THE CHAIN STRUCTURE OF 1,2-POLYBUTADIENES PREPARED WITH MOLYBDENUM CATALYST SYSTEMS

The chain structure of 1,2-polybutadienes prepared with molybdenum catalyst systems has been studied by IR, ~(13)C-NMR and T_g method, and the method to regulate the chain structure investigated. It was found that some polar additives, e. g., allyl halides, are able to regulate not only the content of 1,2-units in the polymer, but also its configuration and sequence distribution. Attempt has been made to estimate the sequence length of stereo-isomers of 1,2-units by statistical theory.     

APPLICATION OF 2D-NMR TECHNIQUES IN THE STRUCTURE DETERMINATION OF HYPODEMATINE

An alkaloid with a novel structure,named Hypodematine,was isolatedfrom Hypodematium sinense Iwatsuki(belonging to Thelypterdaceae).Itsstructure was elucidated by means of the ~1H-~1H COSY' ~1H-~(13)C COSY and long-range~1H-~(13)C COSY spectroscopy to have the skeleton of benzo-aza-cyclooctatetraenewith a phenyl substituent.Such basic structure has not been found in the na-tural product before.     

THE CORRELATION BETWEEN ~(13)C CHEMICAL SHIFTS OF DNA AND INTERSTRAND PURINE-PURINE CLASH

The correlation between ~(13)C chemical shifts of DNA and structure parameters (the mainaxis helix twist angle Ω, base--plane roll angle ρ, main chain torsion angle δ and pro-peller twist angle ω) has been discovered and proved indirectly. The carbons relating tothe structure parameters have been found and interpreted theoretically. Relative variationsin chemical shifts of these carbons obviously reflect purine-purine clash (steric hindrance)and have been compared with sum functions Σ of Calladine--Dickerson rules. It would bepossible to provide the information about conformation of DNA from ~(13)C NMR spectra andto observe the structure parameters of Ω,ρ,δ and ω of DNA in solution.     

Synthesis,Crystal Structure,Two-photon Absorption and Biological Imaging Application of a Water Soluble Carbazole Quaternary Ammonium Compound

A novel carbazole quaternary ammonium compound(abbreviated as T_2) had been synthesized and characterized by ~1H NMR, ~(13)C NMR and Mass spectrometry. The single-crystal structure has been determined by X-ray single-crystal diffraction. The electrochemical and two-photon absorption properties of T_2 were systematically studied by cyclic voltammetry and Z-scan determination methods, respectively. The results suggested that T_2 had a good oxidation-reduction and excellent nonlinear optical property. The two-photon absorption(TPA) value has a maximum corresponding to cross section σ = 7963.3 GM(Goeppert-Mayer units) at 700 nm, indicating potential applications in nonlinear optical materials. Furthermore, attributing to the excellent water solubility and low cytotoxicity, the compound was explored on its primary application in biological imaging.     

Effect of Zr and C Co-doping on the Optical Properties and Electronic Structure of TiO_2

The systematic trends and effect introduced by Zr and C co-doping to TiO2 of electronic structure and optical properties of anatase TiO2 have been calculated by the plane-wave ultra-soft pseudopotential density functional theory (DFT) method within the generalized gradient approximation (GGA) for the exchange-correlation potential. Through the current calculations, the density of states (DOS), energy band structure and optical absorption coefficients have been obtained for TiO2 and compared with the doped TiO2, and the influence of electronic structure and optical properties caused by Zr and C co-doping has been presented qualitatively together. The results revealed that the energy band gap has been decreased owing to the doped Zr and C, whereas the optical absorption coefficients have been increased in the region of 400～800 nm and a red shift of absorption band can be found. Accordingly, photo catalytic activity of TiO2 has been enhanced. The current calculations are in good agreement with the experimental data.     

Highly reversible lead-carbon battery anode with lead grafting on the carbon surface

A novel C/Pb composite has been successfully prepared by electroless plating to reduce the hydrogen evolution and achieve the high reversibility of the anode of lead-carbon battery(LCB). The deposited lead on the surface of C/Pb composite was found to be uniform and adherent to carbon surface. Because lead has been stuck on the surface of C/Pb composite, the embedded structure suppresses the hydrogen evolution of lead-carbon anode and strengthens the connection between carbon additive and sponge lead.Compared with the blank anode, the lead-carbon anode with C/Pb composite displays excellent charge—discharge reversibility, which is attributed to the good connection between carbon additives and lead that has been stuck on the surface of C/Pb composite during the preparation process. The addition of C/Pb composite maintains a solid anode structure with high specific surface area and power volume, and thereby, it plays a significant role in the highly reversible lead-carbon anode.     

