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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。
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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)
{"title":"A comprehensive soil pollution monitoring system based on convolutional recursive sequence network and terahertz spectroscopy","authors":"Ao Feng ,&nbsp;Lijia Xu ,&nbsp;Yuchao Wang,&nbsp;Zhijun Wu","doi":"10.1016/j.aca.2026.345117","DOIUrl":"10.1016/j.aca.2026.345117","url":null,"abstract":"<div><h3>Background</h3><div>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.</div></div><div><h3>Results</h3><div>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 R<sup>2</sup> and RMSE values when the prediction model is constructed for these elements.</div></div><div><h3>Significance</h3><div>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.</div></div>","PeriodicalId":240,"journal":{"name":"Analytica Chimica Acta","volume":"1389 ","pages":"Article 345117"},"PeriodicalIF":6.0,"publicationDate":"2026-01-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145993140","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
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
A novel pyrazine-based Eu-MOFs AIECL immunosensor with antenna effect and Au@Sn3O4 as co-reaction accelerator for ultrasensitive detection of deoxynivalenol 天线效应的新型吡嗪基eu - mof - AIECL免疫传感器,Au@Sn3O4作为共反应促进剂用于脱氧雪腐镰刀醇的超灵敏检测
IF 6 2区 化学 Q1 CHEMISTRY, ANALYTICAL Pub Date : 2026-01-16 DOI: 10.1016/j.aca.2026.345115
Jiayuan Nie , Jing Shi , Chunyan He , Huiling Jiang , Kang Wu , Anping Deng , Xinjian Feng , Jianguo Li

Background

Deoxynivalenol (DON), a widespread mycotoxin produced by Fusarium fungi, contaminates grains like wheat and corn, its thermal/chemical resistance prevents full decomposition during food processing. The severe toxicological impacts of DON have instigated scientific vigilance and elevated public apprehension. The International Agency for Research on Cancer (IARC) assigned deoxynivalenol to its Group 3 classification within its chemical carcinogen taxonomy in 2017. Therefore, it is crucial to detect the content of DON contaminants in grains. In this paper we developed a novel electrochemical luminescence immunoassay based on pyrazine ligands for the detection of DON in grains.

Results

This work presents a significant conceptual and methodological advancement in the field of electrochemiluminescence biosensing. The synthesized Eu-MOF, utilizing 2,3,5,6-tetrakis(4-carboxyphenyl) pyrazine as an AIE (aggregation-induced electrochemiluminescence) ligand and Eu3+ as the metal center, exhibited a significantly enhanced and stable ECL emission compared to the ligand alone, which is attributed to the effective "antenna effect". When integrated with Au@Sn3O4 nanoflowers as a co-reaction accelerator, the ECL intensity was further amplified due to improved electron transfer and catalytic efficiency. After optimizing all parameters, the optimal experimental conditions were determined. The constructed immunosensor demonstrated an excellent wide-range linear response to DON concentrations from 0.007 ng mL−1 to 1000 ng mL−1, with an ultra-low detection limit of 2.3 pg mL−1 (S/N = 3). The sensor also showed high selectivity against other common mycotoxins and satisfactory stability.

