生物荧光探针的纳米晶体量子点合成技术进展

纳米晶体量子点最有前途的应用领域是在生物体系中作为荧光探针,量子点的光学特性与传统的有机荧光染料相比有明显的优越性,如具有宽的激发光谱、窄的发射光谱、高的荧光量子产率,寿命更长等优点。本文评述了作为生物荧光探针的量子点的合成及用于生物探针时的量子点表面修饰技术的最新进展。     

生物荧光探针的纳米晶体量子点合成技术进展

纳米晶体量子点最有前途的应用领域是在生物体系中作为荧光探针，量子点的光学特性与传统的有机荧光染料相比有明显的优越性，如具有宽的激发光谱、窄的发射光谱、高的荧光量子产率，寿命更长等优点。本文评述了作为生物荧光探针的量子点的合成及用于生物探针时的量子点表面修饰技术的最新进展。     

水溶性CdTe/CdS量子点的制备及发光特性

采用水相合成法,以三种不同的稳定剂：巯基乙醇,巯基乙酸和巯基乙胺制备了CdTe/CdS核壳结构的量子点.研究了反应时间和稳定剂的种类对量子点荧光的光学特性的变化趋势的影响.结果表明,随着量子点晶体生长时间的增加,量子点的荧光峰向红移,荧光发射强度增加,半峰宽几乎保持不变.稳定剂的种类对量子点的荧光发射峰的波长有较大的影响.采用CdS对CdTe进行包裹,制备壳核结构的CdTe/CdS量子点.包裹后能增强水相制备过程中量子点在水相中的荧光强度和发光稳定性,改变量子点的荧光特性.采用红外光谱,对稳定剂和量子点之间的连接关系进行了初步探讨,并采用透射电子显微镜,对CdTe/CdS量子点的微观形态进行观察.     

CdTe/CdS核/壳结构纳米晶量子点的结构及荧光性能

采用水相合成法,制备出核/壳结构CdTe/CdS纳米晶量子点,用红外光谱和X射线衍射对其结构进行了表征,并对CdTe纳米晶量子点光稳定性以及CdTe/CdS纳米晶量子点荧光特性影响因素进行了研究.结果表明:随着放置时间的增加,CdTe量子点的光学稳定性下降;随着反应时间的增加和壳/核比例的增加,CdTe/CdS纳米晶量子点的荧光发射波长均发生红移;且反应时间增加,荧光强度增强;当CdS与CdTe壳/核比例为2∶1时,荧光强度最强.     

一种基于碳纳米点的具有生物相容性的荧光墨水

中国科学院长春光学精密机械与物理研究所研制出一种基于碳纳米点的、具有生物相容性的荧光墨水。采用这种方法制备的荧光碳纳米点,可取代所有具有毒性的、含重金属内核的量子点,真正实现多种复杂的应用,特别是在环境和生物领域具有重要的应用价值。长光所发光学及应用国家重点实验室以柠檬酸、尿素为原料,通过微波法制备了高荧光量子效率的碳纳米点。该实验室制备的碳纳米点水溶液经长久放置不产生沉淀,表现出激发波长依赖的荧光发射特     

脂质体包裹的CdTe复合量子点的合成

应用脂质体包裹技术合成了具有生物相容性的CdTe复合荧光量子点，通过透射电子显微镜和荧光谱图证实脂质体包裹复合量子点是成功的．用荧光分光光度计表征了脂质体包裹后的复合量子点，基本上保持了量子点的荧光特性；同时检测到随着脂质体包裹的量子点浓度的由低到高变化，荧光强度先升高后降低。     

量子点特性及荧光标记应用

量子点是直径在1～100 ml的一类半导体纳米粒子.与传统的有机荧光标记物相比,具有独特的光谱特性和良好的光化学稳定性,是一种理想的荧光标记物.本文概述了量子点基本知识及特性、标记方法以及在生物材料荧光标记中的应用及发展前景.量子点在荧光分析领域将开辟一种新的方法,在分析领域的应用也将对生命科学研究产生重要的影响.     

表面处理对反相微乳液中Ⅱ-Ⅵ族量子点的影响(英文)

以对二甲苯为连续相,水为分散相,聚(氧乙烯)-聚(氧丙烯)-聚(氧乙烯)嵌段聚合物为表面活性剂,制备ZnSe和ZnMnSe量子点.在量子点表面覆盖一层Zn(OH)2使其发生钝化,再加水引起相分离,选择合适的有机溶剂可从反相微乳液中成功分离出上述量子点,分离后的量子点保持荧光特性且量子点荧光有显著增强.经11-巯基十一烷酸表面修饰,分离的量子点可分散在水中形成透明溶液.采用X-射线衍射、透射电镜、动态激光光散射和荧光光度计表征晶体结构、形貌、尺寸分布和荧光特性,讨论了使量子点稳定的表面保护机理.研究结果表明,嵌段聚合物分子吸附在量子点表面,阻碍了其氧化进程,表面钝化可修补晶体部分缺陷,使分离的量子点荧光增强,稳定期达数月之久.     

