量子点的荧光特性在生物探针方面的应用

量子点具有传统有机荧光染料无可比拟的光学魅力,在生物医学及材料领域已引起广泛的兴趣,许多科学工作者在量子点用于生物学领域方面已经取得一定进展。目前,量子点最有前途的应用领域是在生物体系中作为荧光标记物。通过观察量子点标记分子与靶分子相互作用的部位,及其在活细胞内的运行轨迹,可能为信号传递的分子机制提供线索,从而为阐明细胞生长发育的调控及癌变规律提供直观依据。文章介绍了量子点研究生物大分子之间的相互作用、生物大分子荧光标记、细胞及生物组织的荧光标记与成像以及活体成像等方面的应用。并概述了纳米量子点作为生物荧光探针的应用前景以及亟待解决的问题。     

DNA纳米传感器荧光成像技术

把基于量子点的DNA纳米传感器模型应用到ICCD荧光显微成像系统中,利用量子点的量子产率高、荧光寿命长、激发谱宽而发射谱窄、发射波长可由材料尺寸调谐等特性,以量子点为供体,Cy5(一种小分子荧光染料)为受体,结合ICCD系统的全内反射荧光成像功能、实时成像功能和双通道成像功能,证实了DNA纳米传感器可以在溶液中检测到含30个碱基的单链目标DNA片段。实时拍摄了溶液中链霉亲和素包被的量子点对两头分别连着Cy5和生物素的单链DNA片段(Cy5-ssDNA-Biotin)的捕获过程。并在活的中国仓鼠卵巢细胞样品中加入链霉亲和素包被的量子点和Cy5-ssDNA-Biotin进行实时荧光成像,拍摄到链霉亲和素包被的量子点和Cy5-ssDNA-Biotin进入细胞中并发生FRET的过程,初步表明了DNA纳米传感器在活细胞内进行DNA(或RNA)片段检测的可行性。     

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和CdTe量子点荧光共振能量转移的荧光场三维数值分析

量子点虽然广泛应用于生物荧光标记,但仍停留在实验阶段,目前还不能通过实验的办法得到量子点的荧光分布特征。利用有限元的方法对量子点的荧光场分布特征进行了数值模拟计算,选取几种不同材料球形量子点进行电磁散射分析,论述了量子点的荧光场分布规律。通过对单个量子点进行荧光场分析,确定了CdSe量子点、CdTe量子点荧光共振能量转移模型,计算结果表明:量子点的荧光场的分布规律可以由量子点的电磁散射场给出,对量子点散射场的分析有助于我们更细致地了解量子点荧光共振能量转移的过程,对于探知一般实验无法得到的量子点荧光场分布规律是可行的。该结果对控制量子点的荧光分布,提高量子点荧光效率具有重要的实际意义。     

适配体传感法快速测定啤酒中赭曲霉毒素A

应用自组装方式,构建了金纳米粒子/核酸适体/氨基碳量子点荧光传感赭曲霉毒素A高灵敏检测方法。在pH 3.0酒石酸-HCl缓冲溶液中,巯基修饰的赭曲霉毒素A核酸适体在金纳米粒子表面自组装,形成金纳米粒子/核酸适体复合物,再在pH 7.0的磷酸盐缓冲溶液中,氨基碳量子点在金纳米粒子/核酸适体复合物上自组装,形成金纳米粒子/核酸适体/氨基碳量子点复合物荧光传感检测体系。金纳米粒子的摩尔吸光系数大、能带宽使其具有强烈的荧光猝灭功能,氨基碳量子点形成金纳米粒子/核酸适体/氨基碳量子点后发生荧光猝灭, 此时体系的荧光为背景荧光,其强度记为F₀;由于金纳米粒子/核酸适体/氨基碳量子点复合物荧光传感检测体系中核酸适体对赭曲霉毒素A具有特异性识别与结合功能,向金纳米粒子/核酸适体/氨基碳量子点复合物荧光传感检测体系溶液中加入赭曲霉毒素A后,赭曲霉毒素A则与复合物中核酸适体立即发生特异性结合并释放出氨基碳量子点,体系荧光恢复,其荧光强度记为F。依据体系荧光强度的变化(F-F₀)与赭曲霉毒素A浓度之间的关系,建立赭曲霉毒素A核酸适体荧光传感检测方法。研究了金纳米粒子和核酸适体摩尔比、孵化时间、pH等因素对传感器性能的影响,确定了最优条件为金纳米粒子∶核酸适体t为1∶190、孵化时间为6 min、pH 7.0时;在最优条件下,赭曲霉毒素A浓度在0.005～1.00 ng·mL-1范围与体系荧光强度变化呈良好线性关系,线性回归方程为：F-F₀=6.499+211.6c(c为赭曲霉毒素A的浓度,单位：ng·mL-1),相关系数r为0.995 5,按3倍标准差与工作曲线的斜率的比值(3σ/k)计算,得检测限为3 pg·mL-1。在实际样品中的回收率在93.3%～108.9%,相对标准偏差小于5%,能满足啤酒样品中赭曲霉毒素A快速检测要求。对13个市售啤酒样品进行检测,其中6个样品检出赭曲霉毒素A,污染率为46.15%。受污染样品的赭曲霉毒素A含量在0.008～0.63 ng·mL-1范围。该荧光传感法检测赭曲霉毒素A具有灵敏性好、特异性高、常见真菌毒素无干扰、方法简单、快速,便于大众化推广应用的优点。     

