Analytical Chemistry最新文献_第4页

A Robust and Automated Platform for Charge Detection Mass Spectrometry of Megadalton Biotherapeutics

IF 7.4 1区化学 Q1 CHEMISTRY, ANALYTICAL

Analytical Chemistry

Pub Date : 2025-02-19 DOI: 10.1021/acs.analchem.4c06397

Samuel E. Janisse, Ryan T. Fellers, Shannon A. Raab, Michael P. Goodwin, Kyle P. Bowen, Zhirui J. Lian, Kenneth R. Durbin, Michael W. Senko, Philip D. Compton, Jared O. Kafader, Neil L. Kelleher

Gene therapies based on adeno-associated viruses are an emerging area with high potential to improve human health. Current quality control techniques to assess contaminates and byproducts from the adeno-associated virus (AAV) production pipelines are lacking in robustness and throughput. To address these limitations, we coupled an automated microfluidic device called SampleStream with Orbitrap-based charge detection mass spectrometry (SS-CDMS). We demonstrate that the SS-CDMS workflow performs AAV analysis in under 15 min per sample in a completely autonomous manner. The SS-CDMS workflow enables rapid assessment of key quality control attributes (CQAs), such as of molecular weight and content ratio of AAV formulations with a small sample requirement (<2 × 10⁹ capsids) without being limited by sample concentration. Additionally, this work shows the potential for the SS-CDMS workflow to be implemented at various stages of the production pipeline through effective sample clean up from more complex AAV matrices such as cell culture media.

{"title":"A Robust and Automated Platform for Charge Detection Mass Spectrometry of Megadalton Biotherapeutics","authors":"Samuel E. Janisse, Ryan T. Fellers, Shannon A. Raab, Michael P. Goodwin, Kyle P. Bowen, Zhirui J. Lian, Kenneth R. Durbin, Michael W. Senko, Philip D. Compton, Jared O. Kafader, Neil L. Kelleher","doi":"10.1021/acs.analchem.4c06397","DOIUrl":"https://doi.org/10.1021/acs.analchem.4c06397","url":null,"abstract":"Gene therapies based on adeno-associated viruses are an emerging area with high potential to improve human health. Current quality control techniques to assess contaminates and byproducts from the adeno-associated virus (AAV) production pipelines are lacking in robustness and throughput. To address these limitations, we coupled an automated microfluidic device called SampleStream with Orbitrap-based charge detection mass spectrometry (SS-CDMS). We demonstrate that the SS-CDMS workflow performs AAV analysis in under 15 min per sample in a completely autonomous manner. The SS-CDMS workflow enables rapid assessment of key quality control attributes (CQAs), such as of molecular weight and content ratio of AAV formulations with a small sample requirement (<2 × 109 capsids) without being limited by sample concentration. Additionally, this work shows the potential for the SS-CDMS workflow to be implemented at various stages of the production pipeline through effective sample clean up from more complex AAV matrices such as cell culture media.","PeriodicalId":27,"journal":{"name":"Analytical Chemistry","volume":"9 1","pages":""},"PeriodicalIF":7.4,"publicationDate":"2025-02-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143443871","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

Outlier Removal with Weight Penalization and Aggregation: A Robust Variable Selection Method for Enhancing Near-Infrared Spectral Analysis Performance

IF 7.4 1区化学 Q1 CHEMISTRY, ANALYTICAL

Analytical Chemistry

Pub Date : 2025-02-19 DOI: 10.1021/acs.analchem.4c07007

Beibei Li, Wenting Li, Junwei Guo, Hongbo Wang, Ran Wan, Yu Liu, Meijuan Fan, Cong Wang, Song Yang, Le Zhao, Cong Nie

