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A highly selective chromo-fluorogenic probe for specific detection of sarin gas simulant diethylchlorophosphate in liquid and vapor phases† 用于在液相和气相中特异性检测沙林毒气模拟物氯磷酸二乙酯的高选择性色荧光探针
IF 3.5 Q2 CHEMISTRY, ANALYTICAL Pub Date : 2024-06-26 DOI: 10.1039/D4SD00169A
Tuhina Sultana, Manas Mahato, Sabbir Ahamed, Najmin Tohora, Jyoti Chourasia, Shreya Ali and Sudhir Kumar Das

Among the various organophosphorus-based chemical warfare agents, nerve agents pose severe threats to national defense and public safety. Among them, sarin gas is a severe one that has been employed in various terrorist activities recently. The development of chromo-fluorogenic probes for their detection is still in its infancy. Aiming in this direction, the present article introduces a highly selective and specific chromo-fluorogenic probe, (E)-3-(((4-(benzo[d]oxazol-2-yl)phenyl)imino)methyl)-2-methoxy-2H-chromen-4-ol (TSB) embracing chromone and benzoxazole moieties, for the recognition of diethyl chlorophosphate (DCP), a sarin gas surrogate, in both gaseous and solution phases, respectively. Upon adding DCP to the TSB solution in pure DMSO and 50% v/v water–DMSO mixture, there is an observable change from very pale yellow to colorless. Additionally, there is a transition from no fluorescence to intense blue-violet photoluminescence enhancement under exposure to a 365 nm UV lamp. These optical signals are found to be due to the development of phosphorylated TSB–DCP products, inhibiting intramolecular charge transfer (ICT) and the excited state intramolecular proton transfer (ESIPT) mechanism involved in TSB. The developed sensor demonstrated the ability to detect DCP even in the presence of various other challenging guest analytes, achieving a recognition and quantification limit in the μM range. Furthermore, to achieve on-site detection of DCP and investigate the practical utility of the developed probe, we have demonstrated the use of a paper strip-based test kit, the “dip-stick” method, and, notably, conducted real sample analysis on spiked soil samples.

在各种以有机磷为基础的化学战剂中,神经毒剂对国防和公共安全构成严重威胁。其中,沙林毒气是最近在各种恐怖活动中使用的一种严重毒气。目前,用于检测它们的色氟探针的开发仍处于起步阶段。针对这一方向,本文介绍了一种高选择性和特异性的色氟探针--(E)-3-(((4-(苯并[d]恶唑-2-基)苯基)亚氨基)甲基)-2-甲氧基-2H-苯并吡喃-4-醇(TSB),该探针包含色酮和苯并恶唑分子,可分别在气相和溶液相中识别沙林毒气的代用品--氯磷酸二乙酯(DCP)。在纯二甲基亚砜和 50% v/v 水-二甲基亚砜混合物中的 TSB 溶液中加入二氯丙醇后,可观察到从淡黄色变为无色。此外,在 365 纳米紫外灯的照射下,还出现了从无荧光到强烈蓝紫色光致发光增强的转变。研究发现,这些光学信号是由于磷酸化 TSB-DCP 产物的产生,抑制了参与 TSB 的分子内电荷转移(ICT)和激发态分子内质子转移(ESIPT)机制。所开发的传感器证明,即使在存在其他各种具有挑战性的受邀分析物的情况下,也能检测出 DCP,其识别和定量限在 µM 范围内。此外,为了实现现场检测 DCP 并研究开发的探针的实用性,我们还演示了纸条式检测试剂盒的使用方法和 "浸签 "法,特别是对添加剂的土壤样品进行了实际样品分析。
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引用次数: 0
Synthesis and fluorescence properties of 2′-benzyloxy flavone—a dual probe for selective detection of picric acid and pH sensing† 2ʹ-苄氧基黄酮的合成与荧光特性--用于选择性检测苦味酸和 pH 值传感的双重探针
IF 3.5 Q2 CHEMISTRY, ANALYTICAL Pub Date : 2024-06-26 DOI: 10.1039/D4SD00151F
Vengatesh Gopal, Jayasankar Sudhakaran, Nirenjana Ramachandran, Thejus Kozhiyottu Mana, Aravind Remesh Kana, Anandhu Omanakuttan Nair, Priyanka Mohan, Tejaswini Madhusudhan, Sankarasekaran Shanmugaraju and Pandurangan Nanjan

