配体对CdTe量子点与BSA的选择性相互作用的影响

以巯基乙酸(TGA)、巯基丙酸(MPA)、巯基甘油(TG)、L-半胱氨酸(L-cys)和谷胱甘肽(GSH)等5种巯基分子为稳定剂, 水相合成了5种CdTe量子点. 以牛血清白蛋白(BSA)作为靶分子, 通过吸收光谱、荧光光谱和时间分辨荧光动力学等手段研究了各种配体分子稳定的CdTe量子点与BSA的直接相互作用. 结果表明, 5种量子点均能有效猝灭BSA的荧光, 其猝灭程度按配体次序为GSH>L-cys>TGA>TG>MPA; 而BSA对不同配体稳定的CdTe量子点的荧光光谱的影响则具有明显的选择性. BSA对TGA-CdTe和MPA-CdTe量子点的荧光先敏化增强而后猝灭下降; L-cys分子由于同时具有氨基和羧基而与BSA的相互作用较强, 因此BSA能显著猝灭L-cys-CdTe量子点的荧光; 而BSA对TG-CdTe量子点的荧光猝灭程度较小; GSH分子的空间效应使GSH-CdTe量子点的荧光被BSA猝灭的程度最小. 吸收光谱和时间分辨荧光动力学研究表明, 5种量子点与BSA之间的相互作用均为静态过程. 探讨了量子点的配体分子结构与蛋白质的相互作用机理.     

紫外-可见吸收、荧光光谱研究CdTe/CdS量子点与盐酸药根碱的相互作用及其应用

合成了巯基乙酸（TGA）修饰的壳核型CdTe/CdS量子点（TGA-CdTe/CdS QDs）。 利用紫外-可见光谱吸收、荧光光谱研究TGA-CdTe/CdS QDs与盐酸药根碱（JH）的相互作用机理。 在pH值为7.4的tris-HCl缓冲溶液介质中,QDs与JH相互作用后使QDs的荧光呈线性猝灭,并有良好的线性关系（r=0.999 1）,线性范围0.011~10 mg/L,检出限（3σ）为3.3×10-3 mg/L,因此可以作为一种快速、简便、定量测定盐酸药根碱的新方法。     

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.     

Preparation,characterization and biocompatibility of aspartic acid modified CdTe quantum dots

This study aims at preparing water soluble aspartic acid （ASP） modified CdTe quantum dots with tunable fluorescence emission controlled by reaction time. The size of the synthesized CdTe quantum dots was evaluated using transmission electron microscope （TEM） and also calculated based on their UV-vis spectra. The optical properties of TGA-CdTe quantum dots were characterized by UV-vis and fluorescence （FL） spectroscopy. The red-shift in the UV-vis absorption and FL emission with the increase of reaction time was observed. The biocompatibility examination indicated that the ASP modified CdTe QDs had low cytotoxicity.     

单-(6-巯基)-β-环糊精修饰的CdTe量子点的合成及与中性红的相互作用

以巯基乙酸(TGA)和单-(6-巯基)-β-环糊精(mono-6-thio-β-CD)作混合稳定剂,通过优化TGA/mono-6-thio-β-CD比例及回流时间,合成出了粒径分布均匀、荧光量子产率高达81.3%的mono-6-thio-β-CD修饰的CdTe量子点(QDs),建立了一种在水相中直接合成β-CD修饰的CdTe的新方法.利用荧光光谱、紫外-可见吸收光谱、共振瑞利散射光谱(RRS)研究了mono-6-thio-β-CD-CdTeQDs与中性红的相互作用,同时通过对比单独使用TGA为稳定剂合成的TGA-CdTeQDs与中性红的相互作用并结合透射电子显微镜(TEM)对反应机理进行了讨论并提出了相应的反应模型.在pH6.1的BR缓冲溶液中,当中性红浓度为7.5×10-6mol/L时,中性红的离子型体HNR+和分子型体NR分别与mono-6-thio-β-CD-CdTeQDs表面的-SCH2COO-和mono-6-thio-β-CD结合达饱和,当中性红浓度大于7.5×10-6mol/L时,中性红开始在mono-6-thio-β-CD-CdTeQDs表面聚集,导致mono-6-thio-β-CD-CdTeQDs粒径增大、荧光急剧猝灭、RRS显著增强.     

