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Singlet Molecular Oxygen (singlet + molecular_oxygen)
Selected AbstractsChemInform Abstract: Photooxygenation of Some Alkaloids by Singlet Molecular Oxygen.CHEMINFORM, Issue 16 2002Shubha Jain Abstract ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a "Full Text" option. The original article is trackable via the "References" option. [source] Structural Changes in the BODIPY Dye PM567 Enhancing the Laser Action in Liquid and Solid Media,ADVANCED FUNCTIONAL MATERIALS, Issue 16 2007I. García-Moreno Abstract In the search for more efficient and photostable solid-state dye lasers, newly synthesized analogs of the borondipyrromethene (BODIPY) dye PM567, bearing the polymerizable methacryloyloxypropyl group at position 2 (PMoMA) or at positions 2 and 6 (PDiMA), have been studied in the form of solid copolymers with methyl methacrylate (MMA). The parent dye PM567, as well as the model analogs bearing the acetoxypropyl group in the same positions, PMoAc and PDiAc, respectively, have been also studied both in liquid solvents and in solid poly(MMA) (PMMA) solution. Although in liquid solution PMoAc and PDiAc have the same photophysical properties as PM567, PDiAc exhibited a photostability up to 10 times higher than that of PM567 in ethanol under 310,nm-irradiation. The possible stabilization factors of PDiAc have been analyzed and discussed on the basis of the redox potentials, the ability for singlet molecular oxygen [O2(1,g)] generation, the reactivity with O2(1,g), and quantum mechanical calculations. Both PMoAc and PDiAc, pumped transversally at 532,nm, lased in liquid solution with a high (up to 58,%), near solvent-independent efficiency. This enhanced photostabilization has been also observed in solid polymeric and copolymeric media. While the solid solution of the model dye PDiAc in PMMA showed a lasing efficiency of 33,%, with a decrease in the laser output of ca.,50,% after 60,000 pump pulses (10,Hz repetition rate) in the same position of the sample, the solid copolymer with the double bonded chromophore, COP(PDiMA-MMA), showed lasing efficiencies of up to 37,%, and no sign of degradation in the laser output after 100,000 similar pump pulses. Even under the more demanding repetition rate of 30,Hz, the laser emission from this material remained at 67,% of its initial laser output after 400,000 pump pulses, which is the highest laser photostability achieved to date for solid-state lasers based on organic polymeric materials doped with laser dyes. This result indicates that the double covalent linkage of the BODIPY chromophore to a PMMA polymeric matrix is even more efficient than the simple linkage, for its photostabilization under laser operation. [source] Effect of the Media on the Quantum Yield of Singlet Oxygen (O2(1,g)) Production by 9H -Fluoren-9-one: Solvents and Solvent MixturesHELVETICA CHIMICA ACTA, Issue 2 2003Claudia We have investigated the effect of a series of 18 solvents and mixtures of solvents on the production of singlet molecular oxygen (O2(1,g), denoted as 1O2) by 9H -fluoren-9-one (FLU). The normalized empirical parameter E derived from ET(30) has been chosen as a measure of solvent polarity using Reichardt's betaine dyes. Quantum yields of 1O2 production (,,) decrease with increasing solvent polarity and protic character as a consequence of the decrease of the quantum yield of intersystem crossing (,ISC). Values of ,, of unity have been found in alkanes. In nonprotic solvents of increasing polarity, ,ISC and, therefore, ,, decrease due to solvent-induced changes in the energy levels of singlet and triplet excited states of FLU. This compound is a poor 1O2 sensitizer in protic solvents, because hydrogen bonding considerably increases the rate of internal conversion from the singlet excited state, thus diminishing ,, to values much lower than those in nonprotic solvents of similar polarity. In mixtures of cyclohexane and alcohols, preferential solvation of FLU by the protic solvent leads to a fast decrease of ,, upon addition of increasing amounts of the latter. [source] Biological hydroperoxides and singlet molecular oxygen generationIUBMB LIFE, Issue 4-5 2007Sayuri Miyamoto Abstract The decomposition of lipid hydroperoxides (LOOH) into peroxyl radicals is a potential source of singlet molecular oxygen (1O2) in biological systems. Recently, we have clearly demonstrated the generation of 1O2 in the reaction of lipid hydroperoxides with biologically important oxidants such as metal ions, peroxynitrite and hypochlorous acid. The approach used to unequivocally demonstrate the generation of 1O2 in these reactions was the use of an isotopic labeled hydroperoxide, the 18O-labeled linoleic acid hydroperoxide, the detection of labeled compounds by HPLC coupled to tandem mass spectrometry (HPLC-MS/MS) and the direct spectroscopic detection and characterization of 1O2 light emission. Using this approach we have observed the formation of 18O-labeled 1O2 by chemical trapping of 1O2 with anthracene derivatives and detection of the corresponding labeled endoperoxide by HPLC-MS/MS. The generation of 1O2 was also demonstrated by direct spectral characterization of 1O2 monomol light emission in the near-infrared region (, = 1270 nm). In summary, our studies demonstrated that LOOH can originate 1O2. The experimental evidences indicate that 1O2 is generated at a yield close to 10% by the Russell mechanism, where a linear tetraoxide