Full-wavelength near-infrared (NIR) spectroscopy faces significant challenges due to the strong collinearity among spectral variables and the presence of variables that are highly sensitive to sample fluctuations. Additionally, not all spectral variables contribute equally to the NIR model. Weakly influential variables, although not important on their own, can provide substantial improvement when combined with stronger variables, thus increasing both model stability and prediction accuracy. Therefore, this study proposes a new variable selection method called outlier removal with weight penalization and aggregation (OR-WPA). The method begins by removing outlier spectral variables with high coefficient of variation, which enhances model stability. During the variable selection process, multiple submodels are constructed based on variable subsets, with variable weights assigned according to the absolute values of regression coefficients. A moving window is applied to average the weights, and variables with excessively high weights are penalized, promoting the selection of weakly influential variables that positively contribute to model accuracy. The variable space is iteratively reduced, and the subset of variables associated with the highest predictive accuracy is selected as the final characteristic variable combination. The OR-WPA method was evaluated on three NIR spectral data sets, involving corn, heated tobacco substrate, and flue-cured tobacco. The results were compared with three advanced variable selection methods: Monte Carlo uninformative variable elimination, competitive adaptive reweighted sampling, and bootstrapping soft shrinkage. The results indicate that OR-WPA demonstrates better predictive performance, particularly in predicting low-content components, where it significantly enhances both the accuracy and stability of the NIR model.

{"title":"Outlier Removal with Weight Penalization and Aggregation: A Robust Variable Selection Method for Enhancing Near-Infrared Spectral Analysis Performance","authors":"Beibei Li, Wenting Li, Junwei Guo, Hongbo Wang, Ran Wan, Yu Liu, Meijuan Fan, Cong Wang, Song Yang, Le Zhao, Cong Nie","doi":"10.1021/acs.analchem.4c07007","DOIUrl":"https://doi.org/10.1021/acs.analchem.4c07007","url":null,"abstract":"Full-wavelength near-infrared (NIR) spectroscopy faces significant challenges due to the strong collinearity among spectral variables and the presence of variables that are highly sensitive to sample fluctuations. Additionally, not all spectral variables contribute equally to the NIR model. Weakly influential variables, although not important on their own, can provide substantial improvement when combined with stronger variables, thus increasing both model stability and prediction accuracy. Therefore, this study proposes a new variable selection method called outlier removal with weight penalization and aggregation (OR-WPA). The method begins by removing outlier spectral variables with high coefficient of variation, which enhances model stability. During the variable selection process, multiple submodels are constructed based on variable subsets, with variable weights assigned according to the absolute values of regression coefficients. A moving window is applied to average the weights, and variables with excessively high weights are penalized, promoting the selection of weakly influential variables that positively contribute to model accuracy. The variable space is iteratively reduced, and the subset of variables associated with the highest predictive accuracy is selected as the final characteristic variable combination. The OR-WPA method was evaluated on three NIR spectral data sets, involving corn, heated tobacco substrate, and flue-cured tobacco. The results were compared with three advanced variable selection methods: Monte Carlo uninformative variable elimination, competitive adaptive reweighted sampling, and bootstrapping soft shrinkage. The results indicate that OR-WPA demonstrates better predictive performance, particularly in predicting low-content components, where it significantly enhances both the accuracy and stability of the NIR model.","PeriodicalId":27,"journal":{"name":"Analytical Chemistry","volume":"8 1","pages":""},"PeriodicalIF":7.4,"publicationDate":"2025-02-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143452158","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

In-Situ Diagnostics of Multi-Thermal Fluid Injection Parameters Using Stray Radiation Suppression and Circular Cell-Enhanced Laser Absorption Spectroscopy.

IF 6.7 1区化学 Q1 CHEMISTRY, ANALYTICAL

Analytical Chemistry

Pub Date : 2025-02-18 Epub Date: 2025-01-30 DOI: 10.1021/acs.analchem.4c05883

Di Wang, Yan Lv, Yu Pu, Yushuang Li, Mingji Wang, Weidong Sun, Dong Li

Multithermal fluid (MTF) component ratios and injection parameters are critical inputs in offshore heavy oil development, such as injection adjustment and monitoring, productivity prediction, and generator combustion process optimization. We implement simultaneous in situ diagnostics of two emblematic injection parameters, the gas-water ratio (GWR) and noncondensable gases proportion (NCGP), in a pilot-scale environment. A system-level integration of a novel laser absorption spectroscopy multigas sensor system based on integrating stray radiation suppression and a circular cell-enhanced strategy is proposed. A structurally optimized extinction thread in front of a photodetector is designed to reduce the absorption signal distortion under the influence of high-temperature radiation. Meanwhile, we break the limitation of the internal dimensions of the injection tube on the long-path absorption of gas molecules and improve the absorbance signal SNR by 3.42-fold. The present work performed experimental tests using diesel as the primary fuel in a laboratory-scale MTF generation system. The results show that the measurement uncertainties for H₂O/CO₂ concentrations are maintained at ±6.34% and ±6.87%, respectively. The proportion of CO₂ in noncondensable gas is comparable to field data, but the GWR of the simulation system at different injection temperatures is much higher than that of the field injection parameters. The measurement system demonstrates remarkable stability and rapid response, marking a significant milestone as the first reported instance of in situ diagnostics of MTF injection parameters conducted in a laboratory bench test.

