KINETICS OF FISCHER-TROPSCH SYNTHESIS OVER PRECIPITATED IRON CATALYST

The rate of Fischer-Tropsch synthesis was measured in an internallyrecycled gradientless reactor at 230-265℃,1.0-2.6 MPa,H_2/CO feedratios of 1.12-2.41 and space velocity of 300-1.000 h~(-1).The inhibitingeffects of CO_2 and H_2O were determined quantitatively and led to the fullowingtwo rate expressions:-R_(H_2)+co=k_1P_((H_2)~2)P_(co)/(P_(H_2)P_(co)+b_1P_(H_2O)),and-R_(H_2)+co=k_2P_(H_2)P_(co)/(P_(co)+b_2P_(H_2O))where k is the kinetic constant for the rata-determining step and b is a functionof temperature only.The two intrinsic kinetic models were derived from relatedreaction mechanisms.First order with respect to H_2 was also sufficient for thecatalyst,probably due to the low synthesis conversions obtained during the testof this catalyst.Kinetics of the WGS reaction which accounted for waterinhibition under FTS conditions was also investigated.     

STUDIES ON THE CRYSTAL STRUCTURE OF Al-(L-TRYPTOPHAN) INSULIN AT 2.1RESOLUTION

In order to study the biological effect of alterations to the N-terminus of the insulin A-chain, we have determined the crystal structure of Al-(L-Trp) insulin and discovered that it belongs to the trigohal system with space group R3. The parameters oof the unit cell are a=b=80.3A, c=37.5A. The model was adjusted and refined by using a stereochemically-restrained least squares program, assisted by manual revision of the model based on the difference Fourier map, to a final R-factor of 0.195. The main and side chains of both Al-(L-Trp) residues in the asymmetric unit are well ordered. It was found that the Al-Trp residue of molecule I occupied two distinct positions. We have proposed from the results of the three-dimensional structure that the 4-zinc insulin hexameric form is a stored state of insulin molecules in a conformation of low activity. The structural details of the insulin molecule and its structure and function relationship have also been discussed.     

A STUDY ON THE STRUCTURAL EFFECT OF DOUBLE-BRIDGED CONJUGATIVE SYSTEMS

In this paper, the following carbonyl-imino bridged compounds and related analogs havebeen synthesized:X= C1, m = 0); and the structural effect of the carbonyl-imino bridges has been studied by means of the UV and other properties of the compounds. A new conception of conjugative segment is put forward. The structural bases for each of the three π-π* bands of (C) are ascertained and verified by modification on structure of segments, such as eliminating, merging, lengthening or shortening of segments. It is demonstrated that both bridges -CO-and -NH- can block the conjugated polarization of the whole molecule so as to form three segments S, M and L of which the λmax each exhibits relative independence. The electronic absorption peaks resulting from different segments can be readily recognized and the existence of each segment can be ascertained. This may provide a new way for structural analysis of bridged compounds.     

QSRR Study on the Components of Styrax Japonicus Sieb Flowers Using Improved Molecular Electronegativity-distance Vector （I-MEDV）

Atoms in most organic molecules are often carbon,oxygen,nitrogen,sulfur,halogens,etc. Based on the three-dimensional structure of a molecule,a molecular structural characterization(MSC) method called improved molecular electronegativity-distance vector(I-MEDV) was developed. It was used to describe the structures of 37 compounds of styrax japonicus sieb flowers. Through multiple linear regression(MLR),a QSRR model was built up. The correlation coefficient(R1) of the model was 0.980. Then,4 vectors were selected to build another model through the method of stepwise multiple regression(SMR) ,and the correlation coefficient(R2) of the model was 0.975. Moreover,all the two models were evaluated by performing the crossvalidation with the leave-one-out(LOO) procedure and the correlation coefficients(Rcv) were 0.948 and 0.968,respectively. The results show that the I-MEDV could successfully describe the structures of organic compounds. The stability and predictability of the models were good.     

