CdSe量子点的合成、功能化及生物应用

量子点是一种新型荧光纳米材料,具有独特而优良的荧光性质,近年来受到研究者的广泛关注。文章综述蛋白质、抗体、肽类以及DNA等对CdSe量子点(CdSe QDs)的表面功能化作用,以及CdSe QDs在生物传感分析中的重要研究进展。具体介绍CdSe量子点的多种合成方法(包括有机相合成、水相合成等),蛋白质、抗体、肽类、DNA利用共价键或静电作用对CdSe量子点修饰方法,以及其在生物医学标记与成像、生物传感、药物载送以及癌症治疗等领域的相关应用,最后针对现有研究的不足进行展望。希望通过对CdSe量子点全方位总结与概述,在一定程度上帮助科研工作者快速、准确了解其相关性质与研究进展。     

Nonlinear optical characterization and measurement of optical limiting threshold of CdSe quantum dots prepared by a microemulsion technique

CdSe quantum dots prepared by micro emulsion technique shows quantum confinement effect and broad emission at 532 nm. These quantum dots have about 4.35 nm size, and they exhibit good nonlinear effects which are measured using z-scan technique. The samples have a reverse saturation in the nonlinear absorption as nonlinear optical absorption coefficient β is 2.545 × 10⁻¹⁰ W m⁻¹ and nonlinear optical refraction coefficient n ₂ is −1.77 × 10⁻¹⁰ esu. The third-order nonlinear optical susceptibility is found to be 4.646 × 10⁻¹¹ esu and also the figure of merit is 2.01 × 10⁻¹² esu m. The optical limiting threshold which is found to be 0.346 GW/cm² makes it a good candidate for device fabrication.     

Surfactant mediated optical properties of cytosine capped CdSe quantum dots

This letter demonstrates the use of one of the nucleobases, ‘cytosine’ as a new capping agent in controlling the size of the nanoparticles. A size dependent blue shift in optical absorption with enhanced luminescence is observed. Since the calculated density of states do not show any change in the band gap of as-prepared quantum dots after capping, the observed blue shift of the absorption peak can solely be attributed to the so-called size-effect whereas the enhancement in luminescence to surfactant mediated defect passivation. It is expected that the observed properties of the cytosine capped CdSe quantum dots would facilitate a better bio-compatibility of tailor-made nanoparticles for bio-imaging applications.     

Cu-In-S三元量子点的合成及其性能调控

采用前驱体分解法制备了Cu-In-S量子点,研究了制备工艺对Cu-In-S量子点的形貌以及光学性能的影响。实验结果表明,反应时间和反应温度可影响Cu-In-S纳米颗粒的尺寸和光学性能。随时间增加,Cu-In-S粒径变大,同时会伴随着棒状晶体的出现,荧光发射谱的峰位发生红移。随反应温度升高,纳米晶的形核速率和长大速率增加,并且粒径也有增大,纳米晶的形状可以由单一的球形变为球形与棒状的混合,荧光谱峰位亦会发生红移。X射线光电子能谱分析表明,所制备颗粒为CuInS2纳米晶。为进一步制备无毒量子点发光器件(QLEDs)奠定了基础。     

Synthesis and characterization studies of ZnSe quantum dots

ZnSe QDs have been synthesized by wet chemical, template free process by zinc acetate and elemental selenium powder in presence of ethylene glycol, hydrazine hydrate and a defined amount of water at 90 °C. The product was in strong quantum confinement regime, having yield as high as 50 %. The transmission electron microscopy image indicated that the particles were well dispersed and spherical in shape. The X-ray diffraction analysis showed that the ZnSe nanoparticles were of the Cubic structure, with average particle diameter of about 3.50 nm. The FTIR characteristic indicates that the N₂H₄ molecule has intercalated into the complex and formed a molecular precursor.     

