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.     

Photoluminescence quenching of CdTe/CdS core-shell quantum dots in aqueous solution by ZnO nanocrystals

Photoluminescence (PL) properties of 3-mercaptopropionic acid (MPA) coated CdTe/CdS core-shell quantum dots (QDs) in aqueous solution in the presence of ZnO colloidal nanocrystals were studied by steady-state and time-resolved PL spectroscopy. The PL quenching of CdTe/CdS core-shell QDs with addition of purified ZnO nanocrystals resulted in a decrease in PL lifetime and a small red shift of the PL band. It was found that CdTe(1.5 nm)/CdS type II core-shell QDs exhibited higher efficiency of PL quenching than the CdTe(3.0 nm)/CdS type I core-shell QDs, indicating an electron transfer process from CdTe/CdS core-shell QDs to ZnO nanocrystals. The experimental results indicated that the efficient electron transfer process from CdTe/CdS core-shell QDs to ZnO nanocrystals could be controlled by changing the CdTe core size on the basis of the quantum confinement effect.     

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.     

Facile synthesis of mercaptosuccinic acid-capped CdTe/CdS/ZnS core/double shell quantum dots with improved cell viability on different cancer cells and normal cells

Water-soluble, mercaptosuccinic acid (MSA)-capped CdTe/CdS/ZnS core/double shell quantum dots (QDs) were prepared by successive growth of CdS and ZnS shells on the as-synthesized CdTe/CdS_thin core/shell quantum dots. The formation of core/double shell structured QDs was investigated by ultraviolet-visible (UV–Vis) absorption and photoluminescence (PL) spectroscopy, PL decay studies, X-ray diffraction (XRD), and X-ray photoelectron spectroscopy (XPS). The core/double shell QDs exhibited good photoluminescence quantum yield (PLQY) which is 70% higher than that of the parent core/shell QDs, and they are stable for months. The average particle size of the core/double shell QDs was ～3 nm as calculated from the transmission electron microscope (TEM) images. The cytotoxicity of the QDs was evaluated on a variety of cancer cells such as HeLa, MCF-7, A549, and normal Vero cells by 3-(4,5-dimethyl-2-thiazolyl)-2,5-diphenyl-2H-tetrazolium bromide (MTT) cell viability assay. The results showed that core/double shell QDs were less toxic to the cells when compared to the parent core/shell QDs. MCF-7 cells showed proliferation on incubation with QDs, and this is attributed to the metalloestrogenic activity of cadmium ions released from QDs. The core/double shell CdTe/CdS/ZnS (CSS) QDs were conjugated with transferrin and successfully employed for the biolabeling and fluorescent imaging of HeLa cells. These core/double shell QDs are highly promising fluorescent probe for cancer cell labeling and imaging applications.     

pH-dependent aggregation and photoluminescence behavior of thiol-capped CdTe quantum dots in aqueous solutions

pH-dependent aggregation of thiol-capped CdTe quantum dots (QDs) in solutions was observed with a confocal microscope. The average size of the QD aggregates increased from 28 nm to 1.4 μm as the pH decreased from 12 to 3. The basic condition improved the dispersion of QDs while the acidic condition caused the detachment of surface ligands, leading to the aggregation of QDs. A PL lifetime of 80 ns was detected for QDs at pH from 12 to 7, while it was shortened to 57 and 34 ns at pH 5 and 3, respectively, due to the formation of surface defects.     

Study on the interaction of CdTe quantum dots with ferulic acid and protocatechuic aldehyde by optical spectroscopy

Luminescent CdTe quantum dots (QDs) were synthesized using thioglycolic acid (TGA) as a stabilizing agent in aqueous medium and were characterized by Fourier transform infrared spectroscopy (FTIR), atomic force microscopy (AFM), and transmission electron microscopy (TEM). In weak basic media the fluorescence of TGA-CdTe QDs was quenched notably by ferulic acid (FA) and protocatechuic aldehyde (PA), and the quenching values were proportional to the concentration of the quenchers in a certain range. The addition of bovine serum albumin (BSA) to TGA-CdTe QDs-FA and TGA-CdTe QDs-PA systems rendered a large recovery of the fluorescence of TGA-CdTe QDs.     

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.     

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.     

Sonoelectrochemical synthesis of water-soluble CdTe quantum dots

A facile and fast one-pot method has been developed for the synthesis of CdTe quantum dots (QDs) in aqueous phase by a sonoelectrochemical route without the protection of N₂. The morphology, structure and composition of the as-prepared products were investigated by high resolution transmission electron microscopy (HRTEM), X-ray diffraction (XRD) and energy dispersive X-ray spectrometer (EDS). The influences of current intensity, current pulse width, and reaction temperature on the photoluminescence (PL) and quantum yield (QY) of the products were studied. The experimental results showed that the water-soluble CdTe QDs with high PL qualities can be conveniently synthesized without precursor preparation and N₂ protection, and the PL emission wavelength and QY can be effectively controlled by adjusting some parameters. This method can be expected to prepare other QDs as promising building blocks in solar cell, photocatalysis and sensors.     