Flavonoids are naturally occurring oxygen-containing heterocyclic systems with unique properties for diverse applications. The present study reports the synthesis of a new 2′-benzyloxy flavone and explores its fluorescence sensing properties towards secondary chemical explosives, such as picric acid, and pH sensing. The target 2′-benzyloxy flavone fluorophore (5) was synthesized in three-step reactions with good yield and was fully characterized using NMR, FTIR spectroscopy, and HRMS. The sensing propensity of 5 towards nitroaromatics and pH was probed using fluorescence spectroscopy. Compound 5 exhibited a preferential sensing property for phenolic nitroaromatics with high quenching efficiency for picric acid and differential fluorescence responses for different pH. The superior selectivity of 5 for picric acid is attributed to the intermolecular hydrogen bonding interactions between the O atoms in 5 and the OH groups of picric acid. The observed experimental results were further validated by computational calculations which strongly supported the hydrogen-bond-driven sensing selectivity. Furthermore, selective sensing of picric acid by 5 was further demonstrated in real-water samples and using paper-based sensing. These studies make compound 5 a potential dual sensor for selective sensing of picric acid and sensing of pH of the medium.

黄酮类化合物是天然存在的含氧杂环系统,具有独特的性能,可用于多种用途。本研究报告了一种新的 2ʹ-苄氧基黄酮的合成,并探讨了其对二次化学爆炸物苦味酸和 pH 值传感的荧光传感特性。目标 2ʹ-苄氧基黄酮荧光团(5)通过三步反应合成,收率良好,并利用核磁共振、傅立叶变换红外光谱和 HRMS 对其进行了全面表征。利用荧光光谱探测了 5 对硝基芳烃和 pH 值的感应倾向。化合物 5 对酚类硝基芳香族化合物具有优先感应特性,对苦味酸具有较高的淬灭效率,并且在不同 pH 值下具有不同的荧光反应。5 号化合物对苦味酸的卓越选择性归因于 5 号化合物中的 O 原子与苦味酸的 OH 基团之间的分子间氢键相互作用。计算结果进一步验证了观察到的实验结果,并有力地支持了氢键驱动的传感选择性。此外,在实际水样中和使用纸质传感技术时,进一步证明了 5 对苦味酸的选择性传感。这些研究使化合物 5 成为一种潜在的双重传感器,既能选择性地感知苦味酸,又能感知介质的 pH 值。
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引用次数: 0
Effect of structure on excited-state intramolecular proton transfer-based sensors for phosphonofluoridate G-series nerve agent vapour detection† 结构对基于激发态分子内质子转移的膦氟化物 G 系列神经毒剂蒸汽检测传感器的影响
IF 3.5 Q2 CHEMISTRY, ANALYTICAL Pub Date : 2024-06-25 DOI: 10.1039/D4SD00120F
Shengqiang Fan, Paul L. Burn, Ian R. Gentle and Paul E. Shaw

Excited-state intramolecular proton transfer (ESIPT) emitters are unique in that the emission is significantly red shifted relative to the absorption spectra. Herein we explore the effect of substituents on the ability of thin films of 2-[1-phenyl-1H-phenanthro[9,10-d]imidazol-2-yl]phenol-based ESIPT reporter compounds to detect hydrogen fluoride found in G-series nerve agents containing a phosphonofluoridate moiety. When the hydroxyl group of the 2-[1-phenyl-1H-phenanthro[9,10-d]imidazol-2-yl]phenol-based reporter compounds was protected as a silyl ether the photoluminescence emission spectra had vibrational structure and emission maxima at around 370 nm. The silyl protecting groups could be cleaved upon exposure to hydrogen fluoride in the G-series nerve agent simulant, di-iso-propyl fluorophosphate, leading to ESIPT emission with a peak maximum at around 470 nm, thus allowing identification of the presence of hydrogen fluoride. Films of the sensing materials with the different silyl protecting groups were found to have different stabilities to ambient conditions and reactivity with hydrogen fluoride, with the larger silyl ethers such as triethylsilyl and t-butyldimethyl silyl performing better overall when compared to the smaller trimethylsilyl ether. Steric encumberance or addition of polar solubilising groups was found to reduce the sensing capability. The optimal sensing material was lipophilic and contained a t-butyldimethyl silyl protecting group, with films capable of detecting hydrogen fluoride at a concentration of 0.1 ppm which, based on a sarin purity of 99%, would enable sarin to be detected at 1.2 ppm, which is below the LC50 five minute exposure limit for sarin of 1.6–3.2 ppm.

