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In-situ laser-induced metal (M = Fe, Co, Ni, Cu)-doped graphene electrode for sensitive uric acid sensing in sweat 原位激光诱导金属(M = Fe, Co, Ni, Cu)掺杂石墨烯电极用于汗液中尿酸敏感传感
IF 6 2区 化学 Q1 CHEMISTRY, ANALYTICAL Pub Date : 2026-01-19 DOI: 10.1016/j.aca.2026.345130
Nannan Ma , Qilin Liu , Nianyang Cai , Fangfang Zhu , Ning Gan , Zhenzhong Yu

Background

Laser-induced graphene (LIG) technology has demonstrated considerable promise for the fabrication of wearable electrochemical sensing devices. However, the pristine LIG typically exhibits suboptimal electrochemical performance, often necessitating heteroatom doping to enhance its functionality. Among these strategies, metal doping has proven particularly effective in significantly boosting sensing capabilities. Conventional doping approaches, however, are frequently hampered by cumbersome pretreatment procedures or weak metal-graphene interfacial interaction, thereby restricting their practical efficacy. Therefore, novel synthetic methodologies are urgently needed for efficient metal-doped LIG fabrication.

Results

This study developed an in-situ laser-induced metal-doped graphene (M-LIG, M = Fe, Co, Ni, Cu) fabrication method. It involved plasma-treating polyimide films to introduce hydrophilic groups for metal ion adsorption, followed by CO2 laser irradiation that achieved atomic-scale metal doping during graphene formation. A systematic investigation of preparation parameters and metal dopant types revealed their significant effects on the morphology, structure, and electrochemical performance of the resulting LIG. These materials were used to construct a portable electrochemical detection system for highly sensitive uric acid monitoring in sweat. Results showed that M-LIG sensors outperformed pristine LIG, with Ni-LIG exhibiting optimal performance of a 10.6-fold reduction in detection limit and a 5-fold enhancement in the upper linear detection range. Density functional theory calculations indicated that Ni active sites played a crucial role in enhancing sensing performance by facilitating analyte adsorption and electron transfer.

Significance

This study presents a universal fabrication strategy for M-LIG, which significantly streamlines the preparation process of LIG and enhances its sensing performance. Demonstrating broad application prospects in electrode surface engineering for wearable electrochemical biosensors, this approach paves a new avenue for the development of advanced devices aimed at precise personalized health monitoring.
激光诱导石墨烯(LIG)技术在制造可穿戴电化学传感器件方面已经显示出相当大的前景。然而,原始的LIG通常表现出不理想的电化学性能,通常需要杂原子掺杂来增强其功能。在这些策略中,金属掺杂已被证明在显著提高传感能力方面特别有效。然而,传统的掺杂方法经常受到繁琐的预处理程序或弱金属-石墨烯界面相互作用的阻碍,从而限制了它们的实际效果。因此,迫切需要新的合成方法来制备高效的金属掺杂LIG。结果本研究开发了一种原位激光诱导金属掺杂石墨烯(M- lig, M = Fe, Co, Ni, Cu)制备方法。它包括等离子体处理聚酰亚胺薄膜以引入亲水基团以吸附金属离子,然后通过CO2激光照射在石墨烯形成过程中实现原子尺度的金属掺杂。系统地研究了制备参数和金属掺杂类型,揭示了它们对所得LIG的形貌、结构和电化学性能的显著影响。利用这些材料构建了一种便携式电化学检测系统,用于汗液中尿酸的高灵敏度监测。结果表明,M-LIG传感器优于原始LIG传感器,其中Ni-LIG传感器表现出最佳性能,检测限降低10.6倍,线性检测范围提高5倍。密度泛函理论计算表明,Ni活性位点通过促进分析物的吸附和电子转移,在提高传感性能方面起着至关重要的作用。本研究提出了一种通用的M-LIG制备策略,大大简化了LIG的制备过程,提高了其传感性能。该方法在可穿戴电化学生物传感器的电极表面工程中具有广阔的应用前景,为开发以精确个性化健康监测为目标的先进设备开辟了新的途径。
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引用次数: 0
Flexible hydrophilic-hydrophobic array detection patch integrated with Au NPs/Cu-TCPP(Fe) biomimetic cascade catalysis reactions for enzyme-free sweat glucose monitoring 集成Au NPs/Cu-TCPP(Fe)仿生级联催化反应的柔性亲疏水阵列检测贴片用于无酶汗液血糖监测
IF 6 2区 化学 Q1 CHEMISTRY, ANALYTICAL Pub Date : 2026-01-17 DOI: 10.1016/j.aca.2026.345105
Chen Yang, Limin Zhang, Zijun Ma, Junhao Gao, Yang Zhou, Bing Li, Jianbo He, Fang Li

Background

The detection and quantification of glucose in human biofluids are critical for the early diagnosis and management of metabolic disorders such as hypoglycemia and diabetes. Non-invasive wearable sensors for sweat glucose monitoring have emerged as promising alternatives to traditional blood glucose testing due to their ease of use, rapid response, and portability. However, the development of stable, cost-effective, and enzyme-free wearable platforms capable of reliable sweat glucose detection remains a significant challenge. Current enzyme-based sensors often suffer from poor stability under ambient conditions, complex fabrication processes, and high costs, limiting their widespread applicability in resource-constrained settings.

