不同巯基试剂修饰的CdTe量子点与BSA相互作用研究

修饰试剂对量子点的合成、性质具有重要的影响,但目前有关修饰试剂对量子点与蛋白质间相互作用的影响尚不清楚。采用紫外-可见吸收光谱、荧光光谱及红外光谱研究了3种巯基化合物(巯基乙酸,TGA;L-半胱氨酸,L-Cys;还原型谷胱甘肽,GSH)修饰的CdTe量子点与牛血清白蛋白(BSA)的相互作用。通过Stern-Volmer方程对数据进行了分析,得到了不同CdTe量子点与BSA相互作用过程的ΔHθ,ΔGθ和ΔSθ,并比较了CdTe量子点的不同修饰剂对BSA荧光猝灭的影响。研究结果表明,3种修饰试剂包覆的CdTe量子点与BSA的相互作用均为静态猝灭过程,猝灭常数KSV(L-Cys)KSV(TGA)≈KSV(GSH);TGA和L-Cys修饰的CdTe量子点与BSA的结合力主要为疏水作用力,而GSH修饰的量子点与其结合力既有氢键作用力又有疏水作用力;这些结果说明量子点与BSA的作用过程与量子点表面修饰试剂的类型有关。     

A confocal laser scanning microscopic study on thermoresponsive binary microgel dispersions incorporated with CdTe quantum dots

Monodisperse poly(N-isopropylacrylamide) (PNIPAM) particles loaded with cadmium telluride (CdTe) quantum dots (QDs) of two different sizes (4.7 nm and 5.6 nm) were synthesized in aqueous medium by bonding the capping agent on the quantum dots to the amide groups of PNIPAM and incubating the samples at 45°C. A huge increase in the photoluminescence (PL) intensity (green and red regions) is observed for the PNIPAM-CdTe QDs composites compared to the parent CdTe QDs. We report here for the first time the imaging of binary dispersion of green and red luminescent PNIPAM-CdTe QDs composites using a fluorescence confocal laser scanning microscope. These composites have potential applications both in material science and biology.     

CdSe量子点膨润土复合材料的制备与表征

首先以CdCl₂·2.5H₂O、SeO₂和NaBH₄为反应物,制备巯基丁二酸稳定的CdSe量子点。然后将有机膨润土与CdSe量子点溶液混合并充分搅拌,制备负载CdSe量子点的膨润土发光材料,用荧光光谱、扫描电镜和X射线粉末衍射等分析测试手段对所得材料的光谱性能与微观结构进行表征。光谱分析表明,量子点膨润土复合材料的发光颜色与量子点溶液非常一致;X射线光电子能谱分析表明,复合后的材料中含有Cd 和 Se两种元素;此外,在量子点膨润土复合材料X射线粉末衍射谱中可见CdSe量子点（111）、（220）及（331）3个晶面的衍射峰,2θ=4.3°处出现膨润土（001）衍射峰。数据表明,在制备的CdSe量子点膨润土复合材料中,量子点和膨润土的结构都没有改变。     

CdTe∶Eu量子点的合成及其光学性能研究

采用1-十八烯作为高温反应溶剂,利用氯化铕和磷酸三丁酯制备铕前驱体。分别采用正三辛基膦和碲粉制备的碲前驱体,以及油胺和二水乙酸镉制备的镉前驱体,在200℃合成Eu掺杂Cd Te量子点。实验发现随着反应溶液中Eu的含量上升,Cd Te量子点的荧光峰发生显著红移,但Eu的含量过高则会导致量子点的荧光强度下降。     

Aqueous synthesis of thiol-capped CdTe quantum dots and its photoluminescence enhancement via room temperature treatment with alkyl chain diamines

In this study the CdTe quantum dots (QDs) are synthesized in aqueous solution with three thiol-contained capping ligands of thioglycollic acid (TGA), 3-mercaptopropionic acid (MPA), and l-cysteine (lCys). The photoluminescence (PL) enhancement of the as-prepared QDs is also conducted via room temperature treatment with alkyl chain diamines. Our measurements on the ultraviolet–visible (UV–vis) absorption and fluorescence emission reveal that both the growth kinetics and the PL efficiency of the QDs vary a lot with the molecular structures of the three involved ligands. In comparison with TGA and lCys, MPA endows the QDs with a wide color tuning range from cyan to deep red and strong PL emission while its full width at half maximum (FWHM) is regretfully large. Notable enhancement on PL emission is achieved for the TGA and MPA capped QDs via room temperature treatment with diamines solutions while in the case of the QDs capped by lCys the enhancement is practically meaningless.     