MOLECULAR STRUCTURE AND ABSOLUTE CONFIGURATION OF SUBEROGORGIN

In the present paper it is reported that the molecular structure and absolute configuration of poisonous suberogorgin are determined by using X-ray diffraction method. The crystal of suberogorgin belongs to orthogonal system with space group D_2~4-P2_12_12_1. The crystallographic parameters are: a=16.135, b=13.189, c=12.901, Z=8. The initial model of the crystal structure was solved by the direct method. The refinement of the strueture parameters was carried out by using the least square method and led to a final R-factor of 0.056. In accordance with the molecular structure of suberogorgin mentioned above, the solvent effect of NMR has been further discussed and the relationship between the molecular structure of suberogorgin and its toxicity has also been preliminarily investigated.     

ASPECTS OF THERMODYNAMICS OF POLYMER MIXTURES

In this brief review article some aspects of the thermodynamics of polymer mixtures are discussed, mainly based on the author's research. The studies of poly (methyl methacrylate)/chlorinated polyethylene (CPE), poly (butyl acrylate)/CPE and CPE/CPE (different chlorine content) mixture verify the "dissimilarity" and "similarity" principles for predicting miscibility of polymer mixtures. The sign of heat of mixing of oligomeric analogues is not sufficient in predicting the miscibility. The Flory equation of state theory has been applied to simulate the phase boundaries of polymer mixtures. The empirical entropy parameter Q_(12) plays an important role in the calculation, this reduces the usefulness of the theory. With energy parameter X_(12)≠0 and Q_(12)≠0 the spinodals so calculated are reasonable compared to experiments. A hole model was suggested for the statistics of polymer mixtures. The new hole theory combines the features of both the Flory equation of state theory and the Sanchez lattice fluid theory and can be reduced to them under some conditions.     

SYNTHESIS AND NMR CHARACTERIZATION OF PRECURSORS OF EPOXY NETWORK AS POLYMER HOST FOR SOLID ELECTROLYTE

To raise the room temperature ionic conductivity and improve the mechanical strength of a PEO-based polymer electrolyte, a noncrystalline two-component epoxy electrolyte system has been prepared. The diglycidyl ether of polyethylene glycols as precursors of the system were synthesized by a two-step process. The presumed structure of the product was characterized, by ~(13)C, ~1H NMR and IR spectroscopy. It was found that a side-reaction occurred between the secondary hydroxyl group of PEG-chlorohydrin and epichlorohydrin in some degree, resulting in a by- product containing—CH_2Cl side group. By selecting a characteristic signal, which is undistorted by the increase in the length of CH_2 CH_2—O segment, a ~1H NMR approach of determining the equivalent epoxy weight (EEW) was proposed. The method is valid to specimens even though the EEW is as high as 2,000. The examination of the specimens by DSC showed that epoxidation greatly depressed the crystallinity of the PEG's, whereas the T_g was raised.     

STUDY ON ORGANIC LIGHT—RARE—EARTH ADSORBENT—CERIUM BIS（OCTYLPHOSPHATE）

The tetravalent metal salts of monoalkyl phosphates[M(R-OPO3)2] are a new kind of stationary phases of chromatography-homogeneous bonded phases.The studies on preparation,structure and gas chromatographic efficiency of cerium bis (octylphosphate) (COPP) are reported in this paper. By using chemical analysis,infrared spectra,x-ray diffraction analysis ,the strong evidence that COPP has a layered structure of the α-zirconium phosphate type was demonstrated,the repetitive unit is C8H17OPO3CeO3POC8H17 and there is a little bending or interpenetration of the alkyl chains within the layers.The thermogravimetic analysis of the COPP indicated that it has much more thermalstability than silica-based packings.The thermodynamic parameters ΔH and molecular connectivity indexes x′ for the adsorption of several dozen compounds on the COPP have also been determined by gas chromatographic method,and the fine linearity between them was shown.     

Structure and properties of Ni(110) surface coadsorbing chlorine and oxygen

The coadsorption of chlorine with oxygen on Ni(110) surface has been investigated by XPS, UPS, AES and work function measurements. The chlorine preadsorption drastically inhibits the further uptake of oxygen. On the contrary, precovered oxygen has hardly any influence on the additional adsorption of chlorine due to the incorporation of precovered oxygen into the subsurface driven by the chlorine coadsorption. ARXPS measurements provide the evidence for this coadsorption model. The thermal desorption of chlorine and oxygen from the coadsorption surface is very similar to that of both individual adsorbates under the same heating conditions, but the desorption temperature of both the adsorbates apparently decreases on the coadsorption surface. The coadsorption and thermodesorption mechanisms are also discussed in detail.     