激发态分子内质子转移(ESIPT)发光体的独特之处在于,相对于吸收光谱,发射光谱会发生明显的红移。在此,我们探讨了取代基对 2-[1-苯基-1H-菲咯并[9,10-d]咪唑-2-基]苯酚基 ESIPT 报告化合物薄膜检测 G 系列神经毒剂中含有的氟化氢的能力的影响。当 2-[1-苯基-1H-菲并[9,10-d]咪唑-2-基]苯酚基报告化合物的羟基被保护为硅基醚时,光致发光发射光谱具有振动结构,发射最大值在 370 nm 左右。当接触到 G 系列神经毒剂模拟物--氟磷酸二异丙酯中的氟化氢时,硅烷保护基团会被裂解,从而产生 ESIPT 发射,其最大峰值在 470 纳米左右,因此可以识别氟化氢的存在。研究发现,带有不同硅基保护基团的传感材料薄膜对环境条件的稳定性不同,与氟化氢的反应活性也不同,与较小的三甲基硅基醚相比,较大的硅基醚(如三乙基硅基醚和 t-丁基二甲基硅基醚)总体性能更好。研究发现,立体累赘或添加极性增溶基团会降低传感能力。最佳传感材料是亲脂性的,并含有一个 t-丁基二甲基硅基保护基团,其薄膜能够检测浓度为 0.1 ppm 的氟化氢,根据沙林纯度为 99%计算,可检测浓度为 1.2 ppm 的沙林,低于沙林的 LC50 5 分钟暴露限值 1.6-3.2 ppm。
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引用次数: 0
Recent advances of optical fiber biosensors based on surface plasmon resonance: sensing principles, structures, and prospects 基于表面等离子体共振的光纤生物传感器的最新进展:传感原理、结构与前景
IF 3.5 Q2 CHEMISTRY, ANALYTICAL Pub Date : 2024-06-08 DOI: 10.1039/D4SD00045E
Jingwei Lv, Jianxin Wang, Lin Yang, Wei Liu, Haihao Fu, Paul K. Chu and Chao Liu

Optical fiber biosensors based on the surface plasmon resonance (SPR) phenomenon are generating increasing interest due to their capability of real-time monitoring of analytes in a biocompatible, label-free, stable, and cost-effective manner. In fact, SPR optical fiber biosensors are becoming very popular in environmental science, clinical diagnosis, disease detection, and food safety. This review provides a comprehensive overview of optical fiber biosensors that utilize SPR. The principles and recent developments of optical fiber sensors are described. Different SPR optical fiber biosensors, including traditional optical fiber SPR biosensors, microstructured optical fiber (MOF) biosensors, grating-assisted plasmon fiber SPR biosensors, and others, are reviewed and the capabilities of common biosensors are compared. This overview aims to provide guidance for future research and development of this important and burgeoning field.

基于表面等离子体共振(SPR)现象的光纤生物传感器以其生物兼容、无标记、稳定和经济高效的方式实时监测分析物的能力,正引起越来越多的关注。事实上,SPR 光纤生物传感器在环境科学、临床诊断、疾病检测和食品安全领域正变得非常流行。本综述全面概述了利用 SPR 技术的光纤生物传感器。文章介绍了光纤传感器的原理和最新发展。综述了不同的 SPR 光纤生物传感器,包括传统光纤 SPR 生物传感器、微结构光纤 (MOF) 生物传感器、光栅辅助等离子体光纤 SPR 生物传感器等,并对常见生物传感器的功能进行了比较。本综述旨在为这一重要而新兴领域的未来研究和发展提供指导。
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引用次数: 0
Circulating microRNA detection using electrochemical biosensor for rapid diagnosis of liver disease in dogs 利用电化学生物传感器检测循环微RNA,快速诊断狗的肝病
IF 3.5 Q2 CHEMISTRY, ANALYTICAL Pub Date : 2024-06-04 DOI: 10.1039/D4SD00031E
Appan Roychoudhury, Federico Diez, Richard J. Mellanby, James W. Dear and Till T. Bachmann

