铜(Ⅱ)配合物与DNA作用的光谱法研究

采用紫外光谱和荧光光谱研究了配离子[Cu(A)₂]2＋(其中A=邻菲络啉(phen),联吡啶(bpy),乙二胺(en))与小牛胸腺DNA的相互作用。实验发现配合物的存在使DNA碱变性的pH增大,变性后增色效应减小。EB-DNA体系的荧光强度随[Cu(phen)₂]2＋的加入迅速减弱。在DNA存在下,配离子被猝灭剂[Fe(CN)₆]4-的发光猝灭程度减小。进一步研究了配体分子平面的大小对配合物与DNA作用的影响。结果表明,铜配合物与DNA之间发生了插入作用,且该作用随配体芳环平面的减小而减弱, 即[Cu(phen)₂]2＋＞[Cu(bpy)₂]2＋＞[Cu(en)₂]2＋。     

钌多吡啶配合物与DNA相互作用的发光动力学分析

采用三能级模型,对六种钌多吡啶配合物[Ru(L)₂(R)]2+(L=bpy,phen,bpy=2,2’-联吡啶, phen=1,10-邻菲咯啉,R=7-CH₃-dppz,7-F-dppz,dpbpd(NH₂)₂)水溶液与小牛胸腺DNA相互作用的时间分辩发光光谱进行对比分析,讨论了取代基对配合物与DNA作用时方式的影响。结果表明:(1) 六种配合物与DNA作用存在侧面插入方式和垂直插入方式,其中垂直插入方式的权重较大;(2) 取代基的性质对两种作用方式的权重有重要影响。上述结论为进一步研究配合物分子与DNA的相互作用的机理提供了动力学依据。     

应用ICP-MS测定两种氮肥中重金属含量

肥料中的重金属可以通过作物直接进入人类食物链对人体产生危害,研究肥料中重金属含量对于农产品安全溯源意义重大。选用北京市场上销售的硫酸铵(NH₄)₂SO₄和尿素CO(NH₂)₂两种氮素肥料作为实验材料,分析了其中的10种有害重金属元素含量。(NH₄)₂SO₄中重金属含量分别是：Al 1 345.13 ng·g-1,Ti 35 120 μg·g-1,Cr 2 539.27, Ni 287.26, Cu 674.05, Zn 270.79, As 42.54, Cd 22.13, Hg 27.20和Pb 123.87 ng·g-1;CO(NH₂)₂中的含量分别是71.59 ng·g-1,5 360 μg·g-1,1 167.71, 188.60, 7.46, 64.45, 10.55, 0.00, 0.09和3.71 ng·g-1。上述结果表明：CO(NH₂)₂氮肥中有害金属含量非常低,尤其是Cd, Hg和Pb含量在10 ng·g-1以下,只有Cr的含量超过1.00 μg·g-1;与CO(NH₂)₂ 相比,(NH₄)₂SO₄中重金属含量虽然符合相关标准,但大部分重金属含量都是CO(NH₂)₂的几十倍,如果长期使用会对土壤环境和农产品安全造成一定影响。所以在施用氮肥时应当尽量选用CO(NH₂)₂。(NH₄)₂SO₄和CO(NH₂)₂中重金属含量差别可能与两种肥料的生产原料和工艺有关。     

氧氟沙星和左氧氟沙星与DNA的相互作用研究

采用紫外光谱、荧光光谱、荧光偏振以及K₃Fe(CN)₆荧光猝灭实验研究了氧氟沙星(Ofloxacin,OFLX)和左氧氟沙星(Levofloxacin,L-OFLX)与小牛胸腺DNA(ctDNA)的相互作用差异性与作用模式。紫外光谱的结果表明,当向OFLX和L-OFLX溶液中加入ctDNA并且浓度增大时,OFLX和L-OFLX的吸收光谱都呈现略微的减色效应,但吸收峰位置没有发生偏移,L-OFLX的减色效应略强于OFLX的减色效应;从荧光光谱以及OFLX和L-OFLX的Scatchard方程,获得其键合常数分别为1.15×105 L·mol-1,3.75×105 L·mol-1,表明L-OFLX与ctDNA的相互作用要略强于OFLX与ctDNA的相互作用;荧光偏振实验、单双链ctDNA与药物作用实验、K₃Fe(CN)₆荧光猝灭实验都表明OFLX、L-OFLX与ctDNA的作用模式可能是沟槽结合。     