{"title":"In-Situ Diagnostics of Multi-Thermal Fluid Injection Parameters Using Stray Radiation Suppression and Circular Cell-Enhanced Laser Absorption Spectroscopy.","authors":"Di Wang, Yan Lv, Yu Pu, Yushuang Li, Mingji Wang, Weidong Sun, Dong Li","doi":"10.1021/acs.analchem.4c05883","DOIUrl":"10.1021/acs.analchem.4c05883","url":null,"abstract":"Multithermal fluid (MTF) component ratios and injection parameters are critical inputs in offshore heavy oil development, such as injection adjustment and monitoring, productivity prediction, and generator combustion process optimization. We implement simultaneous in situ diagnostics of two emblematic injection parameters, the gas-water ratio (GWR) and noncondensable gases proportion (NCGP), in a pilot-scale environment. A system-level integration of a novel laser absorption spectroscopy multigas sensor system based on integrating stray radiation suppression and a circular cell-enhanced strategy is proposed. A structurally optimized extinction thread in front of a photodetector is designed to reduce the absorption signal distortion under the influence of high-temperature radiation. Meanwhile, we break the limitation of the internal dimensions of the injection tube on the long-path absorption of gas molecules and improve the absorbance signal SNR by 3.42-fold. The present work performed experimental tests using diesel as the primary fuel in a laboratory-scale MTF generation system. The results show that the measurement uncertainties for H2O/CO2 concentrations are maintained at ±6.34% and ±6.87%, respectively. The proportion of CO2 in noncondensable gas is comparable to field data, but the GWR of the simulation system at different injection temperatures is much higher than that of the field injection parameters. The measurement system demonstrates remarkable stability and rapid response, marking a significant milestone as the first reported instance of in situ diagnostics of MTF injection parameters conducted in a laboratory bench test.","PeriodicalId":27,"journal":{"name":"Analytical Chemistry","volume":" ","pages":"3536-3544"},"PeriodicalIF":6.7,"publicationDate":"2025-02-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143062321","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

Ag+-Mediated DNA Nanomachine Cascade Nanomaterial Amplification Enable One-Pot Electrochemical Analysis of Circulating Tumor DNA

IF 7.4 1区化学 Q1 CHEMISTRY, ANALYTICAL

Analytical Chemistry

Pub Date : 2025-02-18 DOI: 10.1021/acs.analchem.4c06652

Runlian Qu, Zhen Zeng, Yue Wang, Ke Huang, Zeliang Wei, Kai Li, Weigang Gan, Feng Lin, Piaopiao Chen

Circular tumor DNA (ctDNA) is a trace nucleic acid that functions as an essential tumor marker. In this context, the present study proposes a one-pot electrochemical analysis of ctDNA EGFR L858R in lung cancer leveraging a Ag⁺-mediated DNA nanosphere (I amplification) and cation exchange reaction (II amplification), and Cu²⁺ acts as a signal molecule. Once the target L858R exists, it specifically destroys the structure of DNA nanosphere@Ag⁺, and large amounts of Ag⁺ are released. After the addition of copper sulfide nanoparticles, Cu²⁺ can be replaced by a cation exchange reaction. Eventually, the electrochemical signal of Cu²⁺ is elevated. The analytical performance of the method is satisfactory, L858R can be detected in the linear range of 1 aM-1 fM with a detection limit of 0.3 aM. Furthermore, the system exhibits notable selectivity in differentiating base mismatch targets and other ctDNA sequences. The recovery rate of blood samples is between 95.5 and 105%. The electrochemical results from the analysis of 42 clinical blood samples are consistent with those of the quantitative real-time polymerase chain reaction, computed tomography, and pathology results. In summary, this novel strategy utilizes preprepared functional nucleic acid nanomaterials and cascade amplification, which is expected to contribute to the sensitive and expeditious detection of trace nucleic acids.