小麦条锈病对小麦产量影响的研究——Ⅱ.病害对小麦叶片光合作用的影响初探

利用红外线气体分析仪测定了冬小麦燕大1817和东方红3号在受到条锈菌(Puccinia striiformis West)侵染后叶片光合作用的变化。证明严重度S越高,残余健部光合作用极大值P′_(max)越低,其关系为P′_(max)=P′_(max)(1-0.826*S)。根据试验数据推导建立了条锈病导致的光合产物降低率预测模型:L_(光合)=1-(P_(max)+I_(1α))/(P′_(max)+I_(1α))(1-bS)(1-S),和理论模型L_(光合)=aS~n,n=f(P′_(max)/P_(max))。最后讨论了L_(光合)与验经产量损失模型的关系。     

The Study of Oxygen Transfer Kinetics for MoO_2(S_2CENt_2)_2 in Various Solvents

The reaction kinetics between MoO2 (S2CNEt2)2 and triphenylphos-phine (PPh3) were studied in various organic solvents with the aid of the stopped-flow technique. The linear correlations were found for rate constants or activation energy versus the function of refractive index (n2 - 1)/(2n2 + 1). It was also found that pre-factor increases with the descent of ( n2 - l)/(2n2 - 1) slightly.One step mechanism which supposes the lone pair of electrons on P atom of triphenylphosphine enters directly into the Ⅱ antibonding orbital, which makes the Mo= O bond broken, is suggested.     

FTIR STUDIES ON THE MODEL POLYURETHANE HARD SEGMENTS BASED ON A NEW WATERBORNE CHAIN EXTENDER DIMETHYLOL BUTANOIC ACID （DMBA）

Three model polyurethane hard segments based on dimethylol butanoic acid (DMBA) and 1,6-hexane diisocyanate (HDI), toluene diisocyanate (TDI) and 4,4‘-diphenylmethane diisocyanate (MDI) were prepared by the solution method.Fourier Infrared (FTIR) spectroscopy was employed to study the H-bonds in these model polyurethanes. The model polyurethane hard segment prepared from HDI and 1,4-butanodiol (BDO) was used for comparison. It was found that the incorporation of the pendent carboxyl through DMBA into the model hard segments weakens the original NH…O=C H-bond but gives more H-bond patterns based on the two H-bond donors, urethane NH and carboxylic OH. The carboxylic dimer is one of the main H-bond types and is stronger than another main H-bond type NH…O=C. In addition, the H-bond in aromatic model hard segments is stronger than that of aliphatic hard segments. The appearance of the free C:O and the fact that almost all N-H is H-bonded suggest that there possibly exist either the third H-bond acceptor or the H-bond formed by one acceptor with two donors.     

POLYMERIC IONIC CONDUCTORS MODIFIED WITH POLAR GROUPS: PART Ⅱ. STRUCTURE-IONIC CONDUCTION RELATION IN LI-COMPLEX BASED ON MALEIC ANHYDRID E-COPOLYMERIZED METHACRYLATES

Ringlike polar monomer maleic, anhydride (MAn) was copolymerized with oligo (oxyethylene) methacrylate (MEO_n), and its effect on ion conduction property of the corresponding polymer-salt complexes was studied. As a consequence the introduction of MAn onto polymer chain retards crystallization of the ether pendants considerably, and improves the ion conductivity to a larger degree compared with other polar groups once investigated (σ_(max),25℃=8.5×10~(-5) S/cm). The structure-ion conduction relation in the polymer-salt matrix is also analyzed macroscopically through the correspondence between composition-dependences of polymerization conversion and isothermal ion conductivity, and microscopically through the measurements of cross polarized light and electron transmission.     

A synthetic approach for water soluble hyperbranched poly(N,N-ethylidenebis(N-2-chloroacetyl acrylamide)) with high degree of branching via atom transfer radical polymerization/self-condensing vinyl polymerization

A novel acrylamide A2B2* (A = alkene, B* = alkyl chlorine) type inimer was obtained from commercially available 1,2-ethylenediamine, chloroacetyl chloride and acryloyl chloride. The as-prepared monomer can form water-soluble hyperbranched poly(N,N-ethylidene bis(N-2-chloroacetyl acrylamide))s (HPECA) through atom transfer radical polymerization/self-condensing vinyl polymerization method in the presence alkyl chlorine/CuCl/2,2-bipyridine activation system which can effectively suppress the gelation formation. 1H-NMR spectra and dual detector size exclusion chromatography proved the hyperbranched structure indisputably, and the degree of branching was determined by the detailed analyses of 1H-NMR spectra. The trend of the degree of branching was in consistent with the result of Mark-Houwink exponent a. The experiment results suggested that the conversion was 67%, Mw = 13.2 ? 104, Mark-Houwink a = 0.282 and the degree of branching = 64% when the reaction temperature was 120 oC, reaction time = 168 h and N,N-ethylidene bis(N-2-chloroacetyl acrylamide):Cu(I) = 50:0.62.     

