聚丙烯酸修饰核壳结构水溶性量子点的制备及表征

先用硫脲修饰的量子点为核,再用聚丙烯酸包覆,并用聚乙烯吡咯烷酮K-30为稳定剂,合成粒径分布均匀、性能稳定的核壳结构水溶性量子点荧光体。采用荧光发射光谱、红外光谱和透射电镜对样品进行表征并探索核量子点在聚丙烯酸聚合物溶液中含量对量子点荧光体的影响。结果表明:聚丙烯酸修饰后量子点粒径分布更均匀;荧光发射主峰由548nm蓝移到448nm。红外光谱图中2 092.8和1 384.3cm-1分别归属于羧基的CO和C—O伸缩振动,1 644.5cm-1归属为酰胺键的CO伸缩振动,核量子点在聚丙烯酸聚合物溶液中最佳含量为2.67mg.mL-1。该量子点制备方法简单易行,具有较好的稳定性及高荧光量子效率,为进一步应用于生物标记奠定基础。     

基于超声非线性参数的油水两相流相含率检测

超声法相含率检测,主要基于声速与声衰减这两个声学参数计算流体的分相含率。然而,对于油水两相流,油与水的声速与声衰减差异较小,检测灵敏度较低。相比之下,油水两相介质的超声非线性参数区别较大,在检测灵敏度上有明显优势。本文提出了基于超声非线性参数的油水混合物相含率检测方法,以油水两相混合液体中超声非线性传播模型与混合液体超声非线性参数的混合定则为基础,归纳含水率对流体超声非线性参数的调制规律。结合插入比较法的非线性参数测量方法,明确含水率与二次谐波幅值的关系基础上,构建相含率测量模型,实现油水混合流体相含率准确测量。     

生物偶联过程对于聚合物包覆的水溶性CdSe/ZnS核壳量子点发光的影响

以传统的戊二醛交联的方法实现了聚丙烯酸包覆的CdSe/ZnS量子点和人IgG蛋白分子的偶联,同时研究了偶联过程对量子点发光性能的影响。通过琼脂糖凝胶电泳技术证明量子点和蛋白分子偶联成功。通过稳态光谱和时间分辨光谱研究了偶联过程对量子点荧光性质的影响。发现偶联到量子点表面的戊二醛分子能够破坏量子点的表面从而增加其表面缺陷,使量子点发光效率降低;上述产物进一步与人IgG偶联增强了量子点的荧光强度,这是由于连接到量子点上的蛋白分子修复了量子点的表面,从而降低了表面缺陷所致。     

油水两相流质量流量小波网络软测量模型研究

在工业过程中,油水两相流的测量非常重要.本文研究了一种油水质量流量的软测量方法.此方法采用V型内锥测量油水两相流差压信号,构建了一个多输入单输出的自适应小波网络用于逼近油水两相流质量流量模型,实现总质量流量的软测量.研究重点是均相的油水两相流在水平管道中的质量流量测量.实验结果表明,结合V型内锥差压测量和自适应小波神经网络的软测量方法可以应用于均相的油水两相流的总质量流量测量,测量误差较小.     

油水两相流含水率测量组合传感器

针对水平管油水两相流中水相导电时,实现含水率0~100%范围测量问题,提出一种用于油水两相流含水率测量的电导和电容组合传感器。根据两相流中连续相的不同,选择不同传感器测量数据实现含水率的测量。通过对油水两相流实验测试数据的分析,得到电导和电容传感器在全含率范围测量时的响应特性,并实现传感器间数据选择。实验结果表明,含水率25%是传感器切换关键区域。将电导和电容传感器测试数据与含率测量模型结合,可实现含水率的全范围测量,测量结果具有较高的精度和良好的线性度。     

聚合物作用下油水两相流油泡时频运动特性

本文开展聚合物作用下的油水两相流动态试验,对聚合物作用下油水两相流的流动特性进行了研究。首先,分别配比了两种不同浓度的聚合物水溶液;其次,在内径20 mm的流动环装置上安装纵向多极电导阵列传感器,获取了水包油段塞流和水包油泡状流的传感器波动信号;最后,利用非平稳时频联合表达分析方法和递归图法,分别对聚合物作用下的复杂油水流动系统运动特征及非线性特征进行综合描述,发现时频联合分布特征及递归图纹理结构特征可作为流型变化的有效分析工具。     

