Table of Content

20 November 1995, Volume 31 Issue 6

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Kinetic Studies of Reaction of Oxomolybdenum Tetraphonylporphrin Complex MoO(TPP)Cl with O^-₂ in the Presence of DMSO
(I) Intermediates and Kinetics

CUI Xiaoli,HUANG Wei,YANG Huixing,GAO Panliang,HAN Degang

1995, 31(6):  666-674. 

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The kinetics of the reaction of MoO(TPP)Cl with superoxide anion radical O^-₂ in high concentration of DMSO has been studied, and a series ofintermediates were investigated. The kinetics results were discussed and the kinetic data raported.

Sucrose Chemistry: Studies on the Synthesis of Tri- and Tetra-Saccharides

NING Jiacheng,LI Cuijuan,WANG Shiyu

1995, 31(6):  684-689. 

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Condensation of sucrose acetate with acetylglycosyl bromides in 1:1 benzene-nitromethane in presence of mercuric cyanide,calcium hydride or in dichloromethane in presence of silver carbonate, calcium hydride gave Tri- and Tetra-Saccharides containing sucrose molecule. The configuration of oligosaccharide linkage was clearly shown by ¹H NMR data.

Steady-State and Pulse Kinetics of Redox Mechanism for the Oxidation of CO over SmFeO₃ Catalyst

ZHANG Ruigin,YU Qiquan,JIN Yun

1995, 31(6):  718-725. 

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SmFeO₃ was prepared by the complexation method of citric acid. The perovskite structure of SmFeO₃ was determinated by XRD. The Redoxmechanism for the oxidation of CO was proven by the pulse method of reduction with CO and reoxidation with O₂ over SmFeO₃ catalyst. The steady-state kinetics of oxidation for CO over SmFeO₃ has been investi-gated with an external circulation flow reactor. The parameters of Redox equation were estimated by the method of orthogonol design. The kinetic equation of the reduction stage obeys the Bassett-Habgood equation of pulse method.

Kinetic Studies of Reaction of Oxomolybdenum Tetraphenylporphrin Complex MoO(TPP)Cl with O^-₂ in the presence of DMSO
II The reaction network

CUI Xiaoli,HUANG Wei,YANG Huixing,GAO Panliang,HAN Degang

1995, 31(6):  675-683. 

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The mechanism of the reaction of MoO(TPP)Cl with Superoxide ion O^-₂ has been studied. The Complex MoO(TPP)Cl is reduced by O^-₂to MoO(TPP) in 1:1 dichloromethane-dimethyl sulfoxide with existance of 18-crown-6 via a series of intermediates. The detailed kinetics network of the reaction are given.

Solubilization of Bovin Serum Albumin(BSA) in Saponified P₂₀₄ Microemulsion System

Li Yan,WU Jinguang,XU Guangxian

1995, 31(6):  690-694. 

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The injection method was used in this paper to investigate the solubilization of BSA in microemulsion of saponified bis(2-ethylhexyl)phosphate (P₂₀₄). When the saponification ratio of P₂₀₄is 87%, the volumefraction (φ_BSA) has the largest value. The concentration of BSA in aqueous phase has no obvious effect on φ_BSAwithin the range ofinves-tigation. However, the increase of the concentration of salts decreases the φ value, and when the salt is CaCl₂, φ_BSAhas its largest decrease. The injection volume is relatively higher within the pH range of 4 to 7. These properties will be helpful in the separation and purification of BSA.

Design and Synthesis of Antibacterial and Antitumor Peptides Containing a SPXX Motif

HAO Yan,ZHANG Ruoheng,LI Chongxi,XU Xiaojie

1995, 31(6):  703-710. 

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On the basis of crystal structure and the interaction with DNA of Netropsin, three 10 residues SPXX motif peptides were designed and synthesized. These structures are similiar to Netropsin's. The secondary structures of these peptides have been studied by circular dichroism spectra, which satisfy the criteria of β-turn consistent with those obtained by Chou & Fasman prediction method. Circular dichroismof DNA of calf thymus with diffrent quantities of these peptides revealthat they can bind to DNA. These peptides have antibacterial and antitumoractivities.

