Analytical Chemistry最新文献_第3页

Quantitative Analysis of Multi-Elements in a Micron-Sized Single Particle Based on Laser-Induced Breakdown Spectroscopy Signal Enhancement of an Optical Fiber Collimated System

IF 7.4 1区化学 Q1 CHEMISTRY, ANALYTICAL

Analytical Chemistry

Pub Date : 2025-01-15 DOI: 10.1021/acs.analchem.4c05221

Tingting Chen, Jiaqiang Du, Tianlong Zhang, Hua Li

With rapid, energy-intensive, and coal-fueled economic growth, global air quality is deteriorating, and particulate matter pollution has emerged as one of the major public health problems worldwide. It is extremely urgent to achieve carbon emission reduction and air pollution prevention and control, aiming at the common problem of weak and unstable signals of characteristic elements in the application of laser-induced breakdown spectroscopy (LIBS) technology for trace element detection. In this study, the influence of the optical fiber collimation signal enhancement method on the LIBS signal was explored. Then, the influence of the LIBS signal enhancement system based on an optical fiber collimated system on LIBS spectral signal intensity and signal-to-noise ratio (SNR) was compared, and the influences of different spectral preprocessing methods and different variable selection methods on the prediction performance of the random forest (RF) calibration model were investigated. Finally, the Savitzky–Golay convolution derivative (SG)-variable importance projection (VIP)-mutual information (MI)-RF (Zn), first-order derivative (D1st)-variable importance measurement (VIM)-successive projections algorithm (SPA)-RF (Cu), and D1st-VIM-MI-RF (Ni) optimal models were constructed according to the optimal spectral preprocessing method and the optimal hybrid variable selection method. The prediction performances of their optimal RF model after SG-VIP-MI (Zn), D1st-VIM-SPA (Cu), and D1st-VIM-MI (Ni) spectral preprocessing and hybrid variable selection method are presented as follows: Zn (R_p² = 0.9860; MREP = 0.0590), Cu (R_p² = 0.9817; MREP = 0.0405), and Ni (R_p² = 0.9856; MREP = 0.0875). The above results demonstrate that the RF calibration model based on the optical fiber collimated LIBS signal enhancement method, the optimal spectral preprocessing method, and variable selection strategy overcome the key problems of low SNR and low quantitative accuracy in single particle detection. It is expected to provide a theoretical basis and technical support for in situ online rapid monitoring of particulate matter.

{"title":"Quantitative Analysis of Multi-Elements in a Micron-Sized Single Particle Based on Laser-Induced Breakdown Spectroscopy Signal Enhancement of an Optical Fiber Collimated System","authors":"Tingting Chen, Jiaqiang Du, Tianlong Zhang, Hua Li","doi":"10.1021/acs.analchem.4c05221","DOIUrl":"https://doi.org/10.1021/acs.analchem.4c05221","url":null,"abstract":"With rapid, energy-intensive, and coal-fueled economic growth, global air quality is deteriorating, and particulate matter pollution has emerged as one of the major public health problems worldwide. It is extremely urgent to achieve carbon emission reduction and air pollution prevention and control, aiming at the common problem of weak and unstable signals of characteristic elements in the application of laser-induced breakdown spectroscopy (LIBS) technology for trace element detection. In this study, the influence of the optical fiber collimation signal enhancement method on the LIBS signal was explored. Then, the influence of the LIBS signal enhancement system based on an optical fiber collimated system on LIBS spectral signal intensity and signal-to-noise ratio (SNR) was compared, and the influences of different spectral preprocessing methods and different variable selection methods on the prediction performance of the random forest (RF) calibration model were investigated. Finally, the Savitzky–Golay convolution derivative (SG)-variable importance projection (VIP)-mutual information (MI)-RF (Zn), first-order derivative (D1st)-variable importance measurement (VIM)-successive projections algorithm (SPA)-RF (Cu), and D1st-VIM-MI-RF (Ni) optimal models were constructed according to the optimal spectral preprocessing method and the optimal hybrid variable selection method. The prediction performances of their optimal RF model after SG-VIP-MI (Zn), D1st-VIM-SPA (Cu), and D1st-VIM-MI (Ni) spectral preprocessing and hybrid variable selection method are presented as follows: Zn (Rp2 = 0.9860; MREP = 0.0590), Cu (Rp2 = 0.9817; MREP = 0.0405), and Ni (Rp2 = 0.9856; MREP = 0.0875). The above results demonstrate that the RF calibration model based on the optical fiber collimated LIBS signal enhancement method, the optimal spectral preprocessing method, and variable selection strategy overcome the key problems of low SNR and low quantitative accuracy in single particle detection. It is expected to provide a theoretical basis and technical support for in situ online rapid monitoring of particulate matter.","PeriodicalId":27,"journal":{"name":"Analytical Chemistry","volume":"49 1","pages":""},"PeriodicalIF":7.4,"publicationDate":"2025-01-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142986241","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

Near-Infrared Fluorescent Probe for Simultaneously Imaging Ferrous Ions and Viscosity in a Mouse Model of Hepatocellular Carcinoma

