双量子点纳米复合物NO比率荧光探针的合成与应用

通过静电吸附作用,合成了CdSe@SiO_2-CdTe双量子点的纳米复合物.一氧化氮(NO)与CdTe量子点表面Cd离子结合形成Cd-NO复合物,引起CdTe量子点荧光猝灭,而不影响CdSe量子点的荧光.当NO浓度在0.1~2.2μmol/L之间变化时,该探针荧光强度比值I_(603)/I_(532)符合线性关系(R=-0.995 4),从而实现对NO的定量检测.     

基于银纳米粒子-CdTe量子点复合物荧光探针检测水样和血清中L-半胱氨酸

利用无荧光的碳量子点-银纳米颗粒(CQDs-AgNPs)中Ag~+与CdTe QDs表面S~(2-)的强亲和作用,通过S-Ag键形成弱荧光的CQDs-AgNPs/CdTe QDs纳米复合物探针。L-半胱氨酸(L-Cys)中-S-与复合物探针中Ag~+竞争络合,可使CdTe QDs的荧光恢复,基于L-Cys对复合物探针的荧光恢复作用,建立了水样和血清中L-Cys的荧光检测新方法。最佳条件下,该方法的检出限和相对标准偏差分别为32 nmol/L和2.6%。方法具有灵敏度高、操作简单的优点,已成功应用于水样和人血清中L-Cys的测定。     

不同尺寸量子点-菲啰啉体系对镉检测的影响

采用不同尺寸的高荧光量子产率、单分散性水溶性CdTe量子点(QDs)与菲啰啉(Phen)配体结合,组装成QDs-Phen荧光探针。Phen对不同尺寸量子点荧光猝灭效率以及光致空穴转移效率表现为:2.3 nm的绿色CdTe量子点2.8 nm的黄色CdTe量子点3.3 nm的橙色CdTe量子点;不同粒径QDs-Phen荧光探针对Cd~(2+)的检测发现:粒径2.3 nm QDs-Phen荧光探针对Cd~(2+)检测线性范围为0.02~0.6μmol/L,检测限为0.01 mol/L;粒径2.8 nm QDsPhen荧光探针对Cd~(2+)检测线性范围为0.1 nmol/L~1.0μmol/L,检测限为0.05 nmol/L;而粒径3.3 nm QDs-Phen荧光探针对Cd~(2+)检测线性范围为0.2 nmol/L~1.5μmol/L,检测限为0.1 nmol/L。为选择合适粒径量子点的荧光探针对Cd~(2+)实际检测提供依据。     

基于石墨烯和量子点自组装膜的能量转移构筑的高灵敏度DNA界面荧光传感

以QDs作为荧光探针, HIV1病毒序列DNA为研究对象, 设计了Quartz/PDDA/PSS/PDDA/CdTe/ssDNA自组装膜, 利用氧化石墨烯(GO)猝灭自组装膜上CdTe QDs的荧光, 而靶DNA(tDNA)与自组装膜表面ssDNA的互补配对作用使GO与CdTe QDs的距离增加, 导致自组装膜上量子点的荧光恢复, 由此建立了一种基于GO与QDs自组装膜之间荧光共振能量转移的快速灵敏检测DNA的界面分析方法, 检出限为7.26×10-14 mol/L. 本方法制备的DNA探针操作简单, 自组装膜表面修饰的ssDNA提高了方法的选择性, GO的猝灭作用降低了检测背景, 极大地提高了荧光分析方法的灵敏度.     

基于CdTe量子点的荧光猝灭-恢复法测定L-半胱氨酸

以巯基乙酸为稳定剂,合成了水溶性CdTe量子点(QDs),基于Ni~(2+)存在下,利用CdTe QDs荧光猝灭-恢复技术,建立了测定L-半胱氨酸的新方法。考察了缓冲溶液pH及Ni~(2+)浓度等对测定的影响。在pH=10.0的硼砂缓冲溶液中,Ni~(2+)浓度为40μmol/L条件下,L-半胱氨酸浓度在6.0×10~(-6)~5.0×10~(-5) mol/L范围内与量子点荧光恢复程度呈良好的线性关系,相关系数为0.9990,方法的检出限为2.1×10~(-6) mol/L。该方法应用于果汁和蜂蜜样品中L-半胱氨酸的检测,结果满意。     

