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A dual state emission luminogen based on the 1,3,3-trimethylindoline and chroman-2,4-dione conjugate for highly selective dual channel detection of cyanide ions† 一种基于 1,3,3-三甲基吲哚啉和色烷-2,4-二酮共轭物的双态发射光源,用于高选择性双通道检测氰离子
IF 3.5 Q2 CHEMISTRY, ANALYTICAL Pub Date : 2024-08-02 DOI: 10.1039/D4SD00155A
Snehadrinarayan Khatua, Sumit Kumar Patra, Monosh Rabha, Deikrisha Lyngdoh Lyngkhoi, Jogat Gogoi and Bhaskar Sen

Dual state emission luminogens (DSEgens) with strong fluorescence in both solution and solid states have extensive potential for numerous applications. Herein, a chroman-2,4-dione and indoline conjugate, 2, was synthesized for highly selective and sensitive turn-on fluorescent detection of cyanide ions. Compound 2 behaves as a molecular rotor and shows the dual state emission (DSE) phenomenon and multicolour emission. It displays bright fluorescence in both the concentrated solution and the solid-state. The compound is nonfluorescent in dilute solution, and with increasing concentration, it shows aggregation caused red-shifted emission. With increasing concentration, the emission colour changes from green to yellow to orange-red. The CC bond attached to the indoline moiety is a compelling target for nucleophilic addition. Cyanide ions reacted with the probe which remarkably changed the spectroscopic properties. With the gradual addition of cyanide, the colour of the probe solution was changed from yellow to colorless. The very weakly emissive probe 2 rapidly reacted with CN and emitted strongly due to the inhibition of internal charge transfer (ICT) from indoline to chroman-2,4-dione. The DSEgen properties and CN sensing were thoroughly investigated and supported using spectroscopic studies, TDDFT, and single-crystal X-ray diffraction.

在溶液和固体状态下都具有强荧光的双态发射荧光剂(DSEgen)具有广泛的应用潜力。本文合成了一种铬-2,4-二酮和吲哚啉共轭物 2,用于高选择性和高灵敏度的氰离子荧光检测。化合物 2 表现为分子转子,具有双态发射(DSE)现象和多色发射。它在浓溶液和固态下都能显示出明亮的荧光。该化合物在稀溶液中无荧光,随着浓度的增加,会出现聚集引起的红移发射。随着浓度的增加,发射颜色从绿色变为黄色,再变为橙红色。香豆素分子上的 CC 键是亲核加成的一个重要目标。氰离子与探针发生反应,显著改变了光谱特性。随着氰化物的逐渐加入,探针溶液的颜色从黄色变为无色。由于抑制了从吲哚啉到色满-2,4-二酮的内部电荷转移(ICT),发射性很弱的探针 2 与 CN- 发生了快速反应,并发出强烈的光。利用光谱研究、TDDFT 和单晶 X 射线衍射对 DSEgen 性能和 CN 传感进行了深入研究和支持。
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引用次数: 0
Optimization of solvents, electrolytes, and mediators for polyindole-based electrochemical sensors 基于聚吲哚的电化学传感器
IF 3.5 Q2 CHEMISTRY, ANALYTICAL Pub Date : 2024-08-02 DOI: 10.1039/D4SD00175C
P. C. Pandey, Atul Kumar Tiwari and Roger J. Narayan

Surface-engineered conducting polymers (CPs) have enabled technological advances in chemistry and materials science. Heterocyclic conjugated organic molecules, specifically indole and its derivatives, have the potential to be polymerized under electrochemically controlled conditions in different types of compatible solvent media, including self-assembled nanofluids, for several applications. Polymer-based electrode materials are valuable for the detection of various targeted biomolecules and other analytes. This review outlines the evolution of the electropolymerization technique in recent years, along with developments in the field. With advances in nanoscience, several materials have been used to modify CPs for electrochemical sensing. Several biomedical applications and the role of antifouling agents in the properties of several electropolymerized thin films are highlighted.