IF 7.4 1区化学 Q1 CHEMISTRY, ANALYTICAL

Analytical Chemistry

Pub Date : 2025-01-15 DOI: 10.1021/acs.analchem.4c05120

Rongqing Luo, Li Xu, Jianmei Chen, Wenxuan Zhang, Shumin Feng, Zhenpeng Qiu, Yi Hong, Guoqiang Feng

Abnormal ferrous ion (Fe²⁺) levels lead to an increase in reactive oxygen species (ROS) in cells, disrupting intracellular viscosity and the occurrence of hepatocellular carcinoma (HCC). Simultaneously visualizing Fe²⁺ and intracellular viscosity is essential for understanding the detailed pathophysiological processes of HCC. Herein, we report the first dual-responsive probe, QM-FV, capable of simultaneously monitoring Fe²⁺ and viscosity. QM-FV shows highly selective turn-on near-infrared fluorescence (∼30-fold enhancement at 740 nm) for Fe²⁺ with high sensitivity (LOD = 25 nM) and a significant Stokes shift (290 nm). Moreover, QM-FV shows a distinct orange-red fluorescence enhancement at 587 nm as the viscosity increases. Due to its lower cytotoxicity and high sensitivity, QM-FV can distinguish cancer cells from normal cells by detecting Fe²⁺ and viscosity in dual channels. More importantly, using QM-FV, we found that the levels of Fe²⁺ and viscosity elevated in the precancerous stage of HCC and gradually increased as the disease progressed. Overall, this work provides a new potential tool for investigating viscosity and Fe²⁺-related pathological processes underlying HCC.

{"title":"Near-Infrared Fluorescent Probe for Simultaneously Imaging Ferrous Ions and Viscosity in a Mouse Model of Hepatocellular Carcinoma","authors":"Rongqing Luo, Li Xu, Jianmei Chen, Wenxuan Zhang, Shumin Feng, Zhenpeng Qiu, Yi Hong, Guoqiang Feng","doi":"10.1021/acs.analchem.4c05120","DOIUrl":"https://doi.org/10.1021/acs.analchem.4c05120","url":null,"abstract":"Abnormal ferrous ion (Fe2+) levels lead to an increase in reactive oxygen species (ROS) in cells, disrupting intracellular viscosity and the occurrence of hepatocellular carcinoma (HCC). Simultaneously visualizing Fe2+ and intracellular viscosity is essential for understanding the detailed pathophysiological processes of HCC. Herein, we report the first dual-responsive probe, QM-FV, capable of simultaneously monitoring Fe2+ and viscosity. QM-FV shows highly selective turn-on near-infrared fluorescence (∼30-fold enhancement at 740 nm) for Fe2+ with high sensitivity (LOD = 25 nM) and a significant Stokes shift (290 nm). Moreover, QM-FV shows a distinct orange-red fluorescence enhancement at 587 nm as the viscosity increases. Due to its lower cytotoxicity and high sensitivity, QM-FV can distinguish cancer cells from normal cells by detecting Fe2+ and viscosity in dual channels. More importantly, using QM-FV, we found that the levels of Fe2+ and viscosity elevated in the precancerous stage of HCC and gradually increased as the disease progressed. Overall, this work provides a new potential tool for investigating viscosity and Fe2+-related pathological processes underlying HCC.","PeriodicalId":27,"journal":{"name":"Analytical Chemistry","volume":"74 2 Pt 1 1","pages":""},"PeriodicalIF":7.4,"publicationDate":"2025-01-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142986242","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

Particle Trajectory Simulation Facilitates the Development of an Efficient Sample Introduction System for Single-Particle ICP-MS Analysis

IF 7.4 1区化学 Q1 CHEMISTRY, ANALYTICAL

Analytical Chemistry

Pub Date : 2025-01-14 DOI: 10.1021/acs.analchem.4c05614

Dingyi Wang, Junhui Zhang, Changjun Fan, Xiaodong Li, Lihong Liu, Xueting Yan, Yingying Li, Bin He, Yongguang Yin, Ligang Hu, Guibin Jiang

Inductively coupled plasma mass spectrometry (ICP-MS) has demonstrated significant capabilities in the analysis of single events, such as single cells and particles. Researchers have been actively pursuing innovations in ICP-MS sample introduction systems to enhance their transport efficiency, as this is critical for ensuring the accuracy of single-event analysis. However, the majority of prior studies have relied heavily on empirical approaches, with limited attention given to the individual characteristics of particles from a theoretical perspective and a lack of efficient manufacturing tools for optimizing related components. Herein, we developed a high-efficiency sample introduction system for single-event ICP-MS analysis by integrating the computational simulation-aided design, precise 3D printing manufacturing, and rapid experimental testing process. For the first time, we simulated the transport trajectories of individual particles passing through the spray chamber, providing theoretical guidance for the design and optimization process. The statistical analysis of particle trajectories revealed that under the absorption boundary condition, particles between 20 and 100 nm achieved transport efficiencies exceeding 18.8%. In comparison, particles larger than 100 nm exhibited 0% transport efficiency due to increased deposition within the spray chamber. The spray chamber was fabricated in-house using a range of 3D printing technologies and materials, streamlining the process and reducing the cost for both manufacturing and validation. Further optimization of the operating parameters, including an increase in temperature, resulted in a notable transport efficiency of 61.1%. The workflow introduced in this study has the potential to transform the research and development of critical mass spectrometry components moving forward.

