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Systematic investigation of analyte protectants to overcome matrix effects for gas chromatographic analysis of tobacco alkaloids and primary aromatic amines across diverse matrices 在不同基质的烟草生物碱和伯胺气相色谱分析中克服基质效应的分析物保护剂的系统研究
IF 6.1 1区 化学 Q1 CHEMISTRY, ANALYTICAL Pub Date : 2026-05-15 Epub Date: 2026-01-03 DOI: 10.1016/j.talanta.2025.129343
Yaqiong Qin , Xiaoyu Wang , Lining Pan , Rana Tayyarah , Zhiguo Wang , Yu Liu , Ran Wan , Haijian Su , Xuejie Li , Li Chen , Huapeng Cui
The application of analyte protectants (APs) is recognized as an effective and practical strategy to enhance analyte signals in matrix-free solutions and compensate for matrix effects (MEs) in gas chromatography (GC) analysis. However, systematic investigations into promising APs for basic analytes and elucidation of the underlying molecular mechanisms remain limited. In this study, two classes of basic analytes with diverse polarity and basicity, including tobacco alkaloids (TAs) and primary aromatic amines (PAAs), were selected as target analytes. A total of 29 candidates covering a broad range of polarity, basicity, and volatility were systematically evaluated to identify the promising APs for TAs and PAAs. According to individual and average analyte peak enhancement factors, several polyamines, including diethylenetriamine, tris(2-aminoethyl)amine, spermine, pentaethylenehexamine, and the diamine 1,11-diaminoundecane, were identified as the potential APs. Corresponding combinations of these APs for TAs and PAAs at optimized concentrations were validated to significantly reduce the limits of quantification from 1.58 to 307.85 to 1.26–43.43 ng/mL in solvent and improve recovery rates from 92.3 to 352.1 to 80.3–111.5 % in complex matrices. Consistent signal responses across diverse matrices further highlight the developed APs effectively overcome the MEs, ensuring the accurate and robust determinations in practical applications. Furthermore, density functional theory (DFT) calculations revealed that the superior enhancement effects of these APs are primarily attributed to lower interaction energies and stronger hydrogen-bonding interactions with silanol groups in the GC system.
分析物保护剂(ap)的应用被认为是增强无基质溶液中分析物信号和补偿气相色谱(GC)分析中基质效应(MEs)的一种有效和实用的策略。然而,系统研究有前途的ap基础分析和阐明潜在的分子机制仍然有限。本研究选择两类极性和碱度不同的碱分析物,包括烟草生物碱(TAs)和伯胺(PAAs)作为目标分析物。研究人员对29种候选物质进行了系统评估,以确定有前途的TAs和PAAs ap。根据个体和平均峰增强因子,确定了几种多胺,包括二乙基三胺、三(2-氨基乙基)胺、精胺、五乙基二胺和二胺1,11-二氨基癸烷为潜在的ap。在最佳浓度下,这些ap对应的组合对TAs和PAAs的定量限在溶剂中从1.58 ~ 307.85降低到1.26 ~ 43.43 ng/mL,在复杂基质中回收率从92.3 ~ 352.1提高到80.3 ~ 115%。跨不同矩阵的一致信号响应进一步突出了开发的ap有效克服了MEs,确保了在实际应用中的准确和稳健的测定。此外,密度泛函理论(DFT)计算表明,这些APs的增强效果主要是由于GC体系中较低的相互作用能和较强的与硅烷醇基团的氢键相互作用。
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引用次数: 0
Development and validation of an indirect competitive ELISA for cyenopyrafen detection using a novel monoclonal antibody 基于新型单克隆抗体的cyenopyrafen间接竞争性ELISA检测方法的建立与验证。
IF 6.1 1区 化学 Q1 CHEMISTRY, ANALYTICAL Pub Date : 2026-05-15 Epub Date: 2026-01-14 DOI: 10.1016/j.talanta.2026.129416
Tianyu Lan , Jiexin Zheng , Bo Xu , Kerui Dan , Chunlei Cao , Feng Sun , Qiyang Zhao , Yue He , Jing Li , Yongliang Cui , Yaohai Zhang
Cyenopyrafen is an effective pyrazole acaricide used for mite control on various crops. This study generated high-affinity monoclonal antibodies specific to cyenopyrafen and developed a high-throughput indirect competitive enzyme-linked immunosorbent assay (ic-ELISA) validated for sensitivity, specificity, and reproducibility. The ic-ELISA demonstrated an IC50 of 32.75 ng/mL and a dynamic range of 2.33–293.19 ng/mL, with negligible cross-reactivity (<0.1 %) with related acaricides. Recovery rates in citrus samples were 88.18 %–105.89 %. A strong correlation (R2 > 0.95) was detected between the results of ic-ELISA and UPLC-MS/MS, highlighting the assay's reliability. This immunoassay offers a reliable approach for the determination of cyenopyrafen in the tested citrus and apple samples, and may serve as a basis for broader applications with potential utility in regulatory frameworks.