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。     

桑色素修饰金纳米粒子自组装膜的制备及其性能研究

采用水相硅烷化方法,将γ-氨基丙基三乙氧基硅烷[H₂N(CH₂)₃Si(OC₂H₅)₃](APES)组装在石英表面,在基底表面修饰上氨基为末端的单层膜,并进一步在这种功能化的单层膜基底上组装金纳米粒子得到金纳米粒子/APES/石英的纳米复合结构。以制备的金纳米粒子自组装膜修饰石英为基底及DL-半胱胺酸为中介,利用桑色素(Morin)和DL-半胱胺酸的化学吸附作用,将桑色素间接组装在金纳米粒子自组装膜修饰石英基底表面,所构建的桑色素修饰金纳米粒子自组装膜对三苯基锡有灵敏的荧光识别作用。文章着重研究了桑色素修饰金纳米粒子自组装膜的制备以及组装条件对其荧光行为的影响,探讨了膜的响应特性及响应机理。     

拉曼光谱法研究纳米结构多孔ZnO微球的合成机理

利用拉曼光谱方法,对柠檬酸钠辅助水热合成纳米结构多孔ZnO微球的机理进行了研究。样品的拉曼光谱特征显示,多孔ZnO微球中存在Zn-柠檬酸配合物;分析表明反应溶液中柠檬酸钠水解产生的柠檬酸根与Zn2+结合形成Zn-柠檬酸配合物,该配合物化学吸附在Zn(OH)₂晶核的(204)和(503)晶面,使Zn(OH)₂晶核择优生长形成纳米薄片状结构;水热过程中Zn(OH)₂微晶团聚形成纳米片状结构多孔Zn(OH)₂微球并以沉淀析出。研究发现吸附在薄片表面的Zn-柠檬酸配合物提高了Zn(OH)₂微晶的热稳定性,使得Zn(OH)₂的分解温度高于200 ℃,加热到300 ℃后Zn(OH)₂完全分解获得纳米结构多孔ZnO微球。     

原子吸收光谱法间接研究碱式胱氨酸锌的配合反应

在研究原子吸收间接测定胱氨酸(Cystine, Cys-Cys)时,发现胱氨酸与锌离子在碱性条件下能形成可溶性碱式胱氨酸锌配合物,并在pH 9.4左右时达到最大浓度,经编程计算不同pH下的胱氨酸和锌离子的各种存在形式和分析了拟合分布图,指出在pH 9.4左右时,所形成的可溶性碱式胱氨酸锌配合物是由显电中性的Cys-Cys+-,-1价的Cys-Cys-和-2价的Cys-Cys2-,这三种胱氨酸基同时均可以与Zn(OH)₂配位形成三种可溶性碱式胱氨酸锌配合物,其分子式为[(COO-)CH(NH+₃)CH₂S—SCH₂CH(NH+₃)COO-]Zn(OH)₂, [(COO-)CH(NH+₃)CH₂S—SCH₂CH(NH₂)COO-]Zn(OH)₂,[(COO-)CH(NH₂)CH₂S—SCH₂CH(NH₂)COO-]Zn(OH)₂。理论计算分析的结果与实验数据得到了很好的吻合,并确定了硫化锌法原子吸收间接测定胱氨酸时的配合物反应机理。     

