Time-Resolved Photoluminescence Spectroscopy： A Novel Technique for Determination of Luminescence of Quantum Dots

The time-resolved photoluminescence （PL） spectroscopy measured by the gradually increasing start delay time is utilized as a tool for the determination of the luminescence of quantmn dots （QDs）. The luminescence evolution of self-assembled CdSe QDs during the luminescence decay is fully revealed in terms of the experiment technique. The characteristic narrow luminescence lines of self-assembled CdSe QDs are obtained with increasing start delay time.     

基于谷胱甘肽配体的ZnSe量子点对pH响应的时间分辨荧光光谱特性

当前,有关量子点pH响应方面的研究主要集中在含Cd（镉）类量子点,且都是研究其稳态荧光光谱对pH值的响应。然而,Cd类量子点对生物体系具有一定的毒性,且稳态荧光光谱法由于受浓度等因素的影响具有一定的不稳定性,因此应用于生物体系中作为pH探针具有明显的缺点。基于以上分析,通过水相合成法,我们制备出了基于谷胱甘肽配体的水溶性ZnSe量子点,该量子点具有毒性小,生物兼容性好等特点,适合被应用于生物体系中。利用所制备的ZnSe量子点,采用时间相关单光子计数技术,结合紫外可见吸收光谱和稳态荧光光谱,对pH值在5~11不同环境下的ZnSe量子点荧光动力学进行了系统性的研究。ZnSe量子点荧光衰减具有两个寿命组分,拟合得到分别为4和24 ns。通过采集不同探测波长下ZnSe量子点荧光衰减曲线,发现其长寿命组分随探测波长的增加而增加,而短寿命组分基本不随探测波长的改变而改变,结合有关报道分析判断,短寿命和长寿命组分分别来源于核内非局域载流子复合和表面态局域载流子复合。实验发现,处于不同pH值的环境下的ZnSe量子点具有不同的荧光寿命,其荧光寿命与pH值的变化呈负相关。通过比较ZnSe量子点两种荧光寿命组分随pH值的变化关系,发现ZnSe量子点的荧光寿命对pH值的响应主要来源于长寿命组分即表面态寿命,且在不同pH值范围内响应的灵敏度不同,在6~8的pH值范围内响应最为显著,表现为长寿命组分随pH值的增加出现一个较大幅度的衰减。实验进一步发现,ZnSe量子点两个寿命组分的比值在不同pH值范围内具有较好的线性相关性,但在不同pH值范围内斜率不同,通过比较,最大值在pH值为6~8的范围内。另外,与金属钠离子相互作用实验及相关报道表明,金属离子对ZnSe量子点荧光寿命的影响较小。以上研究表明,ZnSe量子点在生物体系pH值检测中具有良好的应用前景。     

基于固相抗体模式时间分辨荧光免疫分析测定雌三醇

采用二步标记法,借助二乙烯三胺五乙酸酐,将Eu3+标记到雌三醇完全抗原上,基于固相抗体竞争反应模式,建立了时间分辨荧光免疫分析测定雌三醇的新方法。在优化的条件下,方法的线性范围为0.005—1000ng·mL-1,检出限为4pg·mL-1。该方法用于检测血清中雌三醇的含量,结果令人满意。     

产生量子点的一种新方法(英文)

我们提出并试验了一种制备量子点阵的新方法。利用二步法制备的阳极氧化铝上规则排列纳米洞为模板,以紫外脉冲激光(2 48nm)溅射方法将氧化物经过带纳米洞的模板溅射到单晶Si的衬底上。以荧光材料La0 .95Eu0 .0 5BaB9O16 为靶材,初步获得了Si衬底上荧光材料的点阵。     

Time-Resolved Fluorescence Spectroscopy Study on the Photophysical Behavior of Quantum Dots

