两亲性壳聚糖衍生物的制备及其包覆量子点

以天然壳聚糖为功能性高分子的骨架,通过西弗碱还原法,以正辛醛和端醛基聚乙二醇单甲基醚(mPEG aldehyde,mPEG-ald)修饰壳聚糖,制备了具有亲疏水性质的N-辛基化-N-mPEG化壳聚糖衍生物(N-octyl-N-mPEG-chitosan,OPEGC),并且以此两亲性壳聚糖衍生物包覆量子点制备了水溶性聚合物量子点纳米粒子.用FTIR、1H-NMR对壳聚糖衍生物进行了结构表征.制备的水溶性胶束,用动态光散射(DLS)测试其流体力学直径与分布,研究了烷基链接枝比率对粒径大小的影响,研究结果表明:烷基链接枝率越高,聚合物胶束粒径越小.以芘为分子探针,通过荧光光谱法测定了壳聚糖衍生物的临界胶束浓度(CMC)为2.032×10-2mg/mL,并对水溶性聚合物量子点纳米粒子进行了紫外、荧光及形貌表征,结果表明得到了荧光发射产率高的聚合物量子点纳米粒子,且尺寸均一、水溶性好.     

Ultrafine biocompatible chitosan nanoparticles encapsulating multi-coloured quantum dots for bioapplications

Owing to their excellent optical properties, luminescent semi-conductor quantum dots (QDs) have proven themselves to be an attractive choice in biological labeling. However, there exists the concern of cytotoxicity in using these heavy metal-based nanoparticles as molecular probes. In order to improve their general biocompatibility, CdSe/ZnS QDS are encapsulated in the natural biopolymer chitosan, forming monodisperse chitosan nanoparticles in the range of 60 nm in 1 single step. This straight forward method also allows for the synthesis of chitosan nanoparticles encapsulating multi-coloured QDs. In vitro 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide (MTT) cytotoxicity tests on primary myoblast cells suggest that the cytotoxicity of the QDs is greatly reduced after chitosan encapsulation. At the same time, fluorescence confocal microscopy studies also prove that nanoparticles are small enough to be internalized into the myoblast cells. Our results show the ease of synthesizing biocompatible, nanometer-sized chitosan nanoparticles encapsulating QDs and their promise in biological applications such as ultra-sensitive bio-detection and labeling of biomolecules.     

水合肼还原二氧化碲水相合成CdTe量子点

以巯基乙酸为稳定剂, 氯化镉为镉源, 二氧化碲为碲源, 水合肼为还原剂, 一步合成了CdTe量子点. 研究了反应时间、 碲与镉的摩尔比及巯基乙酸与镉的摩尔比等实验条件对CdTe量子点生长过程的影响. 采用荧光光谱、 X射线粉末衍射和透射电子显微镜等对量子点的性能进行了表征. 结果表明, 反应时间及反应物的相对用量对量子点的生长和荧光光谱有明显影响, 所得CdTe量子点具有立方晶型, 发光颜色从绿色到红色连续可调, 荧光量子产率可达26%.     

氨基化单分散量子点/二氧化硅核壳纳米粒子的制备及其细胞标记

通过反向微乳液法, 在油溶性量子点表面包裹二氧化硅外壳, 使油溶性量子点水溶性化, 再利用3-氨丙基三乙氧基硅烷(APTES)在已形成的二氧化硅纳米颗粒表面进行氨基化改性, 制备富含氨基的二氧化硅包裹的量子点荧光纳米球. 通过透射电子显微镜(TEM)、粒径分析、zeta电位检测、紫外-可见分光光度、荧光分光光度和红外光谱等手段对产品进行了表征. 结果表明, 所制备的二氧化硅量子点纳米球(45 nm)具有单分散性、水溶性好及光化学稳定性强等优点. 通过静电作用, 所制备的单分散氨基化二氧化硅量子点对肿瘤细胞表面膜电荷进行了初步标记显像.     

