Analytica Chimica Acta最新文献_第5页

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

Bioorthogonally activatable methylene blue platform for selective prodrug activation and fluorescent imaging in living systems 生物正交激活亚甲基蓝平台选择性前药激活和荧光成像的生命系统

IF 6 2区化学 Q1 CHEMISTRY, ANALYTICAL

Analytica Chimica Acta

Pub Date : 2025-12-05 DOI: 10.1016/j.aca.2025.344988

Linlin Yang , Shiqiong Bai , Yuqing Nie , Yixuan Li , Fei Xin , Panpan Song , Na Gao , Liguo Ji , Lili Li , Guangjie He

Background

The development of fluorescent prodrugs based on bioorthogonal chemistry involves broadening the range of fluorophores that exhibit changes in fluorescence signals and the spatiotemporally regulated release of therapeutic agents upon biorthogonal ligation. However, there are still certain gaps including shallow tissue-penetrating and low drug release efficiency, which limit its application.

Results

Herein, we present a flexible and effective bioorthogonal scaffold that allows targeted medication release with simultaneous fluorescence emission when the targeting groups or prodrugs are conjugated. The scaffold consists of a tetrazine-caged methylene blue (MB-Tz), which serves as a dual switch for the activation of fluorophore and drug. Further encountering the TCO-caged molecular partner (TCO-RGD or TCO-Dox) triggers the NIR fluorescence reinstatement and simultaneously leads to spatiotemporal targeting and selective activation of prodrugs inside cancer cells. It was also demonstrated that bioorthogonal activation successfully inhibited tumor growth by controlled activation in vivo, with minimal systemic toxicity observed.

Significance

We envision that integration of fluorescence and bioorthogonal reactions will serve as a general small-molecule-based strategy for precisely targeted imaging and treatment in chemotherapy.

基于生物正交化学的荧光前药的开发涉及到扩大荧光信号变化的荧光团范围和双正交连接后治疗剂的时空调节释放。但其组织穿透性较浅，药物释放效率较低，存在一定的差距，限制了其应用。结果制备了一种灵活有效的生物正交支架，当靶向基团或前药偶联时，该支架可实现靶向药物释放并同时发出荧光。该支架由四氮笼亚甲基蓝（MB-Tz）组成，作为激活荧光团和药物的双重开关。进一步遇到tco笼中的分子伴侣（TCO-RGD或TCO-Dox）触发近红外荧光恢复，同时导致癌细胞内前体药物的时空靶向和选择性激活。研究还表明，生物正交激活在体内通过控制激活成功地抑制肿瘤生长，并且观察到最小的全身毒性。我们设想，荧光和生物正交反应的整合将作为一种基于小分子的精确靶向成像和化疗治疗策略。

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引用次数: 0

Synergistic Integration of Multidimensional Differential Spectroscopy and Deep Learning for Robust Phenol Monitoring in Complex Industrial Effluents 多维微分光谱和深度学习协同集成用于复杂工业废水中苯酚的鲁棒监测

IF 6.2 2区化学 Q1 CHEMISTRY, ANALYTICAL

Analytica Chimica Acta

Pub Date : 2025-12-05 DOI: 10.1016/j.aca.2025.344989

Junru Zhang, Ying Chen, Junfei Liu, Wanwen Li, Liyong Niu, Qiguang Zhu

Background

Phenol is a key chemical intermediate and a common, toxic pollutant found in industrial wastewater from processes like coking and oil refining. Its leakage and discharge lead to significant contamination, posing a dual threat to ecological systems and human health, making its accurate, real-time monitoring paramount. Current detection methods have significant drawbacks. Chemical sensors can have long response times or insufficient accuracy. Standard optical methods like chromatography are cumbersome and ill-suited for rapid, on-site use. Simple UV-Vis spectroscopy is severely compromised by overlapping spectral interference and environmental instability in complex water samples.