长方体形CdS微粒的合成及光谱性质

采用溶胶法,以硫脲为表面修饰剂,合成了长方体形CdS微粒,并用X射线粉末衍射、透射电子显微镜、红外光谱以及荧光光谱等手段进行了表征。实验结果表明,硫脲分子中的硫原子与CdS纳米晶表面的Cd2+离子存在配位作用;硫脲分子表面修饰的CdS纳米晶为立方闪锌矿结构,具有较好的荧光性质;长方体形CdS微粒可能是由硫脲分子表面修饰的CdS初级纳米晶粒自组装组成。该研究结果为硫脲分子表面修饰的CdS初级纳米晶粒在分子组装及作为新型发光材料方面的进一步研究奠定了基础。     

三种不同的钒氧簇合物的合成和光谱研究

利用水热法合成了三种钒氧簇合物：[{Ni(phen)₂}₂V₄O₁₂]H₂O (Ⅰ),[N(CH₂CH₂)₃NH]Na(H₂O)₆{K₄(H₂O)₄ [V₁₀O₂₈]}(H₂O)₄ (Ⅱ)和[(CH₃)₄N]₆[V₁₅O₃₆Cl] (Ⅲ)。通过用FTIR, UV-Vis DRS和荧光光谱研究了它们的结构和性能的关系。FTIR研究表明,化合物的相关基团的特征振动吸收峰和其结构相关。化合物Ⅰ的固体紫外漫反射光谱在200, 230, 260和350 nm出现四个宽峰,分别对应O_t→V, O_μ→Ni,O_μ→V荷移和phen的π-π*跃迁。文章还对这三个钒氧簇合物的荧光光谱进行了研究。最后,应用Gaussian98的量子化学计算,说明化合物Ⅰ的结构特点。     

Mechanism of fluorescence energy transfer in aqueous solution cadmium sulfide quantum dots

Cadmium sulfide (CdS) quantum dots (QDs) prepared by a convenient chemical method have been characterized using absorption, fluorescence, and photoluminescence excitation techniques. The photoluminescence excitation studies show that there is an electron transfer from the surface adsorbate (thiourea) to CdS QDs in aqueous solution. The excitation band with peak maximum at 5.8 eV is assigned to the electronic transitions in the chemisorbed thiourea, whereas the excitation band between 3.45 and 3.7 eV corresponds to the band-to-band transition within the nanocrystalline CdS host. The absorption spectroscopy of the CdS QD solutions shows a strong absorption peak which is generated from thiourea. The band-edge fluorescence of the CdS QDs has also been investigated. It is shown that the fluorescence property of the CdS QDs can be enhanced by adding cadmium chloride (CdCl₂) solution.     

Cadmium (II) pyrrolidine dithiocarbamate complex as single source precursor for the preparation of CdS nanocrystals by microwave irradiation and conventional heating process

The complex of cadmium with pyrrolidine dithiocarbamate Cd(pdtc)₂ has been used as single source precursor for the synthesis of CdS nanoparticles. The formation of CdS nanostructures was achieved by thermal decomposition of the complex under microwave irradiation and conventional heating in presence of hexadecylamine. The CdS nanoparticles with disordered close-packed structure were obtained under microwave irradiation, whereas wurtzite hexagonal phase CdS nanorods were obtained by conventional heating method (up to 150 °C). Scanning electron microscopy (SEM), energy dispersive X-ray analysis (EDX) and high resolution transmission electron microscopy (HRTEM) studies also were carried out to study the structure and morphology of nanoparticles. The optical property of the CdS nanoparticles was studied by UV-visible and fluorescence emission spectral studies. Fluorescence measurements on the CdS nanoparticles show a strong emission spectrum with two sub bands that are attributed to band-edge and surface-defect emissions. The reduction of a suitable cadmium metal complex is considered to be one of the single pot methods to generate CdS semiconductor nanoparticles with different shapes and high yield.     

