量子点在电化学生物传感研究中的应用

量子点( Quantum dots,QDs )由于具有独特的光学、电化学和电致化学发光特性已受到广泛地重视,而利用量子点构建电化学生物传感器则是量子点最有前途的应用领域之一。量子点具有的高比表面积、高表面活性及小尺寸等特性使它对外界的光、电、温度等十分地敏感,外界环境的微小改变就会迅速引起其表面或界面粒子价态和电子转移行为的显著变化,基于生物大分子引起的QDs表面电化学行为变化而构建的电化学生物传感器,其特点是响应灵敏高、速度快且选择性优良。本文对量子点的光学、电化学和电致化学发光特性作了简单介绍,并重点回顾了其在电致化学发光、免疫分析、DNA杂交、蛋白质检测、农药检测和糖类检测电化学生物传感研究中的应用。同时,对量子点在电化学生物传感研究中的应用前景及研究方向进行了评述和展望。     

Signal Amplification Strategy Based on TiO2-Nanotube Layers and Nanobeads Carrying Quantum Dots for Electrochemiluminescent Immunosensors

Self-organized TiO₂-nanotube layers can be used for immunoassay-type sensing in combination with amplifying CdTe labels in a direct and very sensitive electrochemiluminescent (ECL) configuration. Key properties for this method are the conductivity of the TiO₂ nanotubes, and their transparency for light emitted from the CdTe labels at approximately 2.4 eV. To demonstrate the potential of this platform, we constructed a sandwich-type immunoassay onto the TiO₂-nanotube wall with a layer of (3-aminopropyl)triethoxysilane as the cross-linker for antibody immobilization. For the counter part of the sandwich, we created an amplification system consisting of TiO₂ nanobeads carrying the secondary antibody and multiple CdTe quantum dots (multiQD). For antigen (IgG) detection, we find that this combination of 3D transparent electrode with multiQD labels allows for an ECL detection limit of 0.05 pg mL⁻¹ and a linearity of the signal in the range of 0.1–10⁸ pg mL⁻¹.     

量子点的聚合物表面修饰及其应用

量子点作为新型纳米发光材料备受关注,但由于光学稳定性和生物相容性的问题而在实际应用上受限。聚合物对量子点的修饰能够提供量子点合成的有效支撑基质,而且还可以改善量子点的稳定性和单分散性,进而可以拓展量子点应用于化学、物理以及生物学领域。基于聚合物修饰量子点的优势,本文简述了聚合物表面修饰量子点的方法、合成路线、步骤、特点以及发展现状。其中,双亲分子涂敷的量子点可以改善量子点的水溶性;多基配体包裹的量子点更具有稳定性和功能性;末端功能化聚合物表面修饰的量子点则可以合成更为先进功能的材料;胶封树枝状定域量子点具有单分散和优越发光特性。同时,还综述了各种表面修饰方法的最新研究进展,存在问题以及应用发展趋势。     

Non‐Blinking Semiconductor Colloidal Quantum Dots for Biology,Optoelectronics and Quantum Optics

Twinkle, twinkle: The blinking of semiconductor colloidal nanocrystals is the main inconvenience of these bright nanoemitters. There are various approaches for obtaining non‐blinking nanocrystals, one of which is to grow a thick coat of CdS on the CdSe core (see picture). Applications of this method in the fields of optoelectronic devices, biologic labelling and quantum information processing are discussed.

     

Electrochemiluminescence of Carbon-based Quantum Dots: Synthesis,Mechanism and Application in Heavy Metal Ions Detection

In recent years, carbon-based quantum dots as luminophores and co-reactants have aroused broad interest for their ability to function in electrochemiluminescence (ECL) sensors due to their unique features, including excellent biocompatibility, low toxicity, and water solubility. In this mini review, the synthesis methods of carbon-based quantum dots are firstly introduced. Then, the mechanism of carbon-based quantum dots as luminophores and co-reactants and their latest progress application in the detection of heavy metal ions are explored. Finally, the current challenges and potential future development directions of carbon-based quantum dots in ECL sensing filed for heavy metal ions analysis are summarized.     

