Synthesis of aqueous CdTe quantum dots embedded silica nanoparticles and their applications as fluorescence probes

This paper presents the synthesis of aqueous CdTe QDs embedded silica nanoparticles by reverse microemulsion method and their applications as fluorescence probes in bioassay and cell imaging. With the aim of embedding more CdTe QDs in silica spheres, we use poly(dimethyldiallyl ammonium chloride) to balance the electrostatic repulsion between CdTe QDs and silica intermediates. By modifying the surface of CdTe/SiO₂ composite nanoparticles with amino and methylphosphonate groups, biologically functionalized and monodisperse CdTe/SiO₂ composite nanoparticles can be obtained. In this work, CdTe/SiO₂ composite nanoparticles are conjugated with biotin-labeled mouse IgG via covalent binding. The biotin-labeled mouse IgG on the CdTe/SiO₂ composite nanoparticles surface can recognize FITC-labeled avidin and avidin on the surface of polystyrene microspheres by protein-protein binding. Finally, the CdTe/SiO₂ composite nanoparticles with secondary antibody are used to label the MG63 osteosarcoma cell with primary antibody successfully, which demonstrates that the application of CdTe/SiO₂ composite nanoparticles as fluorescent probes in bioassay and fluorescence imaging is feasible.     

Magnetic targeting and cellular uptake of polymer microcapsules simultaneously functionalized with magnetic and luminescent nanocrystals

By using a flow channel system for modeling the bloodstream in the circulatory system and by locally creating a magnetic field gradient caused by a permanent magnet, we demonstrate specific trapping of polymer capsules simultaneously functionalized with two types of nanoparticles--magnetic and luminescent nanocrystals. In the regions where the capsules were trapped by the magnetic field, drastically increased uptake of capsules by cells has been observed. The uptake of capsules by cells could be conveniently monitored with a fluorescence microscope by the luminescence of CdTe nanocrystals that had been embedded into the shells of the capsules. Our experiments envisage the feasibility of magnetic targeting of polymer capsules loaded by pharmaceutical agents to pathogenic parts of a tissue.     

Luminescent polymer microcapsules addressable by a magnetic field

The simultaneous encapsulation of both luminescent semiconductor and magnetic oxide nanoparticles in polymer microcapsules is demonstrated for the first time. Highly luminescent CdTe semiconductor nanocrystals serve as luminescent markers, while magnetic Fe3O4 nanoparticles allow external manipulation of the capsules by magnetic field. The method introduced is general enough to allow the fabrication of different types of multifunctional capsules in a similar way. The use of multifunctional water-compatible capsules introduced in this paper for the controlled release and directed drug delivery in biological systems is envisaged.     

巯基乙胺稳定的水溶性CdTe纳米粒子的合成与表征

用巯基乙胺(cysteamine，CA)作为稳定剂，在水相中合成了发光可调的CdTe半导体纳米粒子。这些巯基乙胺稳定的CdTe纳米粒子表面带有大量的正电荷。实验结果表明，稳定剂与Cd的比例以及pH等实验条件对CdTe纳米粒子体系的荧光发射强度影响较大。在pH为6.1时，纳米粒子体系在橙红波段的荧光量子产率达到了9%左右。控制实验条件，合成了各种尺寸的CdTe纳米粒子，荧光发射光谱在520～600 nm范围连续可调。分别用X射线光电子能谱(XPS)，透射电子显微镜(TEM)，X射线衍射仪(XRD)，红外吸收     

Optical properties of Ag/CdTe nanocomposite self-organized by electrostatic interaction