Liver disease in dogs is a major cause of morbidity and mortality. Non-invasive diagnosis of liver disease in dogs is a clinical challenge and improved tests which could done at point-of-care are highly desirable. Liver-specific circulating microRNAs have emerged as promising biomarkers for liver injury across many vertebrate species including dogs. MicroRNA-122 (miR-122), originating from the damaged hepatocytes, provides high specificity and sensitivity in detecting liver disease, compared to the traditional biomarkers. In this study, we present the development of a point-of-care compatible electrochemical biosensor for rapid, early diagnosis of liver disease in dogs by detecting miR-122 in clinical samples. Building on our prior work utilising electrochemical impedance spectroscopy (EIS) for direct and amplification-free detection of miR-122 in human drug-induced liver injury, we have used a miR-122 target-specific short probe and implemented target overhang formation during hybridisation in a flow-based sample cycling setup for enhanced detection performance and demonstrated its performance in real clinical dog samples for the first time. We determined the hybridisation performance by analysing miR-122 specificity and sensitivity achieving a limit of detection (LOD) and limit of quantification (LOQ) of 10 pM and 100 pM, respectively, and high specificity over a nearly-complementary sequence of a miR-122 precursor. Using conventional sample preparation, the developed EIS assay was used to analyse serum samples from dogs with liver disease which were identified based on an increased serum alanine aminotransferase concentration. The test successfully distinguished samples from dogs with and without liver disease in comparable performance to the gold-standard real-time polymerase chain reaction (qPCR) detection. We will further focus on developing sample-to-answer test by combining our miR-122 EIS biosensor with a compatible sample preparation to measure miR-122 from dog blood at point of care.

犬肝病是发病和死亡的主要原因。狗肝脏疾病的无创诊断是一项临床挑战,因此非常需要改进可在护理点进行的检测。在包括狗在内的许多脊椎动物中,肝脏特异性循环微RNA已成为肝损伤的有希望的生物标志物。与传统的生物标记物相比,源自受损肝细胞的微RNA-122(miR-122)在检测肝脏疾病方面具有很高的特异性和灵敏度。在这项研究中,我们开发了一种与护理点兼容的电化学生物传感器,通过检测临床样本中的 miR-122,对狗的肝病进行快速、早期诊断。在利用电化学阻抗谱(EIS)直接、无放大检测人类药物性肝损伤中 miR-122 的前期工作基础上,我们使用了 miR-122 靶标特异性短探针,并在基于流动的样品循环装置中杂交过程中形成靶悬垂,以提高检测性能,并首次在真实的临床狗样本中展示了其性能。我们通过分析 miR-122 的特异性和灵敏度确定了杂交性能,其检测限(LOD)和定量限(LOQ)分别为 10 pM 和 100 pM,对 miR-122 前体的几乎互补序列具有高度特异性。利用传统的样品制备方法,所开发的 EIS 检测法被用于分析根据血清丙氨酸氨基转移酶浓度升高而确定的患有肝病的狗的血清样品。该检测方法成功区分了患有和未患有肝病的狗样本,其性能与黄金标准的实时聚合酶链反应(qPCR)检测方法相当。我们将进一步致力于开发从样本到答案的测试,将我们的 miR-122 EIS 生物传感器与兼容的样本制备相结合,在医疗点测量狗血液中的 miR-122。
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引用次数: 0
Point-of-care diagnostic devices for periodontitis – current trends and urgent need 牙周炎护理点诊断设备--当前趋势和迫切需要
IF 3.5 Q2 CHEMISTRY, ANALYTICAL Pub Date : 2024-06-03 DOI: 10.1039/D3SD00317E
Alexandra Griffith, Charmi Chande, Sahitya Kulkarni, Josuel Morel, Yu-Hsuan Cheng, Emi Shimizu, Carla Cugini, Sagnik Basuray and Vivek Kumar