SYNTHESIS OF 1-SUBSTITUTED-BENZENESULFO-NYL-3-(4'''',6''''-DISUBSTITUTED-s-TRIAZIN.2''''-YL)-1,3,2-DIAZAPHOSPHOLIDINES AND THEIR STRUCTURAL ANALYSES

The reaction of N-substituted-benzenesulfonyl-N'-(4,6-disubstituted-s-triazin-2-yl)-ethylene diamines with tri(dialkylamine)phosphine has been studied and the cyclic products have been obtained by one-pot reaction. It was found from ~1H NMR and ~(13)C NMR analyses that the single bond rotation between the nitrogen atom 3 in the 1,3,2-diazaphospholidines and the carbon atom 2 in the s-triazine was hindered at room temperature, which was further confirmed by X-ray diffraction results. The most stable conformation of the phosphorous heterocycle is envelope-form. From the bond length and the hybridization of the nitrogen atom outside the ring, it was deduced that there was a certain contribution of dπ-pπ bond between P and N atoms.     

RING OPENING POLYMERIZATION OF PROPYLENE SULFIDE BY RARE EARTH COORDINATION CATALYSTS*

Ring opening polymerization of propylene sulfide using rare earth coordination catalysts has been investigated for the first time. It has been found that trinary rare earth coordination catslysts composed of rare earth compounds of phosphonate, naphthenate or acetylacetonate, trialkyl sluminum and water are effective catalysts for the polymerization of propylene sulfide. The polymerization in toluene is a homogeneous reaction. High molecular weight as high as several million poly(propylene sulfide) with high yield can be prepared by these catalysts. Kinetic studies showed that the polymerization rate is of first order with respect to both monomer concentration and catalyst concentration. The activation energy of the polymerization reaction is 61.4 k fJ/mol. The structure of the polymers so obtained has also been characterized by ~(13)C NMR spectroscopy, X-ray diffraction, gel permeation chromatography and differential scanning calorimetry.     

STRUCTURE OF (Trp)~(B1)-INSULIN AT 2RESOLUTION

The rhombohedral crystal structure of [Trp]~(B1)-insulin has been refined, using data to 2 and atomic coordinates of 2-zinc porcine insulin as starting model, and through the use of the restrained least-squares method, to an R value of 0.24. The result of refinement shows that in comparison with the 2-zinc insulin structure, some changes in local conformation occur, and are asymmetric for the two independent molecules related by a local two-fold axis. The obvious conformational changes are found to be in molecule 1, at its B-chain N-terminus and A13-residue region.     

Theoretical Studies on the Molecular Structures and Thermodynamic Properties of Polychlorinated Fluoranthenes

DFT-B3LYP/6-311G** method has been used to optimize molecular geometric structures of 527 polychlorinated fluoranthene(PCFRT) congeners and calculate their thermo-dynamic properties in the ideal gas state,such as heat capacity at constant volume(Cv),entropy(S),standard enthalpy of formation(ΔfH) and standard Gibbs free energy of formation(ΔfG).The relations of Cv,S,ΔfH and ΔfG with the number and position of chlorine atoms have also been explored,from which the relative stability of PCFRT congeners was theoretically proposed according to the magnitude of the relative standard Gibbs free energy of formation(Δr,fG).It was found that some of the PCFRT isomers are in a nonplanar configuration and there are intramolecular Cl…Cl weak interactions in some of the isomers.With increasing the number of chlorine atoms,the values of ΔfH and ΔfG of the most stable PCFRT isomers decrease initially and then increase.The values of ΔfH and ΔfG of PCFRT congeners with the same number of chlorine atoms show a strong dependence on the positions of chlorine atoms.The relative thermodynamic stability of PCFRT isomers is determined mainly by intramolecular adjacent Cl…Cl nuclear repulsive interaction between Cl atoms at two different six-membered rings.Most PCFRT congeners are easier to form thermodynamically than their parent compound.     

