非荧光硫化锌纳米簇的合成与表征

合成硫化锌纳米簇并对其进行表征, 建立一种利用硫化锌纳米簇的阳离子交换(CX)反应检测痕量生物分子的方法。采用水热法合成非荧光硫化锌纳米簇(NCCs)并对其进行表征。纳米簇的性能直接影响检测结果。通过透射电镜图像和X射线衍射可知, 纳米簇是多孔的, 可以通过快速阳离子交换反应从纳米簇中释放大量的Zn2+, 在锌响应试剂的作用下产生荧光信号进行荧光检测。其晶体的外部比内部排列松散, 有利于快速阳离子交换, 其晶体尺寸大小与加热时间有关。通过比表面积检测法测定纳米簇的表面积和孔径表明, 最小的纳米簇拥有相对较大的表面积及较高的阳离子交换效率。实验了三种释放方法(酸溶解法、阳离子交换法和微波辅助阳离子交换法)对Zn2+释放性能的影响, 结果表明, 微波辅助阳离子交换法信噪比较高, 操作简便, 可用于硫化锌纳米簇免疫测定法中。比较了Zn2+的释放效率和目标结合力与平均直径之间的关系, 结果表明纳米簇尺寸为44 nm时表现出最高的阳离子交换效率。结论: 所有这些特点, 使ZnS纳米簇阳离子交换放大器在痕量生物分子检测方面成为高度灵敏、生物相容性好、低廉环保的检测工具。     

金纳米簇化学发光体外生物检测应用研究进展

金纳米簇是一种制备工艺简单、具有分子级尺寸和量子效应的新型发光材料,近年来在化学发光检测中得到了广泛应用,特别是较多应用于体外生物检测.本文综述了金纳米簇化学发光(含电化学发光)体系在体外生物检测中的应用进展.首先,阐释了金纳米簇的合成方法、结构、性质及其化学发光基本原理;其次,总结了国内外近年来基于该体系的体外生物检...     

DNA保护银纳米团簇的合成和应用

银纳米团簇因其独特的与尺寸相关的光、电、磁和催化性能,引起了相关研究人员的高度关注,我们团队一直专注于研究用基于DNA保护的银纳米团簇监测DNA、Hg2+和巯基化合物。发现发生在DNA/银纳米复合物与G-四链体/血红素之间光诱导电子转移(PET),伴随着DNA/银纳米荧光减弱。这一新的PET系统使目标生物分子,如DNA和敏感性高的ATP获得特异性和多样性的检测。首次提出一种以DNA单体作为支架的高产率银纳米簇的合成方法。在这项研究中,采用密度泛函计算理论解释了DNA保护的银纳米团簇的形成机理以及为什么富胞嘧啶DNA是荧光银纳米簇的良好支架。研究结果对DNA保护荧光银纳米簇进一步实验和理论研究提供了基本指导思想,最终可能有助于程序化合成具有光致发光性能的DNA稳定银纳米团簇。     

阳离子交换增强β-NaGdF_4∶Yb~(3+),Tm~(3+)纳米晶近红外发光

为了增强β-Na Gd F4∶Yb3+,Tm3+纳米晶的上转换发光,克服外延增长钝化壳增大尺寸的不足,利用阳离子交换法制备核壳纳米结构,研究了样品在980 nm激发下的上转换发光性质。首先,利用高温热分解法制备了直径为10 nm的β-Na Gd F4∶Yb3+,Tm3+纳米晶;然后,将制备的纳米晶与Gd3+在油酸-十八烯混合溶液中在300℃进行交换反应。实验结果表明,随着表面Yb3+和Tm3+被Gd3+取代,钝化壳的形成抑制了内部Yb3+的表面去激发过程,增强了内部Yb3+(2F5)→Tm3+(3H5,3F2,3)的能量传递,上转换发光逐渐增强。交换30min后,Tm3+的3H4→3H6近红外发光增强达到最大,为对照样品的6.5倍,而尺寸基本保持不变。在生物成像方面,上转换纳米晶的尺寸必须与生物分子相匹配,同时发光强度要高,阳离子交换法既能增强近红外发光,又能保持原来小的尺寸,在生物成像领域具有很好的应用前景。     