Cyenopyrafen是一种有效的吡唑类杀螨剂,用于防治各种作物的螨虫。本研究产生了针对cyenopyrafen的高亲和力单克隆抗体,并开发了一种高通量间接竞争性酶联免疫吸附试验(ic-ELISA),其敏感性、特异性和可重复性均得到了验证。ic-ELISA的IC50为32.75 ng/mL,动态范围为2.33 ~ 293.19 ng/mL,与UPLC-MS/MS的交叉反应性可忽略(2 > 0.95),表明了该方法的可靠性。该免疫分析法为柑橘和苹果样品中氰吡虫胺的测定提供了一种可靠的方法,并可作为更广泛应用的基础,在监管框架中具有潜在的效用。
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引用次数: 0
Conformation-gated dual enzyme activity in a hemoglobin-based gadolinium single-atom catalyst for adaptive biosensing 自适应生物传感中基于血红蛋白的钆单原子催化剂构象门控双酶活性。
IF 6.1 1区 化学 Q1 CHEMISTRY, ANALYTICAL Pub Date : 2026-05-15 Epub Date: 2026-01-18 DOI: 10.1016/j.talanta.2026.129420
Yifan Xing, Lexian Wu, Yiting Xu, Haowen Huang
Single-atom catalysts (SACs) are known for their exceptional catalytic efficiency but suffer from structural rigidity, limiting their adaptability in biological environments. Here, we present a hemoglobin-based gadolinium single-atom catalyst (Hb-Gd SAC), in which Gd atoms are site-specifically anchored adjacent to the native heme-Fe center via biomimetic coordination. Leveraging the intrinsic flexibility of the protein scaffold, the system exhibits pH- and conformation-gated switching between two distinct enzymatic modes: peroxidase-like (POD-like) activity under acidic conditions and laccase-like activity at neutral pH. These catalytic modes are mechanistically decoupled—global protein conformation governs POD activity, while localized Gd coordination drives laccase-like function. Allosteric regulation by tartaric acid further fine-tunes this behavior, significantly enhancing performance beyond that of natural horseradish peroxidase. This dual-mode catalysis supports programmable biosensing: POD mode enables detection of thiols and acetylcholinesterase activity, while the laccase mode selectively targets dopamine. Such multimodal detection is particularly relevant for neurodegenerative disease diagnostics, exemplified by Parkinson's disease, where simultaneous monitoring of oxidative stress, cholinergic dysfunction, and dopaminergic signaling is essential. Our findings introduce a reconfigurable SAC platform that couples atomic precision with biomolecular dynamics, advancing the frontier of intelligent catalysis and adaptive biosensing technologies.
