Lifetimes photochemical

D.D. Morgan, D. Warshawsky, T. Atkinson (1977). The relationship between carcinogenic activities of polycyclic aromatic hydrocarbons and their singlet, triplet, and singlet-triplet splitting energies and phosphorescence lifetimes. Photochem. Photo-bioL, 25, 31-38. 

Ozone depleter Ozone depletion potential is the value relative to that of CFC-11. It represents the amormt of ozone destroyed by the emission of gas over its entire atmospheric lifetime. Photochemical ozone creation potential is a relative value to that of ethene to form ozone in an urban environment. Numerous solvents belong to both groups. 

If there are no competing processes the experimental lifetime x should equal Tq. Most connnonly, other processes such as non-radiative decay to lower electronic states, quenching, photochemical reactions or... 

The lifetime of an analyte in the excited state. A, is short typically 10 -10 s for electronic excited states and 10 s for vibrational excited states. Relaxation occurs through collisions between A and other species in the sample, by photochemical reactions, and by the emission of photons. In the first process, which is called vibrational deactivation, or nonradiative relaxation, the excess energy is released as heat thus... 

TBT exists in solution as a large univalent cation and forms a neutral complex with CH or OH . It is extremely surface active and so is readily adsorbed onto suspended particulate material. Such adsorption and deposition to the sediments limits its lifetime in the water column. Degradation, via photochemical reactions... 

Direct photochemical excitation of unconjugated alkenes requires light with A < 230 nm. There have been relatively few studies of direct photolysis of alkenes in solution because of the experimental difficulties imposed by this wavelength restriction. A study of Z- and -2-butene diluted with neopentane demonstrated that Z E isomerization was competitive with the photochemically allowed [2tc + 2n] cycloaddition that occurs in pure liquid alkene. The cycloaddition reaction is completely stereospecific for each isomer, which requires that the excited intermediates involved in cycloaddition must retain a geometry which is characteristic of the reactant isomer. As the ratio of neopentane to butene is increased, the amount of cycloaddition decreases relative to that of Z E isomerization. This effect presumably is the result of the veiy short lifetime of the intermediate responsible for cycloaddition. When the alkene is diluted by inert hydrocarbon, the rate of encounter with a second alkene molecule is reduced, and the unimolecular isomerization becomes the dominant reaction. 

Reactions that proceed photochemically do not necessarily involve observations of an excited state. Long before observations are made, the excited state may have dissociated to other fragments, such as free radicals. That is, the lifetime of many excited states is shorter than the laser excitation pulse. This statement was implied, for example, by reactions (11-46) and (11-47). In these systems one can explore the kinetics of the subsequent reactions of iodine atoms and of Mn(CO)s, a 17-electron radical. For instance, one can study... 

Compared with tar, which has a relatively short lifetime in the marine environment, the residence times of plastic, glass and non-corrodible metallic debris are indefinite. Most plastic articles are fabricated from polyethylene, polystyrene or polyvinyl chloride. With molecular weights ranging to over 500,000, the only chemical reactivity of these polymers is derived from any residual unsaturation and, therefore, they are essentially inert chemically and photochemically. Further, since indigenous microflora lack the enzyme systems necessary to degrade most of these polymers, articles manufactured from them are highly resistant or virtually immune to biodegradation. That is, the properties that render plastics so durable... 

Oxidation-reduction reactions in water are dominated by the biological processes of photosynthesis and organic matter oxidation. A very different set of oxidation reactions occurs within the gas phase of the atmosphere, often a consequence of photochemical production and destruction of ozone (O3). While such reactions are of great importance to chemistry of the atmosphere - e.g., they limit the lifetime in the atmosphere of species like CO and CH4 - the global amount of these reactions is trivial compared to the global O2 production and consumption by photosynthesis and respiration. 

Magnetic field effects on the reaction kinetics or yields of photochemical reactions in the condensed phase have been studied [20-23]. They have proved powerful for verifying the mechanism of photochemical reactions including triplet states. Previously, we obtained photogenerated triplet biradicals of donor-acceptor linked compounds, and found that the lifetimes of the biradicals were remarkably extended in the presence of magnetic fields up to 1T [24]. It has been reported that Cgo and its derivatives form optically transparent microscopic clusters in mixed solvents [25,26]. The clustering behavior of fullerene (C o) is mainly associated with the strong three-dimensional hydrophobic interactions between the C o units. Photoinduced... 

Upon absorption of UV radiation from sunlight the bases can proceed through photochemical reactions that can lead to photodamage in the nucleic acids. Photochemical reactions do occur in the bases, with thymidine dimerization being a primary result, but at low rates. The bases are quite stable to photochemical damage, having efficient ways to dissipate the harmful electronic energy, as indicated by their ultrashort excited state lifetimes. It had been known for years that the excited states were short lived, and that fluorescence quantum yields are very low for all bases [4, 81, 82], Femtosecond laser spectroscopy has, in recent years, enabled a much... 

All the nucleic acid bases absorb UV radiation, as seen in Tables 11-1, 11-2, 11-3, 11-4, and 11-5, making them vulnerable to the UV radiation of sunlight, since the energy of the photons absorbed could lead to photochemical reactions. As already mentioned above, the excited state lifetimes of the natural nucleobases, and their nucleotides, and nucleosides are very short, indicating that ultrafast radiationless decay to the ground state takes place [6], The mechanism for nonradiative decay in all the nucleobases has been investigated with quantum mechanical methods. Below we summarize these studies for each base and make an effort to find common mechanisms if they exist. 

Ultraviolet absorption spectra were obtained from a Cary 118C Spectrophotometer. Luminescence measurements were obtained from a Perkin-Elmer Model MPF-3 Fluorescence Spectrophotometer equipped with Corrected Spectra, Phosphorescence and Front Surface Accessories. A Tektronix Model 510N Storage Oscilloscope was used for luminescence lifetime measurements. Fiber irradiation photolyses were carried out in a Rayonet Type RS Model RPR-208 Preparative Photochemical Reactor equipped with a MGR-100 Merry-go-Round assembly. 

Their distinguishing feature is the high speed of response. This response develops on the scale of fluorescence lifetime of photophysical or photochemical events that provide the response and can be as short as 10 x-10 10 s. Because of that, the fluorescence reporting is never time-limiting, so that this limit comes from other factors, such as the rate of target - sensor mutual diffusion and the establishment of dynamic equilibrium between bound and unbound target. 

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