Analytica Chimica Acta最新文献_第10页

Fe3O4 nanozyme integrated upconversion luminescence synergistic energy transfer composite nanoplatform for the ultrasensitive detection of proGRP Fe3O4纳米酶集成上转换发光协同能量转移复合纳米平台用于proGRP的超灵敏检测

IF 6 2区化学 Q1 CHEMISTRY, ANALYTICAL

Analytica Chimica Acta

Pub Date : 2025-12-09 DOI: 10.1016/j.aca.2025.344997

Shoujun Jian , Xiaoying Niu , Fengzhi Li , Peng Zhang , Hongmin Zhang , Huaixia Yang , Yanju Liu

Background

Progastrin-releasing peptide (proGRP) is a potential high-specificity biomarker for Ewing sarcoma and has important clinical value in early diagnosis and risk stratification. However, the existing detection methods such as enzyme-linked immunosorbent assay (ELISA), chemiluminescence immunoassay (CLIA), and cytometric bead array (CBA) often face the problems of insufficient sensitivity and limited reliability in complex biological matrices, lead to the difficulty of accurate quantification. Therefore, it is of great significance to develop new sensing strategies with higher detection performance for promoting clinical accurate diagnosis.

Results

This study developed a novel biosensing system based on fluorescence enhancement with Förster resonance energy transfer (FRET) for highly sensitive detection of proGRP. The signal amplification unit of this system is composed of DNA1-modified upconversion nanoparticles (UCNPs) as FRET donor and DNA2-modified magnetic nanozyme complexes (Fe₃O₄Ns) as acceptor. Upon competitive binding with proGRP, the dissociated DNA1-UCNPs pair with DNA2-Fe₃O₄Ns. This pairing reduces the donor-acceptor distance, thus activating the FRET process and prompting Fe₃O₄Ns to generate substantial hydroxyl radicals (·OH), which subsequently oxidizes specific substrates to transduce the detection signal. The detection limit of the method was 0.14 pg/mL in PBS and 0.76 pg/mL in serum. The method demonstrated high specificity, excellent reproducibility, and robust anti-interference performance, rendering it robust for the analysis of complex serum matrices.

Significance

This work presents an innovative sensing platform that combines near-infrared light-excited luminescence with nanozyme-mediated signal amplification for the detection of proGRP. The method surpasses conventional assays in sensitivity and operational stability, showing great promise for clinical translation. Its robust performance in serum underscores potential applications in early cancer diagnostics and biomarker-based disease management, providing a valuable tool for disease diagnosis.

背景原胃泌素释放肽（progastrin -releasing peptide, proGRP）是一种潜在的高特异性生物标志物，在尤文氏肉瘤的早期诊断和风险分层中具有重要的临床价值。然而，现有的酶联免疫吸附测定（ELISA）、化学发光免疫测定（CLIA）、细胞头阵列（CBA）等检测方法在复杂的生物基质中往往面临灵敏度不足、可靠性有限的问题，导致难以准确定量。因此，开发具有更高检测性能的新型感知策略对促进临床准确诊断具有重要意义。结果建立了一种基于Förster共振能量转移（FRET）荧光增强的新型生物传感系统，用于proGRP的高灵敏度检测。该系统的信号放大单元由dna1修饰的上转换纳米颗粒（UCNPs）作为FRET供体和dna2修饰的磁性纳米酶复合物（Fe3O4Ns）作为受体组成。在与proGRP竞争结合后，解离的DNA1-UCNPs与DNA2-Fe3O4Ns配对。这种配对减少了供体-受体的距离，从而激活了FRET过程，促使Fe3O4Ns产生大量的羟基自由基（·OH），随后氧化特定的底物来传递检测信号。该方法在PBS中的检出限为0.14 pg/mL，在血清中的检出限为0.76 pg/mL。该方法具有高特异性、重复性好、抗干扰能力强等特点，适用于复杂血清基质的分析。本工作提出了一种结合近红外光激发发光和纳米酶介导的信号放大检测proGRP的创新传感平台。该方法在灵敏度和操作稳定性方面优于传统的检测方法，显示出临床翻译的巨大希望。它在血清中的强大性能强调了其在早期癌症诊断和基于生物标志物的疾病管理方面的潜在应用，为疾病诊断提供了有价值的工具。

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引用次数: 0

Determination of individual biogenic volatile organic compounds in the atmosphere at short time intervals by a combination of in-situ continuous sampling using wet diffusion denuder and off-line laboratory analysis 用湿扩散法和离线实验室分析相结合的原位连续取样法在短时间间隔内测定大气中单个生物源性挥发性有机化合物