单原子催化剂(SACs)以其优异的催化效率而闻名,但其结构刚性限制了其在生物环境中的适应性。在这里,我们提出了一种基于血红蛋白的钆单原子催化剂(Hb-Gd SAC),其中Gd原子通过仿生配位特异性锚定在天然血红素-铁中心附近。利用蛋白质支架固有的灵活性,该系统在两种不同的酶模式之间表现出pH和构象门控切换:酸性条件下的过氧化物酶样(POD样)活性和中性pH下的漆酶样活性。这些催化模式是机械解耦的——整体蛋白质构象控制POD活性,而局部Gd配位驱动漆酶样功能。酒石酸的变构调节进一步微调了这种行为,显著提高了天然辣根过氧化物酶的性能。这种双模式催化支持可编程生物传感:POD模式可以检测硫醇和乙酰胆碱酯酶活性,而漆酶模式可以选择性地靶向多巴胺。这种多模式检测与神经退行性疾病诊断特别相关,例如帕金森病,其中同时监测氧化应激、胆碱能功能障碍和多巴胺能信号是必不可少的。我们的研究结果引入了一个可重构的SAC平台,将原子精度与生物分子动力学相结合,推进了智能催化和自适应生物传感技术的前沿。
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引用次数: 0
Editorial: The 23rd International Conference on flow injection analysis and related techniques (ICFIA2024). 第23届流动注射分析及相关技术国际会议(ICFIA2024)。
IF 6.1 1区 化学 Q1 CHEMISTRY, ANALYTICAL Pub Date : 2026-05-15 Epub Date: 2026-01-20 DOI: 10.1016/j.talanta.2026.129437
Chalermpong Saenjum, Kate Grudpan
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引用次数: 0
Complementary analysis of pristine, UV-aged and extracted microplastics using single particle ICP-MS and OF2i-Raman spectroscopy 利用单颗粒ICP-MS和of2i -拉曼光谱对原始、紫外老化和提取的微塑料进行互补分析
IF 6.1 1区 化学 Q1 CHEMISTRY, ANALYTICAL Pub Date : 2026-05-15 Epub Date: 2026-01-07 DOI: 10.1016/j.talanta.2025.129339
Manuel Candussi , Christian Neuper , Raquel Gonzalez de Vega , Matthias Elinkmann , Harald Fitzek , Christian Hill , Patrizia Marie Schmidt , Svenja Seiffert , David Clases
Microplastics are of growing concern due to their ubiquity and potential risks to ecosystems and human health. Their small size, chemical diversity, and coexistence with natural colloids make comprehensive analysis difficult. Here, we evaluate two emerging single particle techniques, single particle inductively coupled plasma-mass spectrometry (SP ICP-MS) and optofluidic force induction coupled with Raman spectroscopy (OF2i-Raman), for their ability to provide complementary information at single microplastic resolution. SP ICP-MS determined carbon mass per particle and enabled detection of degradation-induced trends in size and abundance, while OF2i-Raman identified polymer type and molecular changes via optical trapping and inelastic light scattering.
OF2i-Raman is a novel method in the field of microplastic research and was therefore first benchmarked by analysing mixed suspensions of polymethylmethacrylate (PMMA), polystyrene (PS), and polyamide-6 (PA-6), as well as PA-6 in a soil extract to assess selectivity under complex matrix conditions. Subsequently, both techniques were applied in parallel to study the UV-induced degradation of PA-6 and low-density polyethylene (LDPE) as relevant industrial polymers. SP ICP-MS detected longitudinal carbon loss and relative changes in particle sizes and numbers, while OF2i-Raman revealed polymer-specific structural alterations and detected spectral fingerprints even after extended irradiation.
Together, SP ICP-MS and OF2i-Raman link elemental mass with molecular identity, providing complementary insights into microplastic degradation. While SP ICP-MS remains confined to controlled laboratory experiments due to its limited selectivity and size range, OF2i-Raman extends the analytical window to complex matrices and mixed polymer systems.
