一锅法制备量子点/琼脂纳米复合凝胶

以天然高分子琼脂为稳定剂,采用简单便捷的一锅法制备Mn掺杂ZnS量子点/琼脂纳米复合凝胶,琼脂不仅作为制备量子点的稳定剂,同时也是纳米复合凝胶的主要成分。对该纳米复合凝胶中量子点的化学结构和尺寸大小进行了表征,并对纳米复合凝胶的荧光性能和凝胶性能进行了研究。结果表明,制备得到的纳米复合凝胶均一稳定,在302nm紫外光下呈现十分明显的橙红色荧光。TEM表征显示,在该纳米复合凝胶中可以观察到大小比较均一、粒径为3nm左右的纳米粒子;光谱分析结果进一步证实纳米复合凝胶中存在Mn掺杂ZnS量子点。该纳米复合凝胶不仅具有良好的荧光性能,还具有温度刺激响应性可逆溶胶-凝胶转变性能,同时具有较高的溶胶转变温度和较好的温度稳定性。利用这些性能特点,可以方便地制备纳米复合凝胶小球。此外,该纳米复合凝胶还有望应用于金属离子的荧光检测分析领域。     

核壳结构ZnS∶Mn/ZnS量子点转光剂的制备及其性能研究

本文以巯基丙酸为稳定剂,采用共沉淀法合成ZnS∶Mn量子点,然后使用核外延法制备了具有将紫外光转红光性能的核壳结构ZnS∶Mn/ZnS量子点转光剂,并使用红外(IR)光谱,透射电镜(TEM)对其官能团结构和形貌进行了表征,采用紫外-可见吸收光谱和荧光光谱对其光学性能进行了研究。另外,考察了Mn的掺杂量,放置时间和不同pH的缓冲溶液对ZnS∶Mn/ZnS量子点荧光的影响。     

ZnS∶Co半导体量子点的制备及其光电化学性质

采用低温水热技术,分别以柠檬酸(CA)和巯基丙酸(MPA)为稳定剂,在70℃的水相中合成了单分散的,粒子尺寸约为4 nm的ZnS∶Co半导体量子点.研究了稳定剂、Co2+掺杂剂及其掺杂量对掺杂量子点发光性能和结构的影响.XRD结果表明,Co2+离子主要掺杂在量子点表面,对主体ZnS晶格没有影响.当采用MPA为稳定剂,掺杂量为5%(摩尔分数)时,掺杂量子点的荧光发射强度最高;而同样掺杂量下采用CA为稳定剂时,量子点的荧光发射强度有所下降.循环伏安研究显示,与空白ZnS量子点相比,Co2+离子的掺杂在ZnS的禁带中形成杂质能级,相应地,ZnS∶Co量子点的吸收边发生红移.与未掺杂ZnS量子点相比,掺杂量子点具有较少的表面非辐射复合中心,因而荧光发射强度显著提高.     

ZnS:Mn/ZnS量子点在DNA定量分析中的应用

以巯基乙酸为稳定剂,采用成核掺杂的方法在水溶液中一步制备得到具有核壳结构的ZnS:Mn/ZnS量子点.研究了荧光、室温磷光产生的机理.基于DNA对量子点发光的增强效应,以ZnS:Mn/ZnS量子点作为标记探针建立了测定DNA的荧光、室温磷光的分析方法.考察了量子点浓度、EDC/NHS用量和反应时间等条件对DNA测定的影...     

核壳结构AgInS2@ZnS量子点的合成及荧光性能

合成了一种新型核壳结构的AgInS₂@ZnS量子点并研究了其荧光性能. AgInS₂@ZnS的合成包括以变性牛血清白蛋白(dBSA)为稳定剂水相法构建AgInS₂核以及形成ZnS壳两部分. 考察了配方和工艺条件对该量子点荧光性能的影响, 并采用X射线粉末衍射(XRD)等手段对制备的纳米粒子进行了表征. 结果表明, AgInS₂@ZnS是一种核壳结构的纳米物质, 其粒径介于5~7 nm之间, 荧光量子产率达35.3%.     

Cu2+掺杂ZnS量子点制备及其特性研究

本实验采用水相合成技术,以N-乙酰-L-半胱氨酸(NAC)为稳定剂,在不同温度下的水溶液中合成了Cu2+掺杂的ZnS:Cu量子点。实验研究了NAC与Zn2+配比、掺杂不同Cu2+离子浓度、老化温度以及老化时间对ZnS:Cu量子点发光性能影响。实验表明,Cu2+离子掺杂在ZnS的禁带中形成杂质能级,使发射边红移。实验结果显示:稳定剂配比为2,掺杂量为2%,搅拌时间为10 min,反应温度为90℃,老化时间为3h时,掺杂量子点荧光发射强度最高。     

单分散CdS纳米晶/PNIPAM复合水凝胶的制备及其温敏荧光特性

采用液体-固体-溶液法(LSS)制备单分散CdS纳米晶;通过自由基聚合制备单分散CdS纳米晶/聚N-异丙基丙烯酰胺(CdS/PNIPAM)复合温敏水凝胶.采用HRTEM、XRD、FTIR、DSC、PL等对CdS纳米晶、CdS/PNIPAM温敏复合凝胶的微观结构与性能进行了表征,变温荧光光谱研究了温度对凝胶荧光性能的影响.结果表明,CdS纳米晶粒径约为2.8 nm,单分散性良好;复合凝胶的荧光发射强度与环境温度存在一定的关联性,且呈可逆性.     