Results

The strategy first leverages phenol's specific bromination to selectively eliminate its spectral signature. A custom dual-channel, variable-path (1-10 cm) system was built to capture this transformation, generating high-dimensional (3D) differential spectral matrices. This 3D data approach reduced the Mean Absolute Error (MAE) by 45.4% compared to conventional 1D spectra (when using the same CNN model). For analysis, a novel Parallel Associative Neural Network (PSNN) was developed, which substantially outperformed a standard CNN by achieving a further 66.7% reduction in MAE. This integrated strategy (3D+PSNN) yielded a final prediction error of 72.09 μg/L under laboratory conditions and an MAE of 172.9 μg/L in field tests against HPLC benchmarks.

Significance and Novelty

This study presents a novel strategy integrating chemical selectivity, multidimensional optical sensing, and a custom Parallel Associative Neural Network (PSNN). The work provides a robust framework for developing highly selective and sensitive intelligent systems for on-line water quality monitoring. The practicality and stability of this integrated approach in complex environments were validated through temperature control experiments and field tests on real industrial wastewater.

苯酚是一种关键的化学中间体，也是焦化和炼油等过程中工业废水中常见的有毒污染物。它的泄漏和排放导致严重污染，对生态系统和人类健康构成双重威胁，因此对其进行准确、实时的监测至关重要。目前的检测方法有明显的缺陷。化学传感器可能有较长的响应时间或准确性不足。标准的光学方法，如色谱法，是繁琐的，不适合快速，现场使用。简单的紫外可见光谱在复杂水样中受到重叠光谱干扰和环境不稳定性的严重损害。结果该策略首先利用苯酚的特异性溴化来选择性地消除其光谱特征。一个定制的双通道，可变路径（1-10厘米）系统被建立来捕捉这种转换，生成高维（3D）微分光谱矩阵。与传统的一维光谱（使用相同的CNN模型）相比，这种3D数据方法将平均绝对误差（MAE）降低了45.4%。为了进行分析，开发了一种新的并行关联神经网络（PSNN），该网络通过进一步降低66.7%的MAE，大大优于标准CNN。该综合策略（3D+PSNN）在实验室条件下的最终预测误差为72.09 μg/L，在HPLC基准的现场测试中，MAE为172.9 μg/L。意义与新颖性本研究提出了一种集成化学选择性、多维光学传感和定制并行关联神经网络（PSNN）的新策略。这项工作为开发高选择性和高灵敏度的智能水质在线监测系统提供了一个强大的框架。通过温度控制实验和实际工业废水的现场测试，验证了该综合方法在复杂环境下的实用性和稳定性。

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引用次数: 0

Multilayer Ag–Au–BP–TIBr–FASnI3 Kretschmann surface plasmon resonance biosensor for high sensitivity refractive index analysis: A computational and machine learning approach 用于高灵敏度折射率分析的多层Ag-Au-BP-TIBr-FASnI3 Kretschmann表面等离子体共振生物传感器：一种计算和机器学习方法

IF 6 2区化学 Q1 CHEMISTRY, ANALYTICAL

Analytica Chimica Acta

Pub Date : 2025-12-05 DOI: 10.1016/j.aca.2025.344991

Ajith.B. Singh , Alavudeen Basha A , Arun Kumar U , Azath Mubarakali

Detection of refractive-index variations is fundamental for the development of next-generation optical sensing platforms capable of supporting future biomedical and chemical monitoring applications. Surface plasmon resonance (SPR) biosensing enables label-free, real-time detection but often faces limits in sensitivity, specificity, and stability. This work introduces a Kretschmann-based SPR biosensor that combines a multilayer stack of silver (Ag), gold (Au), and advanced functional materials including black phosphorus (BP), thallium bromide (TIBr) and formamidinium tin iodide (FASnI₃). Hemoglobin is employed only as a model analyte to evaluate resonance shifts arising from bulk refractive-index variations within the range of 1.33–1.40 RIU. Numerical modeling using COMSOL Multiphysics and transfer matrix analysis showed performance metrics with sensitivities from 145 to 375°/RIU, figure of merit values up to 34.404, and quality factors between 6.450 and 7.917 within a refractive index range of 1.33–1.40 RIU. Optimization demonstrated that Ag thickness of 30–35 nm and functional layer thickness of 1.3–3.5 nm supports deep resonance dips with minimized ohmic losses. Electric-field distribution analysis demonstrates strong plasmon-induced field confinement near the sensing interface, with peak |E| intensities of approximately 2.4 × 10⁵ V/m. Machine learning models predicted sensor behavior across different thicknesses and environmental conditions with coefficients of determination (R²) above 0.979 for layer thickness and 0.985 for refractive index. The resulting design offers high sensitivity refractive-index sensing, broad response range, and provide a foundation for future integration of biochemical functionalization toward selective biomarker detection.