Significance

The successful implementation of this "AIE-antenna" dual-effect strategy provides a new and general paradigm for designing high-performance ECL materials. Furthermore, the constructed immunosensor demonstrates its practical utility for the ultrasensitive monitoring of mycotoxins in food safety. The outstanding analytical performance, as evidenced by the ultra-low detection limit, underscores the reliability of this platform and its great potential for the detection of various trace-level contaminants in complex sample.
脱氧雪腐镰刀菌醇(DON)是由镰刀菌真菌产生的一种广泛存在的霉菌毒素,它会污染小麦和玉米等谷物,其耐热/耐化学性阻止了食品加工过程中的完全分解。DON的严重毒理学影响已经引起了科学界的警惕和公众的担忧。2017年,国际癌症研究机构(IARC)在其化学致癌物分类中将脱氧雪腐镰梨醇列为第3类。因此,检测颗粒中DON污染物的含量至关重要。本文建立了一种基于吡嗪配体的电化学发光免疫分析法,用于检测颗粒中DON的含量。结果本研究在电化学发光生物传感领域取得了重要的概念和方法上的进展。以2,3,5,6-四akis(4-carboxyphenyl) pyrazine为AIE(聚集诱导电化学发光)配体,以Eu3+为金属中心合成的Eu-MOF,与单独的配体相比,具有显著增强和稳定的ECL发射,这归因于有效的“天线效应”。当与Au@Sn3O4纳米花集成作为共反应加速器时,由于电子转移和催化效率的提高,ECL强度进一步增强。对各参数进行优化后,确定了最佳实验条件。所构建的免疫传感器对DON浓度在0.007 ~ 1000 ng mL - 1范围内具有良好的线性响应,超低检出限为2.3 pg mL - 1 (S/N = 3)。该传感器对其他常见真菌毒素也具有较高的选择性和良好的稳定性。这种“aie -天线”双效应策略的成功实施为设计高性能ECL材料提供了一种新的通用范例。此外,所构建的免疫传感器在食品安全真菌毒素的超灵敏监测中具有实用价值。出色的分析性能,超低的检测限证明了该平台的可靠性及其在复杂样品中检测各种痕量污染物的巨大潜力。
{"title":"A novel pyrazine-based Eu-MOFs AIECL immunosensor with antenna effect and Au@Sn3O4 as co-reaction accelerator for ultrasensitive detection of deoxynivalenol","authors":"Jiayuan Nie ,&nbsp;Jing Shi ,&nbsp;Chunyan He ,&nbsp;Huiling Jiang ,&nbsp;Kang Wu ,&nbsp;Anping Deng ,&nbsp;Xinjian Feng ,&nbsp;Jianguo Li","doi":"10.1016/j.aca.2026.345115","DOIUrl":"10.1016/j.aca.2026.345115","url":null,"abstract":"<div><h3>Background</h3><div>Deoxynivalenol (DON), a widespread mycotoxin produced by Fusarium fungi, contaminates grains like wheat and corn, its thermal/chemical resistance prevents full decomposition during food processing. The severe toxicological impacts of DON have instigated scientific vigilance and elevated public apprehension. The International Agency for Research on Cancer (IARC) assigned deoxynivalenol to its Group 3 classification within its chemical carcinogen taxonomy in 2017. Therefore, it is crucial to detect the content of DON contaminants in grains. In this paper we developed a novel electrochemical luminescence immunoassay based on pyrazine ligands for the detection of DON in grains.</div></div><div><h3>Results</h3><div>This work presents a significant conceptual and methodological advancement in the field of electrochemiluminescence biosensing. The synthesized Eu-MOF, utilizing 2,3,5,6-tetrakis(4-carboxyphenyl) pyrazine as an AIE (aggregation-induced electrochemiluminescence) ligand and Eu<sup>3+</sup> as the metal center, exhibited a significantly enhanced and stable ECL emission compared to the ligand alone, which is attributed to the effective \"antenna effect\". When integrated with Au@Sn<sub>3</sub>O<sub>4</sub> nanoflowers as a co-reaction accelerator, the ECL intensity was further amplified due to improved electron transfer and catalytic efficiency. After optimizing all parameters, the optimal experimental conditions were determined. The constructed immunosensor demonstrated an excellent wide-range linear response to DON concentrations from 0.007 ng mL<sup>−1</sup> to 1000 ng mL<sup>−1</sup>, with an ultra-low detection limit of 2.3 pg mL<sup>−1</sup> (S/N = 3). The sensor also showed high selectivity against other common mycotoxins and satisfactory stability.</div></div><div><h3>Significance</h3><div>The successful implementation of this \"AIE-antenna\" dual-effect strategy provides a new and general paradigm for designing high-performance ECL materials. Furthermore, the constructed immunosensor demonstrates its practical utility for the ultrasensitive monitoring of mycotoxins in food safety. The outstanding analytical performance, as evidenced by the ultra-low detection limit, underscores the reliability of this platform and its great potential for the detection of various trace-level contaminants in complex sample.</div></div>","PeriodicalId":240,"journal":{"name":"Analytica Chimica Acta","volume":"1389 ","pages":"Article 345115"},"PeriodicalIF":6.0,"publicationDate":"2026-01-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145995962","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
Smartphone-integrated colorimetric and ratiometric fluorescence sensor for visual detection of HSO4− 用于HSO4-视觉检测的智能手机集成比色和比例荧光传感器
IF 6 2区 化学 Q1 CHEMISTRY, ANALYTICAL Pub Date : 2026-01-16 DOI: 10.1016/j.aca.2026.345118
Yu Ding , Guoxing Zhang , Lishan Chen , Shengwen Yang , Ning Liu , Hao Zhang