微塑料由于其无处不在和对生态系统和人类健康的潜在风险而日益受到关注。它们的体积小,化学成分多样,与天然胶体共存,使综合分析变得困难。在这里,我们评估了两种新兴的单粒子技术,单粒子电感耦合等离子体质谱(SP ICP-MS)和光流力感应耦合拉曼光谱(OF2i-Raman),因为它们能够在单个微塑料分辨率下提供互补信息。SP ICP-MS测定了每个颗粒的碳质量,并检测了降解引起的大小和丰度趋势,而OF2i-Raman通过光学捕获和非弹性光散射鉴定了聚合物类型和分子变化。of2i -拉曼是微塑料研究领域的一种新方法,因此首先通过分析聚甲基丙烯酸甲酯(PMMA)、聚苯乙烯(PS)和聚酰胺-6 (PA-6)的混合悬浮液以及土壤提取物中的PA-6来评估复杂基质条件下的选择性。随后,这两种技术被并行应用于研究PA-6和低密度聚乙烯(LDPE)作为相关工业聚合物的紫外线诱导降解。SP ICP-MS检测到纵向碳损失和颗粒大小和数量的相对变化,而OF2i-Raman显示聚合物特异性结构变化,即使在长时间辐照后也能检测到光谱指纹。SP ICP-MS和OF2i-Raman将元素质量与分子特性联系起来,为微塑料降解提供了互补的见解。SP ICP-MS由于其有限的选择性和尺寸范围,仍然局限于受控的实验室实验,而OF2i-Raman将分析窗口扩展到复杂基质和混合聚合物体系。
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引用次数: 0
Automated sample preparation systems for food analysis: A mini-review 用于食品分析的自动样品制备系统:小型综述
IF 6.1 1区 化学 Q1 CHEMISTRY, ANALYTICAL Pub Date : 2026-05-15 Epub Date: 2026-01-12 DOI: 10.1016/j.talanta.2026.129395
Qiong Xue , Chang Liu , Xiao-Hua Zhou , Dezhao Kong , Jinghui Zhang , Wei Shen , Sheng Tang
Sample preparation has emerged as an essential component in complex food matrix analysis. Automated systems integrate precise machine operation, cutting-edge sample extraction methodologies and sophisticated detection equipment, and have been proven to effectively improve the accuracy and detection efficiency in food analysis. This review provides a mini-overview of automated sample preparation methods currently employed in the field of food analysis. These primarily encompass automated solid-phase extraction methods, microfluidics, robotic systems and integration with detection equipment. In addition, the main challenges currently faced by automated sample preparation were discussed, and suggestions for future research directions were also proposed. This review aims to serve as a reference for researchers in the field and facilitate their work on automated sample preparation methods for food analysis.
样品制备已成为复杂食品基质分析的重要组成部分。自动化系统集成了精密的机器操作,尖端的样品提取方法和精密的检测设备,并已被证明有效地提高了食品分析的准确性和检测效率。这篇综述提供了目前在食品分析领域使用的自动样品制备方法的一个小概述。这些主要包括自动化固相萃取方法、微流体、机器人系统和与检测设备的集成。此外,讨论了自动化样品制备目前面临的主要挑战,并对未来的研究方向提出了建议。本文旨在为该领域的研究人员提供参考,并促进他们在食品分析自动化样品制备方法方面的工作。
{"title":"Automated sample preparation systems for food analysis: A mini-review","authors":"Qiong Xue ,&nbsp;Chang Liu ,&nbsp;Xiao-Hua Zhou ,&nbsp;Dezhao Kong ,&nbsp;Jinghui Zhang ,&nbsp;Wei Shen ,&nbsp;Sheng Tang","doi":"10.1016/j.talanta.2026.129395","DOIUrl":"10.1016/j.talanta.2026.129395","url":null,"abstract":"<div><div>Sample preparation has emerged as an essential component in complex food matrix analysis. Automated systems integrate precise machine operation, cutting-edge sample extraction methodologies and sophisticated detection equipment, and have been proven to effectively improve the accuracy and detection efficiency in food analysis. This review provides a mini-overview of automated sample preparation methods currently employed in the field of food analysis. These primarily encompass automated solid-phase extraction methods, microfluidics, robotic systems and integration with detection equipment. In addition, the main challenges currently faced by automated sample preparation were discussed, and suggestions for future research directions were also proposed. This review aims to serve as a reference for researchers in the field and facilitate their work on automated sample preparation methods for food analysis.</div></div>","PeriodicalId":435,"journal":{"name":"Talanta","volume":"302 ","pages":"Article 129395"},"PeriodicalIF":6.1,"publicationDate":"2026-05-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146074812","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
