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Simultaneous Dissolved Gas Analysis in Transformer Oil via Time-Division-Multiplexed Quartz-Enhanced Photoacoustic Spectroscopy 时分多路石英增强光声光谱法同时分析变压器油中溶解气体
IF 7.4 1区 化学 Q1 CHEMISTRY, ANALYTICAL Pub Date : 2026-02-02 DOI: 10.1021/acs.analchem.5c07335
Jialiang Dai, Yixin Zhang, Jiapeng Wang, Chenglong Wang, Yong Wang, Qingyuan Tian, Yifan Chen, Chaofan Feng, Ruyue Cui, Xukun Yin, Lei Dong, Hongpeng Wu
Dissolved gas analysis (DGA) is an essential method for monitoring and diagnosing faults in oil-immersed transformers. Acetylene (C2H2) and methane (CH4) are key indicator gases for fault identification. We report for the first time a time-division-multiplexed quartz-enhanced photoacoustic spectroscopy (QEPAS) sensing system capable of simultaneously and sensitively detecting dissolved C2H2 and CH4, even with an extremely small amount of required sample gas. The on-beam configuration enhanced the 2f signal amplitude by nearly 20-fold. The sensing system achieved minimum detection limits (MDLs) of approximately 15 ppb for C2H2 and 0.3 ppm for CH4, which are 2–3 orders of magnitude lower than the safety thresholds defined in the relevant industry standards. The detectability of the sensing system satisfies the requirements for DGA in transformer oil. With a gas cell volume of approximately 1.6 mL, the system markedly reduces the required oil sample volume. By integrating headspace degassing with QEPAS, the sensing system enables real-time monitoring and analysis of the oil-gas equilibrium behavior of dissolved C2H2 and CH4. With its high sensitivity, rapid response, and low sample consumption, the proposed sensing system provides a viable and efficient approach for early detection of transformer faults. Furthermore, it establishes a foundation for applying QEPAS to dissolved gas analysis in transformer oil.
溶解气体分析(DGA)是油浸式变压器故障监测和诊断的重要手段。乙炔(C2H2)和甲烷(CH4)是故障识别的关键指示气体。我们首次报道了一种分时复用石英增强光声光谱(QEPAS)传感系统,该系统能够同时灵敏地检测溶解的C2H2和CH4,即使需要极少量的样品气体。梁上结构使2f信号幅度提高了近20倍。该传感系统对C2H2和CH4的最低检测限(MDLs)分别为约15 ppb和0.3 ppm,比相关行业标准中定义的安全阈值低2-3个数量级。该传感系统的可检测性满足变压器油中DGA的要求。该系统的气池体积约为1.6 mL,显著减少了所需的油样体积。通过将顶空脱气与QEPAS相结合,传感系统能够实时监测和分析溶解的C2H2和CH4的油气平衡行为。该传感系统具有灵敏度高、响应速度快、样本消耗少等特点,为变压器故障的早期检测提供了一种可行而有效的方法。为将QEPAS应用于变压器油中溶解气体的分析奠定了基础。
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引用次数: 0
Exploration of Semiconductor Chip-Based Single-Molecule Protein Sequencing for Identification of Hemoglobin Variants 基于半导体芯片的单分子蛋白测序用于血红蛋白变异鉴定的探索
IF 7.4 1区 化学 Q1 CHEMISTRY, ANALYTICAL Pub Date : 2026-02-02 DOI: 10.1021/acs.analchem.5c07226
Ruben Y. Luo, Mathivanan Chinnaraj, Kristin Blacklock, Douglas Pike, Ilya Chorny, John Vieceli, Carolyn V. Wong
Identification of hemoglobin (Hb) variants is of significant value in the clinical diagnosis of hemoglobinopathies. Conventional methods used to identify Hb variants in clinical laboratories can narrow down the range of candidates for a Hb variant sample but are unable to pinpoint the exact Hb variant. In this study, Next-Generation Protein Sequencing (NGPS), a semiconductor chip-based single-molecule protein sequencing (SMPS) technology, was explored as a novel method to identify Hb variants. Two heterozygous Hb variant samples underwent NGPS analysis. Proteotypic peptides corresponding to Hb variants were successfully detected, enabling the identification of the samples as Hb Handsworth (Hb α-Handsworth subunit G18R) and Hb G-Accra (Hb β-G-Accra subunit D73N). The NGPS method has been demonstrated as a potential tool to identify Hb variants. Although there are still limitations to overcome for the wide adoption of NGPS, this exploration supports the potential use of NGPS and other SMPS technologies in clinical applications.
