članak: 1 od 1  
Journal of the Serbian Chemical Society
2004, vol. 69, br. 11, str. 887-899
jezik rada: engleski
izvorni naučni članak
doi:10.2298/JSC0411887J

Sterni efekti na brzinu hidrolize kompleksima paladijuma(II) c-terminalne amidne veze u nizu metioninskih dipeptida acmet-Aa
Department of Chemistry, Iowa State University, Ames

e-adresa: nenad@iastate.edu

National Science Foundation under grant 420-61-52

Sažetak

Niz N-acetilovanih dipeptida AcMet-Aa, koji sadrže metionin i razne aminokiseline Aa, hidrolizuju u vodenom rastvoru na 50 ºC pri 0,95 < pD < 1,10 u prisustvu tri cis-ŠPd(L)(H2O)2Ć2+ kompleksa u kojima je L bidentatni ligand en, Me4en, ili 3-OH-dtco. Reakcije su praćene 1H-NMR spektroskopijom. Konstanta brzine za hidrolitičko kidanje Met-Aa veze opada kako zapremina aminokiseline Aa raste. Ti podaci korelisani su sa Taftovim Es parametrom. Supstituenti na α-C i β-C atomima najviše snižavaju konstantu brzine, oni na γ-C atomu snižavaju je manje, a oni na δ-C atomu nemaju merljivi uticaj. Delimična selektivnost u odnosu na odlazeću aminokiselinu Aa pripisana je razlikama u zapremini bočnog niza i diskriminaciji među odlazećim grupama sličnim po zapremini ali različitim po grananju supstituenata.

Ključne reči

selective cleavage; kinetics; peptides; methionine; palladium(II)

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