In absence of catalysts, Oscillations in the oxidation of KSCN、Na2S2O3 and SC(NH2)2 by H2O2 are observed in CSTR experiments, single-peak and other phenomena are observed in batch experiments. Oscillations in pH and Pt potential are antiphase in H2O2-Na2S2O3-H+ system and H2O2-KSCN-OH- system, but oscillations in pH and Pt potential are synchronous in H2O2-SC(NH2)2-H+ system.

The solubilities of C60 and C70 in toluene, o-xylene and CS2 between melting point and boiling point have been measured. The temperature-dependent solubillty of C60 displays the anomalous behavior. A solubility maximum of C60 around O℃ for toluene and CS2, and around 30℃ for o-xylene was observed. The temperature-dependent solubility of C70 displays the normal behavior in the same solvents.

对用混胶法和共沉淀法分别制备的TiO2－Al2O3复合载体（TiO2含量为0．08g／gγ－Al2O3）进行了对比研究，采用的表征方法有XRD，XPS，LRS等，得出的结论如下：两种载体均保持了γ－Al2O3的骨架结构，但TiO2的分散状态不尽相同．混胶样品中TiO2主要以表面富集的形式分散在γ－Al2O3表面，这有利于集二者的优点于一体；共沉淀样品中TiO2趋于整个体相均匀分散，这有利于相互作用后形成新的性能．

本文采用时间相关单光子计数对卟啉酞菁TTP－（CH2）n－PC模型化合物的光致电子转移进行了研究．发现激发Pc时，呈现单指数衰减，n＝4时电子转移速率最快，激发TTP时呈现双指数衰减，表明除能量转移外，同时存在电子转移，随n的增大电子转移速率减小，活化能、重排能增加, 电子转移效率下降，电子转移反应△GCS与电荷分离活化络合物衰变速率kCT，按以下规律：
△G CS (5) >△G CS (3) >△G CS (4) >△G CS (2)
kCS (2) >kCS (3) >kCS (4) >kCS (5)
其△G CS (4) 与△G CS (3)倒置可按Marcus理论中重排能啬使活化能增加得以解释。

用高时间分辨ESR波谱仪测量了光解苯半醌和2－羟基－2－丙基自由基的CIDEP谱，苯半醌自由基的CIDEP属TM机理．实验研究了微波功率、溶液浓度对苯半醌自由基的CIDEP谱时间演化的影响．2－羟基－2－丙基自由基的CIDEP属RPM机理，实验研究了自旋极化的生成环境．

采用复合电镀的方法将不同球磨时间制备的高催化活性的纳米晶Ni－Mo合金粉直接镀于电极表面，并用稳态极化曲线及交流阻抗技术测试了这些电极析氢的电化学活性，同时用X射线行射、透射电镜及扫描电镜监测了Ni－Mo合金粉的物相结构、晶粒尺寸及复合电极表面的形貌，并初步探讨了这些复合电极的析氢机理．实验结果表明，球磨不仅可使镍钼粉合金化成为纳米晶，同时随着球磨时间的增加，纳米晶晶粒继续细化，电极的析氢催化活性也随之提高．电化学脱附是这些复合电极析氢的速率决定步骤，这种在表面直接复合镀高催化活性粒子的方法是制作电极的一种行之有效的新方法．

采用MNDO（UHF）方法计算了金刚石（100）－（1×1）：2H双氢化表面和（100）－（2×1）：H单氢化表面的脱氢势垒，论证了决定金刚石附氢表面脱氢势垒大小的主要因素是气相－表面吸附氢原子间的相互排斥大小，得出（100）面两种表面结构脱氢势垒的理论预言值分别为71和59kJ•mol-1，均大于（111）面脱氢势垒的理论预言值42kJ•mol-1．揭示了在同等生长条件下金刚石（111）面可供成核和生长的反应基多于（100）面，与实验上得到的同等生长条件下（111）面的相对生长率大于（100）面的结论是一致的。

