荧光碳点对人血淋巴细胞标记成像

以葡萄糖为碳源,采用溶剂热法合成荧光碳点.用紫外-可见分光光度法和荧光光谱法研究了荧光碳点的发光特性.并将其与鼠抗人CD3抗体、羊抗鼠IgG抗体连接制备两种水溶性复合探针,对人血淋巴细胞进行免疫荧光标记成像.结果表明用该探针对人血淋巴细胞成像清晰,72h后细胞仍然保持明亮的荧光.     

CdSe/CdS核壳量子点复合材料合成及其在白光发光二极管中的应用

采用有机化学合成法,利用正三辛基膦(TOP)辅助的快速注入生长方法,改进传统的制备工艺,实现了CdSe/CdS厚壳层核壳(8.6 ML)量子点复合材料的合成制备,并对所合成的核、核壳量子点及其复合材料的晶格结构、形貌特点与发光性质进行了XRD、TEM、SEM、UV-Vis、PL表征和红光补偿效果测试。测试结果表明,CdSe核具有立方纤锌矿晶格结构;CdSe/CdS量子点复合材料直径为45~75μm,呈菱形规则形貌,且颗粒分散性良好。采用该方法,可以提高量子产率,产率由4%(CdSe核)升至48%(CdSe/CdS核壳量子点);可以增强激子态发光能力,CdSe/CdS核壳量子点复合材料的荧光强度约为CdSe核的13倍。将该材料与YAG∶Ce~(3+)黄色荧光粉组合应用,获得了高光效(148.29 lm/W)、高显色指数(Ra为90.1,R9为97.0)的白光发光二级管,表明按照上述方法获得的CdSe/CdS核壳量子点复合材料在白光发光二极管中深红光波段具有较好的补偿效果。     

壳层相关的CdSe核/壳量子点发光的热稳定性

测量了CdSe/ZnS(3 ML)核/壳结构及CdSe/CdS(3 ML)/ZnCdS(1 ML)/ZnS(2 ML)核/多壳层结构量子点在80~460 K范围内的光致发光光谱,研究了壳层结构对CdSe量子点发光热稳定性的影响。详细地分析了CdSe量子点的发光峰位能量、线宽和积分强度与温度之间的关系,发现CdSe量子点的发光热稳定性依赖于壳层结构。CdS/ZnCdS/ZnS多壳层结构包覆CdSe量子点在低温和高温部分的热激活能均大于ZnS壳层包覆的CdSe量子点,具有更好的发光热稳定性。此外,在300-460-300 K加热-冷却循环实验中,CdS/ZnCdS/ZnS多壳层结构包覆CdSe量子点的发光强度永久性损失更少,热抵御能力更强。     

巯基琥珀酸包被的CdTe量子点的制备及其在细胞标记中的应用

以巯基琥珀酸(MSA)作为稳定剂,在水溶液中合成稳定的CdTe纳米量子点,用紫外-可见荧光分光光度和荧光光谱方法研究了CdTe量子点的发光特性.并将其与鼠抗人AFP抗体连接制备水溶性CdTe-AFP复合物探针,对人肝癌细胞进行标记和成像.结果表明所制备的CdTe-AFP复合物探针对人肝癌细胞成像清晰,在生物医学领域具有重要的应用价值.     

CdSe/CdS量子点聚合物复合材料的水致荧光可逆特性

量子点由于其优异的光学和电学特性,在新型光电器件领域是一种极具前景的明星材料。本文通过将核壳CdSe/CdS量子点封装到聚二甲基硅氧烷-聚脲（PDMS-PUa）聚合物基质中制备CdSe/CdS@PDMS-PUa复合材料,发现了其光致发光强度和荧光量子产率的水致增强现象,经荧光衰减曲线和漫反射光谱分析,解释了该现象是来自于水中的H₃O⁺和OH^-对量子点表面缺陷的有效钝化,使得量子点的晶胞更趋于理想化。进一步通过实验发现,当复合材料从水中取出干燥后,由于量子点表面缺陷态又重新暴露,光致发光强度和荧光量子产率又恢复到初始值。受所发现的荧光可逆现象的启发,本文基于CdSe/CdS@PDMS-PUa复合材料提出了一种具有荧光响应的液体高度传感器,通过荧光亮度的变化可以判断容器内液体的高度值。这些发现不仅揭示了CdSe/CdS量子点水致荧光可逆特性,同时拓宽了量子点聚合物复合材料在光电领域的应用,具有重要的科学意义和应用前景。     