IF 6 2区化学 Q1 CHEMISTRY, ANALYTICAL

Analytica Chimica Acta

Pub Date : 2025-12-09 DOI: 10.1016/j.aca.2025.345002

Kamil Křůmal , Gabriela Handlířová , Pavel Mikuška

Background

Biogenic volatile organic compounds (BVOCs) play a key role in atmospheric chemistry and air quality. Accurate quantification of individual BVOCs remains challenging due to their volatility and reactivity in atmosphere. In this study, a wet diffusion denuder used for the continuous sampling of BVOCs into an absorption liquid was evaluated under controlled laboratory conditions in order to determine the collection efficiencies for a large number of BVOCs. All samples with collected BVOCs were offline analysed using gas chromatography with mass spectrometry.

Results

The influence of denuder temperature, air flow rate, relative humidity, type of absorption liquid, and liquid flow rate was systematically investigated. Optimal conditions for field application were selected as a denuder temperature of 20 °C, an air flow rate of 500 mL/min, n-heptane as the absorption liquid, and a liquid flow rate of 0.40 mL/min. Under these conditions, collection efficiencies for most BVOCs exceeded 89 %. Field sampling conducted at two contrasting sites, an agricultural location and a spruce forest, confirmed the applicability of the method and highlighted large differences in monoterpene concentrations between environments. A connection of denuder output with automatic sample collector enables long-term fully automatic sampling of BVOCs in the air at short time intervals. The temporal resolution sampling allows the study of rapid changes in BVOC concentrations in the air.

Significance

A key advantage of the method is that it minimizes the exposure of captured BVOCs in an absorption liquid (n-heptane) to airborne oxidants, thereby reducing the risk of photochemical reaction with air oxidants during sampling, and also the determination of the concentration of individual BVOCs using off-line gas chromatography with mass spectrometry analysis.

生物源性挥发性有机化合物（BVOCs）在大气化学和空气质量中起着关键作用。由于BVOCs在大气中的挥发性和反应性，对其进行准确量化仍然具有挑战性。在本研究中，为了确定大量BVOCs的收集效率，在受控的实验室条件下，评估了用于将BVOCs连续采样到吸收液中的湿扩散珠光器。所有样品均采用气相色谱-质谱法进行脱机分析。结果系统考察了光洁温度、空气流速、相对湿度、吸收液种类、液体流速等因素对光洁液的影响。现场应用的最佳条件为光洁温度20℃，空气流速500 mL/min，正庚烷为吸收液，液体流速0.40 mL/min。在这些条件下，大多数BVOCs的收集效率超过89%。在两个不同地点，一个农业地点和一个云杉林进行的实地抽样证实了该方法的适用性，并强调了不同环境之间单萜烯浓度的巨大差异。denuder输出与自动采样采集器连接，可以在短时间间隔内对空气中的BVOCs进行长期全自动采样。时间分辨率采样允许研究空气中BVOC浓度的快速变化。该方法的一个关键优点是，它最大限度地减少了吸收液（正庚烷）中捕获的BVOCs暴露于空气中的氧化剂，从而降低了采样过程中与空气氧化剂发生光化学反应的风险，也降低了使用离线气相色谱-质谱分析确定单个BVOCs浓度的风险。

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引用次数: 0

Antioxidant 3-hydroxyflavone analogues: Integrated experimental and theoretical insights into lead fluoro-sensing and toxicity mitigation in living systems 抗氧化剂3-羟基黄酮类似物：生命系统中铅荧光感应和毒性缓解的综合实验和理论见解

IF 6 2区化学 Q1 CHEMISTRY, ANALYTICAL

Analytica Chimica Acta

Pub Date : 2025-12-08 DOI: 10.1016/j.aca.2025.344996

Trisha Samanta , Partha Chakrobarty , Suktara Guria , Soumyadeep Basu , Abhijit Karmakar , Anup Pramanik , Sutapa Mukherjee , Naznin Ara Begum

Background

Lead (Pb²⁺) toxicity represents a major public health challenge, underscoring the need for advanced detection and remediation strategies.