Enhanced 2-butanone sensing properties of CeO2/WO3 heterojunction with multilevel channels inherited from pollen biotemplate 花粉生物模板遗传的CeO2/WO3多通道异质结增强2-丁酮传感特性
IF 6.1 1区 化学 Q1 CHEMISTRY, ANALYTICAL Pub Date : 2026-05-15 Epub Date: 2026-01-19 DOI: 10.1016/j.talanta.2026.129436
Chuanxuan Zhou , Shaowei Li , Ziyi Zhang , Dousheng Han , Fuchao Yang
The ultimate optimization of natural systems in terms of “structure-function-environment adaptation” can provide inspiration for the design of advanced materials. Considering the urgent demand for efficient detection of 2-butanone in industrial safety and environmental monitoring, and the limitations of existing WO3-based gas sensors including low response intensity and poor selectivity, this research focuses on developing modified WO3-based composite materials with enhanced gas sensing performance using natural biological templates. In this work, an immersion process combined with calcination technology was employed to successfully replace the biosensitive scaffolds on pollen grains with gas-sensitive CeO2/WO3 composites. This material exhibits outstanding response to 2-butanone at 185 °C, significantly surpassing the undoped sample while maintaining high selectivity. The outstanding sensing performance is attributed to its unique hierarchical structure and the synergistic effect of the CeO2/WO3 heterostructure. This study provides a new perspective for us to explore low-cost gas sensors with natural biological morphologies and opens up new possibilities for expanding the applications of WO3-based composites.
从“结构-功能-环境适应”的角度对自然系统进行终极优化,可以为先进材料的设计提供灵感。考虑到工业安全和环境监测中对2-丁酮高效检测的迫切需求,以及现有wo3基气体传感器响应强度低、选择性差的局限性,本研究重点利用天然生物模板开发具有增强气敏性能的改性wo3基复合材料。本研究采用浸没工艺结合煅烧技术,成功地用气敏CeO2/WO3复合材料代替花粉颗粒上的生物敏感支架。该材料在185°C下对2-丁酮表现出出色的响应,在保持高选择性的同时显著超过未掺杂的样品。优异的传感性能归功于其独特的层次结构和CeO2/WO3异质结构的协同效应。该研究为我们探索具有天然生物形态的低成本气体传感器提供了新的视角,为扩大wo3基复合材料的应用开辟了新的可能性。
{"title":"Enhanced 2-butanone sensing properties of CeO2/WO3 heterojunction with multilevel channels inherited from pollen biotemplate","authors":"Chuanxuan Zhou ,&nbsp;Shaowei Li ,&nbsp;Ziyi Zhang ,&nbsp;Dousheng Han ,&nbsp;Fuchao Yang","doi":"10.1016/j.talanta.2026.129436","DOIUrl":"10.1016/j.talanta.2026.129436","url":null,"abstract":"<div><div>The ultimate optimization of natural systems in terms of “structure-function-environment adaptation” can provide inspiration for the design of advanced materials. Considering the urgent demand for efficient detection of 2-butanone in industrial safety and environmental monitoring, and the limitations of existing WO<sub>3</sub>-based gas sensors including low response intensity and poor selectivity, this research focuses on developing modified WO<sub>3</sub>-based composite materials with enhanced gas sensing performance using natural biological templates. In this work, an immersion process combined with calcination technology was employed to successfully replace the