Point of care (POC) diagnostic devices provide a method for rapid accurate identification of disease through analysis of biologically relevant substances. This review focuses on the utility of POC testing for early detection of periodontitis, a critical factor in treating the disease. Accessing the oral cavity for biological sampling is less invasive when compared to other internal test sites, and oral fluids contain biomarkers indicative of periodontitis. The ease of access makes the mouth an excellent target location for the development of POC devices. In this review, accepted standards in industry by which these devices must adhere, provided by the World Health Organization such as REASSURED and CLIA, are discussed. An overview is provided for many periodontal biomarkers currently being investigated as a means of predicting periodontal disease and its progression. POC devices currently being investigated for the identification and monitoring of periodontal disease such as paper-based and lab-on-a-chip based devices are outlined. Limitations of current POC devices on the market are provided and future directions in leveraging biomarkers as an adjunctive method for oral diagnosis along with AI-based analysis systems are discussed. Here, we present the ESSENCE sensor platform, which combines a porous non-planar electrode with enhanced shear flow to achieve unprecedented sensitivity and selectivity. The combination of the ESENCE chip with an automated platform allows us to meet the WHO's ASSURED criteria. This platform promises to be an exciting POC candidate for early detection of periodontitis.

护理点(POC)诊断设备提供了一种通过分析生物相关物质快速准确识别疾病的方法。本综述将重点讨论 POC 检测在早期发现牙周炎方面的作用,这是治疗牙周炎的一个关键因素。与其他内部检测部位相比,进入口腔进行生物采样的侵入性较小,而且口腔液中含有指示牙周炎的生物标志物。口腔的易接近性使其成为开发 POC 设备的绝佳目标位置。在这篇综述中,讨论了这些设备必须遵守的由世界卫生组织提供的行业公认标准,如 REASSURED 和 CLIA。综述了目前正在研究的许多牙周生物标记物,这些标记物是预测牙周疾病及其进展的一种手段。概述了目前正在研究的用于识别和监测牙周疾病的 POC 设备,如基于纸张和芯片实验室的设备。我们提供了目前市场上 POC 设备的局限性,并讨论了利用生物标记物作为口腔诊断的辅助方法以及基于人工智能的分析系统的未来发展方向。在这里,我们介绍了 ESSENCE 传感器平台,它将多孔非平面电极与增强型剪切流相结合,实现了前所未有的灵敏度和选择性。ESENCE 芯片与自动化平台的结合使我们能够满足世界卫生组织的 ASSURED 标准。该平台有望成为牙周炎早期检测的令人兴奋的 POC 候选产品。
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引用次数: 0
Magneto-plasmonic bionanocomposites for on-site SERS detection of water contaminants† 用于现场 SERS 检测水污染物的磁-质子仿生复合材料
IF 3.5 Q2 CHEMISTRY, ANALYTICAL Pub Date : 2024-05-31 DOI: 10.1039/D4SD00049H
Sofia F. Soares, Nuno M. A. S. Silva, João Brenheiro, Sara Fateixa, Ana L. Daniel-da-Silva and Tito Trindade

Magneto-plasmonic nanosystems have emerged as important multifunctional structures for several sensing applications, including on-site water quality monitoring. In this scenario, these nanosystems can integrate magnetic assisted separation procedures associated with optical detection of water contaminants, by exploring the surface-enhanced Raman scattering effect (SERS). Among the several modalities proposed for such magneto-plasmonic nanosystems, bionanocomposite particles have not been explored in this context. Hence, this research introduces bionanocomposites comprising magnetite cores that have been coupled to Au nanoparticles (NPs) via an intermediate surface modification step using hybrid shells of trimethyl chitosan-SiO2. The magnetic bionanocomposites were decorated with Au NPs by exploring two methods: their assembly with pre-synthesized Au colloids and as heterogeneous substrates for the in situ synthesis of Au NPs. The resulting magneto-plasmonic nanosystems are responsive to an external magnetic gradient and show the localized surface plasmon resonance (LSPR) band ascribed to the Au NPs. Therefore, such multifunctionality was explored here by assessing the SERS performance of the magneto-plasmonic substrates after their use as magnetic nanosorbents for the uptake of organic dyes, specifically methylene blue (MB) and rose bengal (RB), as water contaminant models. The results showed that both types of substrates are effective, though the ex situ bionanocomposites have shown better SERS activity. As such, the latter have been selected to further demonstrate the versatility of the bionanocomposites for the SERS detection of other types of water contaminants, such as salicylic acid (SA), a pharmaceutical compound that is classified as a teratogen substance. Overall, these findings indicate that magneto-plasmonic bionanocomposites, indeed can be explored as more sustainable platforms for analytical purposes, combining the ability for magnetic separation and SERS trace detection.