血红蛋白(Hb)变异的鉴定在血红蛋白病的临床诊断中具有重要价值。在临床实验室中用于识别Hb变异的传统方法可以缩小Hb变异样本的候选范围,但无法确定确切的Hb变异。在这项研究中,下一代蛋白测序(NGPS),一种基于半导体芯片的单分子蛋白测序(SMPS)技术,被探索作为一种鉴定Hb变异的新方法。两个杂合Hb变异样本进行了NGPS分析。成功检测到Hb变异对应的蛋白型肽,鉴定样品为Hb Handsworth (Hb α-Handsworth亚基G18R)和Hb G-Accra (Hb β-G-Accra亚基D73N)。NGPS方法已被证明是鉴定Hb变异的潜在工具。尽管NGPS的广泛应用仍有一些限制需要克服,但这一探索支持了NGPS和其他SMPS技术在临床应用中的潜在应用。
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引用次数: 0
Microneedle-Integrated Wearable Sensors: from Material Designs and Sensing Mechanisms to Diverse Biomarker Monitoring 微针集成可穿戴传感器:从材料设计和传感机制到多种生物标志物监测
IF 7.4 1区 化学 Q1 CHEMISTRY, ANALYTICAL Pub Date : 2026-02-02 DOI: 10.1021/acs.analchem.5c06046
Xin Li,Yu Wang,Huishuang Li,Guixia Ling,Peng Zhang
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引用次数: 0
A Highly Sensitive and High-Throughput Quantitative HILIC-MS/MS Method for Systematic Profiling of RNA Modifications 一种用于RNA修饰系统分析的高灵敏度和高通量HILIC-MS/MS定量方法
IF 7.4 1区 化学 Q1 CHEMISTRY, ANALYTICAL Pub Date : 2026-02-02 DOI: 10.1021/acs.analchem.5c06973
Cheng Guo,Xiujuan Hong,Yiqiu Hu,Tao Pan,Yunxiang Zhou,Haifen Lei,Yuanjiang Pan
Understanding the functions and regulatory mechanisms of the epitranscriptome entails robust and accurate analytical methods to identify and quantify post-transcriptional modifications in RNA. However, there are still various challenges in analyzing multiple modified nucleosides in RNA. Herein, we established a highly sensitive and high-throughput hydrophilic interaction liquid chromatography-tandem mass spectrometry (HILIC-MS/MS) method, in conjunction with a stable isotope-dilution technique, for accurate quantification of 35 nucleosides. By the use of malic acid as a mobile phase additive, the HILIC-based separation of nucleosides was improved and the MS signal response of nucleosides was enhanced by 2.5- to 20.0-fold. Notably, seven groups of isomeric nucleosides with identical multiple-reaction monitoring ion transitions and six groups of nucleosides with identical or similar molecular weights that were indistinguishable by MS were well resolved by optimal HILIC separation. Thirty-five nucleosides were analyzed simultaneously within 12.5 min, and the limits of detection of these nucleosides ranged from 15.0 amol to 43.5 fmol. With this method, we conducted a comprehensive analysis and evaluation of the alteration in the RNA modification profile in breast cancer and assessed the RNA modification patterns across different breast cancer subtypes. The developed HILIC-MS/MS method has excellent capabilities for sensitive and high-throughput detection of multiple modified nucleosides, thereby providing a valuable analytical tool for deciphering the epitranscriptomic landscape and screening nucleosides as biomarkers in future clinical research.