{"title":"Particle Trajectory Simulation Facilitates the Development of an Efficient Sample Introduction System for Single-Particle ICP-MS Analysis","authors":"Dingyi Wang, Junhui Zhang, Changjun Fan, Xiaodong Li, Lihong Liu, Xueting Yan, Yingying Li, Bin He, Yongguang Yin, Ligang Hu, Guibin Jiang","doi":"10.1021/acs.analchem.4c05614","DOIUrl":"https://doi.org/10.1021/acs.analchem.4c05614","url":null,"abstract":"Inductively coupled plasma mass spectrometry (ICP-MS) has demonstrated significant capabilities in the analysis of single events, such as single cells and particles. Researchers have been actively pursuing innovations in ICP-MS sample introduction systems to enhance their transport efficiency, as this is critical for ensuring the accuracy of single-event analysis. However, the majority of prior studies have relied heavily on empirical approaches, with limited attention given to the individual characteristics of particles from a theoretical perspective and a lack of efficient manufacturing tools for optimizing related components. Herein, we developed a high-efficiency sample introduction system for single-event ICP-MS analysis by integrating the computational simulation-aided design, precise 3D printing manufacturing, and rapid experimental testing process. For the first time, we simulated the transport trajectories of individual particles passing through the spray chamber, providing theoretical guidance for the design and optimization process. The statistical analysis of particle trajectories revealed that under the absorption boundary condition, particles between 20 and 100 nm achieved transport efficiencies exceeding 18.8%. In comparison, particles larger than 100 nm exhibited 0% transport efficiency due to increased deposition within the spray chamber. The spray chamber was fabricated in-house using a range of 3D printing technologies and materials, streamlining the process and reducing the cost for both manufacturing and validation. Further optimization of the operating parameters, including an increase in temperature, resulted in a notable transport efficiency of 61.1%. The workflow introduced in this study has the potential to transform the research and development of critical mass spectrometry components moving forward.","PeriodicalId":27,"journal":{"name":"Analytical Chemistry","volume":"28 1","pages":""},"PeriodicalIF":7.4,"publicationDate":"2025-01-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142981254","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

Introducing "Identification Probability" for Automated and Transferable Assessment of Metabolite Identification Confidence in Metabolomics and Related Studies.

IF 6.7 1区化学 Q1 CHEMISTRY, ANALYTICAL

Analytical Chemistry

Pub Date : 2025-01-14 Epub Date: 2024-12-19 DOI: 10.1021/acs.analchem.4c04060

Thomas O Metz, Christine H Chang, Vasuk Gautam, Afia Anjum, Siyang Tian, Fei Wang, Sean M Colby, Jamie R Nunez, Madison R Blumer, Arthur S Edison, Oliver Fiehn, Dean P Jones, Shuzhao Li, Edward T Morgan, Gary J Patti, Dylan H Ross, Madelyn R Shapiro, Antony J Williams, David S Wishart

Methods for assessing compound identification confidence in metabolomics and related studies have been debated and actively researched for the past two decades. The earliest effort in 2007 focused primarily on mass spectrometry and nuclear magnetic resonance spectroscopy and resulted in four recommended levels of metabolite identification confidence─the Metabolite Standards Initiative (MSI) Levels. In 2014, the original MSI Levels were expanded to five levels (including two sublevels) to facilitate communication of compound identification confidence in high resolution mass spectrometry studies. Further refinement in identification levels have occurred, for example to accommodate use of ion mobility spectrometry in metabolomics workflows, and alternate approaches to communicate compound identification confidence also have been developed based on identification points schema. However, neither qualitative levels of identification confidence nor quantitative scoring systems address the degree of ambiguity in compound identifications in the context of the chemical space being considered. Neither are they easily automated nor transferable between analytical platforms. In this perspective, we propose that the metabolomics and related communities consider identification probability as an approach for automated and transferable assessment of compound identification and ambiguity in metabolomics and related studies. Identification probability is defined simply as 1/N, where N is the number of compounds in a database that matches an experimentally measured molecule within user-defined measurement precision(s), for example mass measurement or retention time accuracy, etc. We demonstrate the utility of identification probability in an in silico analysis of multiproperty reference libraries constructed from a subset of the Human Metabolome Database and computational property predictions, provide guidance to the community in transparent implementation of the concept, and invite the community to further evaluate this concept in parallel with their current preferred methods for assessing metabolite identification confidence.