Synthesis,characterizations, and optical properties of copper selenide quantum dots

We demonstrate the synthesis of copper selenide quantum dots (QDs) by element directed, inexpensive, straight forward wet chemical method which is free from any surfactant or template. Copper selenide QDs have been synthesized by elemental copper and selenium in the presence of ethylene glycol, hydrazine hydrate, and a defined amount of water at 70 °C within 8 h. The product is in strong quantum confinement regime, phase analysis, purity and morphology of the product has been well studied by X-ray diffraction (XRD), UV–Visible spectroscopy (UV–Vis), Photo-luminescent spectroscopy (PL), Fourier transform infrared spectroscopy (FTIR), Transmission electron microscopy (TEM), High resolution transmission electron microscopy (HRTEM), and by Atomic force microscopy (AFM) techniques. The absorption and photoluminescence studies display large “blue shift”. TEM and HRTEM analyses revealed that the QDs diameters are in the range 2–5 nm. Due to the quantum confinement effect copper selenide QDs could be potential building blocks to construct functional devices and solar cell. The possible mechanism is also discussed.     

Study on the interaction between CdSe quantum dots and chitosan by scattering spectra

Two different stabilizing agents thioglycolic acid (TGA) and l-cysteine (l-Cys) capped CdSe QDs with the diameter of 2 nm were synthesized, large amounts of stabilizing agents connected to CdSe QDs surface through Cd–S bond. The interaction between chitosan and QDs had been investigated, respectively. The interaction lead to the remarkable enhancement of RRS, RNLS and the enchantments were in proportional to the concentration of chitosan in a certain range. Under the optimal conditions, compared with TGA–CdSe QDs, the interaction between l-Cys–CdSe QDs with chitosan owned more broad linear range 0.042–3.0 μg mL⁻¹ and lower detect limits 1.2 ng mL⁻¹. The influences of factors on the interaction between chitosan with QDs and some foreign substances were all examined, which showed that the methods had a good sensitivity and selectivity. Based on this, it is hoped to build a method for the determination of chitosan using CdSe QDs as probes. Through Fourier transform infrared spectroscopy (FTIR) transmission electron microscopy (TEM), it was speculated that CdSe QDs interacted with chitosan to form a network structure aggregates through electrostatic attraction and hydrophobic forces. The reasons for the enhancement of RRS intensity were assumed as follows: resonance enhanced Rayleigh scattering effect, increase of the molecular volume, and hydrophobic effect.     

Preparation and third-order optical nonlinearity of self-assembled chitosan/CdSe-ZnS core-shell quantum dots multilayer films

The self-assembled chitosan CdSe quantum dots (QDs) and chitosan CdSe-ZnS core-shell QDs films have been prepared by using layer-by-layer electrostatic technique. The well-ordered nanostructure and the layer-by-layer deposition of the QDs are revealed by AFM and exciton absorption spectra, respectively. The optical nonlinearity of the composite films were studied by using Z-scan technique with femtosecond pulses at the wavelength of 790 nm, the value of third-order susceptibility of core-shell QDs are measured to be about 1.1 x 10(-8) esu, which is about 200% larger than that of CdSe QDs of 5.3 x 10(-9) esu. This has potential applications in all-optical switches in optical information processing.     

Sizes of water-soluble luminescent quantum dots measured by fluorescence correlation spectroscopy

In this paper, fluorescence correlation spectroscopy (FCS) was applied to measure the size of water-soluble quantum dots (QDs). The measurements were performed on a home-built FCS system based on the Stokes-Einstein equation. The obtained results showed that for bare CdTe QDs the sizes from FCS were larger than the ones from transmission electron microscopy (TEM). The brightness of QDs was also evaluated using FCS technique. It was found that the stability of the surface chemistry of QDs would be significantly improved by capping it with hard-core shell. Our data demonstrated that FCS is a simple, fast, and effective method for characterizing the fluorescent quantum dots, and is especially suitable for determining the fluorescent nanoparticles less than 10 nm in water solution.     

Luminescent Nanoparticles of Silica‐Encapsulated Cadmium–Tellurium (CdTe) Quantum Dots with a Core–Shell Structure: Preparation and Characterization

