对氨基苯甲酸在不同基底上的SERS研究

用氢气还原氧化银的方法合成了粒径约为100nm的银纳米粒子,然后在表面经PVP修饰的载玻片上以自组装的方式构筑了银纳米粒子单层和双层二维有序阵列,在铝基底上通过对氨基苯甲酸成功构筑了银纳米粒子的有序组装体,用扫描电镜进行了表征;对不同基底二维有序阵列的表面增强拉曼光谱进行了研究,结果表明,对氨基苯甲酸在银和铝基基底上都是垂直吸附,其表面拉曼增强效应是电磁场增强占主导地位,但同时也有化学增强的贡献。     

氧化钨二维微米球腔阵列对聚苯胺电致变色的影响

采用气/液界面自组装方法制备规整排列的聚苯乙烯微球二维单层结构,以此为模板,采用电化学沉积法在电极表面构筑了有序的氧化钨微球腔阵列,进一步在氧化钨球腔内电化学沉积聚苯胺,采用吸收光谱研究了电极表面球腔阵列结构对聚苯胺电致变色行为的影响.     

基于直接胶体晶体刻蚀技术的高度有序纳米硅阵列的尺寸及形貌控制

以自组装单层胶体小球阵列为掩模，采用直接胶体晶体刻蚀技术在硅表面制备二维有序尺寸可控的纳米结构.在样品制备过程中，首先通过自组装法在硅表面制备了直径200nm的单层聚苯乙烯(PS)胶体小球的二维有序阵列；然后对样品直接进行反应离子刻蚀(RIE)，以氧气为气源，利用氧等离子体对聚苯乙烯小球和对硅的选择性刻蚀作用，通过改变刻蚀时间，制备出不同尺寸的PS胶体小球的有序单层阵列；接着以此二维PS胶体单层膜为掩模，以四氟化碳为气源对样品进行刻蚀；最后去除胶体球后得到二维有序的硅柱阵列.SEM和AFM的测量结果表明：改变氧等离子体对胶体球的刻蚀时间和四氟化碳对硅的刻蚀时间，可以控制硅柱的尺寸以及形貌，而硅柱阵列的周期取决于原始胶体球的直径. 关键词： 胶体晶体刻蚀 纳米硅柱阵列     

聚合物绝缘子表面微结构构筑及闪络性能

对聚合物绝缘子表面微形貌的构筑方法及其对沿面闪络性能的影响进行了研究。首先以二氧化硅微球为模板，利用化学模板法在交联聚苯乙烯(CLPS)表面实现了μm级孔穴的构筑，研究了二氧化硅微球的颗粒直径及添加量对微孔参数的影响；其次，利用激光刻蚀的方法在有机玻璃(PMMA)绝缘子表面实现了百μm级三角形凹槽阵列的构筑，探索了激光工艺参数对微槽形貌和结构的影响。通过短脉冲高压测试平台对构筑了两种不同微形貌的绝缘子进行了真空沿面闪络性能测试。结果表明:沿面闪络电压均获得了显著提升，其中表面带有合适微槽的PMMA绝缘子的闪络电压相比于未处理的绝缘子提升了将近150%；与传统的表面机械加工处理方法相比，在聚合物表面实现了从μm到数百μm量级微结构的可控构筑，并使真空沿面闪络电压获得了稳定提升。     

有序Ni纳米线阵列的制备及共磁滞回线

由铝在１５Ａ％硫酸介质中进行电化学氧化而得到的多孔Ａ１２Ｏ３是制备有序纳米线阵列的一种好的样模材料。在该样模中电沉积的有序Ｎi纳米线阵列排布规则、有序。磁滞回线 测量表明长径比为４００的Ｎi纳米线阵列在垂直于Ａ１２Ｏ３表面方向（即平行于Ｎi 纳米线方向）的矫顽力为８３１Ｏe,矩形度达０．９１,具有显著的磁单轴各向异性和磁单 轴各向异性和磁单畴特性。     

模板法自组装银团簇阵列的制备和性质研究

利用自组装的嵌段聚合物有序图案为模板来制备有序金属颗粒纳米阵列是人们关注的热点之一。本文概述了最近利用团簇束流沉积系统将银团簇淀积在聚苯乙烯-聚丁二烯-聚苯乙烯(SBS)三嵌段聚合物自组装形成的有序图案上,制备了有序的银纳米颗粒阵列材料,如线形银团簇颗粒阵列和二维银团簇颗粒阵列。利用自编的径向分布函数计算程序对线形银团簇颗粒阵列进行了定量分析,进一步定标了这种线形阵列的有序度,发现在同一线形阵列内有小部分银团簇是近接排列的,大部分团簇颗粒是等间距排列的。同时探讨了这些有序阵列形成的机制。并讨论了利用紫外-可见分光光度计和拉曼谱仪研究这些有序阵列所得到的相关性质。     

模板法自组装银团簇阵列的制备和性质研究

利用自组装的嵌段聚合物有序图案为模板来制备有序金属颗粒纳米阵列是人们关注的热点之一.本文概述了最近利用团簇束流沉积系统将银团簇淀积在聚苯乙烯-聚丁二烯-聚苯乙烯(SBS)三嵌段聚合物自组装形成的有序图案上,制备了有序的银纳米颗粒阵列材料,如线形银团簇颗粒阵列和二维银团簇颗粒阵列.利用自编的径向分布函数计算程序对线形银团簇颗粒阵列进行了定量分析,进一步定标了这种线形阵列的有序度,发现在同一线形阵列内有小部分银团簇是近接排列的,大部分团簇颗粒是等间距排列的.同时探讨了这些有序阵列形成的机制.并讨论了利用紫外-可见分光光度计和拉曼谱仪研究这些有序阵列所得到的相关性质.     