Ag/CdTe nanocomposite was prepared via self-organization process by electrostatic interaction between positively charged CdTe quantum dots and negatively charged Ag nanoparticles and examined with respect to their optical properties. The positively charged CdTe quantum dots and negatively charged Ag nanoparticles were synthesized separately by modifying nanoparticles surface with cationic and anionic thiol compounds, respectively. The result showed that the mixing ratio of Ag nanoparticles to CdTe quantum dots is an important parameter for controlling resulting composites. The resulting solution is optically transparent if one component is in excess. Photoluminescence of CdTe quantum dots undergoes considerably quenching if CdTe nanocrystals are in excess and SERS spectra of BVPP absorbed on Ag colloid became stronger if Ag nanoparticles are in excess. Nevertheless, while the ratio is approximately 1, micrometer-sized solid composite is obtained with the elapse of 1h after mixing. SERS spectra for solid composite only exhibit the signals of the CdS nanocrystal which reflected that prolonged refluxing during the synthesis leads to a partial hydrolysis of the thiols and to the incorporation of the sulfur from the thiol molecules into the the growing nanoparticles to form mixed CdTe(S) nanocrystal, similar to CdTe/CdS core/shell structure. From the results, we conclude that optical properties of Ag/CdTe are dependent on the mixing ratio of both nanoparticles.     

Study on the resonance light-scattering spectrum of lysozyme-DNA/CdTe nanoparticles system

The interactions of lysozyme and calf thymus DNA (ctDNA) or thioglycolic acid (TGA) modified CdTe nanoparticles in aqueous solution have been studied by resonance light-scattering (RLS) spectroscopy. At pH 7.2 Britton-Robinson (BR) buffer solution and pH 7.4 phosphate buffered saline (PBS), the RLS signals of ctDNA and TGA modified CdTe nanoparticles were greatly enhanced by lysozyme in the region of 220-750 nm characterized by the peak around 306 and 353 nm, respectively. Under optimal conditions, the increase of RLS intensity of the two systems is proportional to the concentration of lysozyme. The linear range is 0.1-25 microg/ml for the lysozyme-ctDNA system, and 0.2-10.7 microg/ml for the lysozyme-TGA modified CdTe nanoparticles system. The detection limit is 0.041 microg/ml for the lysozyme-ctDNA system, and 0.083 microg/ml for the lysozyme-TGA modified CdTe nanoparticles system, respectively. Meanwhile lysozyme can also be used as a probe to determine the ctDNA. The increase of RLS intensity of the system is also proportional to the concentration of ctDNA. The linear range is 0.078-13 microg/ml. The detection limit is 0.024 microg/ml. Three kinds of samples were analyzed with satisfactory results.     

The room-temperature synthesis of anisotropic CdHgTe quantum dot alloys: a "molecular welding" effect

The room-temperature chemical transformation of spherical CdTe nanoparticles into anisotropic alloyed CdHgTe particles using mercury bromide in a toluene/methanol system at room temperature has been investigated. The resulting materials readily dissolved in toluene and exhibited a significant red-shift in the optical properties toward the infrared region. Structural transformations were observed, with electron microscopy showing that the CdTe nanoparticles were chemically attached ('welded') to other CdTe nanoparticles, creating highly complex anisotropic heterostructures which also incorporated mercury.     

Influence of EDTA on the hydrothermal synthesis of CdTe nanocrystallites

Transformation from Te nanorods to CdTe nanoparticles was achieved with the assistance of EDTA as a ligand under hydrothermal conditions. Experimental results showed that at the beginning of reaction Te nucleated and grew into nanorods. With the proceeding of reaction, CdTe nucleus began to emerge on the surface, especially on the tips of Te nanorods. Finally, nearly monodispersed hexagonal CdTe nanoparticles with diameters of about 200 nm were obtained. The effects of EDTA on the morphology and formation of CdTe nanoparticles were discussed in consideration of the strong ligand-effect of EDTA, which greatly decreased the concentration of Cd²⁺. Furthermore, the possible formation process of CdTe nanoparticles from Te nanorods was further proposed. The crystal structure and morphology of the products were investigated by X-ray diffraction (XRD) and scanning electron microscopy (SEM).     