生物相容性量子点的表征及其在细胞标记中的应用

利用无机低温水相合成法制备表面包覆L-半胱氨酸的CdTe/ZnTe核壳型量子点,测量不同溶液以及激发功率激光作用下该量子点的光谱特性。结果表明,该量子点吸收谱和荧光光谱峰值位置不随pH值变化,而荧光光强随pH值升高呈近似线性上升趋势;不同缓冲液对该量子点荧光光强无影响,但随孵育时间延长,荧光强度略有下降;在强激光照射下QDs会被快速光漂白,选择适当的激光功率(<100 μW),可降低漂白速率,实现长时间稳定测量。因此,该量子点具有较好的生物稳定性和光稳定性,将其与血铁蛋白相连形成靶向共轭纳米粒,可成功用于HeLa细胞标记。细胞内量子点光漂白实验表明,细胞微环境会影响量子点的光稳定性,加速量子点的光漂白。     

谷胱甘肽包被的CdSe/CdS量子点的直接水相制备及其对人血淋巴细胞的标记成像

首次用谷胱甘肽(GSH)作为稳定剂,在水溶液中制备了稳定地发射绿色荧光和橙色荧光的两种 CdSe/CdS核/壳结构的纳米量子点。用紫外-可见分光光度和荧光光谱方法研究了CdSe/CdS量子点的发光特性。透射电镜(TEM)结果表明CdSe/CdS量子点近似球形,在水中分散性良好,比CdSe量子点具有更优异的发光特性,发射光谱和吸收光谱都有红移现象。将CdSe/CdS量子点与鼠抗人CD3抗体连接,制备了水溶性CdSe/CdS-CD3复合物探针,对人血淋巴细胞进行标记和成像。结果表明用该探针对人血淋巴细胞成像清晰,其荧光在30 min的连续蓝光激发下无明显衰退,而FITC荧光在20 min内基本完全猝灭。     

叶酸修饰的AgInS2量子点在体外癌细胞成像上的应用

成功制备出高品质的三元AgInS₂量子点。通过配体交换法将油溶性AgInS₂量子点转为水溶性量子点, 通过dBSA修饰水溶性量子点形成配位体壳, 使量子点具有更好的稳定性(4周)。从透射电子显微镜(TEM)观察到dBSA修饰后的量子点的粒径增加, 分散性较好, 并且在可见光区域有明显的光致发光。用叶酸对dBSA-MPA量子点进行修饰, 并通过傅立叶变换红外光谱进行了验证。将得到的FA-dBSA-MPA纳米复合材料应用于能与叶酸受体特异性结合的乳腺癌细胞中, 并在荧光倒置显微镜中检测到量子点成功对乳腺癌细胞进行了标记。与dBSA-MPA量子点相比, 表面被叶酸修饰后的量子点与癌细胞的结合效率显著提高。     

叶酸修饰的AgInS_2量子点在体外癌细胞成像上的应用（英文）

成功制备出高品质的三元Ag In S2量子点。通过配体交换法将油溶性Ag In S2量子点转为水溶性量子点,通过d BSA修饰水溶性量子点形成配位体壳,使量子点具有更好的稳定性(4周)。从透射电子显微镜(TEM)观察到d BSA修饰后的量子点的粒径增加,分散性较好,并且在可见光区域有明显的光致发光。用叶酸对d BSA-MPA量子点进行修饰,并通过傅立叶变换红外光谱进行了验证。将得到的FA-d BSA-MPA纳米复合材料应用于能与叶酸受体特异性结合的乳腺癌细胞中,并在荧光倒置显微镜中检测到量子点成功对乳腺癌细胞进行了标记。与d BSA-MPA量子点相比,表面被叶酸修饰后的量子点与癌细胞的结合效率显著提高。     

用热透镜法测量(口恶)嗪1高氯酸盐的绝对荧光量子效率

本文介绍了一种利用热透镜效应测量激光染料绝对荧光量子效率的简单有效的新方法.利用此法,具体地测量了(口恶)嗪1高氯酸盐(天津市染料所生产)在不同溶剂中、不同浓度下的绝对荧光量子效率,并对该染料溶于二氯乙烷或三氯甲烷中、比溶于乙醇、水等溶剂中的绝对荧光量子效率有明显增加的异常现象作了初步讨论.认为抑制发色团原子间的振动,将是提高激光染料绝对荧光量子效率的有效途径.     