Results

We introduce two synthetic 3-hydroxyflavone (3-HF) analogues: 3′,4′-methylenedioxy-3-hydroxyflavone (1) and 4′-N,N-dimethyl-3-hydroxyflavone (2) as multifunctional “sense-and-treat” agents for Pb²⁺. These probes detect Pb²⁺ via a characteristic excited-state intramolecular proton transfer (ESIPT) fluorescence response, demonstrating excellent sensitivity with detection limits of 1.8 μM for (1) and 4.9 μM for (2), and high selectivity over competing ions such as Hg²⁺ and Cd²⁺. Density functional theory (DFT) calculations confirm that Pb²⁺ chelation at the 3-hydroxy-4-carbonyl motif induces the observed fluorescence shift. The probes enabled real-time fluorescence mapping of Pb²⁺ in live mice hepatocytes with minimal cytotoxicity (>90 % cell viability). Furthermore, probe (1) mitigated Pb²⁺-induced oxidative stress in vivo by sequestering Pb²⁺ into a less reactive complex, restoring redox homeostasis and tissue integrity.

Significance

This study advances the understanding of 3-HF-metal interactions, establishing 3-HF analogues as a promising integrated platform for comprehensive lead toxicity management. These findings have direct applications in environmental monitoring, clinical toxicology, and public health.

铅（Pb2+）毒性是一项重大的公共卫生挑战，强调需要先进的检测和补救策略。结果我们合成了两种3-羟基黄酮（3- hf）类似物：3′，4′-亚甲二氧基-3-羟基黄酮(1)和4′-N， n -二甲基-3-羟基黄酮(2)，作为Pb2+的多功能“感应和处理”剂。这些探针通过激发态分子内质子转移（ESIPT）荧光响应检测Pb2+，具有优异的灵敏度，检测限为1.8 μM(1)和4.9 μM(2)，并且对Hg2+和Cd2+等竞争离子具有很高的选择性。密度泛函理论（DFT）计算证实，Pb2+在3-羟基-4-羰基基基上的螯合引起了观察到的荧光位移。该探针能够以最小的细胞毒性（90%细胞存活率）实时荧光定位活小鼠肝细胞中的Pb2+。此外，探针(1)通过将Pb2+隔离到活性较低的复合物中，恢复氧化还原稳态和组织完整性，减轻了Pb2+诱导的体内氧化应激。本研究促进了对3-HF-金属相互作用的理解，建立了3-HF类似物作为综合铅毒性管理的有前途的综合平台。这些发现在环境监测、临床毒理学和公共卫生方面具有直接的应用价值。

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引用次数: 0

Flexible silver nanoflower SERS substrates with optical spot-size matching: Preparation and high-performance detection of veterinary drug residues 具有光学点尺寸匹配的柔性银纳米花SERS衬底：兽药残留的制备和高效检测

IF 6 2区化学 Q1 CHEMISTRY, ANALYTICAL

Analytica Chimica Acta

Pub Date : 2025-12-08 DOI: 10.1016/j.aca.2025.344998

Deying Wang , Chunsheng Ren , Junfei Chen , Qi Zhang , Yan Chen , Changhao Li , Yong Jin , Xiaohua Qi , Qiang Ma

The reproducibility and reliability of surface-enhanced Raman spectroscopy (SERS) detection are constrained by the heterogeneous distribution of “hot spots”. While conventional physical deposition or template assembly methods can produce rigid and homogeneous substrates, they struggle to precisely regulate the self-assembly behavior of nanoparticles in flexible hydrogels. The core challenge lies in minimizing the variation in “hot spots” density across detection zones within hydrogels to enhance detection consistency and reliability of flexible SERS substrates. To address these issues, this study successfully constructed a flexible SERS substrate that integrates a high density of uniformly distributed SERS “hot spots” and environmental interference resistance. This was achieved by elucidating the synergistic matching mechanism between silver nanoflower morphology and laser spot size, combined with the flexible carrier properties of hydrogel chips. Using veterinary drug enrofloxacin in complex matrices as a model to validate the analytical performance of the SERS substrate, the results demonstrated significant advantages: its sensitivity reached 47.96 ppb, the entire detection process was completed within 20 min, and it effectively resisted background interference. In real milk sample validations, the substrate demonstrated spike recovery rates of 88.3 %–114 %, with relative standard deviation (RSD) controlled within 1.78 %–7.83 % across all concentration gradients. This work establishes a novel, sensitive, and reliable analytical platform for rapid screening of veterinary drug residues in food systems, holding significant application potential in food safety monitoring.