CdSe/CdS/ZnS量子点光纤的增益研究

采用油相法合成了CdSe/CdS/ZnS量子点,相对于CdSe量子点,其吸收光谱、发射光谱均发生了红移。利用COMSOL Multiphysics软件模拟CdSe/CdS/ZnS量子点光纤和甲苯光纤的电场分布,结果表明CdSe/CdS/ZnS量子点光纤的电场强度高于甲苯光纤。采用中心波长为532 nm的稳态半导体激光器作为光源,对甲苯光纤、CdSe/ZnS量子点光纤、CdSe/CdS/ZnS量子点光纤进行电压信号测试,发现CdSe/ZnS量子点光纤和CdSe/CdS/ZnS量子点光纤的电压信号值相对于甲苯光纤电压信号值分别增强了6.28 mV和18.43 mV,表明双壳型量子点光纤的增益高于单壳型量子点。     

ZnS/CdS/ZnS量子点量子阱的荧光衰减

采用反胶束方法制备了ZnS/CdS/ZnS量子点量子阱，并对其光谱性质进行了研究。结果表明所制得的量子点量子阱尺寸分布均匀，平均粒径为4.5nm，发光峰位于515nm左右，归属于CdS体内的施主－受主对复合。ZnS/CdS/ZnS量子点量子阱中CdS的发光比核－壳结构的ZnS/CdS量子点增强了近四倍，荧光寿命也有所增长。     

CdSe量子点凝胶快速制备及其光谱特性

以水为反应溶剂,采用NaBH₄还原SeO₂并与过量CdSO₄反应,制备CdSe量子点凝胶。所得CdSe量子点凝胶直接干燥即得到固态粉体,若用聚乙二醇或谷胱甘肽等作为分散修饰剂可方便的转化成相应的溶胶,制备方法快速简单、成本低。CdSe量子点凝胶、粉体、溶胶均具有良好的光致发光特性,且性质稳定。结果表明反应物CdSO₄与SeO₂用量的摩尔比（Cd/Se值）和反应温度影响CdSe量子点的荧光特性。当制备凝胶的Cd/Se值由2.4:1增加12:1时,CdSe量子点-聚乙二醇溶胶的荧光强度增加,荧光发射峰由560nm红移到610nm;当制备凝胶的反应温度由40℃增加到90℃时,CdSe量子点-聚乙二醇溶胶的荧光发射峰由560nm红移到600nm。CdSe量子点-聚乙二醇溶胶的荧光量子产率20%左右。     

复合荧光CdSe量子点-脂质体的制备与表征

通过脂质体方法成功地将三辛基氧化膦(TOPO)包覆的CdSe发光量子点从非极性有机溶剂转移到生物相容性的水溶液中.分别通过透射电镜(TEM)、荧光Mapping图像,以及光致发光(PL)光谱进行表征.TEM照片显示制备的CdSe核量子点为球形,具有良好的单分散特性,平均粒径约为3nm.CdSe-脂质体复合体的平均尺寸大约20nm,TEM清楚地显示了CdSe量子点被诱捕在脂质体中.荧光Mapping显示了CdSe-脂质体复合体的发光强度分布.脂质体方法转移TOPO包覆的CdSe量子点,借助了磷脂的双分子链与CdSe表面的TOPO配体之间的疏水相互作用,在CdSe的第一配体层外部形成第二配体层,保留了CdSe的存在环境,光致发光光谱表明,量子点-脂质复合体基本保持了CdSe核量子点的发射效率.     

CdSe量子点膨润土复合材料的制备与表征

首先以CdCl₂·2.5H₂O、SeO₂和NaBH₄为反应物,制备巯基丁二酸稳定的CdSe量子点。然后将有机膨润土与CdSe量子点溶液混合并充分搅拌,制备负载CdSe量子点的膨润土发光材料,用荧光光谱、扫描电镜和X射线粉末衍射等分析测试手段对所得材料的光谱性能与微观结构进行表征。光谱分析表明,量子点膨润土复合材料的发光颜色与量子点溶液非常一致;X射线光电子能谱分析表明,复合后的材料中含有Cd 和 Se两种元素;此外,在量子点膨润土复合材料X射线粉末衍射谱中可见CdSe量子点（111）、（220）及（331）3个晶面的衍射峰,2θ=4.3°处出现膨润土（001）衍射峰。数据表明,在制备的CdSe量子点膨润土复合材料中,量子点和膨润土的结构都没有改变。     