CdTe/CdS量子点荧光探针测定司帕沙星含量

在水溶液中合成了巯基乙酸修饰的CdTe/CdS量子点(QDs),基于喹诺酮类抗生素司帕沙星与CdTe/CdS量子点的荧光猝灭作用,建立了用CdTe/CdS量子点作为荧光探针检测微量司帕沙星的新方法.用荧光光谱、紫外光谱研究了CdTe/CdSQDs与司帕沙星的相互作用.研究表明:该荧光猝灭的机理属于静态猝灭,反应的作用机理可能是司帕沙星促使QDs表面键合的有机分子发生变化,在Cd的电子空穴上形成了碲氧复合物,致使荧光猝灭.实验发现,pH为6.50的磷酸缓冲溶液中,量子点的浓度为3.75×10-4mol/L时,司帕沙星的浓度在0.1～50μg/mL范围与CdTe/CdS量子点荧光猝灭强度呈良好的线性关系,相关系数0.9992,检出限0.01399μg/mL.该方法简便、快捷、灵敏、线性范围宽,应用于司帕沙星片剂司帕沙星含量的测定,分析结果与标示量一致;用于牛奶中司帕沙星残留量的检测,回收率在93.1%～102.4%,结果满意.     

CdTe/CdS量子点荧光探针测定环境废水中的痕量银(Ⅰ)

制备了巯基乙酸(TGA)修饰的CdTe/CdS量子点(QDs),并基于pH值为5.80的柠檬酸-柠檬酸钠缓冲溶液和十二烷基苯磺酸钠(SDBS)存在下,Ag(Ⅰ)与CdTe/CdS QDs的荧光猝灭作用,建立了以CdTe/CdS QDs为荧光探针测定样品中痕量Ag(Ⅰ)含量的新方法。室温下,Ag(Ⅰ)的质量浓度在3.0~700μg/L范围内与CdTe/CdS QDs荧光猝灭强度呈线性关系,相关系数为0.9988,方法的检出限为1.0μg/L。方法应用于环境废水中痕量Ag(Ⅰ)含量检测,并做回收试验,测得回收率为95.2%~103.0%。     

CdTe纳米荧光探针的合成及其与DNA的相互作用

以巯基丙酸(RSH)为稳定剂,采用水相法合成了功能性CdTe纳米晶,并通过X射线衍射(XRD)和透射电镜(TEM)对其粒度和形貌进行表征。建立了一种以水溶性CdTe量子点作为荧光探针测定DNA的方法,当DNA浓度为0.2~40μmol.dm-3时,荧光强度与DNA浓度呈良好的线性关系,检测限为80nmol.dm-3,11次重复测定含有5.6μmol.dm-3的小牛胸ctDNA得到的相对标准偏差为3.4%。考察了CdTe量子点浓度、pH值、温度及作用时间等因素对DNA荧光强度的影响。研究发现CdTe纳米粒子与DNA之间存在强烈的相互作用,量子点的荧光猝灭与DNA浓度呈线性关系;作用机理研究表明,CdTe纳米粒子与DNA之间存在静电相互作用,且DNA对CdTe纳米粒子的猝灭为动态猝灭过程。     

基于甲基红-CdTe量子点荧光共振能量转移体系测定痕量强力霉素

本文以甲基红(MR)为能量给体,CdTe量子点(QDs)为能量受体,构建了MRCdTe QDs荧光共振能量转移体系,同时基于荧光猝灭法建立了检测痕量强力霉素(DOX)的新方法。实验表明,在pH=8.0的Tris-HCl缓冲介质中,聚乙烯醇(PVA)胶束能缩短MR与CdTe QDs分子间的距离,二者之间发生有效能量转移,使CdTe QDs荧光强度增强。而强力霉素能够猝灭该体系中CdTe QDs的荧光强度,以此建立了能量转移荧光猝灭法测定痕量强力霉素的新方法。实验表明强力霉素的线性范围为8~350×10-9 mol/L,检出限为2.1×10-9 mol/L。方法可应用于实际样品中强力霉素残留的测定。     

3-巯基丙酸修饰的CdTe量子点荧光探针用于碘酸根离子的检测

以3-巯基丙酸(MPA)为稳定剂,采用水相合成法制备了CdTe量子点(QDs)。基于IO-3可使CdTe QDs荧光显著猝灭的特性,建立了一种检测IO-3的荧光分析新方法。优化了实验条件,在pH=6.0、三酸缓冲溶液浓度为30mmol/L、QDs溶液浓度为8.66×10-6 mol/L、反应时间为24min最佳实验条件下,检测IO-3的线性范围为6.0×10-8~7.2×10-6 mol/L,检出限为4.92×10-8 mol/L,方法相对标准偏差为2.37%。实验表明,IO-3对CdTe QDs的荧光猝灭有较好的选择性。方法用于自来水中IO-3的回收率实验,回收率为92.17%~103.29%。对可能的机理进行了探讨。     

The Influence of Surface Modification on the Photoluminescence of CdTe Quantum Dots: Realization of Bio‐Imaging via Cost‐Effective Polymer

