulating tumor cells (CTCs) present a noninvasive alternative to monitor disease progression in individual patients. However, the heterogeneous lineage specificity of CTCs makes it difficult to isolate and identify possible CTCs by a liquid biopsy. Better label-free methods for the isolation of viable CTCs are needed. Our solution is a combined approach that is inherently epitope independent. Cells are separated by size-sensitive acoustophoresis using an ultrasonic standing wave field, followed by size-insensitive, acoustic barrier-medium focusing, which enables the enrichment of viable cancer cells in blood. With standard acoustophoresis in homogeneous medium, lymphocytes and monocytes were efficiently removed, while removal of granulocytes from the target MCF7 breast cancer cells was not possible due to overlapping acoustic migration velocities for viable cells. Remaining granulocytes were removed by a second separation step with an acoustic impedance barrier-medium selectively blocking the transport of MCF7 cells to generate a clean cancer cell fraction. For two series of 500 mL samples containing 5 × 10<sup>5</sup> white blood cells, spiked with 2 × 10<sup>4</sup> or 1 × 10<sup>3</sup> MCF7 cells, the recovery of MCF7 cells was 77.3% with a 99.9% depletion of white blood cells in the final cancer cell fraction. The most abundant contaminating cell type was granulocytes (85.9% of remaining cells). Nearly all lymphocytes (99.996%) and monocytes (99.995%) were depleted. A two-step acoustic cell separation based on cell size and acoustic impedance is well suited to generate a purified cancer cell fraction as a preparatory step for downstream single-cell analysis.","PeriodicalId":27,"journal":{"name":"Analytical Chemistry","volume":"6 1","pages":""},"PeriodicalIF":7.4,"publicationDate":"2025-01-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142988049","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}
Listeria monocytogenes (L. monocytogenes) is one of the most prevalent threats, capable of inducing diverse illnesses and presenting a serious threat to public health. Herein, we demonstrate a novel dual-mode colorimetric/fluorescence biosensor based on the exponential amplification reaction and strand displacement reactions (EASDR), which has multiplexing capability that significantly promotes the anchoring and trapping of Pt nanoparticles (Pt NPs) and fluorescent dyes for sensitive detection of Listeria monocytogenes (L. monocytogenes). The method works by targeting specific bacteria with aptamers and promoting repeated EASDR to affect the immobilization of Pt NPs and fluorescent dyes in the orifice plate, which could produce changes in fluorescence and colorimetric signals. The assay achieves a detection limit of 38 CFU/mL in colorimetric and 10 CFU/mL in fluorescence. Furthermore, the developed biosensor can be applied to the analysis of raw food samples (milk), and good recoveries were obtained in spiked food samples. In summary, the dual-mode biosensor improves the accuracy of detection by simultaneously outputting two signals and shows great potential in the specific identification and detection of foodborne pathogens.
{"title":"A Dual-Mode Colorimetric and Fluorescence Biosensor Based on a Nucleic Acid Multiplexing Platform for the Detection of Listeria monocytogenes","authors":"Qing Kang, Shuaiqi Zhang, Chenjing Ma, Ruixin Guo, Xin Yu, Tong Lin, Wei Pang, Yidi Liu, Jingbo Jiao, Mingyang Xu, Xinjun Du, Shuo Wang","doi":"10.1021/acs.analchem.4c05861","DOIUrl":"https://doi.org/10.1021/acs.analchem.4c05861","url":null,"abstract":"<i>Listeria monocytogenes</i> (<i>L. monocytogenes</i>) is one of the most prevalent threats, capable of inducing diverse illnesses and presenting a serious threat to public health. Herein, we demonstrate a novel dual-mode colorimetric/fluorescence biosensor based on the <u>e</u>xponential <u>a</u>mplification reaction and <u>s</u>trand <u>d</u>isplacement <u>r</u>eactions (EASDR), which has multiplexing capability that significantly promotes the anchoring and trapping of Pt nanoparticles (Pt NPs) and fluorescent dyes for sensitive detection of <i>Listeria monocytogenes</i> (<i>L. monocytogenes</i>). The method works by targeting specific bacteria with aptamers and promoting repeated EASDR to affect the immobilization of Pt NPs and fluorescent dyes in the orifice plate, which could produce changes in fluorescence and colorimetric signals. The assay achieves a detection limit of 38 CFU/mL in colorimetric and 10 CFU/mL in fluorescence. Furthermore, the developed biosensor can be applied to the analysis of raw food samples (milk), and good recoveries were obtained in spiked food samples. In summary, the dual-mode biosensor improves the accuracy of detection by simultaneously outputting two signals and shows great potential in the specific identification and detection of foodborne pathogens.","PeriodicalId":27,"journal":{"name":"Analytical Chemistry","volume":"44 1","pages":""},"PeriodicalIF":7.4,"publicationDate":"2025-01-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142988053","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}