脂溶性CdSe/ZnS量子点脂质体复合物的制备及表征

在油相中成功合成了脂溶性CdSe/ZnS核壳量子点纳米粒,粒径平均为4.5 nm,量子产率达29%,发射波长为540 nm。通过薄膜分散法,以蛋黄卵磷脂、胆固醇为膜材,将脂溶性的CdSe/ZnS核壳量子点包覆于脂质体磷脂双分子层中,由于磷脂分子的两亲性,使得脂溶性的CdSe/ZnS核壳量子点同时又具有亲水性。通过透射电镜对脂质体形态进行了表征,倒置荧光显微镜证实了发光CdSe/ZnS核壳量子点成功包埋于脂质体双分子层中,包裹的发光CdSe/ZnS核壳量子点具有更稳定的发光及抗光漂白性质。     

CdSe/CdS核壳纳米晶微波水热法一步合成与发光光谱分析

采用微波水热法一步合成了核壳结构的CdSe/CdS纳米晶,讨论了巯基丙酸中S^2-的释放过程对纳米晶生长的影响。XRD和Raman光谱结果表明,140℃合成温度下获得了CdSe/CdS核壳结构的纳米晶。FTIR光谱结果表明,巯基丙酸随时间的分解有助于CdS壳层的形成。PL光谱呈现出CdSe纳米晶的带间发射和缺陷发射,随着核壳结构的形成,CdSe纳米晶的表面缺陷被抑制,相关的荧光发射减弱。     

The Influence of Surface Trapping and Dark States on the Fluorescence Emission Efficiency and Lifetime of CdSe and CdSe/ZnS Quantum Dots

To investigate the influence of surface trapping and dark states on CdSe and CdSe/ZnS quantum dots (QDs), we studied the absorption, fluorescence intensity and lifetime by using one-and two-photon excitation, respectively. Experimental results show that both one- and two-photon fluorescence emission efficiencies of the QDs enhance greatly and the lifetime increase after capping CdSe with ZnS due to the effective surface passivation. The lifetime of one-photon fluorescence of CdSe and CdSe/ZnS QDs increase with increasing emission wavelength in a supralinear way, which is attributed to the energy transfer of dark excitons. On the contrary, the lifetime of two-photon fluorescence of bare and core-shell QDs decrease with increasing emission wavelength, and this indicates that the surface trapping is the dominant decay mechanism in this case.     

Synthesis of CdSe/CdS with a simple non-TOP-based route

A convenient and non-TOP-based route for the synthesis of core-shell CdSe/CdS quantum dots (QDs) is developed for the first time. Simple reagents, such as cadmium oxide, selenium powder, sodium sulfide, paraffin and oleic acid with obvious advantages are used to replace organometallics. This simple route allows the preparation of a series of core-shell CdSe/CdS QDs emitting in a wide wavelength range (from 510 to 615 nm). After passivation of CdSe by CdS shell using sodium sulfide as the source of sulfur at 80 °C, the quantum yields (QYs) are improved from 15-30% to 35-50% and remained stable at least for 4 months. A narrow bandwidth (FWHM<50 nm) indicates that the as-prepared QDs have uniform size distribution, desirable dispersibility and good fluorescence properties. The whole procedure can be carried out either open to air or under nitrogen atmosphere, which is simpler, greener and cheaper as compared with TOP-based route.     

Demonstration of a nanoparticle-based optical diode

We present the operation of an optical device that exhibits diodelike properties based on two adjacent layers of quantum dots (QDs) encased in a fiber-optic jacket. The possibility of a multilayered device is also discussed. A significant change in the emission spectrum of CdSe/ZnS core-shell QDs was observed when excited by the input laser and the fluorescence of other CdSe/ZnS core-shell QDs. The output of the diode can be taken to be either the incoming laser wavelength of light similar to a conventional diode, or the output may be considered to be one of the QD fluorescence wavelengths. Current work has applications in biological fluorescence monitors and sensors as well as in telecommunications applications.     