Room-temperature time-resolved luminescence measurements on single CdSe/ZnS quantum dots (QDs) are presented. Fluorescence emission spectra were recorded over periods of up to 30 minutes with a time resolution as small as 6 ms. For QDs in ambient air, a clear 30–40 nm blue shift in the emission wavelength is observed, before the luminescence stops after about 2–3 minutes because of photobleaching. In a nitrogen atmosphere, the blue shift is absent while photobleaching occurs after much longer times (i.e., 10–15 minutes). These observations are explained by photoinduced oxidation. The CdSe surface is oxidized during illumination in the presence of oxygen. This effectively results in shrinkage of the CdSe core diameter by almost 1 nm and consequently in a blue shift. The faster fading of the luminescence in air suggests that photoinduced oxidation results in the formation of non-radiative recombination centers at the CdSe/CdSeO_x interface. In a nitrogen atmosphere, photoinduced oxidation is prevented by the absence of oxygen. Additionally, a higher initial light output for CdSe/ZnS QDs in air is observed. This can be explained by a fast reduction of the lifetime of the long-lived defect states of CdSe QDs by oxygen.     

水溶性碲化镉量子点测定甲磺酸培氟沙星

合成巯基乙酸修饰的水溶性发光CdTe量子点,构建了CdTe-Al3+-甲磺酸培氟沙星荧光体系。考察了缓冲体系及pH值、表面活性剂的种类、反应时间及共存物质等对测定的影响。在最佳条件下,CdTe量子点发光强度与甲磺酸培氟沙星的浓度在3.6×10-3—4.00μg/mL范围内呈良好线性。该方法可直接用于甲磺酸培氟沙星片剂的测定,结果满意。     

单质碘对水溶性CdTe量子点的荧光猝灭研究

合成了不同尺寸的、巯基丙酸和半胱氨酸修饰的水溶性CdTe量子点,并研究了I2与CdTe量子点的相互作用,实验发现I2能够明显猝灭CdTe量子点的荧光,且猝灭程度与量子点的修饰剂有关,没有表现出明显的尺寸依赖效应。     

荧光光谱法研究水溶性L-Cys-CdS量子点与肌红蛋白的相互作用

以L-半胱氨酸为修饰剂,采用配位化学原理合成具有良好水溶性和生物相容性的L-Cys-CdS量子点.采用紫外-可见光谱及荧光光谱,考察了肌红蛋白(Mb)溶液浓度、酸度对L-Cys-CdS量子点荧光性质的影响.结果表明Mb对量子点荧光有猝灭作用,并且Mb的浓度及酸度对荧光猝灭均有影响,并探讨了导致荧光猝灭的原因以及量子点与肌红蛋白相互作用机理.     

水溶性量子点荧光探针用于帕珠沙星的含量测定

文章采用荧光光谱和紫外光谱研究了CdTe量子点(CdTe QDs)与广谱抗菌药物帕珠沙星的相互作用。结果表明,随着帕珠沙星浓度的增加,CdTe QDs荧光强度有规律的降低,但通过透射电镜图对QDs及加入帕珠沙星后的QDs进行比较,发现QDs仍然均一单分散,表明反应的作用机理可能是帕珠沙星促使QDs表面键合的有机分子发生变化,在Cd空位表现出的表面缺损上形成了碲氧复合物,致使荧光猝灭。因此该反应可作为一种新颖的快速检测帕珠沙星含量的方法。在一定条件下,帕珠沙星溶液的浓度与量子点荧光强度成线性关系,线性范围为10.0～850 μg·mL-1,相关系数r为0.995 4,检测限(S/N=3)为3.254×10-3 μg·mL-1。药物对量子点的猝灭常数为2.188×104 L·mol-1。应用到冻干粉针剂和氯化钠注射液中帕珠沙星的含量测定,所得结果与标示量一致。该方法较常用检测方法具有简便、快捷、灵敏、线性范围宽的优点,并有望进一步开展发药物体内显像及作用机理的研究。     

Quantum Dots Microstructural Metrology: From Time-Resolved Spectroscopy to Spatially Resolved Electron Microscopy

Colloidal quantum dots (QDs) have unique optical and electrical properties with promising applications in next-generation semiconductor technologies, including displays, lighting, solar cells, photodetectors, and image sensors. Advanced analytical tools to probe the optical, morphological, structural, compositional, and electrical properties of QDs and their ensemble solid films are of paramount importance for the understanding of their device performance. In this review, comprehensive studies on the state-of-the-art metrology approaches used in QD research are introduced, with particular focus on time-resolved (TR) and spatially resolved (SR) spectroscopy and microscopy. Through discussing these analysis techniques in different QD system, such as various compositions, sizes, and shell structures, the critical roles of these TR-spectroscopic and SR-microscopic techniques are highlighted, which provide the structural, morphological, compositional, optical, and electrical information to precisely design QDs and QD solid films. The employment of TR and SR analysis in integrated QD device systems is also discussed, which can offer detailed microstructural information for achieving high performance in specific applications. In the end, the current limitations of these analytical tools are discussed, and the future development of the possibility of interdisciplinary research in both QD fundamental and applied fields is prospected.     