了解表转录组的功能和调控机制需要稳健和准确的分析方法来识别和量化RNA中的转录后修饰。然而,在分析RNA中的多个修饰核苷方面仍然存在各种挑战。在此,我们建立了一种高灵敏度和高通量的亲水相互作用液相色谱-串联质谱(HILIC-MS/MS)方法,结合稳定同位素稀释技术,对35种核苷进行精确定量。采用苹果酸作为流动相添加剂,改进了基于hilic的核苷分离,核苷的MS信号响应提高了2.5 ~ 20.0倍。值得注意的是,7组具有相同多反应监测离子转移的同分异构体核苷和6组具有相同或相似分子量的核苷,通过最佳的HILIC分离可以很好地分离出MS无法区分的核苷。在12.5 min内同时分析35种核苷,检出限为15.0 ~ 43.5 fmol。通过这种方法,我们对乳腺癌中RNA修饰谱的变化进行了全面的分析和评估,并评估了不同乳腺癌亚型的RNA修饰模式。所建立的HILIC-MS/MS方法具有灵敏、高通量检测多种修饰核苷的能力,为今后临床研究中破译外转录组图谱和筛选核苷作为生物标志物提供了有价值的分析工具。
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引用次数: 0
Off-Axis Illumination and Epicollection Confocal Brillouin Scattering Microspectroscopy 离轴照明和外聚光共焦布里渊散射显微光谱学
IF 7.4 1区 化学 Q1 CHEMISTRY, ANALYTICAL Pub Date : 2026-02-02 DOI: 10.1021/acs.analchem.5c06290
Hiroharu Yui,Yuui Fujiyama,Shu-hei Urashima,Takeru Ota,Hiroshi Hibino
Viscoelastic properties of tissues and biologically relevant fluids therein are important to maintaining their structures and functions. Confocal Brillouin scattering microspectroscopy (μCBS) is a promising tool to address such local viscoelastic properties in nonlabeling and noninvasive manners. However, since the intensity of Brillouin scattering is extremely weak, the strong background by reflected light and Rayleigh scattering often hinders the quantitative analyses of viscoelastic properties in buried tissues and biological fluid. Here, we report an optical configuration for the reduction of such strong backgrounds based on the combination of off-axis illumination and epicollection for μCBS. As a test sample, aqueous solutions of bovine serum albumin (BSA) with relevant electrolytes were measured through thick glass windows (1.25 mm) of quartz cuvettes. Such thick windows act as strong reflectors and scatterers for the focused illumination light due to interfacial reflections and multiple reflections therein. The series of Brillouin scattering spectra of BSA solutions up to 20 wt % buried under the thick window were successfully analyzed owing to the effective reduction of those strong backgrounds. Further, it was clarified that hydrated water molecules surrounding BSA non-negligibly contribute to Brillouin scattering bandwidth, indicating that it would be also applicable to detect conformational changes of proteins in fluids. The off-axis illumination and epicollection optical configuration would further enhance the μCBS’s ability for its future application in biochemistry and biomedicine to assess the viscoelastic properties of tissues with complex structures and biologically relevant fluids, such as blood and lymph flowing therein.
组织和其中的生物相关流体的粘弹性特性对于维持其结构和功能是重要的。共焦布里渊散射微光谱学(μCBS)是非标记和非侵入性研究这种局部粘弹性特性的一种很有前途的工具。然而,由于布里渊散射的强度极弱,反射光和瑞利散射的强背景往往阻碍了对埋藏组织和生物流体粘弹性特性的定量分析。在这里,我们报告了一种基于离轴照明和μCBS的光采集相结合的光学配置来减少这种强背景。作为测试样品,通过厚玻璃窗(1.25 mm)石英比色皿测量牛血清白蛋白(BSA)水溶液和相关电解质。由于其中的界面反射和多次反射,这种厚窗对聚焦的照明光起到了强反射和散射的作用。由于有效地抑制了强背景,在厚窗下埋入20% wt %的BSA溶液的布里渊散射光谱序列得以分析。此外,澄清了BSA周围的水合水分子对布里渊散射带宽的贡献不可忽略,这表明它也适用于检测流体中蛋白质的构象变化。离轴照明和上聚光结构将进一步增强μCBS在生物化学和生物医学中的应用能力,以评估具有复杂结构的组织及其中血液和淋巴流动等生物相关流体的粘弹性特性。
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引用次数: 0
Dynamic Crystalline Nanofibers for Analyte-Specific Fluorescence Sensing 用于分析物特异性荧光传感的动态晶体纳米纤维
IF 6.7 1区 化学 Q1 CHEMISTRY, ANALYTICAL Pub Date : 2026-02-02 DOI: 10.1021/acs.analchem.5c07757
Lishan Sun, , , Tianyan Zhang, , , Zongjun Yu, , , Chenglong Liao, , , Hongwei Ji, , , Yanjun Gong, , , Wenjing Song, , , Ling Zang*, , , Yanke Che*, , and , Jincai Zhao, 

Dynamic molecular crystals with inherent conformational flexibility could offer a promising platform for fluorescence sensing by exhibiting analyte-specific conformational and fluorescence responses. Herein, we materialize this notion through a donor–acceptor (D–A) molecule featuring a D-D-A-D-D backbone, with a thiadiazolopyridine acceptor flanked by carbazole donors. The molecule self-assembles into crystalline nanofibers endowed with a dynamic conformational twisting capability, which arises from the synergistic effect of the unique A group’s electrostatic repulsion and the spatial freedom provided by the alkyl chains. This dynamic nature is validated by a rapid and reversible emission toggle between yellow and red upon cycling exposure to and evaporation of solvents like n-hexane. Crucially, the dynamic nanofibers also allow analyte binding to drive specific conformational changes, thereby perturbing intermolecular interactions and yielding distinct fluorescence responses. These responses, including variations in kinetics and intensity, enable the multiplexed discrimination of amines with high selectivity and sensitivity against humidity and background volatile organic compounds. The dynamic nanofibers function robustly in complex environments such as hair spray and car exhaust, and exhibit high sensitivity toward amine-type drugs, with detection limits as low as 1 ng for methamphetamine and fentanyl. This work underscores the potential of dynamic molecular crystals to deliver substantially expanded signal diversity for advanced sensing applications.