差压法测量两相流相含率的研究

本文通过差压式测量方法,对气液两相流中含气率及油水两相流中含水率的测量进行了深入的试验研究。通过水平及垂直上升段的结构组合,测量气液两相流中的含气率值,在对流型测量与分析的基础上,建立了不同流型下垂直上升段与水平段摩擦压降间的修正关系式,减小了测量误差;通过采用一缓流的垂直下降段,测量油水两相流中的含水率值,获得了好的结果。     

双环电导探针测量油水两相流相反转的实验研究

本文有别于常规观察法和压降法,采用自行设计的双环电导探针技术,根据油水混合物的电学特性来实验测定和判断油水两相流动中相反转的发生,实验中还同时测量了油水两相流的流动压降以及实验段内的平均截面含水率,以验证电导探针测量结果。实验结果表明:油水两相流相反转发生在水相表观速度较低而油相表观速度较高的情况下,可以通过双环探针的信号较精确地确定反相点发生的范围,该范围内油水两相流的流动佐证了压降陡增为相反转的发生。     

空穴传输材料对CdSe核壳量子点的荧光影响

用稳态光谱和时间分辨光谱技术研究了空穴传输材料对CdSe/ZnSe 与CdSe/ZnS核壳量子点的荧光影响。结果表明,空穴传输材料对量子点有较强的猝灭作用,随空穴传输材料分子浓度的增加,量子点的荧光强度明显地被猝灭,同时量子点的荧光寿命也被减短。两种不同空穴传输分子对CdSe/ZnSe量子点的荧光猝灭明显不同。在与相同空穴传输分子相互作用时,包覆ZnS壳层的CdSe核壳量子点荧光猝灭效率明显低于包覆ZnSe壳层的CdSe核壳量子点。量子点的荧光猝灭过程可以解释为静态猝灭和动态猝灭过程,其中静态猝灭来源于量子点表面与空穴传输材料间相互作用,而动态猝灭则主要来源于量子点到空穴传输材料的空穴转移过程。实验结果表明空穴传输材料的种类以及核壳量子点的壳层结构都对其荧光猝灭效应起关键作用。     

HgTe/CdS/ZnS多壳层量子点的制备与表征

采用一种简单的方法合成HgTe/CdS/ZnS多壳层量子点。首先,以1-硫代甘油为稳定剂,在水相溶液中制备出HgTe核量子点;然后,采用外延生长法依次在HgTe核量子点表面包覆CdS和ZnS壳层,合成出最终具有稳定近红外发光的HgTe/CdS/ZnS多壳层量子点。该合成方法仅需3个步骤,具有操作简单、成本低廉的优点。实验结果显示,当反应温度为90 ℃、反应溶液pH为11.0、反应加热回流时间为4 min时,HgTe/CdS/ZnS多壳层量子点具有最高荧光量子产率36%。     

CdSe/ZnSe/ZnS多壳层结构量子点的制备与表征

展示了一种简捷的多壳层量子点合成路线。在含有过量Se源的CdSe体系中直接注入Zn源,"一步法"合成了CdSe/ZnSe量子点;进一步以CdSe/ZnSe为"核",表面外延生长ZnS壳层制备了核/壳/壳结构CdSe/ZnSe/ZnS量子点。相对于以往报道的多壳层结构量子点的制备方法,该方法通过减少壳层的生长步骤有效地简化了实验操作,缩短了实验周期,同时减少对原料的损耗。对量子点进行高温退火处理,能够大幅提高CdSe/ZnSe/ZnS量子点的发光量子产率。透射电镜、XRD以及光谱研究表明:所制备的量子点接近球形,核与壳层纳米晶均为闪锌矿结构,最终获得的CdSe/ZnSe/ZnS量子点的光致发光量子产率达到53％。为了实现量子点的表面生物功能化,通过巯基酸进行了表面配体交换修饰,使量子点表面具有水溶性的羧基功能团,并且能够维持较高的光致发光量子产率。     