Background

The detection of bisulfate (HSO4) is critical in food preservation and pharmaceutical quality control, as it is a common additive with potential health risks. Existing detection methods often lack the portability for on-site analysis or the capability for cross-validation to ensure accuracy. Establishing a rapid and reliable quantitative method for HSO4 is the prerequisite and core step for precisely controlling related food and pharmaceutical additives.

Results

To address the need for a rapid, reliable, and field-deployable sensing platform that provides intuitive visual feedback and quantitative data for HSO4 detection in complex real-world samples, we engineered a novel Schiff base probe (KF) integrating aggregation-induced emission (AIE), excited-state intramolecular proton transfer (ESIPT), and intramolecular charge transfer (ICT) properties. HSO4 triggers a specific cleavage of the probe's imine bond, inducing a distinct colorimetric change (yellow to colorless) and a ratiometric fluorescence shift (yellow-green to blue). This dual-signal response enables visual qualitative analysis and provides an internal reference for quantitative measurement, with a fluorescence detection limit down to 72.9 nM. We integrated the probe with a smartphone-based RGB analysis platform (ColorPicker App), creating a portable device for on-site, quantitative determination. The platform's efficacy was successfully demonstrated by accurately detecting HSO4 in spiked vegetable and pharmaceutical samples with satisfactory recovery rates (83.1 %–114.4 %).