biosensitive scaffolds on pollen grains with gas-sensitive CeO<sub>2</sub>/WO<sub>3</sub> composites. This material exhibits outstanding response to 2-butanone at 185 °C, significantly surpassing the undoped sample while maintaining high selectivity. The outstanding sensing performance is attributed to its unique hierarchical structure and the synergistic effect of the CeO<sub>2</sub>/WO<sub>3</sub> heterostructure. This study provides a new perspective for us to explore low-cost gas sensors with natural biological morphologies and opens up new possibilities for expanding the applications of WO<sub>3</sub>-based composites.</div></div>","PeriodicalId":435,"journal":{"name":"Talanta","volume":"302 ","pages":"Article 129436"},"PeriodicalIF":6.1,"publicationDate":"2026-05-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146028063","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
In-situ HF-etched MXene as a novel electrode modifier for sensitive detection of bisphenol A 原位hf蚀刻MXene作为灵敏检测双酚a的新型电极改性剂。
IF 6.1 1区 化学 Q1 CHEMISTRY, ANALYTICAL Pub Date : 2026-05-15 Epub Date: 2026-01-10 DOI: 10.1016/j.talanta.2026.129363
Ana Agurto , María Pilar da Silva , Luis Vázquez , María Dolores Petit-Domínguez , Elena Casero , Carmen Quintana , Elias Blanco
This study explores the use of MXene, a relatively recent class of 2D materials, as an innovative modifier of glassy carbon (GC) electrodes for the electrochemical detection of bisphenol A (BPA), a compound of significant environmental and health concern. MXene Ti3C2 was synthesized via in-situ hydrofluoric acid generation using a NaF/HCl mixture that is considered a milder synthetic route in comparison with ex-situ hydrofluoric acid, and safer because it avoids the handling and storage of commercial HF. Nanomaterials obtained at various stages of MXene synthesis were morphologically characterized using scanning electron microscopy. With respect to the bare GC, MXene improved the BPA electroanalysis due to the known MXene properties such as metallic conductivity. This enhanced response was further improved when MXene was exfoliated via a delamination process. Scan rate studies proved that the BPA mechanism was governed by a diffusion-controlled process. Once MXene concentration in aqueous suspensions used to modify the GC surface was optimized, pH and differential pulse parameters were adjusted. The optimal conditions were 0.1 M phosphate buffer at pH 7 as electrolyte, pulse amplitude of 60 mV and scan rate of 20 mV/s. Sensor performance evaluation yielded a detection limit of 0.11 μM. The applicability of the sensor was supported by the analysis of real water samples. Results were corroborated by ultra-high performance liquid chromatographic analysis, demonstrating the sensor's applicability and reliability.
本研究探索了MXene(一种相对较新的二维材料)作为玻璃碳(GC)电极的创新改性剂,用于电化学检测双酚a (BPA),这是一种具有重要环境和健康问题的化合物。MXene Ti3C2是用NaF/HCl混合物通过原位氢氟酸生成的,与非原位氢氟酸相比,这被认为是一种更温和的合成路线,而且由于避免了商业HF的处理和储存,因此更安全。在MXene合成的各个阶段得到的纳米材料用扫描电镜进行了形貌表征。相对于裸气相色谱,由于已知的MXene性质(如金属导电性),MXene改进了双酚a电分析。当MXene通过分层过程去角质时,这种增强的反应进一步得到改善。扫描速率研究证明BPA的机制是由扩散控制的过程控制的。优化了用于修饰气相色谱表面的水悬浮液中MXene的浓度后,调整了pH和差分脉冲参数。最佳条件为0.1 M磷酸盐缓冲液,pH为7,脉冲振幅为60 mV,扫描速率为20 mV/s。传感器性能评估的检测限为0.11 μM。通过对实际水样的分析,验证了传感器的适用性。结果得到了超高效液相色谱分析的证实,证明了该传感器的适用性和可靠性。