Solid state NMR studies of photoluminescent cadmium chalcogenide nanoparticles

Solid state (113)Cd, (77)Se, (13)C and (31)P NMR have been used to study a number of Cd chalcogenide nanoparticles synthesized in tri-n-octyl-phosphine (TOP) with different compositions and architectures. The pure CdSe and CdTe nanoparticles show a dramatic, size-sensitive broadening of the (113)Cd NMR line, which can be explained in terms of a chemical shift distribution arising from multiple Cd environments. From (13)C NMR, it has been discovered that TOP, or its derivatives such as TOPO (trioctylphosphine oxide), is rapidly moving about the surface of the nanoparticles, indicating that it is relatively weakly bound as compared to other materials used as surface ligands, such as hexadecylamine. (31)P NMR of the nanoparticles shows at least five species arising from coordination of the ligands to different surface sites. (113)Cd NMR of CdSeTe alloy and layered nanoparticles has provided crucial information which, in conjunction with results from other techniques (especially optical characterization), has made it possible to develop a detailed picture of the composition and structure of these materials: (i) a true CdSeTe homogeneous alloy nanoparticle, (ii) a nanoparticle segregated into an alloy core region rich in Te, with a CdSeTe (close to 1 : 1 Se : Te) alloy shell and (iii) a CdSe/CdTe/CdSe layered nanoparticle in which the CdTe layer contains a small amount of Se and which forms a Quantum Dot Quantum Well (QDQW) system. The results demonstrate that solid state NMR is a vital tool in the arsenal of characterisation techniques available for nanomaterials.     

Study the damage of DNA molecules induced by three kinds of aqueous nanoparticles

In this paper, the interaction of DNA molecules with aqueous CdTe quantum dots (CdTe QDs), CdTe/SiO₂ composite nanoparticles (CdTe/SiO₂ NPs), and Mn-doped ZnSe quantum dots (Mn:ZnSe d-dots) was studied with ethidium bromide as a probe. The purpose of this work was to study the damage of DNA molecules induced by these three kinds of water-soluble nanoparticles. It was found that ionic strength, pH value and UV irradiation influenced the PL emission properties of CdTe QDs, CdTe/SiO₂ NPs and Mn:ZnSe d-dots, and also influenced the interaction of DNA molecules with them. Among the three kinds of nanoparticles, DNA molecules were most easily damaged by CdTe QDs whether in the dark or under UV irradiation. The CdTe/SiO₂ NPs led to much less DNA damage when compared with CdTe QDs, as a silica overcoating layer could isolate the QDs from the external environment. Mn:ZnSe d-dots as a new class of non-cadmium doped QDs demonstrated almost no damage for DNA molecules, which have great potentials as fluorescent labels in the applications of biomedical assays, imaging of cells and tissues, even in vivo investigations.     

Spectroscopic studies on the interaction between CdTe nanoparticles and lysozyme

Nanoparticles of cadmium telluride (CdTe) coated with thioglycolic acid (TGA) were prepared in the water phase. The interaction between CdTe nanoparticles (NPs) and lysozyme (Lyz) was investigated by fluorescence and circular dichroism (CD) spectroscopy at pH 7.40. It was proved that the fluorescence quenching of Lyz by CdTe NPs was mainly a result of the formation of CdTe-Lyz complex. By the fluorescence quenching results, the Stern-Volmer quenching constant (K(SV)), binding constant (Ka) and binding sites (n) were calculated. The binding distance (r) between Lyz (the donor) and CdTe NPs (the acceptor) was obtained according to fluorescence resonance energy transfer (FRET). Gradual addition of CdTe NPs to the solution of Lyz led to a marked increase in fluorescence polarization (P) of Lyz, which indicated that CdTe NPs were located in a restricted environment of Lyz. The effect of CdTe NPs on the conformation of Lyz has been analyzed by means of synchronous fluorescence spectra and CD spectra, which provided the evidence that the secondary structure of Lyz has been changed by the interaction of CdTe NPs with Lyz.     

