THE INTERACTION OF ETHYL BENZOATE AND TRIFLUOROACETIC ACID IN EXCITED STATE

This paper is concerned with the interaction of ethyl benzoate (EBA) and trifluoroaceticacid (TFA) molecules in the excited state by measurements of steady--state and transient fluo-rescence spectra at room and low temperatures. The results show that not only the 1:1 exci-plex but also the 2:1 triplex between EBA and TFA was formed. The formation pathway ofthe triplex is that the exciplex formed at first, then by the interaction with the EBA mole-cule it transformed into triplex. But it could not be formed by the dimer of EBA by interac-tion with TFA. The dimer of EBA is confirmed in the concentrated solution. So there arefour components in EBA/TFA--concentrated solution and their fluorescence lifetimes aremeasured respectively.     

SYNTHESIS AND CHARACTERIZATION OF ORGANSOLUBLE POLYIMIDE AND COPOLYIMIDES FROM ALICYCLIC DIANHYDRIDE

A kind of highly organsoluble polyimide and copolyimides were successfully synthesized from bicyclo（2.2.2）-oct- 7-ene-2,3,5,6-tetracarboxylic dianhydride （BCDA）, the commercial diamine 4,4＇-methylenedianiline （MDA） and the designed diamine 4,4＇-methylenebis-（2-tert-butylaniline） （MBTBA）. The polyimide from BCDA and MBTBA is highly soluble in conventional low boiling point solvents （such as chloroform, tetrahydrofuran） at room temperature. But the solubility of the copolyimides in conventional solvents decreased with the molar ratio of MBTBA and MDA decreased. When the molar ratio of MBTBA and MDA was larger than 7/3, the copolyimides can be soluble in low boiling point solvents at room temperature to form a transparent, flexible, tough film by solution casting. When the molar ratio of MBTBA and MDA was between 7/3 and 1/9, they can only be soluble in hot dipolar aprotic solvents （such as DMF, NMP etc.） and form films too. The copolyimide was only soluble in m-cresol when the molar ratio of MBTBA and MDA was lower than 1/9. The number-average molecular weights of the soluble copolyimides were larger than 5.8 × 1064 g/mol by GPC and their polydispersity indices were higher than 1.4. Only one glass transition temperature of these copolyimides was detected around 400℃ by DMA. The copolyimides did not show appreciable decomposition up to 430℃ in N2.     

THE CATALYTIC EFFECTS OF OXYGEN AND AMINES IN THE REDOX-INITIATED DIMERIZATION OF N-VINYLCARBAZOLE*

The redox reaction between N-vinylcarbazole (NVC) and various oxidants including Ce(Ⅳ), Fe(Ⅲ)and benzoylperoxide in methanol proceeds via the initial formation of the NVC N-cation radical which in turn leads to the formation of the NVC cyclic dimer, trans-1,2-dicarbazylcyclobutane. Molecular oxygen and a few arylamines are able to accelerate the rate of the formation and increase the yield of the dimer. The mechanism of this process and the functions of oxygen and arylamines are presented as follows: The participation of molecular oxygen is to facilitate the dissociation of the resulting reduced metal ion and the NVC N-cation radical ion pair or charge transfer complex, thereby releasing the free NVC N-cation radical and increase the rate of the formation and yield of the dimer. The arylamine in this reaction between NVC and oxidants can be viewed as electron transfer agent between NVC and the oxidant. Because the amines are present in small amount relative to the oxidants and can be regenerated in pr     

PREPARATION AND ADSORBABILITY OF DEXTRAN MICROSPHERES WITH UNIFORM DIAMETER

The method of preparing uniform dextran microspheres with a narrow diameter distribution was introduced and the adsorbability of these microspheres was evaluated. The microspheres were prepared in W/O microemulsion using 0.5% dextran solution as the aqueous phase and n-hexane as the oil phase. Characteristics of the prepared dextran microspheres were examined with laser light blocking technique, optical microscope and ultraviolet spectrometer. The results show that the prepared dextran microspheres have uniform morphology and narrow diameter distribution, nearly 92% of them having a diameter of 56.6μm. In vitro evaluation of adsorbability, wet dextran microspheres have good adsorption of 98.32mg/g of model drug methylene blue in 20.86mg/L methylene blue solution at 25℃, The adsorption of dried dextran microspheres under the same condition is 132.15mg/g, which is even higher. And the adsorbability of dextran microspheres has significant relationship with the concentration of methylene blue and temperature. The adsorbability is better at lower temperature and higher concentration of methylene blue.     

