• Title/Summary/Keyword: beta-hydrogen transfer

Search Result 14, Processing Time 0.018 seconds

Novel solvothermal approach to hydrophilic nanoparticles of late transition elements and its evaluation by nanoparticle tracking analysis

  • Dutilleul, Marion Collart;Seisenbaeva, Gulaim A.;Kessler, Vadim G.
    • Advances in nano research
    • /
    • v.2 no.2
    • /
    • pp.77-88
    • /
    • 2014
  • Solvothermal treatment of late transition metal acetylacetonates in a novel medium composed either of pure acetophenone or acetophenone mixtures with amino alcohols offers a general approach to uniform hydrophilic metal nanoparticles with high crystallinity and low degree of aggregation. Both pure metal and mixed-metal particles can be accesses by this approach. The produced materials have been characterized by SEM-EDS, TEM, FTIR in the solid state and by Nanoparticle Tracking Analysis in solutions. The chemical mechanisms of the reactions producing nanoparticles has been followed by NMR. Carrying out the process in pure acetophenone produces palladium metal, copper metal with minor impurity of $Cu_2O$, and NiO. The synthesis starting from the mixtures of Pd and Ni acetylacetonates with up to 20 mol% of Pd, renders in minor yield the palladium-based metal alloy along with nickel oxide as the major phase. Even the synthesis starting from a mixed solution of $Cu(acac)_2$ and $Ni(acac)_2$ produces oxides as major products. The situation is improved when aminoalcohols such as 2-aminoethanol or 2-dimethylamino propanol are added to the synthesis medium. The particles in this case contain metallic elements and pairs of individual metals (not metal alloys) when produced from mixed precursor solutions in this case.

Kinetics and Mechanism of the Benzylaminolysis of O,O-Diphenyl S-Aryl Phosphorothioates in Dimethyl Sulfoxide

  • Adhikary, Keshab Kumar;Lee, Hai-Whang
    • Bulletin of the Korean Chemical Society
    • /
    • v.32 no.5
    • /
    • pp.1625-1629
    • /
    • 2011
  • Kinetic studies of the reactions of O,O-diphenyl Z-S-aryl phosphorothioates with X-benzylamines have been carried out in dimethyl sulfoxide at 55.0 $^{\circ}C$. The Hammett (log $k_2$ vs ${\sigma}_X$) and Bronsted [log $k_2$ vs $pK_a(X)$] plots for substituent X variations in the nucleophiles are biphasic concave downwards with a maximum point at X = H, and the unusual positive ${\rho}_X$ and negative ${\beta}_X$ values are obtained for the strongly basic benzylamines. The sign of the cross-interaction constant (${\rho}_{XZ}$) is negative for both the strongly and weakly basic nucleophiles. Greater magnitude of ${\rho}_{XZ}$ value is observed with the weakly basic nucleophiles (${\rho}_{XZ}$ = -2.35) compared to with the strongly basic nucleophiles (${\rho}_{XZ}$ = -0.03). The deuterium kinetic isotope effects ($k_H/k_D$) involving deuterated benzylamines [$XC_6H_4CH_2ND_2$] are primary normal ($k_H/k_D$ > 1). The proposed mechanism is a concerted $S_N2$ involving a frontside nucleophilic attack with a hydrogen bonded, four-center-type transition state for both the strongly and weakly basic nucleophiles. The unusual positive ${\rho}_X$ and negative ${\beta}_X$ values with the strongly basic benzylamines are rationalized by through-space interaction between the ${\pi}$-clouds of the electron-rich phenyl ring of benzylamine and the phenyl ring of the leaving group thiophenoxide.