Results

Au NPs/Cu-TCPP(Fe) nanozymes exhibiting dual peroxidase-like and glucose oxidase-like catalytic activities were synthesized and characterized. These nanozymes catalyze a cascade reaction: glucose oxidation generates H2O2, which is then decomposed to produce hydroxyl radicals that oxidize 3,3′,5,5′-tetramethylbenzidine (TMB), yielding a blue-colored product for colorimetric detection. A flexible, multi-layer hydrophilic-hydrophobic array patch was fabricated by integrating the nanozymes and TMB into a paper-based matrix. This design enables efficient in situ sweat collection, concentration, and colorimetric analysis. The patch exhibits a linear detection range of 20–200 μM with a detection limit of 12.72 μM, suitable for physiological sweat glucose levels. Selectivity tests confirmed negligible interference from common sweat components. A smartphone application was developed to enable real-time, quantitative analysis of colorimetric signals. Clinical validation on multiple volunteers across different skin locations (chest, back, forearm, forehead) showed strong correlation with reference methods (HPLC-MS, commercial glucose detection kit), with relative errors <10 %.

Significance

This study presents a low-cost and enzyme-free sweat glucose detection platform based on Au NPs/Cu-TCPP(Fe) nanozymes. The integration of smartphone technology enables point-of-care testing, making the platform particularly suitable for personalized health monitoring. The successful validation in human subjects demonstrates its potential for real-world applications in diabetes management and early disease detection. This work bridges the gap between nanozyme catalysis and wearable sensor technology, providing a versatile platform for non-invasive biomarker detection.
人体生物体液中葡萄糖的检测和定量对于低血糖和糖尿病等代谢性疾病的早期诊断和管理至关重要。用于汗液血糖监测的非侵入式可穿戴传感器因其易于使用、快速响应和便携性而成为传统血糖检测的有希望的替代品。然而,开发稳定、经济、无酶的、能够可靠检测汗液葡萄糖的可穿戴平台仍然是一个重大挑战。目前基于酶的传感器通常在环境条件下稳定性差,制造工艺复杂,成本高,限制了它们在资源受限环境中的广泛适用性。结果合成了具有双过氧化物酶和双葡萄糖氧化酶催化活性的sau NPs/Cu-TCPP(Fe)纳米酶并对其进行了表征。这些纳米酶催化级联反应:葡萄糖氧化产生H2O2,然后分解产生羟基自由基,氧化3,3 ',5,5 ' -四甲基联苯胺(TMB),产生用于比色检测的蓝色产物。通过将纳米酶和TMB整合到纸基基质中,制备了柔性的多层亲疏水阵列贴片。这种设计可以实现高效的现场汗液收集、浓度和比色分析。该贴片的线性检测范围为20 ~ 200 μM,检出限为12.72 μM,适用于生理汗液葡萄糖水平。选择性测试证实,普通汗液成分的干扰可以忽略不计。开发了一款智能手机应用程序,可以对比色信号进行实时定量分析。对多名志愿者不同皮肤部位(胸部、背部、前臂、前额)的临床验证显示,与参考方法(高效液相色谱-质谱、商用葡萄糖检测试剂盒)有很强的相关性,相对误差为10%。本研究提出了一种基于Au NPs/Cu-TCPP(Fe)纳米酶的低成本无酶汗液葡萄糖检测平台。智能手机技术的集成支持即时检测,使该平台特别适合个性化健康监测。在人类受试者中的成功验证表明其在糖尿病管理和早期疾病检测中的实际应用潜力。这项工作弥合了纳米酶催化和可穿戴传感器技术之间的差距,为非侵入性生物标志物检测提供了一个多功能平台。
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引用次数: 0
Point-of-Need and Portable Sensing Strategies for Quality and Safety Assessment of Traditional Chinese Medicine Products: A Critical Analytical Review 中药产品质量安全评价的需求点和便携式传感策略:关键分析综述
IF 6.2 2区 化学 Q1 CHEMISTRY, ANALYTICAL Pub Date : 2026-01-17 DOI: 10.1016/j.aca.2026.345119
Zihua Wang, Beibei Liu, Altaf Hussain, Zhongke Sun, Le Wang, Peng Li
Sensor technology has emerged as a transformative tool for point-of-need and portable quality control and safety assessment of Traditional Chinese Medicine (TCM) products. Although separation and detection technologies have improved, there is still a strong need to critically evaluate the entire analytical workflow from sample preparation to data interpretation to meet regulatory and routine monitoring requirements. This review critically evaluates the complete analytical workflow—from sample pretreatment to intelligent data interpretation—necessary to bridge the gap between laboratory prototypes and real-world deployment. Additionally, it provides a systematic summary of the mechanisms and applications of common types of sensors, utilizing nanomaterials and molecular recognition elements to overcome the specific challenge of complex TCM matrices. A particular focus is placed on the emerging roles of Artificial Intelligence (AI) and Machine Learning (ML) in resolving high-dimensional spectral data and enhancing pattern recognition accuracy. Furthermore, we critically analyze current bottlenecks, including matrix interference, the lack of standardized validation protocols, and the reliability of portable devices in uncontrolled environments. Future directions are highlighted towards the development of self-validating, cloud-integrated (IoT), and eco-friendly sensing systems, aiming to support the global standardization and safety assurance of TCM products.
传感器技术已经成为一种变革性的工具,用于中药(TCM)产品的即时和便携式质量控制和安全评估。尽管分离和检测技术已经有所改进,但仍然需要严格评估从样品制备到数据解释的整个分析工作流程,以满足法规和常规监测要求。这篇综述批判性地评估了完整的分析工作流程——从样品预处理到智能数据解释——这是弥合实验室原型和现实世界部署之间差距所必需的。此外,它还系统地总结了常用类型传感器的机制和应用,利用纳米材料和分子识别元件来克服复杂TCM矩阵的特定挑战。特别关注人工智能(AI)和机器学习(ML)在解决高维光谱数据和提高模式识别准确性方面的新兴作用。此外,我们批判性地分析了当前的瓶颈,包括矩阵干扰,缺乏标准化的验证协议,以及便携式设备在不受控制的环境中的可靠性。未来的发展方向是自我验证、云集成(IoT)和生态友好型传感系统的发展,旨在支持中医药产品的全球标准化和安全保障。
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引用次数: 0
High-throughput copper speciation with SEC-UV-ICPMS: Insights from Wilson's disease mouse models 用SEC-UV-ICPMS进行高通量铜物种形成:来自威尔逊病小鼠模型的见解
IF 6 2区 化学 Q1 CHEMISTRY, ANALYTICAL Pub Date : 2026-01-17 DOI: 10.1016/j.aca.2026.345113
Yu Zhang , Xueqing Zhao , Beth Crowell , Heinrich Lob , Sarah Hatsell , Aris N. Economides , Evangelos Pefanis , Jikang Wu , Haibo Qiu , Ning Li