具有固有构象灵活性的动态分子晶体通过表现出分析物特异性的构象和荧光响应,为荧光传感提供了一个有前途的平台。在这里,我们通过具有D-D-A-D-D骨架的供体-受体(D-A)分子实现了这一概念,该分子具有噻二唑吡啶受体和咔唑供体的两侧。分子自组装成具有动态构象扭转能力的晶体纳米纤维,这是由于独特的a基团的静电斥力和烷基链提供的空间自由度的协同作用。在循环暴露和蒸发溶剂(如正己烷)时,黄色和红色之间的快速可逆发射切换验证了这种动态性质。至关重要的是,动态纳米纤维还允许分析物结合驱动特定的构象变化,从而干扰分子间相互作用并产生不同的荧光响应。这些反应,包括动力学和强度的变化,使胺对湿度和背景挥发性有机化合物具有高选择性和灵敏度的多重区分。动态纳米纤维在发胶和汽车尾气等复杂环境中功能强大,对胺类药物具有高灵敏度,对甲基苯丙胺和芬太尼的检出限低至1 ng。这项工作强调了动态分子晶体为先进传感应用提供大量扩展信号多样性的潜力。
{"title":"Dynamic Crystalline Nanofibers for Analyte-Specific Fluorescence Sensing","authors":"Lishan Sun,&nbsp;, ,&nbsp;Tianyan Zhang,&nbsp;, ,&nbsp;Zongjun Yu,&nbsp;, ,&nbsp;Chenglong Liao,&nbsp;, ,&nbsp;Hongwei Ji,&nbsp;, ,&nbsp;Yanjun Gong,&nbsp;, ,&nbsp;Wenjing Song,&nbsp;, ,&nbsp;Ling Zang*,&nbsp;, ,&nbsp;Yanke Che*,&nbsp;, and ,&nbsp;Jincai Zhao,&nbsp;","doi":"10.1021/acs.analchem.5c07757","DOIUrl":"10.1021/acs.analchem.5c07757","url":null,"abstract":"<p >Dynamic molecular crystals with inherent conformational flexibility could offer a promising platform for fluorescence sensing by exhibiting analyte-specific conformational and fluorescence responses. Herein, we materialize this notion through a donor–acceptor (D–A) molecule featuring a D-D-A-D-D backbone, with a thiadiazolopyridine acceptor flanked by carbazole donors. The molecule self-assembles into crystalline nanofibers endowed with a dynamic conformational twisting capability, which arises from the synergistic effect of the unique A group’s electrostatic repulsion and the spatial freedom provided by the alkyl chains. This dynamic nature is validated by a rapid and reversible emission toggle between yellow and red upon cycling exposure to and evaporation of solvents like <i>n</i>-hexane. Crucially, the dynamic nanofibers also allow analyte binding to drive specific conformational changes, thereby perturbing intermolecular interactions and yielding distinct fluorescence responses. These responses, including variations in kinetics and intensity, enable the multiplexed discrimination of amines with high selectivity and sensitivity against humidity and background volatile organic compounds. The dynamic nanofibers function robustly in complex environments such as hair spray and car exhaust, and exhibit high sensitivity toward amine-type drugs, with detection limits as low as 1 ng for methamphetamine and fentanyl. This work underscores the potential of dynamic molecular crystals to deliver substantially expanded signal diversity for advanced sensing applications.</p>","PeriodicalId":27,"journal":{"name":"Analytical Chemistry","volume":"98 5","pages":"4339–4348"},"PeriodicalIF":6.7,"publicationDate":"2026-02-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146097816","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
Huev: A Tunable Hue Descriptor for the Quantitative Analysis of Multicolor Optical Sensors 色相:用于多色光学传感器定量分析的可调色相描述符
IF 7.4 1区 化学 Q1 CHEMISTRY, ANALYTICAL Pub Date : 2026-02-01 DOI: 10.1021/acs.analchem.5c06642
Haitao Sun, Paul Nicholas Williams, Zhong Wu, Siliang Zhang, Haiyi Chen, Xing Liu, Chao Han, Jun Luo
