ELECTROCARBOXYLATION OF ORGANIC COMPOUNDS WITH CARBON DIOXIDE CATALYZED BY METALLOPORPHYRINS(Ⅱ)——ELECTROSYNTHESIS OF SOME ORGANIC COMPOUNDS WITH CO_2 CATALYZED BY CoTPP

The catalyzation of CoTPP for electrocarboxylation of alkyl halides, alkenes and ketones with CO_2 are studied. The electrocarboxylation of these organic compounds with CO_2 in the presenec of catalyst can occur at more positive potential than that of no catalyst. The products of electrocarboxylation were identified by UV, IR and GC-MS. The electrocarboxylation mechanisms of different organic compounds are discussed.     

ELECTROCARBOXYLATION OF ORGANIC COMPOUNDS WITH CARBON DIOXIDE CATALYZED BY METALLOPORPHYRINS(Ⅰ)——CATALYTIC ACTIVITIES OF METALLOPORPHYRINS FOR ELECTROCARBOXYLATION OF BENZYL CHLORIDE

The electrocarboxylation of benzyl chloride with CO_2 catalyzed by metalloporphyrins and the effects of different kinds of central metals and ligands on catalytic activities are reported. These metalloporphyrins whose central metals can form corresponding M (Ⅰ) complexes such as CoTPP, FeTPP have high activities. With water-soluble porphyrin ligands such as TPPS, TTMAPI, the corresponding metalloporphyrins have high catalytic activity. Electron-with-drawing groups on the porphyrin ring cause the lowering of activity.     

ELECTROCARBOXYLATION OF ORGANIC COMPOUNDS WITH CARBON DIOXIDE CATALYZED BY METALLOPORPHYRINS(Ⅲ)——EFFECTS OF AXIAL LIGANDS ON CATALYTIC ACTIVITY OF CoTPP

The effects of peptides,amino acids and organic bases as an axial ligand on reaction ac-tivities in the electrocarboxylation of benzyl chloride with CO_2 catalyzed by CoTPP are reported.The imidazole organic base,peptide containing —SH and amino acid containing imidazolyl en-hance the catalytic activity.The effect of imidazole amounts on the catalytic activity of CoTPP isstudied.     

STUDIES OF UNUSUAL OXIDATION STATES OF TRANSITION METALS (Ⅰ)——KINETICS AND MECHANISM OF OXIDATION OF POTASSIUM THIOCYANATE BY DIPERIODATOARGENTATE(Ⅲ) ION IN ALKALINE MEDIUM

The kinetics of oxidation of potassium thiocyanate by diperiodatoargentate (Ⅲ) (DPA) ions was studied in aqueous alkaline medium ([OH~-]=7.00×10~(-3)—0.200 mol. dm~(-3)) at a constant ionic strength (μ=0.30 mol. dm~(-3)). It is found that the reaction order in DPA is unity. The dependence of the rate on [OH~-] implies that there are two pathways through which the reaction proceeds. In each pathway, the order in NCS-is fractional and the kinetic data fit well in with Michaelis-Menten process. The influence of ligand on the reaction is examined and the reactive species are inferred. Two pathways of inner-sphere two-electrons transfer are believed to be involved in the oxidation. The rate equations are derived and all the equilibrium constants and rate constants are evaluated. Activation parameters of one pathway are determined.     

SYNTHESIS OF A GROUP OF MESOGEN JACKETED LIQUID CRYSTAL POLYMERS

A group of the mesogen jacketed liquid crystal polymers based on the monomers 2,5-bis (4-substituted benzoyl)oxystyrenes are synthesized. The substituents include alkoxy, alkyl, and cyano groups. The synthesis and the primary characterization of the liquid crystal phase of the monomers and the polymers are described. While some of the monomers give smectic textures the polymers are found to be nematic above their melting or glass transition temperatures. Interestingly the unsubstituted monomer and its polymer poly 2,5-di( benzoyloxy ) styrene are also liquid crystalline. The single crystal structure of one of the monomers is also discussed.     