用极化曲线方法研究了硫酸和盐酸介质中五种硫脲化合物在纯铁电极表面的阴极吸附行为．从动力学角度推出硫酸介质中硫脲在电极上的吸附遵守Temkin等温式，并参与了铁电极上的阴极析氢反应，属负催化效应. 从热力学角度证明了盐酸介质中硫脲及其衍生物在电极表面的吸附遵守Langmuir等温式，属阴极覆盖效应．

用对称透射法，测试聚酯（PET）取向非晶试样的二维广角X射线散射相干强度Ie（K，α），将不同方位角α上的Ie（K，α）非晶重叠峰曲线进行计算机分解，获得分子链间原子散射引起的二个峰为A（K＝0．126）、B（K＝0．169）；分子链内原子散射引起的五个峰分别为C（K＝0．304）、D（K＝0．553）、E（K＝0．374）、F（K＝0．465）、G（K＝0．606），K单位为nm－1．分析了它们的结构起源以及主要峰参数与α的关系，得到PET取向非晶态的细微结构信息．

用吸收光谱的方法研究了溶液中四－[（4′－N，N，N－三甲基）－苯氧基]－酞菁季铵碘盐及它的锌络合物与四－（4′－磺酸基苯基）卟啉及它的锌络合物通过分子间自组装形成的新一类超分子排列的杂聚体，用Job氏光度滴定的方法确定了它们的组成，为面对面的杂二聚体或三明治式的杂三聚体超分子排列．证实卟啉和酞菁的中心络合金属与溶剂分子之间的轴向配位是决定了卟啉－酞菁杂聚体的组成．发现在超分子体系中卟啉与酞菁能互相猝灭各自的荧光，用纳秒级的激光闪光光解技术观察到卟啉的正离子在600－650nm和酞菁负离子自由基在550－600nm的瞬态吸收光谱．结果表明在超分子体系中存在分子间的光诱导电子转移过程．

The limiting solubilization amount of aqueous solution of electrolytes, including NaCl, KCl, NaBr, NaI, CaCl2 and Na2SO4 in carbon tetrachloride solution of dodecylammonium propoinate was determined as the added amount of aqueous solution at which turbidity began to be visible. All of the results showed that with increasing concentration of electrolytes, the limiting solubilization amount of aqueous electrolyte solution increased first followed by decreased. This phenomenon could be explained as follows. When electrolyte was present in water pool of reverse micelle, it makes easier for surfactant molecules that surrounding the water pool to migrate to organic phase because of salting-out effect, thus the reverse micelle was expanded. This effect increased with increase of electrolyte concentration. On the other hand, surfactant molecules migrating easier to organic phase implies that the force making surfactant molecules to stick on the surface of water pool became weaker. When electrolyte concentration increased to a certain extent, this force became too weak to keep the reverse micelle, thus the limiting solubilization amount of aqueous solution decreased. According to simplified spherical reverse micelle model, the aggregation number as well as the radii of water pool of reverse micelle have been calculated for aqueous sodium chloride solution of different concentrations. The results support the above explanation.

The photochemical and photophysical behaviors of tri(4-tert-butoxycarbonyl oxyphenyl) sulphonium salts have been investigated. In argon-satureted acetonitrile, the quantum yields of Bronsted acid formed during photolysis of these compounds was abount 0.5. In the transient absorption spectrum excited by 266nm in mathanol and dioxane an evident absorption peak at 360 nm decayed in accordance with pseudo-first-order reaction was observed. In the presence of poly-p-hydroxystyrene or diphenyl sulphide, the apparent second-order reaction decay rate constsnts were 107 and 108 L﹒mo-1﹒s-1, respectively. Results indicated that the transient absorption peak at 360nm was attributed to the diphenyl sulphide radical cations formed in photolysis of sulphonium salts, which were proposed by abstraction of hydrogen from solvent or polymer to yield the photonic acid and diphenyl sulphide as listed in eqns. (1) and (2). The influence of non-nuncleophilic anions of title compounds on their photochemical behavior was just less important.

