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Pregled bibliografske jedinice broj: 1064040

Novel Insights into the Thioesterolytic Activity of N-Substituted Pyridinium-4-oximes


Foretić, Blaženka; Damjanović, Vladimir; Vianello, Robert; Picek, Igor
Novel Insights into the Thioesterolytic Activity of N-Substituted Pyridinium-4-oximes // Molecules, 25 (2020), 10; 2385, 16 doi:10.3390/molecules25102385 (međunarodna recenzija, članak, znanstveni)


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Naslov
Novel Insights into the Thioesterolytic Activity of N-Substituted Pyridinium-4-oximes

Autori
Foretić, Blaženka ; Damjanović, Vladimir ; Vianello, Robert ; Picek, Igor

Izvornik
Molecules (1420-3049) 25 (2020), 10; 2385, 16

Vrsta, podvrsta i kategorija rada
Radovi u časopisima, članak, znanstveni

Ključne riječi
acetylthiocholine ; pyridinium-4-oxime-ester ; reaction mechanisms ; energy profiles ; computations

Sažetak
The pyridinium oximes are known esterolytic agents, usually classified in the literature as catalysts, which mimic the catalytic mode of hydrolases. Herein, we combined kinetic and computational studies of the pyridinium-4-oxime-mediated acetylthiocholine (AcSCh+) hydrolysis to provide novel insights into their potential catalytic activity. The N-methyl- and N-benzylpyridinium-4-oximes have been tested as oximolytic agents toward the AcSCh+, while the newly synthesized O-acetyl-N-methylpyridinium-4-oxime iodide was employed for studying the consecutive hydrolytic reaction. The relevance of the AcSCh+ hydrolysis as a competitive reaction to AcSCh+ oximolysis was also investigated. The reactions were independently studied spectrophotometrically and rate constants, koxime, kw and kOH, were evaluated over a convenient pH-range at I = 0.1 M and 25 °C. The catalytic action of pyridinium-4-oximes comprises two successive stages, acetylation (oximolysis) and deacetylation stage (pyridinium-4-oxime-ester hydrolysis), the latter being crucial for understanding the whole catalytic cycle. The complete mechanism is presented by the free energy reaction profiles obtained with (CPCM)/M06–2X/6–311++G(2df, 2pd)//(CPCM)/M06–2X/6–31+G(d) computational model. The comparison of the observed rates of AcSCh+ oximolytic cleavage and both competitive AcSCh+ and consecutive pyridinium-4-oxime-ester hydrolytic cleavage revealed that the pyridinium-4-oximes cannot be classified as non-enzyme catalyst of the AcSCh+ hydrolysis but as the very effective esterolytic agents.

Izvorni jezik
Engleski

Znanstvena područja
Kemija



POVEZANOST RADA


Ustanove:
Institut "Ruđer Bošković", Zagreb,
Medicinski fakultet, Zagreb

Poveznice na cjeloviti tekst rada:

doi www.mdpi.com fulir.irb.hr

Citiraj ovu publikaciju:

Foretić, Blaženka; Damjanović, Vladimir; Vianello, Robert; Picek, Igor
Novel Insights into the Thioesterolytic Activity of N-Substituted Pyridinium-4-oximes // Molecules, 25 (2020), 10; 2385, 16 doi:10.3390/molecules25102385 (međunarodna recenzija, članak, znanstveni)
Foretić, B., Damjanović, V., Vianello, R. & Picek, I. (2020) Novel Insights into the Thioesterolytic Activity of N-Substituted Pyridinium-4-oximes. Molecules, 25 (10), 2385, 16 doi:10.3390/molecules25102385.
@article{article, author = {Foreti\'{c}, Bla\v{z}enka and Damjanovi\'{c}, Vladimir and Vianello, Robert and Picek, Igor}, year = {2020}, pages = {16}, DOI = {10.3390/molecules25102385}, chapter = {2385}, keywords = {acetylthiocholine, pyridinium-4-oxime-ester, reaction mechanisms, energy profiles, computations}, journal = {Molecules}, doi = {10.3390/molecules25102385}, volume = {25}, number = {10}, issn = {1420-3049}, title = {Novel Insights into the Thioesterolytic Activity of N-Substituted Pyridinium-4-oximes}, keyword = {acetylthiocholine, pyridinium-4-oxime-ester, reaction mechanisms, energy profiles, computations}, chapternumber = {2385} }
@article{article, author = {Foreti\'{c}, Bla\v{z}enka and Damjanovi\'{c}, Vladimir and Vianello, Robert and Picek, Igor}, year = {2020}, pages = {16}, DOI = {10.3390/molecules25102385}, chapter = {2385}, keywords = {acetylthiocholine, pyridinium-4-oxime-ester, reaction mechanisms, energy profiles, computations}, journal = {Molecules}, doi = {10.3390/molecules25102385}, volume = {25}, number = {10}, issn = {1420-3049}, title = {Novel Insights into the Thioesterolytic Activity of N-Substituted Pyridinium-4-oximes}, keyword = {acetylthiocholine, pyridinium-4-oxime-ester, reaction mechanisms, energy profiles, computations}, chapternumber = {2385} }

Časopis indeksira:


  • Current Contents Connect (CCC)
  • Web of Science Core Collection (WoSCC)
    • Science Citation Index Expanded (SCI-EXP)
    • SCI-EXP, SSCI i/ili A&HCI
  • Scopus
  • MEDLINE


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