Mn掺杂CdS量子点的微波水相合成

利用微波辐射促进离子扩散的方法,大大降低Mn2+扩散所需温度,在水相中成功制备出CdS Mn量子点.该量子点具有立方闪锌矿结构,荧光发射峰波长可以在530～660 nm之间连续调节,荧光量子产率高达50%,并且具有良好的光稳定性.这种方法可以为其他掺杂量子点的水相合成提供参考.     

荧光聚多巴胺-金量子点应用于癌细胞的高效成像检测

为了准确识别癌细胞,制备了一种具有荧光性能的聚多巴胺-金量子点.该量子点纳米材料是基于前人方法,在室温下以多巴胺为唯一前体控制合成来制备小尺寸聚多巴胺,然后在高温、过氧化氢存在的条件下利用产生的羟基自由基去破坏聚多巴胺的π-π结构来生成具有荧光性能的聚多巴胺量子点,并在其表面通过还原氯金酸形成聚多巴胺-金量子点;利用荧光成像技术,通过观察聚多巴胺-金量子点的荧光淬灭情况来实现对癌细胞中谷胱甘肽(GSH)的检测.结果表明,该量子点纳米材料可以实现对癌细胞的特异性荧光成像检测,为开发高效的识别生物传感器和对癌细胞的精准识别提供了一种有效的策略.     

表面处理对反相微乳液中II-VI族量子点的影响

以对二甲苯为连续相,水为分散相,聚(氧乙烯)-聚(氧丙烯)-聚(氧乙烯)嵌段聚合物为表面活性剂,制备ZnSe和ZnMnSe量子点.在量子点表面覆盖一层Zn(OH)2使其发生钝化,再加水引起相分离,选择合适的有机溶剂可从反相微乳液中成功分离出上述量子点,分离后的量子点保持荧光特性且量子点荧光有显著增强.经11-巯基十一烷酸表面修饰,分离的量子点可分散在水中形成透明溶液.采用X-射线衍射、透射电镜、动态激光光散射和荧光光度计表征晶体结构、形貌、尺寸分布和荧光特性,讨论了使量子点稳定的表面保护机理.研究结果表明,嵌段聚合物分子吸附在量子点表面,阻碍了其氧化进程,表面钝化可修补晶体部分缺陷,使分离的量子点荧光增强,稳定期达数月之久.

Abstract：

The successful extractions of ZnMnSe as well as ZnSe quantum dots (QDs) from a reverse micelle template were reported. The recovered QDs kept their functionality with distinct enhancement in photoluminescence. After being coated with a possible layer of Zn(OH)2 within the template, the QDs were extracted from the template by adding water to induce phase transition and employing specific organic solvent. Thereafter, the extracted QDs were capped with mercapto-undecanoic acid for dispersion in water to render crystal clear solution. Analytical techniques such as X-ray diffraction, transmission electron microscopy, dynamic light scattering, and fluorometer were employed to characterize the crystal structure, morphology, average particle size, and photoluminescence of the samples. The mechanism of the surface protection towards QDs was investigated and discussed. A mechanism was proposed as block copolymer molecular being adsorbed to the QDs surface that retards the oxidation process of QDs during the extraction. Consequently, the extracted QDs demonstrated invariable photoluminescence and consistent stability for months.     

In-situ Synthesis of SnO_2 Quantum Dots/ZnS Nanosheets Heterojunction as a Visible-light-driven Photocatalyst for Degradation of Rhodamine B,Potassium Dichromate and Tetracycline

The SnO_2 quantum dots (SnO_2QDs)/ZnS nanosheets (ZnSNs) heterojunction was fabricated via an in-situ synthetic method at room temperature.Rhodamine B,potassium dichromate,and tetracycline were used to discuss the photocatalytic activities of the as-prepared samples under the visible light illumination.The photocatalytic mechanism of the as-prepared samples was also proposed.The experimental results indicate that the degradation efficiency of the as-prepared SnO_2QDs/ZnSNs heterojunction first increases and then decreases with increasing the usage of ZnSNs.When the mass ratio of SnO_2QDs to ZnSNs is 1:2 in 180 min,the as-prepared samples have the highest degradation efficiency of 89.1% for rhodamine B,97.7% for potassium dichromate,and 83.8% for tetracycline,which are much higher than 51.7%,26.8%,and 0.9% of pure SnO_2QDs as well as 37.9%,87.1%,and 19.1% of pure ZnSNs,respectively.After it is repeatedly degraded for 3 times,it possesses the degradation efficiency of 62.5% for rhodamine B,which increases by 200.5% in comparison with 20.8% of the pure SnO_2QDs.Moreover,the enhanced photocatalytic performances of the as-prepared hybrids are attributed to the formation of heterojunction between the SnO_2QDs and ZnSNs.In addition,hydroxyl radicals and superoxide anion radicals play major roles during the photocatalytic degradation process,while holes play a minor role.     