Significance

This work presents the first multifunctional probe combining AIE, ESIPT, and ICT for HSO4-triggered cleavage, enabling a dual-mode response. This study is significant for establishing a robust, smartphone-integrated sensor that transcends laboratory confines, offering a practical solution for on-site monitoring in food safety and pharmaceutical analysis.
亚硫酸氢盐(HSO4−)是一种常见的添加剂,具有潜在的健康风险,因此检测在食品保存和药品质量控制中至关重要。现有的检测方法往往缺乏现场分析的可移植性或交叉验证的能力,以确保准确性。建立快速、可靠的HSO4−定量方法是精确控制相关食品和药品添加剂的前提和核心步骤。为了满足对快速、可靠、可现场部署的传感平台的需求,为复杂的现实世界样品中的HSO4 -检测提供直观的视觉反馈和定量数据,我们设计了一种新型的希夫碱探针(KF),集成了聚集诱导发射(AIE)、激激态分子内质子转移(ESIPT)和分子内电荷转移(ICT)特性。HSO4−触发探针的亚胺键的特定切割,诱导明显的比色变化(黄色到无色)和比例荧光位移(黄绿色到蓝色)。该双信号响应可实现视觉定性分析,并为定量测量提供内部参考,荧光检测限低至72.9 nM。我们将探针与基于智能手机的RGB分析平台(ColorPicker App)集成在一起,创建了一种用于现场定量测定的便携式设备。结果表明,该平台可准确检测加标蔬菜和药品样品中的HSO4−,回收率为83.1% ~ 114.4%。这项工作提出了第一个结合AIE, ESIPT和ICT的多功能探针,用于HSO4−触发的解理,实现双模响应。这项研究对于建立一种超越实验室限制的强大的智能手机集成传感器具有重要意义,为食品安全和药物分析的现场监测提供了实用的解决方案。
{"title":"Smartphone-integrated colorimetric and ratiometric fluorescence sensor for visual detection of HSO4−","authors":"Yu Ding ,&nbsp;Guoxing Zhang ,&nbsp;Lishan Chen ,&nbsp;Shengwen Yang ,&nbsp;Ning Liu ,&nbsp;Hao Zhang","doi":"10.1016/j.aca.2026.345118","DOIUrl":"10.1016/j.aca.2026.345118","url":null,"abstract":"<div><h3>Background</h3><div>The detection of bisulfate (HSO<sub>4</sub><sup>−</sup>) is critical in food preservation and pharmaceutical quality control, as it is a common additive with potential health risks. Existing detection methods often lack the portability for on-site analysis or the capability for cross-validation to ensure accuracy. Establishing a rapid and reliable quantitative method for HSO<sub>4</sub><sup>−</sup> is the prerequisite and core step for precisely controlling related food and pharmaceutical additives.</div></div><div><h3>Results</h3><div>To address the need for a rapid, reliable, and field-deployable sensing platform that provides intuitive visual feedback and quantitative data for HSO<sub>4</sub><sup>−</sup> detection in complex real-world samples, we engineered a novel Schiff base probe (<strong>KF</strong>) integrating aggregation-induced emission (AIE), excited-state intramolecular proton transfer (ESIPT), and intramolecular charge transfer (ICT) properties. HSO<sub>4</sub><sup>−</sup> triggers a specific cleavage of the probe's imine bond, inducing a distinct colorimetric change (yellow to colorless) and a ratiometric fluorescence shift (yellow-green to blue). This dual-signal response enables visual qualitative analysis and provides an internal reference for quantitative measurement, with a fluorescence detection limit down to 72.9 nM. We integrated the probe with a smartphone-based RGB analysis platform (ColorPicker App), creating a portable device for on-site, quantitative determination. The platform's efficacy was successfully demonstrated by accurately detecting HSO<sub>4</sub><sup>−</sup> in spiked vegetable and pharmaceutical samples with satisfactory recovery rates (83.1 %–114.4 %).</div></div><div><h3>Significance</h3><div>This work presents the first multifunctional probe combining AIE, ESIPT, and ICT for HSO<sub>4</sub><sup>−</sup>-triggered cleavage, enabling a dual-mode response. This study is significant for establishing a robust, smartphone-integrated sensor that transcends laboratory confines, offering a practical solution for on-site monitoring in food safety and pharmaceutical analysis.</div></div>","PeriodicalId":240,"journal":{"name":"Analytica Chimica Acta","volume":"1389 ","pages":"Article 345118"},"PeriodicalIF":6.0,"publicationDate":"2026-01-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145995954","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
Implications of specific ion effects on salt-induced proteome precipitation in organic solvent 有机溶剂中盐诱导蛋白质组沉淀的特定离子效应的意义
IF 6 2区 化学 Q1 CHEMISTRY, ANALYTICAL Pub Date : 2026-01-15 DOI: 10.1016/j.aca.2026.345111
Ziheng Dang, Jessica L. Nickerson , Alan A. Doucette

Background

Solvent-based protein precipitation is an integral component of the proteomics workflow, as a means of concentrating and purifying proteins ahead of digestion and mass spectrometry. We previously disclosed the critical importance of ionic species above a minimal concentration to maximize protein precipitation in 80 % acetone; however, the type of salt was not varied. Specific ion effects have been examined for decades, with many exceptions to the classic Hofmeister series reported. Specifically, the relative influence of various salts has been ranked for their capacity to enhance or reverse protein solubility, but the relevance in proteome sample preparation has yet to be characterized.

Results

We hereby demonstrate that specific ion effects have a controlling influence on modulating protein aggregation efficiency in 80 % acetone. Distinct salts facilitate aggregation of proteins from a proteomic mixture to varying degrees in organic solvent. Moreover, we reveal a salt-specific systematic precipitation efficiency bias correlating to intrinsic protein properties. Sodium salts of chloride and sulfate were shown to strongly correlate with the protein's molecular weight and degree of aromaticity, with higher MW and aromaticity enhancing aggregation. Zinc salts of chloride and sulfate, on the other hand favored aggregation of low MW proteins. Proteins with a higher fraction of basic amino acids also showed higher precipitation efficiency for zinc salts, while higher histidine content favored precipitation with ZnCl2 but not with ZnSO4.

