量子点/环氧树脂复合材料的制备及性能

通过自组装技术将十二胺包覆到CdSe量子点表面实现量子点的氨基改性,并以三乙烯四胺为固化剂制备得到CdSe量子点/环氧树脂复合材料,研究了量子点表面氨基改性对复合材料性能的影响。通过高分辨透射电镜表征量子点的分散情况及粒径大小,X射线能谱表征量子点改性前后元素的变化,动态光散射表征量子点团簇在环氧基体中的粒度分布,紫外-可见光谱表征复合材料的透明性,荧光光谱表征复合材料的荧光性能,冲击试验表征量子点改性前后对复合材料的增韧作用。结果表明,氨基改性量子点/环氧树脂复合材料的透明度为原始量子点/环氧树脂复合材料的2倍,荧光强度为原始量子点/环氧树脂复合材料的4倍。当量子点含量为0.5%时,氨基改性量子点/环氧树脂复合材料的冲击强度达7.28 k J/m~2。     

Preparation and characterization of novel CdSe quantum dots modified with poly (d,l-lactide) nanoparticles

In this paper, novel CdSe quantum dots (QDs) modified with poly (d, l-lactide) (PLA) nanoparticles by nanoprecipitation method was reported. CdSe QDs modified with PLA nanoparticles were characterized by Photon correlation spectroscope (PCS), transmission electron microscope (TEM), flluorescence spectrophotometer and fluorescence microscope. The modified CdSe QDs were spherical and relatively uniform. The modified CdSe QDs were water soluble and their strong yellow fluorescence emission was observed both in vitro and in vivo. The fluorescence of the modified CdSe QDs was stable in aqueous solution for more than 30 d. These modified CdSe QDs are expected to have much potential for biological labeling and diagnostics based on above properties.     

Surface modification of CdSe quantum dots for biosensing applications: Role of ligands

For an optimum performance of colloidal nanocrystal devices for a variety of applications such as photonic devices, solar cells and biological labelling, the determining factors are the nanocrystal surface and size. In this work, these two factors have been tuned via wet chemistry to tailor the material properties: The absorption and emission spectra have been tailored by choice of the nanocrystal size; nanocrystal shape by surface modification and photoluminescence (PL) efficiency determined by surface traps, has been tuned via appropriate selection of the nanocrystal capping ligands. Here, we have shown that through ligand-exchange process, the surface of the CdSe quantum dots (QDs) can be modified by replacing the longer-chain ligands of conventional trioctyl phosphine oxide (TOPO) or oleic acid (OA) with shorter-chain ligand of butyl amine. This imparts colloidal stability and water solubility to CdSe QDs for its potential applications in biosensors and biological imaging. It is conjectured that crystallite sizes, oxidation potential of CdSe QDs and stereochemical compatibility of ligands (TOPO, oleic acid and butyl amine) greatly influences the photophysics and photochemistry of CdSe QDs.     

Encapsulation of CdSe/ZnS nanocrystals within mesoporous silica spheres

Quantum dots (QDs) have attracted much attention on account of their unique optical and electronic properties. Applications of QDs in biological systems face challenges owing to their toxicity and hydrophobicity. Incorporation of QDs in mesoporous silica spheres affords not only hydrophilic shell for QDs in order to enhance their dispersion in aqueous medium, but also offers chemically inert shielding to reduce QD cytotoxicity. In the current work, two types of mesoporous silica encapsulated QDs were synthesized by rationally adjusting the reaction conditions. Mesoporous silica coated single CdSe/ZnS nanoparticles (sCdSe/ZnS@mSiO₂) were prepared through the one-pot reaction. Further modification of this reaction offered hollow mesoporous silica spheres (CdSe/ZnS@HMSS) encapsulating multiple CdSe/ZnS QDs assembled on the internal surface of the spheres. Both of sCdSe/ZnS@mSiO₂ and CdSe/ZnS@HMSS show significant photophysical properties. Possible formation mechanism of the two types of nanostructures was investigated and discussed.     