ZnS:Mn/ZnS量子点在DNA定量分析中的应用

以巯基乙酸为稳定剂,采用成核掺杂的方法在水溶液中一步制备得到具有核壳结构的ZnS:Mn/ZnS量子点.研究了荧光、室温磷光产生的机理.基于DNA对量子点发光的增强效应,以ZnS:Mn/ZnS量子点作为标记探针建立了测定DNA的荧光、室温磷光的分析方法.考察了量子点浓度、EDC/NHS用量和反应时间等条件对DNA测定的影响.结果表明,在最佳测定条件下,荧光、室温磷光两种分析方法测定小牛胸腺DNA的线性区间均为50 ～600 μg/L,检出限分别为39.6、28.5 μg/L,回收率分别为98% ～ 104%、99%～101%,25次重复测定300 μg/L ctDNA的相对标准偏差分别为3.1%、2.3%.该方法简单、安全、灵敏度高.     

Mn2+掺杂ZnSe量子点的制备及表征

利用水相合成法,以Zn(Ac)2、NaBH4、Na2SeO3、Na2S、Mn(Ac)2为原料,N-乙酰-L-半胱氨酸为稳定剂,合成了Mn2+掺杂的ZnSe∶Mn量子点。研究了稳定剂与量子点(Zn2+)配比、Mn2+离子掺杂浓度、老化温度以及老化时间对ZnSe∶Mn量子点发光性能的影响,并对所得量子点固体粉末进行了XRD与IR表征与分析。结果表明该方法是一种简便、快捷且环境友好的合成方法。     

水热法合成AgInS2/ZnS核/壳结构量子点及其荧光性能

以硫脲为硫源,采用谷胱甘肽(GSH)和柠檬酸钠(SC)为配体,通过水热法制备了水溶性AgInS2/ZnS(AIS/ZnS)核/壳结构量子点。系统研究了反应温度和配体用量对量子点的合成及其荧光性能的影响。采用X射线衍射(XRD)、透射电子显微镜(TEM)、紫外可见吸收光谱(UV-Vis)和光致发光光谱(PL)分别对量子点的物相、形貌和光学性能进行了表征,并考察了量子点的稳定性。实验结果表明,随着反应温度从70℃升高至90℃,促进了ZnS壳层的形成,有效地钝化了量子点的表面缺陷,获得的AIS/ZnS核/壳量子点的发光强度显著提高,发光峰位从600 nm蓝移至580 nm。配体的添加可以有效地平衡Zn^2+的化学反应活性,减缓ZnS壳层的生长,抑制核壳界面缺陷的形成,还能消除量子点的表面态,当nGSH/nZn^2+=2.0,nSC/nZn^2+=2.5时,AIS/ZnS量子点的荧光性能最佳。此外,AIS/ZnS核/壳结构量子点还具有优异的光学稳定性。     

A new solid-phase nanoparticle FRET assays based on GO/CS/ZnS nanocomposite film and developed in sensing for bromonium ion

Composite thin films consisting of nano-sized ZnS particles dispersed in chitosan/GO films have been prepared by in-situ method. The films obtained were characterized by FTIR and UV–Vis spectroscopy. The ZnS nanoparticles with 90 nm in diameter were dispersed uniformly in the film matrix. Optical absorption peak due to the size of ZnS particles was observed around 350 nm. The fluorescence emission at 430 nm of the GO/CS/ZnS nanocomposite films is very sensitive to the presence of bromonium ion from aqueous solutions. New solid-phase nanoparticles FRET assays are firstly immobilized on the substrate and then interacted with functionalized acceptor molecules in the solution to trigger the FRET effect to detect Br^–.     

水溶性InP/ZnS量子点的合成及其在指纹显现中的应用

以磷化锌、氯化铟为原料,以十二烷胺为溶剂,在150～200℃下合成了InP量子点,通过相转移和紫外光照得到了巯基乙酸修饰的水溶性InP/ZnS量子点.利用X射线衍射仪、透射电镜、高分辨透射电镜、荧光光谱仪等分析了不同温度下合成的量子点的粒径、形貌、荧光性能及指纹显现效果.结果表明,合成的InP和InP/ZnS量子点为球...     