{"title":"Ag+-Mediated DNA Nanomachine Cascade Nanomaterial Amplification Enable One-Pot Electrochemical Analysis of Circulating Tumor DNA","authors":"Runlian Qu, Zhen Zeng, Yue Wang, Ke Huang, Zeliang Wei, Kai Li, Weigang Gan, Feng Lin, Piaopiao Chen","doi":"10.1021/acs.analchem.4c06652","DOIUrl":"https://doi.org/10.1021/acs.analchem.4c06652","url":null,"abstract":"Circular tumor DNA (ctDNA) is a trace nucleic acid that functions as an essential tumor marker. In this context, the present study proposes a one-pot electrochemical analysis of ctDNA EGFR L858R in lung cancer leveraging a Ag+-mediated DNA nanosphere (I amplification) and cation exchange reaction (II amplification), and Cu2+ acts as a signal molecule. Once the target L858R exists, it specifically destroys the structure of DNA nanosphere@Ag+, and large amounts of Ag+ are released. After the addition of copper sulfide nanoparticles, Cu2+ can be replaced by a cation exchange reaction. Eventually, the electrochemical signal of Cu2+ is elevated. The analytical performance of the method is satisfactory, L858R can be detected in the linear range of 1 aM-1 fM with a detection limit of 0.3 aM. Furthermore, the system exhibits notable selectivity in differentiating base mismatch targets and other ctDNA sequences. The recovery rate of blood samples is between 95.5 and 105%. The electrochemical results from the analysis of 42 clinical blood samples are consistent with those of the quantitative real-time polymerase chain reaction, computed tomography, and pathology results. In summary, this novel strategy utilizes preprepared functional nucleic acid nanomaterials and cascade amplification, which is expected to contribute to the sensitive and expeditious detection of trace nucleic acids.","PeriodicalId":27,"journal":{"name":"Analytical Chemistry","volume":"7 1","pages":""},"PeriodicalIF":7.4,"publicationDate":"2025-02-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143435729","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

Simultaneous Detection of MMP-1 and MMP-12 Using Au–Se Nanoprobe for Advancing NSCLC Diagnosis

IF 7.4 1区化学 Q1 CHEMISTRY, ANALYTICAL

Analytical Chemistry

Pub Date : 2025-02-18 DOI: 10.1021/acs.analchem.4c05846

Zixuan Chang, Keyi Wang, Wenbin Hao, Mingyi Ouyang, Yue Tang, Xiaonan Gao, Bo Tang

This study presents the development and characterization of Au–Se nanoprobes (NPs) for the specific and simultaneous detection of matrix metalloproteinase-1 and -12 (MMP-1/12), key biomarkers in non-small-cell lung cancer (NSCLC). Leveraging the stability of Au–Se bonds against biological thiols, such as glutathione (GSH), the NPs exhibit remarkable resistance to interference, maintaining its fluorescence signal across a wide range of temperatures, pH levels, and in the presence of high concentrations of GSH. The synthesized NPs demonstrate high specificity and sensitivity toward MMP-1/12 in vitro, with optimal imaging achieved after 4 h of incubation in NSCLC A549 cells. Furthermore, confocal imaging experiments successfully distinguished between NSCLC A549 cells and normal lung epithelial cells (Beas-2b), underscoring the potential of these NPs in early NSCLC diagnosis and the study of tumor microenvironments. This work not only introduces a reliable tool for cancer biomarker detection but also contributes to the advancement of nanomaterial applications in NSCLC diagnosis.