Background

Wilson's disease (WD) is a genetic disorder caused by ATP7B gene mutations, impairing copper excretion and leading to toxic copper accumulation in vital organs. Inductively coupled plasma mass spectrometry (ICPMS)-based serum copper analysis has shown reliability in WD studies, with relative exchangeable copper (REC, proportion of exchangeable copper in the blood relative to the total copper) and accurate non-ceruloplasmin-bound copper (ANCC) emerging as promising biomarkers. However, challenges persist in applying these methods in live animal studies because of limited sample volumes and impractical copper specifications, necessitating alternative analytical approaches.

Results

This study comprehensively evaluated a size-exclusion chromatography coupled with ultraviolet (SEC-UV)-ICPMS method for precise copper speciation in mouse serum. This method effectively separated major copper-binding proteins while minimizing sample preparation and consumption. As a comparison, the direct injection-based ICPMS method was optimized to determine relative exchangeable copper (REC), and strong anion exchange (SAX)-ICPMS-based copper speciation approaches were investigated to validate the accuracy of the SEC-UV-ICPMS method, further confirming its robustness for live mouse studies. Further application to WD mouse models (ATP7Btx−J) revealed distinct copper distribution differences between diseased and healthy states. Relative non-ceruloplasmin-bound copper (RNCC) was newly identified as a promising potential biomarker, defining a diagnostic threshold of 52–58 %. By accurately quantifying copper species in mouse serum, this study established a reliable analytical framework that greatly improved our understanding of copper distribution in Wilson's disease research. Our approach demonstrated high specificity, reproducibility, and throughput, suitable for live mouse studies.