半导体红外量子点发展现状与前景

半导体量子点具有独特的光学与电学性质,特别是红外量子点良好的光稳定性和生物相容性等优点使其在光电器件、生物医学等领域受到广泛关注。综述了吸收或发射光谱位于红外波段的量子点在激光、能源、光电探测以及生物医学等方面的应用现状与前景,归纳了适用于红外量子点材料的制备方法,并对比了不同方法在应用中的优势。半导体红外量子点材料选择丰富、应用形式多样:InAs量子点被动锁模激光器在1.3 μm波长处产生7.3 GHz的近衍射极限脉冲输出;InAs/GaAs量子点双波长激光器可泵浦产生0.6 nW的THz波;PbS量子点掺杂光纤放大器可在1.53 μm中心波长处实现10.5 dB光增益,带宽160 nm;CdSeTe量子点敏化太阳能电池、异质结Si基量子点太阳能电池的总转换效率可达8%和14.8%;胶质HgTe量子点制成的量子点红外探测器(QDIP)可实现3 μm~5 μm中波红外探测,Ge/Si量子点可实现3 μm~7 μm红外探测;CdTe/ZnSe核壳量子点可用于检测DNA序列的损伤与突变。半导体红外量子点上述应用形式的发展,将进一步促进红外光电系统向高效、快速、大规模集成的方向演进,也将极大地促进临床医学中活体成像检测的应用推广。     

Fluorescence Imaging of Stem Cells,Cancer Cells and Semi-Thin Sections of Tissues using Silica-Coated CdSe Quantum Dots

Trioctylphosphine oxide capped cadmium selenide quantum dots, synthesized in organic media were rendered water soluble by silica overcoating. Silanisation was done by a simple reverse microemulsion method using aminopropyl silane as the silica precursor. Further, the strong photoluminescence of the silica-coated CdSe quantum dots has been utilized to visualize rabbit adipose tissue-derived mesenchymal stem cells (RADMSCs) and Daltons lymphoma ascites (DLA) cancerous cells in vitro. Subsequently the in vivo fluorescence behaviours of QDs in the tissues were also demonstrated by intravenous administration of the QDs in Swiss albino mice. The fluorescence microscopic images in the stem cells, cancer cells and semi-thin sections of mice organs proved the strong luminescence property of silica-coated quantum dots under biological systems. These results establish silica-coated CdSe QDs as extremely useful tools for molecular imaging and cell tracking to study the cell division and metastasis of cancer and other diseases.     

Neon-, krypton-, and xenon-broadened spectral lines of water vapor

Photoluminescent semiconductor quantum dots (QDs) are widely used in many branches of diagnostics and biomedicine. Using ultrasmall QDs for designing fluorescent nanoprobes increases their capacity for penetrating through cell membranes, which allows one to use them for tracking intracellular processes at the molecular level. Obtaining small-size QDs is usually impeded due to the fast kinetics of reactions of their formation and growth in a colloidal medium. We propose a method of synthesizing defectless CdSe QDs with a diameter of 1.5 nm based on the injection reaction in an organic medium, with superfast termination of the growth of QDs at the early stage of their formation. Separation of QDs by means of gel-permeation chromatography allows one to completely remove the excess of cadmium precursors not entering the reaction, which ensures the subsequent obtaining of QDs with a controllable fluorescence wavelength and high quantum yield in the process of depositing protective epitaxial shells of different compositions. The obtained ultrasmall QDs may find application in developing photoluminescent nanoprobes for visualizing intranuclear processes in cells.     

带有InGaAs覆盖层的InAs量子点红外探测器材料的发光与光电响应

利用分子束外延技术(MBE),在GaAs(001)衬底上自组织生长了不同结构的InAs量子点样品,并制备了量子点红外探测器件。利用原子力显微镜(AFM)和光致发光(PL)光谱研究了量子点的表面结构、形貌和光学性质。渐变InGaAs层的插入有效地释放了InAs量子点所受的应力,抑制了量子点中In组分的偏析,提高了外延层的生长质量,降低了势垒高度,使InAs量子点荧光波长红移。伏安特性曲线和光电流(PC)谱结果表明,生长条件的优化提高了器件的红外响应,具有组分渐变的InGaAs层的探测器响应波长发生明显红移。     

Facile synthesis of mercaptosuccinic acid-capped CdTe/CdS/ZnS core/double shell quantum dots with improved cell viability on different cancer cells and normal cells