Water‐Dispersible Silicon‐Quantum‐Dot‐Containing Micelles Self‐Assembled from an Amphiphilic Polymer

The dispersion of silicon quantum dots (Si QDs) in water has not been established as well as that in organic solvents. It is now demonstrated that the excellent dispersion of Si QDs in water with photoluminescence (PL) quantum yields (QYs) comparable to those for hydrophobic Si QDs can be realized by combining the processes of hydrosilylation and self‐assembly. Hydrogen‐passivated Si QDs are initially hydrosilylated with 1‐dodecence. The toluene solution of the resulting dodecyl‐passivated Si QDs is mixed with the water solution of the amphiphilic polymer of Pluronic F127 to form an emulsion. Dodecyl‐passivated Si QDs are encapsulated in the micelles self‐assembled from F127 in the emulsion. The size of the Si‐QD‐containing micelles may be tuned in the range from 10 to 100 nm. Although self‐assembly in the emulsion causes the PL QY of Si QDs to decrease, after a few days of storage in ambient conditions, Si QDs encapsulated in the water‐dispersible micelles exhibit recovered PL QYs of ≈24% at the PL wavelength of ≈680 nm. The intensity of the PL from Si QDs encapsulated in the water‐dispersible micelles is >90% of the original value after 60 min ultraviolet illumination, indicating excellent photostability.     

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。     

基于量子点-CBP混合层的量子点LED的制备

采用一锅法制备出高质量的具有核壳结构的Cd Se@Zn S、Cd Zn S/Zn S量子点。将量子点混入空穴传输材料CBP中形成复合的有源材料,经过几步简单的旋涂操作,制备出相应的绿光、蓝光量子点LED器件。这种方法利用了油溶性量子点和CBP材料的相容性,减少了旋涂操作的步骤,有利于快速制备基于量子点的电致发光器件。基于两步旋涂操作制备的量子点LED,由于阴极与复合有源层之间的能级差较大,导致需要较高的开启电压。在CBP材料中,注入的载流子有可能会被量子点表面缺陷捕获,形成表面态的发光。表面态发光的相对强度依赖于载流子浓度。     

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.     

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.     

Cell labeling and cytotoxicity of aqueously synthesized CdTe/CdS/ZnS core–shell–shell quantum dots by a water bath-hydrothermal method

CdTe/CdS/ZnS core–shell–shell quantum dots (QDs) were synthesized in aqueous solution via water-bathing combined hydrothermal method using L-cysteine as a stabilizer. The present method features markedly reduced synthesis time, higher fluorescent intensity and lower cytotoxicity of the QDs. Structural and spectroscopic properties of core–shell–shell QDs are well characterized by absorption and fluorescence spectroscopy, X-ray diffraction, transmission electron microscopy, and fourier transform infrared spectroscopy. Both CdS and ZnS shells were capped on the CdTe core and the fluorescence was greatly enhanced by the ZnS coating. The ternary QDs conjugated with transferrins were successfully employed for the biolabeling and fluorescent imaging of HeLa cells. Cytotoxicity evaluation shows that CdTe/CdS/ZnS was less toxic for cells than CdTe and CdTe/CdS due to the presence of a ZnS coating on surface, which inhibited the release of cadmium ions.     

Photoconductivity of composites based on CdSe quantum dots and low-band-gap polymers

Photoconductivity of thin layers prepared by spin coating of blends of CdSe quantum dots (QDs) and a low-band-gap polymer PCDTBT or PTB7 has been studied. It has been found that photocurrent in the composites containing QDs of 10-nm in size is significantly higher than in those of containing 5-nm QDs. Analysis of the results showed that the photoresponse of the thin layers is mainly determined by the relative positions of the frontier energy levels of the materials used, organic semiconductors and QDs. Therefore, the ability to tune the relative positions of these levels by varying the QD size is of special importance, thus allowing the optimization of photodetectors and photovoltaic cells.     

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。