Significance

The SEC-UV-ICPMS platform offers a robust and efficient approach for serum copper speciation and quantification that addresses current limitations in live animal studies. By establishing RNCC as a reliable potential biomarker and enabling detailed copper profiling, this method enhances the precision of copper measurement and supports therapeutic monitoring. The applicability to WD research and capability of absolute quantification of copper species underscore its potential as a critical tool in clinical diagnostics and mechanistic studies, advancing the understanding and treatment of copper metabolism disorders.
威尔逊氏病(WD)是一种由ATP7B基因突变引起的遗传性疾病,铜排泄受损,导致重要器官中有毒铜的积累。基于电感耦合血浆质谱(ICPMS)的血清铜分析在WD研究中显示出可靠性,相对可交换铜(REC,血液中可交换铜相对于总铜的比例)和准确的非铜蓝蛋白结合铜(ANCC)成为有前途的生物标志物。然而,由于样本量有限和铜规格不切实际,这些方法在活体动物研究中的应用仍然存在挑战,因此需要其他分析方法。结果本研究综合评价了用SEC-UV -ICPMS法测定小鼠血清中铜的精确形态。该方法有效地分离了主要的铜结合蛋白,同时减少了样品制备和消耗。作为对比,优化了基于直接注射的ICPMS方法测定相对可交换铜(REC),并研究了基于强阴离子交换(SAX)-ICPMS的铜形态形成方法,以验证SEC-UV-ICPMS方法的准确性,进一步证实了其在活体小鼠研究中的稳健性。进一步应用于WD小鼠模型(ATP7Btx-J)发现,铜在患病和健康状态之间的分布存在明显差异。相对非铜蓝蛋白结合铜(RNCC)最近被确定为一种有前景的潜在生物标志物,其诊断阈值为52-58%。通过准确定量小鼠血清中铜的种类,本研究建立了一个可靠的分析框架,大大提高了我们对Wilson病研究中铜分布的认识。我们的方法具有高特异性、可重复性和高通量,适用于活体小鼠研究。SEC-UV-ICPMS平台为血清铜的形成和定量提供了一种强大而有效的方法,解决了目前活体动物研究中的局限性。通过建立RNCC作为可靠的潜在生物标志物,并实现详细的铜谱分析,该方法提高了铜测量的精度,并支持治疗监测。对WD研究的适用性和铜种类绝对定量的能力强调了其作为临床诊断和机制研究的关键工具的潜力,促进了对铜代谢紊乱的理解和治疗。
{"title":"High-throughput copper speciation with SEC-UV-ICPMS: Insights from Wilson's disease mouse models","authors":"Yu Zhang ,&nbsp;Xueqing Zhao ,&nbsp;Beth Crowell ,&nbsp;Heinrich Lob ,&nbsp;Sarah Hatsell ,&nbsp;Aris N. Economides ,&nbsp;Evangelos Pefanis ,&nbsp;Jikang Wu ,&nbsp;Haibo Qiu ,&nbsp;Ning Li","doi":"10.1016/j.aca.2026.345113","DOIUrl":"10.1016/j.aca.2026.345113","url":null,"abstract":"<div><h3>Background</h3><div>Wilson's disease (WD) is a genetic disorder caused by <em>ATP7B</em> gene mutations, impairing copper excretion and leading to toxic copper accumulation in vital organs. Inductively coupled plasma mass spectrometry (ICPMS)-based serum copper analysis has shown reliability in WD studies, with relative exchangeable copper (REC, proportion of exchangeable copper in the blood relative to the total copper) and accurate non-ceruloplasmin-bound copper (ANCC) emerging as promising biomarkers. However, challenges persist in applying these methods in live animal studies because of limited sample volumes and impractical copper specifications, necessitating alternative analytical approaches.</div></div><div><h3>Results</h3><div>This study comprehensively evaluated a size-exclusion chromatography coupled with ultraviolet (SEC-UV)-ICPMS method for precise copper speciation in mouse serum. This method effectively separated major copper-binding proteins while minimizing sample preparation and consumption. As a comparison, the direct injection-based ICPMS method was optimized to determine relative exchangeable copper (REC), and strong anion exchange (SAX)-ICPMS-based copper speciation approaches were investigated to validate the accuracy of the SEC-UV-ICPMS method, further confirming its robustness for live mouse studies. Further application to WD mouse models (ATP7B<sup>tx−J</sup>) revealed distinct copper distribution differences between diseased and healthy states. Relative non-ceruloplasmin-bound copper (RNCC) was newly identified as a promising potential biomarker, defining a diagnostic threshold of 52–58 %. By accurately quantifying copper species in mouse serum, this study established a reliable analytical framework that greatly improved our understanding of copper distribution in Wilson's disease research. Our approach demonstrated high specificity, reproducibility, and throughput, suitable for live mouse studies.</div></div><div><h3>Significance</h3><div>The SEC-UV-ICPMS platform offers a robust and efficient approach for serum copper speciation and quantification that addresses current limitations in live animal studies. By establishing RNCC as a reliable potential biomarker and enabling detailed copper profiling, this method enhances the precision of copper measurement and supports therapeutic monitoring. The applicability to WD research and capability of absolute quantification of copper species underscore its potential as a critical tool in clinical diagnostics and mechanistic studies, advancing the understanding and treatment of copper metabolism disorders.</div></div>","PeriodicalId":240,"journal":{"name":"Analytica Chimica Acta","volume":"1390 ","pages":"Article 345113"},"PeriodicalIF":6.0,"publicationDate":"2026-01-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145993301","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"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
T4 DNA ligase-mediated RAA coupled with RNA aptamer-driven cascade signal amplification for ultra-sensitive monkeypox virus detection T4 DNA连接酶介导的RAA和RNA适配体驱动的级联信号扩增用于超敏感猴痘病毒检测
IF 6 2区 化学 Q1 CHEMISTRY, ANALYTICAL Pub Date : 2026-01-17 DOI: 10.1016/j.aca.2026.345116
Chenxi Li , He Sun , QingWen Jia , Zebin Zhang , Shengjun Bu , Hongtao Zhou , Longtao Wang , Jiayu Wan

Background

The global dissemination of monkeypox virus (MPXV) poses a formidable challenge to public health systems worldwide, disrupting surveillance and containment strategies. This crisis underscores the urgent demand for rapid diagnostic technologies that balance high sensitivity for detecting low viral loads and strict specificity to prevent cross-reactivity. To address this unmet need, the present study developed a cascade signal amplification system—named “Monkeypox Fluorescent T4-Ligase Assay (MFTA)”—by integrating recombinase-aided amplification (RAA) and fluorescent RNA aptamer sensing technology, with T4 DNA ligase as the core mediator.

Results

MFTA generates single-stranded DNA (ssDNA) templates through 5′-phosphorylated primers combined with Lambda nuclease treatment and employs two specifically designed bifunctional probes: Probe-L, which incorporates a T7 promoter, and Probe-R, which contains a DNA Mango aptamer sequence. In the presence of MPXV, T4 DNA ligase specifically catalyzes probe ligation to form a complete transcription template, further initiating T7 RNA polymerase-mediated in vitro transcription. This process produces abundant RNA Mango aptamers, which specifically bind the TO1 fluorophore to generate a detectable fluorescent signal. The “Identification-Ligation-Transcription-Fluorescence” cascade enables dual verification: RAA ensures target-specific amplification of MPXV sequences, while T4 DNA ligase guarantees precise probe ligation and reduces non-specific background noise. Experiments confirmed MFTA has a detection limit of 1 copy/μL for MPXV, with results consistent with those of qPCR, and effectively discriminates MPXV from other orthopoxviruses.