引用次数: 0

Referenced-Closed Bipolar Electrode to Enable the Photoelectrochemical-Electrochromic Synchronous Biosensing

IF 7.4 1区化学 Q1 CHEMISTRY, ANALYTICAL

Analytical Chemistry

Pub Date : 2025-02-18 DOI: 10.1021/acs.analchem.4c06205

Shuyun Meng, Na Dong, Shuda Liu, Zuo Chen, Mingzhen Zhu, Xueping Zhang, Dong Liu, Tianyan You

The environment of electrolyte solution (e.g., saline, pH, and ascorbic acid) can affect the stability of electrochromic materials in photoelectrochemical (PEC)-electrochromic biosensors. Herein, we develop a referenced-closed bipolar electrode (ref-CBPE)-enabled PEC-electrochromic biosensing platform for synchronous dual-modal detection. The CBPE serves as an engine driving redox reactions in PEC and electrochromic detection cells, effectively avoiding the interference of the electrolyte solution environment with the polyaniline electrochromic material. Furthermore, we discuss how to choose the most appropriate CBPE-enabled PEC-electrochromic type to maximize the biosensor response. The ref-CBPE-enabled PEC-electrochromic biosensor, incorporating a reference electrode to provide stable potential reference, exhibits a higher signal response and 40-fold photocurrent amplification compared to a conventional CBPE configuration. For biosensor design, type II CdSe QDs/ZnO heterojunctions act as the driving anode to provide electrons for polyaniline as the driving cathode, enabling the synchronous acquisition of PEC and electrochromic signals. Taking the Cry1Ab protein as the model target, a miniaturized and portable dual-modal biosensing device is constructed using 3D printing technology, which reveals high portability, selectivity, and accuracy. The work provides a new avenue for developing a portable PEC-electrochromic biosensing device of dual-signal synchronous acquisition.

{"title":"Referenced-Closed Bipolar Electrode to Enable the Photoelectrochemical-Electrochromic Synchronous Biosensing","authors":"Shuyun Meng, Na Dong, Shuda Liu, Zuo Chen, Mingzhen Zhu, Xueping Zhang, Dong Liu, Tianyan You","doi":"10.1021/acs.analchem.4c06205","DOIUrl":"https://doi.org/10.1021/acs.analchem.4c06205","url":null,"abstract":"The environment of electrolyte solution (e.g., saline, pH, and ascorbic acid) can affect the stability of electrochromic materials in photoelectrochemical (PEC)-electrochromic biosensors. Herein, we develop a referenced-closed bipolar electrode (ref-CBPE)-enabled PEC-electrochromic biosensing platform for synchronous dual-modal detection. The CBPE serves as an engine driving redox reactions in PEC and electrochromic detection cells, effectively avoiding the interference of the electrolyte solution environment with the polyaniline electrochromic material. Furthermore, we discuss how to choose the most appropriate CBPE-enabled PEC-electrochromic type to maximize the biosensor response. The ref-CBPE-enabled PEC-electrochromic biosensor, incorporating a reference electrode to provide stable potential reference, exhibits a higher signal response and 40-fold photocurrent amplification compared to a conventional CBPE configuration. For biosensor design, type II CdSe QDs/ZnO heterojunctions act as the driving anode to provide electrons for polyaniline as the driving cathode, enabling the synchronous acquisition of PEC and electrochromic signals. Taking the Cry1Ab protein as the model target, a miniaturized and portable dual-modal biosensing device is constructed using 3D printing technology, which reveals high portability, selectivity, and accuracy. The work provides a new avenue for developing a portable PEC-electrochromic biosensing device of dual-signal synchronous acquisition.","PeriodicalId":27,"journal":{"name":"Analytical Chemistry","volume":"64 1","pages":""},"PeriodicalIF":7.4,"publicationDate":"2025-02-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143443892","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

Functional Aptamers In Vitro Evolution for Protein–Protein Interaction Blockage

IF 7.4 1区化学 Q1 CHEMISTRY, ANALYTICAL

Analytical Chemistry

Pub Date : 2025-02-18 DOI: 10.1021/acs.analchem.4c04609

Tongxuan Wei, Qinguo Liu, Jun Li, Song Song, Liqin Zhang

As aptamer development progresses, their applications have expanded significantly beyond high affinity to include functional capabilities. Currently, the identification of functional aptamers relies on traditional SELEX techniques, followed by functional validation and computer-assisted redesign of high-affinity aptamers. However, high affinity does not guarantee optimal functionality, making the search for functional aptamers from binding pools time-consuming and labor-intensive. Addressing this challenge, we introduce functional aptamers in vitro evolution (FAIVE), a novel screening method that links sequence functionality to fluorescence intensity. We demonstrated the effectiveness of FAIVE by obtaining modified DNA aptamers capable of disrupting the interaction between the SARS-CoV-2 spike receptor-binding domain (RBD) and hACE2, targeting protein–protein interaction inhibition. Furthermore, we investigated the criteria for validating the quality of the bead library generated for selection by modeling the emulsion PCR process, providing theoretical insights for future applications. The concept of incorporating fluorescent signal reporting of aptamer functionality into the aptamer selection process holds the potential to facilitate the identification of aptamers with diverse functionalities and is readily adaptable to various research contexts.

