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。     

ZnS：Mn/SiO2量子点的表面聚乙烯吡咯烷酮修饰及其应用于海水中铅离子检测

制备了二氧化硅壳层修饰的ZnS：Mn量子点,基于聚乙烯吡咯烷酮（PVP）与二氧化硅表面硅羟基的作用,在纳米复合微粒表面进行了PVP的修饰,得到了在海水中荧光性能及胶体稳定性良好的ZnS：Mn/SiO₂/PVP 量子点。在Pb²⁺对所制备纳米微粒具有荧光猝灭效应的基础上,建立了用ZnS：Mn/SiO₂/PVP 量子点作为荧光探针检测海水中微量铅离子的新方法。研究表明,量子点浓度为10^-3 mol/L时,海水中离子浓度在10~100 μmol/L范围内与ZnS：Mn/SiO₂/PVP量子点荧光猝灭强度呈良好的线性关系,相关系数为0.994 6,检出限为8×10^-7 mol/L。     

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。     

硅量子点中电子的荷电动力学特征

利用频率依赖电容谱的测量,对于SiO₂/硅量子点/SiO₂/硅衬底隧 穿电容中硅量子点的荷电特征进行了研究.由于量子点的极小尺寸和良好的均匀性,室温下 在强反型区成功地观察到了与单电子隧穿相关的两个电容和电导共振峰,它们分别对应于硅 衬底导带上的电子与量子点中第一与第二个基态之间直接隧穿过程.实验数据分析给出了量 子点中的库仑荷电能,并进行了讨论. 关键词： 量子点 电容谱 库仑荷电能 直接隧穿     

热分解含硫金属有机配合物制备近红外PbS量子点

以Pb(NO₃)₂, Na(S₂CNEt₂)·3H₂O为反应物, 在去离子水中合成含硫金属有机配合物Pb(S₂CNEt₂)₂. 氩气保护下, 在油酸和十八烯混合溶液中热分解前躯体Pb(S₂CNEt₂)₂, 反应时间分别为30, 60, 90, 120 min, 获得PbS量子点样品a, b, c, d. 通过红外光谱分析和热重-差热等手段对前躯体进行表征, 证明配体Na(S₂CNEt₂)·3H₂O中的两个硫原子与Pb²⁺配位成功. PbS量子点样品X射线衍射和透射电子显微镜分析表明, 合成的PbS为类球形纯立方晶系PbS纳米晶; 对PbS量子点样品紫外-可见吸收光谱和光致发光谱进行研究发现, 吸收光谱和光致发光谱随着反应时间的增加顺序红移, 表明优化热分解反应时间可以调控PbS量子点的吸收光谱和光致发光谱. PbS量子点样品a发射峰在1080 nm, 与硅基太阳能电池相匹配, 可作为硅基荧光太阳能聚集器的荧光材料. 关键词： 热分解法 含硫金属有机配合物 PbS量子点 反应时间     

倒置器件结构及局域等离子体效应对CdSe量子点LED发光性能的改进

研究了倒置器件结构以及CdSe量子点发光材料与金属纳米粒子之间的相互作用对量子点的电致发光性能的影响。利用TiO₂作为电子传输/注入层,成功地制备了倒置结构的量子点电致发光器件。通过对单载流子器件电压-电流特性的分析,证明了ITO作为阴极到TiO₂的电子注入特性与Al作为阴极时的效果几乎相同。观察到金属纳米粒子产生的局域等离子体效应提高了器件的效率,使得效率随电流增大而降低的速度明显减小。在电流密度为200 mA/cm²时,电致发光器件的效率大约提高了42%。     

2018年2期电子期刊

光诱导功能退化是胶体量子点在应用中面临的主要挑战之一,本文针对这一问题研究了使用磁控溅射沉积SiO₂薄膜形成钝化层来提高CdSe/ZnS量子点发光稳定性的方法。首先,通过三正辛基膦辅助连续离子层吸附反应方法合成了615 nm发光的红色CdSe/ZnS量子点。然后将量子点旋涂在SiO₂/Si基片上,再通过磁控溅射方法在量子点上沉积了厚度为20 nm的SiO₂薄膜作为钝化层。使用连续波激光光源分别在空气气氛和真空条件下照射样品,研究了经过不同照射时间后钝化和未钝化量子点的稳态光致发光光谱。结果表明,随着照射时间的延长,没有SiO₂钝化的量子点的PL强度显著降低、PL峰值发生蓝移、FWHM不断增大。对比研究发现,由于SiO₂薄膜能够阻挡空气中的水和氧,减缓了量子点表面的光诱导氧化现象,因此显著提高了CdSe/ZnS量子点的稳定性。     

