Rapid acidolysis of benzyl group as a suitable approach for syntheses of peptides naturally produced by oxidative stress and containing 3-nitrotyrosine

Kód výsledku v IS VaVaI

RIV/61388963:_____/16:00459208 - isvavai.cz

Nalezeny alternativní kódy

RIV/60461373:22330/16:43901710

Výsledek na webu

http://dx.doi.org/10.1007/s00726-015-2163-2

DOI - Digital Object Identifier

10.1007/s00726-015-2163-2

Jazyk výsledku

angličtina

Název v původním jazyce

Rapid acidolysis of benzyl group as a suitable approach for syntheses of peptides naturally produced by oxidative stress and containing 3-nitrotyrosine

Popis výsledku v původním jazyce

3-Nitrotyrosine (Nit) belongs to products of oxidative stress and could probably influence conformation of neurodegenerative proteins. Syntheses of peptides require availability of suitable synthon for introduction of Nit residue. Common phenolic protection groups are more acid labile, when they are attached to Nit residue. We have found that Fmoc-Nit(Bn)-OH is a good building block for syntheses of Nit containing peptides by Fmoc/tBu strategy. Interestingly, the peptides containing multiple Nit residues can be available solely by use of Fmoc-Nit(Bn)-OH synthon. Bn is removed rapidly with ca 80 % trifluoroacetic acid in dark. The cleavage of Bn from Fmoc-Nit(Bn)-OH proceeds via pseudo-first order mechanism with activation barrier 32 kcal mol(-1) and rate k = 15.3 s(-1) at 20 A degrees C. This rate is more than 2,000,000 times faster than that for cleavage of benzyl from Tyr(Bn).

Název v anglickém jazyce

Rapid acidolysis of benzyl group as a suitable approach for syntheses of peptides naturally produced by oxidative stress and containing 3-nitrotyrosine

Popis výsledku anglicky

3-Nitrotyrosine (Nit) belongs to products of oxidative stress and could probably influence conformation of neurodegenerative proteins. Syntheses of peptides require availability of suitable synthon for introduction of Nit residue. Common phenolic protection groups are more acid labile, when they are attached to Nit residue. We have found that Fmoc-Nit(Bn)-OH is a good building block for syntheses of Nit containing peptides by Fmoc/tBu strategy. Interestingly, the peptides containing multiple Nit residues can be available solely by use of Fmoc-Nit(Bn)-OH synthon. Bn is removed rapidly with ca 80 % trifluoroacetic acid in dark. The cleavage of Bn from Fmoc-Nit(Bn)-OH proceeds via pseudo-first order mechanism with activation barrier 32 kcal mol(-1) and rate k = 15.3 s(-1) at 20 A degrees C. This rate is more than 2,000,000 times faster than that for cleavage of benzyl from Tyr(Bn).

Druh

J_x - Nezařazeno - Článek v odborném periodiku (Jimp, Jsc a Jost)

CEP obor

CE - Biochemie

OECD FORD obor

—

Projekt

GA14-00431S: 3-Nitro-L-tyrosin ve strukturách neurodegenerativních proteinů

Návaznosti

I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace

Rok uplatnění

2016

Kód důvěrnosti údajů

S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů

Název periodika

Amino Acids

ISSN

0939-4451

e-ISSN

—

Svazek periodika

48

Číslo periodika v rámci svazku

4

Stát vydavatele periodika

AT - Rakouská republika

Počet stran výsledku

12

Strana od-do

1087-1098

Kód UT WoS článku

000372551100018

EID výsledku v databázi Scopus

2-s2.0-84954319068