Hue-changed sequences of multicolor optical sensors are diverse, whereas hue-quantified sequences of existing quantitative parameters are fixed. Monotonic calibration is unavailable when the two sequences are inconsistent. To overcome this challenge, a hue descriptor named Huev was designed. Its quantification sequence is tunable via a parameter named HT. Furthermore, a method of calculating the optimal HT for each sensor, a Huev-based analytical workflow (including chemical imaging), and a user-friendly analytical platform were developed. We demonstrated that Huev has broader applicability than some existing parameters, calibrated a sensor that cannot be calibrated by existing parameters, transformed qualitative test strips into quantitative tools, and developed a pH imaging method with a broader detection range (0.1–12) than conventional methods. Our work makes it possible to develop a hue-changed phenomenon into a universal optical sensing technique. It promises broad applications in many fields based on analytical chemistry such as point-of-care testing (POCT) and chemical imaging.
多色光学传感器的色彩变化序列是多样的,而现有定量参数的色彩量化序列是固定的。当两个序列不一致时,单调校准不可用。为了克服这个挑战,设计了一个名为Huev的色调描述符。它的量化序列可以通过一个名为HT的参数来调节。此外,还开发了计算每个传感器的最佳高温的方法、基于huv的分析工作流程(包括化学成像)和用户友好的分析平台。我们证明了Huev比一些现有参数具有更广泛的适用性,校准了现有参数无法校准的传感器,将定性试纸转化为定量工具,并开发了一种比传统方法具有更宽检测范围(0.1-12)的pH成像方法。我们的工作使得将色彩变化现象发展成为一种通用的光学传感技术成为可能。它有望在许多基于分析化学的领域得到广泛应用,如即时检测(POCT)和化学成像。
{"title":"Huev: A Tunable Hue Descriptor for the Quantitative Analysis of Multicolor Optical Sensors","authors":"Haitao Sun, Paul Nicholas Williams, Zhong Wu, Siliang Zhang, Haiyi Chen, Xing Liu, Chao Han, Jun Luo","doi":"10.1021/acs.analchem.5c06642","DOIUrl":"https://doi.org/10.1021/acs.analchem.5c06642","url":null,"abstract":"Hue-changed sequences of multicolor optical sensors are diverse, whereas hue-quantified sequences of existing quantitative parameters are fixed. Monotonic calibration is unavailable when the two sequences are inconsistent. To overcome this challenge, a hue descriptor named <i>Hue</i><sub>v</sub> was designed. Its quantification sequence is tunable via a parameter named HT. Furthermore, a method of calculating the optimal HT for each sensor, a <i>Hue</i><sub>v</sub>-based analytical workflow (including chemical imaging), and a user-friendly analytical platform were developed. We demonstrated that <i>Hue</i><sub>v</sub> has broader applicability than some existing parameters, calibrated a sensor that cannot be calibrated by existing parameters, transformed qualitative test strips into quantitative tools, and developed a pH imaging method with a broader detection range (0.1–12) than conventional methods. Our work makes it possible to develop a hue-changed phenomenon into a universal optical sensing technique. It promises broad applications in many fields based on analytical chemistry such as point-of-care testing (POCT) and chemical imaging.","PeriodicalId":27,"journal":{"name":"Analytical Chemistry","volume":"82 1","pages":""},"PeriodicalIF":7.4,"publicationDate":"2026-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146097870","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
Framework Doping Enhances COF-DNA Nanoplatforms for Dual RNA Imaging and Phototherapy 框架掺杂增强COF-DNA纳米平台用于双RNA成像和光疗
IF 7.4 1区 化学 Q1 CHEMISTRY, ANALYTICAL Pub Date : 2026-02-01 DOI: 10.1021/acs.analchem.5c03774
Peng Gao, Mengyao Yu, Ruyue Wei, Kaiye Wang, Xiaohan Liu, Wei Pan, Na Li, Bo Tang