Susceptible Surface Sulfide Regulates Catalytic Activity of CdSe Quantum Dots for Hydrogen Photogeneration

Semiconducting quantum dots (QDs) have recently triggered a huge interest in constructing efficient hydrogen production systems. It is well established that a large fraction of surface atoms of QDs need ligands to stabilize and avoid them from aggregating. However, the influence of the surface property of QDs on photocatalysis is rather elusive. Here, the surface regulation of CdSe QDs is investigated by surface sulfide ions (S^2?) for photocatalytic hydrogen evolution. Structural and spectroscopic study shows that with gradual addition of S^2?, S^2? first grows into the lattice and later works as ligands on the surface of CdSe QDs. In‐depth transient spectroscopy reveals that the initial lattice S^2? accelerates electron transfer from QDs to cocatalyst, and the following ligand S^2? mainly facilitates hole transfer from QDs to the sacrificial agent. As a result, a turnover frequency (TOF) of 7950 h^?1 can be achieved by the S^2? modified CdSe QDs, fourfold higher than that of original mercaptopropionic acid (MPA) capped CdSe QDs. Clearly, the simple surface S^2? modification of QDs greatly increases the photocatalytic efficiency, which provides subtle methods to design new QD material for advanced photocatalysis.     

Optimization of CdSe layer on modified ZnO hierarchical spheres by spin-SILAR for efficient CdS/CdSe co-sensitized solar cells

In this study, after CdS quantum dots sensitized ZnO hierarchical spheres (ZnO HS), we used a simple process to deposit CdSe QDs on ZnO by spin-coating-based SILAR, and applied to photoanodes of quantum dots-sensitized solar cells. Before CdS and CdSe QDs deposition, the ZnO HS photoanodes were modified by Zn(CH₃COO)₂·2H₂O methanol solution to further enhance the open-circuit voltage and power conversion efficiency (PCE). The program of modifying photoanodes and the number of CdSe spin-SILAR cycles are evaluated on the optical and electrochemical properties of the cells. As a result, a high energy conversion efficiency of 2.49 % was obtained by using modified ZnO HS/CdS photoanode under AM 1.5 illumination of 100 mW cm^?2. And further decorated by the CdSe QDs, the ZnO HS/CdS/CdSe cell achieved a PCE of 5.36 % due to the modification of ZnO HS nanostructure, the enhanced absorption in the visible region, the lower recombination reaction and higher electron lifetime.     

Enhanced transport properties of assembled CdSe quantum dot through slow evaporation with mixed solvents

CdSe quantum dots (QDs) were assembled into uniform aligned packed sheets over large area in a mixture of toluene/acetonitrile solvents through slow evaporation, and preferential evaporation of the solvent led to self-assembly under conditions of continuously decreasing solvent quality. Depending on the volume ratio of acetonitrile, the CdSe QDs formed different packing type and coverage. This simple method of depositing assembled CdSe QDs makes it possible to study the novel transport properties of CdSe QDs. The related transport results showed that the increase in photocurrent with hydrazine and post annealing treatment are due to increased QDs surface passivation and decreased QDs spacing.     

Cyto-/genotoxic effect of CdSe/ZnS quantum dots in human lung adenocarcinoma cells for potential photodynamic UV therapy applications