磁性-等离子体纳米系统已成为多种传感应用(包括现场水质监测)的重要多功能结构。在这种情况下,这些纳米系统可以通过探索表面增强拉曼散射效应(SERS),整合与水污染物光学检测相关的磁辅助分离程序。在为此类磁-质子纳米系统提出的几种模式中,仿生复合粒子尚未在此背景下得到探索。因此,本研究引入了由磁铁矿核组成的仿生纳米复合材料,这些磁铁矿核通过使用三甲基壳聚糖-二氧化硅混合壳的中间表面改性步骤与金纳米粒子(NPs)耦合。磁性仿生复合材料通过两种方法进行金纳米粒子装饰:与预合成的金胶体组装,以及作为原位合成金纳米粒子的异质基底。由此产生的磁等离子纳米系统对外部磁梯度具有响应性,并显示出归因于金负电荷的局部表面等离子体共振(LSPR)波段。因此,本文通过评估磁性等离子基底作为磁性纳米吸附剂吸附有机染料(特别是作为水污染模型的亚甲基蓝(MB)和玫瑰红(RB))后的 SERS 性能,探索了这种多功能性。结果表明,这两种基质都很有效,但原位仿生复合材料显示出更好的 SERS 活性。因此,我们选择了后者来进一步证明仿生复合材料在 SERS 检测其他类型水污染物方面的多功能性,如水杨酸(SA),一种被归类为致畸物质的药物化合物。总之,这些研究结果表明,磁-质子仿生复合材料确实可以作为更可持续的分析平台,将磁分离和 SERS 痕量检测能力结合起来。
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引用次数: 0
Enhanced spin-polarization and detection limit in a spin-based optoelectrochemical DNA hybridization sensor induced by circularly polarized light† 圆偏振光诱导自旋光电化学 DNA 杂交传感器增强自旋偏振和探测极限
IF 3.5 Q2 CHEMISTRY, ANALYTICAL Pub Date : 2024-05-28 DOI: 10.1039/D4SD00109E
Mayank Tiwari and Debabrata Mishra

We investigate the influence of the correlation between different types of polarized light (linear and circular) and spin-polarization |Ps| (in %) on the effectiveness of a spin-based quantum dot-modified DNA device for a DNA hybridization sensor. The device exhibits a significant two-fold increase in |Ps| (in %) when exposed to circularly polarized (C.P.) light, in comparison to the state of no illumination. This improvement in |Ps| results in a significant ten-fold enhancement in the limit of detection (L.O.D.) of the electrode under C.P. light illumination, surpassing the conditions without illumination and even achieving a two-fold increase compared to linearly polarized (L.P.) light illumination. These results emphasize the crucial significance of polarized light in maximizing the efficiency of spin-based DNA hybridization sensors. The significant enhancements in the performance observed under C.P. light illumination demonstrate the potential use of our device to function as a highly sensitive and efficient tool in spin-based bio-sensing applications.