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引用次数: 0
N-acetylcysteine-functionalised a multimodal HPLC stationary phase for broad-range separations n -乙酰半胱氨酸功能化的多模态HPLC固定相用于大范围分离。
IF 6.1 1区 化学 Q1 CHEMISTRY, ANALYTICAL Pub Date : 2026-05-15 Epub Date: 2026-01-13 DOI: 10.1016/j.talanta.2026.129397
Hayriye Aral , Tarık Aral , Murat Sunkur , Mehmet Çolak , Mesut Bağcık
In this study, a new multimodal HPLC stationary phase derived from N-acetyl-l-cysteine was synthesized and comprehensively evaluated across a broad polarity spectrum. In chromatographic stationary phase design, two fundamental criteria are particularly important: a facile, low-cost synthesis and broad applicability across diverse analyte classes. The present stationary phase fulfils both requirements, as it is prepared from a commercially available starting material via a simple single-step immobilisation onto silica, providing a practical and economical synthetic route alongside wide analytical utility. The molecular architecture of the ligand, incorporating a pH-responsive carboxyl group, a hydrogen-bond-donating and -accepting amide moiety, a polarisation-sensitive sulfur atom, and hydrophobic methyl and methylene units, creates a versatile interaction environment capable of mediating hydrophobic, polar, dispersive, and weak cation-exchange processes. This multifunctional design enables the stationary phase to adapt its selectivity according to analyte structure and mobile-phase conditions, supporting both reversed-phase-like and HILIC-like retention behaviour within a single chromatographic platform. The chromatographic performance of the NAC-derived stationary phase was systematically evaluated using a wide range of chemically and biologically relevant analytes. Under HILIC conditions, the column successfully resolved 7 of the 9 highly polar nucleobases and nucleosides. In reversed-phase mode, compounds with high hydrophobicity—including 6 alkyl benzenes, 4 polycyclic aromatic hydrocarbons, 6 Sudan dyes, 8 anilines, and 7 benzoic acid derivatives—were efficiently separated. Under the same reversed-phase conditions, the stationary phase successfully resolved 10 analytes from a twelve-analyte plant growth regulator mixture and 9 sulphonamides. In addition, a 6 herbicide was also effectively separated, highlighting the multimodal selectivity of the stationary phase. Retention trends were interpreted using analyte logD and pKa values, clarifying the combined contributions of hydrophobic, polar, and weak ion-exchange interactions to overall selectivity. The N-acetyl-l-cysteine-based stationary phase provides a finely balanced interaction profile, enabling high separation performance for analytes spanning from extreme polarity to pronounced hydrophobicity and demonstrating broad analytical utility.
在本研究中,合成了一种新的n -乙酰-l-半胱氨酸多模态高效液相色谱固定相,并在宽极性谱上进行了综合评价。在色谱固定相设计中,两个基本标准特别重要:简便、低成本的合成和对不同分析物类别的广泛适用性。目前的固定相满足这两个要求,因为它是通过简单的单步固定在二氧化硅上从商业上可用的起始材料制备的,提供了一个实用和经济的合成路线以及广泛的分析用途。配体的分子结构,包括ph响应的羧基、供氢键和接受氢键的酰胺部分、极化敏感的硫原子、疏水的甲基和亚甲基单元,创造了一个多功能的相互作用环境,能够介导疏水、极性、分散和弱阳离子交换过程。这种多功能设计使固定相能够根据分析物结构和流动相条件调整其选择性,在单个色谱平台内支持类似反相和类似hilic的保留行为。使用广泛的化学和生物学相关分析物系统地评估了nac衍生固定相的色谱性能。在HILIC条件下,该柱成功地分离了9个高极性核碱基和核苷中的7个。在反相模式下,高疏水性化合物(包括6种烷基苯、4种多环芳烃、6种苏丹红染料、8种苯胺和7种苯甲酸衍生物)得到了高效分离。在相同的反相条件下,固定相成功地从12种植物生长调节剂混合物中分离出10种分析物和9种磺胺类化合物。此外,还有效分离了一种6除草剂,突出了固定相的多模态选择性。利用分析物logD和pKa值解释了保留趋势,阐明了疏水、极性和弱离子交换相互作用对总体选择性的综合贡献。基于n -乙酰-l-半胱氨酸的固定相提供了一个精细平衡的相互作用剖面,为从极端极性到明显疏水性的分析物提供了高分离性能,并展示了广泛的分析实用性。