{"title":"Introducing \"Identification Probability\" for Automated and Transferable Assessment of Metabolite Identification Confidence in Metabolomics and Related Studies.","authors":"Thomas O Metz, Christine H Chang, Vasuk Gautam, Afia Anjum, Siyang Tian, Fei Wang, Sean M Colby, Jamie R Nunez, Madison R Blumer, Arthur S Edison, Oliver Fiehn, Dean P Jones, Shuzhao Li, Edward T Morgan, Gary J Patti, Dylan H Ross, Madelyn R Shapiro, Antony J Williams, David S Wishart","doi":"10.1021/acs.analchem.4c04060","DOIUrl":"10.1021/acs.analchem.4c04060","url":null,"abstract":"Methods for assessing compound identification confidence in metabolomics and related studies have been debated and actively researched for the past two decades. The earliest effort in 2007 focused primarily on mass spectrometry and nuclear magnetic resonance spectroscopy and resulted in four recommended levels of metabolite identification confidence─the Metabolite Standards Initiative (MSI) Levels. In 2014, the original MSI Levels were expanded to five levels (including two sublevels) to facilitate communication of compound identification confidence in high resolution mass spectrometry studies. Further refinement in identification levels have occurred, for example to accommodate use of ion mobility spectrometry in metabolomics workflows, and alternate approaches to communicate compound identification confidence also have been developed based on identification points schema. However, neither qualitative levels of identification confidence nor quantitative scoring systems address the degree of ambiguity in compound identifications in the context of the chemical space being considered. Neither are they easily automated nor transferable between analytical platforms. In this perspective, we propose that the metabolomics and related communities consider identification probability as an approach for automated and transferable assessment of compound identification and ambiguity in metabolomics and related studies. Identification probability is defined simply as 1/N, where N is the number of compounds in a database that matches an experimentally measured molecule within user-defined measurement precision(s), for example mass measurement or retention time accuracy, etc. We demonstrate the utility of identification probability in an in silico analysis of multiproperty reference libraries constructed from a subset of the Human Metabolome Database and computational property predictions, provide guidance to the community in transparent implementation of the concept, and invite the community to further evaluate this concept in parallel with their current preferred methods for assessing metabolite identification confidence.","PeriodicalId":27,"journal":{"name":"Analytical Chemistry","volume":" ","pages":"1-11"},"PeriodicalIF":6.7,"publicationDate":"2025-01-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142851650","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

Tb-based Metal–Organic Framework-Referenced Fluorescence Assay for Distinguishing Hydroquinone from Its Isomers and Subsequent Quantitative Visual Detection of Cu2+ 基于锑的金属有机框架参考荧光测定法用于区分对苯二酚及其异构体以及随后的 Cu2+ 视觉定量检测

IF 7.4 1区化学 Q1 CHEMISTRY, ANALYTICAL

Analytical Chemistry

Pub Date : 2025-01-14 DOI: 10.1021/acs.analchem.4c05616

Hong Yu, Shuyi Liu, Jiatong Fan, Shuyun Zhu, Xian-En Zhao, Qian Liu

Hydroquinone (HQ) and copper ions (Cu²⁺) are categorized as environmental pollutants that are severely limited in water. Designing a selective assay for discriminating HQ from its two isomers and the convenient determination of Cu²⁺ is of great importance. Herein, a Tb-based metal–organic framework (Tb-MOF) and HQ are assembled innovatively into a ratiometric fluorescence nanoprobe to selectively distinguish HQ and subsequent quantitative visual detection of Cu²⁺. The native blue emission of HQ at 338 nm is used as a response signal, while Tb-MOF with green fluorescence offers a reference signal at 545 nm. Notably, neither resorcinol (RC) nor catechol (CC) exhibits obvious emission under the same experimental conditions, which enables discriminating HQ from its isomers. Thus, a ratiometric fluorescence method has been designed for the selective detection of HQ with the fluorescence intensity ratio F₃₃₈/F₅₄₅ as the readout. The redox reaction between HQ and Cu²⁺ induces fluorescence quenching of HQ and no change to that of Tb-MOF, resulting in a noticeable color variation from blue-green to green via the naked eye. Furthermore, sensitive visual detection of Cu²⁺ is achieved with a low detection limit of 1.67 μM using a smartphone. The satisfactory recoveries and good repeatability of quantitative visualization determined in spiked water samples make this sensing platform suitable for on-site monitoring of environmental samples.