Synthesis,biocompatibility and luminescence properties of quantum dots conjugated with amino acid-functionalized β-cyclodextrin

A series of CdSe and CdSe/CdS quantum dots (QDs) labeled with amino acid-modified β-cyclodextrin (β-CD) was prepared by a simple ultrasonic method. These amino acid-modified β-CD-coated QDs are very soluble and stable in biological buffer. They also have high colloidal stability and strong optical emission properties that are similar to those of untreated tri-n-octylphosphine oxide (TOPO)-coated QDs. The quantum yields (QYs) of these amino acid-modified β-CD-coated CdSe and CdSe/CdS QDs in biological buffer were found to be very high. In particular, the QYs of the positively charged l-His-β-CD-coated CdSe/CdS QDs were as high as 33.5±1.8%. In addition, the fluorescence lifetime of these QDs was also very long in PBS solutions as determined by frequency domain spectroscopy. For example, the lifetime of l-His-β-CD-coated CdSe/CdS QDs was 8.6 ns. The in vitro cytotoxicity of these QDs in ECV-304, SH-SY5Y and HeLa cells was found to be lower. l-His-β-CD-coated CdSe/CdS QDs were the least cytotoxic (IC₅₀ 95.6±3.2 mg mL^?1 in ECV-304 cells after 48 h). The flow cytometry results show that the positively charged amino acid led to a considerable increase in biocompatibility of QDs. This may be attributed to the presence of an amino acid-modified β-CD outer layer, which enhanced the biocompatibility.     

Enhanced Oxidation Stability of Quasi Core-Shell Alloyed CdSeS Quantum Dots Prepared Through Aqueous Microwave Synthesis Technique

Quasi core shell alloyed CdSeS quantum dots (QDs) have been prepared through a facile aqueous-phase route employing microwave irradiation technique. The optical spectroscopy and structure characterization evidenced the quasi core shell alloyed structures of CdSeS QDs. The X-ray diffraction patterns of the obtained CdSeS QDs displayed peak positions very close to those of bulk cubic CdS crystal structures and the result of X-ray photoelectron spectroscopy data re-confirmed the thick CdS shell on the CdSe core. The TEM images and HRTEM images of the CdSeS QDs ascertained the well-defined spherical particles and a relatively narrow size distribution. On the basis, the stability of the obtained QDs in an oxidative environment was also discussed using etching reaction by H₂O₂. The experiments result showed the as-prepared QDs present high tolerance towards H₂O₂, obviously superior to the commonly used CdTe QDs and core-shell CdTe/CdS QDs, which was attributed to the unique quasi core-shell CdSeS crystal structure and the small lattice mismatch between CdSe and CdS semiconductor materials. This assay provided insight to obtain high stable crystal structured semiconductor nanocrystals in the design and synthesis process.     

Synthesis and characterization of water-soluble, stable and highly luminescent itaconic acid/methacrylic acid copolymer-coated CdSe/CdS quantum dots

The itaconic acid/methacrylic acid (PIA-MAA) copolymer ligand (PIA-MAA) with carboxylate anchoring groups was found to efficiently convert CdSe/CdS core-shell quantum dots (QDs) in chloroform to water-soluble PIA-MAA-ligand stabilized nanocrystals (PIA-MAA-QDs). The quantum yield (QY) of the resulting PIA-MAA-QDs was 24%. In addition, the carboxylate-based PIA-MAA-QDs survived UV irradiation in air for at least 16 days. Upon UV irradiation, the PIA-MAA-QDs became about 2 times brighter than the original CdSe/CdS QDs in chloroform, and the UV-brightened photoluminescence (PL) can retain the brightness for at least several months. Experimental results further confirmed that the PIA-MAA-QDs were more stable than the original CdSe/CdS QDs against strong acid, strong oxidant, photochemical and thermal treatments. The PIA-MAA-QDs were soluble and stable in water, some polar solvents and buffer solutions. In addition to good performance of PIA-MAA-QDs, the synthesis of PIA-MAA ligands and the corresponding water-soluble QDs is relatively simple.     

Dendronization of gold and CdSe/cdS (core-shell) quantum dots with tomalia type, thiol core, functionalized poly(amidoamine) (PAMAM) dendrons

Poly(amidoamine) (PAMAM) dendrimers containing disulfide cores (i.e., cystamine) and possessing carboxylic acid or hydroxyl terminal groups were reduced with dithiothreitol (DTT) to yield single site, thiol core, functionalized PAMAM dendron reagents. These thiol functionalized dendron reagents were used to surface modify (dendronize) both gold nanoparticles, as well as CdSe/CdS (core-shell) quantum dots (QDs). Dendronization involved self-assembly of the focal point thiol functional dendrons at the metal interface of both gold and CdSe/CdS QDs by ligand exchange of protective surfactants used for their synthesis. The synthesis, characterization and preliminary luminescence studies of these new dendritic hybrids are reported.