表面增强拉曼光谱（SERS）检测的再现性和可靠性受到“热点”非均匀分布的限制。虽然传统的物理沉积或模板组装方法可以生产刚性和均匀的基底，但它们很难精确地调节纳米颗粒在柔性水凝胶中的自组装行为。核心挑战在于最小化水凝胶内跨检测区域的“热点”密度变化，以提高柔性SERS基板的检测一致性和可靠性。为了解决这些问题，本研究成功构建了一种柔性SERS衬底，该衬底集成了高密度均匀分布的SERS“热点”和抗环境干扰。这是通过阐明银纳米花形态与激光光斑尺寸之间的协同匹配机制，结合水凝胶芯片的柔性载流子特性来实现的。以兽药恩诺沙星在复杂基质中的应用为模型，验证SERS底物的分析性能，结果显示出显著的优势：灵敏度达到47.96 ppb，整个检测过程在20 min内完成，并能有效抵抗背景干扰。在实际牛奶样品验证中，底物的峰值回收率为88.3% ~ 114%，在所有浓度梯度下的相对标准偏差（RSD）控制在1.78% ~ 7.83%。本研究为食品系统中兽药残留的快速筛选建立了一种新颖、灵敏、可靠的分析平台，在食品安全监测中具有重要的应用潜力。

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引用次数: 0

Ultra-low limit heparin detection based on 11-mercaptoundecanoic acid /chitosan functionalized and AuNPs enhanced fiber surface plasma 基于11-巯基癸酸/壳聚糖功能化和AuNPs增强纤维表面等离子体的超低限肝素检测

IF 6 2区化学 Q1 CHEMISTRY, ANALYTICAL

Analytica Chimica Acta

Pub Date : 2025-12-08 DOI: 10.1016/j.aca.2025.345000

Jun Wu, Meijuan Jia, Meihui Zhang, Minglu Li, Shu Fang, Jie Dong, Anhua Dong, Ruotong Tian, Jun Zhou, Changyu Shen

Background

Heparin is a sulfated glycosaminoglycan that is crucial for inhibiting coagulation and maintaining vascular blood flow. Among the existing detection methods, although electrochemical technology has the advantages of rapid detection and strong sample compatibility, it has limitations such as insufficient selectivity and susceptibility to environmental interference in stability. Nuclear magnetic resonance technology can accurately analyze molecular structures, but it is limited by complex sample processing, high equipment costs and large sample size requirements. Therefore, new detection technology with the advantages of operational convenience, rapid response and real-time detection applicability is needed.

Results

We developed unlabeled gold nanoparticles (AuNPs) enhanced surface plasmon resonance (SPR) heparin sensor. Gold coating is applied on the surface of a tilted fiber Bragg grating (TFBG), and a 11-mercaptoundecanoic acid/chitosan (MUA/CS) functional film is modified on the gold film to form a heparin probe. Before detection, the tested heparin solution was functionalized with unlabeled AuNPs, which to can be aggregated on the probe surface to realize the enhancement of the SPR, enabling ultra-low concentration detection of heparin. The experimental results show that the sensor has a sensitivity of 0.29 dB/lg(g/mL) for heparin detection in the wide range of 10⁻²⁴ to 10⁻² g/mL, with a lower limit of detection (LOD) of 0.051 aM, which is more than one order of magnitude lower than that of the similar existing heparin sensors. Meanwhile, the TFBG-SPR sensor has a time response of ∼400 s for heparin detection.

Significance

This sensor demonstrates significant advantages such as label free detection and low detection limit compared to existing technologies. It also provides an innovative strategy for improving detection sensitivity and reducing the detection limit of similar biochemical substances.

肝素是一种磺化糖胺聚糖，对抑制凝血和维持血管血流至关重要。在现有的检测方法中，电化学技术虽然具有检测速度快、样品相容性强等优点，但在稳定性上存在选择性不足、易受环境干扰等局限性。核磁共振技术可以准确分析分子结构，但受样品处理复杂、设备成本高、样本量要求大等限制。因此，需要具有操作便捷性、快速响应性和实时检测适用性的新型检测技术。结果制备了无标记金纳米颗粒（AuNPs）增强表面等离子体共振（SPR）肝素传感器。在倾斜光纤布拉格光栅（TFBG）表面涂上金涂层，在金膜上修饰11-巯基癸酸/壳聚糖（MUA/CS）功能膜，形成肝素探针。检测前，将被测肝素溶液用未标记的aunp进行功能化，使其能够聚集在探针表面，实现SPR的增强，从而实现对肝素的超低浓度检测。实验结果表明，该传感器在10-24 ~ 10-2 g/mL范围内检测肝素的灵敏度为0.29 dB/lg(g/mL)，检测下限（LOD）为0.051 aM，比现有同类肝素传感器低一个数量级以上。同时，TFBG-SPR传感器对肝素检测的时间响应为~ 400秒。与现有技术相比，该传感器具有无标签检测和低检测限等显著优势。为提高同类生化物质的检测灵敏度和降低检测限提供了一种创新策略。

