The formation of pyrroline and tetrahydropyridine rings in amino acids catalyzed by pyrrolysine synthase (PylD).
نویسندگان
چکیده
The dehydrogenase PylD catalyzes the ultimate step of the pyrrolysine pathway by converting the isopeptide L-lysine-Nε-3R-methyl-D-ornithine to the 22nd proteinogenic amino acid. In this study, we demonstrate how PylD can be harnessed to oxidize various isopeptides to novel amino acids by combining chemical synthesis with enzyme kinetics and X-ray crystallography. The data enable a detailed description of the PylD reaction trajectory for the biosynthesis of pyrroline and tetrahydropyridine rings as constituents of pyrrolysine analogues.
منابع مشابه
An asymmetric synthesis of L-pyrrolysine.
An efficient asymmetric synthesis of the 22nd amino acid L-pyrrolysine has been accomplished. The key stereogenic centers were installed by an asymmetric conjugate addition reaction. A Staudinger/aza-Wittig cyclization was used to form the acid-sensitive pyrroline ring. Pyrrolysine was synthesized in 13 steps in 20% overall yield.
متن کاملCrystal structure of methylornithine synthase (PylB): insights into the pyrrolysine biosynthesis.
Pyrrolysine (4, abbreviated as Pyl or O, Scheme 1) is the 22nd amino acid that is encoded by the natural genetic code. In the archaebacterial family Methanosarcinaceae, its incorporation into three proteins (MtmB, MtbB, and MttB) involved in the methylamine catabolic pathway is specified by the amber stop codon UAG. The unusual amino acid was discovered in 2002 by crystallography and mass spect...
متن کاملThe genetic code revisited--four decades after Francis Crick.
The ancient essential process of ribosomal protein synthesis requires twenty sets of aminoacyl-tRNAs (aa-tRNAs), one for each canonical amino acid. Since Crick proposed his adaptor hypothesis (1) it was commonly accepted that all organisms possess twenty aaRSs, each enzyme specific for attaching one amino acid to tRNA. It is now clear that aa-tRNA formation is more varied, as the biosynthetic r...
متن کاملAN INDEX REPRESENTING STRUCTURE-CATABOLIC FATE RELATIONSHIPS OF AMINO ACIDS
Based on the Randic suggestion of the resolution of a structure into shape, size, and function an index representing structure-catabolic fate relationships of amino acids is constructed. The index obtained by multiplying three factors; (nb2 + nr), nc and M; representing shape, size and function respectively, where nb2 = number of double bonds, nr = number of rings, nc = number of carbon atoms, ...
متن کاملInvestigate formation constant of some Amino Acids by p-sulphonato-calix (4) arene in Aqueous Solution
The formation constants (log K), of the complexes formed between a number of amino acids(glycine , L-valine and L-alanine) with p-sulfonatocalix [4] arene at varying temperatures (25± 0.1to 65 ± 0.1 °C) in aqueous solutions and at natural pH of p-sulphonato-calix [4] arene (pH=3.2) bymeans of UV-Vis spectrophotometeric technique have been investigated. At this pH the guestmolecule is in its cat...
متن کاملذخیره در منابع من
با ذخیره ی این منبع در منابع من، دسترسی به آن را برای استفاده های بعدی آسان تر کنید
عنوان ژورنال:
- Angewandte Chemie
دوره 53 31 شماره
صفحات -
تاریخ انتشار 2014