STEADY-STATE AND TIME-RESOLVED FLUORESCENCE STUDY OF TRIPLE EXCIPLEX IN THE SYSTEM OF POLYACENAPHTHALENE AND TEREPHTHALIC DIMETHYLESTER

Triple exciplex formed between polyacenaphthalene and terephthalic dimethylester (TDE) has been studied by means of the steady-state and time-resolved fluorescence spectra. The theoretical model of the triple exciplex formation for a flexible polymer chain in a dilute solution has been proposed. The fluorescence decays of the monomer, the exciplex and the triple exciplex obey a double exponential rule in the pbotophysical processes of the triple exciplex formation. The association rate constant of the exciplex formation is k_3=6.0×10~9s~(-1)(mol/L)~(-1); the association rate constant of the triple exciplex formation is k_6=5.2×10~7s~(-1). A mechanism for the triple exciplex formation from the exciplex to the triple exciplex has been proved through the noncrystal films corresponding to the same concentrations of the solution systems and the fluorescence lifetimes of the intramolecular excimer.     

PREPARATIONS AND PROPERTIES OF METHANOL SYNTHESIS CuO-ZnO CATALYSTS

Methanol synthesis from CO_2 and H_2 over various CuO-ZnO catalystsunder lower pressure has been studied.The properties of CuO-ZnO Catalystschanged with the solution pH value,precipitating agent,coprecipitatingmethod,thermal treating and activation conditions.XRD,BET,and TPR wereused to examine the surface structure and properties of catalysts.When 6.6≤pH≤8.9,copper and zinc cations could completely precipitate simultaneously.The eatalyst with CuO/ZnO wt.ratio of 50/50 has good activity,highmethanol selectivity and methanol yield.Calcination at high temperature andreduction in pure hydrogen would lead up to the decrease in catalytic activity.     

SPATIAL HIERARCHY AND INTERFACIAL STRUCTURE IN INJECTIONMOLDED BARS OF POLYPROPYLENE-BASED BLENDS AND COMPOSITES

The hierarchical structure and interfacial morphology of injection-molded bars of polypropylene （PP） based blends and composites have been investigated in detail from the skin to the core. For preparation of injection-molded bars with high-level orientation and good interfacial adhesion, a dynamic packing injection molding technology was applied to exert oscillatory shear on the melts during solidification stage. Depending on incorporated component, interfacial adhesion and processing conditions, various oriented structure and morphology could be obtained. First, we will elucidate the epitaxial behavior between PP and high-density polyethylene occurring in practical molded processing. Then, the shear-induced transcrystalline structure will be the main focus for PP/fiber composites. At last, various oriented clay structures have been ascertained unambiguously in PP/organoclay nanocomposites along the thickness of molded bars.     

THE ORIENTATION AND CRYSTALLIZATION OF POLYETHYLENE TEREPHTHALATE

The drawing behavior of three types of PET spherulites and PET amorphous samples have beenstudied. Two different sample preparation techniques were used in this study: (1) The films withnormal positive, normal negative or abnormal spherulites were prepared by solution casting tech-niques, then the films were deformed by uniaxial drawing. The uniaxial drawing behavior of PETspherulites appears to be dependent on the angles between the c-axis and the radius direction of thespherulites and that the deformation of spherulites becomes more difficult the larger the angles. (2)Amorphous films of PET were prepared first, then the films were deformed under uniaxial drawingto achieve c-axis orientation at a temperature near the glass transition temperature. The orientedfilms were subsequently annealed with fixed length at 215℃The films prepared in this way ex-hibit excellent c-axis orientation along the stretching direction. The degree of perfection of thecrystalline structure is much greater than that of the spherulites.     