检测折射率变化是下一代光学传感平台开发的基础，能够支持未来生物医学和化学监测应用。表面等离子体共振（SPR）生物传感能够实现无标签、实时检测，但往往面临灵敏度、特异性和稳定性的限制。这项工作介绍了一种基于kretschmann的SPR生物传感器，它结合了银（Ag）、金（Au）的多层堆叠，以及先进的功能材料，包括黑磷（BP）、溴化铊（TIBr）和碘化甲脒锡（FASnI3）。血红蛋白仅被用作模型分析物，以评估在1.33-1.40 RIU范围内由体折射率变化引起的共振位移。利用COMSOL Multiphysics进行数值模拟和传递矩阵分析表明，在1.33-1.40 RIU折射率范围内，灵敏度为145 ~ 375°/RIU，品质系数为34.404，质量因子为6.450 ~ 7.917。优化结果表明，银层厚度为30 ~ 35 nm，功能层厚度为1.3 ~ 3.5 nm，可实现深度共振衰减，且欧姆损失最小。电场分布分析表明，在传感界面附近有强等离子体诱导的场约束，峰值|E|强度约为2.4 × 105 V/m。机器学习模型预测传感器在不同厚度和环境条件下的行为，层厚的决定系数（R2）大于0.979，折射率的决定系数（0.985）大于0.985。由此产生的设计具有高灵敏度的折射率传感，宽响应范围，并为未来整合生化功能化选择性生物标志物检测奠定了基础。

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引用次数: 0

Towards fiber optic chemical sensors for 1,3-butadiene detection in Titan's hydrocarbon lakes 用于探测土卫六碳氢化合物湖中1,3-丁二烯的光纤化学传感器

IF 6 2区化学 Q1 CHEMISTRY, ANALYTICAL

Analytica Chimica Acta

Pub Date : 2025-12-04 DOI: 10.1016/j.aca.2025.344982

Diogo Gonçalves , Cláudia Ribeiro , João P.C. Tomé , Bruno Pedras , Zita Martins

Background

Fiber optic chemical sensors (FOCS) can be rapidly integrated in future instrument suites for in-situ extraterrestrial chemical characterizations. At low development and deployment costs, they can complement the analysis of more capable instruments. The contribution of FOCS can best be exemplified by the detection of 1,3-butadiene in Titan. This analyte is an unsaturated hydrocarbon of relevance for Titan's atmospheric chemistry and geology, but its detection poses challenges for current spectroscopy and mass spectrometry space instruments. Here, we report the design of the sensing core of a future space-mission-ready FOCS tailored to detect 1,3-butadiene in Titan's hydrocarbon environments.

Results

We report the discovery and characterization of the first fluorescent indicator for 1,3-butadiene. The off-on detection strategy is based on an inverse electron demand Diels-Alder click-reaction between the analyte and a tetrazine indicator, yielding emissive 1,4-dihydropyridazine derivatives, as confirmed by NMR. Excitation above 415 nm enables the selective detection of 1,3-butadiene against competing unsaturated hydrocarbons present in Titan. The sensor exhibited a limit of detection of 1.1 ppm (mol mol⁻¹) and a linear response up to the expected saturation concentration in Titan's lakes. Furthermore, the fast and irreversible reaction between the tetrazine indicator and 1,3-butadiene provides rapid sensor responses that increase with temperature. Operating the sensor at high temperatures also mitigates competing photobleaching reactions. The immobilization of the indicator in polystyrene membranes maintained its detection capability for 1,3-butadiene dissolved in hexane, an apolar solvent analogous to Titan's hydrocarbon lakes.

Significance

The demonstration of the solid-state functionality of the indicator marks the last step towards its integration with space-qualified instrumentation. This proof-of-principle detection of 1,3-butadiene highlights the potential of fluorescence sensing for probing exotic planetary environments. Fiber optic architectures are ideal platforms for adapting fluorescence-based chemical sensing strategies to the in-situ characterization of extraterrestrial sites.