Energy/Hole Transfer Phenomena in Hybrid α‐Sexithiophene (α‐STH) Nanoparticle–CdTe Quantum‐Dot Nanocomposites

Considerable attention has been paid to hybrid organic–inorganic nanocomposites for designing new optical materials. Herein, we demonstrate the energy and hole transfer of hybrid hole‐transporting α‐sexithiophene (α‐STH) nanoparticle–CdTe quantum dot (QD) nanocomposites using steady‐state and time‐resolved spectroscopy. Absorption and photoluminescence studies confirm the loss of planarity of the α‐sexithiophene molecule due to the formation of polymer nanoparticles. Upon photoexcitation at 370 nm, a nonradiative energy transfer (73 %) occurs from the hole‐transporting α‐STH nanoparticles to the CdTe nanoparticles with a rate of energy transfer of 6.13×10⁹ s^?1. However, photoluminescence quenching of the CdTe QDs in the presence of the hole‐transporting α‐STH nanoparticles is observed at 490 nm excitation, which is due to both static‐quenching and hole‐transfer‐based dynamic‐quenching phenomena. The calculated hole‐transporting rate is 7.13×10⁷ s^?1 in the presence of 42×10^?8 M α‐STH nanoparticles. Our findings suggest that the interest in α‐sexithiophene (α‐STH) nanoparticle–CdTe QD hybrid nanocomposites might grow in the coming years because of various potential applications, such as solar cells, optoelectronic devices, and so on.     

金纳米棒@碳中空胶囊的制备及催化性能

以聚吡咯为碳壳前驱体制备了金纳米棒镶嵌于碳壳内的中空胶囊.先合成羧基修饰的聚苯乙烯微球和十六烷基三甲基溴化铵稳定的金纳米棒; 再利用二者之间的静电力将金纳米棒组装在聚苯乙烯微球表面; 最后, 通过氧化聚合将聚吡咯壳包覆在聚苯乙烯@金纳米棒复合物的表面.在氮气保护下经高温煅烧, 聚吡咯壳被碳化为碳壳的同时聚苯乙烯微球分解, 从而制得金纳米棒@碳中空胶囊.在煅烧过程中, 由于碳壳的保护, 金纳米棒很好地保持了“棒状”形貌.通过调节吡咯单体的浓度, 可以控制聚吡咯壳和碳壳的厚度.金纳米棒@碳中空胶囊在以NaBH₄为还原剂还原亚甲基蓝的反应中表现出良好的催化活性.     

NHS-mediated QDs-peptide/protein conjugation and its application for cell labeling

3-Mercaptopropyl acid-stabilized CdTe nanoparticles synthesized in aqueous solution are found to be able to conjugate with peptides or proteins mediated by N-hydroxysulfo-succinimide (NHS) but 1-ethyl-3(3-dimethylaminopropyl) carbodiimides hydrochloride (EDC). The reaction time and pH have been optimized. Gel-permeation HPLC was applied following the conjugation, which could quickly and simultaneously detect and purify the quantum dots (QDs) conjugates. The biological activities of QDs conjugates are maintained and give superior results in cell labeling. These results are encouraging regarding the application of QDs molecules for use in living cells, diagnostics and drug delivery.     

Tin Domain Growth on Quasi-Two-Dimensional CdTe and CdSe Nanoparticles

Tin domain growth on quasi-two-dimensional colloidal CdSe and CdTe nanoparticles having the zinc blende structure has been studied. The initial quasi-two-dimensional CdSe and CdTe nanoparticles having lateral sizes of 100–200 nm were prepared by a colloidal method. Tin domain growth was accomplished in tetrahydrofuran via the reduction of a tin(II) salt by tetrabutylammonium borohydride. The tin domains had sizes of 10–20 nm as probed by TEM. In case of CdSe nanoparticles, tin domains were grown inside the inner cavities of initially rolled nanoparticles. A β-tin phase was identified by X-ray diffraction. The absorption spectra featured the broadening of exciton bands corresponding to quasi-two-dimensional nanoparticles, the spectral positions of absorption peaks remaining almost unchanged.     