Syntheses of [α-Alkyl-β-(2,2,3-Trimethyl-3-Cyclopentenyl)Ethyl] Acetate

WAN Xinmin,XU Ruiqiu

1995, 31(6):  639-643. 

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Nine new compounds of [α-Alkyl-β-(2,2,3-Trimethyl-3-Cyclopentenyl)Ethyl] acetate with alkyls as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, n-pentyl, isopentyl have been synthesized from α-pinene through a series of reaction of epoxidation, rearrangement, Grignard reagents addition and esterification etc. These compounds have been identified by GC, MS, IR and NMR.

Syntheses of (α-Alkyl-3, 3-Dimethyl-2-Norboranementhyl) Acetate

WAN Xinmin,XU Ruiqiu

1995, 31(6):  644-648. 

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Nine new compounds of (α-alkyl-3, 3-dimethyl-2-norboranemethyl)acetate with alkyls as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, n-pentyl, isopentyl have been synthesized from camphene through a series of reaction of epoxidation, rearrangement, Grignard reagent addition and esterification etc. These compounds have been identified by GC, MS, IR and NMR.

The Effect of Partial Pressure of Water and Studies on Kinetics of Isomerization for Butene over La₂O₃/SiO₂ Catalyst by the Steady-State and Pulse Methods

HUANG Wei,YU Qiquan,JIN Yun

1995, 31(6):  649-657. 

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The kinetics of isomerization of 1-butene over La₂O₃/SiO₂ catalyst has been investigated by the flow-reciculation glass reactor by the steady-state and pulse methods. The activity of isomerization for butene decreased with increasing the partial pressure of water. The steady-state kinetics of isomerization for butene obeyed the L-H mechanizm kinetic equation, which represented the rate equation of first order approximately. The heats of adsorption for 1-butene, 2-butene and water were determined by the pulse method. The values of adsorption heats for 1-butene, 2-butene and water were coincided with the values estimated by the method of orthoganol design. The pulse kinetics of isomerization for 1-butene obeyed the Bassett equation of first order. The relative activity of isomerization for 1-butene to t-2-butene and c-2-butene by the steady-state method were coincided with the values by the pulse method. The intrinsical activation energy of isomerization for 1-butene to t-2-batene and c-2-butene were coincided with the values by the pulse method.

The Effect of Internal Diffusion on the Kinetics of Isomerization for Butene-1 over CeO₂/SiO₂Catalyst

HUANG Wei,YU Qiquan,JIN Yun

1995, 31(6):  658-665. 

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The effect of internal diffusion on the kinetics of isomerization of butene-1 over CeO₂/SiO₂catalyst has been investigated in an external circulation gradientless reactor. The isomerization of butene-1 occurred in kinetic region with 30～40 mesh catalyst. When the thickness of catalyst was increased to 4mm, the reaction occurred in internal diffusion region. The effectiveness factors of catalyst were in the range of 0.058～0.12, indicating that the reaction was strongly affected by internal diffusion. The effectiveness factors for isomerization of butene-1 to trans-2-butene were larger than those for isomerization of butene-1 to cis-2-butene. The partial pressure profile of butene-1 in catalyst pore was calculated by the Runge-Kutta method.

Study on the Reactions of Mononuclear Copper Complexes Formed by Insertion of CS₂ into Cu-S Bonds with Various Solvents Ⅲ
Formation and Crystal Structure of [CuI(PPh₃)(Py)]₂ and [CH₂(C₅H₅

TANG Kaluo,XIA Tianbing,JIN Xianglin,TANG Youqi

1995, 31(6):  695-702. 