二硫化钼量子点的一步水热法制备与光学性能研究

二硫化钼量子点(MoS₂ QDs)因具有尺寸可控、量子限域效应强等优异的物化特性，故在传感、荧光检测和光催化等领域中具有潜在的应用价值。以钼酸铵为钼源，以谷胱甘肽为硫源，采用一步水热法合成水溶性好、尺寸均一的MoS₂QDs(MoS₂ QDs-1)。为探究不同硫源对MoS₂ QDs尺寸和光学性能的影响，又以钼酸铵和L-半胱氨酸分别为钼源和硫源，通过相同方法制备MoS₂ QDs(MoS₂ QDs-2)。研究了MoS₂ QDs-1和MoS₂ QDs-2样品的结构和光致发光性能。结果表明，与MoS₂ QDs-2样品相比，MoS₂ QDs-1样品的平均晶粒尺寸更小(3.88 nm)、平均晶粒高度更低(4.75 nm)、光学带隙更小(3.65 eV)和荧光量子产率更高(10.8%)。     

内嵌InAs量子点的δ掺杂GaAs/AlxGa1-xAs二维电子气特性分析

采用分子束外延技术对δ掺杂GaAs/Al_xGa_1-xAs二维电子气(2DEG)样品进行了生长. 在样品生长过程中, 分别改变掺杂浓度(N_d)、空间隔离层厚度(W_d) 和Al_xGa_1-xAs中Al组分(x_Al)的大小, 并在双温(300 K, 78 K)条件下对生长的样品进行了霍尔测量; 结合测试结果, 分别对N_d, W_d及x_Al与GaAs/Al_xGa_1-xAs 2DEG的载流子浓度和迁移率之间的关系规律进行了细致的分析讨论. 生长了包含有低密度InAs量子点层的δ掺杂GaAs/Al_xGa_1-xAs 2DEG 样品, 采用梯度生长法得到了不同密度的InAs量子点. 霍尔测量结果表明, 随着InAs量子点密度的增加, GaAs/Al_xGa_1-xAs 2DEG的迁移率大幅度减小, 实验中获得了密度最低为16×10⁸/cm²的InAs量子点样品. 实验结果为内嵌InAs量子点的δ掺杂GaAs/Al_xGa_1-xAs 2DEG的研究和应用提供了依据和参考. 关键词： 二维电子气 InAs量子点 载流子浓度 迁移率     

丁胺包裹的CdSe量子点敏化的TiO2纳米晶薄膜电子转移机制

利用超快光谱技术系统研究了在丁胺包裹的CdSe量子点敏化的TiO₂纳米晶薄膜起始时刻界面间电子转移动力学。与之前的报道不同,该实验结果表明:CdSe量子点经过表面修饰后,两相电子注入机制--热电子和冷电子注入得以被证实,即:电子能分别从CdSe量子点导带中高的振动能级和导带底转移到TiO₂的导带。该机制详细描绘了电子在纳米界面间转移的图景。进一步研究发现:热电子注入的电子耦合强度(3.6±0.1 meV)比弛豫后的基态电子注入高两个数量级,基于Marcus理论,伴随着0.083 eV的重组能,冷电子注入的耦合强度值为~50 μeV。     

Determining the effective density of airborne nanoparticles using multiple charging correction in a tandem DMA/ELPI setup

The cysteamine-modified hyaluronic acid (HA) polymer was employed to coat quantum dots (QDs) through a convenient one-step reverse micelle method, with the final QDs hydrodynamic size of around 22.6 nm. The HA coating renders the QDs with very good stability in PBS for more than 140 days and resistant to large pH range of 2–12. Besides, the HA-coated QDs also show excellent fluorescence stability in BSA-containing cell culture medium. In addition, the cell culture assay indicates no significant cytotoxicity for MD-MB-231 breast cancer cells, and its targeting ability to cancer receptor CD44 has been demonstrated on two breast cancer cell lines. The targeting mechanism was further proved by the HA competition experiment. This work has established a new approach to help solve the stability and toxicity problems of QDs, and moreover render the QDs cancer targeting property. The current results indicate that the HA polymer-coated QDs hold the potential application for both in vitro and in vivo cancer imaging researches.     