Significance

These results point to a combination of protein-ion, protein-solvent, and ion-solvent interactions influencing their solubility in organic solvent, with differing mechanisms of precipitation being strongly salt dependent, and provide a greater understanding of salt-mediated protein precipitation in organic solvent.
基于溶剂的蛋白质沉淀是蛋白质组学工作流程的一个组成部分,是在消化和质谱分析之前浓缩和纯化蛋白质的一种手段。我们之前披露了在80%丙酮中,高于最低浓度的离子种类对最大化蛋白质沉淀的重要性;然而,盐的种类并没有变化。特定的离子效应已经被研究了几十年,除了经典的Hofmeister系列报道的许多例外。具体来说,各种盐的相对影响已经根据它们增强或逆转蛋白质溶解度的能力进行了排名,但在蛋白质组样品制备中的相关性尚未得到表征。结果表明,特异性离子效应对80%丙酮中蛋白质聚集效率的调节具有控制作用。不同的盐在有机溶剂中不同程度地促进蛋白质组混合物中的蛋白质聚集。此外,我们揭示了与内在蛋白质特性相关的盐特异性系统沉淀效率偏差。氯化钠盐和硫酸钠盐与蛋白质分子量和芳香度密切相关,高分子量和芳香度有利于蛋白质聚集。另一方面,氯化锌盐和硫酸锌盐则有利于低分子量蛋白质的聚集。碱性氨基酸含量较高的蛋白质对锌盐的沉淀效率也较高,组氨酸含量较高的蛋白质有利于ZnCl2的沉淀,而不利于ZnSO4的沉淀。这些结果表明,蛋白质、蛋白质-溶剂和离子-溶剂相互作用的组合影响了它们在有机溶剂中的溶解度,不同的沉淀机制强烈依赖于盐,并为有机溶剂中盐介导的蛋白质沉淀提供了更好的理解。
{"title":"Implications of specific ion effects on salt-induced proteome precipitation in organic solvent","authors":"Ziheng Dang,&nbsp;Jessica L. Nickerson ,&nbsp;Alan A. Doucette","doi":"10.1016/j.aca.2026.345111","DOIUrl":"10.1016/j.aca.2026.345111","url":null,"abstract":"<div><h3>Background</h3><div>Solvent-based protein precipitation is an integral component of the proteomics workflow, as a means of concentrating and purifying proteins ahead of digestion and mass spectrometry. We previously disclosed the critical importance of ionic species above a minimal concentration to maximize protein precipitation in 80 % acetone; however, the type of salt was not varied. Specific ion effects have been examined for decades, with many exceptions to the classic Hofmeister series reported. Specifically, the relative influence of various salts has been ranked for their capacity to enhance or reverse protein solubility, but the relevance in proteome sample preparation has yet to be characterized.</div></div><div><h3>Results</h3><div>We hereby demonstrate that specific ion effects have a controlling influence on modulating protein aggregation efficiency in 80 % acetone. Distinct salts facilitate aggregation of proteins from a proteomic mixture to varying degrees in organic solvent. Moreover, we reveal a salt-specific systematic precipitation efficiency bias correlating to intrinsic protein properties. Sodium salts of chloride and sulfate were shown to strongly correlate with the protein's molecular weight and degree of aromaticity, with higher MW and aromaticity enhancing aggregation. Zinc salts of chloride and sulfate, on the other hand favored aggregation of low MW proteins. Proteins with a higher fraction of basic amino acids also showed higher precipitation efficiency for zinc salts, while higher histidine content favored precipitation with ZnCl<sub>2</sub> but not with ZnSO<sub>4</sub>.</div></div><div><h3>Significance</h3><div>These results point to a combination of protein-ion, protein-solvent, and ion-solvent interactions influencing their solubility in organic solvent, with differing mechanisms of precipitation being strongly salt dependent, and provide a greater understanding of salt-mediated protein precipitation in organic solvent.</div></div>","PeriodicalId":240,"journal":{"name":"Analytica Chimica Acta","volume":"1390 ","pages":"Article 345111"},"PeriodicalIF":6.0,"publicationDate":"2026-01-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145968468","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
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Analytica Chimica Acta
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