Purification of denatured bovine serum albumin coated CdTe quantum dots for sensitive detection of silver(I) ions

CdTe quantum dots (QDs) were synthesized in aqueous solution with 3-mercaptopropionic acid as the stabilizer. Chemically reduced bovine serum albumin (BSA) was used to modify the surface of the QDs. Experimental results showed that the denatured BSA (dBSA) could be effectively conjugated to the surface of CdTe QDs. Column chromatography was used to purify the conjugates and determine the optimal ratio of dBSA to QDs. Further experimental results showed that the conjugation of QDs by dBSA efficiently improved the photoluminescence quantum yield, the chemical stability of QDs and their stability against photobleaching. A facile and sensitive method for determination of silver(I) ions was proposed based on the fluorescence quenching of the dBSA–QDs. Under the optimal conditions, the relative fluorescence intensity decreased linearly with the concentration of the silver(I) ions in the range 0.08–10.66 μM. The detection limit was 0.01 μM. This study provides a new method for the detection of metal cations. Figure In this work, denatured BSA was used to modify the surface of CdTe QDs by a simple and rapid method. And the conjugates of dBSA-QDs were purified by column of Sephadex G-100. After the purification of the conjugates, the sensitivity was greatly increased as silver (I) ions probe.     

光谱法研究核壳量子点CdTe/CdS与牛血清白蛋白的相互作用

应用荧光光谱、圆二色光谱和紫外吸收光谱等技术研究核壳量子点CdTe/CdS与牛血清白蛋白(BSA)相互作用的结果表明,CdTe/CdS对BSA的荧光猝灭机理为静态猝灭。根据不同温度下量子点对BSA的荧光猝灭作用计算了结合常数、热力学参数,证明了量子点与BSA相互作用力主要是范德华力或氢键作用力。探讨了量子点对BSA构象的影响。     

CdTe量子点与蛋白质相互作用的荧光猝灭效应

本文在水热法合成水溶性CdTe及核壳结构CdTe/CdS量子点的基础上,分别研究了细胞色素c对CdTe量子点及CdTe/CdS核壳量子点荧光的猝灭效应和CdTe量子点对牛血清白蛋白荧光的猝灭效应,并阐述了猝灭机理。结果显示,细胞色素c对CdTe量子点的荧光猝灭效应具有一定的粒径依赖性,粒径越小,猝灭效应越强;细胞色素c对CdTe/CdS核壳量子点的猝灭效应比对CdTe量子点的更强,揭示了受激电子的表面传递机理。CdTe量子点通过松散牛血清白蛋白的螺旋结构而猝灭其荧光。     

Multi-spectroscopic Study on the Interaction between CdTe Quantum Dots and Bovine Serum Albumin

The interaction between CdTe quantum dots (QDs) and bovine serum albumin (BSA) was systematically investigated by fluorescence, UV‐vis absorption and circular dichroism (CD) spectroscopy under physiological conditions. The experimental results showed that the fluorescence of BSA could be quenched by CdTe QDs with a static quenching mechanism, indicating that CdTe QDs could react with BSA. The quenching constants according to the modified Stern‐Volmer equation were obtained as 1.710×10⁶, 1.291×10⁶ and 1.010×10⁶ L·mol^?1 at 298, 304, and 310 K, respectively. ΔH, ΔS and ΔG for CdTe QDs‐BSA system were calculated to be ?33.68 kJ·mol^?1, 6.254 J·mol^?1·K^?1 and ?35.54 kJ·mol^?1 (298 K), respectively, showing that electrostatic interaction in the system played a major role. According to F?rster theory, the distance between Trp‐214 in BSA and CdTe QDs was given as 2.18 nm. The UV‐vis, synchronous fluorescence and CD spectra confirmed further that the conformations of BSA after addition of CdTe QDs have been changed.     