Study on the Interaction Between Water-Soluble CdTe Quantum Dots and Ovalbumin by Optical Spectroscopy

ABSTRACT

CdTe quantum dots (QDs) modified by 2-mercaptoethylamine hydrochloride (CA) and thioglycolic acid (TGA), respectively, were synthesized in aqueous medium. The interaction of CdTe QDs with ovalbumin has been investigated in depth by Fourier transform infrared spectroscopy (FTIR), UV-Vis absorption, fluorescence-quenching spectrometry, and resonance Rayleigh scattering spectroscopy (RRS). Fluorescence data show that the quenching type of ovalbumin by CA-CdTe QDs is static quenching with the binding constant being 10^?4 M^?1, and the number of binding sites being one. The calculated thermodynamic parameters demonstrate that the main binding forces are hydrophobic interaction and electrostatic attraction. In contrast, the quenching style of ovalbumin by TGA-CdTe QDs is verified to be dynamic quenching. Under suitable acidity conditions, the interaction of CA-CdTe QDs or TGA-CdTe QDs with ovalbumin leads to the remarkable enhancement of RRS, and the increments are found to be proportional to the concentration of ovalbumin in a certain range. A simple and highly sensitive RRS approach for determining ovalbumin is developed. In addition, the causes for the enhancement of RRS and the quenching of fluorescence are investigated to shed light on the quenching mechanism.     

Water-Soluble Conjugates of ZnS:Mn Quantum Dots with Chlorin e6 for Photodynamic Therapy

An algorithm for wavefront calculation of ordinary and extraordinary waves after propagation through hemispherical components made of a uniaxial crystal is developed. The influence of frequency dispersion of n _о and n _e , as well as change in the direction of the optic axis of the crystal, on extraordinary wavefront in hemispheres made of from leuco-sapphire and a plastically deformed analog thereof is determined.     

A Magnetic Nanoparticle-Based Time-Resolved Fluoroimmunoassay for Determination of the Cytokeratin 19 Fragment in Human Serum

A sensitive, rapid and novel measurement method for cytokeratin 19 fragment (CYFRA 21–1) in human serum by magnetic particle-based time-resolved fluoroimmunoassay (TRFIA) is described. Built on a sandwich-type immunoassay format, analytes in samples were captured by one monoclonal antibody coating onto the surface of magnetic beads and “sandwiched” by another monoclonal antibody labeled with europium chelates. The coefficient variations of the method were lower than 7 %, and the recoveries were in the range of 90–110 % for serum samples. The lower limit of quantitation of the present method for CYFRA 21–1 was 0.78 ng/ml. The correlation coefficient of CYFRA 21–1 values obtained by our novel TRFIA and CLIA was 0.980. The present novel TRFIA demonstrated high sensitivity, wider effective detection range and excellent reproducibility for determination of CYFRA 21–1 can be useful for early screening and prognosis evaluation of patients with non-small cell lung cancer.     

神经网络法研究多溴代二苯胺热力学性质

通过时间分辨光谱技术详细地研究了ZnCuInS/ZnSe/ZnS量子点的激子弛豫动力学. 基于速率分布模型,波长依赖的发射动力学表明本征激子、界面缺陷态中的激子、给-受体对态中的激子都会参与量子点的发光过程,整个发光过程主要依赖于给-受体对态发射. 瞬态吸收数据表明激发后本征激子和界面缺陷物种可能会同时出现,在高激发光强下,光强依赖的俄歇复合过程也存在于量子点中     

A Novel LSB Based Quantum Watermarking

Quantum watermarking is a technique which embeds the invisible quantum signal such as the owners identification into quantum multimedia data (such as audio, video and image) for copyright protection. In this paper, using a quantum representation of digital images a new quantum watermarking protocol including quantum image scrambling based on Least Significant Bit (LSB) is proposed. In this protocol, by using m-bit embedding key K₁ and m-bit extracting key K₂ a m-pixel gray scale image is watermarked in a m-pixel carrier image by the original owner of the carrier image. For validation of the presented scheme the peak-signal-to-noise ratio (PSNR) and histogram graphs of the images are analyzed.     