具有光谱可调、高量子产率和稳定性的水溶性CdTe/Cd(OH)2核壳结构纳米粒子的可控水相合成

建立了一种简便的、以易得的无机盐为反应前体的水相法制备水溶性、高量子产率以及良好稳定性的CdTe/Cd(OH)2核壳结构量子点。本方法可以通过控制Cd(OH)2 壳层结构的厚度,使不同粒径量子点的荧光发射光谱由蓝绿色渐变到橙红色。利用透射电镜、X射线粉末衍射光谱、荧光光谱以及紫外可见光谱对该CdTe/Cd(OH)2核壳结构量子点进行了表征。CdTe/Cd(OH)2核壳结构量子点所具备的良好的水溶性可望应用于生物标记。本方法简便、反应条件温和并且容易操作,为无机金属化物包覆量子点提供了一种简便的途径。     

Long-term exposure to CdTe quantum dots causes functional impairments in live cells

Several studies suggested that the cytotoxic effects of quantum dots (QDs) may be mediated by cadmium ions (Cd2+) released from the QDs cores. The objective of this work was to assess the intracellular Cd2+ concentration in human breast cancer MCF-7 cells treated with cadmium telluride (CdTe) and core/shell cadmium selenide/zinc sulfide (CdSe/ZnS) nanoparticles capped with mercaptopropionic acid (MPA), cysteamine (Cys), or N-acetylcysteine (NAC) conjugated to cysteamine. The Cd2+ concentration determined by a Cd2+-specific cellular assay was below the assay detection limit (<5 nM) in cells treated with CdSe/ZnS QDs, while in cells incubated with CdTe QDs, it ranged from approximately 30 to 150 nM, depending on the capping molecule. A cell viability assay revealed that CdSe/ZnS QDs were nontoxic, whereas the CdTe QDs were cytotoxic. However, for the various CdTe QD samples, there was no dose-dependent correlation between cell viability and intracellular [Cd2+], implying that their cytotoxicity cannot be attributed solely to the toxic effect of free Cd2+. Confocal laser scanning microscopy of CdTe QDs-treated cells imaged with organelle-specific dyes revealed significant lysosomal damage attributable to the presence of Cd2+ and of reactive oxygen species (ROS), which can be formed via Cd2+-specific cellular pathways and/or via CdTe-triggered photoxidative processes involving singlet oxygen or electron transfer from excited QDs to oxygen. In summary, CdTe QDs induce cell death via mechanisms involving both Cd2+ and ROS accompanied by lysosomal enlargement and intracellular redistribution.     

Fabrication of a covalently attached self-assembly multilayer film based on CdTe nanoparticles

A precursor film has been fabricated from TGA (thiolglycolic acid)-stabilized CdTe nanoparticles and NDR (nitro-containing diazoresin) using electrostatic interactions and the standard layer-by-layer assembly method; covalent bonds are formed under ultraviolet irradiation. XPS provided evidence for the presence of CdTe nanoparticles within the polymer ultrathin films. UV-visible spectroscopy and FTIR spectroscopy provide evidence for the formation of a covalent linkage. Moreover, the UV-visible spectroscopy and AFM measurement support the improvement of the stability of the hybrid organic/inorganic film toward polar solvents when the linkages between the nanoparticles and polymer changed from ionic bonds to covalent bonds.     

Photoinduced Electron Transfer between CdS and CdTe Nanoparticles in Colloidal Solutions

The photochemical behavior of solutions containing a mixture of CdS and CdTe nanoparticles under pulsed irradiation conditions was investigated. It was shown that electron transfer from the CdS particles to the CdTe nanoparticles occurs during the photoexcitation of such systems. The effectiveness of the process is increased with increase in the size of the CdTe nanoparticles. Such behavior is due to decrease in the potential of the CdTe conduction band with increase in the size of the nanoparticles as a result of the appearance of quantum-dimensional effects.     

CdTe@TiO2复合纳米微粒的制备与表征

利用溶胶-凝胶法合成了CdTe@TiO2复合纳米微粒. 采用扫描和透射电镜对复合微粒的形貌和结构进行了表征, 并探讨了其形成机理. 通过对复合微粒的光谱性质研究发现, 与TiO2复合后, CdTe纳米微粒的荧光有减弱的趋势, 但却具有相似的荧光寿命, 其荧光寿命都短于原CdTe纳米微粒水溶液中的荧光寿命, 说明该材料作为新一代太阳能电池具有非常大的潜力.