The effect of solvent on the crystal structure and size distribution of cadmium sulfide nanocrystals

CdS nanocrystals with different structures were synthesized by the method of solution precipitation using thiourea and cadmium acetate as starting materials in different solvents: water, methanol and N,N-dimethylformamide (DMF). Our results show that the solvent has direct effect on the structure and size of the final nanoparticles. It was found that using DMF, as a solvent, results in producing smaller nanoparticles with the cubic structures, while using the other solvents gives rise to larger nanoparticles with the hexagonal structure. It was also found that using heat during washing the precipitate results in a more homogenous size distribution of CdS nanocrystals. On the basis of our experimental results we also suggest a critical structure transformation size.     

An approach to hybrid inorganic nanoparticles in reactive PS-b-PMSMA amphiphilic copolymers

A series of well-defined amphiphilic poly(styrene)-block-poly 3-(trimethoxysilyl) propyl methacrylate (PS-b-PMSMA) copolymers with controlled molecular weight and block length were prepared by the atom transfer free radical polymerization. The cadmium sulfide (CdS) nanoparticles were fabricated in the spherical micelles self-assembled from these prepared PS-b-PMSMA copolymers. Then, the CdS/PS-b-PMSMA films were obtained by spin coating the CdS/PS-b-PMSMA solution on silicon wafer. The experimental results showed the addition of Cu(II) could decrease the value of polydispersity index for the prepared copolymers. Nuclear magnetic resonance and Fourier transform infrared spectra showed the synthesis of PS-b-PMSMA copolymer. The average roughness and mean square roughness of the prepared CdS/PS-b-PMSMA films obtained from the atomic force microscopy analysis were 3.0–3.4 nm and 1.7–2.0 nm, respectively, indicating the excellent surface planarity. On the other hand, the ratio of block length between PS and PMSMA had a great influence on the micelle size. The larger ratio of PS to PMSMA block length resulted in the larger size of micelles and CdS nanoparticles that caused a red-shift of ultraviolet–visible and photoluminescence spectra. The red-shift of spectra was explained by the quantum confinement effect associated with the tiny size of the CdS nanoparticles.     

水溶性CdTe/CdS纳米晶表面SiO2壳层的反相胶束法包覆

"提出了一种水相中制备CdTe/CdS核壳结构纳米粒子的方法.用Te粉作为碲源,用Na2S作为硫源,在50 ℃下制备了CdTe/CdS核壳结构纳米粒子. 用紫外可见吸收光谱和荧光光谱分析了CdS壳层对CdTe核的影响. 随CdS壳层厚度的增加,紫外可见吸收光谱和荧光光谱均发生了红移. CdS壳层厚度较薄时,CdTe/CdS纳米晶的荧光强度较CdTe纳米粒子有显著提高;而CdS壳层厚度较厚时,CdTe/CdS纳米晶的荧光强度会逐渐降低. 用反相胶束法在CdTe/CdS核壳结构纳米粒子的表面包被一层SiO2,     

Ammonia-free method for synthesis of CdS nanocrystalline thin films through chemical bath deposition technique

The preparation of thin films of CdS by chemical bath deposition is mostly based on the utilisation of ammonia as a complexing agent for cadmium ions. Here we report on a technique based on sodium citrate dihydrate that eliminates the problems of ammonia volatility and toxicity. The crystallites with a size range of 10–20 nm in diameter with zinc blend (cubic) and wurtzite (hexagonal) crystal structures and strong photoluminescence were prepared from the mixture solutions of: cadmium chloride dihydrate as a cadmium source, thiourea as a sulfur source and sodium citrate dihydrate as a complexing agent for cadmium ions. The well-cleaned glass used as a substrate for thin film deposition. The obtained samples were characterized by the techniques such as transmission electron microscopy (TEM), X-ray diffraction (XRD), atomic force microscope (AFM) and fluorescence spectroscopy. Also, the effect of two operating conditions, (i) pH, and (ii) the temperature of reaction on the synthesizing of CdS nanocrystals was examined. Finally, it was found that the CdS nanocrystals showed sharp excitation features and strong ”band-edge” emission.     