FORMATION STUDY OF TOROIDAL CONDENSATION OF DNA

A detailed study of the formation of toroidal condensation produced from the 2700 base pair fragments of plasmid PUCI3 DNA, induced by metal ions, is introduced. We have extracted several typical intermediate structures based on investigation by electron microscopy, and compared their size distributions. The observations suggest that the formation process of DNA condensation is the process of folding and arranging DNA chains and that of disorderorder transition. The result also indicates that the condensed particles are polymeric, but not randomly aggregative, further proving thetoroidal structures are formed in certain regularities.     

THE COURSE OF THE POLYPEPTIDE CHAIN OF TRICHOSANTHIN MOLECULE

The course of the polypeptide chain of Trichosanthin has been determined from the electron density map at 4 resolution. The structure belongs to α+β type. It contains eight α-helices (39% of total residues) and four β-sheets (32% of total residues) which are made up of thirteen β-strands. The α-helices are relatively in the centre of the molecule and surrounded by β-sheets. This is the characteristic feature of Trichosanthin structure. This kind of structural arrangement has not been reported before. The transformation matrix and translation vector, which superpose two molecules in one asymmetric unit, were obtained. The root mean square error is 1.31 for this superposition.     

ENUMERATION OF ISOMERS OF SUBSTITUTED CROWN ETHERS

The graphtheory method is used to enumerate the numbers of constitutions,configurations,chiral and achiral configurations of substituted crown ethers.The numericalresults are tabulated.     

IDENTIFICATION OF DYNAMIC BEHAVIOUR OF LIGHT-POTENTIAL TRANSDUCTION SYSTEM IN PHOTORECEPTOR OF CALLIPHORA ERYTHROCEPHALA USING IRS-STIMULI

The linear dynamic behaviour of the light-potential transduction system in photorceeptor of Calliphora erythrocephala has been studied through the cross-correlation method using InverseRepeat Sequences and the lineal model of phototransduction is provided. The impulse response function and frequency characteristics have been determiued in the condition of background illumination.The results suggest that the R1-6 is equipped with a gain and time constant control mechanism which depends upon the adaptation level of the system under study.It becomes evident that the IRS correlation method is powerful to quantify the dynamic characteristics of the system containing nonlinearities and will become a very popular application for the study of biological sensory systems.The visual receptor cells R1-6 in the fly are the most sensible choice for the study of the light-potential transdnction system of the eye. The input of the system is the temporarily varying light intensity applied upon the eyes of the fly and th     

ISOLATION AND STRUCTURE OF RANAMARGARIN,A NEW TACHYKININ FROM THE SKIN OF CHINESE FROG Rana margaratae

A new tetradecapeptide, ranamargarin, has been isolated by Sep-Pak C_(18) and HPLC from methanol extracts of the skin of the Chinese frogRana margaratae. The sequence of the peptide is: Asp-Asp-Ala-Ser-Asp-Arg-Ala-Lys-Lys-Phe-Tyr-Gly-Leu-Met-NH_2. This structure has been confirmed by synthesis. The peptide is the largest among the amphibian tachykinins and its N-terminal amino acids are quite different from those of the other tachykinins. The formation of the sulfoxide and peak-splitting of ranamargarin during purification procedures are briefly discussed.     

STRUCTURAL STUDY OF BENZYLOXYCARBONYL-PROLYL-ALANYL-THREONYL-TERT-BUTYL ESTER

The crystal structure and molecular conformation of the synthetic oligopeptide (Z-Pro-Ala-Thr (But)_2) have been determined by X-ray analysis. The crystal is orthorhombic, spacegroup P2_12_12_1, with four molecules per unit cell of dimensions: a = 29.557, b = 11.583 andc = 8.830A. The diffraction data were collected using a PW-1100 four-circle diffractometer.The strueture was solved by direct methods, using the MULTAN-80 system of computerprograms and refined by the block-diagonal least-squares method. 7he final R value is 0.088(for non-hydrogen atoms). The Ala residue in this peptide is nearly in an eclipsed conformation. The peptide bondbetween Z and Pro is cis. The two atoms, C~β aud C~γ, are displaced on opposite sides of thepyrrolidine ring plane. The dihedral augles between the neighbouring peptide or carboxylgroups are all close to 90°. Hydrogen bonds link the peptides forming a chain in the zdireetion. The stacking of the peptides in the x and y directions is the result of the van derWaals fo     