Significance

MFTA innovatively integrates the precise specific recognition of target sequences by T4 DNA ligase with the efficient signal amplification capability of RNA aptamers, successfully establishing a novel technical platform for pathogen detection. Its high sensitivity, strong specificity, and favorable scalability make it a valuable tool for MPXV diagnostics, supporting targeted public health responses to outbreaks and aiding in curbing virus spread.
猴痘病毒(MPXV)的全球传播对全球公共卫生系统构成了巨大挑战,扰乱了监测和控制战略。这场危机强调了对快速诊断技术的迫切需求,这种技术要在检测低病毒载量的高灵敏度和防止交叉反应的严格特异性之间取得平衡。为了解决这一未满足的需求,本研究通过整合重组酶辅助扩增(RAA)和荧光RNA适体传感技术,以T4 DNA连接酶为核心介质,开发了一种级联信号扩增系统,名为“猴痘荧光T4-连接酶测定(MFTA)”。结果smfta通过5 ' -磷酸化引物结合Lambda核酸酶处理生成单链DNA模板,并使用两种特殊设计的双功能探针:Probe-L(包含T7启动子)和Probe-R(包含DNA芒果核酸适体序列)。在MPXV存在下,T4 DNA连接酶特异性催化探针连接形成完整的转录模板,进一步启动T7 RNA聚合酶介导的体外转录。这个过程产生了丰富的RNA芒果适体,它们特异性地结合TO1荧光团产生可检测的荧光信号。“鉴定-连接-转录-荧光”级联实现双重验证:RAA确保MPXV序列的靶特异性扩增,而T4 DNA连接酶保证探针的精确连接并减少非特异性背景噪声。实验证实MFTA对MPXV的检出限为1拷贝/μL,与qPCR结果一致,可有效区分MPXV与其他正痘病毒。emfta创新性地将T4 DNA连接酶对靶序列的精确特异性识别与RNA适配体的高效信号扩增能力相结合,成功建立了一种新的病原体检测技术平台。其高灵敏度、强特异性和良好的可扩展性使其成为MPXV诊断的宝贵工具,支持有针对性的公共卫生应对疫情并有助于遏制病毒传播。
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引用次数: 0
A high-throughput detection platform for dried blood spots constructed with DESI-MS/MS 采用DESI-MS/MS构建高通量干血斑检测平台
IF 6 2区 化学 Q1 CHEMISTRY, ANALYTICAL Pub Date : 2026-01-16 DOI: 10.1016/j.aca.2026.345109
Siqi Gao , Jinhui Zhao , Yue Guan , Liyan Liu

Background

Dried blood spot (DBS) technology, as a method of blood collection and preservation, has the advantages of small blood collection, convenient transportation and avoiding the degradation of metabolites. In particular, it has broad clinical application prospects in newborn screening and therapeutic drug monitoring. Desorption electrospray mass spectrometry (DESI-MS) is a simple, rapid and in situ spatial metabolomics detection technique, but its throughput, accuracy and coverage for DBS remain to be investigated compared with traditional methods.

Results

In the UPLC-MS/MS platform, the optimal extraction solvent, extraction solvent volume and extraction method were ACN: H2O (v:v/3:1), 300 μL and ultrasonic extraction, respectively. Based on the DESI-MS/MS platform, the best spray solvent was MeOH: H2O (v:v/3:1), the spray velocity was set at 2 μL/min, the spray needle angle was set at 55°, and the capillary voltage was set at 4.5 kv (DESI+), respectively. The approach delivered consistent data assurance, broad metabolite coverage, and acceptable reproducibility. Finally, these methods were applied to detect the metabolic profiles of subjects before and after drinking sugar-sweetened soy milk, and the metabolic map was well isolated, and the difference metabolites were successfully found.

Significance

Two protocols of metabolic profiles for DBS were constructed and optimized. The good performance of DESI-MS/MS was obtained when comparing to the UPLC-MS/MS. The application of sweetened soy milk showed that the two protocols developed have the practicability of detecting differential changes in metabolic profiles of DBS.
干血斑(DBS)技术作为一种血液采集和保存方法,具有采血量小、运输方便、避免代谢物降解等优点。尤其在新生儿筛查和治疗药物监测方面具有广阔的临床应用前景。解吸电喷雾质谱(DESI-MS)是一种简单、快速、原位的空间代谢组学检测技术,但与传统方法相比,其通量、准确性和覆盖范围有待进一步研究。结果在UPLC-MS/MS平台上,最佳提取溶剂为ACN: H2O (v:v/3:1),最佳提取溶剂体积为300 μL,最佳提取方法为超声提取。基于DESI-MS/MS平台,最佳喷雾溶剂为MeOH: H2O (v:v/3:1),喷雾速度为2 μL/min,喷雾针角为55°,毛细管电压为4.5 kv (DESI+)。该方法提供了一致的数据保证,广泛的代谢物覆盖范围和可接受的可重复性。最后,将这些方法应用于受试者饮用加糖豆浆前后的代谢谱检测,代谢图谱得到了很好的分离,成功发现了差异代谢物。意义构建并优化了两种DBS代谢谱方案。与UPLC-MS/MS相比,DESI-MS/MS具有良好的性能。甜味豆浆的应用表明,这两种方案具有检测DBS代谢谱差异变化的实用性。
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引用次数: 0
A comprehensive soil pollution monitoring system based on convolutional recursive sequence network and terahertz spectroscopy 基于卷积递归序列网络和太赫兹光谱的土壤污染综合监测系统
IF 6 2区 化学 Q1 CHEMISTRY, ANALYTICAL Pub Date : 2026-01-16 DOI: 10.1016/j.aca.2026.345117
Ao Feng , Lijia Xu , Yuchao Wang, Zhijun Wu

Background

Accurate analysis of the total amount of heavy metals and their distribution patterns in soil can aid in determining the extent of soil pollution and iake appropriate remediation measures.Traditional detection methods are inefficient, and standard machine learning approaches are insufficiently sensitive in detecting the range when dealing with several contaminants of heavy metals. In this study, the contents of three heavy metals, cadmium (Cd), nickel (Ni), and zinc (Zn), in soils of different pollution types and concentrations were detected through terahertz spectral curve analysis.

