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Quenching Mechanism (quenching + mechanism)
Selected AbstractsPhotoluminescence of Uranium(VI): Quenching Mechanism and Role of Uranium(V)CHEMISTRY - A EUROPEAN JOURNAL, Issue 27 2010Satoru Tsushima Dr. Abstract The photoluminescence of uranium(VI) is observed typically in the wavelength range 400,650,nm with the lifetime of several hundreds ,s and is known to be quenched in the presence of various halide ions (case,A) or alcohols (case,B). Here, we show by density functional theory (DFT) calculations that the quenching involves an intermediate triplet excited state that exhibits uranium(V) character. The DFT results are consistent with previous experimental findings suggesting the presence of photoexcited uranium(V) radical pair during the quenching process. In the ground state of uranyl(VI) halides, the ligand contributions to the highest occupied molecular orbitals increase with the atomic number (Z) of halide ion allowing larger ligand-to-metal charge transfer (LMCT) between uranium and the halide ion. Consequently, a larger quenching effect is expected as Z increases. The quenching mechanism is essentially the same in cases,A and B, and is driven by an electron transfer from the quencher to the UO22+ entity. The relative energetic stabilities of the triplet excited state define the "fate" of uranium, so that in case,A uranium(V) is oxidized back to uranium(VI), while in case,B uranium remains as pentavalent. [source] Chemopreventive Action of Xanthone Derivatives on Photosensitized DNA Damage,PHOTOCHEMISTRY & PHOTOBIOLOGY, Issue 2 2005Kazutaka Hirakawa ABSTRACT Photosensitized DNA damage participates in solar-UV carcinogenesis, photogenotoxicity and phototoxicity. A chemoprevention of photosensitized DNA damage is one of the most important methods for the above phototoxic effects. In this study, the chemopreventive action of xanthone (XAN) derivatives (bellidifolin [BEL], gentiacaulein [GEN], norswertianin [NOR] and swerchirin [SWE]) on DNA damage photosensitized by riboflavin was demonstrated using [32P]-5,-end-labeled DNA fragments obtained from genes relevant to human cancer. GEN and NOR effectively inhibited the formation of piperidine-labile products at consecutive G residues by photoexcited riboflavin, whereas BEL and SWE did not show significant inhibition of DNA damage. The four XAN derivatives decrease the formation of 8-oxo-7,8-dihydro-2,-deoxyguanosine (8-oxodGuo), an oxidative product of G, by photoexcited riboflavin. The preventive action for the 8-oxodGuo formation of these XAN derivatives increased in the following order: GEN > NOR , BEL > SWE. A fluorescence spectroscopic study and ab initio molecular orbital calculations suggested that the prevention of DNA photodamage is because of the quenching of the triplet excited state of riboflavin by XAN derivatives through electron transfer. This chemoprevention is based on neither antioxidation nor a physical sunscreen effect; rather, it is based on the quenching of a photosensitizer. In conclusion, XAN derivatives, especially GEN, may act as novel chemopreventive agents by the quenching mechanism of an excited photosensitizer. [source] Singlet Energy Dissipation in the Photosystem II Light-Harvesting Complex Does Not Involve Energy Transfer to CarotenoidsCHEMPHYSCHEM, Issue 6 2010Marc G. Müller Dr. Abstract The energy dissipation mechanism in oligomers of the major light-harvesting complex II (LHC II) from Arabidopsis thaliana mutants npq1 and npq2, zeaxanthin-deficient and zeaxanthin-enriched, respectively, has been studied by femtosecond transient absorption. The kinetics obtained at different excitation intensities are compared and the implications of singlet,singlet annihilation are discussed. Under conditions where annihilation is absent, the two types of LHC II oligomers show distributive biexponential (bimodal) kinetics with lifetimes of ,5,20 ps and ,200,400 ps having transient spectra typical for chlorophyll excited states. The data can be described kinetically by a two-state compartment model involving only chlorophyll excited states. Evidence is provided that neither carotenoid excited nor carotenoid radical states are involved in the quenching mechanism at variance with earlier proposals. We propose instead that a chlorophyll,chlorophyll charge-transfer state is formed in LHC II oligomers which is an intermediate in the quenching process. The relevance to non-photochemical quenching in vivo is discussed. [source] Study on the Interaction of Ketoconazole with Human and Bovine Serum Albumins by Fluorescence SpectroscopyCHINESE JOURNAL OF CHEMISTRY, Issue 12 2008Qing-Lian GUO Abstract The binding of ketoconazole to human serum albumin and bovine serum albumin was studied by using fluorescence and ultraviolet spectroscopy. The measurements were performed in 0.1 mol·L,1 phosphate buffer solution at pH=7.40±0.1. Decreasing of quenching constant was observed in association