{"title":"Functional Aptamers In Vitro Evolution for Protein–Protein Interaction Blockage","authors":"Tongxuan Wei, Qinguo Liu, Jun Li, Song Song, Liqin Zhang","doi":"10.1021/acs.analchem.4c04609","DOIUrl":"https://doi.org/10.1021/acs.analchem.4c04609","url":null,"abstract":"As aptamer development progresses, their applications have expanded significantly beyond high affinity to include functional capabilities. Currently, the identification of functional aptamers relies on traditional SELEX techniques, followed by functional validation and computer-assisted redesign of high-affinity aptamers. However, high affinity does not guarantee optimal functionality, making the search for functional aptamers from binding pools time-consuming and labor-intensive. Addressing this challenge, we introduce functional aptamers in vitro evolution (FAIVE), a novel screening method that links sequence functionality to fluorescence intensity. We demonstrated the effectiveness of FAIVE by obtaining modified DNA aptamers capable of disrupting the interaction between the SARS-CoV-2 spike receptor-binding domain (RBD) and hACE2, targeting protein–protein interaction inhibition. Furthermore, we investigated the criteria for validating the quality of the bead library generated for selection by modeling the emulsion PCR process, providing theoretical insights for future applications. The concept of incorporating fluorescent signal reporting of aptamer functionality into the aptamer selection process holds the potential to facilitate the identification of aptamers with diverse functionalities and is readily adaptable to various research contexts.","PeriodicalId":27,"journal":{"name":"Analytical Chemistry","volume":"13 1","pages":""},"PeriodicalIF":7.4,"publicationDate":"2025-02-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143435624","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

Fusion and Solvent Evaporation Ionization Mass Spectrometry for Rapid Detection of Microplastics (MPs).

IF 6.7 1区化学 Q1 CHEMISTRY, ANALYTICAL

Analytical Chemistry

Pub Date : 2025-02-18 DOI: 10.1021/acs.analchem.5c00137

Weiwei Chen, Qing Li, Jing Luo, Yuanjiang Pan, Hongru Feng

Microplastic (MP) pollution has gradually become a significant environmental concern, as MPs are widely present in soil, beaches, oceans, and even the atmosphere. Rapid detection and identification of MPs are crucial for monitoring and assessing environmental pollution. In this study, a fusion and solvent evaporation ionization (FSEI) device, comprising a heated plate and nebulizer, was developed for the direct detection and identification of six types of MPs. In the mass spectra, these MPs presented characteristic mass intervals corresponding to the monomer, realizing a more intuitive identification. After optimization, FSEI-MS demonstrated high sensitivity, good linearity (R² > 0.992), and accuracy (72.7-132.7%). Moreover, FSEI-MS realized discrimination of mixed MPs in terms of both time and spectra dimensions and was successfully applied to the detection of MPs in soil with good recoveries (82.6-117.5%, RSD < 13.2%). Furthermore, FSEI-MS overcame the environmental matrix interference and achieved the direct analysis of MPs in soil by utilizing a commercial spray bottle as the nebulizer. Overall, this research established a comprehensive methodology that integrates time-resolved and MS-based dimensions, offering a concise and efficient solution for MP analysis.