{"title":"Tb-based Metal–Organic Framework-Referenced Fluorescence Assay for Distinguishing Hydroquinone from Its Isomers and Subsequent Quantitative Visual Detection of Cu2+","authors":"Hong Yu, Shuyi Liu, Jiatong Fan, Shuyun Zhu, Xian-En Zhao, Qian Liu","doi":"10.1021/acs.analchem.4c05616","DOIUrl":"https://doi.org/10.1021/acs.analchem.4c05616","url":null,"abstract":"Hydroquinone (HQ) and copper ions (Cu2+) are categorized as environmental pollutants that are severely limited in water. Designing a selective assay for discriminating HQ from its two isomers and the convenient determination of Cu2+ is of great importance. Herein, a Tb-based metal–organic framework (Tb-MOF) and HQ are assembled innovatively into a ratiometric fluorescence nanoprobe to selectively distinguish HQ and subsequent quantitative visual detection of Cu2+. The native blue emission of HQ at 338 nm is used as a response signal, while Tb-MOF with green fluorescence offers a reference signal at 545 nm. Notably, neither resorcinol (RC) nor catechol (CC) exhibits obvious emission under the same experimental conditions, which enables discriminating HQ from its isomers. Thus, a ratiometric fluorescence method has been designed for the selective detection of HQ with the fluorescence intensity ratio F338/F545 as the readout. The redox reaction between HQ and Cu2+ induces fluorescence quenching of HQ and no change to that of Tb-MOF, resulting in a noticeable color variation from blue-green to green via the naked eye. Furthermore, sensitive visual detection of Cu2+ is achieved with a low detection limit of 1.67 μM using a smartphone. The satisfactory recoveries and good repeatability of quantitative visualization determined in spiked water samples make this sensing platform suitable for on-site monitoring of environmental samples.","PeriodicalId":27,"journal":{"name":"Analytical Chemistry","volume":"28 1","pages":""},"PeriodicalIF":7.4,"publicationDate":"2025-01-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142975464","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

Quantitative Analysis of Hepatitis D Virus Using gRNA-Sensitive Semiconducting Polymer Dots

IF 7.4 1区化学 Q1 CHEMISTRY, ANALYTICAL

Analytical Chemistry

Pub Date : 2025-01-14 DOI: 10.1021/acs.analchem.4c04147

Ze Zhang, Yuyang Wu, Jinglun Xu, Zihui Meng, Qingmin Chen, Shengyan Yin

Hepatitis D virus (HDV) significantly influences the progression of liver diseases. Through clinical observations and database analyses, it has been established that patients coinfected with HDV and hepatitis B virus (HBV) experience accelerated progression toward cirrhosis, hepatocellular carcinoma (HCC), and liver failure compared to those infected solely with HBV. A higher viral load correlates with increased replicative activity, enhanced infectivity, and more severe disease manifestations. In this study, we use HDV gRNA-sensitive semiconducting polymer dots (Pdots) as the nanoprobes for the quantitative analysis of HDV copy number variations. The surface of the Pdots is engineered with a clamp design that includes a pair of reporter sequences, protection sequences, and capture sequences tailored to the conserved sequence length of the HDV genome. The capture sequence, comprising leading and trailing chains, specifically binds to the gRNA of the target virus. The protection sequence shields the Pdots from external interference, while the reporter sequence detects the presence of target gRNA through the degradation of fluorescent dye Cy5.5dt. We demonstrate the effectiveness of this assay in a stably transfected cell line derived from HepG2-HDV cells and its translational application in clinical samples from patients. Additionally, this nanobiosensor can accurately detect gRNA at femtomolar (fM) levels, a sensitivity unachievable by previously reported methods. This novel virus quantification system offers significant potential for clinical and virological applications, enhancing screening, early diagnosis, and personalized treatment strategies.

{"title":"Quantitative Analysis of Hepatitis D Virus Using gRNA-Sensitive Semiconducting Polymer Dots","authors":"Ze Zhang, Yuyang Wu, Jinglun Xu, Zihui Meng, Qingmin Chen, Shengyan Yin","doi":"10.1021/acs.analchem.4c04147","DOIUrl":"https://doi.org/10.1021/acs.analchem.4c04147","url":null,"abstract":"Hepatitis D virus (HDV) significantly influences the progression of liver diseases. Through clinical observations and database analyses, it has been established that patients coinfected with HDV and hepatitis B virus (HBV) experience accelerated progression toward cirrhosis, hepatocellular carcinoma (HCC), and liver failure compared to those infected solely with HBV. A higher viral load correlates with increased replicative activity, enhanced infectivity, and more severe disease manifestations. In this study, we use HDV gRNA-sensitive semiconducting polymer dots (Pdots) as the nanoprobes for the quantitative analysis of HDV copy number variations. The surface of the Pdots is engineered with a clamp design that includes a pair of reporter sequences, protection sequences, and capture sequences tailored to the conserved sequence length of the HDV genome. The capture sequence, comprising leading and trailing chains, specifically binds to the gRNA of the target virus. The protection sequence shields the Pdots from external interference, while the reporter sequence detects the presence of target gRNA through the degradation of fluorescent dye Cy5.5dt. We demonstrate the effectiveness of this assay in a stably transfected cell line derived from HepG2-HDV cells and its translational application in clinical samples from patients. Additionally, this nanobiosensor can accurately detect gRNA at femtomolar (fM) levels, a sensitivity unachievable by previously reported methods. This novel virus quantification system offers significant potential for clinical and virological applications, enhancing screening, early diagnosis, and personalized treatment strategies.","PeriodicalId":27,"journal":{"name":"Analytical Chemistry","volume":"22 1","pages":""},"PeriodicalIF":7.4,"publicationDate":"2025-01-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142975340","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

APE1-Activated and NIR-II Photothermal-Enhanced Chemodynamic Therapy Guided by Amplified Fluorescence Imaging 放大荧光成像引导的 APE1 激活和近红外-II 光热增强化学动力疗法

