金属纳米团簇的合成及其光致发光性质的调控

金属纳米团簇是一种既具有出色光物理性质,又具有良好生物相容性的零维材料.利用配体对团簇的热力学稳定产物的选择性和还原剂动力学调控可以合成出结构多样的金属纳米团簇,在光学材料、生物医学和催化材料等领域展示出颇具潜力的应用前景.但金属纳米团簇的稳定性差、发光弱等缺点限制了其实际应用,因此通过聚集诱导发光效应和超分子自组装协同调控金属纳米团簇的稳定性及光学性质,可以构筑出结构与发光可控的金属纳米团簇组装体,有效促进金属纳米团簇的实际可用性.本文简要介绍了不同配体保护的金属纳米团簇的合成,阐述了金属纳米团簇的光致发光性质,总结了聚集诱导发光效应对团簇超分子组装体光致发光性质的影响规律,并分析提出了当前研究仍存在的问题及对未来探究的展望.     

纳米发光银簇的合成与应用研究进展EI北大核心CSCD

纳米发光银簇作为一类新型荧光金属纳米材料,具有优异的光物理性质以及良好的生物相容性,在生物传感和生物显像领域受到了越来越多的关注。本文主要以纳米发光银簇为研究对象,围绕纳米发光银簇的不同合成模板、合成方法及其在不同领域的应用进展作一综述。     

纳米发光银簇的合成与应用研究进展

纳米发光银簇作为一类新型荧光金属纳米材料,具有优异的光物理性质以及良好的生物相容性,在生物传感和生物显像领域受到了越来越多的关注。本文主要以纳米发光银簇为研究对象,围绕纳米发光银簇的不同合成模板、合成方法及其在不同领域的应用进展作一综述。     

电化学发光分析方法在核酸检测中的应用

电化学发光(electrochemiluminescence, ECL)分析方法具有灵敏、快速、准确、分析适应性广等特点。本文首先介绍了ECL的基本原理和特点、ECL核酸分析方法的分类和核酸的钌标记,随后对2003年以来基于磁性微球的ECL与核酸扩增及纳米技术联用在核酸检测中的应用、直接固定的ECL核酸分析方法及毛细管电泳(CE)-ECL核酸分析方法的应用做出了评述,并对ECL核酸分析方法的发展方向进行了展望。     

超四面体硫簇结构调控与电化学发光研究进展

电化学发光(ECL)因其独特的性能特点在生物分析等领域展现出广阔的应用前景,高效ECL试剂的开发则为性能优异的传感器件的发展和临床应用提供了重要工具. 开放骨架超四面体硫簇由于同时具有分子筛的多孔结构和半导体的优异光电性能,在ECL分析中受到了越来越多的关注. 超四面体硫簇的结构组成可以实现原子级别的精确调控,并且其本身还可以作为结构单元来构筑多孔结构半导体材料. 这些特点使通过原子级别的结构组成调节来调控超四面体硫簇的性能成为可能,为发展性能优异的电化学发光材料,拓展其在生化传感、免疫分析和生物成像等方面的应用提供有效工具. 本综述总结了超四面体硫簇的合成、缺陷掺杂、功能调控及ECL生化分析等方面的研究进展,为推进高效ECL新材料的发展和新应用的拓展提供了借鉴.     

金属卤化物钙钛矿纳米晶高效发光二极管的制备与器件性能优化

金属卤化物钙钛矿作为一类新型的离子型直接带隙半导体材料在电致发光二极管(LED)中有着重要应用前景. 但实现其应用的前提在于金属卤化物钙钛矿材料需要保持高的发光效率和好的稳定性. 为了提高金属卤化物钙钛矿作为LED发光层的激子结合效率, 从而提升其发光效率, 设计和合成金属卤化物钙钛矿纳米晶材料是一个有效途径. 目前, 基于纳米晶材料设计的金属卤化物钙钛矿LED在绿光和红光(包括近红外光)范围已经展现了高的发光亮度和外量子效率(EQE), 其中最高EQE已经超过了20%, 但其稳定性仍无法满足器件应用的要求. 此外, 更值得关注且更重要的是, 蓝光钙钛矿LED的发光亮度和EQE目前仍然不高. 如何制备高效、 稳定的金属卤化物钙钛矿纳米晶LED, 特别是蓝光LED, 是一个具有重大应用前景且具有挑战性的课题. 本文重点介绍了金属卤化物钙钛矿纳米发光层的结构设计和合成方法及金属卤化物钙钛矿LED的研究进展, 分析了金属卤化物钙钛矿LED不稳定的原因, 并对金属卤化物钙钛矿LED研究面临的挑战和未来发展方向进行了总结与展望.     