Cancer is a global health challenge that urgently requires more sensitive and effective cancer detection methods. Fluorescence imaging with small molecule fluorescent probes has shown great promise for cancer detection but most of the developed probes lack active tumor cell targeting, which makes them unable to selectively target tumors, thereby reducing the accuracy of in vivo tumor detection. Herein, we report a novel probe Bio-S that combines a viscosity-sensitive and cell membrane targetable fluorescent group with biotin for targeted imaging and precise visualization of tumor cells and tumors. Bio-S exhibits sensitive fluorescence changes for viscosity at ∼660 nm and excellent cell membrane localization and imaging ability (red fluorescence, wash-free, and long-term imaging). Moreover, compared with the nonbiotinylated control probe C6-S, the biotinylated Bio-S can specifically target tumor cell membranes, thereby achieving much higher selectivity and sensitivity in distinguishing tumor cells from normal cells. Mice imaging experiments show that tail vein injection of Bio-S can target tumors and monitor lung cancer metastasis at the in vivo level. Therefore, this work provides an effective new strategy and tool for tumor-targeted detection and precise diagnosis.
{"title":"Biotinylated Viscosity Sensitive Cell Membrane Probe for Targeted Imaging and Precise Visualization of Tumor Cells and Tumors","authors":"Qianhua Li, Zhoupeng Zheng, Yao Chen, Zhijie Li, Shumin Feng, Guoqiang Feng","doi":"10.1021/acs.analchem.4c04513","DOIUrl":"https://doi.org/10.1021/acs.analchem.4c04513","url":null,"abstract":"Cancer is a global health challenge that urgently requires more sensitive and effective cancer detection methods. Fluorescence imaging with small molecule fluorescent probes has shown great promise for cancer detection but most of the developed probes lack active tumor cell targeting, which makes them unable to selectively target tumors, thereby reducing the accuracy of in vivo tumor detection. Herein, we report a novel probe <b>Bio-S</b> that combines a viscosity-sensitive and cell membrane targetable fluorescent group with biotin for targeted imaging and precise visualization of tumor cells and tumors. <b>Bio-S</b> exhibits sensitive fluorescence changes for viscosity at ∼660 nm and excellent cell membrane localization and imaging ability (red fluorescence, wash-free, and long-term imaging). Moreover, compared with the nonbiotinylated control probe <b>C6-S</b>, the biotinylated <b>Bio-S</b> can specifically target tumor cell membranes, thereby achieving much higher selectivity and sensitivity in distinguishing tumor cells from normal cells. Mice imaging experiments show that tail vein injection of <b>Bio-S</b> can target tumors and monitor lung cancer metastasis at the in vivo level. Therefore, this work provides an effective new strategy and tool for tumor-targeted detection and precise diagnosis.","PeriodicalId":27,"journal":{"name":"Analytical Chemistry","volume":"98 1","pages":""},"PeriodicalIF":7.4,"publicationDate":"2025-01-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142988054","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}
Pub Date : 2025-01-16DOI: 10.1021/acs.analchem.4c05940
Ryan A. Smith, Ashraf M. Omar, Fayaj A. Mulani, Qibin Zhang
Double bond (C═C) position isomerism in unsaturated lipids can indicate abnormal lipid metabolism and pathological conditions. Novel chemical derivatization and mass spectrometry-based techniques are under continuing development to provide more accurate elucidation of lipid structure in finer structural detail. Here, we introduce a new ion chemistry for annotating lipid C═C positions, which is highly efficient for liquid chromatography–mass spectrometry-based lipidomics. This ion chemistry relies on the online derivatization of lipid C═C with ozone and nitrogen oxides upon fragmentation by tandem mass spectrometry, yielding characteristic product ions capable of unambiguously annotating C═C regioisomers. The new workflow was thoroughly evaluated with various glycerophospholipids and fatty acids and applied to human plasma lipid extract, successfully identified and quantified 270 glycerophospholipid and 36 fatty acid C═C isomers with an in-house developed software, OzNOx Companion, for automated data analysis.
