Specific Fluorescence Probe for Direct Recognition of Dimethoate Using Molecularly Imprinting Polymer on ZnO Quantum Dots

ZnO quantum dots (QDs) based molecularly imprinting polymer (MIP)-coated composite was described for specific detection of the dimethoate (DM) as a template. The MIP was synthesized by simple self-assembly of 3-aminopropyl triethoxysilane (APTES) monomers and tetraethyl ortho-silicate as cross linking agent in the presence of template molecules. The used imprinting course can improve the tendency of the prepared QDs toward the DM template molecules. The MIP-coated ZnO QDs showed a strong fluorescence emission which undergoes a quenching effect in the presence of DM. So, a selective probe could be designed based on these composites to recognize DM in water samples. Under optimized experimental conditions, a linear relationship between the emission intensity of MIP-coated ZnO QDs and concentration of DM, in the range of 0.02–3.2 mg L^?1 with a detection limit of 0.006 mg L^?1. Combination of high specificity of MIP element and distinct fluorescence features of ZnO QDs provides a sensitive and selective recognizing method for pesticide detection. The developed method was successfully applied for the determination of DM contamination in environmental water samples.     

InN量子点的液滴外延及物性表征

由于1. 55μm波段广泛应用于通信领域,为了探索不同生长温度对InN量子点的形貌影响,并且实现自组装InN量子点在1. 55μm通信波段的发光,对InN量子点的液滴外延及物性进行了相关研究。首先利用射频等离子体辅助分子束外延(PA-MBE)技术在GaN模板上,采用液滴外延方法在3种温度下生长了InN量子点结构。生长过程中靠反射高能电子衍射(RHEED)对样品进行原位监控。原子力显微镜(AFM)表征结果表明随着生长温度升高,量子点尺寸变大,密度减小。在生长温度350℃和400℃下,观测到了量子点;当温度高于450℃时,未观测到InN量子点。当生长温度为400℃时,量子点形貌最好,密度为6×10~8/cm~2,对400℃下生长的InN量子点进行了变温PL测试,成功得到InN量子点在1. 55μm波段附近的光致发光,并且随着测试温度的升高,量子点的发光峰位发生了先红移后蓝移最后又红移的S型曲线变化,这种量子点有望在未来应用于量子通信领域。     

Studies on Interaction of CdTe Quantum Dots with Bovine Serum Albumin Using Fluorescence Correlation Spectroscopy

Luminescent quantum dots (QDs) have widely used in some biological and biomedical fields due to their unique and fascinating optical properties, meanwhile the interaction of QDs with biomolecules recently attract increasing attention. In this paper, we employed fluorescence correlation spectroscopy (FCS) to investigate the nonspecific interaction between CdTe QDs and bovine serum albumin (BSA) as a model, and evaluate their stoichiometric ratio and association constant. Our results documented that BSA was able to bind to CdTe QDs and form the QD–BSA complex by a 1:1 stoichiometric ratio. The association constant evaluated is 1.06 ± 0.14 × 10⁷ M⁻¹ in 0.01 M phosphate buffer (pH = 7.4). Furthermore, we found that QD–BSA complex dissociated with increase of ion strength, and we speculated that the interaction of CdTe QDs with BSA was mainly attributed to electrostatic attraction. Our preliminary results demonstrate that fluorescence correlation spectroscopy is an effective tool for investigation of the interaction between quantum dots (or nanoparticles) and biomolecules.     

Chemiluminescence resonance energy transfer in the luminol-CdTe quantum dots conjugates

The luminol-CdTe quantum dots (QDs) conjugates were prepared through the reaction between -NH₂ and -COOH. The resonance energy transfer between chemiluminescence donor (luminol-H₂O₂ system) and quantum dots (QDs, with different emission peaks) acceptors (CRET) was investigated. The luminescence of QDs in luminol-QDs conjugates in the process of CRET was influenced by the molar ratio of luminol/QDs. It could reach higher luminescence intensity while the luminol/QDs value was 1/1. Quantum yield of QDs and overlapping areas between the emission spectrum of luminol and adsorption spectrum of QDs played important roles in the CRET efficiency of luminol-QDs conjugates. The higher CRET efficiency (21.2%) was observed when the 540 nm QDs were used as acceptors. This work will offer helpful knowledge for the CRET studies based on QDs.     