铜纳米簇聚集体的合成、发光与胞内温度传感

发光的金属纳米簇由于毒性小、成本低和生物相容性好等优势引起了人们的广泛关注,然而制备具有强发光的铜纳米簇聚集体是一个很大的挑战。以手性氨基酸D-青霉胺为原料,“一步法”合成了具有强发光的铜纳米簇聚集体,并通过红外光谱、热重分析、X-射线光电子能谱、X-射线衍射、质谱、扫描电镜、透射电镜、发光光谱和激光共聚焦显微镜表征技术对其进行了详细研究。结果表明：铜纳米簇聚集体的悬浊液和固体显示出很强的发光,绝对发光量子产率高达30.4%。而且,发光的铜纳米簇聚集体细胞毒性很低,可以在人肝癌细胞HepG2中实现胞内成像以及依赖于温度的胞内成像。铜纳米簇聚集体的发光行为在细胞成像方面的应用探索为人们在其它领域进行应用提供了重要参考。     

荧光银纳米簇:从制备到分析应用

由于其优异的发光性质,荧光纳米簇在分析领域展现出广泛的应用前景.其中,荧光银纳米簇因具有尺寸可调、良好的水溶性、生物相容性和优异的光学性能而被大量关注.本文基于课题组前期工作,对荧光银纳米簇的合成、光学性质及分析应用进行综述,并对该领域的未来发展进行展望.     

荧光金属纳米簇的合成及其在生物医学中的应用研究进展

金属纳米簇作为一种新型的荧光纳米材料,展现出良好的生物相容性和优良的物化性质,近年来受到各个领域的关注,尤其在生物医学领域得到了广泛的应用。该文在介绍多种金属纳米簇的合成方法和光学性质的基础上,综述了金属纳米簇在生物传感、生物成像和肿瘤治疗等领域的应用研究进展,并对其面临的挑战和应用前景进行了展望。     

金属有机框架材料在电化学/电化学发光免疫分析中的应用（英文）

设计和研制具有超灵敏、高精度、选择性好的免疫传感器对于疾病的早期诊断和筛查以及疾病治疗过程的监测具有十分重要的意义。其中,电化学免疫分析法和电化学发光(ECL)免疫分析法,由于具有稳定性好、灵敏度高、线性范围宽、可控性好等优点而备受关注,已成为当前的研究热点之一。金属有机框架(MOFs)作为一类新型的多孔晶体材料,由于其具有比表面积大、化学稳定性好、孔径和纳米级骨架结构可调节等优点,在电化学和ECL免疫传感器的制备中得到了广泛的应用。MOFs不仅可以作为固定生物识别分子的敏感平台,还可以用于富集痕量分析物和信号分子来放大分析信号,提高电化学或ECL免疫分析的灵敏度。目前,科研人员已合成各种各样具有不同性能和形貌的MOFs纳米材料,并用于开发高性能的电化学免疫传感器和ECL免疫传感器。本文综述了不同类型的基于MOFs纳米材料的电化学/ECL免疫传感器的制备及其在免疫分析中的检测应用。研究表明,MOFs不仅可以作为电极表面修饰的基底、信号探针(包括电活性标记分子和电化学发光发光标记探针)、催化活性标记物,还可以作为负载各种生物分子、纳米材料的载体,最终可用于灵敏的电化学和ECL检测。此外,...     

Chemiluminescence and electrochemiluminescence applications of metal nanoclusters

Due to strong photoluminescence, extraordinary photostability, excellent biocompatibility, and good water-solubility, metal nanoclusters have attracted enormous attention since discovered. They are found to be novel fluorescence labels for biological applications and environmental monitoring. Recently the chemiluminescence (CL) or electrochemiluminescence (ECL) of metal nanoclusters has received increasing attention. This review covers recent vibrant developments in this field of the past 5 years, and highlights different functions of metal nanoclusters in various CL and ECL systems, such as luminophores, catalysts, and quenchers. Latest synthetic methods of metal nanoclusters used in CL or ECL are also summarized. Furthermore, we discuss some perspectives and critical challenges of this field in the near future.     