光纤化学传感器（FOCS）可以快速集成到未来的仪器套件中，用于原位地外化学表征。在较低的开发和部署成本下，它们可以补充更有能力的仪器的分析。土卫六中1,3-丁二烯的检测最能说明FOCS的贡献。这种分析物是一种与土卫六大气化学和地质相关的不饱和碳氢化合物，但它的探测对目前的光谱和质谱空间仪器构成了挑战。在这里，我们报告了未来太空任务准备的FOCS的传感核心的设计，该FOCS专门用于探测土卫六碳氢化合物环境中的1,3-丁二烯。结果报道了首个1,3-丁二烯荧光指示剂的发现和表征。检测策略是基于被分析物和四嗪指示剂之间的反电子需求Diels-Alder点击反应，产生经核磁共振证实的发射性1,4-二氢吡啶衍生物。415 nm以上的激发可以选择性地检测泰坦中存在的1,3-丁二烯与竞争的不饱和碳氢化合物。该传感器的检测限为1.1 ppm (mol mol−1)，线性响应达到土卫六湖泊中预期的饱和浓度。此外，四氮指示剂与1,3-丁二烯之间的快速不可逆反应提供了快速的传感器响应，随温度升高而增加。在高温下操作传感器也减轻了相互竞争的光漂白反应。该指示剂固定在聚苯乙烯膜中，保持了对溶解在己烷中的1,3-丁二烯的检测能力，己烷是一种类似于泰坦碳氢化合物湖的极性溶剂。该指示器固态功能的演示标志着其与空间合格仪器集成的最后一步。这种1,3-丁二烯的原理验证检测突出了荧光传感探测外来行星环境的潜力。光纤架构是适应基于荧光的化学传感策略的理想平台，用于地外地点的原位表征。

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引用次数: 0

Ultra-sensitive optical fiber SPR biosensor for assisted diagnosis of prostate cancer by label-free detection of miRNA-21 超灵敏光纤SPR生物传感器通过无标记检测miRNA-21辅助诊断前列腺癌

IF 6 2区化学 Q1 CHEMISTRY, ANALYTICAL

Analytica Chimica Acta

Pub Date : 2025-12-04 DOI: 10.1016/j.aca.2025.344985

Jiale Wang , Minghua Deng , Chuanquan Wang , Kunpeng Niu , Ning Wang , Jinhua Li , Binyun Xia , Liyun Ding , Huan Yang , Xiaohan Chen , Jiayi Zhu

Background

Efficient and rapid identification of trace amounts of microRNA-21 (miRNA-21), an oncogenic miRNA, is conducive to the early diagnosis of prostate cancer. Despite extensive research efforts, the development of biosensors capable of achieving clinically relevant sensitivity and limits of detection (LOD) remains challenging, primarily due to the ultralow physiological concentrations of cancer biomarkers in human biological systems. Beyond that, the suboptimal probe designs such as complex sensing structures and unstable sensing materials collectively lead to inadequate repeatability and stability for clinical application.

Results

Hence, in this work, a label-free and highly sensitive optical fiber Surface Plasmon Resonance (SPR) biosensor with ultralow LOD was developed for detecting miRNA-21, which was fabricated simply by coating a layer of Au film and gold nanoparticles (AuNPs) onto a multimode-single-mode-multimode (MSM) optical fiber, and then biofunctionalized with optimized single-stranded DNA (ssDNA) enabling the quantification of miRNA-21. Excitingly, the biosensors, which have a simple composition and demonstrated with excellent linearity, specificity and stability, were experimentally verified to reach an ultra-low LOD of 1.86 × 10^–19 M that significantly lower than current detection method and high sensitivity of 3021.48 RIU/nm. And detection of trace miRNA-21 was enabled without RNA amplification. The sensor's capability to effectively differentiate prostate cancer patients from healthy controls was demonstrated by testing clinical serum samples and the sensor achieved higher detection accuracy compared to the commonly used clinical prostate-specific antigen (PSA) quantification.

Significance

The proposed sensing platform processes the merits of simple configuration as well as low cost and has potential to auxiliary early-stage diagnosis of various cancers by detecting associated biomarkers.