Relativistic density-functional calculations on free Hg2, Hg4, Hg8, Pb2 and Pb4 clusters, and those clusters embedded in an alkali (A) atom surrounding are reported. Heavy metal-metal (M-M) distances, binding energies and effective charges have been calculated. The Hg-Hg distance in the weakly bound free clusters is over 330 pm. Upon embedding in an alkali surrounding, the bonding is strengthened; the bond lengths are reduced for square planar Hg4 to below 300 pm. The bonding in the hypothetical tetrahedral alkali-mercury cluster appear to be quite different, where Hg4 will undergo a transition to four Hg1. This explains the strict preference of square over the tetrahedral geometry of Hg4 clusters in amalgams. Pb4 is predicted to be stable in a pure cluster and does not show significantly different bonding feature in the lead-alkali crystal. The effective charges on Hg and Pb are calculated to be -0.4 and -0.6, respectively. The bonding characteristics are also examined by calculation of the M4-An interaction energies. The amalgamation energies lie in the range of 50 to 70 kJ/molHg. The formation energy of alkali-Pb is up to 150 kJ/molPb, much stronger than that of alkali-Hg.

Highly oriented Bi4Ti3O12 thin films were prepared by Sol-Gel technique on SrTiO3(100) single crystal, using Bi(NO3)3.5H2O, Ti(OC4H9)4 and CH3COOH as raw materials. The c-axis orientation was about 96%. The effect of pH value of solution on quality of the thin films was studied.

Rules of molten salt phase diagrams of binary system MeX-Me’X4 (Me is monovalent metal, Me’ quadrivalent metal, X halides) were investigated using chemical bond parameter and pattern recognition-artificial neural networks method. Formability of intermediate compounds, chemical stiochiometry, melting type (congruent or incongruent) of intermediate compounds Me2Me’X6 and MeMe’X5 were summarized and predicted, the results were of good reliability.

The rhodium-phosphine complex catalyst Rh(CO)(acac)(PPh3)(Ⅰ) for 1-hexene hydroformylation was studied under the following reaction conditions: CO/H2=1(mole rate), pressure 1.0 MPa, temperature 25-120℃, by using the pressurized in-situ 1H NMR technique. Experimental results indicated that the formation of a rhodium hydride complex from (Ⅰ) began at room temperature and its amount increased with increasing of reaction temperature. This intermediate complex began to decompose at 100℃ and disapeared completely at 120℃. The intensity change of the proton signal was parallel to catalytical activity in hydroformylation of olefins. Under pure CO pressure the proton signal of Ph-H bond was not observed. There was a 0.2 ppm difference in proton chemical shifts of Rh-H bond under pure H2 pressure and under H2+CO pressure. The results showed that the rhodium-hydride carbonyl complex is the active intermediate in the industrial hydroformylation process.

Molar conductances of NaCl and KCl in 0~100%(ω/ω) CH3OH-H2O have been measured by using the alternating conductance bridge method resembling that of Shedlovsky. The results show that the limiting molar conductances (Λ0) of both NaCl and KCl have the lowest curve points around 55%(ω/ω) CH3OH and the limiting molar conductances (Λ0) of KCl are larger than that of NaCl in 0~100%(ω/ω) CH3OH-H2O mixtures, which can be accounted for in terms of the micro-structure and ionic solvated situation of NaCl and KCl aqueous methanol solution. Furthermore, experimental limiting molar conductances (Λ0) for KCl-CH3OH-H2O system in this work are critically compared with that of Amis, which shows that measured results in this work are more reliable.

A new permeability coefficient equation was theoretically derived. It contains both the acid concentration of feed solution and the carrier concentration as well as the acid concentration of stripping solution. The relationship of permeability coefficient and acid concentration of stripping solution was further confirmed by the experimental results of Co2+、Ni2+、 Er3+ ions transporting through the supported liquid membranes.