Photoluminescence properties of a novel conjugate of water-soluble CdTe quantum dots to guanine

A novel conjugate of water-soluble CdTe quantum dots to a small biomolecule guanine has been obtained in aqueous phase. The photoluminescence property and the stability of the conjugate increased comparing to CdTe QDs. The interaction between CdTe QDs and guanine was studied by TEM, fluorescence microscope and photoluminescence (PL), IR, UV-Vis spectra. The effects of reflux time, pH value, ionic strength, and the ratio of CdTe QDs to guanine on the photoluminescence properties of conjugate were investigated in detail. The results show that guanine has a great influence on both the photoluminescence property and stability of thioglycolic acid-stabilized CdTe QDs. The formation of coordination and hydrogen bond between guanine molecules and CdTe including thioglycolic acid on its surface may effectively enhance the PL intensity and stability of CdTe QDs. The maximum PL intensity of the conjugate was obtained on the condition with lower ionic strength, less than 30 min reflux time, neutral pH value and 6/1 as molar ratio of guanine to CdTe.     

微波辐射法制备水溶性CdTe量子点及其光谱学研究

用半胱胺作为稳定剂,采用微波辐射加热的方法快速合成了水溶性的CdTe量子点。吸收光谱和荧光光谱表明所合成的量子点具有优异的发光性能。透射电子显微镜(TEM)和X射线粉末衍射(XRD)表征了量子点的结构和粒径分布。通过荧光发射光谱研究了反应温度、加热时间和配体浓度对量子点晶体生长速度的影响。反应温度提高或稳定剂半胱胺的浓度减小,纳米晶体的生长速度加快。在一定温度下,随着反应时间的延长,量子点发射波长发生红移。与传统的水相回流方法相比微波加热制备水溶性的CdTe量子点具有反应速度快、得到的量子点尺寸分布均匀、半峰宽较窄和量子产率较高等特点。     

Electrical and optical properties of colloidal semiconductor nanocrystals in aqueous environments

Microscale and larger semiconductor crystals have electronic and optical properties that depend on their bulk band structures. When these crystals are reduced into the nanoscale, they enter a new regime in which the electrical and optical properties are no longer influenced solely by their bulk band structures, but are influenced by the crystallite size and shape. In this paper, dimensional confinement and proximity phenomena are examined for colloidal semiconductor nanocrystals in several cases of practical importance. Specifically, we determine the effective binding potentials of selected quantum dots in aqueous environments in various colloidal semiconductor nanocrystals and correlate them with experimentally obtained absorption spectra. We also study fluorescence resonance energy transfer (FRET) between semiconductor crystals connected by short peptide chains as well as the shift in photoluminescence spectra of CdTe nanowires made from a chain of CdTe quantum dots.     

CdTe量子点标记雌二醇衍生物的研究

以巯基乙酸为修饰剂合成高量子产率的CdTe量子点,并成功标记生物小分子17β-氨基雌二醇.紫外光谱、荧光光谱、红外光谱以及倒置显微镜照片分析表明CdTe量子点在活化剂N-羟基琥珀酰亚胺的作用下,通过表面的羧基与17β-氨基雌二醇的氨基以共价键结合,这为建立基于量子点探针的新型的药物筛选模型提供了实验基础.     

Cell labeling and cytotoxicity of aqueously synthesized CdTe/CdS/ZnS core–shell–shell quantum dots by a water bath-hydrothermal method

CdTe/CdS/ZnS core–shell–shell quantum dots (QDs) were synthesized in aqueous solution via water-bathing combined hydrothermal method using L-cysteine as a stabilizer. The present method features markedly reduced synthesis time, higher fluorescent intensity and lower cytotoxicity of the QDs. Structural and spectroscopic properties of core–shell–shell QDs are well characterized by absorption and fluorescence spectroscopy, X-ray diffraction, transmission electron microscopy, and fourier transform infrared spectroscopy. Both CdS and ZnS shells were capped on the CdTe core and the fluorescence was greatly enhanced by the ZnS coating. The ternary QDs conjugated with transferrins were successfully employed for the biolabeling and fluorescent imaging of HeLa cells. Cytotoxicity evaluation shows that CdTe/CdS/ZnS was less toxic for cells than CdTe and CdTe/CdS due to the presence of a ZnS coating on surface, which inhibited the release of cadmium ions.     

