Self Assembled Monolayers(SAMs) of a series of mercapto contained azobenzene derivatives with the structure of CnH2n+1AzoO(CH 2)mSH (where n =4,6,8,10,12; with m =3,5 respectively) were prepared and characterized. Wettability measurement of water on the SAMs demonstrates that molecular packing density in the monolayers increases while the alkyl chain in the molecules is lengthened. Both the n and m values have similar contribution to the wetting property of SAMs. The RA IR spectra reveal that the alkyl chains in the SAMs tilt away dramatically from the surface normal direction with the increase in their length. However, the orientation of azobenzene moiety is found to be influenced slightly by the alkyl chain length, which is due to the tenderness of the molecule.

The investigation of the cis-trans conformations and their singlet and triplet electronic configurations of the oxamidato bridged binuclear copper(II) complex unit Cu 2(oxen)(OH) 2 [H 2oxen=N,N′-bis(2-aminoethyl ) oxamide ] has been carried out from ab initio calculation by using Gaussian 94W package and taking LanL2DZ basis set. The stabilities of the cis trans conformations and the S T configurations of the structural unit were discussed. It is indicated from the calculations that the triplet electronic configuration of the complex unit in trans conformation is more stable. The reasons were analysed from the characteristics of its electronic structure, e.g .,the population regularities of the charges and the compositions of the molecular orbitals. The results are in agreement with experimental regularities satisfactorily.

 A study was carried out both theoretically and experimentally on the solute diffusion in gel networks. The emphasis of this study was on the effect of network fluctuation. A model of diffusion was established based on the theory of dynamic disordered hopping, which was originally developed to describe the conduction of charged particles in polyelectrolyte. Temperature sensitive poly(n-isopropylacrylamide) gels were prepared and methyl blue was chosen as a solute for the diffusion experiment. Laser light scattering spectroscopy was used to study the dynamic behaviors of the gel network. Theoretical predictions agree qualitatively with the experimental results.

The influence of alcohol on the aggregation behavior of the zwitterionic surfactant (dodecyldimethylammonium hydroxyl propanesulfonate, DDAHPS) molecules in water has been investigated by the steady state fluorescence quenching technique and the time resolved fluorescence method. The results show that the aggregation number of surfactant ( N ) decreases with the increasing addition of n butanol in 4.0×10 -2 mol•L -1 DDAHPS aqueous solution. Keeping the concentration of alcohol constant(ie. 2.14×10 -2 mol•L -1 ),the longer of the carbon chain of alcohol, the larger of the N value. The addition of n propanol and n butanol decrease the N value, while the n pentanol, n hexanol and n heptanol increase the N value. We also measured the effect of alcohol on the microenvoirnment polarity, pyrene fluorescence lifetime and efficiency of intramicellar excimer formation by pyrene.

The photoelectrochemical behaviors of the mutual modified nanocrystalline Fe 2O 3 and TiO 2 electrodes prepared by different methods (including the mutual doping of metal ions) were studied. With different incident light wavelength, transient photocurrent spectra showed different characteristics. A characteristics of n-type semiconductor appeared in Ti 4+ doped Fe2O3 nanocrystalline electrode; but there was no photoresponse in Fe2O3 coated TiO2 electrodes because of the dismatch of the energy levels of Fe 2O 3 and TiO 2; a characteristics of p n response coexistence appeared in Fe 3+ doped TiO 2 electrode and TiO 2 modified (coated or coupled ) Fe2O3 nanocrystalline electrodes, even the characteristic of p type semiconductor appeared in two special electrodes. All these phenomena can be explained reasonably by the formation of the microzone of p-type semiconductor.

Starting niobium samples with different oxygen contents were produced by arc melting and electron beam melting respectively. The equilibrium oxygen contents of the niobium metal have been measured in the temperature range of 1173-1473K for Ca-CaO-Nb and of 973 and1173K for Mg-M -Nb by an inert gas fusion infrared absorption method. The equilibrium oxygen contents in Nb increases with temperature, which is independent of oxygen concentration of the starting Nb samples. Based on the equilibrium oxygen contents, the Gibbs free energy of the oxygen dissolution in niobium metal, as well as the expressions of oxygen pressure temperature component ( p t x ) for theses two equilibrium systems were obtained. The acquired free energy values a less than that reported in the literature. This difference is mainly attributed to the adoption of different standard formation free energy of CaO.