γ-alumine membranes supported by porous titanium plate were prepared by sol-gel techniqe with alumina isopropoxide. The factors, which influenced membrane per formance, in the membrane preparing process were investigated. A dynamic flow-weighted active pore size distribution apparatus for inorganic membrane were set-up on the basis of Kelvine equation. The results showed that for composite porous membrane the active pore size distribution is about 6-8nm, the most probable pore size is about 7nm and nitrogen permeability is 7.1×10-6mol﹒m-2﹒Pa-1﹒s-2.

We used CD spectroscopy to study the conformations of three cyclic peptides (CP10E: cyclo[Glu(OBz1)-Pro-Gly-Glu(OBzl)-Gly]2, CP10K: cyclo[Lys(Z)-Pro-Gly-Lys(Z)-Gly]2, CP12K: cyclo[Phe-Lys(Z)-Pro-Gly-Lys(Z)-Gly]2 and their correspondent linear peptides (LP10E: Boc-[Glu(OBzl)-Pro-Gly-Glu(OBzl)-Gly]2-OPac, LP10K: Boc-[Lys(Z)-Pro-Lys(Z)-Pro]2-OMe, LP 12K: Bao- [-Lys(Z)-Pro-Gly-Lys(Z)-Gly]2- OMe) in three solvents of different polarity (chloroform, acetonitrile, 2,2,2-triliuroethanol), and it was found that all of linear and cyclicpeptides exists asγ-turn conformation in chloroform, however, in TFE＆ CH3CN solutions, the three linear peptides are inβ Ⅱ-turn conformations. CP10E isβI-turn conformation, CP10K ＆CP12K exists in more than one types of turn conformations. On the basis of our experiments, it was concluded: 1) In the presence of conformational constrained amino acids short linear peptides form obvious secondary structure; 2)The solvent polarity has influence on the peptide conformation and this influence on linear peptides is greater than that on cyclic peptides; 3)The backbone of cyclic peptide has constraint effect on its conformation and makes the secondary structure of cyclic peptide different from that of its relative linear peptide. This information might give some cules in the design of bioactive peptides with different receptor selectivity.

The optimized geometries, energies and harmonic vibrational frequencies of the doublet and quadruplet electronic states of O3- are theoretically predicted at the UHF/631+G*, MCSCF and CISD/MCSCF level. The geometry of the ground has Cs syrnmetry, and bond lengths of 1. 369 and 1.350Å, and a bond angle of 115.7° at the MCSCF level. The excitation energies for transitions 2A2←X2A", 2A’←X 2A" and 2B2← X 2A"I are 2.648, 1.372 and 1 .463 eV, respectively. For the quadruplet states of the ozonide anion the van der Waals complexes only are found. The intra-ionic charge transfers for the X2A", 2A’ and 4∑- states are investigated. The reactions 2A"→2B2→2A",2A’→ 2A1→2A’ and 4∑-→4∑g→4∑- have activation barriers of 1.281, 13.344 and 81.484 kcal﹒mol-1, and rate constants of 3.254×1011 ,4.688×102 and 2.653×10-49 s-1, respectively.

In situ optical emission spectra for an electron assisted hot filament diamond growth process were successfully measured with spatial resolution of better than 1 mm. The emission lines from atomic hydrogen, molecular hydrogen, CH and CH+ radicals were observed in the visible region. Effects of the substrate bias on emission spectra and diamond nucleation were also investigated. It is found that substrate bias can enhance the nucleation density, which may due to the changes of atomic hydrogen concentration and the increase of electron mean temperature.

采用分子轨道从头计算方法，研究了NFCl自由基的基态（X2A″）和激发态（12A′，22A′）．得到了它们的平衡构型和谐振频率．计算确认了第一激发态（12A′）．研究表明第一激发态的平衡构型是弯曲构型，而非前人建议的线形构型．实验观察到的位于300－400nm的吸收谱带归属于12A′←X2A″跃迁．