表面工程导电聚合物(CP)推动了化学和材料科学的技术进步。杂环共轭有机分子,特别是吲哚及其衍生物,有可能在电化学控制条件下在不同的兼容溶剂介质中聚合,包括用于多种应用的自组装纳米流体。基于聚合物的电极材料对于检测各种目标生物分子或其他分析物具有重要价值。本综述概述了近年来电聚合技术的演变以及该领域的发展。随着纳米科学的发展,有多种材料被用于电化学传感方法的 CPs 改性。重点介绍了几种生物医学应用以及防污剂对几种电聚合薄膜特性的作用。
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引用次数: 0
Electrochemical detection of tumor cells based on proximity labelling-assisted multiple signal amplification† 基于近距离标记辅助多重信号放大技术的肿瘤细胞电化学检测技术
IF 3.5 Q2 CHEMISTRY, ANALYTICAL Pub Date : 2024-08-02 DOI: 10.1039/D4SD00217B
Guozhang Zhou, Fei Zhou, Xiaomeng Yu, Daiyuan Zhou, Jiaqi Wang, Bing Bo, Ya Cao and Jing Zhao

Malignant tumors are the second leading cause of human deaths worldwide, and early cancer screening and diagnosis can effectively reduce cancer mortality. Herein, we propose a new electrochemical method for the highly sensitive detection of MUC1-positive tumor cells based on proximity labelling-assisted multiple signal amplification. Specifically, a MUC1 aptamer-modified electrode was prepared for capturing MUC1-positive tumor cells, followed by binding of G4-DNA strands to the cells with the aid of a mild reduction reaction. A hemin/G4-DNA complex was then formed and acted as a mimic of horseradish peroxidase, catalysing the proximal labelling of tyramine-modified gold nanoparticles to induce silver-enhanced electrochemical signal amplification. Electrochemical results demonstrated that the method was able to specially identify MUC1-positive tumor cells and generate corresponding electrochemical responses in the range of 100 cells per mL to 1 × 106 cells per mL with a detection limit of 21 cells per mL. Furthermore, the method displayed good stability and anti-interference performance in complex serum environments. Therefore, our work may provide an effective tool to improve the accuracy of cell-based tissue examination and liquid biopsy for early diagnosis of cancers in the future.

恶性肿瘤是导致全球人类死亡的第二大原因,早期癌症筛查和诊断可有效降低癌症死亡率。在此,我们提出了一种基于近距离标记辅助多重信号放大的高灵敏度检测 MUC1 阳性肿瘤细胞的新型电化学方法。具体来说,我们制备了用于捕获 MUC1 阳性肿瘤细胞的 MUC1 合物修饰电极,然后借助温和的还原反应将 G4-DNA 链与细胞结合。然后形成血红素/G4-DNA 复合物,作为辣根过氧化物酶的模拟物,催化酪胺修饰金纳米粒子的近端标记,诱导银增强电化学信号放大。电化学结果表明,该方法能专门识别 MUC1 阳性肿瘤细胞,并在 100 个细胞/毫升至 1×106 个细胞/毫升的范围内产生相应的电化学反应,检测限为 21 个细胞/毫升。此外,该方法在复杂的血清环境中显示出良好的稳定性和抗干扰性能。因此,我们的工作可为提高基于细胞的组织检查和液体活检的准确性提供有效工具,从而在未来实现癌症的早期诊断。
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引用次数: 0
Direct writing of graphene electrodes for point-of-care electrochemical sensing applications 直接写入石墨烯电极用于护理点电化学传感应用
IF 3.5 Q2 CHEMISTRY, ANALYTICAL Pub Date : 2024-07-31 DOI: 10.1039/D4SD00140K
Lei Zhao, Andrew Piper, Giulio Rosati and Arben Merkoçi

Electrochemical sensors are increasingly garnering attention as valuable tools for point-of-care (POC) testing due to their low costs, high sensitivities, and ease of miniaturization. Graphene-based materials, renowned for their tunable electrical conductivity, high specific surface areas, versatile functionality, and biocompatibility; are highly suited for the fabrication of electrochemical sensors with heightened sensitivities. Non-contact, maskless, direct writing methods allow the rapid, large-scale production of graphene electrodes with high design flexibility. Researchers globally are advancing graphene electrode production, aiming for smaller, faster, and more efficient sensors. This review provides a comprehensive overview of recent advances on the direct writing of graphene electrodes for electrochemical sensing applications. It covers the basics of direct writing techniques, the advancements in graphene ink/precursor preparation, structural design, and device integration, with a focus on POC platforms.