SYNTHESIS AND APPLICATION AS POLYMER ELECTROLYTE OF HOMO- AND COPOLYMERS OF 3-(2-CYANO ETHOXY)METHYL- AND 3-(METHOXY(TRIETHYLENOXY))METHYL-3''''-METHYLOXETANE

Two oxetane-derived monomers, 3-(2-cyano-ethoxy)methyl- and 3-(methoxy-(triethylenoxy))methyl-3'-methyloxetane (COX and MTOX), were prepared from 3-hydroxymethyl-3'-methyloxetane. Their homo- and co-polymerization in solution were carried out by the cationic ring-opening polymerization with BF3·Et2O and 1,4-butanediol as co-initiator. The molecular weight and molecular weight distribution were determined using GPC so as to reveal the competition and interchange between active chain end (ACE) and activated monomer (AM) mechanism in the process. The reactivity ratios of the two monomers were calculated according to Kelen-Tudos using 1H-NMR analysis. The influence of functional side chains in the monomers on the copolymerization behaviors was discussed in virtue of the reactivity ratio data. When doped with lithium salt LiTFSI, the ion conductivity of the homopolymer of MTOX reached 10-3.58 S/cm at 30℃and 10-2.73 S/sm at 80℃, respectively, showing its potential to be used as polymer electrolyte for lithium ion battery.     

EFFECTS OF STRUCTURE ON GROWTH HABITS AND DEFECTIVE FORMATION IN CRYSTAL OF TRI-HYDROXYMETHYLAMINO-METHANE(TAM)

<正> The effects of structure on the growth habits and defective formation in the crystal of Tri-hydroxymethylaminomethane(TAM) have been studied experimentally and structurally. Dependence of orientations and properties in O - H...O and O - H....N hydrogen bridges on the polar growth and on the face development, and relationship between the structural channels in open structure and defective formation, have been dis cussed briefly.     

STUDES ON PREPARATION OF FEED GASFOR METHANOL SYNTHESIS BY CATALYTICOXIDATION OF NATURAL GAS I.EFFECTS OF FEEDSTOCK RATIO AND TEMPERATURE ON THE COMPOSITION OF SYNGAS

The processes for syngas preparation by catalytic oxidation of CH_4 inH_2O-O_2 system have been studied in a combination apparatus of microtubularreactor and chromatograph. The experimental results showed that the CO con-tent increased with temperature when the feedstock ratio was fixed. And at thefixed temperature, the increase of CO content and decrease of CO_2 content wereobserved when the molar concentration of oxygen and steam in the feed gaswere reduced. Under the conditions of CH_4/H_2O/O_2=1: (0.2～0.6): 0.4, 800℃ and 0.1 MPa, the desired feed gas for methanol synthesis in industrywas obtained.     

MORPHOLOGY OF POLYBUTADIENE “SHISH KEBABS”

Shish kebab structure of cis-1 , 4-polybutadiene has been obtained by quiescent solution crystallization at suitable temperature. The morphology and growth mechanism of formation of shish kebab structure have been studied in detail.The higher the molecular weight the faster the sample crystallizes.     

LiFePO4 doped with magnesium prepared by hydrothermal reaction in glucose solution

Lithium iron phosphate （LiFePO4） doped with magnesium was hydrothermally synthesized from commercial LiOH, FeSO4, H3PO4 and MgSO4 with glucose as carbon precursor in aqueous solution. The samples were characterized by X-ray powder diffraction, scanning electron microscopy and constant charge-discharge cycling. The results show that the synthesized powders have been in situ coated with carbon precursor produced from caramel reaction of glucose. At ambient temperature （28±2℃）, the electrochemical performances of LiFePO4 prepared exhibit the high discharge capacity of 135 mAh g^-1 at 5C and good capacity retention of 98% over 90 cycles. The excellent electrochemical performances should be correlated with the intimate contact between carbon and LiFePO4 primary and secondary particles, resulting from the in situ formation of carbon precursor/carbon, leading to the increase in conductivity of LiFePO4.     