CdS纳米粒子的微波法制备及其光谱特性研究

用微波法以硫代乙酰胺为硫源,成功合成了CdS纳米粒子。透射电子显微镜(TEM）对合成的CdS纳米粒子的表征结果为粒径约12 nm, 粒径分布较为均匀,分散性较好。研究了微波功率、pH值、反应时间等因素对其吸收光谱,荧光光谱和粒径的影响。结果表明,在微波功率为30％、初始反应pH 9.0、微波反应时间为25 min时,可合成质量较高的CdS纳米粒子。比较了以硫代乙酰胺、硫脲和硫化钠为硫源合成的CdS纳米粒子,结果表明,以硫代乙酰胺为硫源合成的CdS纳米粒子荧光带边发射强,缺陷发射弱,荧光性质较好;而以硫脲为硫源合成的CdS纳米粒子荧光边带发射弱;以硫化钠为硫源合成的CdS纳米粒子荧光以缺陷发射为主。铜离子在6.4～512 μg·L-1范围内对该纳米粒子荧光的猝灭呈现良好线性, 可用于痕量铜离子的测定。     

CdTe纳米晶及层状纳米晶薄膜的生长及其光荧光性质

用湿化学法在水溶液中合成了单分散的、大小尺寸可控的、巯基包裹的胶体CdTe纳米晶体,并利用CdTe纳米晶体和双功能分子poly（diallyldimethylammonium chloride）（PDDA）在Si衬底表面自组织生长了有序的层状纳米晶薄膜,荧光光谱研究了层状纳米晶体之间的共振能量迁移过程.结果表明：层状自组织生长的样品中纳米晶粒的间隔几乎一样,表明它们是有序排列的;而用直接干燥形成的样品中,小尺寸和大尺寸的纳米晶体之间间隔较短,发生荧光共振能量迁移,较小尺寸的纳米晶粒荧光峰（即波长较短处的晶 关键词： CdTe纳米晶体 量子限制效应 共振能量迁移     

2017年10期电子期刊

为了增强β-NaGdF₄：Yb³⁺,Tm³⁺纳米晶的上转换发光,克服外延增长钝化壳增大尺寸的不足,利用阳离子交换法制备核壳纳米结构,研究了样品在980 nm激发下的上转换发光性质。首先,利用高温热分解法制备了直径为10 nm的β-NaGdF₄：Yb³⁺,Tm³⁺纳米晶;然后,将制备的纳米晶与Gd³⁺在油酸-十八烯混合溶液中在300℃进行交换反应。实验结果表明,随着表面Yb³⁺和Tm³⁺被Gd³⁺取代,钝化壳的形成抑制了内部Yb³⁺的表面去激发过程,增强了内部Yb³⁺（²F₅）→ Tm³⁺（³H₅,³F_2,3）的能量传递,上转换发光逐渐增强。交换30 min后,Tm³⁺的³H₄ →³H₆近红外发光增强达到最大,为对照样品的6.5倍,而尺寸基本保持不变。在生物成像方面,上转换纳米晶的尺寸必须与生物分子相匹配,同时发光强度要高,阳离子交换法既能增强近红外发光,又能保持原来小的尺寸,在生物成像领域具有很好的应用前景。     

氧化硅层中的锗纳米晶体团簇量子点

采用氧化和析出的方法在氧化硅中凝聚生成锗纳米晶体量子点结构. 其形成的锗晶体团簇没有突出的棱角和支晶结构，锗晶体团簇的轮廓较圆混，故可以用球形量子点模型来模拟实际的锗晶体团簇. 对比了在长时间退火氧化条件下和在短时间退火用激光照射氧化条件下所生成的锗纳米晶体结构的PL光谱和对应的锗纳米晶体团簇的尺寸分布. 短时间退火氧化条件下生成的锗纳米晶体较小(3.28—3.96nm)，长时间退火用激光照射氧化条件下所生成的锗纳米晶体较大(3.72—4.98nm)；其分布结构显示某些尺寸的锗纳米晶体团簇较稳定，适当的氧化条件可以得到尺寸分布范围较窄的锗纳米晶体团簇. 用量子点受限模型计算了锗纳米晶体团簇的能隙结构，用Monte Carlo方法模拟了PL光谱和对应的锗纳米晶体团簇的尺寸分布，分别与实验结果符合较好. 关键词： 锗晶体团簇 纳米晶体 量子点 激光照射     