Size-dependent carrier dynamics in self-assembled CdTe/ZnTe quantum dots

We investigate size-dependent carrier dynamics in self-assembled CdTe/ZnTe quantum dots (QDs) grown using molecular beam epitaxy and atomic layer epitaxy. Photoluminescence (PL) spectra show that the excitonic peak corresponding to transitions from the ground electronic subband to ground heavy-hole band in CdTe/ZnTe QDs shifts to a lower energy with increasing ZnTe buffer thicknesses. This shift of the PL peak can be attributed to size variation of the CdTe QDs. In particular, carrier dynamics in CdTe QDs grown on various ZnTe buffer layer thicknesses is studied using time-resolved PL measurements. As a result, the decay time of CdTe QDs is shown to increase with increasing ZnTe buffer layer thicknesses due to the reduction of the exciton oscillator strength in the larger QDs.     

Au纳米颗粒和CdTe量子点复合体系发光增强和猝灭效应

利用金属蒸发真空多弧离子源注入机, 将Au离子注入到高纯石英玻璃来制备镶嵌有Au 纳米颗粒的衬底材料, 随后将化学方法合成的CdTe量子点旋涂在玻璃衬底上制备了Au纳米颗粒和CdTe量子点复合体系. 通过对镶嵌有Au纳米颗粒的衬底进行热退火处理来控制Au纳米颗粒的生长和分布, 系统研究了Au纳米颗粒的局域表面等离子体共振对CdTe量子点光致发光性能的影响. 利用光学吸收谱、原子力显微镜、透射电子显微镜和光致发光谱对样品进行了表征和测试. 光致发光谱表明, Au纳米颗粒的局域表面等离子体对CdTe量子点的发光有增强效应也有猝灭效应. 深入分析了Au纳米颗粒和CdTe量子点之间的相互作用过程, 提出了关于Au-CdTe 纳米复合体系中CdTe 发光增强和猝灭的新机理. 该实验结果为利用金属纳米颗粒表面等离子体技术制备高发光性能的光电子器件提供了较好的参考.     

Synthesis of CdTe quantum dots using a heterogeneous process at low temperature and their optical and structural properties

Luminescent CdTe quantum dots (QDots) have been synthesized through a low-temperature process employing a heterogeneous reaction between cadmium acetate and tri-n-octyl phosphine tellurium (TOPTe) in the presence of tri-n-octyl phosphine oxide (TOPO). UV-visible absorption spectra revealed that monodispersed CdTe QDots were synthesized at 70 °C for 240 min. The as-synthesized CdTe QDots exhibited photoluminescence (PL) with a narrow spectral distribution (FWHM41 nm). Highly luminescent CdTe QDots with PL quantum yield (QY) up to 33% were size selected from the ensemble. X-ray and electron diffraction measurements revealed that CdTe crystallized in a wurtzite-type structure at 70 °C. High-resolution transmission electron microscopic measurements revealed that the CdTe particles were of regular spherical morphology with an average diameter of 2.8 nm. The present experiment demonstrates, in addition to an advantage in green chemistry, that a low-temperature process allows an extended period of time for crystallization that is useful for synthesizing defect-free QDots with higher PL QY. PACS 81.07.-b; 81.20.-n; 81.07.Ta; 78.67.-n; 61.46.+w     

The influence of ligands on the preparation and optical properties of water-soluble CdTe quantum dots

In a systematic investigation has been found that ligands play an important role in both the water-phase preparation and optical properties of CdTe quantum dots. Experiments were performed using three typical thioalkyl acids as ligands, namely mercaptoacetic acid (MAA), l-cysteine (Cys) and reduced glutathione (GSH). The growth rate and size-distribution of CdTe quantum dots (QDs) are shown to depend on the type of ligands. A proper choice of ligand enables to make lager nanocrystals with narrower size-distribution. The effects of pH (buffer solution), illumination, heating and cations on the spectroscopic properties of CdTe QDs for the three ligands are reported. In addition, three same-size CdTe QDs were individually characterized by micellar electrokinetic capillary electrophoresis with laser-induced fluorescent detection, which proved their monodisperse size-distribution and different electric charge distribution on the surface for each of the three different type of QDs.     