DNA-engineered covalent organic frameworks (COFs) hold great promise for cancer theranostics. However, regulating the interaction between COFs and functional DNAs remains a significant challenge, despite its crucial role in ensuring the theranostic performance. In this study, we present a framework doping strategy that simultaneously optimizes the diagnostic imaging and phototherapeutic effects of the COF-DNA nanosystems. In situ doping of porphyrin allows the photocatalytic generation of reactive oxygen species (ROS) by COF nanoparticles and facilitates the adsorption and quenching of fluorescent single-stranded DNA (ssDNA). This enabled the construction of a high-performance COF-DNA nanosystem for RNA-imaging guided phototherapy: the system restored intense fluorescence signals in response to cancer-associated mRNA and miRNA and generated abundant ROS upon laser irradiation, thereby simultaneously lighting up and killing cancer cells. The developed framework doping strategy provides valuable insights into regulating COF-DNA interactions and constructing high-performance theranostic nanosystems.
dna工程共价有机框架(COFs)在癌症治疗方面具有很大的前景。然而,调节COFs和功能dna之间的相互作用仍然是一个重大的挑战,尽管它在确保治疗效果中起着至关重要的作用。在这项研究中,我们提出了一种框架掺杂策略,同时优化了COF-DNA纳米系统的诊断成像和光疗效果。卟啉的原位掺杂允许COF纳米颗粒光催化生成活性氧(ROS),并促进荧光单链DNA (ssDNA)的吸附和猝灭。这使得构建用于rna成像引导光疗的高性能COF-DNA纳米系统成为可能:该系统响应癌症相关mRNA和miRNA恢复强烈的荧光信号,并在激光照射下产生丰富的ROS,从而同时点亮和杀死癌细胞。开发的框架掺杂策略为调节COF-DNA相互作用和构建高性能治疗纳米系统提供了有价值的见解。
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引用次数: 0
Hollow-Structured CNQDs@CTP Z-Scheme Heterojunctions for the Construction of a PEC Sensing Platform: High-Sensitivity Detection of PFOA in Water 用于构建PEC传感平台的中空结构CNQDs@CTP z方案异质结:水中PFOA的高灵敏度检测
IF 7.4 1区 化学 Q1 CHEMISTRY, ANALYTICAL Pub Date : 2026-02-01 DOI: 10.1021/acs.analchem.5c05357
Jing Wang, Xuejing Wang, Hongwei Duan, Yihua Zhu, Jun Shi, Mengge Zhang, Oluwafunmilola Ola, Guanya Ji, Xiuxiu Dong, Qian Liu, Qijian Niu
Perfluorooctanoic acid (PFOA) is an emerging environmental pollutant due to its high bioaccumulation, toxicity, environmental persistence, and widespread presence. Its detection is crucial for assessing water quality safety. In this study, a molecularly imprinted photoelectrochemical (MIP-PEC) sensor based on a Z-scheme heterojunction of covalent organic framework–confined graphitic carbon nitride quantum dots (CNQDs@CTP) was developed for the highly sensitive and selective detection of PFOA in water. First, the novel CNQDs@CTP composite was prepared via a self-templating method, which featured a unique hollow structure. The hollow structure and Z-scheme heterojunction significantly improved light absorption and carrier separation efficiency, with an electron lifetime reaching 6.72 × 10–2 s and high incident photon-to-electron conversion efficiency (IPCE). Furthermore, when combined with molecularly imprinted technology, PFOA-specific recognition sites were constructed on the electrode surface, yielding an imprint factor of 9.3. Under optimized conditions, the sensors had a wide detection range (1.00 × 10–11 to 5.00 × 10–6 mol·L–1) and a low detection limit (5.50 × 10–12 mol·L–1). The water sample detection results were highly consistent with the LC-MS/MS results. The sensors combined high sensitivity, low cost, and ease of operation, providing an innovative solution for the accurate and sensitive detection of PFOA in water.