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引用次数: 0

The influence of homogeneity on the stability assessment of reference materials 均匀性对标准物质稳定性评价的影响

IF 6 2区化学 Q1 CHEMISTRY, ANALYTICAL

Analytica Chimica Acta

Pub Date : 2025-12-08 DOI: 10.1016/j.aca.2025.344987

Kalman Toth, Thomas P.J. Linsinger

Accurate estimation of the uncertainty of stability is crucial for certified reference materials (CRMs), as it forms a component of the overall uncertainty budget. In case of between-unit heterogeneity, results obtained on the same unit of a CRM are not independent which leads to a bias in the estimated uncertainty of stability when used ordinary least squares. This bias depends on the ratio of between-unit heterogeneity to method repeatability and the number of replicate analyses performed per unit and can reach nearly 50 % for as few as three replicates per unit. A study on actual certified values shows that this bias can influence the certified values. The study shows that employing linear mixed-effects models (LME) with restricted maximum likelihood (REML) for parameter estimation provides consistent estimate of uncertainty of stability, even in the presence of significant between-unit heterogeneity. Simpler, alternative approaches for specific scenarios, such as well-balanced datasets are also provided.

稳定不确定度的准确估计对于标准物质是至关重要的，因为它构成了不确定度预算的一个组成部分。在单元间异质性的情况下，在CRM的同一单元上获得的结果不是独立的，这导致使用普通最小二乘法估计稳定性不确定性时存在偏差。这种偏差取决于单位间异质性与方法可重复性的比率，以及每个单位进行的重复分析的数量，在每个单位只有三个重复的情况下，偏差可以达到近50%。对实际认证值的研究表明，这种偏差会影响认证值。研究表明，采用限制最大似然（REML）的线性混合效应模型（LME）进行参数估计，即使在存在显著的单位间异质性的情况下，也能提供稳定不确定性的一致估计。还提供了针对特定场景的更简单的替代方法，例如平衡良好的数据集。

引用次数: 0

Isolation and adsorption of extracellular vesicles using molecularly imprinted cryogel membranes 分子印迹低温凝胶膜对细胞外小泡的分离与吸附

IF 6 2区化学 Q1 CHEMISTRY, ANALYTICAL

Analytica Chimica Acta

Pub Date : 2025-12-07 DOI: 10.1016/j.aca.2025.344993

Almaysh Haidar Rizqullah , Eylul Gulsen Yilmaz , Yeşeren Saylan

Background

Breast cancer is one of the most significant malignancies worldwide, representing one out of every eight cancers diagnosed in women and affecting one in four women across all ages. Early diagnosis is essential for improving survival and overall quality of life, yet limitations such as the lack of affordable traditional tests and technological or biological barriers often delay timely detection. Extracellular vesicles (EVs), which facilitate information exchange among cancer cells, hold strong potential as primary biomarker for cancer detection. However, the lack of simple, reliable, and reproducible platforms for EV isolation and detection remains a major challenge.

Results

In this study, we focus on the selective isolation of EVs cultured and collected on a microfluidic chip engineered to mimic the cancer microenvironment, using molecularly imprinted cryogel membranes. Optimal conditions for EV adsorption onto these membranes were systematically identified in a batch system using a rotator. The resulting cryogel-based platform demonstrated a high adsorption capacity of 1075 particles per gram of cryogel at pH 5.0. The membranes also showed excellent regeneration performance following EV desorption with 1 M NaCl, supporting sustained operational stability. Strong alignment with the Langmuir adsorption model and validation through HPLC analyses provide both mechanistic insight and analytical confidence, positioning this approach as a robust and reproducible alternative to conventional EV isolation strategies.

Significance

Overall, these findings introduce a novel, scalable cryogel-based platform for EV purification, offering high reliability, quantifiability, and reusability. The system’s solid analytical performance and compatibility with downstream processing highlight its broad potential in biochemical, diagnostic, and EV-based research and technologies.