THE PARAMETER KERNELS FOR THE LINEAR INVERSION OF THE FREE OSCILLATION OF THE EARTH (Ⅱ)

This is the second instalment of the paper, in which the method of derivation of the for-mulas of parameter kernels for the spheroidal oscillations are considered. The principle ofRayleigh is used to derive the formulas of the kernels of the two elastic parameters, i.e. μand λ. But for that of ρ, it is found very difficult to get satisfactory results. A new butsimpler approach is followed and very satisfactory results are obtained.     

CALORIMETRIC STUDY OF COLD AND THERMAL DENATURATION OF BOVINE β-LACTOGLOBULIN B

The denaturational behaviour of bovine β-lactoglobulin B has been studied in solutions containing guanidine hydrochloride by differential scanning calorimetry. The experiments have shown that complete peaks of cold denaturation can be recorded also in high concentration of protein solutions. The cold denaturation and the renaturation of the protein are reproducible, but the thermal denaturation is irreversible. The activation energy of thermal denaturation calculated is about 285 kJ/mol.     

CRYSTALLIZATION OF NaY ZEOLITE IN THE PRESENCE OF “CRYSTAL DIRECTION AGENT”AND RECRYSTALLIZATION OF NaA INTO NaY IN THE REACTION MIXTURE

The process of nucleation and crystal growth of NaY zeolite over a temperature rangeof 55°--100℃ in the presence of "crystal direction agent " are studied. The apparent ac-tivation energy for nucleation and that for crystal growth are evaluated. The mechanism ofthe recrystallization of NaA into NaY is investigated by adding NaA zeolite to the reactionmixture in which the crystallization of NaY zeolite is proceeding. The recrystallization ofNaA zeolite does not occur until the NaY crystallization from the reaction mixture is com-pleted. Thus the process of recrystallization of NaA into NaY might be shown as follows: Amorphous aluminosilicate gel→NaY NaA→NaY NaA Scanning electron microscopic observations and the recrystallization curves show that therecrystallization of NaA into NaY is getting n with a degradation and dissolution of surfacecrystals on the NaA zeolite and that the nucleation and crystal growth of NaY take placeimmediately at the surface of NaA crystals.     

DISPERSION STATE OF ZINC OXIDE ON SURFACE OF SILICA GEL AND SURFACE ACIDITY OF ZnO/SiO_2

The dispersion threshold level of zinc oxide on silica gel was determined by X-ray quantitative phase analysis. And the results of XPS experiments show that the surface of the sample is enriched with ZnO and there is a limit for the ZnO amount dispersed on the surface. The value of this limit is corresponding with the threshold level obtained by XRD. The measurements of surfaee acidity show that there are some stronger acid sites on the surface of ZnO/SiO_2, they have not been found on the ZnO or SiO_2 individually, and the total amount of acid increases remarkably. The acidity depends on the ZnO concentration in the surface phase and reaches the maximum at the threshold value.In this paper, we propose a new point of view for the origin of the acidity on surface of the ZnO/SiO_2 samples. ZnO is well dispersed on the surface of SiO_2 gel in a monolayer state. In this situation, some new surface structure units emerge as a result of interaction between dispersed ZnO and the carrier, which are responsible     

ASSIGNMENT OF ~(13)C NMR SPECTRA OF POLYMER WITH SEMIEMPIRICAL METHOD——SURVEY OF SPECTRUM OF SECONDARY CARBON OF 1, 2-PBD