全氟辛酸(PFOA)具有高生物蓄积性、高毒性、环境持久性和广泛存在的特点,是一种新兴的环境污染物。它的检测是评价水质安全的关键。在这项研究中,基于共价有机框架限制石墨氮化碳量子点(CNQDs@CTP)的Z-scheme异质结,开发了一种分子印迹光电化学(MIP-PEC)传感器,用于高灵敏度和选择性地检测水中的PFOA。首先,通过自模板法制备了具有独特中空结构的新型CNQDs@CTP复合材料。空心结构和z型异质结显著提高了光吸收和载流子分离效率,电子寿命达到6.72 × 10-2 s,入射光子到电子转换效率(IPCE)较高。此外,当与分子印迹技术相结合时,在电极表面构建了pfoa特异性识别位点,产生了9.3的印迹因子。优化后的传感器检测范围宽(1.00 × 10-11 ~ 5.00 × 10-6 mol·L-1),检出限低(5.50 × 10-12 mol·L-1)。水样检测结果与LC-MS/MS结果高度一致。该传感器结合了高灵敏度、低成本和易于操作的特点,为准确灵敏地检测水中PFOA提供了一种创新的解决方案。
{"title":"Hollow-Structured CNQDs@CTP Z-Scheme Heterojunctions for the Construction of a PEC Sensing Platform: High-Sensitivity Detection of PFOA in Water","authors":"Jing Wang, Xuejing Wang, Hongwei Duan, Yihua Zhu, Jun Shi, Mengge Zhang, Oluwafunmilola Ola, Guanya Ji, Xiuxiu Dong, Qian Liu, Qijian Niu","doi":"10.1021/acs.analchem.5c05357","DOIUrl":"https://doi.org/10.1021/acs.analchem.5c05357","url":null,"abstract":"Perfluorooctanoic acid (PFOA) is an emerging environmental pollutant due to its high bioaccumulation, toxicity, environmental persistence, and widespread presence. Its detection is crucial for assessing water quality safety. In this study, a molecularly imprinted photoelectrochemical (MIP-PEC) sensor based on a Z-scheme heterojunction of covalent organic framework–confined graphitic carbon nitride quantum dots (CNQDs@CTP) was developed for the highly sensitive and selective detection of PFOA in water. First, the novel CNQDs@CTP composite was prepared via a self-templating method, which featured a unique hollow structure. The hollow structure and Z-scheme heterojunction significantly improved light absorption and carrier separation efficiency, with an electron lifetime reaching 6.72 × 10<sup>–2</sup> s and high incident photon-to-electron conversion efficiency (IPCE). Furthermore, when combined with molecularly imprinted technology, PFOA-specific recognition sites were constructed on the electrode surface, yielding an imprint factor of 9.3. Under optimized conditions, the sensors had a wide detection range (1.00 × 10<sup>–11</sup> to 5.00 × 10<sup>–6</sup> mol·L<sup>–1</sup>) and a low detection limit (5.50 × 10<sup>–12</sup> mol·L<sup>–1</sup>). The water sample detection results were highly consistent with the LC-MS/MS results. The sensors combined high sensitivity, low cost, and ease of operation, providing an innovative solution for the accurate and sensitive detection of PFOA in water.","PeriodicalId":27,"journal":{"name":"Analytical Chemistry","volume":"8 1","pages":""},"PeriodicalIF":7.4,"publicationDate":"2026-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146097865","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
A Direct Near-Infrared Photocage-Blocked Methylation Gate Integrated with an Ultrasensitive Triple-Loop Self-Boosted Exponential Amplification DNA Nanocircuit for High-Fidelity Molecular Imaging 用于高保真分子成像的直接近红外光阱阻断甲基化门与超灵敏三环自增强指数扩增DNA纳米电路集成
IF 7.4 1区 化学 Q1 CHEMISTRY, ANALYTICAL Pub Date : 2026-02-01 DOI: 10.1021/acs.analchem.5c07473
Jingwei Qiu, Cheng-Yu Li
Fluorescent biosensors constructed from sensitive DNA nanocircuits for high-fidelity imaging in live biological samples are in high demand for disease diagnosis. In this contribution, we present a direct near-infrared (NIR) photocage-blocked methylation gate that integrates with an ultrasensitive triple-loop self-boosted exponential amplification DNA nanocircuit. For one thing, a methylation gate is incorporated as a specific component to enhance biorecognition capability, which is then directly blocked by an NIR photocage comprising an upconverting nanoparticle and a photolytic 6-nitropiperonyloxymethyl (NPOM) group. Under exogenous 980 nm NIR-light-transformed ultraviolet upconverting luminescence, the linkage between the NPOM group and adenine is photolytically cleaved to controllably expose the m6A site. For another, by cascading an iterative catalytic hairpin assembly hybridization chain reaction cycle with a self-actuated DNAzyme cleavage that triggers fluorescence output, a robust DNA nanocircuit with triple-loop self-boosted exponential amplification is built. When a model microRNA biomarker (miRNA-155) with elevated expression across various malignant tumors is used for proof-of-concept validation, we show the ultrahigh sensitivity and strong specificity of this fluorescent biosensor. More importantly, the bioanalytical toolbox enables high-fidelity molecular imaging in live-cell and in vivo scenarios, paving the way for the deployment of DNA nanocircuits in disease diagnosis.