Glycosylated Quantum Dots for the Selective Labelling of <Emphasis Type="Italic">Kluyveromyces bulgaricus</Emphasis> and <Emphasis Type="Italic">Saccharomyces cerevisiae</Emphasis> Yeast Strains

Highly fluorescent CdTe quantum dots (QDs) stabilized by thioglycolic acid (TGA) were prepared by an aqueous solution approach and used as fluorescent labels in detecting yeast cells. Sugars (mannose, galactose or glucose) were adsorbed on CdTe@TGA QDs and the interaction of these nanoparticles with yeast cells was studied by fluorescence microscopy. Results obtained demonstrate that galactose and mannose functionalized QDs associate respectively with Kluyveromyces bulgaricus and Saccharomyces cerevisiae yeast strains due to saccharide/lectin specific recognition. Glucose-functionalized CdTe QDs, which are not recognized by cell lectins, preferentially localize in the bud scars of S. cerevisiae.     

以巯基丙酸为稳定剂的水溶性CdTe量子点的水热合成及表征

以巯基丙酸(MPA)为稳定剂,采用水热合成方法在160 ℃下合成水溶性CdTe量子点。研究了不同反应时间及反应前驱体溶液的不同pH值对合成的CdTe量子点光学性质的影响。结果表明:所制得的CdTe量子点的荧光发射波长在510~661 nm范围内连续可调,并且CdTe量子点的光学性质强烈地依赖于反应前驱体溶液的pH值,最佳pH值为9。透射电子显微镜和X射线衍射分析表明所制备的CdTe量子点的形状接近于球形,粒径分布较均匀。与回流方法制备的水溶性量子点相比,高温条件下的水热合成方法简单,反应时间短,CdTe量子点生长速度快,100 min就可生长到3.5 nm,并且所制得的CdTe量子点荧光强度高,稳定性好,荧光量子产率也较高,最高可达44.6%。     

Two distinct photoluminescence responses of CdTe quantum dots to Ag (I)

Four sizes of water-soluble thiol-capped CdTe quantum dots (QDs) have been synthesized and used to investigate the photoluminescence (PL) responses to Ag⁺ ions. For small particles, the CdTe QDs exhibit PL enhancement in the presence of lower concentration of Ag⁺ but show obvious quenching with the further increase of Ag⁺; for larger particles, however, PL of CdTe QDs is quenched all the time with the Ag⁺ addition, no PL enhancement is observed. Mechanism study shows that small QDs with more traps on the particle surface are effectively passivated by initial adsorbed Ag⁺, which accounts for the PL enhancement observed; after the initial traps are saturated, the excess Ag⁺ facilitates nonradiative recombination, resulting in PL quenching. For larger particles, the nonradiative recombination dominates the whole process even for the lower concentration of Ag⁺, due to the fewer traps on the QD surface. Compared with larger particles, the small CdTe QDs are more suitable for sensing Ag⁺ because of the more sensitive and selective PL response. To our best knowledge, this is the first systematical study on the interaction of Ag⁺ with different-sized CdTe QDs.     

水溶性碲化镉量子点测定甲磺酸培氟沙星

合成巯基乙酸修饰的水溶性发光CdTe量子点,构建了CdTe-Al3+-甲磺酸培氟沙星荧光体系。考察了缓冲体系及pH值、表面活性剂的种类、反应时间及共存物质等对测定的影响。在最佳条件下,CdTe量子点发光强度与甲磺酸培氟沙星的浓度在3.6×10-3—4.00μg/mL范围内呈良好线性。该方法可直接用于甲磺酸培氟沙星片剂的测定,结果满意。     

Modified spontaneous emission of CdTe quantum dots inside a photonic crystal

The angular dependence of the spontaneous emission of CdTe quantum dots (QDs) inside a photonic crystal with a pseudogap is reported. The sensitive dependences of the radiative lifetime and the photoluminescence spectrum of CdTe QDs on the observation angle demonstrate the effect of the photonic bandgap on the spontaneous emission of the QDs.     

Anti-Reflection Characteristics of Si Nanowires for Enhanced Photoluminescence from CdTe/CdS Quantum Dots

CdTe/CdS quantum dots(QDs) are fabricated on Si nanowires(NWs) substrates with and without Au nanoparticles(NPs). The formation of Au NPs on Si NWs can be certified as shown in scanning electron microscopy images. The optical properties of samples are also investigated. It is interesting to find that the photoluminescence(PL) intensity of Cd Te/Cd S QD films on Si nanowire substrates with Au NPs is significantly increased,which can reach 8-fold higher than that of samples on planar Si without Au NPs. The results of finite-difference time-domain simulation indicate that Au NPs induce stronger localization of electric field and then boost the PL intensity of QDs nearby. Furthermore, the time-resolved luminescence decay curve shows the PL lifetime, which is about 5.5 ns at the emission peaks of QD films on planar, increasing from 1.8 ns of QD films on Si NWs to4.7 ns after introducing Au NPs into Si NWs.     

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。