Quantum dots (QDs) are luminescent nanoparticles (NPs) with promising potential in numerous medical applications, but there remain persistent human health and safety concerns. Although the cytotoxic effects of QDs have been extensively investigated, their genotoxic effects remain under-explored. This study scrutinized the cyto- and genotoxic effects of QDs with a Cadmium selenide/Zinc sulfide (CdSe/ZnS) core/shell, and suggests comprehensive guidelines for the application of QDs in cancer therapy. QDs were used to treat A549 cells in the presence and absence of ultraviolet A/B (UVA/UVB) irradiation. QD-induced cell death was evaluated by 3-(4,5-Dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide (MTT), apoptosis, and lactate dehydrogenase (LDH) assays, as well as by real-time PCR analysis of differential mRNA levels of genes, such as ataxia telangiectasia mutated (ATM), p53, and caspase-9, involved in apoptosis. The genotoxic effect of CdSe/ZnS QDs was measured in human cancer cells, for the first time, by comet and micronucleus assays. Treatment with CdSe/ZnS QDs and UVB irradiation resulted in the most severe extent of cell death, indicating strong induction of phototoxicity by CdSe/ZnS QDs in the presence of UVB. Both apoptotic and necrotic cell death were observed upon QDs and UVB combined treatment. The induction of Olive tail moments and micronuclei formation was also most significant when CdSe/ZnS QDs and UVB irradiation were combined. Our results on the genotoxic effect and mechanistic details of CdSe/ZnS QD-induced cell death suggest that UVB irradiation is the most effective method for increasing the potency of QDs during photodynamic cancer therapy.     

A highly effective and facile way to prepare cellular labelling quantum dots with cetyltrimethylammonium bromide

We report a facile and effective way to prepare cell labelling quantum dots (QDs) using cetyltrimethylammonium bromide (CTAB) and to enhance biocompatibility of the QD labels. There are several reports on the use of this ligand to encapsulate nanoparticles including QDs. However, due to its high cellular toxicity, CTAB has still not been employed to prepare QDs for cellular labelling. After removing the free ligand by dialysis, we could successfully use CdSe/CdS/ZnS (core/shell/shell) QDs for cellular labelling. In addition, we found that the simple introduction of a sonication step to cause the emulsion of the QDs in the aqueous surfactant solution could lead to a five-times higher encapsulation of the QDs as compared to other methods. Fluorescent microscopy images of HeLa cells revealed that the QDs were evenly dispersed inside them. Furthermore, fluorescent morphological images of the QD labelled cells were more distinct than bright field images.     

Study on the photoluminescence character of water-soluble CdSe nanocrystals under ambient conditions

Water soluble, thioglycolic acid (TGA) modified CdSe nanocrystals (NCs) have been prepared in aqueous media by the reaction between Cd2+ and NaHSe. Although initially these quantum dots (QDs) display photoluminescence (PL) with very low quantum yields (QY), upon prolonged exposure to ambient light, a strong PL enhancement by illumination is observed which leads to water soluble QDs with high luminescence. This result may have important application potential in biological or other fields. The primary reason for the luminescence enhancement is concluded to be the incorporation of sulfide ions from TGA into the lattice of CdSe NCs and the subsequent formation of alloy structures. Moreover, the CdSe/CdS core-shell structured QDs synthesized in aqueous solutions also consolidate this conclusion.     

Capillary electrophoresis method for the characterization and separation of CdSe quantum dots

This paper presents a simple and rapid methodology to separate and characterize free CdSe quantum dots (QDs) in aqueous medium by capillary electrophoresis (CE). First, we describe a controlled derivatization procedure to obtain water-soluble QDs through noncovalent interactions. This derivatization methodology was based on the formation of a complex between the QDs and several types of surfactants to enhance the hydrophilicity and stability of the CdSe QDs. The surfactants used to achieve the surface functionalization were trioctylphosphine oxide/trioctylphosphine (TOPO/TOP) and sodium dodecyl sulfate (SDS). Different CdSe QDs core sizes were synthesized as function of the nanocrystals growing time and then subjected to controlled coating. These free QDs were separated by capillary zone electrophoresis (CZE) based on the differences in the charge-to-mass ratio of the QDs-TOPO/TOP-SDS complexes, and the detection was carried out with UV-vis and laser-induced fluorescence (LIF) techniques obtaining detection limits 5 times lower with CE-LIF. Under the optimal working conditions, four different-sized QDs were successfully separated whose average sizes were 3.1, 3.6, 4.3, and 4.9 nm, and the size distribution was less than 7% for all of them [calculated from the full width at half-maximum (fwhm) of the fluorescence spectra and confirmed by high-resolution transmission electron microscopy (HTEM)]. Therefore, we were able to separate QDs that differ in only 0.5 nm in diameter and 19 nm in fluorescence emission maximum. This corresponds to the better resolution achieved in the analysis of these kinds of nanoparticles. Finally, a correlation between the migration times plus or minus peak width and the core sizes plus or minus size distribution was established.     