不同巯基试剂修饰的CdTe量子点与BSA相互作用研究

修饰试剂对量子点的合成、性质具有重要的影响,但目前有关修饰试剂对量子点与蛋白质间相互作用的影响尚不清楚。采用紫外-可见吸收光谱、荧光光谱及红外光谱研究了3种巯基化合物(巯基乙酸,TGA;L-半胱氨酸,L-Cys;还原型谷胱甘肽,GSH)修饰的CdTe量子点与牛血清白蛋白(BSA)的相互作用。通过Stern-Volmer方程对数据进行了分析,得到了不同CdTe量子点与BSA相互作用过程的ΔHθ,ΔGθ和ΔSθ,并比较了CdTe量子点的不同修饰剂对BSA荧光猝灭的影响。研究结果表明,3种修饰试剂包覆的CdTe量子点与BSA的相互作用均为静态猝灭过程,猝灭常数KSV(L-Cys)KSV(TGA)≈KSV(GSH);TGA和L-Cys修饰的CdTe量子点与BSA的结合力主要为疏水作用力,而GSH修饰的量子点与其结合力既有氢键作用力又有疏水作用力;这些结果说明量子点与BSA的作用过程与量子点表面修饰试剂的类型有关。     

基于Mn掺杂ZnS量子点-BSA纳米复合材料检测头孢曲松钠

以3-巯基丙酸(MPA)为稳定剂,采用水相合成法合成了具有优良光学性质的Mn掺杂ZnS量子点。该量子点在室温条件下即可发射较强的磷光信号。将量子点与牛血清蛋白(BSA)偶联后,形成了纳米复合材料。由于BSA对量子点表面缺陷进行了有效修复,量子点发出的磷光明显增强。当加入头孢曲松钠后,头孢曲松钠与BSA的相互作用使量子点的磷光被有效猝灭,该磷光猝灭量(△P)与头孢曲松钠的浓度在一定范围内呈良好的线性关系(R=0.99)。量子点与BSA偶联的最佳条件为:pH=7.4,反应温度37 ℃,反应时间40 min,BSA浓度80 mg·L^-1,量子点浓度40 mg·L^-1。反应形成新的生物纳米复合材料,作为头孢曲松钠的磷光探针,其线性范围为0~30 μmol·L^-1,相关系数R=0.99,检出限为0.14 μmol·L^-1,相对标准偏差为1.63%。     

Multi-spectroscopic techniques to evaluate the toxicity of alloyed CdSeS quantum dots

Alloyed CdSeS quantum dots (QDs) were successfully synthesized in aqueous phase using microwave irradiation. UV–vis spectroscopy, fluorescence spectroscopy, transmission electron microscopy (TEM) and X-ray diffraction (XRD) techniques proved that the prepared alloyed QDs are composed of a CdSe-rich core and thick CdS shell with homogeneous size distributions. In order to study its biological toxicity, multi-spectroscopic techniques were adopted to investigate their conjugation with BSA. Fluorescence quenching methods indicated the prepared CdSeS QDs strongly quenched the fluorescence of BSA due to the formation of non-fluorescence ground-state complex. UV–vis absorbance spectra, synchronous fluorescence spectra and CD spectra further confirmed the alloyed CdSeS QDs binded with BSA and destroyed their hydrogen bonding networks, which induced the conformation changes of this macromolecule.     

