TiO_2 nanocrystalline films were prepared on glass, ITO and p-Si substrates. Degradation of Rhodamine B was used to assess the photocatalytic activity of the films. It was found that photocatalytic activity of TiO2 films on ITO and p-Si are higher than that on glass, and the film grown on ITO is the best. In addition, crystalline phases and surface morphology of TiO_2films were also affected by different substrates. Surface Photovoltage Spectra was used to analyze surface states and energy levels of the films. Separation of photogenerate electrons and holes was promoted due to matching of the energy levels between TiO_2 films and ITO as well as p-Si. High photocatalytic activity was then obtained because more photogenerate electrons and holes took part in photocatalytic reaction on TiO_2 surfaces.

Titania gel is very sensitive to change of color to blue-purple by UV irradiation and to brown color under extra electric field polarzation. The UV absorption spectra of the photochromic (PC) and electrochromic(EC) titania gel are different to that of the nanocrystalline TiO_2 which changes to blue color by UV irradiation or under extra electric field polarization. The steady-state ESR measurements at room temperature indicate that ESR signals of Ti3+ appeared in PC and EC titania gel with the g values corresponding to 1.9505 and 1.9512, respectively.

采用Ｘ射线衍射技术研究了Al_0.9Fe_0.1和Al_0.9Fe_0.05Ce_0.05合金的液态结构及Al_0.9Fe_0.05Ce_0.05合金的非晶结构，并采用ＤＳＣ热分析研究了非晶合金的晶化行为．发现液态和非晶态合金的结构因子曲线上都存在明显的预峰，所对应的化学短程有序结构随温度降低，尺寸不断增大，但其结构单元的尺寸保持不变．Ce的加入使液态合金中化学短程有序及其结构单元的尺寸增大，并有利于原子间交互作用增强，从而提高非晶形成能力．预峰所对应的化学短程有序结构单元是以Fe原子为中心的二十面体准晶结构，这种结构在液态已形成，并保留在非晶中.

在ＲＨＦ／６－３１１Ｇ**、ＲＨＦ／６－３１１＋Ｇ**和Ｂ３ＬＹＰ／６－３１１＋Ｇ**水平，优化得到１，２－二硫方酸（３，４．二羟基－３－环丁烯－１，２－二硫酮）三种平面构象异构体的平衡几何构型．进一步用ＭＰＺ（full）／６－３１１＋Ｇ**／／ＲＨＦ／６－３１１＋Ｇ**方法计算三种异构体的单点能量，发现ＺＺ型异构体是能量最低构象，且ＺＺ和ＺＥ型能量非常接近．用优化的最稳定构象ＺＺ型异构体，在ＲＨＦ／６－３１１Ｇ**／／ＲＨＦ／６－３１１Ｇ**、ＲＨＦ／６．３１１＋Ｇ**／／ＲＨＦ／６－３１１＋Ｇ**、ＭＰＺ（full）／６．３１１＋Ｇ**／／ＲＨＦ／６－３１１＋Ｇ**和Ｂ３ＬＹＰ／６－３１１＋Ｇ**和Ｂ３ＬＹＰ／６－３１１＋Ｇ**水平，计算其气相酸性（△Ｇ＿２９８_Θ），并用同键反应方法在同样水平计算其芳香性稳定化能．用基团加和法（group increment approach）在ＲＨＦ／６．３１１＋Ｇ**／／ＲＨＦ／６－３１１＋Ｇ**和Ｂ３ＬＹＰ／６－３１１＋Ｇ**／／Ｂ３ＬＴｈ／６－３１１＋Ｇ**水平计算其磁化率增量（Λ）．计算结果指出，标题合物的键长发生了平均化，芳香性稳定化能和磁化率增量均为负值，表明它具有芳香性，实现了标题化合物芳香.