Three-dimensional Quantitative Structure-activity Relationship Models of HIV-1 Integrase Inhibitors of DKAs

As one of the three viral encoded enzymes of HIV-1 infection, HIV-1 integrase has become an attractive drug target for the treatment. Diketoacid compounds (DKAs) are one kind of potent and selective inhibitors of HIV-1 IN. In the present work, two three-dimensional QSAR techniques (CoMFA and CoMSIA) were employed to correlate the molecular structure with the activity of inhibiting the strand transfer for 147 DKAs. The all-oritation search (AOS) and all-placement search (APS) were used to optimize the CoMFA model. The diketo and keto-enol tautomers of DKAs were also used to establish the CoMFA models. The results indicated that the enol was the dominant conformation in the HIV-1 IN and DKAs complexes. It can provide a new method and reference to identify the bioactive conformation of drugs by using QSAR analysis. The best CoMSIA model, with five fields combined, implied that the hydrophobic field is very important as well as the steric and electrostatic fields. All models indicated favorable internal validation. A comparative analysis with the three models demonstrated that the CoMFA model seems to be more predictive. The contour maps could afford steric, electrostatic, hydrophobic and H-bond information about the interaction of ligand-receptor complex visually. The models would give some useful guidelines for designing novel and potent HIV-1 integrase inhibitors.     

THE INFLUENCE OF HEAT TREATMENT ON STRUCTURES OF THE AGGREGATED STATE OF POLYAMIDE-1010

The structural parameters of the aggregated state of polyamide (PA)-1010 annealedat various temperatures were computed by means of the desmearing intensity from SmallAngle X-ray Scattering (SAXS) measurements and by using the concept of the distance dis-tribution function. The results indicated that the structural parameters of the aggregatedstate were strongly dependent upon heat treatment conditions and the maximum valuesof the structural parameters were obtained for the samples annealed at T = 175℃. Theparticle size Z annealed at different temperature was ranged between 8.1--12.8nm, and thevalues of the distance distribution function P_(max)(Z) were obtained when Z = 4.0--6.8nm.Using one dimension electron density correlation function (1D EDCF) method long period(L) and thickness of the lamellar (d_0) were estimated and were found to increase with theincrease of the degree of crystallinity.     

The thermal decomposition of N,N-dimethyl-3-oxa-glutaramic acid and the kinetics of its second-stage thermal decomposition reaction

N,N-dimethyl-3-oxa-glutaramic acid was purified and characterized by 1H-NMR, Fourier transform in-frared spectroscopy (FT-IR) and elemental analysis. The thermal decomposition of the title compound was studied by means of thermogravimetry differential thermogravimetry (TG-DTG) and FT-IR. The ki-netic parameters of its second-stage decomposition reaction were calculated and the decomposition mechanism was discussed. The kinetic model function in a differential form, apparent activation energy and pre-exponential constant of the reaction are 3/2 [(1-α) 1/3-1]-1, 203.75 kJ-mol-1 and 1017.95s-1, respec-tively. The values of ΔS≠, ΔH≠ andΔG≠ of the reaction are 94.28 J-mol-1-K-1, 203.75 kJ-mol-1 and 155.75 kJ-mol-1, respectively.     

RESEARCH ON TRINUCLEAR MOLYBDENUM CLUSTER COMPOUNDS——CRYSTAL AND MOLECULAR STRUCTURE OF Mo_3(μ_3—O)(μ_2—S_2)_3[S_2P(OEt)_2]_3I

The title crystals are golden yellow rhomboic plates, belonging to the monoelinic system. The space group is P_(B_1)/n with unit cell parameters a=16.570(2), b=12.370(1), c=20.007(2), β=99.97(1)°, Z=4, D_c=1.938 g.cm~(-3). The crystal structure was solved mainly by the heavy atom method and refined by the full-matrix least-squares to a final R factor of 0.047 based on 4387 unique reflections with intensities I≥2σ(I). The results show that the crystal structure consists of neutral mono-oxo-capped trinuclear molybdenum cluster molecules with an average Mo-Mo bond length of 2.626(4) and an average Mo-O bond length of 2.036(2) respectively. Each pair of Mo atoms is further bridged by an S_2~(2-) radical, in which one S atom is essentially situated on the triangular plane formed by these three Mo atoms and the other one is situated on the side of the plane opposite to the μ_3-O atom. Besides, each Mo atom is coordinated to two S atoms belonging to an [S_2P(OEt)_2]~-radical so as to complete a nearly pen     