基于上转换发光的碳量子点制备及应用研究

碳量子点具有易制备、低毒性、化学惰性高、荧光特性稳定等特点,和其他碳纳米材料(如富勒烯、碳纳米管和石墨烯等)一样引起了研究者的广泛关注。本文将从碳量子点的合成、特性、改性和应用等方面进行阐述,并对其受长波长光激发后可发出短波长光的这一上转换发光特性进行重点综述,为今后碳量子点的合成、改性以及应用提供一定的参考。     

Aptamer‐Based Turn‐On Detection of Thrombin in Biological Fluids Based on Efficient Phosphorescence Energy Transfer from Mn‐Doped ZnS Quantum Dots to Carbon Nanodots

This paper presents the first example of a sensitive, selective, and stable phosphorescent sensor based on phosphorescence energy transfer (PET) for thrombin that functions through thrombin–aptamer recognition events. In this work, an efficient PET donor–acceptor pair using Mn‐doped ZnS quantum dots labeled with thrombin‐binding aptamers (TBA QDs) as donors, and carbon nanodots (CNDs) as acceptors has been constructed. Due to the π–π stacking interaction between aptamer and CNDs, the energy donor and acceptor are taken into close proximity, leading to the phosphorescence quenching of donors, TBA QDs. A maximum phosphorescence quenching efficiency as high as 95.9 % is acquired. With the introduction of thrombin to the “off state” of the TBA‐QDs‐CNDs system, the phosphorescence is “turned on” due to the formation of quadruplex‐thrombin complexes, which releases the energy acceptor CNDs from the energy donors. Based on the restored phosphorescence, an aptamer‐based turn‐on thrombin biosensor has been demonstrated by using the phosphorescence as a signal transduction method. The sensor displays a linear range of 0–40 nM for thrombin, with a detection limit as low as 0.013 nM in pure buffers. The proposed aptasensor has also been used to monitor thrombin in complex biological fluids, including serum and plasma, with satisfactory recovery ranging from 96.8 to 104.3 %. This is the first time that Mn‐doped ZnS quantum dots and CNDs have been employed as a donor–acceptor pair to construct PET‐based biosensors, which combines both the photophysical merits of phosphorescence QDs and the superquenching ability of CNDs and thus affords excellent analytical performance. We believe this proposed method could pave the way to a new design of biosensors using PET systems.     

基于WS2量子点材料固定葡萄糖氧化酶的直接电化学及其生物传感研究

采用水热法制备水溶性WS₂量子点（WS₂ QDs）材料,并将该材料进一步用于葡萄糖氧化酶（GOx）的有效固定,构建GOx/W₂ QDs/GCE传感界面. 采用透射电镜、紫外-可见光谱和电化学等方法对材料的形貌、GOx的固定化过程,以及传感器的直接电化学和电催化性能进行了表征. 结果表明,WS₂ QDs材料能够有效促进GOx与电极之间的直接电子转移. 并且,基于该传感器对葡萄糖良好的电催化作用,该方法有效实现了对葡萄糖的高灵敏检测,其线性范围为25 ~ 100 μmol·L^-1和100 ~ 600 μmol·L^-1,检测限为5.0 μmol·L^-1（S/N=3）. 该传感器具有良好的选择性、重现性和稳定性,可用于实际样品血糖的分析测定.     

Protein‐Directed Synthesis of Mn‐Doped ZnS Quantum Dots: A Dual‐Channel Biosensor for Two Proteins