{"title":"Fusion and Solvent Evaporation Ionization Mass Spectrometry for Rapid Detection of Microplastics (MPs).","authors":"Weiwei Chen, Qing Li, Jing Luo, Yuanjiang Pan, Hongru Feng","doi":"10.1021/acs.analchem.5c00137","DOIUrl":"https://doi.org/10.1021/acs.analchem.5c00137","url":null,"abstract":"Microplastic (MP) pollution has gradually become a significant environmental concern, as MPs are widely present in soil, beaches, oceans, and even the atmosphere. Rapid detection and identification of MPs are crucial for monitoring and assessing environmental pollution. In this study, a fusion and solvent evaporation ionization (FSEI) device, comprising a heated plate and nebulizer, was developed for the direct detection and identification of six types of MPs. In the mass spectra, these MPs presented characteristic mass intervals corresponding to the monomer, realizing a more intuitive identification. After optimization, FSEI-MS demonstrated high sensitivity, good linearity (R2 > 0.992), and accuracy (72.7-132.7%). Moreover, FSEI-MS realized discrimination of mixed MPs in terms of both time and spectra dimensions and was successfully applied to the detection of MPs in soil with good recoveries (82.6-117.5%, RSD < 13.2%). Furthermore, FSEI-MS overcame the environmental matrix interference and achieved the direct analysis of MPs in soil by utilizing a commercial spray bottle as the nebulizer. Overall, this research established a comprehensive methodology that integrates time-resolved and MS-based dimensions, offering a concise and efficient solution for MP analysis.","PeriodicalId":27,"journal":{"name":"Analytical Chemistry","volume":" ","pages":""},"PeriodicalIF":6.7,"publicationDate":"2025-02-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143447434","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

Background-Free Mid-Infrared Photothermal Microscopy via Single-Shot Measurement of Thermal Decay

IF 7.4 1区化学 Q1 CHEMISTRY, ANALYTICAL

Analytical Chemistry

Pub Date : 2025-02-18 DOI: 10.1021/acs.analchem.4c03689

Rylie Bolarinho, Jiaze Yin, Hongli Ni, Qing Xia, Ji-Xin Cheng

Mid-infrared photothermal (MIP) microscopy is an emerging tool for biological imaging, offering high sensitivity, subcellular resolution, and rapid image acquisition. However, the MIP signal of low concentration molecules in biological systems is often hindered or masked by background absorption, largely contributed by water, resulting from the H–O–H scissors-bending band in the fingerprint window or the bend-libration combination band in the cell-silent window. To preserve all desired signals while suppressing the background, we report a single-shot time-resolved MIP measurement that allows differentiation between the background and analyte signal based on their distinct photothermal dynamics. The results show that the thermal decay of the background is significantly longer than that of the desired intracellular signal, mainly due to the larger mass and heat capacity of water compared to those of intracellular features. Through two-component exponential fitting, we successfully differentiated and suppressed the background, while preserving the desired intracellular signal in both the fingerprint and cell-silent windows. By leveraging the thermal dynamics differences obtained from a single-shot measurement, we effectively remove the background and enhance the detection of small signals in a biological system.

{"title":"Background-Free Mid-Infrared Photothermal Microscopy via Single-Shot Measurement of Thermal Decay","authors":"Rylie Bolarinho, Jiaze Yin, Hongli Ni, Qing Xia, Ji-Xin Cheng","doi":"10.1021/acs.analchem.4c03689","DOIUrl":"https://doi.org/10.1021/acs.analchem.4c03689","url":null,"abstract":"Mid-infrared photothermal (MIP) microscopy is an emerging tool for biological imaging, offering high sensitivity, subcellular resolution, and rapid image acquisition. However, the MIP signal of low concentration molecules in biological systems is often hindered or masked by background absorption, largely contributed by water, resulting from the H–O–H scissors-bending band in the fingerprint window or the bend-libration combination band in the cell-silent window. To preserve all desired signals while suppressing the background, we report a single-shot time-resolved MIP measurement that allows differentiation between the background and analyte signal based on their distinct photothermal dynamics. The results show that the thermal decay of the background is significantly longer than that of the desired intracellular signal, mainly due to the larger mass and heat capacity of water compared to those of intracellular features. Through two-component exponential fitting, we successfully differentiated and suppressed the background, while preserving the desired intracellular signal in both the fingerprint and cell-silent windows. By leveraging the thermal dynamics differences obtained from a single-shot measurement, we effectively remove the background and enhance the detection of small signals in a biological system.","PeriodicalId":27,"journal":{"name":"Analytical Chemistry","volume":"13 1","pages":""},"PeriodicalIF":7.4,"publicationDate":"2025-02-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143443891","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

Advancing Biomarker Research: In Situ Cu Isotope Analysis in Liver Tumors by LA-MC-ICP-MS