我们研究了不同类型的偏振光(线性偏振光和圆偏振光)与自旋偏振 |Ps|(%)之间的相关性对基于自旋量子点修饰的 DNA 器件在 DNA 杂交传感器中的有效性的影响。与无光照状态相比,该装置在圆偏振光(C.P.)照射下的|Ps|(单位:%)显著增加了两倍。在 C.P. 光照射下,|Ps|的提高使电极的检测限(L.O.D.)显著提高了十倍,超过了无照射条件,甚至比线性偏振光(L.P.)照射下提高了两倍。这些结果表明,偏振光对于最大限度地提高自旋 DNA 杂交传感器的效率至关重要。在 C.P.光照射下观察到的性能大幅提高表明,我们的设备有可能在基于自旋的生物传感应用中发挥高灵敏度和高效工具的作用。
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引用次数: 0
A triphenylamine scaffold for fluorogenic sensing of noxious cyanide via the ICT mechanism and its bioimaging application† 通过 ICT 机制实现有毒氰化物荧光感应的三苯胺支架及其生物成像应用
IF 3.5 Q2 CHEMISTRY, ANALYTICAL Pub Date : 2024-05-23 DOI: 10.1039/D4SD00018H
Amitav Biswas, Rimi Mukherjee, Atanu Maji, Rahul Naskar, Krishnendu Aich, Nabendu Murmu and Tapan K. Mondal

A novel triphenylamine benzimidazole based fluorogenic chemosensor named (2E,2′E)-3,3′-((phenylazanediyl)bis(4,1-phenylene))bis(2-(1H-benzo[d]imidazol-2-yl)acrylonitrile) (PBIA) has been successfully generated and characterized by varoius spectroscopic techniques. Among various screened anions, only cyanide (CN) showed a distinct fluorogenic property towards PBIA. Hence, the optical properties of PBIA were investigated in the presence of cyanide (CN) by means of UV-vis spectrophotometry and fluorescence spectroscopy in DMSO, where we observed that, upon treatment with CN to the probe solution, the orange fluorescence of the ligand showed a blue shift and the orange fluorescence changed to greenish-yellow under an UV lamp. The hypsochromic shift in fluorescence maxima upon the addition of cyanide was attributed to nucleophilic addition of cyanide to PBIA inhibiting the electron flow within the molecule and disrupting the ICT process. The interaction behind the sensing of cyanide was investigated by 1H-NMR titration, a mass spectroscopic study and DFT calculations, which supported the mechanism. The limit of detection (LOD) was calculated and found to be in the order of 10−8 (M). PBIA showed an immediate response in the spectral pattern (<20 s) towards its target cyanide ion, and the effectiveness of the chemosensor was also examined in the presence of competing anions. Furthermore, the practical efficacy of the PBIA was established by a dipstick experiment along with cyanide detection in various natural water resources. Human breast cancer cells MDA-MB 231 were made susceptible to CN sensing in a biological system.

一种基于三苯胺苯并咪唑的新型荧光化学传感器--(2E,2'E)-3,3'-((苯基氮二基)双(4,1-亚苯基))双(2-(1H-苯并[d]咪唑-2-基)丙烯腈)(PBIA)已被成功制备出来,并通过各种光谱技术对其进行了表征。在筛选出的各种阴离子中,只有氰化物(CN-)对 PBIA 具有明显的致氟特性。因此,我们通过紫外-可见分光光度法和二甲基亚砜中的荧光光谱法研究了 PBIA 在氰化物(CN-)存在下的光学特性,观察到在探针溶液中加入 CN- 后,配体的橙色荧光发生蓝移,在紫外灯下橙色荧光变为灰黄色。在加入氰化物后,荧光最大值发生了同色转移,这是因为氰化物与 PBIA 的亲核加成抑制了分子内的电子流,破坏了 ICT 过程。通过 1H-NMR 滴定、质谱研究和 DFT 计算研究了氰化物传感背后的相互作用,结果支持了这一机制。经计算发现,其检测限(LOD)约为 10-8(M)。PBIA 在光谱模式中对目标氰离子显示出即时响应(20 秒),并在存在竞争阴离子的情况下检验了化学传感器的有效性。此外,探针 PBIA 的实际功效还通过浸渍棒实验和各种天然水资源中的氰化物检测得到了证实。人类乳腺癌细胞 MDA-MB 231 使其在生物系统中易受氯化萘感应。
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引用次数: 0
Antibody fluorescein-doped silica nanobioconjugates for the ultrasensitive detection of prostate-specific antigen† 用于超灵敏检测前列腺特异性抗原的抗体荧光素掺杂二氧化硅纳米生物共轭物
IF 3.5 Q2 CHEMISTRY, ANALYTICAL Pub Date : 2024-05-17 DOI: 10.1039/D4SD00119B
Tumelo Msutu, Omotayo Adeniyi and Philani Mashazi