Discrete size series of CdSe quantum dots: a combined computational and experimental investigation

Ab initio computational studies were performed for CdSe nanocrystals (NCs) over a wide variety of sizes ranging from 8 to 150 atoms in conjunction with recent experimental work. The density functional based calculations indicate substantial relaxations. Changes in coordination of surface atoms were found to play a crucial role in determining the NC stability and optical properties. While optimally (threefold) coordinated surface atoms resulted in stable closed-shell structures with large optical gaps, sub-optimal coordination gave rise to lower stability and negligible optical gaps. These computations are in qualitative agreement with recent chemical etching experiments suggesting that closed shell NCs contribute strongly to photoluminescence quantum yield while clusters with nonoptimal surface coordination do not.     

CdSe／CdS核壳量子点拉曼光谱的表面模分析

研究了不同壳层厚度(0～5.5ML)的CdSe/CdS核壳量子点的一次和高次拉曼散射,具体分析了CdSe和CdS的表面模随着壳层厚度的变化情况.结果表明,随着壳层厚度的增加,CdSe表面模(SO1)从198cm-1频移到185cm-1,CdS的表面模(SO2)从275cm-1频移到267cm-1,并且SO1和SO2试验结果与由介电连续模型得到的理论值很接近.此外,根据CdSe表面模的频移,对随着CdS壳层厚度的增加而引起的核层(CdSe)的介电常数随环境的变化做出了修正.     

The empirical correlation between size and two-photon absorption cross section of CdSe and CdTe quantum dots

The tuning of CdSe quantum dot (QDs) sizes, and consequently their corresponding two-photon absorption (TPA) cross section, has been systematically investigated. As the size (diameter) of the quantum dots increases, the TPA cross section is found to be empirically related via a power-law proportionality of 3.5+/-0.5 and 5.6+/-0.7 to the diameters of CdSe and CdTe QDs, respectively. The results are tentatively rationalized via a theoretical model of two-photon excitation properties in a system incorporating excitons and defects.     

Recombination dynamics in CdTe/CdSe type-II quantum dots

Recombination dynamics in CdTe/CdSe core-shell type-II quantum dots (QDs) has been investigated by time-resolved photoluminescence (PL) spectroscopy. A very long PL decay time of several hundred nanoseconds has been found at low temperature, which can be rationalized by the spatially separated electrons and holes occurring in a type-II heterostructure. For the temperature dependence of the radiative lifetime, the linewidth and the peak energy of PL spectra show that the recombination of carriers is dominated by delocalized excitons at temperatures below 150?K, while the mixture of delocalized excitons, electrons and holes overwhelms the process at higher temperature. The binding energy of delocalized excitons obtained from the temperature dependence of the non-radiative lifetime is consistent with the theoretical value. The energy dependence of lifetime measurements reveals a third power relationship between the radiative lifetime and the radius of QDs, the light of which can be shed by the quantum confinement effect. In addition, the radiative decay rate is found to be proportional to the square root of excitation power, arising from the change of wavefunction overlap of electrons and holes due to the band bending effect, which is an inherent character of a type-II band alignment.     

CdSe and CdSe/ZnS quantum dots for the detection of C-reactive protein

In this study, a method for the detection of C-reactive protein (CRP) using CdSe and CdSe/ZnS quantum dots (QDs) is proposed. CdSe and CdSe/ZnS core-shell QDs are synthesised by using 2-mercaptosuccinic acid (MSA) as a capping agent. These QDs were then subjected to various characterisation studies, namely X-ray diffraction and transmission electron microscope for size and structure, Fourier transform infrared spectroscopy for the confirmation of functional groups, ultraviolet–visible absorption and fluorescence spectroscopy for optical characteristics and dynamic light scattering for hydrodynamic changes of QDs. Two biochemical mixtures were developed: one by mixing blood serum containing CRP and CdSe-phosphorylethanolamine (PEA) and the other by mixing blood serum with CdSe/ZnS-PEA. When these mixtures are observed for fluorescence due to interaction of QDs with CRP, a correlation between changes in fluorescence for different concentrations of CRP is noted. The result demonstrates that CRP can be detected with the help of QDs without using any antibodies.     