Thermal decomposition of Pr[(C_5H_8NS_2)_3(C_(12)H_8N_2)]

The thermal behavior of the complex Pr[(C5H8NS2)3(C12H8N2)] in a dry nitrogen flow was examined by TG-DTG analysis. The TG-DTG investigations indicated that Pr[(C5H8NS2)3-(C12H8N2)] was decomposed into Pr2S3 and deposited carbon in one step where Pr2S3 predominated in the final products. The results of non-isothermal kinetic calculations showed that the decomposition stage was the random nucleation and subsequent growth mechanism (n = 2/3), the corresponding apparent activation energy ?was 115.89 kJ·mol-1 and the pre-expo-nential constant ln[A/s] was 7.8697. The empirical kinetics model equation was proposed as/(α) =3/2(1-α)[-ln(1-α)]1/3.The X-ray powder diffraction patterns of the thermal decomposition products at 800℃under N2 atmosphere show that the product can be indexed to the cubic Pr2S3 phase. The transmission electron microscopy (TEM) of the final product reveals the particle appearance of a diameter within 40 nm. The experimental results show that the praseodymium sulfide nanocrystal can be prepared from thermal decomposition of Pr[(C5H8NS2)3(C12H8N2)].     

Synthesis,Structure and Spectral Properties of a Novel Triaryl Substituted Triazole and Its Co(Ⅱ) Complex

The new compound 3-(2-pyridyl)-4-(p-methoxyphenyl)-5-(2-thienyl)-1,2,4-triazole L was synthesized and characterized by elemental analysis,IR,1H NMR,13C NMR,MS,UV and photoluminescent spectra.The complex CoL2(NCS)2 was prepared by the reaction of ligand L with Co(SCN)2,and its structure was characterized by single-crystal X-ray diffraction,IR,UV,elemental analysis and MS.The complex crystallizes in monoclinic,space group P21/n with a=13.7639(19),b=7.6641(11),c=18.409(3),β=101.549(3)o,V = 1902.6(5) 3,Z=2,C38H28CoN10O2S4,Mr=843.87,Dc=1.473 g/cm3,μ=0.720 mm-1,S=1.075,F(000)=866.0,the final R=0.0825 and wR=0.2149 for 2566 observed reflections(I2σ(I)).In the crystal structure,the cobalt atom adopts a distorted octahedral environment with two NCS-ions in the axial positions and two bidentate chelating L ligands in the equatorial plane.The extended 2D network of the complex is formed by intermolecular C-H…N hydrogen bonds together with π-π stacking interactions.     

THE MECHANISM OF COPOLYMERIZATION OF VINYL AND DIVINYL MONOMER Ⅵ: A STUDY ON THE MECHANISM OF THE STRUCTURE FORMATION OF CROSSLINKED POLYSTYRENE

In order to study the mechanism of the formation of maeroporous copolymer, the overall reaction kinetics, phase separation and gelation of the S/EGDM in the presence of inert solvents and the physical properties of the eopolymer were investigated and compared with the corresponding system of S/DVB and S/DVB/MMA. The formation of the network structure of the macroreticular polymer was studied and a model of the mechanism suggested.     

Crystal Structure of 5—（l—Menthyloxy）—3—chloro—4— Pyrrolidinyl—2（5H0—f

The molecular structure of the title compound 5-(l-menthyloxy)-3-chloro-4-pyrrolidinyl-2(5H)-furanone, C18H28ClNO3(Ⅰ), has been determined by X-ray diffraction at 296(1)K. The crystal is monoclinic with space group P21, a=9.457(3), b=10.413(3), c=9.525(2), β=95.19(2)°, V=934(1) 3, Z=2, Mr=341.88, Dx=1.22 g/cm3, μ=2.15 cm-1, F(000)=368. The final R factor is 0.059, and Rw is 0.065 for 1020 observed reflections with I≥3σ(I). The absolute configuration at C(14) of the acetal carbon was proved to be S, taking into account the known configuration of 1R, 2S, 5R-menthyl moiety. There are three rings in the molecule of this compound: the furanone ring, the pyrrolidine ring and the mentholoxy group ring. The franone ring is connected with the pyrrolidine ring and the mentholoxy ring by N atom and μ2-O bridge atom respectively.