背景微量的microRNA-21 （miRNA-21）是一种致癌miRNA，缺乏和快速的鉴定有助于前列腺癌的早期诊断。尽管进行了大量的研究工作，但能够达到临床相关灵敏度和检测限（LOD）的生物传感器的开发仍然具有挑战性，这主要是由于人类生物系统中癌症生物标志物的生理浓度极低。除此之外，不理想的探针设计，如复杂的传感结构和不稳定的传感材料，共同导致临床应用的可重复性和稳定性不足。结果通过在多模-单模-多模（MSM）光纤表面包覆一层Au膜和金纳米粒子（AuNPs），利用优化后的单链DNA （ssDNA）进行生物功能化处理，制备了一种低LOD、无标记、高灵敏度的光纤表面等离子体共振（SPR）生物传感器，用于miRNA-21的检测。令人兴奋的是，该生物传感器组成简单，具有良好的线性、特异性和稳定性，实验验证了该传感器的超低LOD为1.86×10-19 M，显着低于现有检测方法，灵敏度为3021.48 RIU/nm。并且痕量miRNA-21无需RNA扩增即可检测。通过测试临床血清样本，该传感器能够有效区分前列腺癌患者和健康对照，与常用的临床前列腺特异性抗原（PSA）定量相比，该传感器的检测精度更高。该传感平台具有结构简单、成本低等优点，具有通过检测相关生物标志物辅助各种癌症早期诊断的潜力。

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引用次数: 0

Lipid droplet-targeted and ratiometric fluorescent probe for imaging ClO− in Rheumatoid arthritis model 靶向脂滴和比例荧光探针在类风湿关节炎模型中的ClO-成像研究

IF 6 2区化学 Q1 CHEMISTRY, ANALYTICAL

Analytica Chimica Acta

Pub Date : 2025-12-04 DOI: 10.1016/j.aca.2025.344990

Peng Lei , Pengjia Wei , Lingjie Hou , Chuan Dong , Shaomin Shuang , Ruifang Wang

Background

Rheumatoid arthritis (RA) is a long-term, systemic autoimmune disease that primarily affects the synovial joints, causing chronic inflammation and eventual joint destruction. The underlying cause of RA is strongly associated with the excessive production of hypochlorite (ClO⁻). Increased levels of ClO⁻ can lead to oxidative damage in cells, playing a crucial role in the development and progression of the disease. Despite advances in research, detecting RA at its early stages remains difficult, especially since existing ratiometric fluorescent probes face significant challenges in accurately identifying changes in ClO⁻ levels.

Results

To address this challenge, a new fluorescence probe, PT, was designed and synthesized for the detection and imaging of ClO⁻. The design of PT incorporates an electron-rich phenothiazine core, which acts as both the recognition site and electron donor for ClO⁻, while the benzothiazole unit serves as the electron acceptor. This creates a donor-π-acceptor structure that produces a clear ratiometric fluorescence signal at 490/664 nm. Notably, PT exhibits aggregation-induced emission (AIE) properties, demonstrating strong affinity for the co-localization imaging of lipid droplets, allowing for effective visualization of ClO⁻ in lipid droplets in living organisms. Moreover, PT was successfully used to detect elevated ClO⁻ levels in a collagen-induced arthritis (CIA) mouse model, indicating that ClO⁻ could serve as a potential biomarker for the diagnosis of RA.

Significance

The fluorescent probe PT offers a highly effective and reliable tool for imaging of the Rheumatoid arthritis with its excellent ratiometric fluorescence response and AIE properties. The unique ratiometric nature of PT allows for precise detection of ClO⁻ levels in the RA mice model, while AIE characteristics of PT enable clear imaging and visualization of key pathological features in vivo.

