Bisphosphines related to bis(diphenylphosphino)ethane (dppe) and their gold complexes are described that are active in a spectrum of transplantable tumor models. When administered ip on days 1-5 at its maximally tolerated dose (MTD) of 40 mumol/kg, dppe reproducibly gives 100% increase in life span (ILS) in mice bearing ip P388 leukemia. Coordination of chlorogold(I) to each phosphine in dppe gave a complex that had similar activity but at a much lower dose level than dppe; the MTD for the gold(I) complex was 7 mumol/kg. Among other metal complexes of dppe, the Au(III) complex was active (greater than 50% ILS) whereas Ag(I), Ni(II), Pt(II), Pd(II), and Rh(I) complexes were inactive. Among dppe analogues, replacement of phenyl groups with ethyl or benzyl groups resulted in inactivity for both ligands and the corresponding gold complexes whereas substitution with cyclohexyl or heterocyclic ring systems yielded ligands and/or gold complexes with antitumor activity. Among substituted-phenyl dppe and dppe(AuCl)2 analogues, 3-fluoro, 4-fluoro, perdeuterio, 4-methylthio, and 2-methylthio analogues were active; 4-methyl, 3-methyl, 4-methoxy, 4-dimethylamino, and 4-trifluoromethyl analogues were marginal or inactive. Analogues in which the ethane bridge of dppe or dppe(AuCl)2 was varied between one and six carbons, unsaturated or substituted, revealed that activity was maximal with ethane or cis-ethylene. Compounds with good P388 activity were also active in other animal tumor models.

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ABSTRACT:The urushi fraction of several samples of the sap of Rhus verniciflua was analyzed by a combination of capillary gas chromatography, supercritical fluid chromatography, high resolution NMR spectroscopy and two techniques of mass spectrometry.

The optical activities of poly‐(R)‐lactide, poly‐(S)‐lactide, poly(β‐hydroxybutyrate) and two β‐hydroxyvalerate copolymers were measured in solution, as solid powders in suspension, and where possible, as films. Poly‐(+)‐3‐methyl‐1‐pentene was also reinvestigated. In some cases the specific rotation values of powder samples showed significant differences from the values of the solution measurements. The discrepancies of the data observed seem to reflect the local environment of the polymer chains in supermolecular assemblies and consequently the solid state structure(morphology)of the polymers. The circular dichroism (CD) spectra of the polymers were also measured in solution and in the form of their films. For comparison, the CD spectra of the naturally occurring protein casein and of the synthetic polypeptide poly‐(L)‐proline were also measured.

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ABSTRACT:This paper describes interesting results based on the preparation and utilization of UV stabilizers for Urushi. Ultraviolet stabilizers suitable for protecting coatings of oriental lacquers against the damaging effects of UV radiation were synthesized. 2-(2-Hydroxy-3-tertiarybutyl-5-[3'-hydroxypropyl]phenyl)-2H-benzotriazole (Bzt) was esterified with three unsaturated carboxylic acids: oleic, linoleic, and linolenic acid. The benzotriazole derivatives were characterized by their molecular weight (K +10s mass spectrum), by their UV spectra and by their gas chromatographic behavior. The compounds were added to three types of oriental lacquer and the compositions were cured. The curing consists of the copolymerization of the active urushi compound, mostly trienes, with the polymerizable UV stabilizers. Simulated testing of the coatings of cured oriental lacquer containing these polymerizable UV stabilizers by exposing the coatings to intensive white light showed that the UV stabilizer containing coatings were several fold more stable than unstabilized urushi coatings.

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Helical macromolecules which are configurationally and conformationally specific can now be synthesized. Monomer structures must be selected that demand spacial restriction for monomer addition. High specificity of monomer addition during polymerization has parallels in crystallization of some inorganic salts from aqueous solution. Initiation of highly specific polymerizations with chiral initiators give helical polymers with substantial one‐handedness. Nucleation of certain inorganic salts with chiral nucleating agents, the enantiomers of the salts produce enantiomerically pure chiral salts.