STRUCTURES OF CRUST AND UPPER MANTLE AND THEIR RELATION TO CENOZOIC TECTONISM IN NORTHERN PART OF NORTH CHINA

On the basis of deep seismic profiling carried out in the past six years, the velocity, gcoelectrical and geothermal structures of the crust and upper mantle and tectonic frames of the Moho discontinuity and asthenosphere have been determined for the northern part of North China. A close relationship exists between Cenozoic teetonism and the geodynamic processes in the crust and upper mantle. We surmise that the intense inhomogeneous activities of the asthenospherc between the late Cretaceous and the Cenozoic may have given rise to the following processes: lithospheric breakup, basalt eruptions, increase in geothermal gradient, lower crustal creep, upper crustal spreading, subsidence and the accumulation of sedimentary deposits as well as the development of shallow-level normal faults. The dip angles of such faults gradually decrease with depth and thus disappear in the low velocity layer of the crust.     

LIPOGENESIS STIMULATORY AND INHIBITORY ACTIVITIES OF THE INSULIN MEDIATORS

Incubating plasma membranes prepared from pig liver with varying concentrations of insulin (50—1000 μU/ml) resulted in the release of at least two insulin chemical mediators. One of them was fraction 1 of insulin mediator (M. W. 3700—4000 daltons) which had a significant lipogenesis-stimulatlug activity. The other was fraction 2 of insulin mediator (M. W. about 1000 daltons) which exhibited a lipogenesis-inhibitory activity.The ratio of yield between the two mediators produced from the membranes was not only dependent on the concentration but also on the potency of insulin and its analogs added. The result showed that there was more production of fraction 2 than fraction 1 with the inducer at low concentration (100 μU/ml), while the production of fraction 1 from the plasma membranes incubated with high concentration of insulin (300 μU/ml) was higher than fraction 2. On the other hand, insulin and its analogs which have different biological activities and receptor bindtng activities have been used t     

HYDROBORATION OF ALKYNES WITH DICHLOROBORANE-DIMETHYL SULFIDE——SYNTHESES AND SPECTROSCOPIC CHARACTERISTICS OF gem-DIBORON AND ALKENYLBORON COMPOUNDS

The reactions of alkynes with dichloroborane-dimethyl sulfide (HBCl_2·SMe_2) in the presence of boron trichtoride in pentane have been investigated.Both internal and terminal alkynes react with HBCl_2·SMe_2 in the molar ratio 1:2 at 0℃ to give dihydroborating products, gem-bis (dichloroboryl)alkanes, in good yield. Since the dihydroboration of alkynes is suppressed considerably at lower temperature, the internal alkynes and HBCl_2·SMe_2 react quantitatively in the molar ratio 1.4:1 at-20℃ or -30℃ to give the expected alkenyldichloroboranes.Under the same conditions,the terminal alkynes, however, undergo both monohydroboration and chloroboration.When terminal alkynes react with boron trichloride in the molar ratio 1 :1.1 in pentane, the chloroborating products, 2-chloro-1-alkenyldichloroboranes have been obtained in high yield.All dichloroboranes are readily converted by alcoholysis into the corresponding boronic esters.The resulting compounds have been characterized by IR, ~1H,~(11)B, and ~(13)C N     

Novel smart supramolecular metallo-hydrogel that could selectively recognize and effectively remove Pb2+ in aqueous solution

