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(1923-07-21)July 21, 1923
DiedOctober 31, 1994(1994-10-31) (aged 73)
Known forphotochemistry
Scientific career
Fieldschemistry
molecular biology

Early life and education

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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]

Awards and honors

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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.

Contributions

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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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Notes

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  1. ^ "Special Highlights | Redoxoma Newsletter". redoxomanewsletter.iq.usp.br. Retrieved 2021-06-01.
  2. ^ Giuseppe Cilento – Membros da ONMC[permanent dead link]
  3. ^ "Prizes and Awards". The World Academy of Sciences. 2016.
  4. ^ "John Simon Guggenheim Foundation | Giuseppe Cilento". Retrieved 2021-06-01.
  5. ^ "001. Science and Literature: Global and Local Perspectives" (PDF).
  6. ^ a b c Baader, Wilhelm J.; Stevani, Cassius V.; Bechara, Etelvino J. H. (2015). ""Photo" Chemistry Without Light?". Journal of the Brazilian Chemical Society. doi:10.5935/0103-5053.20150257. ISSN 0103-5053.
  7. ^ Hopper, Christopher P.; De La Cruz, Ladie Kimberly; Lyles, Kristin V.; Wareham, Lauren K.; Gilbert, Jack A.; Eichenbaum, Zehava; Magierowski, Marcin; Poole, Robert K.; Wollborn, Jakob; Wang, Binghe (2020-12-23). "Role of Carbon Monoxide in Host–Gut Microbiome Communication". Chemical Reviews. 120 (24): 13273–13311. doi:10.1021/acs.chemrev.0c00586. ISSN 0009-2665. PMID 33089988. S2CID 224824871.
  8. ^ Hopper, Christopher P.; Zambrana, Paige N.; Goebel, Ulrich; Wollborn, Jakob (2021). "A brief history of carbon monoxide and its therapeutic origins". Nitric Oxide. 111–112: 45–63. doi:10.1016/j.niox.2021.04.001. PMID 33838343. S2CID 233205099.