混合量子点QLED结构性能研究

为研究基于混合量子点的QLED结构与性能,利用红光量子点以及绿光量子点两种材料制备了橙光QLED器件,并对其性能进行了表征。实验制备的器件结构为ITO/PEDOT∶PSS/poly-TPD/混合QDs/Zn O/Al,其中发光层采用了3种混合量子点的混合结构方案。方案一先旋涂红光量子点层,后旋涂绿光量子点层;方案二先旋涂绿光量子点层,后旋涂红光量子点层;方案三将红光、绿光量子点1∶1混合后制备为发光层。实验结果表明:方案一制备的器件电流密度最大,发光亮度最低,且只有红光谱;方案二制备的器件具有最小的电流密度,同时具有红、绿光谱,在8 V电压下,电流效率约为4.69 cd/A;方案三制备的器件同时具有红、绿光谱,电流密度与发光特性介于方案一与方案二之间。实测数据与理论分析是一致的,方案二制备的器件存在双能量陷阱,能够将注入的空穴以及电子同时限制在红光量子点层内。通过调节各功能层厚度使得载流子注入平衡,可进一步增大发光电流,提高器件效率。     

基于半导体量子点的片上手性纳米光子器件

手性量子光学在量子信息技术研究领域中受到了广泛的关注,其主要研究光在微纳结构中自旋依赖的手性耦合及传输行为。利用手性光与物质的相互作用可以增强光子与量子发射器的耦合,赋予纳米光子器件新的功能和应用,从而推动手性量子光学在量子信息领域中的大规模应用。主要对基于半导体量子点的片上手性纳米光子器件进行了综述,重点讨论了半导体量子点的光学性质和手性光与物质相互作用的物理机制,在此基础上对近年来应用手性耦合原理实现的多功能手性光子器件进行了总结,并对手性量子光学的未来应用场景进行了展望。     

Aqueous Synthesis of Water-Soluble Citrate-Modified Cadmium Selenide/Cadmium Sulfide/Zinc Sulfide Quantum Dots

Water-soluble cadmium selenide/cadmium sulfide/zinc sulfide core/shell/shell quantum dots were synthesized in aqueous solution using trisodium citrate as modifier. The crystal structure, morphology, component, and spectral properties of cadmium selenide/cadmium sulfide/zinc sulfide core/shell/shell quantum dots were characterized by X-ray power diffraction, transmission electron microscope, energy dispersive X-ray analysis, infrared spectrum, ultraviolet–visible absorption spectrum, and fluorescence spectrum. The results show that the spherical citrate-modified cadmium selenide/cadmium sulfide/zinc sulfide core/shell/shell quantum dots with diameter around 3.6 nm belong to the cubic zinc blende structure. The citrate-modified cadmium selenide/cadmium sulfide/zinc sulfide core/shell/shell quantum dots show a narrow, symmetric, and strong fluorescence emission spectrum band with narrow full width at half maximum of 53 nm, and the fluorescence quantum yield can reach up to 37.3%. The high-quality citrate-modified cadmium selenide/cadmium sulfide/zinc sulfide core/shell/shell quantum dots with good fluorescence properties have potential for application in biological fluorescence analysis.     

A Novel Quantum Image Compression Method Based on JPEG

Quantum image processing has been a hot topic. The first step of it is to store an image into qubits, which is called quantum image preparation. Different quantum image representations may have different preparation methods. In this paper, we use GQIR (the generalized quantum image representation) to represent an image, and try to decrease the operations used in preparation, which is also known as quantum image compression. Our compression scheme is based on JPEG (named from its inventor: the Joint Photographic Experts Group) — the most widely used method for still image compression in classical computers. We input the quantized JPEG coefficients into qubits and then convert them into pixel values. Theoretical analysis and experimental results show that the compression ratio of our scheme is obviously higher than that of the previous compression method.