Fe 2O 3 K 2O Catalysts with different content of K 2O and calcined at different temperature were characterized by using Mossbauer spectroscopy. It was found from the experiments that only a sextuplet assignable to Fe 3+ of α Fe 2O 3 could be detected while the K 2O content in these catalysts were lower than 5%and the calcination temperature was below 900℃;and complex spectra ,which could be fitted with several sextuplets of trivalent irons present in α Fe 2O 3, KFeO 2, K 1+ x Fe 11 O 17 and α FeOOH ,and a doublet of Fe 3+ in γ FeOOH ,would be observed if the K 2O content were 10%～27%and the calcination temperature were 800～900℃. The γ FeOOH, as a hydrous iron oxide ,was the decomposition product of KFeO 2 which was strong hydroscopic by absorbing moisture from the atmosphere. The results also suggested that Mossbauer spectroscopy was a better mean than XRD for the characterizations of Fe 2O 3-K 2O catalysts,by which ,α-FeOOH ,γ-FeOOH and α Fe 2O 3 in amorphous or crystallite forms ( unable to be found by XRD ) could be detected . It was also shown from the Mossbauer spectroscopy and a TPR studies that potassium could retard the reduction of Fe(III) to Fe(II) in the Fe 2O 3 K 2O catalysts. 

Several chiral clusters RuCoMo(μ-3 S)(CO) 8C 5H 4C(O)R were synthesized by the thermal reaction of the precursor (μ-3 S)RuCo2(CO) 9 with functionally substituted cyclopentadienyl tricarbonyl metal complex anions [M(CO) 3(η5-C5H4)C(O)R] -(R=H,CH3,C6H5,C 6H 4C(O)OCH 3;M=Mo,W)in THF. All of these clusters were characterized by C/H elemental analysis, IR and 1H NMR. Crystal structure of the cluster (μ-3 S)RuCoMo(CO)8CpCOC6H5 has also been solved by single crystal X ray diffraction.

The mechanism of the reaction HNCO +OH→H2 O +NCO has been studied by using ab initio MO method(at UMP4/6 31G** level) with energy gradient technique. The reaction path was traced with Fukui’s theory of intrinsic reaction coordinate (IRC). Along the IRC, some dynamics properties were investigated by applying reaction path Hamiltonian theory. On this basis, the rate constants of the reaction at different temperatures were calculated by transition state theory with correction of quantum effect. The theoretically calculated rate constants are in od agreement with experimental results. This shows that the reaction is a direct reaction of hydrogen abstraction with only one step.

The reactions of different iron porphrin complexes Fe Ⅲ(TPP)Cl [tetraphenylporphinatoiron(III) chloride],Fe Ⅲ(TMOPP)Cl [tetrakis(4-methoxy-phenyl)porphinatoiron(III) chloride] and Fe Ⅲ(TFPP)Cl [tetrakis(pentafluoro-phenyl)porphinatoiron(III) chloride] with single oxygen atom donor m chloroperoxybenzoic acid ( m CPBA) under ambient conditions has been investigated by rapid mixing stopped flow spectrophotometry. It is shown that the same oxoiron(IV) porphyrin complexes intermediates are produced, and the Fe Ⅲ(TFPP)Cl model system that incorporated electronic and steric protection of the oxidation vulnerable meso position is more stable. Preliminary substituent effect data reveal the following trends for Fe Ⅲ(Pro.)Cl decomposition: Fe Ⅲ(TMOPP)Cl > Fe Ⅲ(TPP)Cl > Fe Ⅲ(TFPP)Cl. Epoxidization reactivity of 1,4 diphenylbutadiene by Fe Ⅲ(TPP)Cl or Fe Ⅲ(TMOPP)Cl with m CPBA is enhanced, although the catalytic reactivity of Fe Ⅲ(TFPP)Cl m CPBA model system in CH 2Cl 2 is lower, but is faster in the presence of methanol.