研究了乙醇在碱性介质（１．０ｍｏｌ•Ｌ－１ＮａＯＨ）中电沉积制备的Ｐｄ／ＧＣ、Ｐｔ／ＧＣ和Ｐｄ．Ｐｔ／ＧＣ电极上的电催化氧化．实验结果表明：由此法制备的钯铂系列合金电极对乙醇的电催化氧化表现出明显的协同效应——乙醇在含把原子分数ｙPｂ＝０．３３６的Ｐｄ－Ｐｔ／ＧＣ合金电极上的阳极交换电流密度是其在纯铂电极上的３０多倍．

从发展复合肥料出发，研究了CaSO4-Ca (H2PO4 ) 2-H2O体系及其三元边界体系Ca(H2PO4 )2-CO(NH2 )2-H2O 在２５℃时的等温溶度. 三元体系中形成一个新化合物Ca(H2PO4)2• CO(NH2 )2．四元体系溶度图可以指导商品普钙磷肥转化为含脲络合复肥．

在308.15 K、６~１２MPa范围内，测定了CO_2及CO_2-正戊烷、CO_2-正庚烷二元混合流体的密度，并计算了溶质的偏摩尔体积．在此基础上，将偏摩尔体积与Monte Carlo分子模拟研究相结合，研究了CO_2-正戊烷、CO_2-正庚烷二元系中的分子间相互作用和溶液的结构随压力和密度的变化．

通过ab ignition HF/6-31G*计算求得叠氮化氢二聚体（HN3）2. 势能面上四种优化构型，经MP4SDTQ电子相关校正和基组叠加误差校正求得这些构型下的分子间相互作用能．结果表明，在四种优化构型中N3H…NHN2也以最稳定，其分子间相互作用能为-16.07 kJ•mol-1.

研究了A3C60和A2BC60晶体的结构和稳定性．计算了它们的Madelung常数、结合能、晶格常数和体积弹性模量，并讨论了晶体中的短程相互作用．结果显示，短程相互作用对晶体结构和八面体空隙碱金属的稳定性具有极大的影响．CsK2C60、RbK2C60和K3C60的晶格常数计算结果与实验测量值非常符合．

在不同表面压的ＬＢ膜上，应用光谱学和原子力显微镜学研究了由罗丹明标记的磷脂分子形成的多种聚集态．这些分子聚集态使光谱的峰值位移，谱带加宽．ＡＦＭ的形貌图进一步说明了膦脂单分子膜的不均一性．根据激子理论，以４５°取向角存在的罗丹明染料聚集体更符合π－Ａ曲线．

以γ射线辐照硫代硫酸钠和硫酸镍的混合水溶液，所得沉淀物经乙醇多次清洗后６０℃下烘干、将所得粉末样品分别在氩气氛中１６０—５００℃焙烧４ｈ，使用Ｘ射线衍射（ＸＲＤ）及扩展Ｘ光吸收精细结构（ＥＸＡＦＳ）分析样品的结构．结果表明，１６０℃以下烘于所得样品为纳米非晶，其Ｎｉ－Ｓ壳层为四配位结构，Ｎｉ—Ｓ键长为０．２２１ｎｍ．经３００℃焙烧后，非晶转变为ＮＩＳ微晶，Ｎｉ－Ｓ壳层变为八面体六配位（红镍矿型）结构，Ｎｉ—Ｓ键长增加至０２３８ｎｍ．进一步提高焙烧温度时，所形成ＮｉＳ晶粒逐渐长大，对经５００℃焙烧样品，Ｘ射线衍射检测到很尖锐的对应单一ＮｉＳ物种的衍射峰．

Phase state and structure of liquid crystal in sodium dodecylsulfonate middle phase microemulsion were studied. The following facts has been proved by 2H NMR quarsplitting and small angle X-ray diffraction techniques, two kinds of lamellar liquid crystal were coexisted in suitable salt concentration. Order parameters of liquid crystal were calculated from ESR anti-isotropic spectrum.

A new method was used to prepare a calix [4] arene-bonded silica stationary phase. The chemically modified calix[4] arene 1 was attached to silica gel via the silane coupling reagent γ-(ethylenediamino ) -propyl-triethoxyl-silane. The resulting bonded phase was characterized by 29 Si and 13C cross polarization/magic angle spinning(CP/MAS) nuclear magnetic resonance(NMR) techniques.