Water‐soluble thioglycolic acid (TGA)‐capped CdTe quantum dots (QDs) were synthesized in aqueous medium, and then encapsulated in a silica nanosphere by copolymerization of the TGA‐capped CdTe conjugated with (3‐aminopropyl)triethoxysilane (APS‐CdTe conjugate), free (3‐aminopropyl)triethoxysilane (=3‐(triethoxysilyl)propan‐1‐amine; APS), and tetraethyl orthosilicate (TEOS) in a H₂O‐in‐oil reverse microemulsion consisting of Triton X‐100, octanol, cyclohexane, and H₂O in the presence of aqueous NH₃ solution. The characterizations by transmission electron microscopy (TEM) and luminescence spectroscopy shows that the luminescent nanoparticles are monodisperse, spherical, and uniform in size, ca. 50 nm in diameter with a regular core–shell structure. In addition, primary amino groups directly introduced to the nanoparticle's surface by using free APS in the nanoparticle preparation enable the nanoparticles to be used easier as a biolabel. The effects of pH and metal cations on the luminescence of the nanoparticles also suggest that the new nanoparticles could be useful probes for luminescent sensings of pH and Cu²⁺ ion.     

Synthesis and suspension rheology of titania nanoparticles grafted with zwitterionic polymer brushes

Thin films of polydimethylsiloxane (PDMS) and ZnO quantum dots (QDs) were built up as multilayers by spin-coating. The films are characterized by a UV-blocking ability that increases with increasing number of bilayers. Photoluminescence (PL) emission spectra of the thin films occur at 522 nm, which is the PL wavelength of the ZnO QDs dispersion, but with a lower intensity and a quantum yield (QY) less than 1% that of the dispersion. Cross-linking has introduced new features to the absorption spectra in that the absorption peak was absent. These changes were attributed to the morphological and structural changes revealed by transmission electron microscopy (TEM) and Fourier transform infrared spectroscopy (FTIR), respectively. TEM showed that the ZnO particle size in the film increased from 7 (±2.7) nm to 16 (±7.8) upon cross-linking. The FTIR spectra suggest that ZnO QDs are involved in the cross-linking of PDMS and that the surface of the ZnO QDs has been chemically modified.     

Fe_3O_4/CdTe/聚氨酯纳米复合物的制备及其性能研究

由共沉淀法和Stober法制备了伯胺基功能化SiO2稳定的Fe3O4磁性纳米粒子Fe3O4@SiO2-NH2;Fe3O4@SiO2-NH2与二异氰酸酯及咪唑阳离子二醇、聚乙二醇的反应使其表面形成阳离子型聚氨酯稳定层;通过阳离子型聚氨酯与CdTe量子点表面修饰的巯基乙酸间的电荷相互作用,制备得到了Fe3O4/CdTe/聚氨酯纳米复合物.用X射线衍射(XRD)、红外吸收光谱(FTIR)、热重分析(TGA)、透射电子显微镜(TEM)、磁强计(VSM)、紫外吸收光谱(UV)、荧光发射光谱(PL)表征了该纳米复合物的结构与性能.结果表明,CdTe量子点均匀地分散在Fe3O4@SiO2磁性纳米粒子周围,所得纳米复合物在溶剂中分散均匀,不团聚,且具有超顺磁性,并保持了CdTe量子点的荧光性能.     

Influence of cerium concentration on the structure and properties of silica-methacrylate sol–gel coatings

The aim of this work was to study the effect of the incorporation of cerium nitrate in a silica-methacrylate sol–gel hybrid matrix reinforced with silica nanoparticles. Sols, coatings and powders have been studied, focusing specially in the determination of the redox ratio Ce³⁺/Ce⁴⁺ and films structure. Sols have been characterised using viscosity measurements and FT-IR spectroscopy, and powders and coatings obtained with different Ce contents through UV–Vis and FT-IR spectroscopy, TGA, TEM, AFM and FE-SEM. The goal was to reach the best compromise between maximum cerium concentration and coating stability to better understand the mechanisms acting in active anti-corrosive processes.     

基于水溶性CdTe量子点-绿原酸-血管紧张素Ⅰ 相互作用的荧光可逆调控

在水相中合成了巯基丙酸(MPA)包覆的CdTe量子点(QDs), 采用透射电子显微镜和原子力显微镜对其进行表征. 利用荧光光谱、紫外-可见吸收光谱和红外光谱研究了CdTe QDs与绿原酸(CHA)的相互作用. 结果表明, CHA可显著猝灭CdTe QDs的荧光, 在一定的浓度范围内, 荧光猝灭值与CHA的浓度呈现一定的线性关系. 推断其主要猝灭机理为动态猝灭, 并实现了荧光光谱法测定CHA. 向CdTe QDs-CHA体系中加入血管紧张素Ⅰ(AngⅠ)后, CdTe QDs荧光在一定浓度范围内逐渐恢复, 从而实现了CdTe QDs的荧光可逆调控. CdTe QDs荧光的猝灭与恢复过程对于荧光传感的设计以及荧光可逆调控机理的研究具有指导意义.     