{"title":"OzNOxESI: A Novel Mass Spectrometry Ion Chemistry for Elucidating Lipid Double-Bond Regioisomerism in Complex Mixtures","authors":"Ryan A. Smith, Ashraf M. Omar, Fayaj A. Mulani, Qibin Zhang","doi":"10.1021/acs.analchem.4c05940","DOIUrl":"https://doi.org/10.1021/acs.analchem.4c05940","url":null,"abstract":"Double bond (C═C) position isomerism in unsaturated lipids can indicate abnormal lipid metabolism and pathological conditions. Novel chemical derivatization and mass spectrometry-based techniques are under continuing development to provide more accurate elucidation of lipid structure in finer structural detail. Here, we introduce a new ion chemistry for annotating lipid C═C positions, which is highly efficient for liquid chromatography–mass spectrometry-based lipidomics. This ion chemistry relies on the online derivatization of lipid C═C with ozone and nitrogen oxides upon fragmentation by tandem mass spectrometry, yielding characteristic product ions capable of unambiguously annotating C═C regioisomers. The new workflow was thoroughly evaluated with various glycerophospholipids and fatty acids and applied to human plasma lipid extract, successfully identified and quantified 270 glycerophospholipid and 36 fatty acid C═C isomers with an in-house developed software, OzNOx Companion, for automated data analysis.","PeriodicalId":27,"journal":{"name":"Analytical Chemistry","volume":"40 1","pages":""},"PeriodicalIF":7.4,"publicationDate":"2025-01-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142986223","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}
Pub Date : 2025-01-16DOI: 10.1021/acs.analchem.4c05786
Luiz O. Orzari, Cristiane Kalinke, Habdias A. Silva-Neto, Danielly S. Rocha, Jéssica R. Camargo, Wendell K.T. Coltro, Bruno C. Janegitz
A few decades ago, the technological boom revolutionized access to information, ushering in a new era of research possibilities. Electrochemical devices have recently emerged as a key scientific advancement utilizing electrochemistry principles to detect various chemical species. These versatile electrodes find applications in diverse fields, such as healthcare diagnostics and environmental monitoring. Modern designs have given rise to innovative manufacturing protocols, including screen and additive printing methods, for creating sophisticated 2D and 3D electrochemical devices. This perspective provides a comprehensive overview of the screen-printing and additive-printing protocols for constructing electrochemical devices. It is also informed that screen-printed sensors offer cost-effectiveness and ease of fabrication, although they may pose challenges due to the use of toxic volatile inks and limited design flexibility. On the other hand, additive manufacturing, especially the fused filament fabrication (or fused deposition modeling) strategies, allows for intricate three-dimensional sensor designs and rapid prototyping of customized equipment. However, the post-treatment processes and material selection can affect production costs. Despite their unique advantages and limitations, both printing techniques show promise for various applications, driving innovation in the field toward more advanced sensor designs. Finally, these advancements pave the way for improved sensor performance and expand possibilities for academic, environmental, and industrial applications. The future is full of exciting opportunities for state-of-the-art sensor technologies that will further improve our ability to detect and determine various substances in a wide range of environments as researchers continue to explore the many possibilities of electrochemical devices.