A Unique 2D Layered Fe~(Ⅲ) Coordination Polymer with only Formate Ligand as Bridges: Synthesis,Crystal Structure and Magnetic Properties

A novel two-dimensional layered Fe~(Ⅲ) formate, Fe(HCO_2)_2ClH_2O, has been synthesized by solvothermal reaction. The structure of complex is characterized by single-crystal X-ray diffraction. The complex crystallizes in tetragonal space group P4/nmm with a = 5.9588(6), c = 8.3831(17) ?, V = 297.66(7) ?~3, Z = 2, F(000) = 198, Dc = 2.224 g/cm~3, Mr = 199.35, μ = 2.927 mm~(-1), the final R = 0.0231 and w R = 0.0585(I 2σ(I)) for all data. Single-crystal structure analysis indicates that the complex has a 2D metal formate structure with only formate anions as bridges. The anti-anti formats link the FeⅢ ions to form a(4, 4) net, while the chlorine ions and water molecules coordinate to Fe~(Ⅲ) on both sides of the layer. Magnetic study have shown that an antiferromagnetic interactions between the FeⅢ ions in the complex. And a field induced spin-flop was detected at low temperature.     

SULFONATION OF A NEW POLYETHERETHERKETONE PREPARED FROM PHENOLPHTHALEIN

A novel polyetheretherketone (PEK-C) prepared from phenolphthalein has been synthesized. In order to improve some of its properties for application in high performance membrane, the PEK-C has been sulfonated with concentrated sulfuric acid. Degree of sulfonation can be regulated by controlling the temmperature and time of sulfonation. The characterization of the sulfonated PEK-C in sodium salt form has been made by IR, ~1H NMR and ~(13)C NMR etc. It is shown that the sulfonation appears to take place exclusively in the ortho position to phenolic ether of phenolphthalein unit. The result is in agreement with theoretical deduction. Some properties of the sulfonated PEK-C, such as solubility, transition temperature, thermal degradation and hydrophilicity have also been discussed.     

SYNTHESIS AND MORPHOLOGICAL STRUCTURE OF POLY (PHENYLENE SULFIDE AMIDE)

Poly (phenylene sulfide amide) (PPSA) has been synthesized by using sulfur as Ssource which reacts with dichlorobenzamide (DCBA) and alkali in polar organic solvent atthe atmospheric pressure. The polymer structures were determined by elemental analysis,FT-IR and ~1H-NMR. It is shown that the yielded polymer has linear structure and itsstructure unit is -p-C_6H_4-CONH-p-C_6H_4-S-. The polymer morphology was studied byX-ray diffraction and polarized microscopy. The results show that PPSA is a crystallinepolymer and its spherulites are the aggregation of nontwisting lamella or micro-threadstructure. Under shearing force, these crystals are dispersed to form micro-fibrillarstructure. The decomposition kinetics of PPSA was also studied at different beating rates.The decomposition energy of PPSA is higher than that of PPS.     

2D NMR Spectroscopic Studies of the Toxic Alkaloid from Oxytropis Glabra D C.

The Oxytropis, legume genus, is native in the northwest of China, and some of its members have been reported to be toxic to grazing livestock. In the course of studying toxic reason of this legume, a toxic alkaloid was isolated from Oxytropis glabra D C. grown in the Inner Mongolian Autonomous Region. The LD+(50) of (—)-thermopsine(Ⅰ) was shown to be 89.98 mg/kg(in mice). This paper reports an approach to the structure elucidation of(-)-thermopsine by combining 2D NMR[~1H-~1H and ~1H-~(13)C (one-bond and long-range) COSY] and other physicochemical methods. The stereochemistry of compound Ⅰ is also discussed.     

STUDIES ON THE MECHANISM OF INDIRUBIN ACTION IN THE TREATMENT OF CHRONIC GRANULOCYTIC LEUKEMIA——V.BINDING BETWEEN INDIRUBIN AND DNA AND IDENTIFICATION OF THE TYPE OF BINDING

The binding between indirubin and calf thymus DNA in vitro has been verified by meansof the isotope labelling method, spectrophotometric method and thermal denaturation meas-urements. The λ_max 207 nm of indirubin shifted toward longer wave length with decrease ofabsorbance after the incubation of indirubin with DNA. The escalation of Tm value of DNAinduced by indirubin was about 2.4°C and it was reproducible. The binding force between themwas rather weak, as indirubin molecules were easily released during the precipitation withalcohol or the gel filtration. The binding was not affected by sodium chloride even at high con-centration but greatly decreased (to 20-30% of the control) in the presence of 8 M urea.These results showed that the binding between indirubin and DNA might be of hydrogen bondrather than ionic. The amount of bound ~3H-indirubin was directly proportional to the con-centration of indirubin. However, it increased abruptly when the concentration of indirubinreached 1.5×10~(-4) M. This