The photodissociation of oxalyl chloride and 2,3 butanedione at 193nm and 248nm have been studied by Time resolved FTIR emission spectroscopy. The IR fluorescence emission was observed and the rotational and vibrational populations of the CO product were obtained. It is suggested that the photolysis mechanism is two RCO radicals formed via a fission of C-C bond, followed by a decomposition of the RCO intermediate to vibrationally excited CO( v ) and R radical.

The standard electromotive forces of the reversible cells consisted of the Corning monovalent general cation selective electrode (M + ISE) and chloride selective electrode (Cl ISE), namely
Cl --ISE｜RbCl( m ),H 2O(1- x ),DMF( x )｜M +-ISE
have been measured, and the standard free energies of transfer(ΔStΘ) of RbCl from H2O to mixtures of H2O DMF have been calculated, the standard transfer entropies(ΔStΘ) have been also calculated from temperature coefficients ofΔStΘof RbCl at seven temperatures from 283.15 K to 318.15 K. The behavior of change ofΔStΘof RbCl with experimental temperature and mole fraction ( x ) of DMF in the mixed solvents and its influence on the structure of the mixed solvents were discussed on the basis of solvation theory ofelectrolyte solution.

Distribution coefficient K of C n H 2 n +1 OH between micellar phase and water phase in CTAB/C n OH/H 2O O/W system increases with the increase of alcohol chain length. The relationship between solubilization Gibbs free energyΔGmΘ(A) of alcohol in CTAB micellar system and alcohol chain length( n C.) is given by an equation,viz: ΔGmΘ(A)  = -6.82-1.175 n C. The measurement of cyclic voltammetry shows that the second cmc of CTAB reduces with the addition of alcohol and the increase of alcohol chain length, which is advantageous to the CTAB micelle sphere to rod transition.

 The thermograms of the germination and growth of rice and tree seeds were determined and studied by using a newly constructed microcalorimeter build in this laboratory at Wuhan University. The thermograms show the existence of physiological triphasic patterns (including imbibition, activation and growth stages)in the germination and growth process. Nonequilibrium thermodynamics of the germination and growth of seeds was considered under given conditions, and the thermodynamic functions of the germination and growth of seeds were calculated.

The amorphous V 2O 5 films prepared by vacuum evaporation are unstable and easily dissolved by electrolyte during the electrochromic process, so unfit to make electrochromic materials. We found that the annealed films have enhanced stability and electrochromic properties. We studied the microstructural changes during the electrochromic process by Raman spectra and discussed the mechanism for the enhancement. The results indicated that the amorphous films annealed by 400-500℃became polycrystalline and the films contained (V 2O 5)n ordered chains which prevented the films from solution effectively and enhanced the electrochromic characteristics. When colored and decolored, the microstructure of the polycrystalline V 2O 5 films changed inversely. During the cathodic polarization process, Li+ inserted into the V 2O 5 crystal cell , formed V-O-Li band, disordered the films and UV absorption of the films blue shifted. On the contrary , during the anodic polarization process, Li +escaped from the crystal cell. The films largely restored .

With high presure in situ 1H NMR technique, the alternative copolymerization of CO with ethylene catalyzed by Pd(Ⅱ)-DPPPr-CF3COOH catalyst were studied under 2.0MPa CO/ethylene(1:1 ,molar ratio) using CD 3OD and CD 3COCD 3 as solvents. The 1H NMR signals of coordinated ethylene and methylene linked to Pd(Ⅱ) were observed, which showed that ethylene was activated by coordination with Pd(Ⅱ) during the copolymerization before it's insertion into Pd—C bond to achieve the chain propagation. But the signal of Pd—H bond was not observed in all the in situ 1H NMR experiments, which indicated that the copolymerization initiation was not caused by Pd—H bond, or Pd—H initiation was very few in alcoholic solvent.