Electrostatic assembles and optical properties of Au–CdTe QDs and Ag/Au–CdTe QDs

Au–CdTe and Ag/Au–CdTe assembles were firstly investigated through the static interaction between positively charged cysteamine-stabilized CdTe quantum dots (QDs) and negatively charged Au or core/shell Ag/Au nano-particles (NCs). The CdTe QDs synthesized in aqueous solution were capped with cysteamine which endowed them positive charges on the surface. Both Au and Ag/Au NCs were prepared through reducing precursors with gallic acid obtained from the hydrolysis of natural plant poly-phenols and favored negative charges on the surface of NCs. The fluorescence spectra of CdTe QDs exhibited strong quenching with the increase of added Au or Ag/Au NCs. Railey resonance scattering spectra of Au or Ag/Au NCs increased firstly and decreased latter with the concentration of CdTe QDs, accompanied with the solution color changing from red to purple and colorless at last. Experimental results on the effects of gallic acid, chloroauric acid tetrahydrate and other reagents demonstrated the static interaction occurred between QDs and NCs. This finding reveals the possibilities to design and control optical process and electromagnetic coupling in hybrid structures.     

The role of potassium tellurite as tellurium source in mercaptoacetic acid-capped CdTe nanoparticles

Water-soluble CdTe nanoparticles were synthesized in aqueous solution with the assistance of mercaptoacetic acid (MAA) molecules by wet chemical route and microwave-assisted method. A series of cadmium telluride (CdTe) nanoparticles capped with a bifunctional molecule, which contains both thiols and carboxylic acid groups were prepared using different pH values and using potassium tellurite as tellurium source. Thiol-capped nanocrystals of CdTe can be isolated as powders using 2-propanol. The synthesized thiol-capped CdTe were characterized with EDAX, TEM, Raman, FT–IR, UV–Visible absorption, fluorescence spectroscopy and X-ray diffraction (XRD) for the particle size determination and to understand their optical properties. The particles crystallize predominantly in cubic phase with narrow photoluminescence emission. Potassium tellurite as source of tellurium improves the photoluminescence efficiency and also avoids the cumbersome processes associated with H₂Te or NaHTe sources.     

Photoinduced interaction between MPA capped CdTe QDs and certain anthraquinone dyes

Photoinduced interaction of mercapto propionic acid (MPA) capped CdTe quantum dots (QDs) with certain anthraquinone dyes namely alizarin, alizarin red S, acid blue 129 and uniblue has been studied by steady state and time resolved fluorescence measurements. Addition of anthraquinone dyes to CdTe QDs results in the reduction of electron hole recombination has been observed (i.e., fluorescence quenching). The Stern-Volmer constant (K_SV), quenching rate constant (k_q) and association constants (K) were obtained from fluorescence quenching data. The interaction of anthraquinone dyes with QDs occurs through static quenching was confirmed by unaltered fluorescence lifetime. The occurrence of electron transfer quenching mechanism has been proved by the negative free energy change (ΔG_et) obtained as per the Rehm-Weller equation.     

Luminescence of the cadmium telluride quantum dots in the porous silicon oxide

The luminescence of the CdTe quantum dots deposited on glass substrate and introduced into the porous silicon oxide matrix is investigated. The experimental results on the photoluminescence with one- and two-photon excitation and cathodoluminescence indicate that the quantum dots introduced into the matrix retain the luminescence properties. The coefficient of the two-photon absorption of the CdTe quantum dots on the glass substrate is determined.     

Preparation of water-soluble CdTe/CdS core/shell quantum dots with enhanced photostability

CdTe/CdS core/shell quantum dots (QDs) have been synthesized in an aqueous phase using thioacetamide as a sulfur source. The quantum yield was greatly enhanced by the epitaxial growth of a CdS shell, which was confirmed by X-ray photoelectron spectroscopy (XPS) results. The quantum yield of as-prepared CdTe/CdS core/shell QDs without any post-preparative processing reached 58%. The experimental results illustrate that the QDs with core/shell structure show better photostability than thioglycolic acid (TGA)-capped CdTe QDs. The cyclic voltammograms reveal higher oxidation potentials for CdTe/CdS core/shell QDs than for TGA-capped CdTe QDs, which explains the superior photostability of QDs with a core/shell structure. This enhanced photostability makes these QDs with core/shell structure more suitable for bio-labeling and imaging.     