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。     

Photostability comparison of CdTe and CdSe/CdS/ZnS quantum dots in living cells under single and two-photon excitations

The photostability is an outstanding feature of quantum dots (QDs) used as fluorescence probes in biological staining and cell imaging. To find out the related factors in the QD photostability, the photobleaching of naked CdTe QDs and BSA coated CdSe/CdS/ZnS QDs in human hepatocellular carcinoma (QGY) cells and human nasopharynx carcinoma (KB) cells were studied under single photon excitation (SPE) and two-photon excitation (TPE). In these two cell lines the cellular QDs were irradiated by a 405 nm continuous wave laser for SPE or an 800 nm femto-second (fs) laser for TPE. The QD photobleaching with the irradiation time was found to fit a biexponential decay. The fast decay plays a dominant role in the bleaching course and thus can be used as the parameter to quantitatively evaluate the QD photostability. The TPE decreased the QD photobleaching as compared to SPE. The BSA coated core/shell QDs had improved the photostability up to 4-5 times than the naked QDs due to the shielding effect of the QD shell. Therefore, it is better to use core/shell structured QDs as the fluorescence probe combining with a TPE manner for those long-term monitoring studies.     

Preparation of water-soluble CdTe/CdS core/shell quantum dots with enhanced photostability

CdTe/CdS core/shell quantum dots (QDs) have been synthesized in an aqueous phase using thioacetamide as a sulfur source. The quantum yield was greatly enhanced by the epitaxial growth of a CdS shell, which was confirmed by X-ray photoelectron spectroscopy (XPS) results. The quantum yield of as-prepared CdTe/CdS core/shell QDs without any post-preparative processing reached 58%. The experimental results illustrate that the QDs with core/shell structure show better photostability than thioglycolic acid (TGA)-capped CdTe QDs. The cyclic voltammograms reveal higher oxidation potentials for CdTe/CdS core/shell QDs than for TGA-capped CdTe QDs, which explains the superior photostability of QDs with a core/shell structure. This enhanced photostability makes these QDs with core/shell structure more suitable for bio-labeling and imaging.     

基于氢化物发生技术的CdSe量子点水相制备新方法研究及其用于银的高灵敏传感分析

报道了一种新型的利用氢化物发生技术水相合成高质量硒化镉量子点(CdSe QDs)的方法。通过将硼氢化钾与亚硒酸混合产生H_2Se气体,并将其可调控地引入到含镉溶液中,从而制备出化学性质稳定、荧光性能良好的CdSe量子点。所合成的量子点被成功应用于环境水样及细胞样品中痕量银的分析,分析检出限为0.005μg·mL~(-1),相对标准偏差小于2.7%(n=7),分析结果令人满意。该方法具有操作简单、稳定性好、灵敏度高、绿色环保等优点。     

CdS量子点超声水相制备、表征及与萘的相互作用

在室温条件下,用超声水相制备CdS量子点(QDs),并用透射电镜、X射线衍射、紫外光谱法、荧光光谱法等手段表征.探讨了初始pH、反应物配比、超声时间、熟化时间等因素对CdS量子点制备的影响.初步研究了该方法制备的CdS量子点与萘的相互作用,线性范围为0.002-0.025mg/mL,r<'2>=0.9965.CdS量子...     

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.     

含有量子点的双波长LED的光谱调控

本文通过对含有高In组分量子点的双波长LED进行了模拟计算, 并对器件的能带结构、载流子浓度、复合速率和辐射光谱进行了研究. 通过对器件结构的调整与对比, 发现蓝绿双波长LED的绿光量子阱中加入高In组分量子点后可以拓宽辐射光谱, 使LED光谱具有更高的显色指数, 为实现无荧光粉的白光LED提供指导. 量子点对载流子具有很强的束缚能力, 并且载流子在量子点处具有更短的寿命, 载流子优先在量子点处复合, 量子点处所对应的黄光与量子阱润湿层所对应的绿光的比例随量子点浓度的增大而增大, 载流子浓度较低时以量子点处的黄光辐射为主, 载流子浓度变大后, 量子点复合逐渐达到饱和, 绿光辐射开始占据主导. 对间隔层厚度和间隔层掺杂浓度的调节可以很方便地调控载流子的分布, 从而实现对含有量子点的双波长LED两个活性层辐射速率的调控. 结果表明, 通过对量子点浓度、间隔层厚度、间隔层掺杂浓度的控节可以很好地实现对LED辐射光谱的调控作用. 关键词： GaN 量子点 光谱调控 双波长LED     