电化学传感器因其低成本、高灵敏度和易于微型化等特点,正日益受到人们的关注,成为进行床旁(POC)检测的重要工具。石墨烯基材料以其可调导电性、高比表面积、多功能性和生物兼容性而闻名,非常适合制造灵敏度更高的电化学传感器。通过非接触、无掩模、直接写入的方法,可以快速、大规模地生产具有高度设计灵活性的石墨烯电极。全球的研究人员正在推进石墨烯电极的生产,目标是制造出更小、更快、更高效的传感器。本综述全面概述了直接写入石墨烯电极用于电化学传感应用的最新进展。它涵盖了直接写入技术的基础知识、石墨烯墨水/前驱体制备的进展、结构设计和器件集成,重点关注 POC 平台。
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引用次数: 0
Synthesis and characterization of La QDs: sensors for anions and H2O2† La QDs 的合成与表征:阴离子和 H2O2 传感器
IF 3.5 Q2 CHEMISTRY, ANALYTICAL Pub Date : 2024-07-26 DOI: 10.1039/D4SD00142G
Amit Sahoo and Achyuta N. Acharya

The development of sensitive and accurate fluorescence sensors for the detection of anions and reactive oxygen species (ROS, H2O2) is essential as they play significant roles in biological and chemical processes. In this work, semiconductor La QDs were synthesized. The synthesized La QDs were determined to be pure with 100% La element using EDS technique. La QDs were observed in both cubic and hexagonal lattice configurations through powder XRD analysis. The morphology of the La QDs was characterized using HRTEM and FESEM data as tiny, spherical, homogenous QDs with a diameter ranging from 2 to 6 nm. The fluorescence characteristics of the synthesized La QDs were examined by studying their sensing properties that increased with an increase in anion concentration and decreased with an increase in [H2O2]. The variation in emission intensity at 315 nm and 440.5 nm satisfied the Stern–Volmer equation. The LOD and LOQ of H2O2 and anion sensing with La QDs were studied in the μM range. The Langmuir binding plots and FTIR spectra supported the concept that the surface functionalization of La QDs occurred in the presence of anions. With two band gap energies of about 3.26 eV and 4.66 eV, the synthesized La QDs are a mixture of two (binary) semiconductors.

由于阴离子和活性氧(ROS、H2O2)在生物和化学过程中发挥着重要作用,因此开发用于检测阴离子和活性氧的灵敏而准确的荧光传感器至关重要。本研究合成了半导体 La QDs。利用 EDS 技术确定合成的 La QDs 纯度为 100%。通过粉末 XRD 分析,观察到 La QDs 具有立方和六方两种晶格构型。利用 HRTEM 和 FESEM 数据对 La QDs 的形态进行了表征,发现它们是微小、球形、均匀的 QDs,直径在 2 到 6 nm 之间。通过研究合成的 La QDs 的传感特性,考察了它们的荧光特性,即随着阴离子浓度的增加而增加,随着[H2O2]的增加而减少。在 315 nm 和 440.5 nm 处的发射强度变化符合 Stern-Volmer 方程。研究了 La QDs 在 μM 范围内传感 H2O2 和阴离子的 LOD 和 LOQ。朗缪尔结合图和傅立叶变换红外光谱支持了 La QDs 在阴离子存在时发生表面官能化的概念。合成的 La QDs 具有约 3.26 eV 和 4.66 eV 的两个带隙能,是两种(二元)半导体的混合物。
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引用次数: 0
Optimized gadolinium-DO3A loading in RAFT-polymerized copolymers for superior MR imaging of aging blood–brain barrier† 优化 RAFT 聚合共聚物中的钆-DOTA 负载,为老化血脑屏障提供优质磁共振成像
IF 3.5 Q2 CHEMISTRY, ANALYTICAL Pub Date : 2024-07-25 DOI: 10.1039/D4SD00063C
Hunter A. Miller, Aaron Priester, Evan T. Curtis, Krista Hilmas, Ashleigh Abbott, Forrest M. Kievit and Anthony J. Convertine