组氨酸、谷胱甘肽混合修饰金纳米团簇的光稳定性研究

金纳米团簇(简称金簇)由几到几百个金原子及修饰试剂组成,由于其尺寸接近于电子费米波长,表现出良好的发光特性及生物相容性,是一类新型纳米标记探针。目前,金纳米团簇在生物检测、细胞成像、癌症诊断及治疗等领域受到研究者的广泛关注。然而,对于光照条件下金簇的稳定性还不清楚。在合成组氨酸、谷胱甘肽混合修饰金簇的基础上,系统研究了光照条件下金簇在不同pH(5.0,7.4和9.0)的荧光变化规律,结果表明,在氙灯强光照射下,金纳米团簇的荧光会随着照射时间的增加逐渐降低,在pH 9.0条件下比pH 5.0及7.4时降低更快,说明金簇在pH 5.0及7.4时光稳定性更好。在此基础上,采用紫外-可见吸收光谱、红外光谱等手段研究了光照前后金簇表面基团的变化规律,发现光照后金簇的紫外可见吸收光谱及红外光谱均发生了明显的变化,说明光照导致金簇表面修饰基团发生了变化。当向体系中通入氮气后,金簇最大发射波长处荧光强度随照射时间的变化明显变慢,说明金簇表面基团与溶液中溶解氧发生了反应,导致金簇表面电荷及修饰试剂状态发生变化,从而导致金簇荧光产生猝灭。相关研究结果对于金纳米团簇在生命科学及分析化学等领域的进一步应用具有一定的参考价值。     

基于聚腺嘌呤单链DNA-金纳米簇的荧光法高灵敏快速检测汞离子

聚腺嘌呤-金纳米簇（聚A-AuNCs）制备简单,快速,且具有优良的荧光性能和光学稳定性。基于聚A单链DNA为模板合成的金纳米簇,构建了一种灵敏、简单、快速的新传感方法用于检测汞离子。以柠檬酸钠为还原剂,通过水浴加热法合成金纳米簇。用荧光光谱仪和透射电镜对金纳米簇的荧光性能和微观形貌进行了表征。结果表明：合成的金纳米簇为球形,分散性良好,平均粒径约为7 nm。金纳米簇在280 nm紫外光激发下,于471 nm处发射出强烈的蓝色荧光,且金纳米簇的光学稳定性良好。溶液在4 ℃下避光保存1个月,金纳米簇的荧光强度变化很小。当汞离子存在时,汞离子与纳米金之间的高亲和力,可以有效地猝灭金纳米簇的荧光。文中讨论了反应体系中缓冲溶液pH值和反应时间对传感器性能的影响,发现缓冲溶液pH值对该方法的影响不大。汞离子对金纳米簇的荧光猝灭反应非常迅速,1 min之内就可以完成,所以后续反应仅需简单的混合即可进行荧光的测定。在最优化实验条件下,对一系列汞离子浓度进行了检测,线性方程为：y=-335.57x+541.35,检测线性范围在0.01~1 μmol·L-1之间,相关系数为0.992 6。根据空白的三倍标准偏差原则确定检测下限为3 nmol·L-1。该方法选择性好,通过9种金属离子的加入对金纳米簇的荧光信号并无明显影响,验证了金纳米簇对汞离子检测的特异性。用该方法检测了环境水样中的汞离子,加标回收率在95.33％~103.8％之间,相对标准偏差（RSD）不大于4%,可用于实际样品中Hg2+的检测。该法仅需将溶液简单混合即可实现对汞离子的检测,具有操作简便、快速、灵敏度高和选择性好等优点。     

Synthesis of ZnS nanoparticles on a solid surface: Atomic force microscopy study

In this work, zinc sulfide (ZnS) nanoparticles had been synthesized on DNA network/mica and mica surface, respectively. The synthesis was carried out by first dropping a mixture of zinc acetate and DNA on a mica surface for the formation of the DNA networks or zinc acetate solution on a mica surface, and subsequently transferring the sample into a heated thiourea solution. The Zn²⁺ adsorbed on DNA network/mica or mica surface would react with S²⁻ produced from thiourea and form ZnS nanoparticles on these surfaces. X-ray diffraction and atomic force microscopy (AFM) were used to characterize the ZnS nanoparticles in detail. AFM results showed that ZnS nanoparticles distributed uniformly on the mica surface and deposited preferentially on DNA networks. It was also found that the size and density of ZnS nanoparticles could be effectively controlled by adjusting reaction temperature and the concentration of Zn²⁺ or DNA. The possible growth mechanisms have been discussed in detail.     