较系统地研究了在有氨和无氨缓冲体系中pH变化对羧酯脱酰反应速度和胶团催化作用的影响．提供在两种缓冲体系中反应速度随溶液pH变化的规律．结果表明CTAB胶团对对硝基本酚丙酸酯和乙酸酯碱水解反应的催化效率随溶液pH上升而削弱．对硝基本酚丙酸酯和乙酸酯在含氨的缓冲体系中有水解和氨解反应同时进行．CTAB胶团对水解反应有正催化作用，而对氨解反应则显示负催化作用．这使得NH3－NH4Br缓冲体系中CTAB胶团对体系总反应速度的影响随溶液pH降低从正催化变为负催化．

考察了Pt／HZSM－5、Ga／HZSM-5和Pt－Ga／HZSM-5上的丙烷芳构化反应．其中Pt－Ga／HZSM-5双组份催化剂上有较高的丙烷反应活性和芳烃选择性．用程序升温还原（TPR）和H2化学吸附法表征催化剂，发现Pt与Ga的协同相互作用促进了Ga3＋的还原，使其峰温向低温移动约70℃，且取组分催化剂中Pt的H2吸附性能大大降低，使催化剂表面乙烯加氢能力降低，从而提高了产物芳烃的选择性．Pt－Ga／HZSM－5中Pt有助于提高催化剂的稳定性．提出Pt与Ga的双功能作用．

用MINDO／3方法研究SCRCR′CO的热重排反应的机理，给出了活化能和IRC途径，讨论了活化能与取代基R′和迁移基R的性质之间的内在联系．

以IR光谱和程序升温硫化方法对近年来催化研究和应用较多的几种杂多酸在H2S作用下的硫化过程进行了研究．在SiW12、PW12和PMo12三种杂多酸中，PMo12最易发生硫化作用，其两种桥氧比端氧易硫化的倾向也最大．PW12次之．在初始硫化阶段，杂多酸中的部分氧原子在维持其Keggin骨架结构情况下被硫原子取代．在这一条件下硫氧交换是可逆的．对于PMo12，可维持其Keggin结构的温度接近室温，对于SiW12和PW12，该温度在673K～723K之间．当超过这一特定温度时，杂多酸的硫化作用不再可逆，深度硫化作用可能伴随Keggin骨架结构的解体．

通过一系列电解质体系水的拉曼光谱测量，得到了阴、阳离子种类和浓度引起的水伸缩振动和弯曲振动谱带丰富的变化信息．ClO4－能有效地破坏水分子间的氢键，随着ClO4－浓度的增加，水分子间的氢键并非逐步被打断，而是氢键被破坏的水分子越来越多，从而使水分子有序度增大，这种氢键破坏方式符合水的混合模型（Mixture Model）．SO42－浓度的增加对水的Raman光谱影响较小，是由于SO42－与水分子间有氢键作用的结果．虽然阳离子浓度对水的Raman光谱影响很小，但不同阳离子体系水的Raman谱有较大的差别，Li十与Cs十会引起水分子的拉曼谱较大的变化，Na十与K十对水的拉曼谱影响都不大．

采用VUV同步辐射光源，在超声射流冷却条件下研究了二氯甲烷（CH2Cl2）光电离及其解离电离的动力学过程，测得CH2Cl2的电离能（IP）为11．32士0．01eV．通过对CH2Cl2光解离电离过程产生的碎片离子的出现势（AP）的测定，并结合有关中性分子的热力学数据，估算出该体系中有关离子的标准生成焓、中性分子和离子型分子中的键能及母体离子的解离能（DE）等一系列热力学数据．对CH2Cl2分子VUV光解离电离通道进行了细致的分析．

用旋转环（Au）－盘（热解石墨，PG）电极研究了氧在聚钴原卟啉二甲酯膜（PolyCoPP）上的电催化还原．实验发现在0．1mol•L－1NaOH，O2饱和的溶液中，当盘电位在低极化区时，氧的还原主要是二电子还原过程，HO2－为主要产物，不会再进一步还原为OH－；而在高极化区时，氧既有四电子的直接还原，也有HO2－的进一步还原．

讨论了沸点升高法测定混和溶剂汽化热和汽化熵的原理，并用拟静态法测定了乙醇－丙酮，苯－四氯化碳和苯－甲苯三组混和溶剂在不同组成下的正常沸点，根据沸点数据求得了混和溶剂的微分汽化热和汽化熵．实验结果表明，二元混和溶剂与理想溶液偏离不大时，其正常汽化熵符合Trouton规则．

Polyaniline and its derivatives is one kind of important conductive polymer. In this paper, the active mechanism of substitution and doping on conductivity of polyanilines was studied by means of EHMO-CO method. The result showed that doping and substitution had different active mechanism on conductivity of polyanilines, doping lowered markedly the exciting energy of carrier, while substitution altered chiefly the band width.