IF 7.4 1区化学 Q1 CHEMISTRY, ANALYTICAL

Analytical Chemistry

Pub Date : 2025-01-14 DOI: 10.1021/acs.analchem.4c05274

Xiaofeng Bi, Jinyue Feng, Xiyuan Feng, Dianpeng Li, Yumin Wang, Shulin Zhao, Liangliang Zhang

The development of intelligent nanotheranostic technology that integrates diagnostic and therapeutic functions holds great promise for personalized nanomedicine. However, most of the nanotheranostic agents exhibit “always-on” properties and do not involve an amplification step, which may largely limit imaging contrast and restrict therapeutic efficacy. Herein, we construct a novel nanotheranostic platform (Hemin/DHPs/PDA@CuS nanocomposite) by assembling DNA hairpin probes (DHPs) and hemin on the surface of PDA@CuS nanosheets that enables amplified fluorescence imaging and activatable chemodynamic therapy (CDT) of tumors. The cancer-relevant APE1 triggers nucleic acid amplification with DHPs to generate activatable and amplified fluorescence signals for discriminating cancer cells from normal cells. Meanwhile, excessive G-quadruplex/hemin-based DNAzyme are also activated, and they function as Fenton-like catalysts to catalyze the production of highly toxic hydroxyl radicals (•OH) for CDT. Moreover, owing to the excellent photothermal conversion efficiency in the near-infrared-II (NIR-II) window, the PDA@CuS not only improves the catalytic performance of CDT but also furnishes PTT. A remarkable antitumor therapeutic effect is demonstrated both in vitro and in vivo. Therefore, the Hemin/DHPs/PDA@CuS nanocomposite is expected to provide a promising avenue for precise imaging-guided antitumor therapy.

{"title":"APE1-Activated and NIR-II Photothermal-Enhanced Chemodynamic Therapy Guided by Amplified Fluorescence Imaging","authors":"Xiaofeng Bi, Jinyue Feng, Xiyuan Feng, Dianpeng Li, Yumin Wang, Shulin Zhao, Liangliang Zhang","doi":"10.1021/acs.analchem.4c05274","DOIUrl":"https://doi.org/10.1021/acs.analchem.4c05274","url":null,"abstract":"The development of intelligent nanotheranostic technology that integrates diagnostic and therapeutic functions holds great promise for personalized nanomedicine. However, most of the nanotheranostic agents exhibit “always-on” properties and do not involve an amplification step, which may largely limit imaging contrast and restrict therapeutic efficacy. Herein, we construct a novel nanotheranostic platform (Hemin/DHPs/PDA@CuS nanocomposite) by assembling DNA hairpin probes (DHPs) and hemin on the surface of PDA@CuS nanosheets that enables amplified fluorescence imaging and activatable chemodynamic therapy (CDT) of tumors. The cancer-relevant APE1 triggers nucleic acid amplification with DHPs to generate activatable and amplified fluorescence signals for discriminating cancer cells from normal cells. Meanwhile, excessive G-quadruplex/hemin-based DNAzyme are also activated, and they function as Fenton-like catalysts to catalyze the production of highly toxic hydroxyl radicals (•OH) for CDT. Moreover, owing to the excellent photothermal conversion efficiency in the near-infrared-II (NIR-II) window, the PDA@CuS not only improves the catalytic performance of CDT but also furnishes PTT. A remarkable antitumor therapeutic effect is demonstrated both in vitro and in vivo. Therefore, the Hemin/DHPs/PDA@CuS nanocomposite is expected to provide a promising avenue for precise imaging-guided antitumor therapy.","PeriodicalId":27,"journal":{"name":"Analytical Chemistry","volume":"41 1","pages":""},"PeriodicalIF":7.4,"publicationDate":"2025-01-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142975461","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

Directed Evolution of Multicyclic Peptides Using Yeast Display for Sensitive and Selective Fluorescent Analysis of CD28 on the Cell Surface 利用酵母展示法定向进化多环肽，对细胞表面的 CD28 进行灵敏、选择性荧光分析

IF 7.4 1区化学 Q1 CHEMISTRY, ANALYTICAL

Analytical Chemistry

Pub Date : 2025-01-14 DOI: 10.1021/acs.analchem.4c05681

Chaoying Xu, Xiaoting Meng, Ping Chai, Hongtan Liu, Zengping Duan, Yu-Hsuan Tsai, Chuanliu Wu

CD28 is a costimulatory receptor that provides the second signal necessary for T-cell activation and is associated with diseases, including rheumatoid arthritis, asthma, and cancer. Targeting CD28 is crucial for both functional bioanalysis and therapeutic development. Molecular probes, particularly fluorescent probes, can enhance our understanding of CD28′s cellular roles. However, existing antibody-based probes face challenges such as high production costs, low stability, and large size, which limit their bioanalytical applications. Thus, there is a need for smaller, robust probes that enable the sensitive and selective targeting of CD28. Multicyclic peptides have emerged as promising candidates for novel therapeutics and molecular probes. Recently, we identified disulfide-directed multicyclic peptides (DDMPs) that bind CD28 with submicromolar affinity; however, their relatively low affinity limits further applications. In this study, we develop a DDMP evolving system based on yeast display and error-prone PCR to identify high-affinity peptide binders. We obtained DDMPs with a picomolar affinity for CD28, exceptional binding specificity, and remarkable oxidative folding efficiency. Furthermore, we developed fluorescent probes and labeling strategies for detecting and visualizing CD28 expression in human T cells. This advancement opens new avenues for studying T-cell dynamics and activation states, which are essential for understanding immune responses and developing targeted therapies. Our study not only produces potent CD28 binders and probes but also establishes a robust platform for optimizing other multicyclic peptide-based probes and therapeutics.