Herein, we report the bioconjugation of anti-prostate-specific antigen polyclonal antibodies (pAb) onto the fluorescein-doped silica nanoparticles to detect prostate-specific antigen (PSA). Fluorescein-isothiocyanate (FITC), a fluorescent dye, was reacted with (3-aminopropyl)triethoxysilane (APTES) to form the FITC-APTES organosilane precursor. FITC-APTES was mixed with tetraethoxysilane (TEOS) to form fluorescent silica nanoparticles (FITC@SiO2NPs) containing 3% and 6% of dye loading. The silica nanoparticles prevented the dye from leaching and promoted the fluorescent signal amplification for the detection of PSA. Phenylboronic acid (PBA) was coated onto the fluorescent silica nanoparticles for the oriented antibody immobilization via the boronate ester to form FITC@SiO2-PBA-pAb. The fluorescent silica nanobioconjugates exhibited an emission peak at 518 nm, which was stable over time. A fluorescence sandwich-type immunoassay was used for the detection of PSA using FITC@SiO2-PBA-pAb. Alkaline hydrolysis of the sensing nanobioconjugates afforded enhanced sensitivity by releasing FITC molecules. In buffer samples, the fluorescent immunosensor exhibited a linear correlation range from 2.0 pg mL−1 to 50 ng mL−1. The linear range was from 2.0 pg mL−1 to 100 ng mL−1 in newborn calf serum (representing real samples). The limit of detection (LOD) was 8.25 fg mL−1 with a limit of quantification (LOQ) of 27.2 fg mL−1 in PBS (pH 7.4) after NaOH dissolution. A fluorescence immunosensor was used to detect PSA in spiked newborn calf serum with NaOH dissolution. It exhibited an LOD value of 33.0 fg mL−1 and LOQ value of 0.109 pg mL−1. The developed fluorescence immunosensor showed high selectivity and specificity for PSA. The detection of prostate-specific antigen in newborn calf serum samples exhibited no matrix interferences.

在此,我们报告了将抗前列腺特异性抗原多克隆抗体(pAb)生物共轭到掺杂荧光素的二氧化硅纳米颗粒上以检测前列腺特异性抗原(PSA)的方法。使用的荧光染料是荧光素-异硫氰酸酯(FITC),它与(3-氨基丙基)三乙氧基硅烷(APTES)反应生成 FITC-APTES 有机硅烷前体。将 FITC-APTES 与四乙氧基硅烷(TEOS)混合,形成含有 3% 和 6% 染料的荧光纳米二氧化硅颗粒(FITC@SiO2NPs)。二氧化硅纳米粒子可防止染料浸出,并促进荧光信号放大,用于检测 PSA。将苯硼酸(PBA)涂布在荧光纳米二氧化硅颗粒上,通过硼酸酯将抗体定向固定,形成 FITC@SiO2-PBA-pAb。这种荧光纳米二氧化硅生物共轭物在 518 纳米波长处显示出强烈的激发依赖性发射,并且长期稳定。利用 FITC@SiO2-PBA-pAb 的荧光夹心型免疫测定法检测 PSA。传感纳米生物共轭物经碱性水解后释放出 FITC 分子,从而提高了灵敏度。在缓冲液样品中,荧光免疫传感器的线性相关范围为 2.0 pg.mL-1 至 50 ng.mL-1。在新生小牛血清(代表真实样本)中,线性范围为 2.0 pg.mL-1 至 100 ng.mL-1。在 NaOH 溶解后的 PBS 缓冲液(pH 7.4)中,检测限(LOD)为 8.25 fg.mL-1,定量限(LOQ)为 27.2 fg.mL-1。研究了一种荧光免疫传感器,用于检测添加 NaOH 溶解物的新生小牛血清中的 PSA。LOD为33.0 fg.mL-1,LOQ为0.109 pg.mL-1。所开发的荧光免疫传感器对前列腺特异性抗原具有很高的选择性和特异性。在检测新生小牛血清样品中的前列腺特异性抗原时,未发现基质干扰。
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引用次数: 0
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Sensors & diagnostics
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