The thermograms of Brucalles Br﹒10 and Br﹒981 have been determined. From the thermograms, a thermokinetic equation ln|[(P/Pmax)1-m-1]| =lnb - kt could be established for the limited growth of bacteria. From this equation, the growth constant k, the intial growth rate b, the mean specific growth rate k/m, and the mean thermal power increasing rate Pmaxk/(2m + 2) were calculated. This equation is very significant for the study of bacteria growth and their characteristics.

Formation and structure of liquid crystal in lecithin-water-oleic acid system were studied. It was found that different from the lecithin-water system, there are two types of liquid crystal present. The lamellar liquid crystal was formed at lower content of oleic acid, the values of interlayer spacing are larger than the values in the corresponding liquid crystal without oleic acid. The inverse hexangonal liquid crysta1 was formed at higher content of oleic acid. In lecithin-water-oleic acid(containing 15℅ cholesterol) system the phase behavior of liquid crystal is similar to that in the lecithin-water-oleic acid system. The solubilization rate of solid cholesterol in lamellar liquid crystal of lecithin-water-oleic acid system is more faster than that of lecithin-water system.

研究了不同磺化度的酞菁在甲醇－水混合溶剂中的聚集行为．通过紫外－可见光谱测定，发现磺化度在1．0以上时染料在稀溶液中主要以单体和二聚体的形式存在，并可用简便的方法计算出聚集平衡常数和平衡时单体所占的百分比，得到磺化度越低越易聚集的结论．有关激发态的实验表明，增加酞菁磺化度有助于提高表观荧光量子产率，但对荧光寿命影响较小．

The vapor heat capacities of acetic acid, propionic acid, n-butyric acid at various temperatures under atmospheric pressure were measured with a multicomponent vapor flow calorimeter. The results show that the vapor heat capacities of carboxylic acids are much larger than those of the ideal gases at the same temperature and that the vapor heat capacities decrease with increasing temperature. The effect of association in the vapor phase on the vapor heat capacity was studied.

The effect of pH on the adsorption of anionic dye Titan yellow on the activated carbon from aqueous solution has been studied. It has been found that the Zeta potential of the activated carbon has a great effect on adsorption capacity of Titan yellow. The kinetic and the thermodynamic parameters of adsorption as a function of pH has been evaluated. The mechanism for adsorption of anionic dye Titan yellow on the activated carbon has also been discussed.

The photovoltaic features and photo-induced interfacial charge transfer of CuPc-modified Q-CdS films were investigated by surface photovoltage spectra and optical absorption spectra. The results show that the interfacial charge transfer and photosensitization between CuPc and Q-CdS occur under illumination. Based on the observations, the generation and processes of the charge transfer are proposed and discussed.

The activation energies and the reaction orders of the thermal decomposition of three arnmonium molybdates in air were calculated for the first time according to Kissinger method from the DSC curves of their mixture at different heating rates.

Copper oxide cluster ions CunOm n=1-22, m=1-12 are generated by 523 nm laser ablation of CuCO3 solid sample with Time of Flight Mass Spectrometer detection. By changing precursor, we get similar TOF MS from Cu(NO3)2 sample, but narrower mass distribution from CuO sample. We suggest that this is caused by collisionally stabilization. Small gas molecules CO2 and NO2, generated by laser ablation of CuCO3 and Cu(NO3)2, act as buffer gas in supersonic molecular beams, and they are helpful for the production of high mass clusters.