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Electron-transfer Reactions (electron-transfer + reaction)
Selected AbstractsNuclear-Spin Polarization in Electron-Transfer Reactions of AminesHELVETICA CHIMICA ACTA, Issue 12 2006Heinz Abstract Chemically induced dynamic nuclear polarization (CIDNP) observed during electron transfer (ET) reactions of tertiary amines such as DABCO (1) or Et3N (2) with a wide range of electron acceptors support the involvement of amine radical-cations (e.g., 1.+ or 2.+) as key intermediates. Radical ions such as 2.+ may be deprotonated, generating neutral aminoalkyl radicals (e.g., 2.). When generated by reaction with an electron acceptor of energetically low triplet state such as naphthalene (1Naph*), the resulting pair 2.+/Naph., reacts mostly by reverse electron transfer (RET) from triplet pairs populating the naphthalene triplet state. [source] Tetraalkylammonium salt as photoinitiator of vinyl polymerization in organic and aqueous media: A mechanistic and laser flash photolysis studyJOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 7 2002María L. Gómez Abstract N -Dimethyl- N -[2-(N,N -dimethylamino)ethyl]- N -(1-methylnaphthyl)ammonium tetrafluoroborate (I) was synthesized with the aim of obtaining a versatile photoinitiator for vinyl polymerization in organic solvents and water. Salt I was able to trigger the polymerization of acrylamide, 2-hydroxyethylmethacrylate and styrene even at very low concentrations of the salt (,1.0 × 10,5 M). Using laser flash photolysis and fluorescence techniques and analyzing the photoproduct distribution, we were able to postulate a mechanism for the photodecomposition of the salt. With irradiation, I undergoes an intramolecular electron-transfer reaction to form a radical ion pair (RIP). The RIP intermediate decomposes into free radicals. The RIP and the free radicals are active species for initiating the polymerization. Depending on the concentration of the vinyl monomers studied, the initiation mechanism of the polymerization reaction changes. At large monomer concentrations, the RIP state is postulated to trigger the reaction by generating the anion radical of the olefin substrate. At a low monomer concentration, the free radicals produced by the decomposition of I are believed to start the chain reaction. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 901,913, 2002; DOI 10.1002/pola.10166 [source] Photodegradation mechanism and stabilization of polyphenylene oxide and rigid-rod polymersPOLYMER INTERNATIONAL, Issue 2 2006Ying-Hung So Abstract Poly(2,4-dimethyl-1,4-phenylene oxide) (PPO), poly(benzo[1,2- d:5,4- d,]bisoxazole-2,6-diyl-1,4-phenylene) (PBO) and poly(benzo[1,2- d:4,5- d,]bisthiazole-2,6-diyl-1,4-phenylene) (PBZT), which are polymers with extended conjugated structures, undergo a self-sensitized photo-induced electron-transfer reaction. A second component is not required. This article presents many similar observations on these polymers when they are exposed to light and evidence to support the proposed photo-induced electron-transfer mechanism. Methods to stabilize these polymers against photo-oxidation are also described. Workers investigating other conjugated polymeric systems may find the experimental methods, observations and polymer stabilization approaches discussed in this review useful. Copyright © 2005 Society of Chemical Industry [source] Ultrahigh-resolution structure of high-potential iron,sulfur protein from Thermochromatium tepidumACTA CRYSTALLOGRAPHICA SECTION D, Issue 7 2002Lijun Liu Crystals of the high-potential iron,sulfur protein (HiPIP) from Thermochromatium tepidum diffract X-rays to 0.80,Å using synchrotron radiation at 100,K. The crystal structure of this HiPIP was refined at this ultrahigh resolution with anisotropic temperature factors for all atoms to conventional crystallographic R factors of 0.092 and 0.101 for Fo > 4,(Fo) and all reflections, respectively. The present structure provides a more precise picture than the previous 1.5,Å structure and allows location of the positions of most H atoms. The structure revealed a partly hydrophobic cavity near the main hydrophobic area and a much larger inter-cluster approach distance (23.454,Å, the c constant of the unit cell) in the crystal packing than other types of HiPIPs. The structural features involved in the electron-transfer reaction of HiPIP are discussed. [source] Eosin Y-Sensitized Artificial Photosynthesis by Highly Efficient Visible-Light-Driven Regeneration of Nicotinamide CofactorCHEMBIOCHEM, Issue 10 2009Sahng Ha Lee Abstract Dye-sensitized photosynthesis: Eosin Y (EY), a dye photosensitizer, works efficiently as a molecular photoelectrode by catalyzing the visible-light-driven electron-transfer reaction for efficient regeneration of NADH through a photosensitizer,electron relay dyad. Injection of the photosensitized electron resulted in highly accelerated regeneration of NADH, which can be used by glutamate dehydrogenase for the photosynthesis of L -glutamate. [source] Redox Couple of DNA on Multiwalled Carbon Nanotube Modified ElectrodeELECTROANALYSIS, Issue 14 2009Hongxia Luo Abstract It has been envisioned that carbon nanotubes could promote electron-transfer reactions when used as electrode materials in electrochemical cells. In the present study, calf thymus DNA was electrochemically oxidized at an electrode modified with multiwalled carbon nanotubes. The potentials for DNA oxidation at pH,7.0 were found to be 0.71 and 0.81,V versus SCE, corresponding to the oxidation of guanine and adenine residues, respectively. An initial oxidation of adenine was observed in the first scan, which