CdTe量子点的光谱特性及其应用

研究了水相CdTe量子点的共振散射光谱、荧光光谱和吸收光谱特性。结果表明,随着量子点粒径(d)的增大,CdTe量子点的荧光峰(λ_F)发生红移,吸收峰也发生红移,且吸收峰(λ_A)的峰形变宽、吸光度(A)降低,λ与ln(d)均存在较好的线性关系。其函数关系为λ_A =126.74 ln(d)+395.92和λ_F=155.01 ln(d) +415.5。共振散射光谱研究表明, 共振散射波长λ_R与CdTe量子点粒径（3.8～8.6 nm）的对数存在较好的线性关系,线性回归方程为λ_R=148.37 ln(d)+418.08, 相关系数为0.995 2,而且同一粒径的CdTe量子点,共振散射强度与CdTe量子点的浓度也存在良好的线性关系,粒径为3.8 nm的CdTe量子点在波长597 nm处的线性范围,回归方程,相关系数分别为：22.5～180.0 μmol·L-1;I_{597 nm}=0.572 1c+5.884,0.997 5。共振散射光谱法作为检测CdTe量子点粒径的一种新方法,具有简便快速及较好的应用价值。     

Preparation and purification of l-cysteine capped CdTe quantum dots and its self-recovery of degenerate fluorescence

l-cysteine capped CdTe quantum dots (QDs) were prepared in aqueous solution by a simple and efficient method, showing many advantages such as short synthesis period, the broaden range of starting pH value and the wide fluorescence emission wavelength range. A novel purification process was designed to remove excess Cd²⁺ which has potential cytotoxicity for bio-analysis. Three-dimensional fluorescence charts of pre- and post-purification showed that the purified QDs were of better luminescent performance. The prepared QDs were of cubic crystal structure with an average size of 2-6 nm, which were characterized by XRD and HRTEM. It is confirmed by IR spectra that the l-cysteine ligands were conjugated with CdTe cores via covalent bond. The degenerate fluorescence of QDs can be self-recovered in the presence of l-cysteine without other processing steps.     

单质碘对水溶性CdTe量子点的荧光猝灭研究

合成了不同尺寸的、巯基丙酸和半胱氨酸修饰的水溶性CdTe量子点,并研究了I2与CdTe量子点的相互作用,实验发现I2能够明显猝灭CdTe量子点的荧光,且猝灭程度与量子点的修饰剂有关,没有表现出明显的尺寸依赖效应。     

水溶性CdTe量子点的稳态和纳秒时间分辨光致发光光谱

报道了以飞秒脉冲激光为激发光源的水溶性CdTe量子点(QDs)的稳态荧光光谱和纳秒时间分辨荧光光谱.实验发现CdTe量子点的荧光光谱峰值位置随激发波长变化发生明显移动，激发脉冲波长越长，荧光峰位红移越大.荧光动力学实验数据显示，在400nm和800nm脉冲激光激发下，水溶性CdTe量子点的荧光光谱中均含有激子态和诱捕态两个衰减成分，两者的发射峰相距很近，诱捕态的发射峰波长较长.在800nm脉冲激光激发下的诱捕态成分占总荧光强度的比重比400nm激发下的约高3倍，其相对强度的这种变化导致了稳态荧光发射峰位的红移. 关键词： CdTe 量子点 时间分辨 荧光光谱 上转换荧光     

水溶性量子点荧光探针用于帕珠沙星的含量测定

文章采用荧光光谱和紫外光谱研究了CdTe量子点(CdTe QDs)与广谱抗菌药物帕珠沙星的相互作用。结果表明,随着帕珠沙星浓度的增加,CdTe QDs荧光强度有规律的降低,但通过透射电镜图对QDs及加入帕珠沙星后的QDs进行比较,发现QDs仍然均一单分散,表明反应的作用机理可能是帕珠沙星促使QDs表面键合的有机分子发生变化,在Cd空位表现出的表面缺损上形成了碲氧复合物,致使荧光猝灭。因此该反应可作为一种新颖的快速检测帕珠沙星含量的方法。在一定条件下,帕珠沙星溶液的浓度与量子点荧光强度成线性关系,线性范围为10.0～850 μg·mL-1,相关系数r为0.995 4,检测限(S/N=3)为3.254×10-3 μg·mL-1。药物对量子点的猝灭常数为2.188×104 L·mol-1。应用到冻干粉针剂和氯化钠注射液中帕珠沙星的含量测定,所得结果与标示量一致。该方法较常用检测方法具有简便、快捷、灵敏、线性范围宽的优点,并有望进一步开展发药物体内显像及作用机理的研究。