Pre‐oxidation of Gold Nanoclusters Results in a 66 % Anodic Electrochemiluminescence Yield and Drives Mechanistic Insights

Gold nanoclusters (AuNCs) are attractive electrochemiluminescence (ECL) emitters because of their excellent stability, near IR emission, and biocompatibility. However, their ECL quantum yield is relatively low, and our limited fundamental understanding has hindered rational improvement of this parameter. Herein, we report drastic enhancement of the ECL of ligand‐stabilized AuNCs by on‐electrode pre‐oxidation with triethylamine (TEA) as a co‐reactant. The l ‐methionine‐stabilized AuNCs resulted in a record high ECL yield of 66 %. This strategy was successfully extended to other AuNCs, and it is more effective for ligand shells that allow more effective electron transfer. In addition, excitation of the pre‐oxidized ECL required a lower potential than conventional methods, and no additional instrument was required. This work opens avenues for solving a challenging problem of AuNC‐based ECL probes and enriches fundamental understanding, greatly broadening their potential applications.     

Self-assembly Induced Enhanced Electrochemiluminescence of Copper Nanoclusters Using DNA Nanoribbon Templates

Copper nanoclusters (CuNCs) are attractive electrochemiluminescence (ECL) emitters as Cu is comparatively inexpensive, nontoxic, and highly abundant. However, their ECL yield is relatively low. Herein, we report that orderly self-assembly of CuNCs using DNA nanoribbon as the template (DNR/CuNCs) conferred the CuNCs with improved ECL properties compared with individual CuNCs in both annihilation and co-reactant processes. The DNR/CuNCs resulted in a high ECL yield of 46.8 % in K₂S₂O₈, which was ≈68 times higher than that of individual CuNCs. This strategy was successfully extended to other ECL emitters, such as gold nanoclusters and the Ru(bpy)₃²⁺/TPrA system. Furthermore, as an application of DNR/CuNCs, a DNR/CuNC-based ECL biosensor with higher sensitivity was constructed for dopamine determination (two orders of magnitude lower than that previously reported), showing that DNR/CuNCs have a potential for application in ECL bioanalysis as a new type of superior luminophore candidate.     

A Highly Sensitive Electrochemiluminescence Spermine Biosensor Based on Au−Ag Bimetallic Nanoclusters

In this study, we found that spermine (SPM) could enhance electrochemiluminescence (ECL) intensity of Au−Ag bimetallic nanoclusters (Au−Ag BNCs) with triethylamine (TEA) as a co-reactant. An ECL sensor was fabricated to detect SPM, which contained Au−Ag BNCs as ECL emitters and conductive hydrogel containing polyaniline-amino trimethylene phosphonic acid (PANI-ATMP) as an immobilizing matrix. The increased ECL intensity of SPM was linear with the logarithm of concentrations of SPM in the range of 1 pM to 10 μM with high selectivity, excellent stability, and the limit of detection is 0.11 pM (S/N=3). This sensor realized the detection of SPM in urine samples, which was fast and economic, possessing potential applications for SPM detection in clinical and bioanalysis.     

Synergistic Enhancement Effects of Carbon Quantum Dots and Au Nanoclusters for Cathodic ECL and Non‐enzyme Detections of Glucose

In this study, we found that glucose enhance electrochemiluminescence (ECL) intensity of both Au nanoclusters (Au NCs) and carbon quantum dots (CQDs) with K₂S₂O₈ as the co‐reactants. The enhancing effects by Au NCs and CQDs were overlapped, enabling the detection of glucose. The increased ECL intensity of glucose was linear with the logarithm of concentrations of glucose in the range of 50 μM–3.0 mM, and the limit of detection is 20 μM. Anti‐interruption ability was achieved, and ascorbic acid, urea, and uric acid had little influence to glucose detection. This method realized the direct detection of glucose by enhancing ECL of Au NCs and CQDs, which was fast and economic, possessing potential applications for glucose detection in human serum.     