{"title":"Screen-Printing vs Additive Manufacturing Approaches: Recent Aspects and Trends Involving the Fabrication of Electrochemical Sensors","authors":"Luiz O. Orzari, Cristiane Kalinke, Habdias A. Silva-Neto, Danielly S. Rocha, Jéssica R. Camargo, Wendell K.T. Coltro, Bruno C. Janegitz","doi":"10.1021/acs.analchem.4c05786","DOIUrl":"https://doi.org/10.1021/acs.analchem.4c05786","url":null,"abstract":"A few decades ago, the technological boom revolutionized access to information, ushering in a new era of research possibilities. Electrochemical devices have recently emerged as a key scientific advancement utilizing electrochemistry principles to detect various chemical species. These versatile electrodes find applications in diverse fields, such as healthcare diagnostics and environmental monitoring. Modern designs have given rise to innovative manufacturing protocols, including screen and additive printing methods, for creating sophisticated 2D and 3D electrochemical devices. This perspective provides a comprehensive overview of the screen-printing and additive-printing protocols for constructing electrochemical devices. It is also informed that screen-printed sensors offer cost-effectiveness and ease of fabrication, although they may pose challenges due to the use of toxic volatile inks and limited design flexibility. On the other hand, additive manufacturing, especially the fused filament fabrication (or fused deposition modeling) strategies, allows for intricate three-dimensional sensor designs and rapid prototyping of customized equipment. However, the post-treatment processes and material selection can affect production costs. Despite their unique advantages and limitations, both printing techniques show promise for various applications, driving innovation in the field toward more advanced sensor designs. Finally, these advancements pave the way for improved sensor performance and expand possibilities for academic, environmental, and industrial applications. The future is full of exciting opportunities for state-of-the-art sensor technologies that will further improve our ability to detect and determine various substances in a wide range of environments as researchers continue to explore the many possibilities of electrochemical devices.","PeriodicalId":27,"journal":{"name":"Analytical Chemistry","volume":"31 1","pages":""},"PeriodicalIF":7.4,"publicationDate":"2025-01-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142986221","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}
The accurate quantification of multicomponents using LC-MS is pivotal for ensuring the quality control of herbal medicine, as well as the investigation of their analysis of biological tissue distribution. However, two significant challenges persist: the scarcity of authentic standards and the selection of appropriate internal standards. In this study, we present a highly sensitive isotope-coded equivalent reporter ion assay (iERIA) that combines equivalently quantitative ion and isotope-coded derivatization strategies. This method offers triple functionality: enabling the semidetermination of multiple components using a single standard, introducing stable isotope-labeled internal standards, and enhancing MS detection signals. Using four isocoumarins as a model, namely, 5-carboxylmellein, 5-hydroxymethylmellein, 5-methylmellein, and 5-hydroxymellein, we successfully quantified these compounds across various matrices, including herbal extracts, plasma, urine, and liver tissue. Reporter ions at m/z 170 and 234 generated by the dansulfonyl derivatives of isocoumarins, were subsequently detected for calculating the concentrations of samples based on the equivalent ion method. It is very beneficial for trace detection in biological samples free of any concentration steps, with an increased LOD of 50 times after dansyl chloride derivatization. Additionally, the introduction of stable isotope-labeled internal standards using d6-dansyl chloride mitigated matrix effects and instrument drift, ensuring the accuracy and precision of the semiquantification. This practical UPLC–MS/MS strategy significantly expands the applicability of multicomponent determination, with promising implications in diverse domains such as herbal medicine active ingredient analysis, food function and safety assessment, and metabolomics research.
{"title":"Development and Validation of a Highly Sensitive Isotope-Coded Equivalent Reporter Ion Assay for the Semi-Quantification of Isocoumarins in Complex Matrices","authors":"Xiao-Feng Huang, Peng-Yu Liang, Xiao-Dan Yin, Yue-Cai Hou, Tian-Tian Wang, Ruo-Wen Li, Zhifeng Zhang, Xiaojun Yao, Pei Luo, Lin-Sen Qing","doi":"10.1021/acs.analchem.4c05069","DOIUrl":"https://doi.org/10.1021/acs.analchem.4c05069","url":null,"abstract":"The accurate quantification of multicomponents using LC-MS is pivotal for ensuring the quality control of herbal medicine, as well as the investigation of their analysis of biological tissue distribution. However, two significant challenges persist: the scarcity of authentic standards and the selection of appropriate internal standards. In this study, we present a highly sensitive isotope-coded equivalent reporter ion assay (iERIA) that combines equivalently quantitative ion and isotope-coded derivatization strategies. This method offers triple functionality: enabling the semidetermination of multiple components using a single standard, introducing stable