Stability and luminescence properties of CsPbBr3/CdSe/Al core-shell quantum dots

To improve the stability and luminescence properties of CsPbBr₃ QDs, we proposed a new core-shell structure for CsPbBr₃/CdSe/Al quantum dots (QDs). By using a simple method of ion layer adsorption and a reaction method, CdSe and Al were respectively packaged on the surface of CsPbBr₃ QDs to form the core-shell CsPbBr₃/CdSe/Al QDs. After one week in a natural environment, the photoluminescence quantum yields of CsPbBr₃/CdSe/Al QDs were greater than 80%, and the PL intensity remained at 71% of the original intensity. Furthermore, the CsPbBr₃/CdSe/Al QDs were used as green emitters for white light-emitting diodes (LEDs), with the LEDs spectrum covering 129% of the national television system committee (NTSC) standard color gamut. The core-shell structure of QDs can effectively improve the stability of CsPbBr₃ QDs, which has promising prospects in optoelectronic devices.     

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.     

Effect of surface oxygen vacancy defects on the performance of ZnO quantum dots ultraviolet photodetector

The slower response speed is the main problem in the application of ZnO quantum dots (QDs) photodetector, which has been commonly attributed to the presence of excess oxygen vacancy defects and oxygen adsorption/desorption processes. However, the detailed mechanism is still not very clear. Herein, the properties of ZnO QDs and their photodetectors with different amounts of oxygen vacancy (V_O) defects controlled by hydrogen peroxide (H₂O₂) solution treatment have been investigated. After H₂O₂ solution treatment, V_O concentration of ZnO QDs decreased. The H₂O₂ solution-treated device has a higher photocurrent and a lower dark current. Meanwhile, with the increase in V_O concentration of ZnO QDs, the response speed of the device has been improved due to the increase of oxygen adsorption/desorption rate. More interestingly, the response speed of the device became less sensitive to temperature and oxygen concentration with the increase of V_O defects. The findings in this work clarify that the surface V_O defects of ZnO QDs could enhance the photoresponse speed, which is helpful for sensor designing.     

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。     

聚乙烯亚胺包覆的CdZnTe量子点荧光探针测定痕量Pb~(2+)

在水相中制备了聚乙烯亚胺(PEI)包裹的水溶性PEI-CdZnTe量子点。研究了反应时间,酸度及不同常见金属离子对PEI-CdZnTe量子点荧光效率的影响。基于Pb~(2+)对CdZnTe量子点具有选择性荧光猝灭作用,建立了用CdZnTe量子点为探针灵敏测定痕量Pb~(2+)的新方法。研究了不同浓度Pb~(2+)对CdZnTe量子点荧光强度猝灭情况,结果表明,Pb~(2+)对CdZnTe量子点的荧光猝灭过程可以很好地用Stern-Volmer荧光猝灭方程来描述。当Pb~(2+)浓度在0.05~3.0μg·mL~(-1)范围内,CdZnTe量子点的荧光强度F_0/F与Pb~(2+)浓度之间具有较好的线性关系,线性相关系数为0.998 8,检测限为0.01μg·mL~(-1)。该量子点荧光分析方法简便快速、灵敏度高、选择性好,能够应用于实际水样中Pb~(2+)的分析与测定。     

Studies on the interactions of fluorescent-magnetic nanocomposites with biomolecules and cells labeling

In this study, the fluorescent-magnetic nanocomposites were synthesized. The interactions between nanocomposites and bovine serum albumin (BSA) were studied by absorption and FL titration experiments. The experiments show that binding of nanocomposites and BSA may be caused by the formation of QDs-BSA complex. A magnetic separation method was designed to directly demonstrate the interactions between the surface of bifunctional nanocomposites with CdSe/CdS quantum dots (QDs) and biomolecules (BSA and DNA). The fluorescence (FL) labeling on the Escherchia coli (E. coli) cells was also successfully developed for studying the biolabeling of the bifunctional nanocomposites. The results directly reveal that the bifunctional nanocomposites can separate biomolecules and label cells. The studies we have performed showed that the fluorescent-magnetic nanocomposites are proved to be a kind of novel biofuctional materials, which can be used in bioseparation and biolabeling applications.