阳极氧化法制备Y型TiO2纳米管

在含有质量分数为0.5%的NH₄F和体积分数为5% 的H₂O的乙二醇混合溶液中,采用三步阳极氧化法制备了表面形貌高度有序的Y型TiO₂纳米管阵列。讨论了钛片预处理过程对优化TiO₂纳米管阵列表面形貌的影响以及采用升温法制备Y型TiO₂纳米管的内在机理,并在较宽的温度范围内(20~60 ℃)对钛片进行阳极氧化。实验结果表明当阳极氧化第三步的电解液温度设置在40 ℃以上时,Y型TiO₂纳米管阵列的顶端将出现环状纳米线、管壁破裂以及管长减小等现象,不利于保证Y型TiO₂纳米管阵列的整体质量。因此,30~40 ℃是选取阳极氧化第三步温度的理想范围。     

基于Ag三角阵列的表面增强红外基底的制备

利用聚苯乙烯(PS)微米球模板技术来制备表面增强红外基底,首先在氟化钙窗片表面自组装一层PS小球,并真空蒸镀银金属。接着除掉PS小球及其顶端的银膜之后,即可在氟化钙表面制备有序的银三角阵列结构。用光学显微镜和傅里叶变换红外光谱仪(FTIR)对制备的银三角阵列基底进行了表征。结果表明,其表面等离子激元吸收在中红外波段。     

银电极表面上C60薄膜的表面增强拉曼光谱研究

在银电极表面形成一层C60薄膜,分别在乙腈溶液和水溶液中进行表面增强拉曼光谱(SERS)研究并将两者进行比较,从而消除了溶液中的C60干扰表面吸附C60的SERS谱图的可能性.研究结果表明,C60分子对称性的降低导致SERS谱峰发生了分裂;表面电磁场的作用使得光谱选律在SERS效应中被拓宽,产生了新的拉曼谱峰.该结果与团簇吸附在粗糙银电极表面的C60分子的研究结果相似.与之不同的是在乙腈溶液和水溶液中的SERS谱图的低波数区内分别在348和311 cm-1左右出现一个新峰,经过分析可认为该峰与C60-金属基底的相互作用有关.     

Quenching of Pyrene Fluorescence by Calix[4]arene and Calix[4]resorcinarenes

Interactions involving calixarene and its derivatives are of major importance due to their widespread applications as unique hosts. Fluorescence from a common probe pyrene is used to study interactions involving calix[4]resorcinarene [1a] and its tetra-morpholine derivative [1b] in 1 M aqueous NaOH. These compounds efficiently quench the pyrene fluorescence. A comparison with the fluorescence quenching behavior of N-methylmorpholine clearly indicates the presence of long-range interactions involving 1a and 1b; the interactions are specific to the calixarene molecular framework. This is not the case for a tetra-nitro-substituted calix[4]arene [2b], an electron/charge acceptor quencher, as p-nitrophenol also shows similar interactions with pyrene. Effectiveness of cesium as the quencher of pyrene fluorescence is reduced in the presence of electron/charge donating 1b; fluorescence enhancement is observed upon addition of cesium as the concentration of 1b is increased in the solution. The role of calixarene framework in interactions involving such compounds is established.     

Spectrophotometric Studies on the Complexes of 25,26,27,28-Tetraepoxypropoxy-p-tert-butylcalix[4]arene and 25,26,27,28-Tetrahydroxypropilaminoxy-p-tert-butylcalix[4]arene with Iodine

Two p-tert-butylcalix[4]arene derivatives were synthesized from the reaction of calixarene with epichlorohydrine and then its reaction of ammonia. These donor macromolecular compounds were interacted with iodine in chloroform and interaction was investigated by using a UV-visible spectrophotometer. The chargetransfer spectra of n-[sgrave] type interactions were observed at 362 nm and 369 nm. The stability constants and some thermodynamic parameters were found.     

Studies on the adsorption of arsenic on calix[6]arene

p‐tert‐butyl calix[6]arene (PTC6) was synthesized and characterized by solid‐ and liquid‐state NMR and LC‐MS techniques. The adsorption of arsenite and arsenate on calix[6]arene under different pH conditions and adsorbate doses was studied. The maximum adsorption of arsenic species on calix[6]arene was observed around neutral pH and the adsorption density of As (III) was higher than that of As (V). The adsorption of neutral H₃AsO₃ and negatively charged H₂AsO molecules on calix[6]arene was attributed to the condensation reaction between hydroxyl groups of PTC6 and arsenic species. The complexation of arsenite with phenolic oxygen was confirmed by solid‐state ¹³C NMR CP‐MAS. Exo attack mechanism was proposed to describe the interaction of arsenous and arsenic acid molecules with PTC6. The specific interaction between calix[6]arene and arsenic species was further substantiated by zeta‐potential (ζ‐potential) measurements and free energy of adsorption. The free energy of adsorption ( ) estimated from Stern–Grahame equation was found to be 25 kJ/mole for As (III) and 19 kJ/mole for As (V). Copyright © 2010 John Wiley & Sons, Ltd.     

