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71.
Adams CM Kjeldsen F Zubarev RA Budnik BA Haselmann KF 《Journal of the American Society for Mass Spectrometry》2004,15(7):1087-1098
First results are reported on the application of ECD in analysis of 2+ and 3+ ions of stereoisomers of Trp-cage (NLYIQWLKDGGPSSGRPPPS), the smallest and fastest-folding protein, which exhibits a tightly folded tertiary structure in solution. The chiral recognition based on the ratios of the abundances of z(18) and z(19) fragments in ECD of 2+ ions was excellent even for a single amino acid (Tyr) D-substitution (R(chiral) = 8.6). The chiral effect decreased with an increase of temperature at the electrospray ion source, as well as at a higher degree of ionization, 3+ ions (R(chiral) = 1.5). A general approach is suggested for charge localization in n+ ions by analysis of ECD mass spectra of (n + 1)+ ions. Application of this approach to 3+ Trp-cage ions revealed the protonation probability order in 2+ ions: Arg(16) > Gln(5) > approximately N-terminus. The ECD results for native form of the 2+ ions favor the preservation of the solution-phase tertiary structure, and chiral recognition through the interaction between the charges and the neutral bond network. Conversely, ECD of 3+ ions supports the dominance of ionic hydrogen bonding which determines a different gas-phase structure than found in solution. Vibrational activation of 2+ ions indicated greater stability of the native form, but the fragmentation patterns did not provide stereoisomer differentiation, thus underlying the special position of ECD among other MS/MS fragmentation techniques. Further ECD studies should yield more structural information as well as quantitative single-amino acid D/L content measurements in proteins. 相似文献
72.
DTA was used to study thermal properties and thermal stability of (50-x)Li2O-xTiO2-50P2O5 (x=0–10 mol%) and 45Li2Ot-yTiO2-(55-y)P2O5 (y=5–20 mol%) glasses. The addition of TiO2 to lithium phosphate glasses results in a non-linear increase of glass transition temperature. All prepared glasses crystallize
under heating within the temperature range of 400–540°C. The lowest tendency towards crystallization have the glasses with
x=7.5 and y=10 mol% TiO2. X-ray diffraction analysis showed that major compounds formed by annealing of the glasses were LiPO3, Li4 P2O7, TiP2O7 and NASICON-type LiTi2(PO4)3. DTA results also indicated that the maximum of nucleation rate for 45Li2O-5TiO2-50P2O5 glass is close to the glass transition temperature. 相似文献
73.
Levy JN Latham CM Roisin L Kandziora N Di Fruscia P White AJ Woodward S Fuchter MJ 《Organic & biomolecular chemistry》2012,10(3):512-515
A synthetic route towards a number of novel IBiox N-heterocyclic carbene (NHC) ligands has been developed. The resulting ligands have restricted flexibility and high steric demand. Preliminary studies have shown these ligands to give high levels of asymmetric induction in the copper-free allylic alkylation of cinnamyl bromide. 相似文献
74.
U. Ceren Başköse Sevgi Haman Bayarı Semran Sağlam Hacı Özışık 《Central European Journal of Chemistry》2012,10(2):395-406
The conformational analysis of rasagiline [N-propargyl-1(R)-aminoindan] was performed by the density functional theory (DFT) B3LYP method using the 6–31++G (d,p) basis set. A single
point energy calculations based on the B3LYP optimized geometries were also performed at MP2/6-31++G (d, p) level. The vibrational
frequencies of the most stable conformer of rasagiline was calculated at the B3LYP level and vibrational assignments were
made for normal modes on the basis of scaled quantum mechanical force field (SQM) method. The influence of mesylate and ethanedisulfonate
salts on the geometry of rasagiline free base and its normal modes are also discussed.
相似文献
75.
