Search results for "PHOTODISSOCIATION"
showing 10 items of 90 documents
The behavior of interstitial oxygen atoms induced by F2 laser irradiation of oxygen-rich glassy SiO2
2002
Abstract Interstitial oxygen atoms in glassy silicon dioxide were created by photolysis of pre-existing interstitial oxygen molecules O 2 with a fluorine excimer laser (7.9 eV). The concentration of atomic oxygen interstitials was indirectly monitored by the disappearance and subsequent recovery of interstitial molecules which were monitored by their 1272 nm photoluminescence band. Most of the oxygen interstitials (>95%) are immobile at room temperature. The onset of their mobility occurs between 200 and 400 °C where around 95% of them recombine to form O 2 molecules. The high stability of interstitial oxygen atoms is consistent with the theoretical prediction that they are incorporated int…
Photocyclization of a bichromophoric phenol/olefi system substituted at the methylene spacer - Zwitterions versus H-bridged intermediates in the exci…
2002
Photolysis of (E)- and (Z)-2-(1-ethyl-3-phenylpropenyl)phenol (1 and 2) under a variety of conditions produces a mixture of dihydrobenzopyrans 3 and 4, dihydrobenzofuran 5, cyclopropanes 6 and 7, and rearranged olefin 8. Acidic treatment of 1 and 2 gives a mixture of the six-membered ring products 3 and 4. Remarkable differences, associated with the nature of the precursor and the reaction conditions, are observed in the regiochemistry of cyclization and in the stereochemistry of the dihydrobenzopyrans (3/4 ratio). This points in favour of an H-bridged intermediate, rather than a fully zwitterionic species, as the direct precursor of the photocyclized products.
Unveiling the timescale of the R-T transition in human hemoglobin.
2010
Time-resolved wide-angle X-ray scattering, a recently developed technique allowing to probe global structural changes of proteins in solution, was used to investigate the kinetics of R-T quaternary transition in human hemoglobin and to systematically compare it to that obtained with time-resolved optical spectroscopy under nearly identical experimental conditions. Our data reveal that the main structural rearrangement associated with the R-T transition takes place approximately 2 mus after the photolysis of hemoglobin at room temperature and neutral pH. This finding suggests that the 20-mus step observed with time-resolved optical spectroscopy corresponds to a small and localized structural…
Observing heme doming in myoglobin with femtosecond X-ray absorption spectroscopy.
2015
International audience; We report time-resolved X-ray absorption measurements after photolysis of carbonmonoxy myoglobin performed at the LCLS X-ray free electron laser with nearly 100 fs (FWHM) time resolution. Data at the Fe K-edge reveal that the photoinduced structural changes at the heme occur in two steps, with a faster (∼70 fs) relaxation preceding a slower (∼400 fs) one. We tentatively attribute the first relaxation to a structural rearrangement induced by photolysis involving essentially only the heme chromophore and the second relaxation to a residual Fe motion out of the heme plane that is coupled to the displacement of myoglobin F-helix
O2(a1Δg) + Mg, Fe, and Ca: experimental kinetics and formulation of a weak collision, multiwell master equation with spin-hopping
2012
The first excited electronic state of molecular oxygen, O(2)(a(1)Δ(g)), is formed in the upper atmosphere by the photolysis of O(3). Its lifetime is over 70 min above 75 km, so that during the day its concentration is about 30 times greater than that of O(3). In order to explore its potential reactivity with atmospheric constituents produced by meteoric ablation, the reactions of Mg, Fe, and Ca with O(2)(a) were studied in a fast flow tube, where the metal atoms were produced either by thermal evaporation (Ca and Mg) or by pulsed laser ablation of a metal target (Fe), and detected by laser induced fluorescence spectroscopy. O(2)(a) was produced by bubbling a flow of Cl(2) through chilled al…
Radiative Cooling of a Small Metal Cluster: The Case ofV13+
1999
Size-selected stored metal cluster ions, ${\mathrm{V}}_{13}^{+}$, have been heated by photoexcitation ( $\ensuremath{\lambda}\phantom{\rule{0ex}{0ex}}=\phantom{\rule{0ex}{0ex}}730$ to 229 nm) to well-defined excitation energies corresponding to temperatures between 1000 and 2100 K. A millisecond pump-probe photodissociation technique was applied to measure the time-resolved radiative cooling. The observed decay rates are directly related to the radiative energy loss and are explained quantitatively by the competing processes of photoemission and atom evaporation.
Luminescence and Raman Detection of Molecular Cl2 and ClClO Molecules in Amorphous SiO2 Matrix
2017
The support from the Latvian Research Program project IMIS 2 (L.S., K.S.) and Latvian Science Council Grant 302/2012 (A.S.) is acknowledged. K.K. was partially supported by the Collaborative Research Project of Materials and Structures Laboratory, Tokyo Institute of Technology. H.H. was supported by the MEXT Element Strategy Initiative to form research cores.
Photochemical intermediates of trans-Rh(CO)L2Cl where L=PMe3, PBu3, and i-Pr2HN and cis-Rh(CO)2(i-Pr2HN)Cl in frozen organic glasses
2002
International audience; The Nujol glass matrix photolyses of Rh(CO)(PMe3)2Cl (1), Rh(CO)(PBu3)2Cl (2), Rh(CO)2(i-Pr2HN)Cl (3), and Rh(CO)(i-Pr2HN)2Cl (4), have been examined. Phototolysis of 1 (λirr>400 nm) and 2 (350<λirr<400 nm) give new species, A, with carbonyl stretching bands slightly below the parent bands. In the case of 1 this species appears to give rise to a second product, C, upon either extended photolysis or annealing. High-energy photolysis of 1, 2, and 4, result in loss of CO and formation of an IR silent species, RhL2Cl. In the case of 1 a new carbonyl species, B, is observed upon high-energy photolysis or annealing of a matrix containing CO and Rh(PMe3)2Cl. B may be conver…
Mechanistic studies on the photogeneration of o- and p-xylylenes from α,α′-dichloroxylenes
1998
Two-colour two-laser techniques have unambiguously proved that photolysis of the o-/p-(chloromethyl)benzyl radical leads to the sequential two-photon generation of o-/pxylylene from α,α'-dichloro-o-/p-xylene. Perez Prieto, Julia, Julia.Perez@uv.es
X-ray structure determination of a metastable state of carbonmonoxy myoglobin after photodissociation.
1996
The x-ray structure of carbon monoxide (CO)-ligated myoglobin illuminated during data collection by a laser diode at the wavelength lambda = 690 nm has been determined to a resolution of 1.7 A at T = 36 K. For comparison, we also measured data sets of deoxymyoglobin and CO-ligated myoglobin. In the photon-induced structure the electron density associated with the CO ligand can be described by a tube extending from the iron into the heme pocket over more than 4 A. This density can be interpreted by two discrete positions of the CO molecule. One is close to the heme iron and can be identified to be bound CO. In the second, the CO is dissociated from the heme iron and lies on top of pyrrole ri…