Controlled synthesis, characterization and optical properties of CdS nanocrystalline thin films via chemical bath deposition (CBD) route

In this study, the CdS nanocrystalline thin films obtained from an ammonia-free chemical bath deposition process. The crystallites with a size range of 10–20 nm in diameter with zinc blend (cubic) and wurtzite (hexagonal) crystal structure and strong photoluminescence were prepared from the mixture solutions of: cadmium chloride dihydrate as a cadmium source, thiourea as a sulfur source and sodium citrate dihydrate as a complexing agent for cadmium ions. The well-cleaned glass used as a substrate for thin films deposition. The obtained samples were characterized by the techniques such as scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD), X-ray photoelectron spectra (XPS), atomic force microscopy (AFM) and fluorescence spectroscopy. Also, the effect of two parameters such as pH and temperature of reaction on the synthesis of CdS nanocrystals was studied. Finally, it was found the CdS nanocrystals showed sharp excitation features and strong “band-edge” emission.     

CdS/ZnO纳米复合结构制备及荧光特性研究

为增强CdS纳米粒子的荧光强度,以及稳定性,研究了Cd,S不同质量比,有无稳定剂等条件下CdS纳米粒子的制备及荧光特性。在碱性条件下,利用水热法合成了CdS/ZnO的纳米复合结构,并对所有样品进行了XRD、荧光光谱和SEM表征。测试结果表明所制备的CdS纳米粒子和CdS/ZnO的纳米复合结构粒子成分单一且纯净;ZnO复合在CdS表面;在紫外光(328.5 nm)激发下,CdS/ZnO纳米复合结构的发射峰位于463 nm处,峰形窄而对称,CdS/ZnO纳米复合结构的荧光强度比CdS纳米粒子的荧光强度有显著增强,且CdS和ZnO物质量之比为1∶1条件下,荧光强度最高,其荧光效率比单一CdS纳米粒子高出11%。通过第一性原理计算结果表明,CdS能带结构中,Cd-4d,S-3p和Cd-5s能带分别由5条、3条和1条能级构成,对比不同轨道的分态密度强度,看出CdS的导带边主要由Cd-5s轨道贡献,而价带边主要由S-3p轨道贡献,能量在-7 eV附近的电子态主要由Cd-4d轨道贡献。而ZnO上价带主要由O-2p电子构成,靠近费米能级的价带区域则主要由Zn-3d电子贡献,在导带部分,主要来源于Zn-4s和O-2p电子。由于在两种材料的复合结构中Zn-3d电子的能级和S-3p电子的能级接近,存在着二型带阶结构使能带变窄,容易形成跃迁,减小电子-空穴的复合,从而促进复合结构荧光效率的提高。     

CdS/ZnS core–shell nanoparticles in arachidic acid LB films

Core–shell CdS/ZnS nanoparticles in arachidic acid film were prepared through a novel Langmuir–Blodgett (LB) approach. Post-deposition treatment of the precursor LB multilayers of cadmium arachidate with H₂S gas followed by intercalation of Zn²⁺ ions and further sulfidation result in the formation of CdS/ZnS nanoparticles in the LB film. The formation of these nanoparticles and resulting changes in layered structures were studied by FTIR and X-ray reflection measurements. The optical properties were studied using UV–vis absorption and photoluminescence spectroscopy. A red-shift in the absorption spectrum and enhancement of CdS excitonic emission together with reduction of surface states emission suggest that after the intercalation step, a thin layer of ZnS surrounds the CdS nanoparticles, thus forming a core–shell structure. Subsequent to the second sulfidation, a further red-shift in absorption suggests the formation of a thicker ZnS coating on CdS. Electron diffraction of CdS nanoparticles coated with thicker ZnS showed the diffraction patterns of only ZnS, as expected for core–shell structures.