高灵敏CdTe量子点探针的构建及与金属离子的作用

采用变性的牛血清白蛋白(dBSA)对水相合成的CdTe量子点进行修饰, 构建了高灵敏金属离子探针, 研究了其对重金属离子的检测性能并对机理进行了探讨. 通过优化反应条件, 合成了具有高量子产率的以巯基乙酸为稳定剂的水溶性CdTe量子点, 并采用变性的牛血清白蛋白分别对不同粒径的CdTe量子点进行修饰, 确定变性的牛血清白蛋白与不同粒径量子点之间的最佳比例. 在纯化变性的牛血清白蛋白修饰的量子点(dBSA-QDs)的基础上, 研究了该量子点与不同金属离子的作用. 结果表明, 量子点经修饰后, 其量子产率、 抗光漂白性及稳定性得到显著提高; 而且dBSA-QDs的荧光可被重金属离子有效猝灭, 与巯基乙酸稳定的量子点(TGA-QDs)相比, 检测灵敏度显著提高.     

Synthesis of functionalized CdTe/CdS QDs for spectrofluorimetric detection of BSA

Luminescent quantum dots (QDs)-semiconductor nanocrystals are a promising alternative to organic dyes for fluorescence-based applications. We have developed procedures to use CdS to encapsulate CdTe and synthesize a new kind of functionalized CdTe/CdS QDs for the quantitative and selective determination of bovine serum albumin (BSA). Maximum fluorescence intensity was produced at pH 6.83, with excitation and emission wavelengths at 336 and 524 nm, respectively. Under optimal conditions, the straight line equation: DeltaF=6.84+62.29C (10(-6) mol dm(-3)) was found between the relative fluorescence intensity and the concentration of BSA in the range of 0-1.2 x 10(-6) mol dm(-3), and the limit of detection was 5.4 x 10(-8) mol dm(-3). Based on this approach, a novel quantitative method for the determination of BSA is presented in this paper.     

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。     

不同环境因素对水热法合成碲化镉量子点的影响

对比了不同巯基稳定剂和前体浓度对水热环境CdTe量子点的生长过程和光物理性质的影响。结果表明,巯基丙酸与镉前体的结合能力较强,一定程度上减小了前体溶液中镉的浓度,故CdTe量子点生长速率较慢;空间位阻较大的硫普罗宁与镉前体的结合相对较弱,因此导致CdTe量子点生长较快。巯基丙酸有利于制备发光波长较短的高荧光强度CdTe 量子点,而硫普罗宁有利于制备发光波长较长的高荧光强度CdTe量子点。前体浓度对CdTe量子点的生长速率和光物理性质的影响不明显。在上述实验结果基础上,考察了水溶性乙酸钠和聚丙烯酸钠电解质对水热环境中CdTe量子点的生长过程和光物理性质的影响。结果表明,添加乙酸钠后可提高CdTe量子点的生长速率,进而导致CdTe量子点的表面重构和钝化能力下降,使荧光强度降低;聚丙烯酸钠对镉单体独特的固定作用导致CdTe量子点生长缓慢,尺寸集中化受限,钝化能力降低,使荧光强度下降更加明显。     

水溶性的高荧光CdTe/CdSeⅡ型核壳量子点的合成与表征

用L-半胱氨酸(L-cysteine)作为稳定剂,以制备的CdTe量子点为核模板,水相合成了具有近红外发光的Ⅱ型核壳CdTe/CdSe半导体量子点。实验考察了合成温度,核模板的尺寸和组分比等因素对合成高质量的CdTe/CdSe量子点的影响。用紫外-可见吸收和荧光光谱研究了合成的量子点的光学性质。在优化的合成条件下,荧光发射光谱在586～753nm范围连续可调,荧光量子产率高达68%;通过X-射线衍射(XRD),X射线光电子能谱(XPS)和透射电镜(TEM)对合成的Ⅱ型核壳CdTe/CdSe量子点进行了结构和形貌表征。     

Luminescent properties of water-soluble denatured bovine serum albumin-coated CdTe quantum dots

Chemically reduced bovine serum albumin (BSA) has been used to modify the surface of water-soluble CdTe quantum dots (QDs). It is demonstrated that the denatured BSA (dBSA) can be conjugated to the surface of CdTe QDs and thereby efficiently improve the chemical stability and the photoluminescence quantum yield (PL QY) of the QDs. It is inferred that a shell-like complex structure CdTe(x)(dBSA)(1-x) will form on the surface of the CdTe "core", resulting in the enhancement of PL intensity and the blue shift of the PL peak. This study of the effects of pH and dBSA concentration on optical properties of dBSA-coated QDs suggests that, at pH 6-9, the solution of dBSA-coated CdTe QDs can keep substantial stability and fluorescent brightness, whereas further increase of pH value leads to a dramatic decrease in PL QY and chemical stability. On the other hand, too high or too low initial dBSA concentration in the QD solution results in a decrease of PL QY for dBSA-coated CdTe QDs. This study provides a new approach of preparing stable water-soluble QDs with high PL QY and controllable luminescent colors for biological labeling applications.     