金属纳米簇在CO2光催化还原中的研究进展

化石燃料的大量燃烧不仅造成能源危机，而且排放的二氧化碳（CO2）会使气候变暖。以清洁、储量丰富的太阳光作为能量来源，将CO2光催化还原为高附加值的化学产品是缓解当前环境问题和能源问题的主要方法之一。然而，CO2在常温常压下非常的稳定，因此需要设计并构筑高效光催化剂来捕捉和转化CO2，以达到高效光催化CO2还原的目的。在众多研究的光催化剂中，金属纳米簇因其具有独特的结构特点、优异的物理和化学性质，所以在光催化CO2还原领域得到了广泛的应用。基于此，我们首先对金属纳米簇进行了分类，将其分为贵金属纳米簇和非贵金属纳米簇；然后分别对贵金属和非贵金属纳米簇在光催化CO2还原中的研究进展进行了归纳与总结。本文通过及时全面概述近几年该领域的研究进展，从而为未来研究方向提供新思路。     

二氧化硅纳米颗粒表面原位还原银纳米簇电化学发光传感界面的构建与分子识别

通过牛血清蛋白(BSA)对二氧化硅纳米颗粒(SiO₂ NPs)表面进行氨基、 巯基功能化, 随后以BSA同时作为模板和还原剂, 原位生成银纳米簇(Ag NCs), 获得显著增强阴极电化学发光(ECL)信号的Ag NCs-SiO₂ NPs复合纳米材料. 结果表明, 当测试溶液中含有L-半胱氨酸(L-Cys)时, 其与传感界面上的Ag NCs发生共价结合作用, 从而猝灭其ECL信号. 基于该原理, 构建了“开-关”型ECL信号响应模式的L-Cys生物传感器. 该传感器检测L-Cys的浓度范围为50 nmol/L~50 μmol/L, 最低检测限达到13.7 nmol/L, 能够实现L-Cys的高灵敏及特异性分析, 有望在生物、 医学等领域得到广泛应用.     

高核Ag/S纳米团簇合成的研究进展

硫醇配体保护的高核银纳米团簇具有丰富的结构和性能, 在光致发光、 生物传感、 纳米材料等方面具有广阔的应用前景. 然而, 精确控制高核Ag/S纳米团簇的尺寸和结构面临着巨大的挑战, 构建高核Ag/S纳米团簇的可行策略也一直是人们关注的焦点. 近年来, 随着合成方法和表征技术的不断发展, 高核Ag/S纳米团簇的合成和性能研究方面均取得了显著的成就. 本文总结了含20个或以上Ag原子的Ag/S纳米团簇的合成方法(直接还原法、 阴离子模板法及配体交换法), 对部分高核Ag/S纳米团簇的结构进行了探讨, 并展望了未来研究的趋势.     

Electrochemiluminescence Single-cell Analysis on Nanostructured Interface

Due to the heterogeneity of single cells, the development of single-cell analysis methods is conducive to the research of cellular mechanisms, clinical diagnosis, and treatment. Electrochemiluminescence (ECL) has the advantage of being controllable in time and space. Compared with spectroscopy, ECL does not require a light source, thus avoiding the interference of scattered light and luminescent impurities. Therefore, ECL is playing an increasingly important role in the field of single-cell analysis. In ECL single-cell analysis, it is important to construct a suitable nanostructure interface to realize signal conversion. This review first briefly introduced the ECL system commonly used in single-cell analysis, then focused on the recent developments in ECL single-cell analysis on nanostructure interface, finally discussed the future challenges and outlooks of ECL single-cell analysis.     

Dual Enhancement of Gold Nanocluster Electrochemiluminescence: Electrocatalytic Excitation and Aggregation-Induced Emission

Ligand-protected gold nanoclusters (AuNCs) have emerged as a new class of electrochemiluminescence (ECL) luminophores for their interesting catalytic and emission properties, although their quantum yield (Φ_ECL) in aqueous medium is low with a poor mechanistic understanding of the ECL process. Now it is shown that drying AuNCs on electrodes enabled both enhanced electrochemical excitation by an electrocatalytic effect, and enhanced emission by aggregation-induced ECL (AIECL) for 6-aza-2-thiothymine (ATT) protected AuNCs with triethylamine (TEA) as a coreactant. The dried ATT-AuNCs/TEA system resulted in highly stable visual ECL with a Φ_ECL of 78 %, and a similar enhancement was also achieved with methionine-capped AuNCs. The drying enabled dual-enhancement mechanism has solved a challenging mechanistic problem for AuNC ECL probes, and can guide further rational design of ECL emitters.