Search results for "electron transfer"
showing 10 items of 282 documents
A photoresponsive graphene oxide-C60 conjugate.
2014
An all-carbon donor-acceptor hybrid combining graphene oxide (GO) and C60 has been prepared. Laser flash photolysis measurements revealed the occurrence of photoinduced electron transfer from the GO electron donor to the C60 electron acceptor in the conjugate
The coupling between electron transfer and protein dynamics in the bacterial photosynthetic reaction center: trapping of conformational substates in …
2004
The photosynthetic reaction center (RC) from purple bacteria is becoming a prototype in exploring the coupling between internal protein motions and long-range electron transfer (ET). This interplay has been extensively investigated by hampering RC substate interconversion and relaxations at low temperatures (McMahon et al., 1998, Biophys. J. 74, 2567). As a complementary approach for limiting RC dynamics at room temperature we embedded the protein within a dehydrated trehalose matrix. Spectroscopic studies and molecular dynamics simulations performed on myoglobin/trehalose/water systems have shown that the nonharmonic contributions to the protein motions (attributed to thermal fluctuations …
Fluorinated Heterocyclic Compounds. A Photochemical Approach to a Synthesis of Fluorinated Quinazolin-4-ones
2004
An efficient and generalized photochemical methodology for the preparation of fluorinated quinazolin-4-ones is described. Depending on the starting substrate, quinazolin-4-ones bearing a perfluoroalkyl- or perfluoroaryl- substituent in position 2 or fluorine atoms on any positions of the benzo-fused moiety can easily be obtained. 5-Aryl-3-perfluoroalkylpentafluorophenyl- or 5-polyfluoroaryl-3-phenyl(methyl)-1,2,4-oxadiazoles, respectively, can be considered as ideal precursors that can be transformed into the target quinazolin-4-ones by irradiation in the presence of triethylamine (TEA) (at λ = 313 nm) or pyrene (at λ = 365 nm) in dry methanol or acetonitrile as solvent. Some mechanistic co…
Magnetism and variable temperature and pressure crystal structures of a linear oligonuclear cobalt bis-semiquinonate
2016
The crystal structure of the first oligomeric cobalt dioxolene complex, Co3(3,5-DBSQ)2((t)BuCOO)4(NEt3)2, 1, where DBSQ is 3,5-di-tert-butyl-semiquinonate, has been studied at various temperatures between 20 and 200 K. Despite cobalt-dioxolene complexes being generally known for their extensive ability to exhibit valence tautomerism (VT), we show here that the molecular geometry of compound 1 is essentially unchanged over the full temperature range, indicating the complete absence of electron transfer between ligand and metal. Magnetic susceptibility measurements clearly support the lack of VT between 8 and 300 K. The crystal structure is also determined at elevated pressures in the range f…
Photochemical and photobiological studies with acridine and phenanthridine hydroperoxides in cell-free DNA.
1997
The acridine and phenanthridine hydroperoxides 3 and 7 were synthesized as photochemical hydroxyl radical sources for oxidative DNA damage studies. The generation of hydroxyl radicals upon UVA irradiation (lambda = 350 nm) was verified by trapping experiments with 5,5-dimethyl-1-pyrroline N-oxide and benzene. The enzymatic assays of the damage in cell-free DNA from bacteriophage PM2 caused by the acridine and phenanthridine hydroperoxides 3 and 7 under near-UVA irradiation revealed a wide range of DNA modifications. Particularly, extensive single-strand break formation and DNA base modifications sensitive to formamidopyrimidine DNA glycosylase (Fpg protein) were observed. In the photooxidat…
Ultrafast electron transfer in photosynthesis: reduced pheophytin and quinone interaction mediated by conical intersections.
2006
The mechanism of electron transfer (ET) from reduced pheophytin (Pheo(-)) to the primary stable photosynthetic acceptor, a quinone (Q) molecule, is addressed by using high-level ab initio computations and realistic molecular models. The results reveal that the ET process involving the (Pheo(-) + Q) and (Pheo + Q(-)) oxidation states can be essentially seen as an ultrafast radiationless transition between the two hypersurfaces taking place via conical intersections (CIs). According to the present findings, an efficient ultrafast ET implies that the Pheo- and Q move toward each other in a given preferential parallel orientation, reaching the most effective arrangement for ET at intermolecular…
Toward an Understanding of Ultrafast Electron Transfer in Photosynthesis
2008
The mechanism of electron transfer (ET) from reduced pheophytin (Pheo−) to the primary stable photosynthetic acceptor, a quinone (Q) molecule, is addressed by using high-level ab initio computations and realistic molecular models. The results reveal that the ET process involving the (Pheo−+Q) and (Pheo+Q−) oxidation states can be seen essentially as an ultrafast radiationless transition between the two hypersurfaces taking place via conical intersections (CIs) and is favoured when the topology of the interacting moieties makes possible some overlap between the lowest occupied molecular orbitals (LUMO) of the two systems. Thus, it is anticipated that large scale motions, which are difficult …
Studies on the mechanism of photosystem II photoinhibition I. A two-step degradation of D1-protein
1990
The role of D1-protein in photoinhibition was examined. Photoinhibition of spinach thylakoids at 20°C caused considerable degradation of D1-protein and a parallel loss of variable fluorescence, QB-independent electron flow and QB-dependent electron flow. The breakdown of D1-protein as well as the loss of variable fluorescence and QB-independent electron flow were largely prevented when thylakoids were photoinhibited at 0°C. The QB-dependent electron flow markedly decreased under the same conditions. This inactivation may represent the primary event in photoinhibition and could be the result of some modification at the QB-site of D1-protein. Evidence for this comes from fluorescence relaxati…
Changes of the Quantum Yield of Oxygen Evolution and the Electron Transport Capacity of Isolated Spinach Thylakoids during Photoinhibition
1992
Summary Isolated spinach thylakoids can be protected from photoinhibitory loss of electron transport capacity by the radical defense system composed of the enzymes SOD and catalase, as well as the antioxidants glutathione and ascorbate. With these compounds present at saturating concentrations, thylakoids not only retain a high photochemical capacity but also do not suffer D1-protein degradation during photoinhibition. However, a strong decrease in the quantum yield of oxygen evolution, Φ O 2 , occurs with the same thylakoids. These results support the view that the photochemical capacity and the quantum yield of oxygen evolution decline due to different mechanisms during photoinhibition. T…
Intramolecular Electron Transfer between Tyrosine and Tryptophan Photosensitized by a Chiral π,π* Aromatic Ketone
2005
The photochemical reaction of Trp and Tyr and related peptides with Suprofen (SUP) as sensitizer in H2O/CH3CN (28:1 v/v) solutions has been studied by time-resolved spectroscopy. The results show that SUP induces oxidation of both Trp and Tyr, as well as intramolecular-ET reactions in the related peptides. The influence of photosensitizer configuration on the involved processes has been studied by using the enantiomerically pure compounds. A significant chiral recognition is observed in which the concentration of the radicals formed after triplet quenching depends on the configuration of the chiral center; the quenching process is higher when using the (R)-SUP enantiomer.