类风湿性关节炎（RA）是一种长期的系统性自身免疫性疾病，主要影响滑膜关节，引起慢性炎症和最终的关节破坏。类风湿性关节炎的根本原因与次氯酸盐（ClO-）的过量产生密切相关。ClO-水平升高可导致细胞氧化损伤，在疾病的发生和发展中起着至关重要的作用。尽管研究取得了进展，但在早期阶段检测RA仍然很困难，特别是因为现有的比例荧光探针在准确识别ClO水平变化方面面临重大挑战。结果为解决这一难题，设计并合成了一种用于ClO-检测和成像的新型荧光探针PT。PT的设计包含一个富电子的吩噻嗪核，作为ClO-的识别位点和电子供体，而苯并噻唑单元作为电子受体。这创造了一个供体-π-受体结构，产生一个清晰的比例荧光信号在490/664纳米。值得注意的是，PT具有聚集诱导发射（AIE）特性，对脂滴的共定位成像具有很强的亲和力，可以有效地可视化生物体中脂滴中的ClO-。此外，PT被成功用于检测胶原诱导关节炎（CIA）小鼠模型中升高的ClO-水平，表明ClO-可以作为诊断RA的潜在生物标志物。荧光探针PT以其优异的比例荧光响应和AIE特性，为类风湿关节炎的影像学诊断提供了一种高效可靠的工具。PT独特的比例特性可以精确检测RA小鼠模型中的ClO-水平，而PT的AIE特性可以清晰地成像和可视化体内关键病理特征。

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引用次数: 0

Construction of WO3/InWO4 heterojunction for NO2 detection at room temperature under UV activation 紫外活化下室温NO2检测用WO3/InWO4异质结的构建

IF 6 2区化学 Q1 CHEMISTRY, ANALYTICAL

Analytica Chimica Acta

Pub Date : 2025-12-04 DOI: 10.1016/j.aca.2025.344938

Zhihua Ying , Yi Zhong , Yan Liu , Wenjun Yan

Background

Nitrogen dioxide (NO₂) is a hazardous atmospheric pollutant, driving demand for highly sensitive and reliable monitoring sensors. A significant challenge in this field is enhancing the performance of metal-oxide-based gas sensors, particularly their response and operating temperature. Current materials often exhibit insufficient sensitivity at room temperature, limiting their practical application. This work addresses the problem of developing a high-performance NO₂ gas sensor that operates effectively at room temperature.

Results

We present a novel WO₃/InWO₄ heterojunction sensor that demonstrates dramatically enhanced NO₂ sensing under UV activation. The key result is a response value of 116.03 to 3 ppm NO₂ at room temperature, which is 3.55 times higher than that of a pure InWO₄ sensor. The composite sensor showed a response time of 68 s and a recovery time of 43 s, representing a slight increase and decrease, respectively, compared to the pure material. This performance is attributed to the synergistic effects of the constructed heterojunction, which promotes charge separation, alongside optimized oxygen vacancy concentration and UV light activation. The method was comprehensively validated through material characterization and gas-sensing tests, confirming that this composite structure effectively improves surface reactions with NO₂ molecules.

Significance

This study conclusively demonstrates that the WO₃/InWO₄ heterojunction strategy is highly effective for NO₂ sensing. The significance lies in achieving exceptional sensor response at room temperature, providing a valuable pathway for developing low-power, high-performance gas sensing devices.

二氧化氮（NO2）是一种有害的大气污染物，推动了对高灵敏度和高可靠性监测传感器的需求。该领域的一个重大挑战是提高金属氧化物气体传感器的性能，特别是它们的响应和工作温度。目前的材料在室温下往往表现出不够的灵敏度，限制了它们的实际应用。这项工作解决了开发在室温下有效工作的高性能二氧化氮气体传感器的问题。结果我们设计了一种新型的WO3/InWO4异质结传感器，该传感器在紫外激活下对NO2的传感能力显著增强。关键结果是室温下的响应值为116.03 ~ 3ppm NO2，比纯InWO4传感器高3.55倍。复合传感器的响应时间为68 s，恢复时间为43 s，与纯材料相比，分别略有增加和减少。这种性能归因于构建的异质结的协同效应，它促进了电荷分离，同时优化了氧空位浓度和紫外光活化。通过材料表征和气敏测试对该方法进行了全面验证，证实该复合结构有效改善了与NO2分子的表面反应。本研究最终证明了WO3/InWO4异质结策略对NO2传感是非常有效的。其意义在于在室温下实现了优异的传感器响应，为开发低功耗、高性能的气体传感器件提供了有价值的途径。

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引用次数: 0