The phase diagrams of Na_2CrO_4- (NH_4)_2CrO_4-H_2O system at 20℃ and 50℃ have been determined by solubility method. The experimental results have also been verified by mathematical method. The phase diagrams show that there is a double salt of NaNH_4Cro_4• 2H_2O formed in the system, which will decrease the purity of (NH_4)_2CrO_4 Consequently, a method is found to separate the fixture of ammonium chromate and double salt by analysing the phase diagrams.

The standard enthalpy of formation (f, Hm,298.2K= -1342. 11 KJ• mol--1 ) of the double salt of Zn2HIO6. 1. 25H2O was determined by calorimetry in a new model isoperibel reaction calorimeter. The calorimetric solvent is an acid solution consisting of 3 mol• L-1 HNO3.

Penicillin-G potassium salt (Pen-K) shows hydrotropic action to the system of CTAB/ n-C5H11OH/H2O, due to the interaction between the polar groups of Pen-K and CTAB. Pen-K can be solubilized in the pro-oil side of the interphase of O/W and W/O microemulsion droplets, the water penetrating into the interphase of the droplets is prevented from contacting with Pen-K by n-C5H11OH which is solubilized in the polar group side, so that the stability of Pen-K was enhanced compared with that in water. However, Pen-K can not show hydrotropic action in SDS and Triton X-100 systems, and the hydrolytic rate of the Pen-K in the system of SDS and Triton X-100 is the same as that in water because of the effect of surfactant charge.

A new chemical method to calibrate the instrument constants of conduction calorimeter, including the cooling constant a of thermal system and the cooling constant β of thermal element which are related with thermal conductivity of the thermal system, has been proposed on the basis of the single parameter or double parameters theoretical model of conduction calorimeter and thermokinetic equation of chemical reaction. This method has been applied to calibrate RD496 II microcalorimeter，and a significant result has been obtained.

The reaction of silver and sulfur clusters was studied with Laser Double Ablation Reactor-Tandem TOF MS, and [AgS4]+, [AgS8] +, [AgS12] + and [AgS16] + were detected as the main products. The 193nm laser photodissociation of [AgS12] +. and [AgS16] + gave mainly [AgS4] + and [AgS8] + respectively. Photodissociation products of [AgS8]+ were Ag+, [AgS2] + and [AgS4] +, and that of [AgS4] + was not detected. We also discussed the possible mechanism of the reactions forming Products [AgS12 ] + and [AgS16] +.

负载型金属催化剂上甲烷催化部分氧化制合成气反应机理存在着燃烧-重整机理和直接氧化机理之争. 如果反应按燃烧-重整机理进行, 则CO2 是反应的一次产物而CO是二次产物 ;如果反应按直接氧化机理进行 ,则CO是一次产物. 本文采用同位素瞬变技术 ,对Ni/Al2O3 催化剂上甲烷部分氧化制合成气反应中CO2 的来源进行了研究 ,结果表明CO2 同CO一样 ,主要来源于催化剂表面NiO与甲烷分解生成的NixC的反应 ,这就有力地证明了反应按直接氧化机理进行. 研究结果还表明 ,CO歧化或进一步氧化不是CO2 的主要来源.在实验条件下 ,CO的歧化反应受到热力学平衡的限制 ,转化率很低 ;但反应进行得很快 ,通过该可逆反应气相CO中的C可以与催化剂表面的C进行交换.

The surface structure of Cu, Al and γ Al2O3 have been investigated by SEELFS and obtained nearest neighbor distances of the central atoms. The value s compared with those calculated according to theories shows that the errors wer e about 0.01－0.03nm before correcting the phase shifts. These results show the possibility of performing SEELFS technique by Auger electron spectrometer.

研究了不同载量时Mg(NO3)2 在γ-Al2O3 上存在状态和热分解行为差异. 考察了Mg含量不同时MgO/γ-Al2O3 的碱性变化情况 ,并与水滑石焙烧产物Mg(Al)O的碱性进行了对比.结果表明, Mg(NO3)2 可单层分散于γ-Al2O3 表面 ,Mg(NO3)2 的分散决定了MgO的分散阈值 ;单层态的Mg(NO3)2 比晶态的分解温度低 ;MgO/γ-Al2O3 在阈值附近具有单位表面最高碱量 ,碱位分布与Mg(Al)O相似 ,单位表面碱量高于Mg(Al)O. 由于γ-Al2O3 的织构可以方便地调节 ,且MgO/γ-Al2O3很容易制备, MgO/γ-Al2O3 是一个很有应用前景的固体碱.

