Chromophore photodegradation

Another common hydrogen transfer reaction of carbonyl triplet is the photoenolization of the c-methylbenzoyl chromophore, illustrated in reaction 3 for the syn conformer of c-methylaceto-phenone (j+). Reaction 3 can act as a very efficient energy sink, and a number of properties of this group led us to believe that this process could be used to reduce photodegradation i.e. the excellent absorption characteristics of the chromophore, the short triplet lifetime and the fact that the disappearance of the carbonyl triplet does not take place at the expense of the formation of another excited state. 

Perhaps the most interesting feature is exhibited by the copolymers, rather than the homopolymers. We find that the reduction in the quantum yield of photodegradation always exceeds the abundance of o-methylbenzoyl chromophores (5.) Table I illustrates this effect. 

The ordinary monomer units of PVC are not expected to absorb any terrestrial solar radiation (1>.2>.3 A) Thus, under the usual ambient conditions, photodegradation of the polymer must be initiated by chromophoric impurities. These impurities may simply be structural defects in the PVC itself, or they may be extraneous substances that have been incorporated into the polymer. Several of these potential photosensitizers are discussed in the following sections. 

Physical disinfection of drinking water is mainly carried out through photodegradation by ultraviolet radiation (UV). Because many pharmaceuticals have chromophores that absorb UV wavelength, UV irradiation can lead to some transformation. Comparing to chemical oxidation, such as chlorination, UV disinfection has an advantage of minimizing the formation of DBPs [73]. However, at a... 

One attractive possibility is the use of the a-keto-oxime chromophore. It has a strong absorption at 220 nm whose tail, which extends to 240-250 nm, would improve the absorption characteristics of PMMA. Also, the esters possess a N-O bond which is photochemically labile yet sufficiently thermally stable so as to be compatible with the various processing steps. The solution degradation of a-keto oximino methacrylate esters upon irradiation with light of X365 nm has been reported by Delz-enne (2), and we proceeded to investigate the solid state photodegradation of similar copolymers and their possible utility as deep UV photoresists. 

Another important consideration was the fact that the absorption maxima of oxime acrylate monomers could be tuned to the desired wavelength by the selection of desired ketone or aldehyde chromophore from whence the oxime was originally synthesized. In our design, UV photocrosslinking followed dye-sensitized visible polymerization which formed a soft gel. It is very important to be able to choose the absorption window for the crosslinking reaction to prevent interfering absorption, if any, from the residual dye initiator. Acyl oximes as part of the backbone of a photodegrading polymer chain have been studied by Smets [217],... 

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