A series of novel and simple ligands based on a biscarboxyl-functionalized benzimidazole derivative were synthesized.The experiments showed that the ligand L2 as a low molecular weight(LMW) hydrogelator could form stable metallo-hydrogels in the presence of up to 0.3 equiv.of lead ions.The metallo-hydrogels were characterized using powder X-ray diffraction,scanning electron microscopy(SEM),and Fourier transform infrared(FT-IR) spectroscopic techniques.When the molar ratio of L2:Pb2+ was in the range of 1:0.3 to 1:0.5 a translucent gel was produced.When the L2:Pb2+ molar ratio was higher than 1:0.5 the resulting gel tended to be opaque.The morphologies of these metallo-hydrogels were L2/Pb ratio dependent,ranging from worm-like to rod-shaped and nanofibrous.The FT-IR and X-ray diffraction(XRD) studies revealed that L2-Pb complexation was the main driving force for the formation of the metallo-hydrogels.In addition,these metallo-hydrogels exhibited outstanding thermostability and thermoreversibility,and displayed a reversible sol-gel transition induced by changes in pH and EDTA concentration.Importantly,ligand L2 showed an excellent capacity for the removal of Pb 2+ in aqueous solution through the formation of metallo-hydrogels.At a L2:Pb molar ratio of 1:0.5 and below,the concentration of residual Pb2+ was as low as 7.6×10-5 mol/L in aqueous solution,and the removal ratio was as high as 95.4%.These results demonstrate that multi-channel responsive smart metallo-hydrogels have the potential to be widely applied in materials science,and might provide the basis for lead pollution capture and removal.     

O_2 SPECIES ON La_2O_3/MgO CATALYS FOR OXIDATIVE COUPLING OF METHANE AND ITS INTERACTION WITH CARBON DIOXIDE

The formation of O_2~- ions on La_2O_3/MgO Catalyst for oxidative cou-pling of methane and its interaction with CO_2 have been studied by EPR andFT-IR.The O_2~- ions with EPR parameters valued at g_(xx)=1.999,g_(yy)=2.018,g_n=2.061;A_(xx)=5.0G,A_(yy)=7.6G,are unstable at 573 K under vacuum.They could react with CO_2 at room temperature leading to the decrease of theirEPR signal intensities and the appearance of a new carbonate species with IRabsorption bands at 1628cm~(-1) and 1335 cm~(-1),in comparison with the CO_2 ab-sorption on the O_2~-free sample.It appears unlikely that the O_2~- ions are theactive oxygen species for the activation of methane.     

INTERNALIZATION OF GAP JUNCTIONS BETWEEN NEURON AND GLIAL CELL AND FORMATION OF ANNULAR LAMELLAR BODIES IN CHINESE LEECH Whitmania pigra

This paper reveals the formation of annular lamellar body (ALB) in the ganglion of leech by means of in situ fixation and the lanthanum nitrate tracer technique. This formation involves both wrapping and internalization of the gap junctions between glial processes themselves, as well as between neuron and glial process. The results indicate that there is probably an active process of internalization of membrane structures involving gap junctions between neuron and glial cell in the central nervous system in leech. The functions of ALB are discussed.     

ELECTROCHEMICAL POLYMERIZATION OF ANILINE IN PHOSPHORIC ACID AND THE PROPERTIES OF POLYANILINE

The behavior of the electrochemical polymerization of aniline in a weak acid, phosphoric acid, is very similar to that in strong acids, i.e. its polymerization rate increases quickly with the electrolysis time. The FTIR spectra of polyaniline samples synthesized in phosphoric acid indicate that the counter ion H2PO4^- is present in both the oxidized form and the reduced form of polyaniline. The counter ion plays an important role in adjusting the pH value at the electrode surface of polyaniline during the oxidation and reduction processes. As a result, a pair of redox peaks still appear in cyclic voltammograms of polyaniline in a solution of sodium sulfate of pH 5.5 and in a solution of NaH2PO4 of pH 7.0,respectively, at low potential scan rate; and the color of polyaniline film also changes with applied potential at pH 7.0. Thus,the pH region for the electrochemical activity and the electrochromism of polyaniline is extended to pH 5.5 for a solution of sodium sulfate and to pH 7.0 for a solution of NaH2PO4. The conductivity of polyaniline is 3.3 S cm^-1, depending on the concentration of phosphoric acid used in the stage of polymerization of aniline. The result of elemental analysis of polyaniline is presented here.