Water-soluble, mercaptosuccinic acid (MSA)-capped CdTe/CdS/ZnS core/double shell quantum dots (QDs) were prepared by successive growth of CdS and ZnS shells on the as-synthesized CdTe/CdS_thin core/shell quantum dots. The formation of core/double shell structured QDs was investigated by ultraviolet-visible (UV–Vis) absorption and photoluminescence (PL) spectroscopy, PL decay studies, X-ray diffraction (XRD), and X-ray photoelectron spectroscopy (XPS). The core/double shell QDs exhibited good photoluminescence quantum yield (PLQY) which is 70% higher than that of the parent core/shell QDs, and they are stable for months. The average particle size of the core/double shell QDs was ～3 nm as calculated from the transmission electron microscope (TEM) images. The cytotoxicity of the QDs was evaluated on a variety of cancer cells such as HeLa, MCF-7, A549, and normal Vero cells by 3-(4,5-dimethyl-2-thiazolyl)-2,5-diphenyl-2H-tetrazolium bromide (MTT) cell viability assay. The results showed that core/double shell QDs were less toxic to the cells when compared to the parent core/shell QDs. MCF-7 cells showed proliferation on incubation with QDs, and this is attributed to the metalloestrogenic activity of cadmium ions released from QDs. The core/double shell CdTe/CdS/ZnS (CSS) QDs were conjugated with transferrin and successfully employed for the biolabeling and fluorescent imaging of HeLa cells. These core/double shell QDs are highly promising fluorescent probe for cancer cell labeling and imaging applications.     

Influence of nanomechanical force on the electronic structure of InAs/GaAs quantum dots

We show nanomechanical force is useful to dynamically control the optical response of self-assembled quantum dots, giving a method to shift electron and heavy hole levels, interval of electron and heavy hole energy levels, and the emission wavelength of quantum dots (QDs). The strain, the electron energy levels, and heavy hole energy levels of InAs/GaAs(001) quantum dots with vertical nanomechanical force are investigated. Both the lattice mismatch and nanomechanical force are considered at the same time. The results show that the hydrostatic and the biaxial strains inside the QDs subjected to nanomechanical force vary with nanomechanical force. That gives the control for tailoring band gaps and optical response. Moreover, due to strain-modified energy, the band edge is also influenced by nanomechanical force. The nanomechanical force is shown to influence the band edge. As is well known, the band offset affects the electronic structure, which shows that the nanomechanical force is proven to be useful to tailor the emission wavelength of QDs. Our research helps to better understand how the nanomechanical force can be used to dynamically control the optics of quantum dots.     

Successful growth of two different quantum dots on one substrate

We report the successful growth of ZnSe and ZnTe quantum dots (QDs) embedded in ZnS on GaAs substrate. These QDs have good optical properties and show quantum confinement effect. High-resolution electron scanning microscope studies show that these QDs are grown in Volmer–Weber mode. It is found that the size of the QDs is controlled by the growth duration. When the growth time is short, high density of QDs could be fabricated, but with a long growth time the small QDs get together to form a large cluster. We also show that with this growth method it is possible to grow both ZnSe quantum and ZnTe QDs on one substrate at the same time. For this dual QDs system, two peaks corresponding to the emission from the ZnSe dots (3.0 eV, blue–violet) and ZnTe dots (2.6 eV, green–blue) could be observed at the same time in the photoluminescence measurement.     

ZnO@GQDs核壳结构量子点的制备及性能研究

采用原位聚合法制备了以ZnO量子点为核、石墨烯量子点（GQDs）为壳的ZnO@ GQDs核壳结构量子点。通过TEM和HR-TEM对量子点进行形貌和结构的分析表征。结果表明,合成的ZnO@ GQDs核壳结构量子点为球形,粒径为～7 nm,且尺寸均匀。PL光谱研究表明,新型量子点的发射峰位于369 nm,发光峰窄、强度高;相对于ZnO的本征发射峰,GQDs的引入使得ZnO@GQDs核壳量子点的荧光发射峰出现蓝移、强度变高,从而使复合量子点的荧光具有较纯的色度和较高的强度,说明GQDs的引入具有协同优化效应。该量子点有望应用于LED显示器件。     

Creating W-type entangled states in quantum dot systems

We show that three initially nonresonant quantum dots (QDs) could be used to generate W-type entangled states with the application of a single detuned light via the ac Stark effect. This gives a way to prepare the highly entangled excitonic states in the picosecond time scale by controlling the interactions between QDs.     

CdTe量子点标记雌二醇衍生物的研究

以巯基乙酸为修饰剂合成高量子产率的CdTe量子点,并成功标记生物小分子17β-氨基雌二醇.紫外光谱、荧光光谱、红外光谱以及倒置显微镜照片分析表明CdTe量子点在活化剂N-羟基琥珀酰亚胺的作用下,通过表面的羧基与17β-氨基雌二醇的氨基以共价键结合,这为建立基于量子点探针的新型的药物筛选模型提供了实验基础.