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Brazilian biochemist (1923-1994) From Wikipedia, the free encyclopedia
Giuseppe Cilento (July 21, 1923 in Sorrento, Italy – October 31, 1994 in São Paulo) was a Brazilian chemist who was born in Italy. He held a professorship at the University of São Paulo and was Professor Emeritus at the State University of Campinas.
Giuseppe Cilento | |
---|---|
Born | |
Died | October 31, 1994 73) | (aged
Known for | photochemistry |
Scientific career | |
Fields | chemistry molecular biology |
Cilento attended the Department of Chemistry, Faculty of Philosophy, Science and Letters, University of São Paulo, São Paulo, Brazil.
Cilento completed a post-doc at Harvard University.[1]
He received the grã-cruz ("Great Cross") of the Ordem Nacional do Mérito Científico ("National Order of Scientific Merit") of Brazil[2] and the TWAS Prize in 1993.[3]
Cilento may have been awarded fellowship by the John Simon Guggenheim Memorial Foundation in 1977 and 1981.[4]
The Rockefeller Foundation awarded $4,905 to Cilento and Heinrich Hauptmann for biochemistry research in 1958.
Throughout his career, Cilento published over 150 papers.[5]
Cilento was an early pioneer of the paradoxical hypothesis of "photochemistry without light".[6] The hypothesis was based on chemiluminescence and bioluminescence originating from enzymatic and non-enzymatic pathways that produce unstable peroxide intermediates such as 1,2-dioxetanes that fluoresce, ejecting a photon within "dark" biological organisms potentially triggering physiological or pathophysiological responses.[6] He had profound interest in horseradish peroxidase.
An example mechanism resides in keto acids such as phenylpyruvic acid, which under certain circumstances tautomerizes to form a reactive enol. Peroxidation, initiated by reactive oxygen species by enzymatic peroxidases or non-enzymatic pathways, react with the benzylic carbon and alpha-keto carbonyl to form a "squaric" 1,2-dioxetane/dioxetanol. This intermediate is unstable, resulting in the ejection of a photon and subsequent formation of oxalic acid and benzaldehyde in the triplet state.[7] The pathway competes with formation of a peroxylactone that forms benzaldehyde and carbon dioxide and carbon monoxide. Cilento and Villablanca were interested in the biological significance of this specific pathway among others.[8]
Among Cilento's collaborators, many publications on dark-photochemistry were authored with Prof. Waldemar Adam at University of Würzburg. Cilento and Adam described how 1,2-dioxetanes can induce chemical modification of DNA including formation of cyclobutane pyrimidine dimers and oxidation of guanine (from a triplet-state carbonyl and subsequent reactivity with oxygen, exemplified by the phenylpyruvate 1,2-dioxetanol pathway).[6]
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