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Mononuclear copper complexes with structures of (Ph₃P)₂Cu(S₂CSR), formed by insertion of CS₂ into Cu-S bonds, can react with a various solvents undergoing some nucleophilic reactions. The two title compounds(IV, V)were obtained from the reaction of starting material(R=Bu^t, C₆H₂Prⁱ₃-2, 4, 6) with CH₂I₂-acetone mixed-solvent in the presence of pyridine and then self-assemblyin the same solution. Crystal data for compound IV: space group C₂/c, a=26.112(6), b=14.499(3), c=11.357(2)Å, β=95.18(2)Å, V=4282(15)ų, Dc=1.650g/cm³, Z=4, R=0.0334 for 2182 independent reflections. Crystal data for compound V: space group P2₁/n, a=11.389(4), b=11.698(5), c=13.227(7)Å, β=114.99(4)°, V=1597(13)ų, Dc=2.563g/cm³, Z=4, R=0.0627 for 1891 independent reflection.

Vibrational Spectroscopic Studies on the Acid Salts of Capric Acid and Lauric Acid

BIAN Jiang,WENG Shifu,WU Jinguang,XU Guangxian,SHI Nai

1995, 31(6):  711-717. 

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Fatty acid and their alkali soaps were well known as biosurfactants in living system, however, very few works had been published before on the fatty acid-soap complexes, which were revealed here possessing unusual structures and properties. The acid sodium salts and acid potassium salts in molar ratio of 1:1 of both capric acid and lauric acid were investigated by FTIR and FT-Raman spectroscopies. Two dominant features were determined. One was that the very strong and broad ν(OH) modes of fatty acids was absent above 1800 cm^-1 in the infrared spectra, and the other was the characteristic ν_as(COO^-) vibrations of alkali soaps could not be observed in both infrared and Raman spectra. The spectral results showed that a very strong hydrogen bond formed between carboxylate groups. In the infrared spectra of acid salts, a diffuse weak absorption in the region of 1500-800 cm^-1 was found and ascribed to the ν(OH) mode. In order to explain the unusual weakness of ν(OH)vibrations, the possibility of proton motions was discussed depending on the structural features of acid salts of fatty acids. The weak bands at 200cm^-1in the Raman spectra of acid salts other than the acids or salts showed that there may be some a defect conformation in the alkyl chains of the acid salts.

Syntheses of [α-Alkyl-β-(2,2,3-Trimethyl-3-Cyclopentenyl)Ethy1] Acetate

WAN Xinmin,XU Ruiqiu

1995, 31(6):  639-644. 

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Nine new compounds of [α-alkyl-β-(2, 2, 3-trimethyl-3-cyclopentenyl)ethyl] acetate with alkyls as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, n-pentyl, isopentyl have been synthesized from α-pinene through a series of reaction of epoxidation, rearrangement, Grignard reagentsaddition and esterification etc. These compounds have been identified by GC, MS, IR and NMR.

The Morphology of Endocrine Cells in the Gut Mucosa of the Giant Panda

YANG Guibo,CHEN Maosheng,DENG Zepei,WANG Ping

1995, 31(6):  732-738. 

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Endocrine cells containing 5-hydroxytryptamine, somatostatin, gastrin, cholecystokinin, neurotensin, motilin, gastric inhibitorypeptide, glucagon, vasoactive intestinal polypeptide, and endorphin in the mucosae of the fundus, pylorus, duodenum, jejunum, ileum, colon, and rectum of 2 giant pandas were studied by PAP method to gain an insight into the adaptive characteristics for the special feeding habit. The former 8 kinds of endocrine cells were detected in the mucosae of the 2 giant pandes. The distribution of cell types categorized by the cytoplasmic process indicated that in the 7-year old giant panda, the fundic endocrinecells were mostly round or ovoid, apical and basal cytoplasmic processes were rarely seen; many pyloric endocrine cells pocessed both apical and basal processes; while endocrine cells in the small intestine only pocessed apical process. In the 75-day old giant panda, the cell types of the gut endocrine cells are few than those of the 7-year old one. These results indicate that the structure and the distribution of the morphological types of the endocrine cells in the mucosa of the giant panda might be related to their specific feeding habit.

