Resonance Raman spectra of tris(acetylacetonato)iron(III) and ruthenium(III) complexes and their solvent effect

The resonance Raman spectra of tris(acetylacetonatoiron(III)) and ruthenium(III) complexes in various solvents and in water-acetonitrile (W-AN) mixtures were measured. The resonance Raman spectra of both complexes indicated peaks near 460 and around 1580 cm^–1. Thev(C-O) peak (around 1580 cm^–1) is shifted to low frequency with an increase in the dielectric constant _T of the solvents, whereas thev(M-O) (M=Fe and Ru, near 460 cm^–1) are constant, independent of _T. It implies that the C-O bond in the acac^– ligand is lengthened by the polarizability effect of the solvents, while both the Fe-O and Ru-O bonds, which are located in the inside of the complexes, are not influenced by the solvents indicating that the interaction does not depend on the properties of individual solvent molecules but on those of the aggregate.     

Dynamics and thermodynamics of dimerization of parallel G-quadruplexed DNA formed from d(TTAGn) (n=3-5)

Parallel G-quadruplexes formed from oligonucleotide sequences, d(TTAGn), where n = 3-5, have been shown to form a dimer through end-to-end stacking of 3'-terminal G-tetrads. The monomers and dimers of the G-quadruplexes are in dynamic equilibrium with an exchange rate of approximately 1 s-1. A thermodynamic study demonstrated that the dimerization of the G-quadruplexes is largely enthalpic in origin.     

Mechanism of charge–transfer polymerization. II. Propagation mechanism of the polymerization of N-vinylcarbazole with organic electron acceptors

Copolymerizations of N-vinylcarbazole with both isobutyl vinyl ether and N-vinyl-pyrrolidone initiated by some organic electron acceptors have been investigated for the purpose of elucidating the propagation mechanism in the charge-transfer polymerization. Copolymerizations of the same system catalyzed by authentic cationic catalysts have also been made for comparison. The results indicate that the propagation mechanism of the charge-transfer polymerization studied is catio ie.     

Influence of amino acid side chain packing on Fe-methionine coordination in thermostable cytochrome C

Paramagnetic NMR and optical studies of the oxidized forms of mesophile Pseudomonas aeruginosa cytochrome c(551) and its quintuple mutant (F7A/V13M/F34Y/E43Y/V78I), and thermophile Hydrogenobacter thermophilus cytochrome c(552) demonstrated that the amino acid side chain packings in the protein interior influence the coordination bond between the heme iron and the axial methionine in the proteins. The strength of heme axial coordinations was found to correlate with the overall protein thermostability.     

A new Zn(II) coordination polymer with 4-pyridylthioacetate: assemblies of homo-chiral helices with sulfide sites

A coordination polymer [Zn(pyta)(OH)] (pyta = 4-pyridylthioacetate), was synthesized and structurally characterized; it is constructed by an alternating assembly of two types of homo-chiral helices, [Zn-OH] and [Zn-pyta], in which the sulfide moieties are fastened in the latter columns.     

Development of a new file search system for nuclear magnetic resonance spectra: Production of an Enlarged Data Base and Search Test

A practical search system for proton n.m.r. spectra is reported. The coding rules and search algorithms are described in detail. Data for 8000 spectra have been converted into a computer-readable file from printed charts. Several search tests are used to evaluate the usefulness of the search system, and various effects of experimental conditions such as different instruments, frequencies and solvents on recall efficiency are described. The results presented indicate that the system should be applicable to routine analytical work.     

Intermolecular methyl transfer on pyrolysis of carpronium chloride

The methyl transfer occurring in the production of methyl N,N-dimethyl-γ-aminobutyrate by pyrolysis of carpronium chloride was examined by means of pyrolysis gas chromatography mass spectrometry with the aid of some deuterated compounds. The mass spectra of methyl N,N-dimethyl-γ-aminobutyrate, produced from deuterated derivatives of carpronium chloride, showed inter alia, characteristic molecular ion peaks which indicated that the methyl of the trimethylammonium group transfers and displaces the methyl of the carbomethoxy group of the tertiary amino compound. The results show that an intermolecular methyl transfer occurs in part on pyrolysis of carpronium chloride, to form methyl N,N-dimethyl-γ-aminobutyrate in which the methyl oxygen is replaced by a methyl from the nitrogen of the original compound. The mechanism presented involves the bimolecular reaction between zwitterionic intermediates formed by ionic O-demethylation of carpronium chloride.     

Diinsertion of fluorenylidene into a sulfur-sulfur bond of diaryl disulfides

Upon irradiation (>340 nm) of a benzene solution of diazofluorene with di-p-tolyl- or di-p-anisyl disulfide, the corresponding 9,9′-bis(arylmercapto)bifluorenyl was afforded in moderate to good yield accompanied by formation of 9,9′-bis(arylmercapto)fluorene. The major reaction pathway is considered to be a disulfur ylide formation followed by two times of successive Stevens rearrangement or by concerted electron redistribution via [2,3]sigmatropic rearrangement.     

Pyrolysis reaction of carpronium chloride and its structurally related compounds. 2—a mass spectrometric study of the lactonization mechanism

The mechanism of the pyrolysis reaction of carpronium chloride [(CH₃)₃N⁺? (CH₂)₃? COOCH₃CI^?] leading to γ-butyrolactone and tetramethylammonium chloride was investigated by means of thermal analysis, pyrolysis gas chromatography mass spectrometry and field desorption mass spectrometry, using deuterium labelling. The results indicated that carpronium chloride pyrolysed to yield equimolar amounts of γ-butyrolactone and tetramethylammonium chloride, methyl transfer occurred between N and O during the pyrolysis process. The mechanism is discussed on the basis of the experimental results, and with the aid of the theoretical results calculated by the CNDO/2 method. The mechanism presented is as follows. γ-Butyrolactone is formed by the intramolecular migration of the π-orbital of C?O to the carbon adjacent to [(CH₃)₃N]⁺ via a 5-membered ring transition state, accompanied by a bimolecular reaction between [(CH₃)₃N]⁺ and the CH₃ of O? CH₃, resulting in the formation of tetramethylammonium chloride in an amount equimolar with γ-butyrolactone.     

Dynamic coordination polymers with 4,4'-oxybis(benzoate): reversible transformations of nano- and nonporous coordination frameworks responding to present solvents

Reversible construction of a nanoporous framework from a nonporous framework has been found in the zinc(II) coordination polymer with 4,4'-oxybis(benzoate) (oba). [Zn(2)(oba)(2)(dmf)(2)].2DMF (1), which has 1 nm scale channels, transforms to the nonporous coordination polymer [Zn(oba)(H(2)O)] (2) with the loss of the open framework. Compound 2 on treatment with DMF reversibly yields nanoporous compound 1.