以半经验分子轨道方法计算吲哚酚衍生物的分子结构参数. 以主因子分析法和多元线性回归法研究了吲哚酚衍生物的式电位与其分子结构参数间的关系.研究发现, 在所选择的19个分子结构参数中, 双中心电子交换能(Eex(2)/eV), O -C键的共振能(Er(C1-O)/eV)和分子的电离势(Ip/eV)与其式电位有较好的相关性. 其回归方程为:y=1.47×10-3Eex(2) -5.74×10-2 Er(C1-O) -1.41×10-2Ip(RC=0.9999,SD=0.00424). 由分子结构与式电位关系及中间产物的稳定性可推测, 在吲哚酚的氧化机理中氢的电离反应优先于电子转移过程.

在微波辐照和丙酮存在下 ,进行了苯乙烯(ST)和甲基丙烯酸甲酯(MMA)的无皂乳液聚合. 当丙酮的含量在50%以下时 ,可以得到稳定的窄分布的纳米粒子胶乳.丙酮的含量由0增加到50 % ,粒子的平均水化半径由278nm降低到35.4nm.在一定的浓度范围内 ,固定引发剂过硫酸钾 (KPS)的用量 ,则粒子的平均水化半径与单体的浓度成正比 ;当单体浓度一定时,随着引发剂浓度的增加 ,粒子平均水化半径从25nm减少到22nm然后又增大. 考虑到引发剂既是粒子表面电荷的来源 ,又增加了体系的离子强度 ,在粒子形成过程中 ,起着稳定和絮凝的双重作用 ,我们得到了一个简单的公式用以描述粒子的平均水化半径和单体-引发剂质量比(mm/mi)之间的关系.加入少量的MMA单体 ,则共聚物粒子的体积明显减少 ,从35.4减少到16.0nm. 这表明增加粒子表面的亲水性 ,使得分散体系变得稳定. 用减压蒸馏的办法可以除去体系中的丙酮 ,蒸馏前后粒子的大小和分布都不变. 本方法很方便地得到了高浓度窄分布的无皂分子纳米胶乳.

采用溶胶-凝胶法 ,以正硅酸乙酯 (TEOS)为前驱体 ,用脂肪醇聚氧乙烯醚 (AEO)为改性剂制备结构可控的多孔SiO2 干凝胶. 结果表明 :通过调节添加量和聚合度以及溶胶老化时间可以对SiO2 干凝胶织构性质进行有效的调控 ;采用不同的环境气氛对SiO2 AEO干凝胶进行热处理 ,则AEO表现出不同的热稳定性 ;经热处理后 ,AEO等有机残留物被脱除的同时 ,SiO2-AEO干凝胶柔性骨架得到加强 ,孔分布更趋集中 ,干凝胶结构的热稳定性得到进一步提高.

XRD研究表明 ,作为乙苯脱氢催化剂中的氧化铁活性组分 ,具有反式尖晶石结构的Fe3O4 比刚玉型的α-Fe2O3 更易与钾助催化剂发生相互作用 :α Fe2O3-K2O需经850℃煅烧才能生成多铁酸钾 ,但在Fe3O4 -K2O体系中只需700℃即可.而且 ,钾还可抑制Fe3O4 被氧化为α-Fe2O3 的进程 ,在空气中 ,Fe3O4 只需300℃煅烧即可明显转化为α-Fe2O3 ,但同样的转化在Fe3O4-K2O体系中要经700℃煅烧才会明显地发生.实验结果表明 ,某种形态的多铁酸钾可能是催化剂中的储钾相.

基于作者提出的诱导极性叠加原理 ,设计了包括与诱导极性叠加总量相关的能量项的烷烃异构体的标准生成焓估算的新方法.与前人方法比较 ,它具有较高的计算精度、较少的参数 ,各参数物理意义明确 ,而且理论上可以推广到含多种杂原子的衍生物的标准生成焓的计算.