IF 7.4 1区化学 Q1 CHEMISTRY, ANALYTICAL

Analytical Chemistry

Pub Date : 2025-02-18 DOI: 10.1021/acs.analchem.4c05626

Mathias Schannor, Marcus Oelze, Heike Traub, Yubei He, Robin Schmidt, Luisa Heidemann, Lynn Jeanette Savic, Jochen Vogl, Björn Meermann

Stable metal isotopes have received increasing attention as medical biomarkers due to their potential to detect changes in metal metabolism related to diseases. In particular, copper stable isotopes are a powerful tool to identify isotopic variation between tumors and healthy tissue, suggesting application in cancer diagnosis. However, potential mechanisms causing isotope fractionation, such as redox- or bond-forming reactions and interactions of metals during transmembrane import and export, are less well understood. Here, we established an in situ method using laser ablation-multicollector-inductively coupled plasma-mass spectrometry (LA-MC-ICP-MS) to advance our understanding of the underlying processes responsible for isotope fractionation between normal and diseased tissues. Gelatin-based bracketing standards and quality control reference materials, crucial for laser ablation analysis, were developed to allow correction for instrumentally induced isotope fractionation during LA-MC-ICP-MS analysis. Using such matrix-matched standards, the method achieved intermediate precisions for delta values of better than 0.15 ‰ (2 s) for inorganic reference materials and of better than 0.17 ‰ (2 s) for biological reference materials. The developed routine was tested on rabbit VX2 liver tumor samples, a model system resembling human hepatocellular carcinoma (HCC) used to study liver cancer. In situ Cu isotope compositions between healthy (<msubsup><mrow><mi>δ</mi></mrow><mrow><mi>NIST</mi><mn>976</mn></mrow><mrow><mi>65/63</mi></mrow></msubsup><mrow><mo stretchy="false">(</mo><mi>Cu</mi><mo stretchy="false">)</mo></mrow></math>' role="presentation" style="position: relative;" tabindex="0">𝛿65/63<span style="position: ab

{"title":"Advancing Biomarker Research: In Situ Cu Isotope Analysis in Liver Tumors by LA-MC-ICP-MS","authors":"Mathias Schannor, Marcus Oelze, Heike Traub, Yubei He, Robin Schmidt, Luisa Heidemann, Lynn Jeanette Savic, Jochen Vogl, Björn Meermann","doi":"10.1021/acs.analchem.4c05626","DOIUrl":"https://doi.org/10.1021/acs.analchem.4c05626","url":null,"abstract":"Stable metal isotopes have received increasing attention as medical biomarkers due to their potential to detect changes in metal metabolism related to diseases. In particular, copper stable isotopes are a powerful tool to identify isotopic variation between tumors and healthy tissue, suggesting application in cancer diagnosis. However, potential mechanisms causing isotope fractionation, such as redox- or bond-forming reactions and interactions of metals during transmembrane import and export, are less well understood. Here, we established an in situ method using laser ablation-multicollector-inductively coupled plasma-mass spectrometry (LA-MC-ICP-MS) to advance our understanding of the underlying processes responsible for isotope fractionation between normal and diseased tissues. Gelatin-based bracketing standards and quality control reference materials, crucial for laser ablation analysis, were developed to allow correction for instrumentally induced isotope fractionation during LA-MC-ICP-MS analysis. Using such matrix-matched standards, the method achieved intermediate precisions for delta values of better than 0.15 ‰ (2 s) for inorganic reference materials and of better than 0.17 ‰ (2 s) for biological reference materials. The developed routine was tested on rabbit VX2 liver tumor samples, a model system resembling human hepatocellular carcinoma (HCC) used to study liver cancer. In situ Cu isotope compositions between healthy (<msubsup><mrow><mi>&#x3B4;</mi></mrow><mrow><mi>NIST</mi><mn>976</mn></mrow><mrow><mi>65/63</mi></mrow></msubsup><mrow><mo stretchy=\"false\">(</mo><mi>Cu</mi><mo stretchy=\"false\">)</mo></mrow></math>' role=\"presentation\" style=\"position: relative;\" tabindex=\"0\">𝛿65/63<span style=\"position: ab","PeriodicalId":27,"journal":{"name":"Analytical Chemistry","volume":"21 1","pages":""},"PeriodicalIF":7.4,"publicationDate":"2025-02-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143435625","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