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引用次数: 0
Self-oxidation and proximity crosslinking of G-quadruplex in G-quadruplex /hemin peroxidase system g -四聚体/血红素过氧化物酶体系中g -四聚体的自氧化和近交联
IF 6.1 1区 化学 Q1 CHEMISTRY, ANALYTICAL Pub Date : 2026-05-15 Epub Date: 2026-01-08 DOI: 10.1016/j.talanta.2025.129344
Xiaojuan Yang , Jin Zhou , Dihua Shangguan
G-quadruplex (G4)/hemin peroxidase has emerged as a robust platform for signal amplification in biosensors. While offering distinct advantages over protein enzymes, its susceptibility to inactivation often results in low apparent catalytic activity, thereby limiting broader applications. To address this, we investigated the side reactions occurring during the catalytic process of G4/hemin DNAzyme in both N-acetyl-cysteine (NAC) and H2O2 systems. Notably, high-molecular-weight products were observed when the hemin/G4 ratio exceeded 10. Further analysis revealed that these products primarily resulted from the self-oxidation of G4 sequences or proximity cross-linking with hemin fractions, substrates, and coexisting DNA sequences. Our findings provide critical insights into the inactivation mechanism and offer guidance for enhancing the catalytic efficiency of G4-based biosensors.
g -四联体(G4)/血红素过氧化物酶已成为生物传感器信号放大的强大平台。虽然与蛋白酶相比具有明显的优势,但其易失活往往导致低表观催化活性,从而限制了其更广泛的应用。为了解决这个问题,我们研究了在n -乙酰半胱氨酸(NAC)和H2O2体系中G4/hemin DNAzyme催化过程中发生的副反应。值得注意的是,当hemin/G4比值超过10时,可以观察到高分子量的产物。进一步分析表明,这些产物主要是由G4序列的自氧化或与血红蛋白组分、底物和共存的DNA序列的近交联引起的。我们的发现对g4生物传感器的失活机制提供了重要的见解,并为提高g4生物传感器的催化效率提供了指导。
{"title":"Self-oxidation and proximity crosslinking of G-quadruplex in G-quadruplex /hemin peroxidase system","authors":"Xiaojuan Yang ,&nbsp;Jin Zhou ,&nbsp;Dihua Shangguan","doi":"10.1016/j.talanta.2025.129344","DOIUrl":"10.1016/j.talanta.2025.129344","url":null,"abstract":"<div><div>G-quadruplex (G4)/hemin peroxidase has emerged as a robust platform for signal amplification in biosensors. While offering distinct advantages over protein enzymes, its susceptibility to inactivation often results in low apparent catalytic activity, thereby limiting broader applications. To address this, we investigated the side reactions occurring during the catalytic process of G4/hemin DNAzyme in both N-acetyl-cysteine (NAC) and H<sub>2</sub>O<sub>2</sub> systems. Notably, high-molecular-weight products were observed when the hemin/G4 ratio exceeded 10. Further analysis revealed that these products primarily resulted from the self-oxidation of G4 sequences or proximity cross-linking with hemin fractions, substrates, and coexisting DNA sequences. Our findings provide critical insights into the inactivation mechanism and offer guidance for enhancing the catalytic efficiency of G4-based biosensors.</div></div>","PeriodicalId":435,"journal":{"name":"Talanta","volume":"302 ","pages":"Article 129344"},"PeriodicalIF":6.1,"publicationDate":"2026-05-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145924398","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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