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Reactive Center (reactive + center)
Selected AbstractsProton-Coupled Electron Transfer of Unsaturated Fatty Acids and Mechanistic Insight into LipoxygenaseHELVETICA CHIMICA ACTA, Issue 10 2006Shunichi Fukuzumi Abstract A proton-coupled electron transfer (PCET) process plays an important role in the initial step of lipoxygenases to produce lipid radicals which can be oxygenated by reaction with O2 to yield the hydroperoxides stereoselectively. The EPR spectroscopic detection of free lipid radicals and the oxygenated radicals (peroxyl radicals) together with the analysis of the EPR spectra has revealed the origin of the stereo- and regiochemistry of the reaction between O2 and linoleyl (=,(2Z)-10-carboxy-1-[(1Z)-hept-1-enyl]dec-2-enyl) radical in lipoxygenases. The direct determination of the absolute rates of H-atom-transfer reactions from a series of unsaturated fatty acids to the cumylperoxyl (=,(1-methyl-1-phenylethyl)dioxy) radical by use of time-resolved EPR at low temperatures together with detailed kinetic investigations on both photoinduced and thermal electron-transfer oxidation of unsaturated fatty acids provides the solid energetic basis for the postulated PCET process in lipoxygenases. A strong interaction between linoleic acid (=,(9Z,12Z)-octadeca-9,12-dienoic acid) and the reactive center of the lipoxygenases (FeIIIOH) is suggested to be involved to make a PCET process to occur efficiently, when an inner-sphere electron transfer from linoleic acid to the FeIII state is strongly coupled with the proton transfer to the OH group. [source] Correlating the positional reactivity of a masked electrophilic center to the topology of the electron densityINTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY, Issue 5 2005Harry L. Price Abstract Masking of electrophilic centers in biological molecules via structural modifications serves to control chemical reactivity and in some cases may affect the regioselectivity of a reaction. In the work presented the regioselective reactivity of the electrophilic cyclopropylpyrrololindole (CPI) center in the DNA alkylator CC-1065, a highly toxic antibiotic that has served as a structural template for the development of a series of novel anticancer drugs containing the CPI reactive center has been examined. The CPI reactive center is an interesting example of chemical masking as it relates to acid-dependent electrophilicity, and regioselective addition of a nucleophile to an electrophilic center. In an effort to better understand the reactivity of the CPI center, calculations using the B3LYP density functional theory (DFT) method, the 6-31G(d) basis set, and the atoms in molecules (AIM) theory were performed on unprotonated and protonated forms of the CPI reactive center. The results of these calculations demonstrate that activation of the CPI group via protonation induces significant changes in the electron density (,), the Laplacian of the density (,2,), and the bond ellipticity (,), and that these changes are linked to the observed reactivity of the CPI reaction center. © 2005 Wiley Periodicals, Inc. Int J Quantum Chem, 2005 [source] Superelectrophilic Activation of N -Substituted Isatins: Implications for Polymer Synthesis, a Theoretical StudyMACROMOLECULAR THEORY AND SIMULATIONS, Issue 2 2009Daniel Romero Nieto Abstract The stability and reactivity of mono- and multi-protonatred N -substituted isatin derivatives were studied at PBE0/aug-cc-pvtz//PBE0/6-31+G** level of theory in triflic acid (TFSA) solution. Calculations showed that the monocationic intermediates are the principal reactive species in the reaction of hydroxyalkylation of isatin derivatives in TFSA media. Electron-withdrawing substituents on the nitrogen atom increase the reactivity of isatin-containing electrophiles towards aromatic hydrocarbons, in accordance with their expected electronic influence. Steric factors also play an important role in the reactivity of isatin-containing electrophiles, especially in the second reaction step, due to their more sterically hindered reactive center. [source] Crystal structure of viral serpin crmA provides insights into its mechanism of cysteine proteinase inhibitionPROTEIN SCIENCE, Issue 8 2000Miljan Simonovic Abstract CrmA is an unusual viral serpin that inhibits both cysteine and serine proteinases involved in the regulation of host inflammatory and apoptosis processes. It differs from other members of the serpin superfamily by having a reactive center loop that is one residue shorter, and by its apparent inability to form SDS-stable covalent complexes with cysteine proteinases. To obtain insight into the inhibitory mechanism of crmA, we determined the crystal structure of reactive center loop-cleaved crmA to 2.9 Å resolution. The structure, which is the first of a viral serpin, suggests that crmA can inhibit cysteine proteinases by a mechanism analogous to that used by other serpins against serine proteinases. However, one striking difference from other serpins, which may be significant for in vivo function, is an additional highly charged antiparallel strand for , sheet A, whose sequence and length are unique to crmA. [source] Multiple strategies for O2 transport: from simplicity to complexityIUBMB LIFE, Issue 8-9 2007Paolo Ascenzi Abstract O2carriers (extracellular and intracellular as well as monomeric and multimeric) have evolved over the last billion of years, displaying iron and copper reactive centers; very different O2carriers may co-exist in the same organism. Circulating O2carriers, faced to the external environment, are responsible for maintaining an adequate delivery of O2to tissues and organs almost independently of the environmental O2partial pressure. Then, intracellular globins facilitate O2transfer to mitochondria sustaining cellular respiration. Here, molecular aspects of multiple strategies evolved for O2transport and delivery are examined, from the simplest myoglobin to the most complex giant O2carriers and the red blood cell, mostly focusing on the aspects which have been mainly addressed by the so called 'Rome Group'. [source] Shielding Effects in Polymer-Polymer Reactions, 1MACROMOLECULAR THEORY AND SIMULATIONS, Issue 6 2007Z-RAFT Star Polymerization of Four-Arm Stars Abstract Shielding effects of the surrounding arms and chains on the reactive centers taking part in RAFT four-arm star polymerization following the Z-group approach are calculated by means of exact enumeration of star/chain samples prepared by Monte Carlo techniques. The shielding effect, which can be relieved when using expanded core moieties, increases with increasing chain (arm) lengths. This leads to a reduction of the contact probability according to a power law with an exponent of ,0.4 to ,0.45. Additionally, characteristic chain properties and shape parameters are calculated as a function of the distance between the center of the star and the end of the linear chain in order to gain deeper insight into the mechanism of contact formation preceding the actual reaction. [source] Advances in Photoelectrocatalysis with Nanotopographical PhotoelectrodesCHEMPHYSCHEM, Issue 8 2010A. G. Muñoz Dr. Abstract The design of photoelectrodes for high efficiency solar fuel energy conversion devices is based on the search for adequate surface conditioning to achieve efficient light harvesting, stability, minimized surface recombination losses and high electron-transfer rates at the electrolyte interface. An overview on established and novel approaches is given. A recent viable solution is provided by electroplating of nanoscale catalytic metals on passivated semiconductor surfaces, thereby forming reactive centers and avoiding contact between the semiconductor surface and the electrolyte. At these nano-dimensioned Schottky-type junctions, light-induced excess minority carriers are scavenged and transferred to the electrolyte. Various possible device configurations are outlined and envisaged systems for hydrogen or oxygen evolution and carbon dioxide reduction are presented. The role of ultrathin passivating films is emphasized and methods to fabricate open as well as compact conformal films are described. [source] |