A reaction cascade comprising a rhodium-catalyzed C-H activation, a subsequent hydrometalation of an alkylidene cyclopropane in vicinity, regioselective C-C bond activation of the flanking cyclopropane ring, followed by reductive elimination of the resulting metallacycle, opens a new entry into functionalized cycloheptene derivatives. This crossover of C-H activation and higher order cycloaddition has been performed in two different formats, either using alkylidenecyclopropanes with a lateral vinylpyridine moiety or with a pending aldehyde group as the trigger. The reaction tolerates various functional groups, leaves chiral centers alpha to the reacting sites unaffected, and proceeds with excellent stereoselectivity. Labeling experiments support the proposed mechanism explaining the observed net cycloisomerization process. 相似文献
76.
Diemer V Berthelot A Bayardon J Jugé S Leroux FR Colobert F 《The Journal of organic chemistry》2012,77(14):6117-6127
A new aryne-mediated tandem cross-coupling/P-cyclization sequence starting from tertiary phosphine-boranes and 1,2-dibromobenzenes is reported. P-chirogenic dibenzophospholes become accessible in a regio-, chemo-, and diastereoselective way. 相似文献
77.
Anaïs Geny Dr. Nicolas Agenet Dr. Laura Iannazzo Max Malacria Prof. Dr. Corinne Aubert Dr. Vincent Gandon Dr. 《Angewandte Chemie (International ed. in English)》2009,48(10):1810-1813
Cobalt cyclopentadienyl complexes incorporating a fumarate and a CO ligand (see picture) efficiently catalyze inter‐ and intramolecular [2+2+2] cycloadditions of alkynes, nitriles, and/or alkenes to give benzenes, pyridines, or 1,3‐cyclohexadienes. Unlike catalysts such as [CpCo(CO)2] or [CpCo(C2H4)2] (Cp=C5H5), they are air‐stable, easy to handle, compatible with microwave conditions, and do not necessarily require irradiation to be active.
78.
Xin Zhang Ruibo Wu Lingchun Song Yuchun Lin Menghai Lin Zexing Cao Wei Wu Yirong Mo 《Journal of computational chemistry》2009,30(15):2388-2401
Combined QM(PM3)/MM molecular dynamics simulations together with QM(DFT)/MM optimizations for key configurations have been performed to elucidate the enzymatic catalysis mechanism on the detoxification of paraoxon by phosphotriesterase (PTE). In the simulations, the PM3 parameters for the phosphorous atom were reoptimized. The equilibrated configuration of the enzyme/substrate complex showed that paraoxon can strongly bind to the more solvent‐exposed metal ion Znβ, but the free energy profile along the binding path demonstrated that the binding is thermodynamically unfavorable. This explains why the crystal structures of PTE with substrate analogues often exhibit long distances between the phosphoral oxygen and Znβ. The subsequent SN2 reaction plays the key role in the whole process, but controversies exist over the identity of the nucleophilic species, which could be either a hydroxide ion terminally coordinated to Znα or the μ‐hydroxo bridge between the α‐ and β‐metals. Our simulations supported the latter and showed that the rate‐limiting step is the distortion of the bound paraoxon to approach the bridging hydroxide. After this preparation step, the bridging hydroxide ion attacks the phosphorous center and replaces the diethyl phosphate with a low barrier. Thus, a plausible way to engineer PTE with enhanced catalytic activity is to stabilize the deformed paraoxon. Conformational analyses indicate that Trp131 is the closest residue to the phosphoryl oxygen, and mutations to Arg or Gln or even Lys, which can shorten the hydrogen bond distance with the phosphoryl oxygen, could potentially lead to a mutant with enhanced activity for the detoxification of organophosphates. © 2009 Wiley Periodicals, Inc. J Comput Chem, 2009 相似文献
79.
80.
Åse Støg»rd 《Chemical physics letters》1975,36(3):357-360
Ab initio as well as semi-empirical SCF MO calculations are presented for ClCN and ONCl. The relative intensities for Cl Kβ emission in the two molecules were calculated. The calculated spectra from the ab initio wavefunctions are in excellent agreement with experiments. 相似文献