利用纳米粒子组装技术制备出金基底/巯基苯胺自组装膜偶联层/金纳米粒子的“三明治”结构. 实验结果显示, 该结构对偶联层分子的喇曼光谱显示出很好的增强效应 ,增强因子可达105 ;在表面粒子密度(粒子覆盖度)较低时 ,表面增强喇曼散射(SERS)强度与表面粒子密度近似呈线性关系 ,随着表面粒子密度的增加 ,这种线性关系出现负偏差并在表面粒子密度较高区域出现一个平台 ;在60 -110nm范围内大粒径金粒子对喇曼光谱的增强效果强于小粒径金粒子. 高增强因子出现的原因是体系中存在化学增强效应以及纳米粒子与金基底之间的电磁偶合作用 ,初步解释了喇曼强度随粒子密度的变化规律.

研究了超临界CO2 中聚氨酯对乙醇、麝香草酚和β-苯乙醇等小分子的吸附作用 ,观测了超临界CO2 的温度、压力、吸附时间和聚氨酯厚度对小分子吸附量的影响以及小分子在聚氨酯中的释放规律 ,并探讨了小分子的渗透机理.

按碳原子及键合特性分类定义并计算了链烃包括烷、烯、炔、双烯、烯炔烃的分子距离-边数矢量(MDE), 将153个链烃的MDE矢量与相应的沸点相关联,得到了良好的线性模型.复相关系数R=0.9976,均方根误差RMS=4.69K.同时还进行了随机检验和交互检验,其复相关系数和均方根误差分别为R=0.9975、RMS=4.72K和R=0.9972、RMS=5.13K.结果表明模型具有良好的稳定性和预测能力.进一步对杂原子用染色因子进行标识,提出了一种适用于含杂原子体系分子结构描述的MDE矢量,并以72种脂肪醛和脂肪酮的沸点为例,进行了定量结构-性质关系 (QSPR)研究,同样得到了满意的结果:分子定量建模、随机抽样建模和定量预测的复相关系数及均方根误差分别为R=0.9989、0.9990、0.9980及RMS=3.93K、4.12K、5.52K.表明MDE矢量与链烃及醛酮的沸点均具有良好的相关性,肯定了该矢量的合理性和有效性,可望在定量结构-性质/活性 (QSPR/QSAR)研究中获得广泛应用.

Realumination of dealuminated Hβ, prepared by calcination in air and /or by leaching in HCl solution has been studied by Infrared Spectroscopy. The result shows that the majority of the aluminium defect sites, produced by calcination in air, could be subsequently reinserted by aluminium in the framework under mild condition of alumination, while reinsertion of Al in the defect sites of Hβ framework created by acid leaching was difficult under the same realumination condition.

The enthalpies of dilution of L serine in ethanol water mixtures (with 0.05 increments ranging from 0.05 to 0.40 ethanol by weight) have been measured with LKB 2277 Bio Activity Monitor at 298.15 K. Calculations show that the value of pairwise enthalpic interaction coefficients h2 is negative and minimized at 0.25 ethanol in mixtures.

Thermal decomposition reaction mechanism of the precursor gel made by sol gel process for nano-crystalline BaTiO3 was studied by TG DTG and FTIR techniques. The reaction proceeded in three stages: solvents removing, organic ligands decomposing, and amorphous solid BaTiO3 forming. The differential and intergral mechanism functions and activation energy for the third stage were obtained by calculation and comparson.

Codeposition mechanism of phosphorus with nickel on an Ni Ag alloy electrode has been investigated by means of in situ surface enhanced Raman spectroscopy(SERS) and electrochemical method to obtain new information about the phosphorus incorporation mechanism during electrodeposition of Ni-P alloys. The intermediate, Ni(PH3)n, in the electrodeposition of Ni P alloy was detected with in situ surface Raman spectroscopy for the first time. The experimental results showed that in the solution without NiSO4,hypophosphite was reduced only to Ni-phosphine compound, while in the case where NiSO4 coexisted in the solution, the Ni-phosphine compound, as an intermediate, was oxidized by Ni2＋to elemental phosphorus in alloys with nickel acting as the catalyst.