{"title":"Directed Evolution of Multicyclic Peptides Using Yeast Display for Sensitive and Selective Fluorescent Analysis of CD28 on the Cell Surface","authors":"Chaoying Xu, Xiaoting Meng, Ping Chai, Hongtan Liu, Zengping Duan, Yu-Hsuan Tsai, Chuanliu Wu","doi":"10.1021/acs.analchem.4c05681","DOIUrl":"https://doi.org/10.1021/acs.analchem.4c05681","url":null,"abstract":"CD28 is a costimulatory receptor that provides the second signal necessary for T-cell activation and is associated with diseases, including rheumatoid arthritis, asthma, and cancer. Targeting CD28 is crucial for both functional bioanalysis and therapeutic development. Molecular probes, particularly fluorescent probes, can enhance our understanding of CD28′s cellular roles. However, existing antibody-based probes face challenges such as high production costs, low stability, and large size, which limit their bioanalytical applications. Thus, there is a need for smaller, robust probes that enable the sensitive and selective targeting of CD28. Multicyclic peptides have emerged as promising candidates for novel therapeutics and molecular probes. Recently, we identified disulfide-directed multicyclic peptides (DDMPs) that bind CD28 with submicromolar affinity; however, their relatively low affinity limits further applications. In this study, we develop a DDMP evolving system based on yeast display and error-prone PCR to identify high-affinity peptide binders. We obtained DDMPs with a picomolar affinity for CD28, exceptional binding specificity, and remarkable oxidative folding efficiency. Furthermore, we developed fluorescent probes and labeling strategies for detecting and visualizing CD28 expression in human T cells. This advancement opens new avenues for studying T-cell dynamics and activation states, which are essential for understanding immune responses and developing targeted therapies. Our study not only produces potent CD28 binders and probes but also establishes a robust platform for optimizing other multicyclic peptide-based probes and therapeutics.","PeriodicalId":27,"journal":{"name":"Analytical Chemistry","volume":"52 1","pages":""},"PeriodicalIF":7.4,"publicationDate":"2025-01-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142975468","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

Colorimetric Xylenol Orange: A Long-Buried Aggregation-Induced Emission Dye and Restricted Rotation for Dual-Mode Sensing of pH and Metal Ions

IF 7.4 1区化学 Q1 CHEMISTRY, ANALYTICAL

Analytical Chemistry

Pub Date : 2025-01-14 DOI: 10.1021/acs.analchem.4c05819

Yu Li, Kechun Yu, Huihui Li, Shiyu Li, Jingxuan Han, Dong-Yu Guo, Shengming Chen, Qinhe Pan

As the third largest class of dyes in the world, triphenylmethane dyes are widely applied in colorimetric sensing. However, triphenylmethane dyes are commonly nonfluorescent, which limits their sensing applications. It is worthwhile to study the fluorescence off/on control of triphenylmethane dyes and promote the applications of triphenylmethane dyes in sensing technology. In this work, the fluorescence off/on control was investigated by employing a triphenylmethane dye xylenol orange (XO), which is a colorimetric indicator for pH and metal ions. It was discovered that XO exhibited aggregation-induced emission (AIE), and thus, its fluorescence off/on was controlled by intramolecular rotation. This discovery broadens the optical properties of XO and transforms XO from a colorimetric dye to a colorimetric/fluorescent dual-mode AIE dye. It was further verified that the AIE-based fluorescence off/on control improved the sensing performance of XO. A bovine serum albumin-based rotation suppression method was applied to enhance the fluorescence emission of XO for colorimetric/fluorescent dual-mode indication of pH and metal ions. Compared with colorimetric sensing, colorimetric/fluorescent dual-mode sensing exhibits higher accuracy, ascribed to the self-validation effect. This work uncovers AIE-based fluorescence off/on control of triphenylmethane dyes and breathes new life into the sensing applications of triphenylmethane dyes.