Results

A convolutional recursive sequence network (CRST) with cascaded convolutional kernel and cyclic sequence structure was designed to further improve the soil heavy metal detection accuracy by capturing and integrating the sequence dependencies in the continuous terahertz bands. We compared common machine learning models with feature extraction algorithms, and the experimental results show that the CRST method can accurately identify soil heavy metal contamination species under the combined model of all data. The CARS-CRST combination achieved a classification accuracy of 99.54 % when the soil was contaminated with a single heavy metal. The CARS-CRST combination achieved a classification accuracy of 95.26 % when the soil was contaminated with a mixture of heavy metals. The CRST method can also accurately determine the heavy metal content in soil for Cd, Ni, and Zn, achieving optimal R2 and RMSE values when the prediction model is constructed for these elements.

Significance

Based on terahertz spectroscopy and machine learning technology, this study conducted both qualitative and quantitative research on soil heavy metals, providing robust technical support for the scientific management and precise monitoring of soil.The results show that terahertz technology and machine learning technology can bring new ideas and prospects for soil pollution detection.
准确分析土壤重金属总量及其分布格局有助于确定土壤污染程度,并采取相应的修复措施。传统的检测方法效率低下,标准的机器学习方法在处理多种重金属污染物时检测范围不够灵敏。本研究通过太赫兹光谱曲线分析,检测了不同污染类型和浓度土壤中镉(Cd)、镍(Ni)和锌(Zn)三种重金属的含量。(84)结果设计了具有级联卷积核和循环序列结构的卷积递归序列网络(CRST),通过捕获和整合连续太赫兹波段的序列依赖关系,进一步提高了土壤重金属的检测精度。我们将常见的机器学习模型与特征提取算法进行了比较,实验结果表明,在所有数据的组合模型下,CRST方法可以准确地识别土壤重金属污染种类。当土壤被单一重金属污染时,CARS-CRST组合的分类准确率达到99.54%。当土壤中重金属混合污染时,CARS-CRST组合的分类准确率达到95.26%。CRST方法还能准确测定土壤中重金属元素Cd、Ni和Zn的含量,在构建预测模型时获得最佳R2和RMSE值。(143)意义本研究基于太赫兹光谱和机器学习技术,对土壤重金属进行了定性和定量研究,为土壤的科学管理和精准监测提供了有力的技术支撑。结果表明,太赫兹技术和机器学习技术可以为土壤污染检测带来新的思路和前景。(52)
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引用次数: 0
Highly sensitive chemiluminescence immunoassay utilizing functionalized magnetic metal-organic framework materials for the detection of CEA and CA199 功能化磁性金属-有机骨架材料的高灵敏度化学发光免疫分析法检测CEA和CA199
IF 6 2区 化学 Q1 CHEMISTRY, ANALYTICAL Pub Date : 2026-01-16 DOI: 10.1016/j.aca.2026.345114
Xiaomin Zuo , Wenxia Chen , Xianlong Lu , Rui Yuan , Shuangyi Hu , Yangyang Xue , Wei Chen , Rui Yang

Background

In response to the urgent need for highly sensitive and rapid combined detection of multiple tumor markers for the early diagnosis of colorectal cancer, this work innovatively constructs a magnetically-driven chemiluminescence (CL) immunosensing platform (CoFe2O4@ZIF-8/luminol-Au NPs).