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.     

碲化镉量子点光催化降解溴化乙锭的研究

以巯基乙酸为稳定剂, 水相合成出不同粒径的碲化镉量子点, 对其进行适当的光照处理, 以提升其光学性质和稳定性. 将其用作光催化剂, 以紫外灯为光源, 降解具有强诱变作用的常用核酸荧光染料——溴化乙锭. 考察了光照时间和溶液 pH 对降解率的影响. 以溴化乙锭在620 nm处的特征荧光发射峰为参数表征降解率, 在反应4 h后, 对15 mg/L溴化乙锭水溶液的降解率近90%, 同时, 对琼脂糖凝胶中的溴化乙锭也有降解作用.     

CdX(X=Se,Te,Te/ZnS)量子点脂质体的制备及毒性比较

在水相中以巯基乙酸(mercaptoacetic acid, MA)为稳定剂合成了CdSe、CdTe、CdTe/ZnS量子点及谷胱甘肽(glutathione, GSH)为稳定剂合成了CdTe量子点,然后通过卵磷脂和胆固醇修饰制得相应的量子点脂质体。溶血实验证实GSH修饰量子点的溶血率低于MA修饰的量子点45%;脂质体修饰后,量子点的溶血率＜5%,达到生物医用材料要求。不同表面修饰的量子点对小鼠毒性存在明显差异,荧光显微镜观察组织切片证实量子点在小鼠体内主要分布在肺、肾、胸腺等组织中,而脂质体量子点在脑组     

Studying the interaction between CdTe quantum dots and Nile blue by absorption,fluorescence and resonance Rayleigh scattering spectra

Thioglycolic acid (TGA) capped CdTe quantum dots (QDs) with the diameter of 2–3 nm were synthesized. The interaction between CdTe QDs and Nile blue (NB) was investigated by ultraviolet–visible (UV–vis) absorption, resonance Rayleigh scattering (RRS) and fluorescence spectroscopy. UV–vis absorption spectrum of CdTe QDs and NB obviously changed, showing that CdTe QDs could associate with NB to form a new complex. At pH 6.8, NB effectively quenched the fluorescence of CdTe QDs. It was proved that the fluorescence quenching of CdTe QDs by NB was mainly result of the formation of CdTe QDs–NB complex, electrostatic attraction and hydrophobic forces played a major role in stabilizing the complex. The binding molar ratio of CdTe QDs and NB was 5:1 by a mole-ratio method. The interaction between CdTe QDs and NB lead to the remarkable enhancement of RRS and the enchantments were in proportional to the concentration of NB in a certain range. The mechanism of the interaction between CdTe QDs and NB, reasons for the enhancement of RRS intensity were also discussed. The obtained results suggested the more satisfactory mechanism for the interaction between CdTe QDs and NB.     

Preparation of giant unilamellar CdTe quantum dot vesicles and their metabolic pathway in vivo

Glutathione (GSH) capped CdTe quantum dots (QDs) with photoluminescence quantum yields of 61% and the maximum emitting at 601.2 nm were prepared in water phase. Giant unilamellar CdTe quantum dot vesicles (GUVs-CdTe), with diameters larger than 1.5 μm, were obtained using lower-pressure evaporation techniques with soybean lecithin. Compared with other QD liposomes, the entrapment efficiency of GUVs-CdTe for QDs has been significantly improved to 86.3%. After GUVs-CdTe were injected into mice through the tail vein, the fluorescence microscopy of tissue sections showed that GUVs-CdTe could not pass through the blood-brain barrier and air-blood barrier, which were removed mostly by the reticuloendothelial system and were widely distributed in the spleen and the liver. This behavior is the same as the character of the metabolic pathway of giant unilamellar vesicles by intravenous injections in mice.