The development of gadolinium-based contrast agents (GBCAs) has been pivotal in advancing magnetic resonance imaging (MRI), offering enhanced soft tissue contrast without ionizing radiation exposure. Despite their widespread clinical use, the need for improved GBCAs has led to innovations in ligand chemistry and polymer science. We report a novel approach using methacrylate-functionalized DO3A ligands to synthesize a series of copolymers through direct reversible addition-fragmentation chain transfer (RAFT) polymerization. This technique enables precise control over the gadolinium content within the polymers, circumventing the need for subsequent conjugation and purification steps, and facilitates the addition of other components such as targeting ligands. The resulting copolymers were analysed for their relaxivity properties, indicating that specific gadolinium-DO3A loading contents between 12–30 mole percent yield optimal MRI contrast enhancement. Inductively coupled plasma (ICP) measurements corroborated these findings, revealing a non-linear relationship between gadolinium content and relaxivity. Optimized copolymers were synthesized with the claudin-1 targeting peptide, C1C2, to image BBB targeting in aged mice to show imaging utility. This study presents a promising pathway for the development of more efficient GBCA addition to copolymers for targeted drug delivery and bioimaging application.

钆基造影剂(GBCAs)的开发在推动磁共振成像(MRI)方面发挥了关键作用,它能在不暴露于电离辐射的情况下增强软组织造影效果。尽管钆基造影剂已广泛应用于临床,但对改进型钆基造影剂的需求促使配体化学和聚合物科学不断创新。我们报告了一种使用甲基丙烯酸酯功能化 DOTA 配体,通过直接可逆加成-碎片链转移(RAFT)聚合合成一系列共聚物的新方法。这种技术可以精确控制聚合物中的钆含量,省去了后续的共轭和纯化步骤,并有利于添加靶向配体等其他成分。对所得共聚物的弛豫特性进行了分析,结果表明,钆-DOTA 的具体装载量在 12-30 摩尔% 之间,能产生最佳的磁共振成像对比度增强效果。电感耦合等离子体 (ICP) 测量证实了这些发现,揭示了钆含量与弛豫性之间的非线性关系。优化后的共聚物与 claudin-1 靶向肽 C1C2 合成,在老龄小鼠的 BBB 靶向成像中显示出成像效用。这项研究为开发更高效的 GBCA 添加到共聚物中,用于靶向给药和生物成像应用提供了一条前景广阔的途径。
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引用次数: 0
Detection of surfactants using a hydrophobic natural deep eutectic solvent and smartphone† 使用疏水性天然深共晶溶剂和智能手机检测表面活性剂
IF 3.5 Q2 CHEMISTRY, ANALYTICAL Pub Date : 2024-07-24 DOI: 10.1039/D4SD00196F
Vagner Bezerra dos Santos, Lucas B. Ayres, Helayne Santos de Sousa, Carlos D. Garcia and Willian Toito Suarez

We report on the advantages of a green method to detect surfactants in environmental water samples. The approach is based on the use of a hydrophobic natural deep eutectic solvent (NADES) to extract the complexes formed by the surfactants and methylene blue. The concentration of the surfactant is then determined by measuring the color intensity in the organic phase using a smartphone. Under optimized conditions, an aliquot of 3 mL of the NADES was mixed with 15 mL of water, and then allowed to settle (to enable the separation of the two phases) for 5 min. The procedure allowed quantification of sodium dodecyl sulfate (SDS), as a proxy for alkyl surfactants in the range from 0.010 mg L−1 to 0.600 mg L−1, with a detection limit of 2.0 μg L−1. Besides being a simple alternative to the traditional method (which requires chloroform and a spectrophotometer), the proposed approach offers low waste generation, low power-consumption, and fast analysis time, and is fully compatible with the plastic supplies (e.g. cuvettes, pipettes, tips, etc.) typically used for on-site analysis. The applicability of the approach was demonstrated by measuring various surface water samples and the overall green score of the method was calculated to be 96%.