Results

CoFe2O4 NPs were firstly aminated via solvothermal method and lysine modification to provide specific binding sites. ZIF-8 was then grown in situ to form a core-shell structure with high specific surface area for efficient luminol loading. Finally, Au NPs were generated in situ within ZIF-8, simultaneously immobilizing luminol to form composite signal units. This design integrates magnetic separation, confinement effects, and signal amplification, generating an ideal microenvironment for enhanced CL reactions. The label-free CL immunoassay achieves an impressive limit of detection (LOD) of 22 fg/mL for CEA and 5.4 fg/mL for CA199, with broad linear ranges spanning over 5 orders of magnitude. The entire detection process is completed within 30 min, and the analysis of real serum samples demonstrates good recoveries.
为响应结直肠癌早期诊断对多种肿瘤标志物高灵敏度、快速联合检测的迫切需求,本工作创新构建了磁驱动化学发光(CL)免疫传感平台(CoFe2O4@ZIF-8/luminol-Au NPs)。结果首先通过溶剂热法和赖氨酸修饰对scofe2o4 NPs进行胺化,获得了特定的结合位点。然后原位生长ZIF-8,形成具有高比表面积的核壳结构,用于高效负载鲁米诺。最后,在ZIF-8中原位生成Au NPs,同时固定化luminol形成复合信号单元。该设计集成了磁分离、约束效应和信号放大,为增强CL反应提供了理想的微环境。无标记CL免疫分析法的检测限(LOD)令人印象深刻,CEA为22 fg/mL, CA199为5.4 fg/mL,具有超过5个数量级的宽线性范围。整个检测过程在30分钟内完成,对真实血清样品的分析显示出良好的回收率。
{"title":"Highly sensitive chemiluminescence immunoassay utilizing functionalized magnetic metal-organic framework materials for the detection of CEA and CA199","authors":"Xiaomin Zuo ,&nbsp;Wenxia Chen ,&nbsp;Xianlong Lu ,&nbsp;Rui Yuan ,&nbsp;Shuangyi Hu ,&nbsp;Yangyang Xue ,&nbsp;Wei Chen ,&nbsp;Rui Yang","doi":"10.1016/j.aca.2026.345114","DOIUrl":"10.1016/j.aca.2026.345114","url":null,"abstract":"<div><h3>Background</h3><div>In response to the urgent need for highly sensitive and rapid combined detection of multiple tumor markers for the early diagnosis of colorectal cancer, this work innovatively constructs a magnetically-driven chemiluminescence (CL) immunosensing platform (CoFe<sub>2</sub>O<sub>4</sub>@ZIF-8/luminol-Au NPs).</div></div><div><h3>Results</h3><div>CoFe<sub>2</sub>O<sub>4</sub> NPs were firstly aminated via solvothermal method and lysine modification to provide specific binding sites. ZIF-8 was then grown in situ to form a core-shell structure with high specific surface area for efficient luminol loading. Finally, Au NPs were generated in situ within ZIF-8, simultaneously immobilizing luminol to form composite signal units. This design integrates magnetic separation, confinement effects, and signal amplification, generating an ideal microenvironment for enhanced CL reactions. The label-free CL immunoassay achieves an impressive limit of detection (LOD) of 22 fg/mL for CEA and 5.4 fg/mL for CA199, with broad linear ranges spanning over 5 orders of magnitude. The entire detection process is completed within 30 min, and the analysis of real serum samples demonstrates good recoveries.</div></div>","PeriodicalId":240,"journal":{"name":"Analytica Chimica Acta","volume":"1389 ","pages":"Article 345114"},"PeriodicalIF":6.0,"publicationDate":"2026-01-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145995955","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"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
Specific lysine guanidination and long alkyl chain tagging-assisted negative enrichment strategy enables comprehensive profiling of protein N-terminal acetylome 特异性赖氨酸胍和长烷基链标记辅助负富集策略可以全面分析蛋白质n端乙酰基
IF 6 2区 化学 Q1 CHEMISTRY, ANALYTICAL Pub Date : 2026-01-16 DOI: 10.1016/j.aca.2026.345112
Yang Li , Yu He , Weijie Zhang , Mengqing Yang , Wei Yu , Zhenbin Zhang

Background

Protein N-terminal acetylation (Nt-acetylation) is a widespread and essential modification in both eukaryotes and prokaryotes. To achieve in-depth profiling of Nt-acetylome, enrichment of Nt-acetylated peptides prior to mass spectrometry (MS) analysis is crucial, as their inherently low ionization efficiency is further suppressed in complex peptide mixtures. However, current methods are constrained by low enrichment selectivity and insufficient proteolytic digestion efficiency toward Nt-acetylated peptides.

Results

Herein, we present a novel and effective enrichment method involving the specific blocking of lysine ε-amino groups by guanidination and long alkyl chain tagging to N-terminal/internal peptides with free α-amino groups. Due to their enhanced hydrophobicity, the alkylated N-terminal/internal peptides could be efficiently depleted via a C18 column, thus achieving the negative enrichment of Nt-acetylated peptides. Specific guanidination of lysine residues ensures high enrichment selectivity and efficient tryptic digestion of Nt-acetylated peptides. In a single-shot analysis of HeLa cells, our method yielded a significant 4-fold increase in the identification number of Nt-acetylated peptides compared to direct analysis. When coupled with high-pH C18 fractionation, this approach identified 4957 unique Nt-acetylated peptides, corresponding to 3042 acetylated N-termini and 902 putatively neo-acetylated N-termini, markedly expanding the identification coverage of current Nt-acetylation dataset. Furthermore, this method was successfully applied to the quantification of N-terminal acetylome in hippocampal tissues from Alzheimer's disease (AD) mice modeled by amyloid-beta (Aβ) hippocampal injection.