STRENGTH OF THE RAMAN SCATTERED HE II EMISSION LINES IN SYMBIOTIC STARS AND PLANETARY NEBULAE

  • LEE HEE-WON
    • Journal of The Korean Astronomical Society
    • /
    • v.36 no.2
    • /
    • pp.55-60
    • /
    • 2003
  • In Lee, Kang & Byun (2001) the discovery of Raman scattered 6545 A feature was reported in symbiotic stars and the planetary nebula M2-9. The broad emission feature around 6545 A is formed as a result of Raman scattering of He II n = 6 $\to$ n = 2 photons by atomic hydrogen. In this paper, we introduce a method to compute the equivalent width of He II $\lambda$ 1025 line and present an optical spectrum of the symbiotic star RR Telescopii as an example for a detailed illustration. In this spectrum, we pay attention to the broad H$\alpha$ wings and the Raman scattered He II 6545 feature. The broad Ha wings are also proposed to be formed through Raman scattering of continuum around Ly$\beta$ by Lee (2000), and therefore we propose that the equivalent width of the He II $\lambda$ 1025 emission line is obtained by a simple comparison of the strengths of the 6545 feature and the broad H$\alpha$ wings. We prepare a template H$\alpha$ wing profile from continuum radiation around Ly$\beta$ with the neutral scattering region that is supposed to be responsible for the formation of Raman scattered He II 6545 feature. Isolation of the 6545 feature that is blended with [N II] $\lambda$ 6548 is made by using the fact that [N II] $\lambda$ 6584 is always 3 times stronger than [N II] $\lambda$ 6548. We also fit the 6545 feature by a Gaussian which has a width 6.4 times that of the He II $\lambda$ 6527 line. A direct comparison of these two features for RR Tel yields the equivalent width $EW_{Hel025} = 2.3{\AA}$ of He II $\lambda$ 1025 line. Even though this far UV emission line is not directly observable due to heavy interstellar extinction, nearby He II lines such as He II $\lambda$ 1085 line may be observed using far UV space instruments, which will verify this calculation and hence the origins of various features occurring in spectra around H$\alpha$.

The Gene Encoding γ-Glutamyl Transpeptidase II in the Fission Yeast Is Regulated by Oxidative and Metabolic Stress

  • Kang, Hyun-Jung;Kim, Byung-Chul;Park, Eun-Hee;Ahn, Ki-Sup;Lim, Chang-Jin
    • BMB Reports
    • /
    • v.38 no.5
    • /
    • pp.609-618
    • /
    • 2005
  • $\gamma$-Glutamyl transpeptidase (GGT, EC 2.3.2.2.) catalyzes the transfer of the $\gamma$-glutamyl moiety from $\gamma$-glutamyl containing ompounds, notably glutathione (GSH), to acceptor amino acids and peptides. A second gene (GGTII) encoding GGT was previously isolated and characterized from the fission yeast Schizosaccharomyces pombe. In the present work, the GGTII-lacZ fusion gene was constructed and used to study the transcriptional regulation of the S. pombe GGTII gene. The synthesis of $\beta$-galactosidase from the GGTII-lacZ fusion gene was significantly enhanced by NO-generating SNP and hydrogen peroxide in the wild type yeast cells. The GGTII mRNA level was increased in the wild-type S. pombe cells treated with SNP. However, the induction by SNP was abolished in the Pap1-negative S. pombe cells, implying that the induction by SNP of GGTII is mediated by Pap1. Fermentable carbon sources, such as glucose (at low concentrations), lactose and sucrose, as a sole carbon source, enhanced the synthesis of $\beta$-galactosidase from the GGTII-lacZ fusion gene in wild type KP1 cells but not in Pap1-negative cells. Glycerol, a non-fermentable carbon source, was also able to induce the synthesis of $\beta$-galactosidase from the fusion gene, but other non-fermentable carbon sources such as acetate and ethanol were not. Transcriptional induction of the GGTII gene by fermentable carbon sources was also confirmed by increased GGTII mRNA levels in the yeast cells grown with them. Nitrogen starvation was also able to induce the synthesis of $\beta$-galactosidase from the GGTII-lacZ fusion gene in a Pap1-dependent manner. On the basis of the results, it is concluded that the S. pombe GGTII gene is regulated by oxidative and metabolic stress.