Preparation,characterization and biocompatibility of aspartic acid modified CdTe quantum dots

This study aims at preparing water soluble aspartic acid （ASP） modified CdTe quantum dots with tunable fluorescence emission controlled by reaction time. The size of the synthesized CdTe quantum dots was evaluated using transmission electron microscope （TEM） and also calculated based on their UV-vis spectra. The optical properties of TGA-CdTe quantum dots were characterized by UV-vis and fluorescence （FL） spectroscopy. The red-shift in the UV-vis absorption and FL emission with the increase of reaction time was observed. The biocompatibility examination indicated that the ASP modified CdTe QDs had low cytotoxicity.     

Synthesis of new nanocrystal-polymer nanocomposite as the electron acceptor in polymer bulk heterojunction solar cells

A hydroxyl-coated CdSe nanocrystal (CdSe-OH) and a CdSe-polymer nanocomposite were synthesized and used as the electron acceptors in polymer solar cells (PSCs). The CdSe-polymer composite was prepared via atom transfer radical polymerization (ATRP) of N-vinylcarbazole on functionalized CdSe quantum dots. Physical properties and photovoltaic characteristics of the CdSe-poly(N-vinylcarbazole) (CdSe-PVK) nanocomposite have been investigated. Thermogravimetric analysis (TGA) results displayed higher thermal stability for CdSe-PVK nanohybrid in comparison with the linear-type PVK polymer. Differential scanning calorimetry (DSC) studies indicated that CdSe-PVK had a lower glass-transition temperature (T_g) in comparison with PVK due to the branch effect of the star-shaped polymer hybrid. Cyclic voltammetric (CV) measurements were performed to obtain HOMO and LUMO values of PVK and CdSe-PVK. TEM and SEM micrographs exhibited CdSe nanoparticles were well coated with PVK polymer. Both CdSe-OH and CdSe-PVK were blended with poly(3-hexylthiophene) (P3HT) and used as the active layer in bulk heterojunction solar cells. Polymer solar cell based on CdSe-PVK as acceptor revealed that the photovoltaic properties can be significantly improved when PVK polymer chains were grafted on surfaces of CdSe nanocrystals. In comparison with the P3HT:CdSe-OH system, PSC based on P3HT:CdSe-PVK showed an improved power conversion efficiency (0.02% vs. 0.001%). Film topography studied by AFM further confirmed the better device performance was due to the enhanced compatibility between P3HT and CdSe-PVK.     

Full polysaccharide chitosan‐CMC membrane and silver nanocomposite: synthesis,characterization, and antibacterial behaviors

Chitosan‐carboxymethyl cellulose (CMC) full polysaccharide membrane was prepared by cross‐linking of chitosan with CMC dialdehyde and subsequent reductive amination. CMC dialdehyde molecule was prepared by periodate oxidation of CMC and then applied as a cross‐linking agent to form a new membrane network. The properties of oxidized CMC were investigated by various methods such as Fourier transform infrared (FT‐IR) spectroscopy, ¹H NMR spectroscopy, and viscosity test. Then, novel chitosan‐CMC silver nanocomposite was prepared using chitosan‐CMC as a carrier. The structure of the chitosan‐CMC membrane and the silver nanocomposite were confirmed by FT‐IR spectroscopy, scanning electron microscopy (SEM), transmission electron microscopy (TEM), and thermogravimetric analysis (TGA). TEM images indicate that the chitosan‐CMC nanocomposite comprises silver nanoparticles with diameters in the range of about 5–20 nm. The antibacterial studies of the nanocomposite were also evaluated. The chitosan‐CMC silver nanocomposite demonstrates good antibacterial activity against Staphylococcus aureus, Pseudomonas aeruginosa, and Escherichia coli. Copyright © 2016 John Wiley & Sons, Ltd.     