Significance

Our method exhibits high enrichment selectivity, efficient proteolytic efficiency and minimal bias toward Nt-acetylated peptides in complex samples. This robust and versatile strategy offers an efficient alternative for comprehensive profiling of Nt-acetylome, thereby facilitating deeper insights into the physiological and pathological functions of Nt-acetylation across diverse biological systems.
蛋白n端乙酰化(Nt-acetylation)是真核生物和原核生物中广泛而必需的修饰。为了实现对nt -乙酰化酶的深入分析,在质谱分析(MS)之前富集nt -乙酰化肽是至关重要的,因为它们固有的低电离效率在复杂的肽混合物中会进一步受到抑制。然而,目前的方法受到富集选择性低和对nt -乙酰化肽的蛋白水解消化效率不足的限制。结果本文提出了一种新的、有效的富集方法,即通过胍基化和长烷基链标记来特异性阻断赖氨酸的ε-氨基,并将游离α-氨基标记在n端或内部肽上。由于其增强的疏水性,烷基化的n端/内部肽可以通过C18柱有效地耗尽,从而实现nt -乙酰化肽的负富集。赖氨酸残基的特异性胍化确保了高富集选择性和高效的t-乙酰化肽的胰蛋白酶消化。在HeLa细胞的单次分析中,与直接分析相比,我们的方法在nt -乙酰化肽的识别数量上显著增加了4倍。当与高ph C18分离相结合时,该方法鉴定出4,957个独特的nt -乙酰化肽,对应于3,042个乙酰化n端和902个假定的新乙酰化n端,显着扩大了当前nt -乙酰化数据集的鉴定范围。此外,该方法还成功地应用于β淀粉样蛋白(Aβ)海马注射模型阿尔茨海默病(AD)小鼠海马组织中n端乙酰基的定量。我们的方法在复杂样品中具有高富集选择性,高效的蛋白水解效率和对nt -乙酰化肽的最小偏倚。这种强大而通用的策略为nt -乙酰化的全面分析提供了一种有效的替代方案,从而促进了对nt -乙酰化在不同生物系统中的生理和病理功能的深入了解。
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引用次数: 0
On-exosome-membrane DNA polymerization-powered magneto-electrochemical aptasensing for osteosarcoma 外泌体膜DNA聚合驱动的磁电化学适体感应治疗骨肉瘤
IF 6 2区 化学 Q1 CHEMISTRY, ANALYTICAL Pub Date : 2026-01-16 DOI: 10.1016/j.aca.2026.345093
Guang-Xian Zhong , Huang-Feng Lin , Fei-Huan Fu , Jing-Wei Zhou , Chong-Yu Chen , Chao-Yang Wu , Jian-Ping Lin , Xiong-Wei Xu , Jian-Hua Lin , Jin-Yuan Chen

Background

The development of exosomes-based non-invasive liquid biopsy method is essential for an early diagnosis of cancers such as osteosarcoma (OS). The emerging isothermal nucleic acid amplification (NAA)-integrated electrochemical aptasensor (E-aptasensor) holds a great promise due to its affordability, rapid response, high sensitivity, and multiplexing capability. However, these aptasensors often require a challenging and complicated integration of signal trigger sequences into the parent aptamers that regulates the NAA. Thus, it is highly desirable to develop a template-free and universal isothermal NAA-intergrated E-aptasensor for OS-derived exosome detection.

Results

Herein, via terminal deoxynucleotidyl transferase (TdTase)-mediated DNA polymerization on exosome membrane, we firstly proposed a membrane-initiated enzymatic polymerization (MIEP)-based magneto-driven E-aptasensor for an ultrasensitive detection of OS cell-derived exosomes. Specifically, the LC09 aptamers-modified magnetic microbeads (MMBs) efficiently captured the specific exosomes. Afterwards, the direct on-exosome membrane DNA polymerization was performed by TdTase and then large amounts of horseradish peroxidases were bound via immunoreaction, leading to a strong catalytic current in the substrate of 3,3′,5,5′-tetramethylbenzidine/hydrogen peroxide on the surface of a magnetic glassy carbon electrode. This MIEP-based E-aptasensor reported a satisfactory detection result, displaying a broad linear range (6 × 107∼6 × 1010 particles/mL), a low detection limit (60 particles/μL), a good specificity toward other tumor cell-derived exosomes, and a good recovery (87.9 %–98.3 % in human plasma). Finally, this method was applied to different clinical samples of micro-volume plasma and distinguished them successfully.

Significance

The proposed aptasensor can serve as a powerful and potential tool for liquid biopsy of OS, owing to its high generality, low sample demand, and high practicability. Furthermore, the innovative design strategy established in this work provides a new and versatile avenue for the construction of advanced exosome biosensors, thereby broadening their application in clinical research and precision medicine.
基于外泌体的非侵入性液体活检方法的发展对于骨肉瘤(OS)等癌症的早期诊断至关重要。新兴的等温核酸扩增(NAA)集成电化学aptassensor (e - aptassensor)因其价格合理、反应速度快、灵敏度高、多路复用等优点,具有广阔的应用前景。然而,这些适体传感器通常需要将信号触发序列整合到调节NAA的亲本适体中,这具有挑战性和复杂性。因此,开发一种无模板的通用等温naa集成e- aptassensor用于os衍生的外泌体检测是非常必要的。结果在本文中,通过末端脱氧核苷酸转移酶(TdTase)介导的外泌体膜DNA聚合,我们首次提出了一种基于膜启动酶促聚合(MIEP)的磁驱动e-适体传感器,用于超灵敏检测OS细胞来源的外泌体。具体来说,LC09适配体修饰的磁微珠(MMBs)有效地捕获了特定的外泌体。然后,通过TdTase直接在外泌体膜上进行DNA聚合,然后通过免疫反应结合大量的辣根过氧化物酶,在磁性玻璃碳电极表面的3,3 ',5,5 ' -四甲基联苯胺/过氧化氢底物中产生强催化电流。该基于miep的e - aptas传感器报告了令人满意的检测结果,显示出宽的线性范围(6×107 ~ 6×1010颗粒/mL),低检测限(60颗粒/μL),对其他肿瘤细胞来源的外泌体具有良好的特异性,并且回收率良好(人血浆中87.9% ~ 98.3%)。最后,将该方法应用于临床不同的微体积血浆样品,并成功地进行了区分。本文提出的适体传感器具有通用性强、样本量少、实用性强等优点,可作为OS液体活检的有力工具。此外,本研究建立的创新设计策略为构建先进的外泌体生物传感器提供了一条新的、通用的途径,从而扩大了其在临床研究和精准医学中的应用。
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引用次数: 0
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Analytica Chimica Acta
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