利用灵敏的DNA纳米电路构建的荧光生物传感器对活体生物样品进行高保真成像,在疾病诊断中有很高的需求。在这篇文章中,我们提出了一个直接近红外(NIR)光笼阻断甲基化门,集成了一个超灵敏的三环自增强指数扩增DNA纳米电路。首先,甲基化门作为增强生物识别能力的特定组分被纳入,然后由上转换纳米粒子和光解6-硝基酰氧甲基(NPOM)基团组成的近红外光笼直接阻断。在外源980 nm nir光转换的紫外线上转换发光下,NPOM基团与腺嘌呤之间的连接被光解裂解,以可控地暴露m6A位点。另一方面,通过将迭代催化发夹组装杂交链反应循环与触发荧光输出的自驱动DNAzyme切割级联,构建了具有三环自增强指数扩增的强大DNA纳米电路。当在各种恶性肿瘤中表达升高的模型microRNA生物标志物(miRNA-155)用于概念验证时,我们展示了这种荧光生物传感器的超高灵敏度和强特异性。更重要的是,生物分析工具箱能够在活细胞和体内场景中实现高保真分子成像,为在疾病诊断中部署DNA纳米电路铺平了道路。
{"title":"A Direct Near-Infrared Photocage-Blocked Methylation Gate Integrated with an Ultrasensitive Triple-Loop Self-Boosted Exponential Amplification DNA Nanocircuit for High-Fidelity Molecular Imaging","authors":"Jingwei Qiu, Cheng-Yu Li","doi":"10.1021/acs.analchem.5c07473","DOIUrl":"https://doi.org/10.1021/acs.analchem.5c07473","url":null,"abstract":"Fluorescent biosensors constructed from sensitive DNA nanocircuits for high-fidelity imaging in live biological samples are in high demand for disease diagnosis. In this contribution, we present a direct near-infrared (NIR) photocage-blocked methylation gate that integrates with an ultrasensitive triple-loop self-boosted exponential amplification DNA nanocircuit. For one thing, a methylation gate is incorporated as a specific component to enhance biorecognition capability, which is then directly blocked by an NIR photocage comprising an upconverting nanoparticle and a photolytic 6-nitropiperonyloxymethyl (NPOM) group. Under exogenous 980 nm NIR-light-transformed ultraviolet upconverting luminescence, the linkage between the NPOM group and adenine is photolytically cleaved to controllably expose the m<sup>6</sup>A site. For another, by cascading an iterative catalytic hairpin assembly hybridization chain reaction cycle with a self-actuated DNAzyme cleavage that triggers fluorescence output, a robust DNA nanocircuit with triple-loop self-boosted exponential amplification is built. When a model microRNA biomarker (miRNA-155) with elevated expression across various malignant tumors is used for proof-of-concept validation, we show the ultrahigh sensitivity and strong specificity of this fluorescent biosensor. More importantly, the bioanalytical toolbox enables high-fidelity molecular imaging in live-cell and <i>in vivo</i> scenarios, paving the way for the deployment of DNA nanocircuits in disease diagnosis.","PeriodicalId":27,"journal":{"name":"Analytical Chemistry","volume":"42 1","pages":""},"PeriodicalIF":7.4,"publicationDate":"2026-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146097882","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
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Analytical Chemistry
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