我们报告了一种检测环境水样中表面活性剂的绿色方法的优点。该方法基于使用疏水性天然深共晶溶剂(NADES)来提取表面活性剂与亚甲基蓝形成的复合物。然后使用智能手机测量有机相中的颜色强度,从而确定表面活性剂的浓度。在优化条件下,将等分的 100 µL NADES 与 15 mL 水混合,然后静置 5 分钟(使两相分离)。该方法可定量检测十二烷基硫酸钠(SDS),作为烷基表面活性剂的替代物,检测范围为 0.010 mg L-1 至 0.600 mg L-1,检测限为 2.0 µg.L-1。除了可以简单地替代传统方法(需要氯仿和分光光度计)外,该方法还具有废物产生少、耗电量低、分析时间快等优点,并且与现场分析通常使用的塑料用品(如比色皿、移液管、吸头等)完全兼容。通过测量各种地表水样本,证明了该方法的适用性,并计算出该方法的总体绿色得分率为 96%。
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引用次数: 0
Highly efficient WS2 QD-based non-enzymatic fluorescent biosensor for ofloxacin and ciprofloxacin monitoring in aquatic media† 基于 WS2QDs 的高效非酶促荧光生物传感器用于监测水生介质中的氧氟沙星和环丙沙星
IF 3.5 Q2 CHEMISTRY, ANALYTICAL Pub Date : 2024-07-24 DOI: 10.1039/D4SD00148F
Sunayana Bora and Chandan Upadhyay

Quantum dot-based biosensors have gained prominence in recent times for the detection of biological and chemical hazards present in aquatic media which essentially contribute to the degradation of the environment and human health. Within this work, we demonstrate a WS2 QD-induced turn-on fluorescent probe for specific monitoring of ofloxacin (OFL) and ciprofloxacin (CIP) residues in water. An efficient one-pot hydrothermal approach is applied for fluorescent water-soluble WS2 QD preparation. The WS2 QDs possess excellent photostability and monodispersity along with a superior shelf life. The WS2 QDs interacting with FQns (OFL and CIP) showed a systematically enhanced fluorescence in varying FQn concentrations from 0 μM to 3 μM. Also, all the measurements showed excellent results for sensitivity along with superior specificity as well as anti-interference ability over other interfering substances like various metal ions and antibiotic derivatives. The proposed sensor allows the quantification of FQns in the range of 0–3 μM with the lowest detectable amount (LOD) of 0.08 μM and 0.06 μM and the minimal limit of quantification (LOQ) of 0.26 μM and 0.21 μM for both OFL and CIP, respectively, at natural pH. It achieved higher sensitivity than many established techniques and materials making up the gap of other existing systems in this range. We observed excellent results for the rapid in situ detection of FQns by implementing WS2 QDs. The findings show potential for future use in real-time applications for FQns.

近来,基于量子点的生物传感器在检测水生介质中存在的生物和化学危害方面日益突出,这些危害从根本上导致了环境和人类健康的恶化。在这项工作中,我们展示了一种 WS2QDs 诱导的开启荧光探针,用于特异性监测水中的氧氟沙星(oflx)和环丙沙星(cprx)残留。该研究采用高效的一锅水热法制备了荧光水溶性 WS2QDs。WS2QDs 具有出色的光稳定性和单分散性,而且保存期极长。与 FQns(oflx 和 cprx)相互作用的 WS2QDs 在不同浓度(0μM 至 3μM)的 FQns 中显示出系统增强的荧光。此外,所有测量结果都显示出卓越的灵敏度、特异性和抗干扰能力,不受其他干扰物质(如各种金属离子和抗生素衍生物)的影响。在自然 pH 条件下,该传感器可对 0 μM-3 μM 范围内的 FQns 进行定量,最低检测量(LOD)分别为 0.12μM 和 2.02μM,最低定量限(LOQ)分别为 0.36μM 和 6.11μM。与许多已有的技术和材料相比,它实现了更高的灵敏度,弥补了其他现有系统在这一范围内的空白。通过使用 WS2QDs,我们观察到了快速原位检测 FQns 的出色结果。这些研究结果表明,它在未来的 FQns 实时应用中具有很大的潜力。
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引用次数: 0
A handheld laser-cut device for the size-controlled assembly and electrical characterisation of lipid bilayers† 用于控制脂质双分子层的尺寸和电学特性的手持式激光切割装置
IF 3.5 Q2 CHEMISTRY, ANALYTICAL Pub Date : 2024-07-24 DOI: 10.1039/D4SD00076E
Ji Huang, Yuval Elani and Mark S. Friddin