乳腺癌是世界上最严重的恶性肿瘤之一，每8个女性确诊癌症中就有1个患有乳腺癌，在所有年龄段的女性中，每4个女性中就有1个患有乳腺癌。早期诊断对于改善生存和整体生活质量至关重要，但缺乏负担得起的传统检测以及技术或生物障碍等限制往往会延误及时发现。细胞外囊泡（EVs）促进癌细胞之间的信息交换，作为癌症检测的主要生物标志物具有很强的潜力。然而，缺乏简单、可靠和可重复的EV隔离和检测平台仍然是一个主要挑战。结果在模拟肿瘤微环境的微流控芯片上，利用分子印迹低温凝胶膜对体外培养和收集的ev进行了选择性分离。利用旋转器在间歇系统中系统地确定了EV吸附在这些膜上的最佳条件。结果表明，在pH 5.0下，每克低温凝胶的吸附量为1075个颗粒。在1 M NaCl脱附EV后，膜也表现出良好的再生性能，支持持续的运行稳定性。与Langmuir吸附模型高度一致，并通过HPLC分析验证，提供了机制洞察力和分析可信度，将该方法定位为传统EV分离策略的可靠且可重复的替代方法。总体而言，这些发现为EV净化提供了一种新颖的、可扩展的基于低温的平台，具有高可靠性、可量化性和可重用性。该系统可靠的分析性能和与下游处理的兼容性突出了其在生化、诊断和基于ev的研究和技术方面的广泛潜力。

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引用次数: 0

A scalable electrochromic aptasensing interface as a highly selective Apta-Chip for visual detection of methamphetamine 一种可扩展的电致变色aptassensing接口作为高选择性apta芯片用于甲基安非他明的视觉检测

IF 6 2区化学 Q1 CHEMISTRY, ANALYTICAL

Analytica Chimica Acta

Pub Date : 2025-12-06 DOI: 10.1016/j.aca.2025.344970

Faezeh Shahdost-Fard , Zeynab Khorablou , Habib Razmi , Maliheh Arhami

Background

Methamphetamine (MAMP) is an arousing addictive drug and its close tracing in human biofluids or suspected shipments to diagnose poisoning or aid in its induced death investigation is legally important. This study presents a rapid and visual measurement of MAMP based on a novel platform involving the electrochromic properties of polyaniline (PANI). PANI film has been electrochemically deposited on the surface of indium tin oxide (ITO) to achieve the desired electrochromic behavior and also embed a suitable platform for the attachment of the aptamer (Apt) as the bioreceptor for MAMP with high affinity.

Results

For the first time, an electrochromic aptasensing interface, referred to as the Apta-Chip, has been created by combining two electrochemical and optical methods for measuring MAMP. The developed Apta-Chip based on the PANI/ITO surface displays a wide range of colors at close potentials, serving as an electrochromic optical detector. The presence of MAMP on the embedded surface increases the resistance in the circuit, affecting the PANI oxidation states, creating a different electrochromic response that depends on MAMP concentration. Thereby, the optical detection of MAMP is performed with the naked eye, yielding highly favorable outcomes for MAMP monitoring in human serum, urine and saliva samples, as biofluid samples. Compared to conventional MAMP sensors, the proposed Apta-Chip provides a multicolor behavior with vivid tonality from dark blue, green and dark yellow for different MAMP concentrations.

Significance

The molecular dynamics (MD) simulation has been carried out to predict how Apt links to MAMP visually. Additionally, the greenness of the applied methodology has been well evaluated by two international criteria based on the green chemistry principles. The developed Apta-Chip holds promise to reasonably distinguish MAMP with the naked eye in real clinical or street narcotic samples.

甲基苯丙胺（MAMP）是一种令人兴奋的成瘾药物，在人体生物体液或可疑运输中对其进行密切追踪以诊断中毒或协助其诱发死亡的调查具有重要的法律意义。本研究提出了一种基于聚苯胺（PANI）电致变色特性的新平台的MAMP快速可视化测量方法。将聚苯胺薄膜电化学沉积在氧化铟锡（ITO）表面，以获得所需的电致变色行为，并嵌入合适的平台，作为高亲和力的MAMP生物受体适配体（Apt）的附着。结果结合电化学和光学两种测量MAMP的方法，首次建立了电致变色apta感应界面，称为apta芯片。基于聚苯胺/ITO表面开发的apta芯片在接近电位下显示广泛的颜色，可作为电致变色光学探测器。嵌入表面上的MAMP的存在增加了电路中的电阻，影响了聚苯胺的氧化态，产生了不同的电致变色反应，这取决于MAMP的浓度。因此，MAMP的光学检测是用肉眼进行的，对作为生物流体样本的人血清、尿液和唾液样本中的MAMP监测产生了非常有利的结果。与传统的MAMP传感器相比，所提出的Apta-Chip提供了多色行为，具有鲜明的色调，从深蓝色，绿色和暗黄色到不同的MAMP浓度。意义通过分子动力学（MD）模拟直观地预测了Apt与MAMP的连接方式。此外，基于绿色化学原理的两个国际标准对应用方法的绿色度进行了很好的评价。开发的Apta-Chip有望在真实的临床或街头麻醉品样品中用肉眼合理地区分MAMP。

