Search results for " photolysis"
showing 10 items of 41 documents
Ship-in-a-bottle synthesis of triphenylamine inside faujasite supercages and generation of the triphenylamminium radical ion
2005
Abstract The ship-in-a-bottle synthesis of triphenylamine encapsulated within basic X zeolite has been accomplished by reacting sodium diphenylamide with bromobenzene in the presence of a bifunctional palladium (Hartwig–Buchwald conditions). The presence of incarcerated triphenylamine was demonstrated by dissolving the zeolite with concentrated HF and analyzing the organic material in the dichloromethane extract. Laser flash photolysis (266 nm) gives rise to the generation of triphenylamminium radical cation detected as a transient species decaying in hundreds of microseconds. Upon repetitive cyclic voltammograms, zeolite encapsulated triphenylamine shows a reversible oxidation–reduction pr…
Photochemical behavior in azobenzene having acidic groups. Preparation of magnetic photoresponsive gels
2011
[EN] The photochemistry of three azobenzenes representing contrasting photochemical behaviors is described in the present work. Thus, Methyl Orange (MO, 4-[[(4-dimethylamino)phenyl]-azo]benzenesulfonic acid sodium salt, hereinafter (1) and 4-hydroxyazobenzene-4'-sulfonic acid (2) undergo in water fast photochemical proton shift, with decays in the microsecond timescale. In contrast to the previous cases, azobenzene-4,4'-dicarboxylic acid (3) undergoes photoisomerization in water. This photochemical behavior allows the preparation of aqueous gels with Aerosil as gelating agent (5% weight) exhibiting high cyclability and photoreversible isomerization of the trans to cis (300 nm irradiation) a…
Helium gas pressure cell for pressures up to 1 kbar (0.1 GPa) in conjunction with the cold head of a closed-cycle He refrigerator
1997
A helium gas pressure cell for pressures up to 1 kbar (0.1 GPa) has been developed in conjunction with a closed-cycle He refrigerator allowing variable temperatures between 15 and 300 K. Both cell and refrigerator are equipped with optical windows suitable for photophysical measurements, such as temperature- and pressure-dependent absorption spectroscopy or laser flash photolysis. Examples of measurements on iron(II) spin-crossover systems are given. In these compounds, comparatively small external pressures induce significant changes in the thermodynamic equilibrium as well as in the relaxation dynamics.
The Monod-Wyman-Changeux allosteric model accounts for the quaternary transition dynamics in wild type and a recombinant mutant human hemoglobin
2012
International audience; The acknowledged success of the Monod-Wyman-Changeux (MWC) allosteric model stems from its efficacy in accounting for the functional behavior of many complex proteins starting with hemoglobin (the paradigmatic case) and extending to channels and receptors. The kinetic aspects of the allosteric model, however, have been often neglected, with the exception of hemoglobin and a few other proteins where conformational relaxations can be triggered by a short and intense laser pulse, and monitored by time-resolved optical spectroscopy. Only recently the application of time-resolved wide-angle X-ray scattering (TR-WAXS), a direct structurally sensitive technique, unveiled th…
Iodine and mercury resonance lamps for kinetics experiments and their spectra in the far ultraviolet
2000
Electrodeless iodine and mercury iodide radio-frequency discharge lamps have been made to provide intense sources of resonance radiation of iodine and mercury in the 183-253 nm region. Production technology and emission spectra in the ultraviolet and vacuum ultraviolet regions are described. Both lamps (iodine and mercury iodide) are designed and used for monitoring the iodine 2P1/2 (206.163 nm) and 2P3/2 (183.038 nm) level population kinetics after flash photolysis of I2 or other precursor molecules in laboratory experiments. The technique is suitable for the investigation of the gas phase reaction kinetics following the photolysis of I2 in the presence of O3.
Internal dynamics and protein-matrix coupling in trehalose-coated proteins.
2005
Abstract We review recent studies on the role played by non-liquid, water-containing matrices on the dynamics and structure of embedded proteins. Two proteins were studied, in water–trehalose matrices: a water-soluble protein (carboxy derivative of horse heart myoglobin) and a membrane protein (reaction centre from Rhodobacter sphaeroides ). Several experimental techniques were used: Mossbauer spectroscopy, elastic neutron scattering, FTIR spectroscopy, CO recombination after flash photolysis in carboxy-myoglobin, kinetic optical absorption spectroscopy following pulsed and continuous photoexcitation in Q B containing or Q B deprived reaction centre from R. sphaeroides . Experimental result…
Photobinding of Tiaprofenic Acid and Subprofen to Proteins and Cells: A Combined Study Using Radiolabeling, Antibodies and Laser Flash Photolysis of …
1998
Drug photoallergy is a matter of current concern. It involves the formation of drug-protein photoadducts (photoantigens) that may ultimately trigger an immunological response. Tyrosine residues appear to be key binding sites in proteins. The present work has investigated the photobinding of tiaprofenic and (TPA) and the closely related isomer suprofen (SUP) to proteins and cells by means of radioactive labeling and drug-directed antibodies. To ascertain whether preassociation with the protein may play a role in photoreactivity, two model bichromophoric compounds (TPA-Tyr and SUP-Tyr) have been prepared and studied by laser flash photolysis. The results of this work show that (a) TPA and SUP…
Chiral synthetic pseudopeptidic derivatives as triplet excited state quenchers
2009
The behavior of 6 pseudopeptidic models, synthesized by connecting different protected amino acids (Trp, Tyr, Phe, and Lys) with various diamino spacers, as quenchers of the triplet excited state of tiaprofenic acid (and its methyl ester), has been investigated. A series of quenching constants have been determined, which depend on the nature of the quencher and on the stereochemistry of the excited drug. A significant degree of stereodifferentiation has been found for the peptidomimetic synthesized with Phe and Tyr linked by a piperazine bridge. The obtained results support the utility of laser flash photolysis (LFP) as a tool to investigate the interactions between photoexcited drugs and s…
Light-Induced Protein-Matrix Uncoupling and Protein Relaxation in Dry Samples of Trehalose-Coated MbCO at Room Temperature
2005
In humid samples of trehalose-coated carboxy-myoglobin (MbCO), thermally driven conformational relaxation takes place after photodissociation of the carbon monoxide (CO) molecule at room temperature. In such samples, because of the extreme viscosity of the external matrix, photodissociated CO cannot diffuse out of the protein and explores the whole (proximal and distal side) heme pocket, experiencing averaged protein heme pocket structures, as a result of the presence of Brownian motions. At variance, in very dry samples, a lower portion of the photodissociated CO diffuses from the distal to the proximal heme pocket side probing in nonaveraged structures. We revisit here the flash photolysi…
Estimation of the emission temperature of an electrodeless discharge lamp and determination of the oscillator strength for the I(2P3/2) 183.038 nm re…
2001
Abstract The 183.038 nm resonance absorption transition of I( 2 P 3/2 ) has been studied using a flash photolysis set-up for gas-phase chemistry and a radio frequency powered electrodeless discharge lamp filled with iodine. The dependence of self-absorption and self-reversal on iodine partial pressure in the discharge volume was measured. The optimum iodine partial pressure, with self-absorption minimized and acceptable intensity, is determined to be approximately 2.5×10 −3 mbar. A method is described to estimate the temperature of the emitting atoms using direct measurements of relative absorption at different absorber concentrations. This yields an emission temperature of 923±50 K. Using …