Synthesis and characterization of cysteamine-CdTe quantum dots via one-step aqueous method

A novel approach has been developed to synthesize cysteamine (CA)-CdTe quantum dots (QDs) in an aqueous medium. Compared with previous reports, the proposed method involves a one-step synthesis using TeO₂ to replace Te or Al₂Te₃ as tellurium source. The influences of the precursor Cd/Te molar ratios and the pH of the original solution on the quantum yield (QY) of the obtained CdTe QDs were investigated systematically. Green- to orange-emitting CdTe QDs, with a maximum photoluminescence QY of 10.73%, were obtained. X-ray powder diffraction and transmission electron microscopy were used to characterize the crystalline structure and shape of the materials. CdTe QDs with CA modification exhibit a zinc-blended crystal structure in a sphere-like shape.     

Dipolar structures in colloidal dispersions of PbSe and CdSe quantum dots

We show by cryogenic transmission electron microscopy that PbSe and CdSe nanocrystals of various shapes in a liquid colloidal dispersion self-assemble into equilibrium structures that have a pronounced dipolar character, to an extent that depends on particle concentration and size. Analyzing the cluster-size distributions with a one-dimensional (1D) aggregation model yields a dipolar pair attraction of 8-10 kBT at room temperature. This accounts for the long-range alignment of the crystal planes of individual nanocrystals in self-assembled superstructures and for anisotropic nanostructures grown via oriented attachment.     

CdSe量子点的制备及荧光性能改善

主要讨论了CdSe量子点的制备及荧光性能的改善.采用水相合成方法制备了CdSe量子点,并用X射线粉末衍射仪对所合成的量子点进行表征,用荧光分光光度计研究了量子点的荧光性质.结果表明,采用样品处理温度的调节和ZnS壳层的包覆能在一定程度上改善CdSe量子点的荧光性能.     

Synthesis and photoluminescence of bright water-soluble CdSe/ZnS quantum dots overcoated by hybrid organic shell

Photoluminescence properties from water soluble CdSe/ZnS QDs encapsulated with hybrid trioctylphosphine-poly(acrylamide-co-acrylic acid)-ethanolamine (TOPO-PSMA-EA) shell have been investigated. It was found that PL efficiency of CdSe/ZnS QDs in water was increased 5–30% after introducing PSMA-EA polymers to encapsulate CdSe/ZnS-TOPO QDs. Higher PSMA concentrations were found to enhance the PL efficiency of QDs up to 1.8 folds, which is ascribed to a better packing and passivation of the TOPO-PSMA-EA shell over the QDs. Time-resolved photoluminescence suggested that the mean lifetime of photoexcited carriers in the water-soluble CdSe/ZnS-TOPO-PSMA-EA QDs elongated 2–17 ns compared with that of uncoated samples, indicating that PL quenching defects were effectively removed for CdSe/ZnS QDs with hybrid TOPO-PSMA-EA shell.     

Synthesis of N-acetyl-L-cysteine-capped ZnCdSe quantum dots via hydrothermal method and their characterization

Compared with the most studied green-red emitting (530–650 nm) quantum dots (QDs), the preparation of short-wavelength-emitting QDs remains difficult. Besides, one of the representative short-wavelength QDs materials, ZnCdSe, has a shortcoming of high content of toxic cadmium metal. In this paper, we report the synthesis of high-quality water-soluble ZnCdSe QDs via optimized one-step hydrothermal method with a new thiol as ligand, within a short time of 65 min. The emission wavelength of prepared QDs is tunable in the range of 425–540 nm by merely controlling the molar ratio of Cd:Zn or Se:Zn, and the quantum yield reaches 35%. More importantly, the maximum Cd:Zn molar ratio has been reduced to 0.04:1.0, much lower than that reported in the literature (0.5:1.0), resulting in excellent biological compatibility of prepared QDs and thus their promising applications in biological fields. Moreover, the transmission electron microscopy was employed to examine the effect of Cd:Zn ratio on the size of prepared ZnCdSe QDs, which were also characterized by x-ray photoelectron spectroscopy and electron diffraction spectroscopy.     

