Search results for "PHOTOCHEMISTRY"
showing 10 items of 2034 documents
Hydrogen abstraction by photoexcited benzophenone: consequences for DNA photosensitization
2016
International audience; We report a computational investigation of the hydrogen abstraction (H-abstraction) induced by triplet benzophenone (3BP) on thymine nucleobase and backbone sugar. The chemical process is studied using both high level multiconfigurational perturbation and density functional theory. Both methods show good agreement in predicting small kinetic barriers. Furthermore the behavior of benzophenone in DNA is simulated using molecular dynamics and hybrid quantum mechanics/molecular mechanics methods. The accessibility of benzophenone to the labile hydrogens within B-DNA is demonstrated, as well as the driving force for this reaction. We evidence a strong dependence of the H-…
Excitation-Wavelength-Dependent Photocycle Initiation Dynamics Resolve Heterogeneity in the Photoactive Yellow Protein from Halorhodospira halophila
2018
Photoactive yellow proteins (PYPs) make up a diverse class of blue-light-absorbing bacterial photoreceptors. Electronic excitation of the p-coumaric acid chromophore covalently bound within PYP results in triphasic quenching kinetics; however, the molecular basis of this behavior remains unresolved. Here we explore this question by examining the excitation-wavelength dependence of the photodynamics of the PYP from Halorhodospira halophila via a combined experimental and computational approach. The fluorescence quantum yield, steady-state fluorescence emission maximum, and cryotrapping spectra are demonstrated to depend on excitation wavelength. We also compare the femtosecond photodynamics …
Molybdenum Trioxide Nanoparticles with Intrinsic Sulfite Oxidase Activity
2014
Sulfite oxidase is a mitochondria-located molybdenum-containing enzyme catalyzing the oxidation of sulfite to sulfate in the amino acid and lipid metabolism. Therefore, it plays a major role in detoxification processes, where defects in the enzyme cause a severe infant disease leading to early death with no efficient or cost-effective therapy in sight. Here we report that molybdenum trioxide (MoO3) nanoparticles display an intrinsic biomimetic sulfite oxidase activity under physiological conditions, and, functionalized with a customized bifunctional ligand containing dopamine as anchor group and triphenylphosphonium ion as targeting agent, they selectively target the mitochondria while bein…
A theoretical insight into the photophysics of psoralen
2006
Psoralen photophysics has been studied on quantum chemistry grounds using the multiconfigurational second-order perturbation method CASPT2. Absorption and emission spectra of the system have been rationalized by computing the energies and properties of the low-lying singlet and triplet excited states. The S1 ππ* state has been determined to be responsible of the lowest absorption and fluorescence bands and to initially carry the population in the photophysical processes related to the phototherapeutic properties of psoralen derivatives. The low-lying T1 ππ* state is, on the other hand, protagonist of the phosphorescence, and its prevalent role in the reactivity of psoralen is suggested to b…
Modeling of an annular photocatalytic reactor for water purification: oxidation of pesticides.
2004
Photocatalytic oxidation (PCO) over titanium dioxide (TiO2) is a “green” sustainable process for the treatment and purification of water and wastewater. However, the application of PCO for wastewater treatment on an industrial scale is currently hindered by a lack of simple mathematical models that can be readily applied to reactor design. Current models are either too simplistic or too rigorous to be useful in photocatalytic reactor design, scale-up, and optimization. In this paper a simple mathematical model is presented for slurry, annular, photocatalytic reactors that still retains the essential elements of a rigorous approach while providing simple solutions. The model extends the appl…
Effects of photodynamic processes and ultraviolet light on duck and hen egg-white lysozymes.
1973
— The photochemical yields for inactivation and amino acid destruction in hen and duck egg-white lysozyme are presented. Duck lysozyme II is devoid of histidine but it has two more tyrosine residues than does hen lysozyme. The data indicate that sensitized oxidation of the single histidine residue of hen lysozyme is of no significance for the inactivation of this lysozyme. The ultraviolet destruction of tryptophan and cystine residues appears to be equally related with the loss in enzymatic activity of hen lysozyme. In the case of duck lysozyme, however, the ultraviolet inactivation appears to be predominantly governed by the destruction of cystine residues.
Preparation of Biomolecule Microstructures and Microarrays by Thiol-ene Photoimmobilization
2009
A mild, fast and flexible method for photoimmobilization of biomolecules based on the light-initiated thiol-ene reaction has been developed. After investigation and optimization of various surface materials, surface chemistries and reaction parameters, microstructures and microarrays of biotin, oligonucleotides, peptides, and MUC1 tandem repeat glycopeptides were prepared with this photoimmobilization method. Furthermore, MUC1 tandem repeat glycopeptide microarrays were successfully used to probe antibodies in mouse serum obtained from vaccinated mice. Dimensions of biomolecule microstructures were shown to be freely controllable through photolithographic techniques, and features down to 5 …
Bio serves nano: biological light-harvesting complex as energy donor for semiconductor quantum dots.
2012
Light-harvesting complex (LHCII) of the photosynthetic apparatus in plants is attached to type-II core-shell CdTe/CdSe/ZnS nanocrystals (quantum dots, QD) exhibiting an absorption band at 710 nm and carrying a dihydrolipoic acid coating for water solubility. LHCII stays functional upon binding to the QD surface and enhances the light utilization of the QDs significantly, similar to its light-harvesting function in photosynthesis. Electronic excitation energy transfer of about 50% efficiency is shown by donor (LHCII) fluorescence quenching as well as sensitized acceptor (QD) emission and corroborated by time-resolved fluorescence measurements. The energy transfer efficiency is commensurable …
Reaction of melatonin with lipoperoxyl radicals in phospholipid bilayers.
1997
Melatonin, at 5 to 500 microM was incorporated in unilamellar soybean phosphatidylcholine (PC) liposomes, the peroxidation of which was induced by 2,2'-azobis (2-amidinopropane-hydrochloride) (AAPH), and measured as production of conjugated diene lipid hydroperoxides. Concentration as low as 5 and 10 microM were poorly effective in reducing lipid peroxidation. Melatonin at 30 to 500 microM caused short inhibition periods, increasing with, but not linearly related to concentration, with a concurrent net decrease of the propagation rate. The time course of melatonin oxidation, measured as loss of fluorescence, was studied during the AAPH-stimulated peroxidation of soybean PC liposomes, or whe…
Polymerization of Lipid and Lysolipid Like Diacetylenes in Monolayers and Liposomes
1980
The bilayer type lipid membrane has a variety of important functions that are necessary in order to sustain life. A lot of these functions have been studied with artificial model membranes such as black lipid membranes (BLM) or liposomes. A great disadvantage of all these models is their instability — BLM for instance can only exist for minutes or hours and only under the presence of water. Therefore, it was the aim of this work to produce simple model membranes that can retain their structure under a variety of test conditions. The route chosen to obtain such membranes was through the polymerization of lipid and lysolipid like molecules in monolayers at the gas-water interface or in liposo…