Enhanced electron transfer rate for quantum dot sensitized solar cell based on CNT-TiO2 film

In this paper, we have fabricated a quantum dot sensitized solar cell (QDSSC) based on carbon nanotube (CNT) doped TiO2 mesopores film. As revealed by field emission scanning electron microscopy and absorption spectra, the CdSe QDs were adsorbed onto CNT-TiO2 nanocomposite. An improved efficiency is achieved for the CNT-TiO2/CdSe devices compared to that of TiO2/CdSe, which is due to the increased surface area and reduced charge recombination in TiO2 film by the presence of CNTs. A power conversion efficiency of the as-prepared QDSSC of 0.98% was obtained under 100 mW/cm2 solar irradiation. The emission decay profile demonstrates that the electrons transfer from CdSe QDs to CNT-TiO2 is faster than that from CdSe QDs to TiO2, resulting in the reduction of the charge recombination, leading to a higher FF value in QDSSC. The average lifetime of CdSe QDs adsorbed on TiO2 doped with CNT is 6.2 ns and the electron transfer rate constant of 1.1 x 10(8) s(-1) can be calculated.     

CNT–CdSe QDs nanocomposites: synthesis and photoluminescence studies

In this study, synthesis of carbon nanotube (CNT)–CdSe Quantum dots (QDs) nanocomposites has been investigated. CdSe QDs were synthesized via hydrothermal process. The chemical tendency of CNT and QDS was increased by precipitation after surface functionalization of CNTs (by carboxylated groups) and CdSe QDs (by silane groups), separately. The structure of nanocomposites was amorphous with a little amount of nanocrystalline cubic CdSe. The Fourier-transform infrared (FTIR) spectra and Raman spectrum revealed the strong chemical tendency of linkage between CNTs and QDs after functionalization on the surface of them. The morphology of nanocomposites depended on the QDs concentration and changed from aggregates of CNTs to the marvelous decoration of quantum dots on the ropes of CNTs. Transmission electron microscope (TEM) and atomic force microscope (AFM) images confirmed the adorable coatings of CNTs with CdSe QDs. The nanocomposites emitted in blue–green region with a maximum peak at 490 nm under the exposure of Ultraviolet (UV) light. Below 50 wt% QDs, the emission was quenched completely.     

Extracellular biosynthesis of biocompatible CdSe quantum dots

An extracellular biosynthesis method has been developed to prepare cadmium selenide (CdSe) quantum dots (QDs) with strong fluorescence emission by incubating cheap Cd and Se inorganic salts with Escherichia coli (E.coli) bacteria. Ultraviolet–visible absorption spectra, photoluminescence (PL) spectra, and high‐resolution transmission electron microscopy analysis showed that the biosynthesised CdSe QDs have an average size of 3.1 nm, the excellent optical properties with fluorescence emission around 494 nm, and the good crystallinity. It was found that addition of 80 mg of mercaptosuccinic acid resulted in the formation of CdSe QDs with highest PL intensity. Furthermore, Fourier‐transform infrared spectra of as‐synthesised CdSe QDs confirmed the presence of a surface protein capping layer. The biosynthesised CdSe QDs were incorporated into the yeast cells as illustrated by laser confocal scanning microscopy images, showing a great potential in bio‐imaging and bio‐labelling application.Inspec keywords: microorganisms, molecular biophysics, fluorescence, visible spectra, nanofabrication, nanobiotechnology, proteins, cellular biophysics, nanostructured materials, wide band gap semiconductors, cadmium compounds, semiconductor quantum dots, II‐VI semiconductors, transmission electron microscopy, photoluminescence, optical microscopy, ultraviolet spectra, Fourier transform infrared spectra, biological techniques, semiconductor growthOther keywords: biocompatible CdSe quantum dots, extracellular biosynthesis method, cadmium selenide quantum dots, high‐resolution transmission electron microscopy analysis, biosynthesised CdSe QDs, Fourier‐transform infrared spectra, Escherichia coli, ultraviolet‐visible absorption spectra, PL intensity, fluorescence emission, photoluminescence spectra, optical properties, surface protein capping layer, laser confocal scanning microscopy images, bioimaging, biolabelling application, yeast cells, f mercaptosuccinic acid, CdSe     

