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21.
Some derivatives of azaglycine and azaphenylalanine are described. Esters of acetyl- and benzoyl-aza-amino-acids rapidly cyclise to stable oxadiazolones and it is concluded that similar derivatives would be unsuitable for aza-peptide synthesis. t-Butyloxycarbonyl-azaglycine azide was too unreactive for use in peptide synthesis. Benzoyl-azaglycylphenylalanine ethyl ester and acetyl-azaphenylalanylphenylalanine ethyl ester were prepared by coupling benzoyl hydrazide and N-acetyl-N'-benzylhydrazide respectively with 2,4-dinitrophenyloxycarbonyl-phenylalanine ethyl ester. 相似文献
22.
Funk T Kennepohl P Di Bilio AJ Wehbi WA Young AT Friedrich S Arenholz E Gray HB Cramer SP 《Journal of the American Chemical Society》2004,126(18):5859-5866
We show that X-ray magnetic circular dichroism (XMCD) can be employed to probe the oxidation states and other electronic structural features of nickel active sites in proteins. As a calibration standard, we have measured XMCD and X-ray absorption (XAS) spectra for the nickel(II) derivative of Pseudomonas aeruginosa azurin (NiAz). Our analysis of these spectra confirms that the electronic ground state of NiAz is high-spin (S = 1); we also find that the L(3)-centroid energy is 853.1(1) eV, the branching ratio is 0.722(4), and the magnetic moment is 1.9(4) mu(B). Density functional theory (DFT) calculations on model NiAz structures establish that orbitals 3d(x2-y2) and 3d(z2) are the two valence holes in the high-spin Ni(II) ground state, and in accord with the experimentally determined orbital magnetic moment, the DFT results also demonstrate that both holes are highly delocalized, with 3d(x2-y2) having much greater ligand character. 相似文献
23.
Amashukeli X Gruhn NE Lichtenberger DL Winkler JR Gray HB 《Journal of the American Chemical Society》2004,126(47):15566-15571
Inner-sphere electron-transfer reorganization energies of Zn(protoporphyrin IX) and Zn(octaethylporphyrin) are determined from band-shape analyses of the first ionization obtained by gas-phase valence photoelectron spectroscopy. The experimentally determined total inner-sphere reorganization energies for self-exchange (120-140 meV) indicate that structural changes upon oxidation are largely confined to the porphyrin ring, and substituents on the ring or solvent and other environmental factors make smaller contributions. Computational estimates by different models vary over a wide range and are sensitive to numerical precision factors for these low reorganization energies. Of current computational models that are widely available and practical for molecules of this size, functionals that contain a mixture of Hartree-Fock exchange and DFT exchange-correlation appear to be the most applicable. 相似文献
24.
P. W. Gray 《Journal of Radioanalytical and Nuclear Chemistry》1986,102(1):59-67
When a gamma-ray spectrum contains a number of photopeaks originating from the same nuclide, the calculation of nuclide activity depends not only on the values of, and uncertainties in, the photopeak areas, photopeak efficiencies, gamma-ray emission probabilities and peak area correction factors, but also on the correlations that exist between these quantities. When photopeaks corresponding to a group of nuclides overlap or are unresolved, simultaneous estimation of the activities of all the nuclides present in the group is necessary if the information contained in the spectrum is to be used efficiently — a procedure which can prove important when the only prominent photopeak associated with a nuclide of interest overlaps with the photopeak of another nuclide. Two procedures for activity estimation are described: both procedures take correlations into account; one procedure deals with the special case of activity estimation for a single nuclide, where unresolved photopeaks are absent or neglected; the other procedure deals with simultaneous activity estimation using all the photopeaks associated with an interrelated group of nuclides. 相似文献
25.
26.
Balest R Cho K Ford WT Lohner M Park H Rankin P Smith JG Alexander JP Bebek C Berger BE Berkelman K Bloom K Browder TE Cassel DG Cho HA Coffman DM Crowcroft DS Dickson M Drell PS Dumas DJ Ehrlich R Elia R Gaidarev P Garcia-Sciveres M Gittelman B Gray SW Hartill DL Heltsley BK Henderson S Jones CD Jones SL Kandaswamy J Katayama N Kim PC Kreinick DL Lee T Liu Y Ludwig GS Masui J Mevissen J Mistry NB Ng CR Nordberg E Patterson JR Peterson D Riley D Soffer A Avery P Freyberger A Lingel K Prescott C 《Physical review letters》1995,75(21):3809-3813
27.
Barish B Chadha M Chan S Cowen DF Eigen G Miller JS O'Grady C Urheim J Weinstein AJ Acosta D Athanas M Masek G Paar HP Gronberg J Kutschke R Menary S Morrison RJ Nakanishi S Nelson HN Nelson TK Qiao C Richman JD Ryd A Tajima H Sperka D Witherell MS Procario M Balest R Cho K Daoudi M Ford WT Johnson DR Lingel K Lohner M Rankin P Smith JG Alexander JP Bebek C Berkelman K Bloom K Browder TE Cassel DG Cho HA Coffman DM Crowcroft DS Drell PS Ehrlich R Gaidarev P Galik RS Garcia-Sciveres M Geiser B 《Physical review D: Particles and fields》1995,51(3):1014-1033
28.
Bartelt J Csorna SE Egyed Z Jain V Gibaut D Kinoshita K Pomianowski P Barish B Chadha M Chan S Cowen DF Eigen G Miller JS O'Grady C Urheim J Weinstein AJ Würthwein F Asner DM Athanas M Bliss DW Brower WS Masek G Paar HP Gronberg J Korte CM Kutschke R Menary S Morrison RJ Nakanishi S Nelson HN Nelson TK Qiao C Richman JD Roberts D Ryd A Tajima H Witherell MS Balest R Cho K Ford WT Lohner M Park H Rankin P Smith JG Alexander JP Bebek C Berger BE Berkelman K Bloom K Browder TE Cassel DG Cho HA 《Physical review D: Particles and fields》1995,52(9):4860-4867
29.
Balest R Cho K Daoudi M Ford WT Johnson DR Lingel K Lohner M Rankin P Smith JG Alexander JP Bebek C Berkelman K Bloom K Browder TE Cassel DG Cho HA Coffman DM Drell PS Ehrlich R Gaiderev P Garcia-Sciveres M Geiser B Gittelman B Gray SW Hartill DL Heltsley BK Jones CD Jones SL Kandaswamy J Katayama N Kim PC Kreinick DL Ludwig GS Masui J Mevissen J Mistry NB Ng CR Nordberg E Patterson JR Peterson D Riley D Salman S Sapper M Würthwein F Avery P Freyberger A Rodriguez J Stephens R Yang S Yelton J 《Physical review letters》1994,72(15):2328-2331
30.