In chain molecules of 1, 2-PBD, there are two kinds of gauche arrangements, which is the cause of making the spectrum of the secondary carbon in main chain of the polymer split. In such a complex system, the gauche arrangements of the secondary carbon and the tertiary carbon occupy an important position. Hence, the contribution of the tertiary carbon to the chemical shifts of the secondary carbon has a decisive effect on the sequence structure distribution. In comparison the contribution of vinyl groups is much less. The γ values are: γ_1=-6.37～-6.41 ppm represents the effect of the tertiary carbon and γ_2=0.0～-1.56 ppm the contribution of vinyl. The mean square errors are 0.364 and 0.166×10~(-2) ppm~2, respectively in the two cases of considering the effect of vinyl and vice versa. In this paper, we discuss the effects of model chain type, chain length and temperature on the bond probability. Meanwhile, it is pointed out that there exist a few cases, which are not in accord with the usual distrib     

GROUP TRANSFER POLYMERIZATION OF ETHYL ACRYLATE WITH LEWIS ACID CATALYST

This paper reports the kinetics of group transfer polymerization (GTP)of ethyl acrylate (EA)with zinc iodide catalyst in 1,2-dichloroethane using dimethyl ketene methyl trimethylsilyl acetal (MTS) as initiator at 0℃and above 0℃. The amount of catalyst used was studied. When zinc iodide catalyst used is more than 10mol% relative to monomer, the rate of polymerization is proportional to the concentration of monomer, whereas zinc iodide catalyst used is less than 10 mol% of the monomer, the rate of polymerization is independent of the monomer concentration.In the GTP of EA an induction period was observed when the zinc iodide contents are less than l0mol%. If the reaction temperature is over 0℃, living species become unstable and diminish, leading to incomplete monomer conversion. The reaction curves equations are obtained. The polymers have narrow molecular weight distributions which are not changed as decreasing zinc iodide contents. The polydispersity is about 1.2.     

STRUCTURE-REACTIVITY STUDIES ON THE EXTRACTION OF RARE EARTHS BY DIALKYL ISOPROPYLPHOSPHONATES

Dialkyl isopropylphosphonates with various alkyl groups are synthesized for the structure-reactivity studies on the extraction of rare earths. Steric effect of ligands on the extrac-tion behaviour of rare earth is well demonstrated due to the lanthanide contraction. Thethermodynamic functions of the extraction reaction are estimated and the influence of chem-ical structure of extractants is discussed. By the method of continuous variation as well asthe elementary analysis, the composition of the extracted species is deduced as Ln(NO_3)_3·3L.The structure of the coordination compound is further elucidated by IR and NMR spectra.The magnetic property and the differential thermal analysis of the complexes are also studied.     

THE ESTIMATION OF ORDERING DEGREE OF CORONA-POLED NONLINEAR OPTICAL POLYMER FILMS

The investigation of electrochromic effect of corona-poled nonlinear optical polymer films is an effective method for the estimation of poling level and the selection of poling conditions. The poling electric field E_p and orientational order parameter Φ, which are the important parameters to predict d_(33) of poled films, can be calculated by a simple operation from the number of red shift of charge transfer absorption band. The calculated results are in good agreement with the experimental data.     

STUDIES ON CAUSES OF THE POCKMARKED DISEASE OF CHINESE ANGELICA

The present studies show that there is a biocommunity including 59 kinds of organisms in and around the focus of angelica pockmarked disease to form a soil food web. These results add new content to the relationship among food webmembersr~[1, 2]. The studies prove that 6 species of Fusarium are pathogenes, the wounds caused by underground insects and artificial factors are beneficial to pathogene infection, and invertebrates carrying pathogenes aggravate the disease. According to the tests, a disease control method is proposed and applied to 14, 000 mu in Gansu Province, and economic and social benefits have been obtained. The present studies are part of the state projects on technological development of agriculture, animal husbandry and fishery.