水溶性的CdSe/CdS/ZnS量子点的合成及表征

用L-半胱氨酸盐(Cys)作为稳定剂,合成了水溶性的双壳结构的CdSe/CdS/ZnS半导体量子点。吸收光谱和荧光光谱结果表明,双壳结构的CdSe/CdS/ZnS纳米微粒比单一的CdSe核纳米粒子和单核壳结构的CdSe/CdS纳米粒子具有更优异的发光特性。用透射电子显微镜(TEM)、ED、XRD、XPS和FTIR等方法对CdSe核和双壳层的CdSe/CdS/ZnS纳米微粒的结构、分散性及形貌分别进行了表征。     

3-巯基丙酸修饰的CdSe/ZnS量子点的合成及测定牛血清白蛋白的研究

以3-巯基丙酸作为修饰剂,在水溶液中合成了稳定的CdSe/ZnS量子点(QDs),透射电镜观察所合成量子点的形貌近似球形,粒径约为25 nm.吸收光谱与荧光光谱的研究表明,CdSe QDs在410 nm处有最大吸收峰,而CdSe/ZnS QDs的最大吸收峰在470 nm处,CdSe/ZnS QDs的荧光强度是CdSe QDs的11倍.考察了缓冲溶液的体积、pH值、反应温度、反应时间对体系荧光的影响.在最佳实验条件下,体系的荧光强度与BSA的浓度呈线性关系,线性响应范围为0.746×10-7～4.48×10-7 mol/L,检出限为3.846×10-10 mol/L.并且CdSe/ZnS QDs荧光强度基本保持稳定,可达两个多月.该方法应用于合成样品的测定,结果满意.     

DNA detection based on Mn-doped ZnS quantum dots/methylene blue nanohybrids

Nanohybrids were formed from 3-mercaptopropionic acid(MPA)-coated Mn-doped ZnS quantum dots(QDs) and methylene blue(MB) via electrostatic interaction, and then used in the detection of trace DNA.The principle of detection is as follows: MB binds with Mn-doped ZnS QDs via electrostatic interaction,and then quenches the room temperature phosphorescence(RTP) of the QDs through photoinduced electron-transfer(PIET). After the addition of DNA, MB binds with DNA through intercalation and electrostatic interaction, and desorbs from the surfaces of Mn-doped ZnS QDs, which recovers the RTP of the QDs. On this basis, a DNA detection method based on the properties of RTP was set up. This method shows a detection range of 0.2–20 mg/L, and a detection limit of 0.113 mg/L. Since this method is based on the RTP of QDs, it is not interfered by the background fluorescence or scattering light in vivo, and thus,avoids complex sample pretreatment. Thus, this method is very feasible for detection of trace DNA in biofluids.     

Electrochemiluminescence of Dendritic Magnetic Quantum Dots Nanostructure and Its Quenching by Gold Nanoparticles for Cancer Cells Assay

A novel dendritic CdS‐ZnS‐Quantum Dots (QDs) nanocomposite with intense electrochemiluminescence (ECL) and excellent magnetism was prepared, which was applied to the cancer cells assay based on ECL quenching of QDs by gold nanoparticles (NPs). DNA conjugation, gold NPs linking and sensing target cells can be directly performed on the magnetic nanocomposites, which is more rapid, convenient, and has better reproducibility than the conventional methods. So far, this is the first report on magnetic electrochemiluminescent QDs nanocomposites for cell detection based on ECL quenching, which opens a new approach for developing multifunctional QDs nanocomposite for ECL assays of cancer cells.     

基于Mn掺杂ZnS量子点的室温磷光传感应用的研究进展

与一般有机染料分子相比,半导体材料量子点具有优异的光学性能,在多个领域得到了广泛的应用.量子点具有窄而对称且可调的发射波长、宽激发强吸收、抗光漂白能力强以及水溶性好等诸多优势,引起了研究者广泛关注.为了增加量子点的斯托克斯位移从而很好地避免量子点的自猝灭现象,引入掺杂物是一种很有效的方式.掺杂量子点不仅保留了量子点原有的优点,而且还赋予量子点额外的优异性能.如Mn掺杂ZnS量子点生物相容性好,不含Cd和Hg等有害元素,而且Mn2+的加入使其具有优异的室温磷光特性.磷光检测能很好地避开生物背景荧光的干扰,使得Mn掺杂ZnS量子点能够广泛应用于磷光生物分析.本文综述了Mn掺杂ZnS量子点在室温磷光分析中的研究进展,着重介绍了几种具有启发意义的设计策略,包括其发光机理以及应用于离子、分子以及生物大分子等的检测.     