was followed by a quasi-reversible redox process of the oxidation product in the subsequent scans. [source] Computational study of titanium (IV) complexes with organic chromophoresINTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY, Issue 6 2006Ivan Kondov Abstract A computational study of small titanium complexes with the chromophores catechol, alizarin, and coumarin 343 is presented. Employing density functional theory (DFT), the ground-state geometries, energies, and harmonic frequencies of the different compounds are calculated. Furthermore, time-dependent DFT and the configuration interaction singles (CIS) method are used to determine excitation energies and excited-state gradients. Based on these results, the character of the excited states as well as electronic-vibrational coupling strengths are analyzed, and the implications for electron-transfer reactions at dye,semiconductor interfaces are discussed. © 2005 Wiley Periodicals, Inc. Int J Quantum Chem, 2006 [source] Water-soluble anionic conjugated polymers for metal ion sensing: Effect of interchain aggregationJOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 19 2009Yi Chen Abstract Three sulfonato-containing fluorene-based anionic water-soluble conjugated polymers, which are specially designed to link fluorene with alternating moieties such as bipyridine (P1), pyridine (P2), and benzene (P3) have been synthesized via the Pd-catalyzed Sonogashira-coupling reaction, respectively. These polymers had good solubility in water and showed different responses for transition metal ions with different valence in aqueous environments: the fluorescence of bipyridine-containing P1 can be completely quenched by addition of all transition metal ions selected and showed a good selectivity for Ni2+; the pyridine-containing P2 had a little response for monovalent and divalent metal ions while showed good quenching with the addition of trivalent metal ions (with a special selectivity for Fe3+); P3 had responses only for the trivalent metal ions within the ionic concentration we studied. After investigation of the UV-vis absorption spectra, PL emission spectra, DLS, and fluorescence lifetime of P1,P3 in aqueous solution when adding transition metal ions, we found that the different spectrum responses of these polymers are attributed to the different coordination ability of the units linked with fluorene in the main chain. The energy or electron-transfer reactions were the main reason for fluorescence quenching of P1 and P2. On the other hand, interchain aggregation caused by trivalent metal ions lead to fluorescence quenching for P3 and also caused partly fluorescence quenching of P1 and P2. These results revealed the origin of ionochromic effects of these polymers and suggested the potential application for these polymers as novel chemosensors with higher sensing sensitivity in aqueous environments. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 5057,5067, 2009 [source] Evaluation of the Chemical Reactions from Two Electrogenerated Species in Picoliter Volumes by Scanning Electrochemical MicroscopyCHEMPHYSCHEM, Issue 13 2010Qian Wang Abstract The volume created by the positioning of two scanning electrochemical microscope (SECM) probes (tip and substrate) at a micrometric distance defines a "picoliter beaker" where homogeneous electron-transfer reactions are studied. The SECM is used to concurrently electrogenerate in situ two reactive species and to evaluate the possibility of detecting their reactivity. Two reaction cases are studied: the first, called the "reversible case", occurs when the electrochemically generated species at the substrate electrode can also react at the tip to yield the same product as the reaction in the gap. The second case, named the "irreversible case", occurs when the electrochemically generated species at the substrate are not able to react at the tip. Digital simulations are performed and compared to experimental studies. These show that an unusual compensation between collection and feedback effects render the analysis inapplicable in the "reversible case". The "irreversible case" is shown experimentally. [source] Low-Temperature EPR and Mössbauer Spectroscopy of Two Cytochromes with His,Met Axial Coordination Exhibiting HALS Signals,CHEMPHYSCHEM, Issue 6 2006Giorgio Zoppellaro Dr. Abstract C-type cytochromes with histidine,methionine (His,Met) iron coordination play important roles in electron-transfer reactions and in enzymes. Low-temperature electron paramagnetic resonance (EPR) spectra of low-spin ferric cytochromes c can be divided into two groups, depending on the spread of g values: the normal rhombic ones with small g anisotropy and gmax below 3.2, and those featuring large g anisotropy with gmax between 3.3 and 3.8, also denoted as highly axial low spin (HALS) species. Herein we present the detailed magnetic properties of cytochrome c553 from Bacillus pasteurii (gmax 3.36) and cytochrome c552 from Nitrosomonas europaea (gmax 3.34) over the pH range 6.2 to 8.2. Besides being structurally very similar, cytochrome c553 shows the presence of a minor rhombic species at pH 6.2 (6,%), whereas cytochrome c552 has about 25,% rhombic species over pH 7.5. The detailed Mössbauer analysis of cytochrome c552 confirms the presence of these two low-spin ferric species (HALS and rhombic) together with an 8,% ferrous form with parameters comparable to the horse cytochrome c. Both EPR and Mössbauer data of axial cytochromes c with His,Met iron coordination are consistent with an electronic (dxy)2 (dxz)2 (dyz)1 ground state, which is typical for Type I model hemes. [source] | |||||||||||||