To impart biocompatibility, stability, and specificity to quantum dots (QDs)—and to reduce their toxicity—it is essential to carry out surface modification. However, most surface‐modification processes are costly, complicated, and time‐consuming. In addition, the modified QDs often have a large size, which leads to easy aggregation in biological environments, making it difficult to excrete them from in vivo systems. To solve these problems, three kinds of conventional polymers, namely, polyvinyl alcohol (PVA, neutral), sodium polystyrene sulfonate (PSS, negative charged), and poly(diallyl dimethyl ammonium chloride) (PDDA, positive charged) were selected to modify the surface of QDs at low cost via a simple process in which the size of the QDs was kept small after modification. The effect of polymer modification on the photoluminescence (PL) properties of the QDs was systematically investigated. High quantum yields (QYs) of 65 % were reached, which is important for the realization of bio‐imaging. Then, the cytotoxicity of CdTe QD–polymer composites was systematically investigated via MTT assay using the Cal27 and HeLa cell lines, especially for high concentrations of QD–polymer composites in vitro. The experimental results showed that the cytotoxicity decreased in the order CdTe‐PDDA>CdTe>CdTe‐PSS>CdTe‐PVA, indicating that PSS and PVA can reduce the toxicity of the QDs. An obvious cytotoxicity of CdTe‐PVA and CdTe‐PSS was present until 120 h for the Cal27 cell line and until 168 h for the HeLa cell line. At last, the Cal27 cell line was selected to realize bio‐imaging using CdTe‐PSS and CdTe‐PVA composites with different emission colors under one excitation wavelength.     

磁性量子点电致化学发光法测定李氏禾提取液中的过氧化氢

利用巯基乙酸水热法合成出表面修饰—COOH的CdTe量子点,并将CdTe量子点(QDs)连接在Fe3O4纳米粒子表面,制备出CdTe/Fe3O4磁性量子点。通过磁力将磁性量子点修饰于石墨电极表面。在pH7.5的PBS缓冲溶液中,H2O2可使CdTe量子点产生电致化学发光,H2O2浓度在4～100μmol/L范围内与CdTe量子点的电致化学发光强度呈良好的线性关系,检出限为0.24μmol/L。据此建立了测定样品中过氧化氢含量的电致化学发光分析法,并成功地应用于李氏禾草汁原液中过氧化氢含量的测定。该研究借助纳米Fe3O4的磁力特征,使敏感膜易于形成和更新分离,简化了实验操作,同时起到增强发光强度的作用。     

Synthesis of positively charged CdTe quantum dots and detection for uric acid

The CdTe dots (QDs) coated with 2-Mercaptoethylamine was prepared in aqueous solution and characterized with fluorescence spectroscopy, UV-Vis absorption spectra, high-resolution transmission electron microscopy and infrared spectroscopy. When the λex=350 nm, the fluorescence peak of positively charged CdTe quantum dots is at 592 nm. The uric acid is able to quench their fluorescence. Under optimum conditions, the change of fluorescence intensity is linearly proportional to the concentration of uric acid in the range 0.4000-3.600 μmol L(-1), and the limit of detection calculated according to IUPAC definitions is 0.1030 μmol L(-1). Compared with routine method, the present method determines uric acid in human serum with satisfactory results. The mechanism of this strategy is due to the interaction of the tautomeric keto/hydroxyl group of uric acid and the amino group coated at the CdTe QDs.     

The preparation of glutathione-capped CdTe quantum dots and their use in imaging of cells

In this paper, different sizes of glutathione-capped CdTe (GSH/CdTe) quantum dots (QDs) have been prepared directly in aqueous solution. The QDs have tunable fluorescence in the range of 510-670 nm, and they also have high photoluminescence quantum yield (PLQY) without any postpreparative treatment. Furthermore, the QDs have strong resistance to photobleaching, and they also have to be considered as cytocompatible. In addition, for the first time, folic acid was covalently conjugated to the GSH/CdTe QDs for imaging of cancer cells, demonstrating their potentially broad application as biolabels.     

Aqueous synthesis of type-II core/shell CdTe/CdSe quantum dots for near-infrared fluorescent sensing of copper(II)

Type-II core/shell CdTe/CdSe quantum dots (QDs) were synthesized in aqueous medium by employing thiol-capped CdTe QDs as core template and CdCl(2) and Na(2)SeSO(3) as shell precursors, respectively. Compared with the original CdTe cores, the core/shell CdTe/CdSe QDs showed an obvious red-shifted emission with the color-tune capability to the near-infrared (NIR) wavelength, because of the formation of an indirect excitation. The prepared QDs exhibited high stability and moderate fluorescence quantum yields (10-20%), and their core/shell heterostructure was characterized by UV-vis absorption, steady-state and time-resolved fluorescence spectra, X-ray powder diffraction, X-ray photoelectron spectroscopy and high-resolution transmission electron microscopy. The fluorescence of the core/shell QDs could be markedly quenched by Cu(II), and approximate concentrations of other physiologically important cations, such as Zn(II), Ca(II), Na(I) and K(I) etc., had no effect on the fluorescence. Based on this, a simple and rapid method for Cu(II) determination was proposed using the NIR CdTe/CdSe QDs as fluorescent probes. Under optimal conditions, the response was linearly proportional to the concentration of Cu(II) between 0.05 to 50.0 x 10(-6) mol L(-1), the limit of detection was 2.0 x 10(-8) mol L(-1). The developed method was successfully applied to the detection of trace Cu(II) in real samples.     

