Naslov
SINGLE CRYSTAL X-RAY CRYSTALLOGRAPHY AS A METHOD OF CHOICE IN BIOMIMETIC MODELING

Autori
Višnjevac, Aleksandar

Vrsta, podvrsta i kategorija rada
Sažeci sa skupova, sažetak, znanstveni

Izvornik
19th Slovenian-Croatian Crystallographic Meeting, Book of Abstracts / Leban, Ivan ; Popović, Stanko - Ljubljana : Slovensko kristalografsko društvo, 2010, 16-16

Skup
19th Slovenian-Croatian Crystallographic Meeting

Mjesto i datum
Strahinj, Slovenija, 16.06.2010. - 20.06.2010

Vrsta sudjelovanja
Plenarno

Vrsta recenzije
Međunarodna recenzija

Ključne riječi
single crystal X-ray crystallography, biomimetic modelling

Sažetak
Information flowing over the border between chemistry and biology have led to the development of the biomimetic chemistry, a field where new things are invented, inspired by the principles developed by Nature. Two different chemical systems, N1-sulfonylpyrimidines and resorcinarene-based Zn(II)-complexes, will be presented as the rationally designed biomimetic models of nucleotides (as the building blocks of nucleic acids) and metalloenzyme active sites, respectively. Coordination of various transition metals, stabilization of the unusual nucleobase tautomers, or steric hindrances easily disrupt the usual hydrogen bonding arrangement and lead to mutagenic base mispairing in nucleic acids. We have used simple N1-sulfonyl derivatives of various pyrimidine nucleobases to investigate the relative stability of tautomers in presence of different transition metal ions. The study of two dinuclear Pd(II) complexes of N1-(p-toluenesulfonyl)cytosine revealed the stabilization of the minor iminooxo form of N1-substituted cytosine upon Pd(II) coordination. Cu(II) coordination to N1-(p-toluenesulfonyl)cytosine led to the formation of two pseudopolymorphs, only in one of which the geometry of the pyrimidine ring suggests the stabilization of the rare tautomer. N1 - substituted uracil and thymine derivatives: N1 - (p-toluenesulfonyl) uracil, N1 - (p-toluenesulfonyl) thymine, 5 – bromo - N1 - (p-toluenesulfonyl) uracil, N1-(methanesulfonyl) uracil, N1 - (1-naphthylsulfonyl) uracil, and N1 - (1-naphthylsulfonyl) thymine were employed to study the influence of the various substituents of the pyrimidine nucelobases to the hydrogen bonding arrangements. The bowl-shaped resorcin[4]arene-based ligand was prepared as a model of the trihistidine coordination core present in many mononuclear metalloenzymes. The -CH2-O-CH2- linkers connecting the imidazoles to the cavity allow three imidazoles to simultaneously bind a metal ion, and favor cis-coordination of two exchangeable ligands. The corresponding mononuclear Zn-complexes were shown to be capable of the selective guest binding and exchange at both endo and exo positions.

Izvorni jezik
Engleski

Znanstvena područja
Kemija

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