ESR study of calix[4]arene by spin-trapping method

Electron spin resonance (ESR) measurements are introduced to investigate the interaction between 5,11,17,23-tetrabromo-25,26,27,28-tetramethoxycalix[4]arene (II ₄) and 2-methyl-2-nitrosopropane (MNP) or nitrosodurene (ND) which are used as spin-trapping reagents under ultraviolet irradiation. In most cases, the complicated ESR spectra were observed because of the overlap of ESR signals attributed to several spin adducts in different conformations or in an inclusion state. However, after the optimum amount of ND was added into theII ₄ solution, the ESR spectrum showed that each nitrogen hyperfine line was further split to 1:2:1 triplet lines, and this is a typical spectrum ascribed to the spin adduct of ND at one para position ofII ₄.     

Inelastic neutron scattering spectroscopy of C60@calix[8]arene

The vibrational dynamics of the p-rert-butylcalix[8]arene and the 1:1 inclusion complex C₆₀@p-tert-butylcalix[8]arene are investigated by a combination of inelastic neutron scattering (INS) and MM3 molecular mechanics calculations. The results show that the isolated, single molecule approximation breaks down and is not sufficient to explain the features observed experimentally. The origin of the line broadening in the low energy region is discussed in terms of intermolecular interactions: this effect is sharper in the case of the complex with the C₆₀ molecule, due to the high number of co-conformers allowed by the mismatch between the circumferences of the host and the guest. The successful interpretation of the INS spectra validates the use of the model adopted.     

Scanning tunneling microscopy on self-assembled calix[4]resorcinarene monolayer adsorbates on Au(111)

Self-assembled Monolayers of calix[4]resorcinarene receptor molecules on Au(111) were studied by UHV scanning tunneling microscopy and X-ray photoelectron spectroscopy. Highly ordered monolayers were observed with domains oriented at an angle of 60° relative to each other. Molecularly resolved images were investigated and lattice constants found which depended on the preparation solvent. The STM images of two samples, one prepared in 1 mM chloroform/ethyl alcohol adsorbate solution and one in 1 mM hexane adsorbate solution are consistent with having a ×2 and 4×2 lattice, respectively. Received: 22 September 1999 / Accepted: 28 March 2000 / Published online: 11 May 2000     

Aspects of proton transport in calix[6]arene sulfonic acid

The features of proton transport and proton hydration shell structure of calix[6]arene sulfonic acid were studied. XRD and NMR data indicate the existence of crystalline and amorphous phases and various conformations in the acid structure. The hydration process occurs in three stages by thermal analysis and IR spectroscopy. The change in the composition of the hydrate affected the conductivity only at low humidity; an inverse relationship between the water uptake and the activation energy of conductivity is observed in the entire investigated range of humidity.     

荧光光谱法研究对-二甲氨甲基-杯[8]芳烃与DNA相互作用

首次采用阿霉素作荧光探针研究了水溶性对-二甲氨甲基-杯[8]芳烃(简称杯[8]胺或CX8)与小牛胸腺DNA相互作用,并考察了溶液的pH值、离子强度及解链DNA对DNA和杯[8]胺相互作用的影响。实验发现,DNA能猝灭阿霉素的荧光,向该体系中加入杯[8]胺时荧光又逐渐增强,这说明杯[8]胺能与DNA的磷氧负离子强烈作用。通过Scatchard图等进一步分析发现,杯[8]胺对DNA-阿霉素的影响表现为混合模式,一方面,在中性或酸性的条件下,杯[8]胺能中和DNA上的磷氧负离子,导致DNA收缩,从而影响DNA的构象,使嵌入的阿霉素从DNA中部分游离出来,荧光增强;另一方面,杯[8]胺与阿霉素也存在静电位点竞争。     

Luminescence spectra of a supramolecular complex of uranyl and a star-shaped polymer based on calix[8]arene

The luminescence spectra of the supramolecular complex of an uranyl ion and a ring calix[8] arene polymer have been obtained. It has been found that a significant reconstruction of light-emitting levels takes place in the temperature range 130–180 K. It has been assumed that the observed features are due to excitation transfer between the uranyl ion and the complex-forming polymer.     

Spatial structure of dimeric capsules of tetraurea calix[4]arenes in solutions according to 2-D NMR (NOESY) spectroscopy

Spatial structure of calixarene has been investigated by two-dimensional nuclear magnetic resonance (nuclear Overhauser effect) spectroscopy. Interproton distances for the given compound in solutions of benzene and cyclohexane have been measured and the experimental values have been compared with theoretically predicted ones.