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引用次数: 0

Development of a high-throughput LLE-UPLC-QqQ-MS/MS method and comprehensive profiling of urinary steroid hormones in Chinese elderly adults 高通量LLE-UPLC-QqQ-MS/MS方法的建立及中国老年人尿类固醇激素的综合分析

IF 6 2区化学 Q1 CHEMISTRY, ANALYTICAL

Analytica Chimica Acta

Pub Date : 2025-12-06 DOI: 10.1016/j.aca.2025.344994

Xiao Ma , Huimin Ren , Li Zhao , Xiaojie Guo , Jiran Zhang , Juan Liu , Xiaona Wang , Mengyao Wang , Yifu Lu , Shilu Tong , Hongyang Cui , Hong Chang , Yu'e Cha , Song Tang , Xiaoming Shi

Background

Steroid hormones (SHs) in human urine are critical for understanding physiological processes, but their analysis is challenged by intricate urine matrices and diverse SHs physicochemical properties. Existing methods often lack sensitivity, throughput, or comprehensiveness for simultaneous qualitative and quantitative profiling. Thus, there is a need for a state-of-the-art, ultra-sensitive, high-throughput method to comprehensively and simultaneously characterize urinary SHs.

Results

The improved liquid-liquid extraction (LLE) and ultra-performance liquid chromatography coupled with triple quadrupole tandem mass spectrometry (UPLC-QqQ-MS/MS) method, developed by optimizing mass spectrum parameters and pretreatment conditions to address urine matrix complexity and SHs diversity, identified 133 SHs and quantified 103. The improved experimental protocol was as follows: sample volume, 1 mL; extraction solvent, methyl tert-butyl ether/ethyl acetate (MTBE/EtAc, 1/1, v/v); solvent volume, 2 mL; extraction times, 2; pH, 9; enzyme activity, 1700 U/mL; eluent A, water; eluent B, methanol. Post-extraction samples were analyzed using UPLC-QqQ-MS/MS, with quantification of method-validated SHs reliably performed through internal standards (ISs) calibration. Validated metrics included excellent linearity (R² > 0.990, 1–500 ng/mL), the method detection/quantitation limit (MDL, 0.003–0.740 ng/mL; MQL, 0.01–2.465 ng/mL), matrix effects (ME, −0.46 %–46.56 %), recoveries (72.31 %–129.80 %), and precision/stability (RSDs <20 %). Applied to 76 elderly adults, it revealed gender-specific temporal variations, with significant 5-month declines in androgens and glucocorticoids.

Significance

This method enables comprehensive, sensitive urinary SHs profiling, offering a powerful tool for in-depth research on elderly hormonal dynamics. Its ability to capture gender and temporal variations enhances understanding of age-related hormonal changes.

人类尿液中的类固醇激素（SHs）对于理解生理过程至关重要，但它们的分析受到复杂的尿液基质和SHs不同的物理化学性质的挑战。现有的方法往往缺乏敏感性，吞吐量或全面性，同时定性和定量分析。因此，需要一种先进的、超灵敏的、高通量的方法来全面、同时地表征尿源性SHs。结果通过优化质谱参数和预处理条件，建立了改进的液液萃取-超高效液相色谱-三重四极杆串联质谱（UPLC-QqQ-MS/MS）方法，鉴定出133种SHs，定量103种SHs。改进后的实验方案为：进样量1 mL；萃取溶剂：甲基叔丁基醚/乙酸乙酯（MTBE/EtAc, 1/1, v/v）；溶剂体积：2ml；提取次数，2次；pH值,9;酶活性，1700 U/mL；A、水；洗脱液B，甲醇。提取后样品采用UPLC-QqQ-MS/MS进行分析，通过内标（ISs）校准可靠地定量方法验证的SHs。验证指标包括良好的线性关系（R2 > 0.990, 1-500 ng/mL），方法检测/定量限（MDL, 0.003-0.740 ng/mL； MQL, 0.01-2.465 ng/mL），基质效应（ME, - 0.46% - 46.56%），回收率（72.31% - 129.80%），精密度/稳定性（rsd < 20%）。对76名老年人进行研究后发现，男性和糖皮质激素在5个月内显著下降。意义该方法可实现全面、灵敏的尿SHs谱分析，为深入研究老年人激素动态提供有力工具。它捕捉性别和时间变化的能力增强了对年龄相关激素变化的理解。