Three-pulse photon echo induced by the optical transition of excitons in core-shell CdSe/ZnS nanocrystal quantum dots

The femtosecond three-pulse photon echo phenomena induced by the optical transition of 1s_e1s_h exciton in a core-shell CdSe/ZnS nanocrystal quantum dot (NQD) are theoretically investigated basing on the optical Bloch equations. The parameter dependence of the photon echo signals is discussed. The numerical calculation results reveal that three-pulse photon echo signals are sensitive to the variation of the size and structure of NQD. The corresponding mechanism has been discussed in terms of quantum size confined effect theory.     

Effect of dispersed CdSe/ZnS quantum dots on optical and electrical characteristics of nematic liquid crystal cells

We have studied the electrical and optical characteristics of cells filled with nematic liquid crystal (NLC) based on cyanobiphenyls with positive dielectric anisotropy, containing dispersed 3.5-nm-sized CdSe/ZnS composite semiconductor nanoparticles (quantum dots, QDs) with a concentration of 0.1–0.2 wt %. In addition to a decrease in the threshold voltage of the electrooptical splay effect, the doping with QDs leads also to a decrease in the phase delay of light and the effective dielectric permittivity of NLC cells. These characteristics are reduced by half during the storage of NLC cells containing about 0.2 wt % QDs, which is related to the self-organization of QDs.     

Synthesis, nonlinear optical properties and photoluminescence of ZnSe quantum dots in stable solutions

ZnSe quantum dots (QDs) were synthesized by using a novel oleic acid-controlled hydrothermal route. The as-synthesized QDs were easily dispersed in nonpolar solvents to form highly stable homogenous solutions, on the basis of which their optical properties were systematically investigated. It was found that the QDs had multiple optical properties of both obvious optical nonlinearity with a frequency-doubled Nd:YAG laser (532 nm) used as inducing beam and a strong photoluminescence emission at ca. 458 nm, suggesting that they have potential applications in complex functional optical devices.     

Size selective excitonic transition energies in strongly confined CdSe quantum dots

We report on the synthesis of CdSe nanocrystal quantum dots (QDs) of different radii (R). Size dependent optical properties like increase in the confinement energy with decreasing radius for different excitonic transitions are studied. Different excitonic transitions are calculated from the second derivative of UV-vis absorption spectra of as synthesized CdSe QDs. The transitions are assigned to specific states by calculating the transition energies using effective mass approximation. A close matching of the transition energies with the experiment suggesting that the second derivative of the absorption spectra could provide a direct knowledge of the electronic transition for the direct band gap semiconductor quantum dots.     

The effect of solvent dependent local field factor in the optical properties of CdTe quantum dots

CdTe quantum dots (QDs) are synthesized at room temperature in aqueous solvents of different dielectric constants and characterized using optical spectroscopy. Absorption spectra of the QDs obtained is used to calculate the size dependent dielectric function of the QDs using Kramers–Kronig relation and iterative matrix inversion method. Effect of solvent dielectric constant on optical properties of QDs is studied theoretically using Maxwell–Garnett effective medium theory. Direct correlation between absorption intensity and solvent dielectric constant is explained on the basis of decreasing local field factor of the solvents. Emission rates of QDs is also found to have dependence on the dielectric constant of the solvent. Spontaneous emission rates of QDs in Ionic liquid environment is studied theoretically using Maxwell–Garnett effective medium theory. Our results show that variation in dielectric constant of Ionic liquids have a significant impact on spontaneous emission properties of the QDs.