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.     

RGDS-conjugated CdSeTe/CdS quantum dots as near-infrared fluorescent probe: preparation,characterization and bioapplication

In the experiments, high-quality, water-soluble and near-infrared (NIR)-emitting CdSeTe and CdSeTe/CdS quantum dots (QDs) were successfully prepared. The average size of CdSeTe?CdS QDs was 7.68 nm and CdSeTe QDs was 4.33 nm. Arginine-glycine-aspartic-serine acid (RGDS) peptides were linked to CdSeTe/CdS QDs by N-(3-(dimethylamino)propyl)-N′-ehtylcarbodiimide hydrochloride (EDC) and N′-hydroxysuccinimide (NHS). The prepared RGDS-tagged NIR CdSeTe/CdS QDs (denoted as RGDS-CdSeTe/CdS) had an average diameter of 24.83 nm and were used for cancer cell immunofluorescence imaging. The characteristics of RGDS-conjugated CdSeTe/CdS such as morphology, structure, spectra, stability, cytotoxicity, and near-infrared microscopic imaging were investigated in detail. HepG2 cells were incubated with the novel fluorescent probe (RGDS-CdSeTe/CdS), which realized immunofluorescence targeting and imaging. The results reported here open up new perspectives for integrin-targeted near-infrared imaging and may aid in tumor detection including imaging-guided surgery.     

Enhancement of Intracellular Delivery of CdTe Quantum Dots (QDs) to Living Cells by Tat Conjugation

Quantum dots (QDs), as novel fluorescence probes, have shown a great potential for bio-molecular labeling and cellular imaging. To stain cellular targets, the sufficient intracellular delivery of QDs is required. In this work the tat, a typical membrane-permeable carrier peptide, was conjugated with thiol-capped CdTe QDs to form CdTe Tat-QDs, and the intracellular deliveries of CdTe QDs or CdTe Tat-QDs were compared in human hepatocellular carcinoma (QGY) cells and human breast cancer (MCF7) cells in vitro by means of confocal laser scanning microscopy. Added into the cell dishes, both QDs and Tat-QDs adhered to the outer leaflet of the plasma membrane of cells within a few minutes, but the binding amount of Tat-QDs was obviously higher than that of QDs. Then both QDs and Tat-QDs can penetrate into cells, and their cellular contents increased with incubation time but both saturated after 3 hours incubation. However the cellular levels of Tat-QDs were higher than those of QDs, with the ratio of 2.1 (±0.3) times in QGY cells and 1.5 (±0.2) times in MCF7 cells, demonstrating the enhancing effect of Tat conjugation on the intracellular delivery of QDs.     

Robust Aqueous Quantum Dots Capped with Peptide Ligands as Biomaterials: Facile Preparation,Good Stability,and Multipurpose Application

We have obtained robust peptide‐capped quantum dots (QDs) using a facile approach. The pentapeptide Cys‐Ala‐Leu‐Asn‐Asn (CALNN) is involved as the capping ligand, forming a self‐assembly monolayer on the surface of QDs, and solubilization of hydrophobic QDs in water is realized by simply mixing with the ligands in sodium hydroxide solution. All of the characterization results show that the prepared small‐sized QDs have excellent stability in acidic and high salt solutions. Additionally, the protein‐mimicking surface property of the peptide‐capped QDs eliminates the nonspecific cellular interaction, which in combination with the low cytotoxicity promises an ideal biomaterial in the future. Further functionalization and achievement of fluorescence resonance energy transfer (FRET) to graphene also display great potential for analytical applications.     