We report the rapid fabrication of a handheld laser cut platform that can support the assembly, functionalisation, size-control and electrical characterisation of lipid bilayers. We achieve this by building a modular DIY platform that can support the lowering of a Ag/AgCl electrode through a phase transfer column consisting of an upper oil phase containing lipids, and a lower aqueous phase containing buffer.

我们报告了手持激光切割平台的快速制造过程,该平台可支持脂质双层膜的组装、功能化、尺寸控制和电学表征。我们通过构建模块化 DIY 平台来实现这一目标,该平台可支持通过由含有脂质的上层油相和含有缓冲液的下层水相组成的相转移柱来降低银/氯化银电极。
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引用次数: 0
DNA walker coupled with nicking endonuclease for sensitive electrochemical detection of saxitoxin† 与核酸内切酶联用的 DNA 步行器用于灵敏的沙西毒素电化学检测
IF 3.5 Q2 CHEMISTRY, ANALYTICAL Pub Date : 2024-07-24 DOI: 10.1039/D4SD00167B
Yiwei Liu, Shumin Feng, Ruoxi Zhong, Yuanchang Peng, Guoyuan Mu, Jiayi Bai, Wei Chen and Zhan Qu

Saxitoxin (STX) as one of the paralytic shellfish toxins has become a serious public health and environmental issue. In this regards, developing highly sensitive and selective biosensors may help find a solution. Herein, a ferrocene (Fc)-labeled DNA walker coupled with nicking endonuclease Nb.BbvCI was used to construct a sensitive electrochemical aptasensor for STX detection. First, an amplified DNA, aptamer and DNA walker formed a sandwich structure on a gold electrode. This structure was disintegrated when STX was added, resulting in the hybridization of the amplified DNA and DNA walker. Thereafter, the DNA walker was activated by Nb.BbvCI to achieve stepwise cleavage of the hybridized amplified DNA. The released Fc-amplified DNA generated an electrochemical signal that decreased linearly with the logarithm value of STX concentration in the range of 1 pM–100 nM with a detection limit of 0.58 pM. Meanwhile, the proposed aptasensor exhibited good selectivity and recovery rate. The DNA walker coupled with the nicking endonuclease provides effective signal amplification for the detection of toxins and fabrication of sensitive aptasensors.

沙西毒素(STX)作为麻痹性贝类毒素之一,已成为一个严重的公共卫生和环境问题。为此,开发高灵敏度和高选择性的生物传感器可能有助于找到解决方案。在此,研究人员利用二茂铁(Fc)标记的DNA步行器与核酸内切酶Nb.BbvCI联用,构建了一种用于检测STX的灵敏电化学传感器。首先,扩增 DNA、适配体和 DNA 走行子在金电极上形成了一个三明治结构。当加入 STX 时,该结构被瓦解,从而导致扩增 DNA 和 DNA walker 杂交。之后,DNA walker 被 Nb.BbvCI 激活,从而逐步裂解杂交扩增的 DNA。释放的 Fc 扩增 DNA 产生的电化学信号在 1 pM-100 nM 范围内随 STX 浓度的对数值线性下降,检测限为 0.58 pM。同时,该传感器还具有良好的选择性和回收率。DNA 步行器与核酸内切酶的结合为检测毒素和制造灵敏的适配传感器提供了有效的信号放大。
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引用次数: 0
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Sensors & diagnostics
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