Chemical Research in Chinese Universities

Ruthenium Coordination Compounds with Polypyridines ——Interaction of Ruthenium Polypyridine Complexes with Calf Thymus DNA —An Example of Non intercalative Binding

YANG Guang, WANG Lei, WU Jian-zhong, ZENG Tian-xian, JI Liang-nian

1997, 13(4): 283-288.

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Two new ruthenium polypyridine complexes, L₂RuL^'2+ (L represents 2,2'-bipyridine(bpy) or 1,10-phenanthroline(phen); L' represents Schiff base derived from 4,5-diazafluoren-9-one(AFO) and n-propylamine) have been prepared and characterized by means of elementary analyses, electronic absorption and IR spectra. The binding of the complexes to calf thymus DNA has been investigated via absorption, emission spectrometry, emission quenching, equilibrium dialysis and circular dichroism spectrometry. The experimental results show that these two complexes bind to calf thymus DNA by electrostatic mode and by non-ntercalative binding mode respectively.

Synthesis and Magnetism of 2 Hydroxy 1,3 propylene bis(oxamato) bridged Co^ⅡCu^ⅡCo^Ⅱ Complexes

MIAO Ming-ming, CHENG Peng, LIAO Dai-zheng-JIANG Zong-hui, WANG Geng-lin

1997, 13(4): 289-293.

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Four new heterotrinuclear complexes have been synthesized and characterized, namely [(CoL₂)₂Cu(pbaOH)](ClO₄)₂, where pbaOH denotes 2-hydroxy-1,3-propylenebis(oxamato) and L stands for 1,10-phenanthroline(phen), 5-nitro 1,10-phenanthroline(NO₂ phen), 2,2'-bipyridyl(bpy) and 4,4'-dimethyl-2,2'-bipyridyl(Me 2bpy). The temperature dependence of the magnetic susceptibility of [(Cophen₂)₂Cu(pbaOH)](ClO₄)₂·H₂O has been studied in the range of 4—300 K, the plot of χ_M T_vs. T exhibits a minimum at about 120 K, but abnormal magnetic behavior below 78 K.

Synthesis, Structure and Properties of α Keggin type of K₆H₃[ZnW₁₁ O₄₀ Al]·9.5H₂O

YANG Qi-hua, FU Qiang, LIU Jing-fu, XING Yan, LIN Yong-hua, JIA Heng-qing

1997, 13(4): 294-298.

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A new heteropolycomplex, K₆H₃[ZnW₁₁ O₄₀ Al]·9.5H₂O was prepared and characterized by means of elemental analysis, IR, UV spectroscopy, ²⁷Al NMR , electrochemistry and X ray crystallography. The crystal of K₆H₃[ZnW₁₁ O₄₀ Al]·9.5H₂O is cubic, space group Fm-3m , with lattice constants a=b=c =2.144 8(2) nm, V =9.866(2) nm³, Mo radiation, R =0.057 8 for 497 independent data with [ I>2δ(I) ]. The anion is of α type Keggin structure with C_s symmetry.

The Synthesis of Star Style Metalloporphyrin

TONG Shan-ling, ZHA NG Jing-yan, ZHEN Kai-ji, FANG Chi-guang

1997, 13(4): 299-303.

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The present paper covers a novel star style metalloporphyrin [tetra(4-(4'-methoxycarbonylbenzoxyl)phenyl)porphyrin cobalt, TMBPPCo] with four paw groups [4-(4'-methoxycarbonylbenzoxyl)phenyl(—C₆H₄CO₂C₆H₄CO₂CH ₃)]. Its structure was characterized by means of UV-Vis, IR, ¹H NMR and MS spectrometries.

An Electrochemical Study of Prussian Blue Microcrystallines Mixed in PEO₄₀₀ Polymer Electrolyte by Solid-state Voltammetry

GUO Li-ping, LIN Xiang-qin

1997, 13(4): 304-311.

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The electrochemistry of Prussian blue mixed in a polymer medium containing MClO₄(M=Li⁺, Na⁺, K⁺, TBA⁺) as the supporting electrolyte was studied by means of solid -state voltammetry. This approach is new in Prussian blue studies. The behavior of PB in polymer electrolytes is somewhat similar to the well-known behavior for an electrochemically synthesized PB film in aqueous media. Besides, K⁺, Li⁺ and Na⁺ ions can also transport through the crystal of PB because of its zeolitic nature. The transport of TBA⁺ ions is possible. Kinetic control lies in the diffusion of cations in and out of the lattice of Prussian blue. Reduction waves of Prussian blue depend on both the size and type of cations. PB is very stable upon electrochemical cycling in polymer electrolytes and air. This system may be used in rechargeable batteries and electrochromic devices.

Synthesis and Characterization of Sn-W Complexes and Crystal Structure of Ph₃SnW(CO)₃C₅H₄CH₃

WANG Ji-Tao, HE Hai-Yang, XU Yu-Ming, ZHANG Yun-Wen, LIU Hong-Zhou

1997, 13(4): 312-318.

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The present paper covers the reaction of sodium tricarbonyl cyclopentadienyl or substituted cyclopentadienyl tungsten with triphenyl(tribenzyl) tin chloride or diphenyl(dibenzyl) tin dichloride to yield bimetallic complexes R₃SnW(CO)₃Cp^* or trimetallic complexes R₂Sn[W(CO)₃Cp^*]₂(R=Ph, PhCH₂; Cp^*=C₅H₅, CH₃C₅H₄, CH₃COC₅H₄, 1,2,4-Ph₃C₅H₂). They were characterized by means of elemental analysis, IR and ¹H NMR. The crystal of Ph₃SnW(CO)₃C₅H₄CH₃ is orthorhombic, space group is P_bca with a =1.146 5(2) nm, b =1.674 7(6) nm, c =2.496(1) nm, Z =8 and Sn—W bond length of 0.283 22 nm.