Zinc sulfide nanoparticles: Spectral properties and photocatalytic activity in metals reduction reactions

Formation of zinc sulfide nanocrystals in aqueous solutions of various polymers has been studied. Spectral properties of ZnS nanoparticles have been investigated, the structure of the long-wave edge of the fundamental absorption band of ZnS nanocrystals has been analyzed. It has been shown that the variation of the synthesis conditions (stabilizer nature and concentration, solution viscosity, ZnS concentration, etc.) allows tailoring of the ZnS nanocrystals size in the range of 3–10 nm. Photochemical processes in colloidal ZnS solutions, containing zinc chloride and sodium sulfite, have been investigated. It has been found that the irradiation of such solutions results in the reduction of Zn(II), the rate of this reaction growing at a decrease in the size of ZnS nanoparticles. Kinetics of photocatalytic Zn(II) reduction has been studied. It has been concluded that two-electron reduction of adsorbed Zn(II) species is the rate-determining stage of this reaction. Photocatalytic activity of ZnS nanoparticles in KAu(CN)₂ reduction in aqueous solutions has been discovered. Spectral characteristics and kinetics of ZnS/Au⁰ nanocomposite formation have been studied. It has been shown that the photoreduction of gold(I) complex is the equilibrium reaction due to the reverse oxidation of gold nanoparticles by ZnS valence band holes.     

Photoluminescence of Cu:ZnS, Ag:ZnS, and Au:ZnS nanoparticles applied in Bio-LED

In this work, transition elements, including Cu²⁺, Ag⁺, and Au³⁺, were used to dope in zinc sulfide (ZnS) by chemical solution synthesis to prepare Cu:ZnS, Ag:ZnS, and Au:ZnS nanoparticles, respectively. Transition elements doping ZnS nanoparticles form the electronic energy level between the conduction band and valance band, which will result in the green light emission. There is a zinc sulfide emission shift from blue (~3.01 eV) to green light (~2.15 eV). We also found that Au:ZnS nanoparticles will emit a green light (~2.3 eV) and a blue light (~2.92 eV) at the same time because the mechanism of blue light emission was not broken after Au element had been doped. Furthermore, we used sodium chlorophyllin copper salt to simulate chlorophyll in biological light emission devices (Bio-LED). We combined copper chlorophyll with Cu:ZnS, Ag:ZnS, and Au:ZnS nanoparticles by a self-assembly method. Then, we measured its photoluminescence spectroscopy and X-ray photoelectron spectroscopy to study its emission spectrum and bonding mode. We found that Au:ZnS nanoparticles are able to emit green and blue light to excite the red light emission of copper chlorophyll, which is a potential application of Bio-LED.     

氧化锌荧光粉合成的热力学计算

六面体的ZnO:Zn,因其具有较高的导电率和光电导特性,故在低能的电子激发下就能发光,目前已广泛地被用为低压显示器件的发光层涂料.ZnO:Zn的发光机理,早就有学者提出了一些假设,有的认为它的绿色发光是由过量锌引起的,也有认为是过量的锌和氧的空位存在所致.总之,ZnO:Zn之所以会发光.     

A detailed study of physical properties of ZnS quantum dots synthesized by reverse micelle method

In this article, zinc sulfide nanocrystal quantum dots were synthesized by reverse micelle method using polyvinyl pyrrolidone as surfactant. The various crystallite properties of these nanocrystals such as, size, d-spacing, lattice parameter, microstrain, intrinsic stress, X-ray density, specific surface area, dislocation density, porosity, and agglomeration number have been analyzed using X-ray diffraction spectrum. The transmission electron microscopy was used to calculate the size and monitoring morphology of the nanocrystals, while the scanning electron microscopy was utilized to investigate the surface morphology of nanoclusters. The various optical properties of zinc sulfide quantum dots such as absorption coefficient, extinction coefficient, optical band gap energy, Urbach energy, and threshold wavelength have been analyzed using UV-visible data. The photoluminescence was used to study the emission spectra of produced ZnS quantum dots. Moreover, Furrier Transform-Infrared studies revealed that ZnS quantum dots are pure.     

Mercaptopropionic acid capped CdSe/ZnS quantum dots as fluorescence probe for lead(II)

MPA stabilized CdSe/ZnS NCs was applied as a fluorescent probe for the sensitive detection of Pb²⁺ in water. The microreaction was demonstrated as a facile method for the reproducible synthesis of CdSe/ZnS NCs with a high quantum yield. The good stability of CdSe/ZnS NCs was proved by the significant maintaining of photoluminescent (PL) after the ligand exchange with MPA, and was further demonstrated by the excellent PL property in water solution with various pH values. The cation exchange of Zn with Pb led to the linear quenching of PL with the concentration of Pb²⁺, which provided as an opportunity to apply MPA stabilized CdSe/ZnS NCs as fluorescent probes for Pb²⁺. A facile method by adjustment of QDs concentration was demonstrated as a suitable way to approach different detection limits. The detection limits of 0.03 and 3.3 μM were achieved by setting QDs solutions with the absorbance of the first exciton peak as 0.05 and 0.15, respectively.     