Self-surface passivation of CdX (X = Se, Te) quantum dots

A small portion of a reaction mixture including unpurified CdX (X = Se or Te) quantum dots (QDs), in which unreacted Cd and Se ions were left together with coordinating solvents, was dropped into an organic solvent. The CdX QDs in this organic solution showed enhancement of photoluminescence (PL) efficiency, growth of particles, and focusing of size distribution for more than 10 h at room temperature (RT, -23 degrees C). These effects were attributed to passivation of QDs' surface by Cd and X ions present in the solution. No external energy source was used for these achievements; therefore, the process is termed as self-surface passivation. The self-surface passivation was reproduced using purified CdX QDs with additional Cd and X ions in an organic solvent. The self-surface passivation method was applied to RT-synthesized CdSe QDs, which is characterized by a broad PL spectrum (fwhm - 150 nm) for monodispersed QDs, to modify their emission characteristics. On self-surface passivation, the broad PL spectrum was narrowed (fwhm - 35 nm) and the QDs were grown. The X-ray diffraction measurements of RT-synthesized CdSe QDs and that subsequently aged in 1-butanol showed that crystallinity of the samples was improved on aging.     

Preparation and characterization of overcoated II-VI quantum dots

A convenient route for the synthesis of high-quality overcoated II-VI quantum dots (QDs) is reported in this paper. Simple salts, such as Cd(Ac)2 and Zn(Ac)2 were used to replace organometallics, whose disadvantage is obvious. Size-tunable core/shell structured QDs (CdSe/ZnS, CdSe/CdS, etc.) were synthesized. They were of narrow size distribution and had good monodispersivity and photoluminescence (PL) properties. The spectrum was symmetrical and sharp-pointed (with the full width at half-maximum (fwhm) of about 20-30 nm). The quantum yield (QY) was improved to 60-80% from 20-30% for bare QDs and remained stable at least for 6 months. The primary overcoated QDs were modified with biomacromolecules by a direct mechanical rubbing strategy, which is very simple and fast. The results obtained by UV-vis, PL, atomic force microscopy (AFM), and fluorescence microscopy imaging showed that the modified QDs were of good fluorescent and monodisperse characteristics. They are likely to be used further for biological labels.     

Organic light-emitting devices fabricated utilizing core/shell CdSe/ZnS quantum dots embedded in a polyvinylcarbazole

Electrical and the optical properties of organic light-emitting devices (OLEDs) fabricated utilizing core/shell CdSe/ZnS quantum dots (QDs) embedded in a polyvinylcarbazole (PVK) layer were investigated. An abrupt increase of the current density above an applied voltage of 12 V for OLEDs consisting of Al/LiF/4,7-diphenyl-1,10-phenanthroline/bis-(2-methyl-8-quinolinolate)-4-(phenylphenolato) aluminium/[CdSe/ZnS QDs embedded in PVK]/poly(3,4-ethylenedioxythiophene) and poly(styrenesulfonate)/ITO/glass substrate was attributed to the existence of the QDs. Photoluminescence spectra showed that the peaks at 390 and 636 nm corresponding to the PVK layer and the CdSe/ZnS QDs were observed. While the electroluminescence (EL) peak of the OLEDs at low voltage range was related to the PVK layer, the EL peak of the OLEDs above 12 V was dominantly attributed to the CdSe/ZnS QDs. The Commission Internationale de l’Eclairage (CIE) chromaticity coordinates of the OLEDs at high voltages were (0.581, 0.380) indicative of a red color. When the holes existing in the PVK layer above 12 V were tunneled into the CdSe/ZnS QDs, the holes occupied by the CdSe/ZnS QDs combined with the electrons in the PVK layer to emit a red color related to the CdSe/ZnS QDs.     