Proteins typically have nanoscale dimensions and multiple binding sites with inorganic ions, which facilitates the templated synthesis of nanoparticles to yield nanoparticle–protein hybrids with tailored functionality, water solubility, and tunable frameworks with well‐defined structure. In this work, we report a protein‐templated synthesis of Mn‐doped ZnS quantum dots (QDs) by exploring bovine serum albumin (BSA) as the template. The obtained Mn‐doped ZnS QDs give phosphorescence emission centered at 590 nm, with a decay time of about 1.9 ms. A dual‐channel sensing system for two different proteins was developed through integration of the optical responses (phosphorescence emission and resonant light scattering (RLS)) of Mn‐doped ZnS QDs and recognition of them by surface BSA phosphorescent sensing of trypsin and RLS sensing of lysozyme. Trypsin can digest BSA and remove BSA from the surface of Mn‐doped ZnS QDs, thus quenching the phosphorescence of QDs, whereas lysozyme can assemble with BSA to lead to aggregation of QDs and enhanced RLS intensity. The detection limits for trypsin and lysozyme were 40 and 3 nM , respectively. The selectivity of the respective channel for trypsin and lysozyme was evaluated with a series of other proteins. Unlike other protein sensors based on nanobioconjugates, the proposed dual‐channel sensor employs only one type of QDs but can detect two different proteins. Further, we found the RLS of QDs can also be useful for studying the BSA–lysozyme binding stoichiometry, which has not been reported in the literature. These successful biosensor applications clearly demonstrate that BSA not only serves as a template for growth of Mn‐doped ZnS QDs, but also impacts the QDs for selective recognition of analyte proteins.     

Electrochemistry in Carbon‐based Quantum Dots

Electrochemistry belongs to an important branch of chemistry that deals with the chemical changes produced by electricity and the production of electricity by chemical changes. Therefore, it can not only act a powerful tool for materials synthesis, but also offer an effective platform for sensing and catalysis. As extraordinary zero‐dimensional materials, carbon‐based quantum dots (CQDs) have been attracting tremendous attention due to their excellent properties such as good chemical stability, environmental friendliness, nontoxicity and abundant resources. Compared with the traditional methods for the preparation of CQDs, electrochemical (EC) methods offer advantages of simple instrumentation, mild reaction conditions, low cost and mass production. In return, CQDs could provide cost‐effective, environmentally friendly, biocompatible, stable and easily‐functionalizable probes, modifiers and catalysts for EC sensing. However, no specific review has been presented to systematically summarize both aspects until now. In this review, the EC preparation methods of CQDs are critically discussed focusing on CQDs. We further emphasize the applications of CQDs in EC sensors, electrocatalysis, biofuel cells and EC flexible devices. This review will further the experimental and theoretical understanding of the challenges and future prospective in this field, open new directions on exploring new advanced CQDs in EC to meet the high demands in diverse applications.     

Employing Core‐Shell Quantum Dots as Triplet Sensitizers for Photon Upconversion

A new family of surface‐functionalized CdSe/ZnS core‐shell quantum dots (csQD) has been developed, which work as triplet sensitizers for triplet‐triplet annihilation‐based photon upconversion (TTA‐UC). The surface modification of csQD with acceptor molecules plays a key role in the efficient relay of the excited energy of csQD to emitter molecules in the bulk solution, where the generated emitter triplets undergo triplet‐triplet annihilation that leads to photon upconversion. Interestingly, improved UC properties were achieved with the core‐shell QDs compared with core‐only CdSe QDs (cQD). The threshold excitation intensity, which is defined as the necessary irradiance to achieve efficient TTA process, decreases by more than a factor of four. Furthermore, the total UC quantum yield is enhanced more than 50‐fold. These enhancements should be derived from better optical properties of csQD, in which the non‐radiative surface recombination sites are passivated by the shell layer with wider bandgap.     