Optical Characteristics of InAs Quantum Dots on GaAs Matrix by Using Various InGaAs Structures

The effcts of various InGaAs layers on the structural and optical properties of InAs self-assembled quantum dots（ QDs ） grown by molecular-beam epitaxy （MBE） were investigated. The emission wavelength of 1317 nm was obtained by embedding InAs QDs in InGaAs / GaAs quantum well. The temperature-dependent and time-resolved photoluminescence （ TDPL and TRPL ） were used to study the dynomic characteristics of carriers. InGaAs cap layer may improve the quality of quantum dots for the strain relaxation around QDs, which results in a stronger PL inteasity and an increase of PL peak lifetime up to 170 K. We found that InGaAs buffer layer may reduce the PL peak lifetime of InAs QDs, which is due to the buffer layer accelerating the carrier migration. The results also show that InGaAs cap layer can increase the temperature point when the thermal reemission and nonradiative recombination contribute significantly to the carrier dynamics.     

无膦溶剂制备带隙可调谐ZnS1—xSex量子点

本文利用将硒（Se）粉直接置于十八烯（ODE）溶剂搅拌形成悬浮液获得Se前驱体（ODE—Se）代替传统的三丁基膦一硒（TBP—Se）,制备无镉（Cd）的硒硫锌（ZnSl-xSex）合金量子点。紫外可见吸收光谱及发光光谱测试表明,当ODE—S：ODE—Se由7：3逐渐减少到0：10时,其吸收边由350nm红移到420nm,激子发光峰位从378nm红移到429nm．表明通过调节前驱体比例成功实现了对ZnSI—xSex量子点能带的调控。另外,为了理解ODE—Se与传统TBP—Se的差异。分别用这两种前驱体制备了纯ZnSe量子点。研究结果表明,相比于三丁基膦一硒（TBP—Se）,利用ODE—Se为Se前驱体制备的ZnSe量子点尺寸更大并分布更宽,证明ODE—Se的活性强于TBP—Se。     

通讯波段低密度InAs量子点的研究

1.3和1.5μm波长低密度自组织双层量子点被期望首先用在在单个光子光纤传输中,这种结构是基于由一薄层GaAs隔离的双层InAs量子点实现的,由于应变场的存在,第一层量子点为第二层量子点提供了一个成核区,低温生长的双层InAs量子点发光主要来自于顶层量子点,顶层量子点发光波长会向长波长移动。在本论文中,利用低密度InAs量子点作为获得长波长双层InAs的种子层,实验制备的双层InAs量子点,波长约为1.4μm。     

Luminescent properties dependence of water-soluble CdTe quantum dots on stabilizing agents and reaction time

The influence of stabilizing agents and reaction time on the luminescent properties of water-soluble CdTe quantum dots (QDs) was discussed. The thioglycolic acid (TGA)-CdTe ODs were characterized by TEM, XRD and FTIR. It is found that larger-size QDs can be synthesized more easily when L-cysteine (Cys) or golutathione (GSH) is chosen as stabilizing agent and TGA is proper to prepare highly luminescent QDs because of the effect between Cd²⁺ and sulfhydryl group. Furthermore, the absorption wavelength, full width at half maximum (FWHM), stokes shift, photoluminescence (PL) quantum yield and PL stability of TGA-CdTe are strongly dependent on reaction time, in which the absorption wavelength changes against reaction time with an exponential function. The TGA-CdTe QDs prepared at 2 h possess more excellent luminescent properties.     

Mn^2＋和Ce^3＋共掺杂的CdS量子点制备及其光谱研究

采用低温水热技术,以硫脲为稳定剂,在90℃的水相中合成了发蓝色荧光的Mn^2＋和Ce^3＋共掺杂的CdS体量子点。用透射电子显微镜对该量子点形貌进行了表征,其直径约为10 nm的球形颗粒。研究了该量子点的紫外-可见吸收光谱、荧光发射光谱以及荧光光谱随时间的变化。结果表明,Mn^2＋和Ce^3＋共掺杂使CdS量子点的发光强度提高10倍;该量子点具有较好的发光稳定性。     

CdS:Co掺杂量子点的合成与表征

通过微波辐射技术,过度金属钴离子可以成功地掺杂到CdS量子点内部.由于钴离子占据了量子点的中心位置,随着辐射时间的增加,钴离子逐渐向外渗透扩散,伴随此过程,掺杂后的量子点的紫外吸收峰和荧光发射峰都相应地发生了红移.通过X射线衍射和高分辨投射电镜表征发现,掺杂后的晶体依然为立体闪锌矿结构,并且具有量子点的晶体特征;经过紫外吸收和荧光光谱表征发现,与CdS量子点相比,除了荧光光谱的发射峰范围扩宽了50 nm,荧光稳定性和化学稳定性得到了很大的提高.