Amorphous Ni-B/SiO2 catalysts were prepared by chemical reduction of Ni2＋with KBH4. ICP was used to analyze the composition of alloys. XRD,TEM,SAED and HREM were used to examine the structures of samples fresh and after thermal treatment in different atmospheres. The results indicated that the supported NiB has a higher structural stability than ultrafine NiB amorphous alloy. Low temperature pretreatment in hydrogen can reduce nickel oxide on the surface of catalysts. However, treatment in hydrogen is more favorable than in atmosphere and nitrogen for keeping it in stable state.

Measured by gel electrophoresis scanning, it was shown that the double strand breaks (DSBs) of pBR322 irradiated by γ rays were constituted by two parts, αDSB and βDSB, and the relationship between α,β and scavenging capacity σ was obtained. Results showed that β/α non linearly decreased with increasing σ. Moreover, the yield of the OH free radicals reacting with DNA was analyzed.

Enthalpy changes for the protonation of carboxyl group of four α amino acids(glycine, L –α-alanine, L-valine and L-serine) were measured in water ethanol mixtures (10－70wt％) at 298.15K using LKB-2277 Bioactivity Monitor. The corresponding entropy and Gibbs energy changes were also calculated. The results show that both enthalpy changes and entropy changes are favorable to the protonation of carboxyl groups of the investigated amino acids in water ethanol mixtures. However, the influence of the composition of ethanol in the mixed solvents on the enthalpy change and entropy changes is complicated . Both sσΔH1Θand sσΔS1Θ,the differences of enthalpy changes and entropy changes in mixed solvents and in pure water respectively, show a minimum approximately at xEtOH=0.1.The effects of side chains on the enthalpy change and entropy changes were also investigated using the proton transfer process between glycine and the other three amino acids. The results demonstrate that the proton transfer processes for alanine and valine are spontaneous but not for serine, which could be interpreted in terms of the electrostatic interaction between amino group and carboxyl group within the molecule and the interaction between carboxyl group and the solvent.

An experimental set up was designed to separately test how sedimentation and convection driven flows affect the perikinetic coagulation process in a ground based experiment. The experiment showed that the sedimentation slightly accelerates the coagulation process and weak free convection driven flows do not noticeably contribute to coagulation for 2 μm particles' dispersion.

通过CATALYST软件包得到了两类HCV NS3丝氨酸蛋白酶抑制剂的三维药效团模型.尽管这两类抑制剂具有完全不同的骨架结构,但得到的药效团却具有共同的特性. 这表明当这两类抑制剂和受体发生相互作用时,可能采用了相似的结合模式. 根据药效团模型,进行了三维构效关系的研究. 结果表明 ,得到的药效团模型具有很好的预测能力 (线性回归系数R=0.89).

采用水相硅烷化方法 ,将3-氨基丙基-三甲氧基硅烷(APS)组装在湿化学法处理的单晶硅表面上.接触角、原子力显微镜(AFM)、X射线光电子能谱(XPS)表征结果显示得到了平整均匀的具有氨基表面的自组装膜. SEM观察表明 ,16nm的金纳米粒子可以在上述氨基表面上形成均匀的亚单层排布 ,得到具有Au纳米粒子/APS/Si形式的纳米复合结构 ,进一步的处理可以使金纳米粒子在表面上的排列由随机趋于有序化.

通过反-1-(4-联苯基)-2-(4-吡啶基)乙烯(E-I)在稀硫酸中的光二聚反应合成了r-1,c-2, t-3, t-4-1, 3-双(4-联苯基)-2, 4-二(4-吡啶基)环丁烷(II). 用X射线衍射法测定了其结构. 晶体II为单斜晶系,空间群为P21/n,晶胞参数:a=1.0038(2), b=1.8995(4), c=1.4647(3)nm, β=98.82(3)°,晶胞内分子数为4. 在II的分子中,其四元环呈蝶式构象. 研究发现,在短波紫外光照射下,II容易发生光解开环反应生成其反式单体E I,随后新生成的E-I经反顺异构化反应转变为其顺式异构体(Z-I),最后反顺异构化反应达到平衡.光解II或E-I得到同样的反顺异构体混合物.