Chemical Functionalisation and Photoluminescence of Graphene Quantum Dots

Chemical modification of graphene quantum dots (GQDs) can influence their physical and chemical properties; hence, the investigation of the effect of organic functional groups on GQDs is of importance for developing GQD–organic hybrid materials. Three peripherally functionalised GQDs having a third‐generation dendritic wedge (GQD‐ 2 ), long alkyl chains (GQD‐ 3 ) and a polyhedral oligomeric silsesquioxane group (GQD‐ 4 ) were prepared by the Cu^I‐catalysed Huisgen cycloaddition reaction of GQD‐ 1 with organic azides. Cyclic voltammetry indicated that reduction occurred on the surfaces of GQD‐ 1 – 4 and on the five‐membered imide rings at the periphery, and this suggested that the functional groups distort the periphery by steric interactions between neighbouring functional groups. The HOMO–LUMO bandgaps of GQD‐ 1 – 4 were estimated to be approximately 2 eV, and their low‐lying LUMO levels (<?3.9 eV) were lower than that of phenyl‐C₆₁‐butyric acid methyl ester, an n‐type organic semiconductor. The solubility of GQD‐ 1 – 4 in organic solvents depends on the functional groups present. The functional groups likely cover the surfaces and periphery of the GQDs, and thus increase their affinity for solvent and avoid precipitation. Similar to GQD‐ 2 , both GQD‐ 3 and GQD‐ 4 emitted white light upon excitation at 360 nm. Size‐exclusion chromatography demonstrated that white‐light emission originates from the coexistence of differently sized GQDs that have different photoluminescence emission wavelengths.     

聚甲基丙烯酰胺包覆的ZnO发光量子点及其在细胞成像中的应用

通过溶胶-凝胶法合成了在水溶液中稳定发光、荧光颜色可调的ZnO@polymer核壳型纳米粒子, 并研究了这种量子点对人类宫颈癌HeLa细胞的毒性以及细胞吞噬后激光共聚焦成像的效果. 这种荧光探针的外壳是一种通过配位键与ZnO内核结合的共聚物, 该共聚物外层是亲水的聚甲基丙烯酰胺, 内层是疏水的聚甲基丙烯酸酯. 细胞毒性实验证明, 该材料有良好的生物兼容性, 适用于生物荧光标记. 共聚焦荧光成像结果显示, 这些纳米粒子可以穿透HeLa细胞膜并在细胞质中稳定发光.     

电化学发光生物传感技术在快速检测心肌梗死标志物中的研究进展

设计和发展简便、高灵敏、高选择性的分析手段以检测低浓度急性心肌梗死生物标志物是目前临床诊断迫切的需求。 电化学发光分析法由于具有稳定性好、灵敏度高、线性范围宽及可控性强等优点,能有效地进行低浓度样品检测。 该方法与生物传感技术相结合,有利于实现生物体液等复杂样品中极低含量急性心肌梗死生物标志物的快速检测。 本文综述了电化学发光生物传感技术在快速检测心肌梗死标志物中近5年的进展,介绍了电化学发光探针和共反应物,以及多组分生物传感检测技术等,并对其在心肌梗死标志物分析中的应用进行了总结。     

超小荧光二硫化钨量子点的水热合成及细胞成像应用

以钨酸钠和半胱氨酸为原料, 采用水热法一步合成了具有超小粒径(约2 nm)的二硫化钨荧光量子点(WS₂ QDs). 利用透射电子显微镜(TEM)、 荧光光谱、 X射线光电子能谱(XPS)、 红外光谱(FTIR)和X射线衍射光谱(XRD)对其进行了表征, 并考察了其稳定性和细胞毒性. 结果表明, 制备的WS₂ QDs具有水溶性好、 稳定性高和细胞毒性低的优点. 将此WS₂ QDs用于人乳腺癌细胞(MCF-7)的成像, 并通过溶酶体荧光探针进行共定位, 发现此WS₂ QDs可能借助溶酶体进入细胞内.     

Fluorescence and Sensing Applications of Graphene Oxide and Graphene Quantum Dots: A Review

Graphene oxide and graphene quantum dots are attractive fluorophores that are inexpensive, nontoxic, photostable, water‐soluble, biocompatible, and environmentally friendly. They find extensive applications in fluorescent biosensors and chemosensors, in which they serve as either fluorophores or quenchers. As fluorophores, they display tunable photoluminescence emission and the “giant red‐edge effect”. As quenchers, they exhibit a remarkable quenching efficiency through either electron transfer or Förster resonance energy transfer (FRET) process. In this review, the origin of fluorescence and the mechanism of excitation wavelength‐dependent fluorescence of graphene oxide and graphene quantum dots are discussed. Sensor design strategies based on graphene oxide and graphene quantum dots are presented. The applications of these sensors in health care, the environment, agriculture, and food safety are highlighted.