STUDIES OF ELECTRON SPIN RESONANCE ON BILIRUBIN FREE RADICALS

The nature of ESR signals derived from bilirubin-Ⅸα has been studied by focusing onthe samples treated with free radical generating and inhibiting systems, i.e. X-XOD, Fe/EDTA, SOD, mannitol/ascorbate, CO, KCN, etc. In all the cases, the stable signals comprisethose originated from semiquinone radical (g = 2.0012) and superoxide free radical (g_∥=2.041, g_⊥= 2.0040). The superoxide is shown binding with certain metal ions chelated bybilirubin. The free radical scavengers are able to destroy these radicals. The kinetic curveof the regeneration of bilirubin radicals has been determined and the reaction follows azero order mechanism. It is likely that both the physiological and toxic actions of bilirubinare related to the characters of its free radicals. Bilirubin is discussed as "active oxygensink" in mammalians.     

Enhancive Synthesis of(±)-1β,11-Diol-4-en-eudesmol

An enhancive synthesis of (±)-1β, 11-diol-4-en-eudesmol,starting from 2-chloroacrylonitrile, is described. The effect oftemperature on the Diels-Alder reaction of 2-chloroacrylonitrilewith 2-methylfuran and the condition of cationic cyclization ofdiene were discussed in detail.     

液相色谱专家系统中柱系统推荐规则的建立和验证

把分子结构和分子、离子静电作用力作为影响溶质保留值和选择性的基本点,提出了液相色谱专家系统柱系统推荐的基本规则,由此可以从溶质所包含的基团或官能团的信息进行色谱柱系统推荐。为了验证这些规则的正确性,应用几类常用的或典型的样品从分子结构通道进行液相色谱柱系统推荐,获得满意的结果。     

An unexpected ring-opening in the reissert reaction on 2,3-diphenylquinoxaline-n-oxide.

When quinoxaline-N-oxide 1 is reacted with KCN and benzoyl chloride in water (the Reissert reaction) or methanol, the products are 2-,5- and 6- chloroquinoxaline (the latter being the major product: 42±6 %) and small amounts of 2-cyanoquinoxaline. Using three equivalents of trimethylsilyl cyanide instead of KCN, and dichloromethane as the solvent, leads to a 72 % yield of 2-cyanoquinoxaline. The reaction of trimethylsilyl cyanide and benzoyl chloride with 2,3-diphenylquinoxaline-N-oxide 2 leads to an unexpected ring-opening product 13; its structure is based on spectroscopic data and on an X-ray crystallographic analysis.     

Hydroformylation and hydrocarbethoxylation of 1,2-dicarbethoxy-1,2,3,6-tetrahydropyridazine and 1,2-dicarbethoxy-1,2,3,4-tetrahydropyridazine

The unsaturated compounds 1,2-dicarbethoxy-1,2,3,6-tetrahydropyridazine 1 and 1,2-dicarbethoxy-1,2,3,4-tetrahydropyridazine 2 have been hydroformylated and hydrocarbethoxylated in the presence of some well known cobalt, rhodium, palladium and platinum catalysts. The hydroformylation reaction can be tuned by a suitable choice of the catalyst precursor and reaction conditions, thus allowing the synthesis with high selectivity of one of the two possible isomeric aldehydes. The carbonylation reaction is less synthetically useful, since it shows low activity and unsatisfactory chemo- and regio-selectivity. However, the ester 1,2,4-tricarbethoxyhexahydropyridazine 10 can be prepared in good yield from olefin 1 by using the complex [PdCl₂(PPh₃)₂] as the catalyst precursor.     

Metal---metal bond formation promoted by steric effects: The structural chemistry of μ-dichlorobis(di-t-butyl-p-tolylphosphine)tetracarbonyldiruthenium(I)

The bulky teratiary phosphines P-t-Bu₂Ph and P-t-Bu₂-p-tol, provide binuclear ruthenium(I) complexes. An X-ray analysis of [Ru₂Cl₂(CO)₄(P-t-Bu₂-p-tol)₂] shows the RuCl₂Ru bridge to be non-planar and to have an Ru---Ru distance of 2.632Å.     

Conformational deformation of ring C in 14β-estra- 1,3,5(10) 15-tetraen-17-ones

High-field n.m.r. analysis of four 3-methoxy-14β-estra-1,3,5(10), 15-tetraen-17-ones provides evidence for conformational deformation of ring C to a twist-boat form in solution. These observations are supported by molecular mechanics (MM2) calculations, which predict that the ring C chair and ring C twist-boat conformers have similar steric energies, slightly favouring the latter. An X-ray crystal structure determination on 3-methoxy-14-methyl-14β-estra-1,3,5(10), 15-tetraen-17-one revealed that ring C does indeed adopt a twist-boat conformation in the solid state.     

Ion chromatography of nitrite and carbonate in inorganic matrices on an octadecyl—poly(vinyl alcohol) gel column using acidic eluents

Low levels of carbonate and nitrite contained in inorganic matrices were determined by ion chromatography on an Asahipak ODP-50 poly(vinyl alcohol) gel-based reversed-phase column. With an acidic mobile phase, inorganic matrix anions and cations eluted near the void volume of the column, whereas carbonate and nitrite were retained and separated completely from the matrix ions. After the separation column, the peak response was enhanced using a cation-exchange hollow fibre and 25 mM sodium sulphate or alkaline enhancers. Sea-water samples can be applied directly for the determination of carbonate and added nitrite at ppm levels. The maximum sample volume that can be loaded on the column without peak deformation depended on the pH of the sample solution and the sulphuric acid concentration in the eluent. A 50 μl sea-water sample was applicable with a 2.5 mM acid eluent.     

A New Triterpenoid Saponin and a New Glycoside from Epigynum aurilum

A new triterpenoid saponin with novel sugar moiety (1), a new trisaccharide derivative (2), as well as a known monosaccharide derivative (3), were isolated from the dried stem of Epigyhum aurilum. The structures of compounds 1 and 2 were determined by MS and NMR spectram analyses.     

Studies on the disposable obstetrical dressings sterilized by radiation and the effect of its application

In order to attain an optimum sterilization treatment to obstetric dressings, a new product made by us, with ⁶⁰Coγ-ray, the effects of radiation on standard bacteria pseudomonas aeruginosa ATcc27853, Escherichia coli ATcc25922, Staphylococcus aureus ATcc25923, Clostridium PB6KA, short Bacillus E60163202 and HBSAg were studied. Results showed that at the absorbed dose of 10 kGy, all the bacteria, bacillus and HBSAg were killed off, and sterilized with the dose, the dressings can completely accord with the demands of hygiene, which was further confirmed by microbiological and poisonous tests and the effects of clinical application. In Nov. 1988, the dressings was awarded the excellent prize in the 1st international exhibition of patent, new technique and new equipment in Guangzhou; its effective application is also reported in the paper.