Study of optical and thermal properties in nickel doped ZnS nanoparticles using surfactants

The presence of surfactants polyethylene glycol (PEG), polyvinyl pyrrolidone (PVP), sodium hexameta polyphosphate (SHMP) and tri-octyl phosphine oxide (TOPO) on the surface of Ni²⁺ doped ZnS (ZnS:Ni²⁺) nanoparticles resulted variation in their optical properties. The optical properties of each surfactant-capped ZnS:Ni²⁺ nanoparticles were investigated using UV–visible (UV–Vis) absorption and photoluminescence (PL) techniques. The absorption spectra and fluorescent emission spectra showed a significant blue shift compared to that of the bulk zinc sulfide. The effect of the optical properties in colloidal form (wet) and dry samples were investigated. Enhanced PL emission was observed for the dry samples at 80 °C. Thermal properties of the ZnS:Ni²⁺ was also studied using thermo gravimetric-differential thermal analysis (TG-DTA), Fourier transform infra-red spectrometer (FT-IR) and X-ray diffraction (XRD). The results are presented and discussed.     

Inhibition effects of protein-conjugated amorphous zinc sulfide nanoparticles on tumor cells growth

In this article, a facile and environmentally friendly method was applied to fabricate BSA-conjugated amorphous zinc sulfide (ZnS) nanoparticles using bovine serum albumin (BSA) as the matrix. Transmission electron microscopy analysis indicated that the stable and well-dispersed nanoparticles with the diameter of 15.9 ± 2.1 nm were successfully prepared. The energy dispersive X-ray, X-ray powder diffraction, Fourier transform infrared spectrograph, high resolution transmission electron microscope, and selected area electron diffraction measurements showed that the obtained nanoparticles had the amorphous structure and the coordination occurred between zinc sulfide surfaces and BSA in the nanoparticles. In addition, the inhibition effects of BSA-conjugated amorphous zinc sulfide nanoparticles on tumor cells growth were described in detail by cell viability analysis, optical and electron microscopy methods. The results showed that BSA-conjugated amorphous zinc sulfide nanoparticles could inhibit the metabolism and proliferation of human hepatocellular carcinoma cells, and the inhibition was dose dependent. The half maximal inhibitory concentration (IC50) was 0.36 mg/mL. Overall, this study suggested that BSA-conjugated amorphous zinc sulfide nanoparticles had the application potential as cytostatic agents and BSA in the nanoparticles could provide the modifiable site for the nanoparticles to improve their bioactivity or to endow them with the target function.     

Synthesis and Characterization of Surface Modified,Fluorescent and Biocompatible ZnS Nanoparticles with a Hydrophobic Chitosan Derivative

The introduction of a hydrophobic moiety on chitosan enhances the self-assembling properties, mucoadhesion, the permeability of the macromolecule and aids in target specific delivery. Our group synthesized a hydrophobic trans N-(6,6-Dimethyl-2-hepten-4-ynyl)chitosan derivative (CSD) and studied the surface modification of ZnS nanoparticles in a single pot reaction. X-ray diffraction studies and FESEM imaging confirms the nano size and morphology of the surface modified Zinc sulfide nanoparticles (ZnS-CSD NPs). The proposed ZnS-CSD NPs showed excellent emission at 457 nm. Photostability studies indicate that the surface modified ZnS-CSD NPs possess better photostability than Rhodamine B and FITC. Cell viability tests confirmed the biocompatibility of the modified nanoparticles. All these features of ZnS- CSD NPs makes these candidates an excellent choice in a wide range of in vitro or in vivo studies as fluorescent biological labels.     

Optical measurements of ZnS nanoparticles aqueous solution

We synthesized zinc sulfide (ZnS) nanopowders with size ranging from 2 to 100 nm by a simple, low-cost, and mass production chemical method. The nanoparticles (NPs) were characterized by X-ray powder diffraction (XRD), atomic force microscopy (AFM), transmission electron microscopy (TEM), and UV-vis absorption spectroscopy. Our study concerns also the change in the refractive index of deionized water in presence of ZnS nanospheres. We present experimental results on effective index variation of water dispersed ZnS NPs at different wavelengths in visible spectrum.