The effect of metal oxides on the oxidation of polybutadiene

Carboxy-terminated polybutadiene (CTPB) was oxidised as a coating on various metal oxides by heating in air on a thermobalance. The oxidation was found to be free from diffusion control and was catalysed by certain of the oxides. The catalysis was shown to be independent of semiconductor type and to be associated with those oxides for which the width of the forbidden zone between the valence and conduction bands (U) is less than 1.9 eV. In general, low values of U result in high catalytic activity. It is proposed that catalysis occurs by a redox mechanism, viz. RO₂H + p → RO₂^. + H⁺, RO₂H + e → RO^. + OH^?.     

Structure and extinction of counterflow diffusion flames above condensed fuels: Comparison between poly(methyl methacrylate) and its liquid monomer,both burning in nitrogen–air mixtures

Since poly(methyl methacrylate) is known to depolymerize largely to its monomer when heated, the chemical kinetics in the gaseous diffusion flame produced by this polymer in a fire may coincide with that of burning liquid methyl methacrylate. To test this hypothesis, flat diffusion flames were probed and extinguished adjacent to surfaces of each of these fuels. Profiles of temperature and of concentrations of stable chemical species are reported, as are gas velocities of approach flow required to produce extinction for various oxygen/nitrogen ratios of the stream. Results revealed structural differences attributable to differing thermal properties of the fuels. Many fuel species were observed in the gas phase, their profiles being partially rationalized on the basis of a suggested decomposition mechanism for gaseous methyl methacrylate. Overall kinetic parameters for gasphase combustion, obtained by use of extinction results in a previously developed theory, are nearly the same for the polymer and monomer but appear to differ by amounts exceeding experimental uncertainties. It is suggested that this may be traced to small differences in fuel species leaving the condensed phase which, for the polymer, is covered by a thin, two-phase region.     

Imidazopyeidine derivatives as polymethine dyes

Several new polymethine dyes of the cyanine and merocyanine series with 1-methyl-1H-imidazo [4,5-b]pyridine residues were synthesized, and their colors were studied. Replacement of the benzimidazole residue in the cyanine dyes by a l-methyl-1H-imidazo[4,5-b]-pyridine residue leads to deepening of the dye color.See [1] for communication II.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 11, pp. 1561–1565, November, 1971.     

Nα,Nim-di-tert-alkoxycarbonyl derivatives of histidine

The acylation of histidine with di-tert-butyl and di-tert-amyl pyrocarbonates has given the corresponding N,N_im-di-tert-alkoxycarbonyl derivatives. The N,N^im-di-tert-butoxycarbonyl derivative was obtained in the crystalline form by crystallization from benzene or carbon tetrachloride, or in the form of salts with cyclohexylamine, dicyclohexylamine, and diethylamine. N,N^im-di-tert-amyloxycarbonyl-histidine was characterized in the form of the salt with dicyclohexylamine.Institute of Biological and Medicinal Chemistry, Academy of Medical Sciences of the USSR, Moscow. Translated from Khimiya Prirodnykh Soedinenii, No. 3, pp. 379–383, May–June, 1980.     

Spectrophotometric determination of rhenium with di(2-pyridyl)ketone-2-furancarbothiohydrazone and other thiohydrazones

A simple rapid method is proposed for the determination of rhenium (as perrhenate) in which the brown-violet complex produced is measured at 546 nm. The system obeys Beer's law in the range 0.7–14.0 μg Re ml^-1; the molar absorptivity is 1.51 × 10⁴ l mol^-1 cm^-1 in ethanol and 1.64 × 10⁴ l mol^-1 cm^-1 for the complex extracted into methyl isobutyl ketone. Molybdenum (100-fold), tungsten (40-fold), copper (10-fold), and palladium (10-fold) are tolerable. Reactions of other metal ions such as Cu(II), Ni(II), Co(II) and Fe(II) with this ligand and reactions of perrhenate with analogous reagents are discussed.     

Structure and conformational isomerism of the major dimer of 2,3-naphthoquinodimethane

The major product from 2,3-naphthoquinodimethane formed by cyclisation of $\text{o}$-dipropadienylbenzene was found to be the dimer 5 containing an eight-membered ring, for which the inversion barrier was determined by dynamic ¹H NMR spectrometry, ΔG3 = 18 kcal/mole.     

INTRAMOLECULAR EXCIPLEX FORMATION IN Nα-ACETYL-1-PYRENYLALANYL-1-METHYLTRYPTOPHAN METHYLESTER

Abstract— The synthesis, absorption and emission properties of erythro (e) and threo (t) Na-acetyl-1-pyrenylalanyl-1-methyltryptophan methylester (APTE) are reported. From the dependency of the exciplex emission maximum on the solvent polarity, the exciplex dipole moment of erythro and threo APTE were calculated. The evolution of the ratio of the quantum yield of exciplex emission and the quantum yield of emission from the locally excited state is correlated with solvent polarity and with the tendency of the solvent to interact with the peptide chain through hydrogen bonding. It is shown that solvents, inert towards the peptide function, shift the equilibrium between the two ground state conformations towards C₇, in which an exciplex geometry can be reached. Hydrogen accepting solvents shift the conformational equilibrium towards C₅, which cannot form an exciplex directly within the lifetime of excited pyrene.     

Interactions intramoléculaires en série cyclohexanique: Partie II. Spectres photoélectroniques de chloro-2 cyclohexanones

The photoelectronic spectra of cis-2-chloro, 4-tert-butylcyclohexanone and cis-2-methyl-2-chlorocyclohexanone have been analysed. These analyses have been used in an investigation into the nature of the orbital interactions in these molecules, and into the dependence of these interactions on the axial or equatorial position of the halogen atom. The preferential conformations of 2-chlorocyclohexanone and 4,4-dimethyl-2-chlorocyclo-hexanone have thus been obtained.     

Excitation energy effects in the photophysics of trans-stilbene in solution

Excitation of trans-stilbene with 306 nm pulses generates a narrower transient spectrum than with 265 nm. These spectra do not evolve in the same manner, suggesting that the spectral changes with 265 nm result from vibrational cooling. Spectral differences at longer times suggest there is a slow cross-relaxation component in the inhomogeneous distribution.     

Glycosides of marine invertebrates. XXVI. Holothurin A from the Pacific Ocean holothurianHolothvria squamifera. Isolation of the native aglycone

The known triterpene tetraoside holothurin A has been isolated from the Pacific Ocean holothurianHolothuria squamifera. By using two independent methods — enzymatic cleavage and two-stage Smith degradation — 22,25-epoxyholost-9(11)-ene-3β,12α,17α-triol, C₃₀H₄₆O₆, which is the native aglycone of holothurin A, was obtained. The structure of the native aglycone has been established on the basis of the results of IR, mass, and PMR spectroscopy.