Cytotoxicity and fluorescence studies of silica-coated CdSe quantum dots for bioimaging applications

The toxicological effects of silica-coated CdSe quantum dots (QDs) were investigated systematically on human cervical cancer cell line. Trioctylphosphine oxide capped CdSe QDs were synthesized and rendered water soluble by overcoating with silica, using aminopropyl silane as silica precursor. The cytotoxicity studies were conducted by exposing cells to freshly synthesized QDs as a function of time (0–72 h) and concentration up to micromolar level by Lactate dehydrogenase assay, MTT [3-(4,5-Dimethylthiazol-2-yl)-2,5-Diphenyltetrazolium Bromide] assay, Neutral red cell viability assay, Trypan blue dye exclusion method and morphological examination of cells using phase contrast microscope. The in vitro analysis results showed that the silica-coated CdSe QDs were nontoxic even at higher loadings. Subsequently the in vivo fluorescence was also demonstrated by intravenous administration of the QDs in Swiss albino mice. The fluorescence images in the cryosections of tissues depicted strong luminescence property of silica-coated QDs under biological conditions. These results confirmed the role of these luminescent materials in biological labeling and imaging applications.     

Study on the interaction of CdTe quantum dots with ferulic acid and protocatechuic aldehyde by optical spectroscopy

Luminescent CdTe quantum dots (QDs) were synthesized using thioglycolic acid (TGA) as a stabilizing agent in aqueous medium and were characterized by Fourier transform infrared spectroscopy (FTIR), atomic force microscopy (AFM), and transmission electron microscopy (TEM). In weak basic media the fluorescence of TGA-CdTe QDs was quenched notably by ferulic acid (FA) and protocatechuic aldehyde (PA), and the quenching values were proportional to the concentration of the quenchers in a certain range. The addition of bovine serum albumin (BSA) to TGA-CdTe QDs-FA and TGA-CdTe QDs-PA systems rendered a large recovery of the fluorescence of TGA-CdTe QDs.     

Improving colloidal properties of quantum dots with combined silica and polymer coatings for in vitro immuofluorenscence assay

Semiconductor quantum dots (QDs) are promising fluorescence probes for immuofluorescence assay in the biological applications. However, water solubilization and non-specific binding are two critical issues to be addressed for the practical uses. Here, we reported a new type of QDs with combined silica and polymer coating. QDs with excellent colloidal properties were prepared via carboxylation of the amino groups on the surface of silica-coated QDs by reacting with multi-carboxyl poly (acrylic acid) (PAA). Hydrodynamic size of PAA-functionalized silica-coated QDs was around 40 nm. They were highly fluorescent (about 47.8% quantum yield). No precipitate of QDs was observed after 3 month storage at 4 °C. When cancer cells (HeLa) were used, the functionalized QDs exhibited little or no non-specific cellular binding. The results from in vitro experiments indicated that PAA-functionalized silica-coated QDs-antibody bioconjugates had excellent antigen-capture ability and exhibited little or no non-specific binding to polystyrene spheres which were used to immobilize the antigen for immuoflurescence assay. The PAA-functionalized silica-coated QDs with improved colloidal properties could serve as excellent alternative fluorescent probes for biodetection.     

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。     

基于CdSe@ZnS量子点水溶性纳米粒子的制备及荧光性能

作为一种新型的荧光探针,量子点（QD）已经受到越来越多的重视,制备工艺也显得格外重要。水相中合成的量子点效率低,油相中的量子点经过转相以后效率也大大衰减。本论文利用再沉淀包覆的方法制备了具有良好的水溶性的掺杂绿光CdSe@ZnS的纳米颗粒G-NPs（534 nm）和掺杂红光CdSe@ZnS的纳米颗粒R-NPs（610 nm）,具有窄的半峰宽（G-NPs~29 nm,R-NPs~31 nm）,较小的粒径（45 nm）,并在此基础上通过发射光谱与荧光衰减研究了量子点之间的能量传递现象。该方法保留了量子点原来的性质,基于其优良的光学性质,对人类肝细胞肝癌细胞株（HepG2）进行了荧光标记,从共聚焦成像实验结果看出,纳米颗粒得到了良好的吞噬效果。