Studies on Electron Impact Mass Spectra of Some Anhydro-sugars

YU Jian-xin, LIU Yu-ting, WANG Yo-ng-fu, O'YANGLi, DONG Ying, CAIMeng-shen

1997, 13(4): 319-323.

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The fragmentation patterns of anhydro sugars 1—6 in electron impact mass spectrometry have been proposed, and verified by means of metastable ions scanning method.

Theoretical Studies on the Mechanism of Mannich Reaction Involving Iminium Salt as Potential Mannich Reagent(1) ——Use Acetaldehyde as Pseudo-acid Component

XIAO He-ming, LING Yue, ZHAI Yu-feng, LI Yu-min

1997, 13(4): 324-329.

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This paper is one of a series of reports of theoretical researches on the mechanism of the Mannich reaction using the iminium salt as the potential Mannich reagent. According to the results of AM1 dynamic calculations, the activation energies of key steps in conventional Mannich reactions between ammonia, formaldehyde and acetaldehyde in neutral and acidic media are 438.8 kJ/mol and 393.9 kJ/mol respectively. The activation energy of the rate-controlling step of the Mannich reaction which contains the potential Mannich reagent is 274.7 kJ/mol. Therefore, it can be derived that the potential Mannich reagent can increase the rate of the reaction remarkably. The reasons for this have been discussed in terms of the orbital match and electrostatic interaction between the atoms of reactant complexes. In this paper another different conjectured mechanism of the potential Mannich reagent which can reduce the activation energy is considerably studied.

Effect of pH on the Rheology of A1-Mg M iteed Meta1 Hydroxide——Montmorillonite Aqueous Suspension

HOU Wan-guo, SUN De-jun, WU Tao, SONG Shu-e, ZHANG Chun-guang

1997, 13(4): 330-335.

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The effects of the pHs of Mtsuspension(pH_Mt),AMH sol(pH_A)and mixedsuspension(pH_mix)on the rheology of mixed su sp en sion w ere studied.The mixed suspension consisted of the alum in ium magnesium mixed metal hydroxide(AM H) colloidal prt icles which possessed permanent positive charges and the Na-montmorillon ite(M t)particles which po ssessed permanent nega tive charges.The results showed that the pHs did not affect the Bingham yield poin t(YP)of the mixed suspen sionsin the various pHs(i.e.,pH_Mt,pH_A and pH_mix)range of 8—10 almost. When the pH values were above 10 the YPs increased ma rked ly w ith increa sing pH_Mt and pH_mix,but decreased sharply with increasing pH_A.The mechanisms of the effect of pH on the rheology of mixed suspensions were also investigated.

Studies on Hepatocyte-Targeting Magnetic Resonance Imaging Macromolecular Contrast Media

FU Yan-jun, ZHUO Ren-xi

1997, 13(4): 336-343.

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DTPA was covalently conjugated to the copolymer of L-lysine and L-tyrosine, then transchelated with Gd-EDTA,the resultant polymer chelates were further reacted with 6-O-bromoacety-l-D-galactose or methyl lactobionyloxyacetate to give PLT(Gd-DTPA) with galactose moiety as liver- targeting group.These macromolecular MRI contrast agents were characterized by means of FT-IR, ICP-AES, elementary analyses and UV-Vis spectrophotometry. Their in vitro relaxivity and liver targeting property in mice were also investigated.

The Polymerization of Methyl Methacrylate with a New Nd(O——i-Pr)₃—AI( i-Bu)₃ Catalyst System

SUN Jun-quan

1997, 13(4): 344-349.

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Methyl methacrylate (MMA) was polymerized with the rare earth coordination catalyst system of Nd(O——i-Pr)₃ in toluene. The influences of various ligands in neodymium complexes, molar ratio of Al/Nd, catalyst concentration, catalyst aging time, solvents, the third component CCl₄, temperature and time on the polymerization of MMA were studied. The results showed that the polymerization conversion reached more than 80% at a catalyst concentration of 9.2×10^-3 mol/L. The appropriate molar ratio of CCl₄/Nd was 4. Hydrocarbon was preferred for the polymerzation to obtain a high conversion and a highM_W of PMMA. The ¹H NMR spectra of PMMA indicated that the lower the temperature, the higher the syndiotactic content of PMMA was obtained.

Synthesis and Investigation of Monoesters of Polymaleic Acids with Azo-Group

SU Feng-yu, LI Yan, TANG Jun, TIAN Yan-qing, ZHAO Ying-ying, ZHOU En-le

1997, 13(4): 350-354.

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A series of amphiphilic polymers, monoesters of polymaleic acid containing azo side groups (PMAN-A_n Me) was synthesized by the reaction of alcohol(A_n Me) with polymaleic anhydride (PMAN) for Langmuir-Blodgett assembly. The effects of the length of flexible spacer in the side chain on the π-A isotherms and LB films were investigated. The UV-Vis and infrared linear dichroism spectra showed that the azo-side groups were highly oriented in PMAN A-₆Me LB film deposited on silica or CaF₂ substrate.

Oxidation of CO on Nanometer Metal Oxides at Low Temperatures

ZHANG Wen-xiang, JIA Ming-jun, ZHAO Jing-zhe, ZHANG Chun-lei, WU Tong-hao, WANG Xue-guang

1997, 13(4): 355-357.

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