Studies on TEM of Valleriite, Laiyuan, Hebei Province, China

WANG Qiming,CAO Zhengmin,QIN Shan

1995, 31(6):  726-731. 

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Valleriite belongs to trigonal mineral with the characteris-tics of interlayering sulfide (Cu, Fe)S and brucite (Mg, Fe)(OH)₂ layers. Previous study proposes a superlattice hypothesis both on the c- and a-axes due to the mismatch of the sulfide and brucite lattices. The size of the superlattice depends on the value of mismatch of the two sub-unit cells. However TEM study on valleriite shows that it is of textural structure with no indication of presence of superlattice diffractions on a-axis, nor on c-axis. Along c-axis valleriite presents ruther well orderdinterlayering properties, showing a strong 1.14nm reflection, whereas along a-axis splits streaks of reflections occurred, indicating mis-orientation of brucite arrangement with respect to sulfide. Valleriite is formed as the result of the alteration of pyrite or chalcopyrite withthe initial process of forming about 10nm size micro-crystals of (Cu, Fe)Ssulfides. Later those micro-crystals of sulfides react with serpentines to obtain brucite layers to finally producing valleriite.

Model of Cd-thio Clusters in Metallothionein and Design for Its Modification

YANG Zhiwei,WANG Wenqing,SHENG Xiangrong,KUANG Bao,RU Bingeng

1995, 31(6):  739-744. 

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With the aid of computer imaging, the structure models of Cd-thio clusters in Cd-metallothioneins are provided based on the propertiesof MT conformation and acquisition of the mutated protein are proposed. According to the results of calculation, it is difficult to add a cadimumion in α-domain without a drastic change of the peptide backbone and the structure of the cluster. However, it is possible to add a cadimum ion in β-domain by inserting or mutating a few amino acid residues.

The Comparative Wood Anatomy of Vernicia fordii, Vernicia montana and Aleurites moluccana (Euphorbiaceae)

LING Jianqun,ZHANG Xinying,CHEN Yaotang

1995, 31(6):  745-751. 

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The studies of wood anatomy of 3 species Vernicia fordii(Hemsl)Airy Shaw, V. montnana Lour. and Aleurites moluccana (L.) Willd were carried out. In the woods of Vernicia fordii and V.montana, growth ring distinct, semi-ring porous, axial parenchyma diffuse, most of the rays uniseriate, less biseriate or triseriate, mostly Het III type rays, crystal sin ray cells and axial parenchyma; but on the wood of Aleurites moluccana, growth ring distinct to faint, diffuse porous, axial parenchyma diffuse-diffuse-in-aggregate, most of the rays biseriate, less uniseriate, mostly Het I type rays, crystals only in axial parenchyma. In percentage of solitary vessel and inter-vessel diameters, there were differences among Vernicia fordii,Vernicia montana and Aleurites moliccana. So the differences in these wood characters were distinct among Vernicia fordii, V.montana and Aleurites moluccana. On the other hand, some quantitative and anatomical characters such as: frequency of vessels and rays, the length of vessel members and fibers, the perforation types, inter-vessel pitting, the 3 species were very similar, In addition, the systematic status of Vernicia Lour. and Aleurites J. R. et G. Forst. was discussed with reference of the data obtained in this work.

Construction and Expression of the Gene for Des-terpeptide of C-terminal Human Proinsulin

HUNG Chunmei,CHEN Laitong,CHEN Renxin,HU Meihao

1995, 31(6):  752-757. 

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A proinsulin analog gene (B^-3CA) has been constructed in which the coden of C-terminal three residues of B chain were deleted, and was recombined with pBV220, an expression vector with P_R P_Lpromoter, Because of the difficulty to remove the N-terminal initiator methionine residue of recombinant protein in E.coli, another mutegenesiswas made by PCR to insert a Lys coden between the coden of initiator methionine and of the first residue Phe. After expressed in E.coli with the level accounting for 12% of total bacterial protein, the product was purified and processed to Desterpeptide of C-terminal human insulin which remained only 49% radioimmuno activity and 45% receptor binding activity of porcine insulin.