Effect of surfactants in synthesis of CsH<Subscript>2</Subscript>PO<Subscript>4</Subscript> as protonic conductive membrane

Cesium dihydrogen phosphate (CDP) powders were synthesized by cetyltrimethylammoniumbromide (CTAB), polyoxyethylene-polyoxypropylene (F-68) and mixture of both surfactants F-68: CTAB with two molar ratios 0.06 and 0.12 as surfactant solutions at room temperature. The synthesized CsH₂PO₄ is characterized by ICP, XRD, TEM, SEM, FT-IR, BET and IS techniques. Based on the width of the (011) XRD diffraction peak and BET measurement, the average size of nanoparticles was ∼ 10 nm in diameter, while the TEM images indicate smaller size than both techniques. The analysis reveals existence of P and Cs with mole ratio 1.02 ± 0.03 which is compatible to molar ratio CsH₂PO₄ formula. The experimental results show that the conductivities increase in the order of CDP_CTAB > CDP_{(F-68: CTAB)0.12} > CDP_{(F-68:CTAB)0.06} > CDP_F-68. The sequence of increasing conductivity is in accordance with the ion exchange capacities of the samples that has direct proportional effect on the proton mobility of samples. Indeed CTAB as cationic surfactant shows the highest proton mobility in the as-obtained samples.     

A novel method to enhance quantum yield of silica-coated quantum dots for biodetection

In this paper, based on selecting the appropriate type of quantum dots (QDs), a novel method is developed to enhance the quantum yield (QY) of silica-coated QD nanoparticles (SQDNPs). The effect of varying types of QDs on the QY after silica encapsulation is systematically studied. The results show that QDs with appropriate structure and composition of shells can much better retain the initial QY after silanization. The seven-layered shell/core QDs with QY of 47.8% nearly completely retain the original QY and is the best type among six types of QDs for silica modification. In the aspect of shell composition, the CdS plays an important role for QY retention since the lattice mismatch between CdSe and CdS is lower than that of CdSe and ZnS. After the appropriate type of QDs is chosen for silica coating, the highly fluorescent SQDNPs are chemically modified with amine, thiol and carboxyl groups, and then labeled by antibodies for particle-based immunofluorescence assay. The results indicate that the SQDNPs-antibody bioconjugates are alternative fluorescent probes useful for biodetection.     

In vitro degradation of porous poly(lactic acid)/quantum dots scaffolds

In this study, cadmium selenide/zinc sulfide (CdSe/ZnS) quantum dots (QDs) were introduced into poly(lactic acid) (PLA) for fabrication of photoluminescent PLA/QDs scaffolds. TEM images revealed that the QDs were uniformly dispersed in the PLA. Compressive modulus and thermal stability of the PLA/QDs scaffolds are higher than those of the unfilled PLA scaffold. Cytotoxicity test results confirmed the non-cytotoxicity of the PLA/QDs scaffolds. During the process of in vitro degradation, the degradation rate of the PLA was accelerated by the presence of the QDs, and the molecular weight distributions of the PLA/QDs scaffolds were much broader when compared with the unfilled PLA ones. During the first 84 weeks of the degradation process, the photoluminescence (PL) intensity of the PLA/QDs scaffolds decreased with almost the same degradation ratio. The results suggested that the CdSe/ZnS QDs have potential applications for monitoring in vivo degradation of tissue engineering scaffolds.