intermediate is formed in the combination of two peroxyl radicals. In addition to LOOH, other biological hydroperoxides, including hydroperoxides formed in proteins and nucleic acids, may also participate in reactions leading to the generation 1O2. This hypothesis is currently being investigated in our laboratory. [source] Vitamin B2 -sensitized Photo-oxidation of DopaminePHOTOCHEMISTRY & PHOTOBIOLOGY, Issue 5 2008Walter A. Massad Kinetics and mechanism of the photo-oxidation of the natural catecholamine-type neurotransmitter dopamine (DA) has been studied in aqueous solution, under aerobic conditions, in the presence of riboflavin (Rf, vitamin B2) as a photosensitizer. Results indicate the formation of a weak dark complex Rf,DA, with a mean apparent association constant Kass = 30 m,1, only detectable at DA concentrations much higher than those employed in photochemical experiments. An intricate mechanism of competitive reactions operates upon photoirradiation. DA quenches excited singlet and triplet states of Rf, with rate constants of 4.2 × 109 and 2.2 × 109 m,1 s,1, respectively. With the catecholamine in a concentration similar to that of dissolved molecular oxygen in air-saturated water, DA and oxygen competitively quench the triplet excited state of Rf, generating superoxide radical anion (O2,,) and singlet molecular oxygen (O2(1,g)) by processes initiated by electron and energy-transfer mechanisms, respectively. Rate constants values of 1.9 × 108 and 6.6 × 106 m,1 s,1 have been obtained for the overall and reactive (chemical) interaction of DA with O2(1,g). The presence of superoxide dismutase increases both the observed rates of aerobic DA photo-oxidation and oxygen uptake, due to its known catalytic scavenging of O2,,, a species that could revert the overall photo-oxidation effect, according to the proposed reaction mechanism. As in most of the catecholamine oxidative processes described in the literature, aminochrome is the DA oxidation product upon visible light irradiation in the presence of Rf. It is generated with a quantum yield of 0.05. [source] Sensitized Photooxidation of Thyroidal Hormones.PHOTOCHEMISTRY & PHOTOBIOLOGY, Issue 2 2005Evidence for Heavy Atom Effect on Singlet Molecular Oxygen [O2(, g)]-mediated Photoreactions ABSTRACT Thyronine derivatives are essential indicators of thyroid gland diseases in clinical diagnosis and are currently used as standards for developing ordinary biochemical assays. Photooxidation of gland hormones of the thyronine (TN) family and structurally related compounds (TN, 3,5-diiodo-thyronine,3,3,,5-triiodothyronine and 3,3,,5,5,-tetraiodothyronine or thyroxine) was studied using rose bengal, eosin and perinaphthenone (PN) as dye sensitizers. Tyrosine (Tyr) and two iodinated derivatives (3-iodotyrosine and 3,5-diiodotyrosine) were also included in the study for comparative purposes. Irradiation of aqueous solutions of substrates containing xanthene dyes with visible light triggers a complex series of competitive interactions, which include the triplet excited state of the dye (3Xdye*) and singlet molecular oxygen [O2(1,g)]-mediated and superoxide ion-mediated reactions. Rate constants for interaction with the 3Xdye*, attributed to an electron transfer process, are in the order of 108 -109M,1 s,1 depending on the dye and the particular substrate. The photosensitization using PN follows a pure Type-II (O2(1,g) mediated) mechanism. The presence of the phenolic group in Tyr, TN and iodinated derivatives dominates the kinetics of photooxidation of these compounds. The reactive rate constants, kr, and the quotient between reactive and overall rate constants (krlkt values, in the range of 0.7,0.06) behave in an opposite fashion compared with the overall rate constants and oxidation potentials. This apparent inconsistency was interpreted on the basis of an internal heavy atom effect, favoring the intersystem-crossing deactivation route within the encounter complex with the concomitant reduction of effective photooxidation. [source] A comparative kinetic study on the singlet molecular oxygen-mediated photoxidation of ,- and ,-chymotrypsinsCHEMICAL BIOLOGY & DRUG DESIGN, Issue 1 2003M.A. Biasutti Abstract: Kinetic aspects of the sensitized photooxidation of ,- and ,-chymotrypsins have been studied at pH 6 and 8. The sensitization, employing classical O2(1,g)-photogenerators, such as xanthene dyes, is a kinetically intricate process because of the presence of ground state dye,protein associations and to the simultaneous participation of superoxide ion and singlet molecular oxygen [O2(1,g)]. Both proteins, that possess the same distribution pattern of photooxidizable amino acids, suffer a pure O2(1,g)-mediated photodynamic attack, using the carbonylic sensitizer Perinaphthenone. Overall and reactive rate constants for the O2(1,g)-quenching (in the order of 108 and 107/M/s, respectively), and rates of oxygen consumption determined by time-resolved, spectroscopic and polarographic methods indicate that ,- and ,-chymotrypsins are less photooxidizable at pH 6, as a result of an enhancement of the O2(1,g)-physical quenching component. In general terms, ,-chymotrypsin exhibits the greater overall proclivity to interact with O2(1,g), whereas structural factors, possibly evidenced by a higher exposure of the reactive tryptophan residues, impart an increased photooxidation degree to the proteins at pH 8, specially to the ,-chymotrypsin. [source] | |||||||||||||