Laser flash photolysis of titanium dioxide suspensions for the evaluation of solvent-mediated radical reactions.

The chemistry originating from the scavenging of the highly electrophilic hole in TiO2 can be readily monitored using laser flash photolysis techniques. Dilute suspensions are sufficiently transparent in the UV region that long lived signals from reactions of solvent radicals with 1,1-diphenylethylene can be readily monitored. Transient signals originating from hole, electron and trapped radicals are extremely long lived showing stretched exponentials (nanoseconds to milliseconds), adequately described by fractal models.

Two novel "release-on-demand" fluorescent biosensors for probing UV-induced DNA damage induced in single stranded and double stranded DNA: Comparative study.

Light in the UVC spectral region damages both single-strand (ssDNA) and double-strand DNA (dsDNA), and contributes to the formation of mutagenic photoproducts. In-vivo studies show greater damage for ssDNA compared to dsDNA. However, excited-state spectroscopy shows that dsDNA has longer excited-state lifetime than ssDNA, which increases the probability of damage for dsDNA. However, lack of a direct comparison of in-vitro ssDNA and dsDNA damage rates precludes the development of a model that elucidates the molecular factors responsible for damage. In this work, two novel sensitive "release-on-demand" biosensors are developed for the selective probing of DNA-damage and comparing the rate of DNA damage in ssDNA and dsDNA. The two biosensors involve the use of EvaGreen and Hoechst dyes for the sensitive probing of DNA-damage. The results show that ssDNA is damaged at a faster rate than dsDNA in the presence of UVC light (200-295 nm). Furthermore, we examined the effect of G/C composition on the damage rate for mostly A/T ssDNA and dsDNA oligonucleotides. Our results show that DNA damage rates are highly dependent on the fraction of guanines in the sequence, but that in-vitro dsDNA always exhibits an overall slower rate of damage compared to ssDNA, essentially independent of sequence.

Highly Electrophilic Titania Hole as a Versatile and Efficient Photochemical Free Radical Source.

Photogenerated holes in nanometric semiconductors, such as TiO2, constitute remarkable powerful electrophilic centers, capable of capturing an electron from numerous donors such as ethers, or nonactivated substrates like toluene or acetonitrile, and constitute an exceptionally clean and efficient source of free radicals. In contrast with typical free radical precursors, semiconductors generate single radicals (rather than pairs), where the precursors can be readily removed by filtration or centrifugation after use, thus making it a convenient tool in organic chemistry. The process can be described as an example of dystonic proton coupled electron transfer.