with temperature increase. Our findings show that the quenching mechanism of fluorescence of serum albumins by ketoconazole was static quenching because of compound formation. The thermodynamic parameters ,G, ,H, and ,S at different temperatures were calculated, showing that the electrostatic interactions and hydrophobic interaction are the main forces for the binding of ketoconazole to serum albumins. The distance r between the donor (Trp-214) and acceptor (ketoconazole) was obtained according to fluorescence resonance energy transfer theory. [source] On the interstellar medium and star formation demographics of galaxies in the local universeMONTHLY NOTICES OF THE ROYAL ASTRONOMICAL SOCIETY, Issue 1 2009Matthew S. Bothwell ABSTRACT We present a demographic analysis of integrated star formation and gas properties for a sample of galaxies representative of the overall population at z, 0. This research was undertaken in order to characterize the nature of star formation and interstellar medium (ISM) behaviour in the local Universe, and test the extent to which global star formation rates (SFRs) can be seen as dependent on the interstellar gas content. Archival 21-cm derived H i data are compiled from the literature, and are combined with CO (J =1 , 0) derived H2 masses to calculate and characterize the total gas content for a large sample of local galaxies. The distribution in stellar mass-normalized H i content is found to exhibit the noted characteristic transition at stellar masses of ,3 × 1010 M,, turning off towards low values, but no such transition is observed in the equivalent distribution of molecular gas. H, based SFRs and specific star formation rates (SSFRs) are also compiled for a large (1110) sample of local galaxies. We confirm two transitions as found in previous work: a turnover towards low SFRs at high luminosities, indicative of the quenching of SF characteristic of the red sequence; and a broadening of the SF distribution in low-luminosity dwarf galaxies, again to extremely low SFRs of <10,3 M, yr,1. However, a new finding is that while the upper luminosity transition is mirrored by the turnover in H i content, suggesting that the low SFRs of the red sequence result from a lack of available gas supply, the transition towards a large spread of SFRs in the least luminous dwarf galaxies is not matched by a prominent increase in scatter in gas content. Possible mass-dependent quenching mechanisms are discussed, along with speculations that in low-mass galaxies, the H, luminosity may not faithfully trace the SFR. [source] Excited-State Dynamics of Cytosine Reveal Multiple Intrinsic Subpicosecond PathwaysCHEMPHYSCHEM, Issue 17 2008Hanneli R. Hudock Dr. The road not taken: Many paths diverge on the road to photodamage prevention in cytosine. Previous work has focused on determining a dominant relaxation mechanism. Ab initio excited-state molecular dynamics studies show that there is not a single dominant path, but rather many distinct paths involving different quenching mechanisms (see figure). [source] A Close Look at Fluorescence Quenching of Organic Dyes by TryptophanCHEMPHYSCHEM, Issue 11 2005Sören Doose Dr. Abstract Understanding fluorescence quenching processes of organic dyes by biomolecular compounds is of fundamental importance for in-vitro and in-vivo fluorescence studies. It has been reported that the excited singlet state of some oxazine and rhodamine derivatives is efficiently and almost exclusively quenched by the amino acid tryptophan (Trp) and the DNA base guanine via photoinduced electron transfer (PET). We present a detailed analysis of the quenching interactions between the oxazine dye MR121 and Trp in aqueous buffer. Steady-state and time-resolved fluorescence spectroscopy, together with fluorescence correlation spectroscopy (FCS), reveal three contributing quenching mechanisms: 1) diffusion-limited dynamic quenching with a bimolecular quenching rate constant kdof 4.0×109s,1,M,1, 2) static quenching with a bimolecular association constant Ksof 61,M,1, and 3) a sphere-of-action contribution to static quenching described by an exponential factor with a quenching constant , of 22,M,1. The latter two are characterized as nonfluorescent complexes, formed with ,30,% efficiency upon encounter, that are stable for tens of nanoseconds. The measured binding energy of 20,30 kJmol,1is consistent with previous estimates from molecular dynamics simulations that proposed stacked complexes due to hydrophobic forces. We further evaluate the influence of glycerol and denaturant (guanidine hydrochloride) on the formation and stability of quenched complexes. Comparative measurements performed with two other dyes, ATTO 655 and Rhodamine 6G show similar results and thus demonstrate the general applicability of utilizing PET between organic dyes and Trp for the study of conformational dynamics of biopolymers on sub-nanometer length and nanosecond time-scales. [source] | ||||||||||