isotope-labeled internal standards, and enhancing MS detection signals. Using four isocoumarins as a model, namely, 5-carboxylmellein, 5-hydroxymethylmellein, 5-methylmellein, and 5-hydroxymellein, we successfully quantified these compounds across various matrices, including herbal extracts, plasma, urine, and liver tissue. Reporter ions at <i>m</i>/<i>z</i> 170 and 234 generated by the dansulfonyl derivatives of isocoumarins, were subsequently detected for calculating the concentrations of samples based on the equivalent ion method. It is very beneficial for trace detection in biological samples free of any concentration steps, with an increased LOD of 50 times after dansyl chloride derivatization. Additionally, the introduction of stable isotope-labeled internal standards using <i>d</i><sub><i>6</i></sub>-dansyl chloride mitigated matrix effects and instrument drift, ensuring the accuracy and precision of the semiquantification. This practical UPLC–MS/MS strategy significantly expands the applicability of multicomponent determination, with promising implications in diverse domains such as herbal medicine active ingredient analysis, food function and safety assessment, and metabolomics research.","PeriodicalId":27,"journal":{"name":"Analytical Chemistry","volume":"44 1","pages":""},"PeriodicalIF":7.4,"publicationDate":"2025-01-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142988292","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}
Pub Date : 2025-01-15DOI: 10.1021/acs.analchem.4c03855
Xiaofeng Xie, Jianfeng Xiang, Huanhuan Zhao, Bingrun Tong, Lei Zhang, Xiaonan Kang, Siyuan Kong, Tao Wang, Weiqian Cao
The role of peripheral blood platelets as indicators of cancer progression is increasingly recognized, and the significance of abnormal glycosylation in platelet function and related disorders is gaining attention. However, the potential of platelets as a source of protein site-specific glycosylation for cancer diagnosis remains underexplored. In this study, we proposed a general pipeline that integrates quantitative proteomics with site-specific glycoproteomics, allowing for an in-depth investigation of the platelet glycoproteome. With this pipeline, we generated a data set comprising 3,466 proteins with qualitative information, 3,199 proteins with quantitative information, 3,419 site-specific glycans with qualitative information and 3,377 site-specific glycans with quantitative information from peripheral blood platelets of hepatocellular carcinoma (HCC) patients, metastatic liver cancer (mLC) patients, and healthy controls. The integrated analysis revealed significant changes in platelet protein N-glycosylation in liver cancer patients. Further systems biology analysis and lectin pull-down-coupled ELISA assays in independent clinical samples confirmed two N-glycoproteins with specific glycan types, complement C3 (C3) with oligomannose modification and integrin β-3 (ITGB3) with sialylation, as potential biomarkers distinguishing liver cancer patients from healthy individuals, without differentiating between HCC and mLC patient group. These findings highlight the potential of platelet protein glycosylation as biomarkers.
{"title":"Integrative Quantitative Analysis of Platelet Proteome and Site-Specific Glycoproteome Reveals Diagnostic Potential of Platelet Glycoproteins for Liver Cancer","authors":"Xiaofeng Xie, Jianfeng Xiang, Huanhuan Zhao, Bingrun Tong, Lei Zhang, Xiaonan Kang, Siyuan Kong, Tao Wang, Weiqian Cao","doi":"10.1021/acs.analchem.4c03855","DOIUrl":"https://doi.org/10.1021/acs.analchem.4c03855","url":null,"abstract":"The role of peripheral blood platelets as indicators of cancer progression is increasingly recognized, and the significance of abnormal glycosylation in platelet function and related disorders is gaining attention. However, the potential of platelets as a source of protein site-specific glycosylation for cancer diagnosis remains underexplored. In this study, we proposed a general pipeline that integrates quantitative proteomics with site-specific glycoproteomics, allowing for an in-depth investigation of the platelet glycoproteome. With this pipeline, we generated a data set comprising 3,466 proteins with qualitative information, 3,199 proteins with quantitative information, 3,419 site-specific glycans with qualitative information and 3,377 site-specific glycans with quantitative information from peripheral blood platelets of hepatocellular carcinoma (HCC) patients, metastatic liver cancer (mLC) patients, and healthy controls. The integrated analysis revealed significant changes in platelet protein N-glycosylation in liver cancer patients. Further systems biology analysis and lectin pull-down-coupled ELISA assays in independent clinical samples confirmed two N-glycoproteins with specific glycan types, complement C3 (C3) with oligomannose modification and integrin β-3 (ITGB3) with sialylation, as potential biomarkers distinguishing liver cancer patients from healthy individuals, without differentiating between HCC and mLC patient group. These findings highlight the potential of platelet protein glycosylation as biomarkers.","PeriodicalId":27,"journal":{"name":"Analytical Chemistry","volume":"147 1","pages":""},"PeriodicalIF":7.4,"publicationDate":"2025-01-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142981243","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}
京公网安备 11010802042870号
京ICP备2023020795号-1
扫码关注我们
求助内容：
应助结果提醒方式：