谷胱甘肽稳定的CdTe量子点荧光猝灭法测定痕量过氧化氢

以谷胱甘肽稳定的CdTe量子点作为荧光探针,基于荧光猝灭法对过氧化氢进行了定量检测,考察了缓冲溶液体系、量子点浓度、反应时间等多种因素的影响。实验结果表明,在pH=7.2的Na2HPO4-NaH2PO4缓冲液中,反应时间为15min,过氧化氢浓度为1.0×10-6～3.0×10-5 mol/L范围时,其线性回归方程为△F=9.78+7.56c(10-6 mol/L),线性相关系数和检测限分别为0.9992和1.27×10-8 mol/L。谷胱甘肽稳定的CdTe量子点荧光猝灭法已用于水样的测定,回收率在96%～103%之间,相对标准偏差RSD不大于3.3%,结果令人满意。     

CdTe量子点荧光猝灭法测定奥沙利铂中微量银

以谷胱甘肽作为稳定剂,100℃恒温回流,直接合成水溶性CdTe量子点。基于Ag+对合成的CdTe量子点的荧光猝灭效应,建立了测定抗癌药物奥沙利铂中微量银的方法。考察了量子点浓度、缓冲液种类、缓冲液浓度、缓冲液pH和反应时间对银离子测定的影响。当量子点浓度为0.004 g/L时,在0.10 mmol/LpH7.4的磷酸缓冲溶液中,反应时间为5 min,体系的相对荧光强度与Ag+的质量浓度呈良好的线性关系,其线性范围为16.42～98.50μg/L,线性相关系数为0.9975,检出限为0.12μg/L。     

表面修饰CdTe量子点的合成及其光学特性

在水相中合成高发光性能的CdTe量子点,研究以巯基乙酸(TGA)为稳定剂对CdTe表面进行修饰,制备在水中分散性良好的纳米晶,通过对CdTe量子点合成反应条件的摸索,掌握了其合成的反应规律.同时用紫外分光光度计、荧光分光光度计和透射电子显微镜对其进行了表征.结果表明,回流时间、n(Cd2+):n(HTe-)、反应物浓度、TGA用量、反应体系pH值,对纳米晶的光学性质具有显著影响.回流2 h制得的CdTe纳米粒子直径约为5 nm,其发射峰窄且对称,表现出良好稳定的光学性质.     

CdTe/CdS半导体量子点作为农药百草枯的高灵敏传感器

用硫普罗宁(Tiopronin,TP)作为稳定剂合成了水溶性的高荧光CdTe/CdS量子点.研究了该量子点与10种农药的相互作用.实验发现,当农药浓度为4.76×10-6mol/L时,农药百草枯(Paraquat)能显著猝灭CdTe/CdS量子点的荧光,使其荧光强度下降87.3%,而分别加入乙酰甲胺磷及辛硫磷等其它9种农药,仅能使CdTe/CdS量子点的荧光强度下降0.1%～5.1%,显示了该CdTe/CdS量子点对百草枯的特异性传感作用.采用吸收光谱和时间分辨荧光动力学研究了百草枯对CdTe/CdS量子点的荧光猝灭机理.计算得出荧光强度猝灭的Stern-Volmer常数K为2.03×106,而寿命猝灭的Stern-Volmer常数K为4.25×105.结果表明,百草枯对CdTe/CdS量子点的荧光猝灭主要为静态过程,而动态过程的贡献较小.利用二者的猝灭作用建立了对农药百草枯的高灵敏检测新方法,校正曲线的线性范围为9.90×10-9～1.50×10-6mol/L,检出限为6.35×10-9mol/L,R=0.999.用该方法对3种食品和3种水样中残留农药进行了检测,加标回收率均在82.2%～98.5%之间,其相对标准偏差为2.62%～8.35%.     

CdTe量子点与罗丹明6G间的荧光共振能量转移机理研究

本文在合成水溶性巯基乙酸修饰的CdTe量子点的基础上,研究了CdTe量子点与罗丹明6G之间的荧光共振能量转移.实验结果表明:构建的CdTe量子点(供体)-罗丹明6G(受体)荧光共振能量转移体系在磷酸盐缓冲溶液中有较好的转移效果.当磷酸缓冲溶液pH值为7.4,NaCl浓度为1.0 mol/L时,构建的CdTe量子点-罗丹...