Preparation and characterization of thiacalix[4]arene coated water-soluble CdSe/ZnS quantum dots as a fluorescent probe for Cu2+ ions

Highly fluorescent water-soluble CdSe/ZnS (core/shell) quantum dots (QDs) as a fluorescent Cu2+ ion probe were synthesized using thiacalix[4]arene carboxylic acid (TCC) as a surface coating agent. Hydrophobic trioctylphosphine oxide (TOPO) capped CdSe/ZnS QDs were overcoated with TCC in tetrahydrofuran at room temperature, and deprotonation of the carboxyl groups of TCC resulted in the formation of water-soluble QDs. The surface structure of the QDs was characterized by using transmission electron microscopy (TEM) and fluorescence correlation spectroscopy (FCS). TEM images showed that TCC-coated QDs were monodispersed with the particle size (core-shell moiety) of approximately 5 nm. Hydrodynamic diameter of the TCC-coated QDs was determined to be 8.9 nm by FCS, showing that the thickness of the surface organic layer of the QDs was approximately 2 nm. These results indicate that the surface layer of TCC-coated QDs forms a bilayer structure consisting of TOPO and TCC molecules. TCC-coated CdSe/ZnS QDs were highly fluorescent (quantum yield, 0.21) compared to the QDs surface-modified with mercaptoacetic acid and mercaptoundecanoic acid. Fluorescence of the TCC-coated QDs was effectively quenched by Cu2+ ions even in the presence of other transition metal ions such as Cd2+, Zn2+, Co2+, Fe2+, and Fe3+ ions in the same solution. The Stern-Volmer plot for the fluorescence quenching by Cu2+ ions showed a linear relationship up to 30 microM of Cu2+ ions. The ion selectivity of TCC-coated QDs was determined by measurements of fluorescence responses towards biologically important transition metal ions (50 microM) including Fe2+, Fe3+, Co2+>Zn2+, Cd2+. The fluorescence of TCC-coated QDs was almost insensitive to other biologically important ions such as Na+, K+, Mg2+, and Ca2+, suggesting that TCC-coated QDs can be used as a fluorescent Cu2+ ion probe for biological samples. A possible quenching mechanism by Cu2+ ions was also discussed on the basis of a Langmuir-type adsorption isotherm.     

硫脲修饰ZnSe:Cu量子点的水相合成及荧光特性

以3-巯基丙酸为稳定剂在水相中合成了Cu掺杂的ZnSe量子点(QDs), 并利用硫脲(CH₄N₂S)对其进行表面修饰, 制备出核壳结构的ZnSe:Cu/ZnS 量子点. 制得的量子点呈闪锌矿结构, 尺寸约为5 nm, 有较好的分散性, 其荧光发射峰在460 nm左右. 经CH₄N₂S修饰后, 量子点表面形成了宽禁带的ZnS包覆层, 将电子和空穴限域在了ZnSe:Cu 核内, 减少了表面发生非辐射复合的载流子, 显著提高了量子点的荧光强度. 与Na₂S、硫代乙酰胺(TAA)等常用硫源相比, 以CH₄N₂S为硫源制得的ZnSe:Cu/ZnS 量子点壳层厚度可控, 表面钝化效果更好, 显示出更佳的荧光效率和稳定性. ZnSe:Cu/ZnS 量子点经过紫外线照射后消除了表面的悬空键, 进一步提高了其量子产率, 最终获到了具有较好荧光性质的ZnSe:Cu/ZnS量子点.     

Synthesis and spectroscopic characterization of water-soluble Mn-doped ZnO(x)S(1-x) quantum dots

A non-cadmium and water-soluble Mn-doped ZnO(x)S(1-x) QDs was synthesized with denatured bovine serum albumin (dBSA) as stabilizer under nitrogen atmosphere, and the as-prepared products were characterized by X-ray powder diffraction (XRD), UV-vis absorption spectroscopy, fluorescence (FL) emission spectroscopy, high resolution transmission electronmicroscopy (HRTEM) and Raman spectrum. XRD patterns indicate that the Mn-doped ZnO(x)S(1-x) QDs have a zinc-blende structure, and that manganese emerges in the form of divalent manganese (Mn(2+)) and trivalent manganese (Mn(3+)) (the intermediate of the reaction). The size of Mn-doped ZnO(x)S(1-x) QDs is about 3.2±0.7 nm according to HRTEM imaging. The FL spectra reveal that the Mn-doped ZnO(x)S(1-x) QDs have two distinct emission bands: the defect-related emission and the Mn(2+)-related emission, which exhibit a competing process. A good FL signal of the transition of Mn(2+) ((4)T(1)-(6)A(1)) is observed when the doping amounts are 1.0% and 20% respectively, and the as-prepared solutions are stable for more than 6 months at 4°C. This method has the advantages of good stability and environment-friendly stabilizer, for involving no heavy metal ions or toxic reagents.