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引用次数: 0

Radiometrically characterised ultraviolet light-emitting diode (UVLED) based micro-photoreactors for rapid, safe and portable screening of organic peroxide explosives 基于辐射特性的紫外发光二极管（UVLED）微光反应器用于快速、安全、便携地筛选有机过氧化物炸药

IF 6 2区化学 Q1 CHEMISTRY, ANALYTICAL

Analytica Chimica Acta

Pub Date : 2025-12-06 DOI: 10.1016/j.aca.2025.344992

Chowdhury Kamrul Hasan , Fazria Tanjum , Parvez Mahbub

Background

Screening organic peroxide explosives (OPEs) such as hexamethylene triperoxide diamine (HMTD), methyl ethyl ketone peroxide (MEKP), and triacetone triperoxide (TATP) from ambient interferents (e.g. household H₂O₂, perfume, and nail polish remover) at the security heightened areas has been a significant challenge for the security authorities worldwide. The present research aims to overcome this challenge for the first time by integrating a UV LED based micro-photoreactor with an in-house developed stabilising reagent to screen the OPEs from household H₂O₂.

Results

Since OPEs along with H₂O₂ upon their exposure to UV radiation spontaneously generate peroxy moieties and radicals, the aqueous stabilising reagent, composed of dimethyl sulfoxide (100 mM), sodium thiosulfate (100 μM), and cobalt chloride (10 μM), was developed to effectively stabilise these peroxy moieties. We confirmed this stabilising phenomenon by investigating GC-MS profile of OPE samples with/without activating the micro-photoreactor, revealing controlled stabilisation of photodegradation products from MEKP and significant stabilisation of those from HMTD and TATP. Notably, we observed how the swabs of OPEs from skin surfaces, when immersed in the screening reagent prior to their transfer via the active micro-photoreactor (driven with radiometrically optimised parameters e.g., 800 KHz, 3.3 V, and 0.13 Amp), enabled flow injection analysis-chemiluminescence (FIA-CL) signals remarkably distinguishable from that of H₂O₂ within 10 s.

Significance and novelty

We present a novel screening mechanism of OPEs from household products using in-house developed and radiometrically characterised UVLED based portable micro-photoreactors as well as stabilising reagent to stabilise the photodegradation of OPEs. This study affords selective and ultra-trace level of screening of HMTD (0.12 μM, n = 3, RSD 6 %), MEKP (0.08 μM, n = 3, RSD 6 %) and TATP (0.16 μM, n = 3, RSD 7 %) from H₂O₂, highlighting its potential for real-world explosive screening applications in security heightened settings in a rapid, safe, and effective manner.

背景：在安全警戒区域筛选有机过氧化物炸药（OPEs），如六亚甲基三过氧化物二胺（HMTD）、甲基乙基过氧化物酮（MEKP）和三过氧化物三丙酮（TATP）免受环境干扰（例如家用H2O2、香水和洗甲水）一直是世界各地安全当局面临的重大挑战。目前的研究旨在首次克服这一挑战，将基于UV LED的微光反应器与内部开发的稳定试剂集成在一起，以筛选家用H2O2中的OPEs。结果由于OPEs与H2O2在紫外线照射下会自发产生过氧基团和自由基，因此制备了由二甲亚砜（100 mM）、硫代硫酸钠（100 μM）和氯化钴（10 μM）组成的水稳定剂，可以有效地稳定这些过氧基团。我们通过研究有/没有激活微光反应器的OPE样品的GC-MS谱证实了这种稳定现象，揭示了MEKP光降解产物的可控稳定性以及HMTD和TATP的显著稳定性。值得注意的是，我们观察到皮肤表面的OPEs，在通过有源微光反应器（由辐射优化参数驱动，例如800 KHz， 3.3 V和0.13安培）转移之前浸泡在筛选试剂中，如何在10秒内使流动注射分析-化学发光（FIA-CL）信号与H2O2显著区分。我们提出了一种从家用产品中筛选OPEs的新机制，该机制使用了自主开发的基于UVLED的便携式微光反应器和稳定试剂来稳定OPEs的光降解。本研究提供了H2O2对HMTD （0.12 μM, n = 3, RSD 6%）、MEKP （0.08 μM, n = 3, RSD 6%）和TATP （0.16 μM, n = 3, RSD 7%）的选择性和超痕量筛选，突出了其在现实世界中快速、安全、有效地筛选爆炸物的潜力。

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引用次数: 0