{"title":"Colorimetric Xylenol Orange: A Long-Buried Aggregation-Induced Emission Dye and Restricted Rotation for Dual-Mode Sensing of pH and Metal Ions","authors":"Yu Li, Kechun Yu, Huihui Li, Shiyu Li, Jingxuan Han, Dong-Yu Guo, Shengming Chen, Qinhe Pan","doi":"10.1021/acs.analchem.4c05819","DOIUrl":"https://doi.org/10.1021/acs.analchem.4c05819","url":null,"abstract":"As the third largest class of dyes in the world, triphenylmethane dyes are widely applied in colorimetric sensing. However, triphenylmethane dyes are commonly nonfluorescent, which limits their sensing applications. It is worthwhile to study the fluorescence off/on control of triphenylmethane dyes and promote the applications of triphenylmethane dyes in sensing technology. In this work, the fluorescence off/on control was investigated by employing a triphenylmethane dye xylenol orange (XO), which is a colorimetric indicator for pH and metal ions. It was discovered that XO exhibited aggregation-induced emission (AIE), and thus, its fluorescence off/on was controlled by intramolecular rotation. This discovery broadens the optical properties of XO and transforms XO from a colorimetric dye to a colorimetric/fluorescent dual-mode AIE dye. It was further verified that the AIE-based fluorescence off/on control improved the sensing performance of XO. A bovine serum albumin-based rotation suppression method was applied to enhance the fluorescence emission of XO for colorimetric/fluorescent dual-mode indication of pH and metal ions. Compared with colorimetric sensing, colorimetric/fluorescent dual-mode sensing exhibits higher accuracy, ascribed to the self-validation effect. This work uncovers AIE-based fluorescence off/on control of triphenylmethane dyes and breathes new life into the sensing applications of triphenylmethane dyes.","PeriodicalId":27,"journal":{"name":"Analytical Chemistry","volume":"74 1","pages":""},"PeriodicalIF":7.4,"publicationDate":"2025-01-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142981255","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 Vitro Isolation of Quick-Response High-Affinity Aptamers for Continuous and Reagentless Detection of Thrombin 体外分离快速反应高亲和性抗原，用于连续无残留检测凝血酶原

IF 7.4 1区化学 Q1 CHEMISTRY, ANALYTICAL

Analytical Chemistry

Pub Date : 2025-01-14 DOI: 10.1021/acs.analchem.4c04808

Yajing Gao, Ronghui Zhang, Qiao Na, Jing Li, Yi Zhang, Yu Zhang, Keyi Hu, Guangxin Zhang, Xin Zhang, Xinhui Lou

Continuous and reagentless biomolecular detection technologies are bringing an evolutionary influence on disease diagnostics and treatment. Aptamers are attractive as specific recognition probes because they are capable of regeneration without washing. Unfortunately, the affinity and dissociation kinetics of the aptamers developed to date show an inverse relationship, preventing continuous and reagentless detection of protein targets due to their low dissociation rates. Here, we describe an in vitro aptamer isolation strategy that enriches quick-response, high-affinity bivalent protein-binding aptamers. The method is general, as evidenced by the isolation of aptamers targeting thrombin and human serum albumin. We then demonstrated the excellent regeneration capability of the isolated thrombin aptamers using biolayer interferometry. The sensors instantly responded to alternating concentration changes of thrombin at nanomolar levels (200–500 nM), reaching highly consistent equilibrium signals within 10 s. In contrast, the well-known thrombin-binding aptamers, TBA-15 and TBA-29, were not capable of regeneration. Our study provides a simple means to obtain quick-response, high-affinity protein-binding aptamers. It can also be used for the isolation of aptamer pairs, which has been demonstrated to be quite challenging. Our study also provides insights into the rational design of aptamers to control their binding thermodynamics and kinetics.

{"title":"In Vitro Isolation of Quick-Response High-Affinity Aptamers for Continuous and Reagentless Detection of Thrombin","authors":"Yajing Gao, Ronghui Zhang, Qiao Na, Jing Li, Yi Zhang, Yu Zhang, Keyi Hu, Guangxin Zhang, Xin Zhang, Xinhui Lou","doi":"10.1021/acs.analchem.4c04808","DOIUrl":"https://doi.org/10.1021/acs.analchem.4c04808","url":null,"abstract":"Continuous and reagentless biomolecular detection technologies are bringing an evolutionary influence on disease diagnostics and treatment. Aptamers are attractive as specific recognition probes because they are capable of regeneration without washing. Unfortunately, the affinity and dissociation kinetics of the aptamers developed to date show an inverse relationship, preventing continuous and reagentless detection of protein targets due to their low dissociation rates. Here, we describe an in vitro aptamer isolation strategy that enriches quick-response, high-affinity bivalent protein-binding aptamers. The method is general, as evidenced by the isolation of aptamers targeting thrombin and human serum albumin. We then demonstrated the excellent regeneration capability of the isolated thrombin aptamers using biolayer interferometry. The sensors instantly responded to alternating concentration changes of thrombin at nanomolar levels (200–500 nM), reaching highly consistent equilibrium signals within 10 s. In contrast, the well-known thrombin-binding aptamers, TBA-15 and TBA-29, were not capable of regeneration. Our study provides a simple means to obtain quick-response, high-affinity protein-binding aptamers. It can also be used for the isolation of aptamer pairs, which has been demonstrated to be quite challenging. Our study also provides insights into the rational design of aptamers to control their binding thermodynamics and kinetics.","PeriodicalId":27,"journal":{"name":"Analytical Chemistry","volume":"97 1","pages":""},"PeriodicalIF":7.4,"publicationDate":"2025-01-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142975460","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