Full polysaccharide crosslinked-chitosan and silver nano composites,for use as an antibacterial membrane

Full polysaccharide crosslinked-chitosan membranes were prepared by crosslinking of chitosan with chitosan dialdehyde followed by reduction with sodium borohydride. Partially oxidized chitosan, generated from periodate oxidation of chitosan, was used as a crosslinker. The modulus values and elongation at break were increased with increasing the crosslinker weight ratio. The rheological measurements showed that depolymerization of chitosan can take place rapidly in the presence of the oxidizing agent. The weight reduction of crosslinked-chitosan membrane after 12 h, at pH = 4 and pH = 2 was found to be 85.0% and 90.0%, respectively. The structure of the crosslinked-chitosan and the silver nanocomposite were confirmed by FTIR spectroscopy, scanning electron microscopy(SEM), and thermogravimetric analysis(TGA). Transmission electron microscopy(TEM) reveals the presence of well-separated Ag nanoparticles with diameters in the range of 4–10 nm. The silver ion loading increases with increasing the silver ion concentration, and decreasing the crosslink density. The MBC/MIC ratio of 2.0, 2.0, and 1.0 was achieved for E. coli, S. aureus, and P. aeruginosa, respectively.     

耦联剂辅助吸附法制备CuInS2量子点敏化太阳电池

分别以CuI 和InAc3 作为铜源和铟源, 十二硫醇(DDT)作为硫源, 采用直接加热法合成不同尺寸的CuInS₂ (CIS)量子点. 运用X射线衍射(XRD), 拉曼光谱(Raman), 高分辨率透射电镜(HRTEM), 紫外-可见(UVVis)吸收光谱表征其相结构、形貌及光学性能. 结果表明: 制备的CIS量子点为黄铜矿结构, 且随着时间的延长, 量子点逐渐长大, 吸收光谱的激子吸收峰逐渐红移, 表现出量子尺寸效应. 采用巯基乙酸为双功能耦联剂辅助吸附法制备CIS敏化的TiO₂薄膜. 通过衰减全反射红外光谱(ATR-FTIR)分析得出, 巯基乙酸上的羧基与TiO₂表面羟基连接, 另一端上的巯基代替长链的DDT与CIS 耦联, 将CIS 成功锚定在TiO₂表面. 该方法不仅操作简单, 而且容易实现CIS在TiO₂表面的吸附. 太阳电池光电性能测试表明, 粒径大小约为3.6 nm的CIS量子点表现出最优的吸附能力以及光电转换性能. 进一步采用连续离子吸附层法对CIS敏化的TiO₂薄膜进行CdS包覆, 光电转换性能大大提高, 其效率达到2.83%, 这主要源于CdS的包覆钝化了CIS 的表面缺陷, 有效地降低了电子复合.     

Synthesis and characterization of a novel hydroxypropyl chitosan-graft-β-Cyclodextrin copolymer as potential drug carrier

Abstract

One of the most attractive fields in drug delivery is the design of nanoparticles that could be used to transport drugs into the target place at appropriate time. This paper describes the preparation of a novel hydroxypropyl chitosan-graft-β-cyclodextrin (HPCS-g-β-CD) copolymer using the 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride (EDC) and N-hydroxysuccinimide (NHS) promoted condensation reaction. Structural characterization was finished with FTIR and ¹H NMR spectra, which confirmed the grafting of β-cyclodextrin (β-CD) onto hydroxypropyl chitosan (HPCS). The thermal properties were studied based on DSC and TGA analyses, which revealed the fact that grafting of β-CD onto HPCS resulted in obvious enhancement of the decomposition temperature of the copolymer. Aqueous solution of HPCS-g-β-CD copolymer was stable at pH 7-8 based on the Zeta potential test. The morphological characteristics were investigated by SEM, TEM and AFM analysis, and the results indicated that this copolymer had three-dimensional structure which was suitable for loading drugs.     

CdTe量子点DNA荧光纳米探针的合成及表征

采用水相合成法合成了巯基乙酸(TGA)修饰的水溶性CdTe量子点,通过反相微乳液法制备了二氧化硅及壳聚糖修饰的核壳型复合荧光纳米粒子,将其与DNA吸附连接,得到CdTe量子点DNA荧光纳米探针。用扫描电镜、透射电镜、荧光光谱、红外光谱、紫外光谱、ζ电位等测试方法对产物的理化性质进行了分析表征。结果表明制备了表面富含氨基的复合荧光纳米粒子,其对DNA具有良好的吸附作用。