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Cys-X-Y Cys with NH…S hydrogen bond
Journal of Inorganic ~ioc~e~is~~y96 (2003)
Solution structures i “+/Cys-X-Y-Cys wit Masahiro Kato, GradGate School of Science, Osaka University, Japan amura, Graduate School of Science, Osaka University, Japan Hitoshi ~amarn~tQ, Graduate School ofScience, Osaka University, Japan Worikazu Ueyama, Graduate School of Science, Osaka UniversiQ, Japm Cys-X-Y-Cys is an ammo acid sequence that is often found in the active center of a protein, rubredoxin and Zinc finger as thiolate chelating ligands, and tb~o~-protein oxidored ase s transferase as ~ncleophile. The crystallographic analysis of these enzymes have been suggest catalytic activities is associated with the NH+3 hydrogen bond between the S atom of~yste~~~ r of peptide main chain. We report the synthesis of X”+/Z-Cys(l)-Pro-Leu-Cys(2)-OMe (X”+=NEt and the relations between the NH-4 hydrogen bond and the secondary structure. Several stu correlation between cellular toxicity of cis-diamminedi~hlorop~atinum(~1) (cisp!atin) and i~bib~t the thioredoxin system. Therefore Pt2+/Cys-X-Y-Cys complex is im~o~ant to support the solution o~rn~~~a~~srn~ 733, and Na complexes were synthesized by the reaction of Z-Cys-Pro-Leu-Cys-OMe with @Et,) Bu) or ~a(~~~~?, respectively. The solution structures in acetonitrile of the thiol state and the NEt4 complex were determin by “13h&R using a simulated annealing method. The only thiolate anion states form a folded hairpin turn st an ~ntrarnoi~~~~a~ N&4 hydrogen bond behveen the Cys(l) S atom and the amide NH of Leu and Cys(2). The anion states in Na compiex indicate clear amide NH signals in acetonitrile, bu amide signals. Inte~o~ecuiar NH-4 hydrogen bond between Cys(2) sulfur and 0th broadness ~famide NH signals with these small T, values. Pt(IT) complex was synthesized by the reaction Pt (WEt,),(Z-Cys(S-)-Pro-Leu-Cys(S-)-OMe). Formation of a ternary plex has been co~~rrn~ which exhibited signals at m/z 955.2 [Pt(bpy)(Z-Cys-Pro-Leu-Cys) e + Na?].
Figure. Nim structure of Z-cys(1)-Pr0-Leu-Cys(2)-0Me in the thiol state andN-E~~ compkx; b) the mono(tbiolate anion) and c) the dithiolate anion states.
a) rhr: qwClZlS’i ;ri01,
Solution structures i “+/Cys-X-Y-Cys wit Masahiro Kato, GradGate School of Science, Osaka University, Japan amura, Graduate School of Science, Osaka University, Japan Hitoshi ~amarn~tQ, Graduate School ofScience, Osaka University, Japan Worikazu Ueyama, Graduate School of Science, Osaka UniversiQ, Japm Cys-X-Y-Cys is an ammo acid sequence that is often found in the active center of a protein, rubredoxin and Zinc finger as thiolate chelating ligands, and tb~o~-protein oxidored ase s transferase as ~ncleophile. The crystallographic analysis of these enzymes have been suggest catalytic activities is associated with the NH+3 hydrogen bond between the S atom of~yste~~~ r of peptide main chain. We report the synthesis of X”+/Z-Cys(l)-Pro-Leu-Cys(2)-OMe (X”+=NEt and the relations between the NH-4 hydrogen bond and the secondary structure. Several stu correlation between cellular toxicity of cis-diamminedi~hlorop~atinum(~1) (cisp!atin) and i~bib~t the thioredoxin system. Therefore Pt2+/Cys-X-Y-Cys complex is im~o~ant to support the solution o~rn~~~a~~srn~ 733, and Na complexes were synthesized by the reaction of Z-Cys-Pro-Leu-Cys-OMe with @Et,) Bu) or ~a(~~~~?, respectively. The solution structures in acetonitrile of the thiol state and the NEt4 complex were determin by “13h&R using a simulated annealing method. The only thiolate anion states form a folded hairpin turn st an ~ntrarnoi~~~~a~ N&4 hydrogen bond behveen the Cys(l) S atom and the amide NH of Leu and Cys(2). The anion states in Na compiex indicate clear amide NH signals in acetonitrile, bu amide signals. Inte~o~ecuiar NH-4 hydrogen bond between Cys(2) sulfur and 0th broadness ~famide NH signals with these small T, values. Pt(IT) complex was synthesized by the reaction Pt (WEt,),(Z-Cys(S-)-Pro-Leu-Cys(S-)-OMe). Formation of a ternary plex has been co~~rrn~ which exhibited signals at m/z 955.2 [Pt(bpy)(Z-Cys-Pro-Leu-Cys) e + Na?].
Figure. Nim structure of Z-cys(1)-Pr0-Leu-Cys(2)-0Me in the thiol state andN-E~~ compkx; b) the mono(tbiolate anion) and c) the dithiolate anion states.
a) rhr: qwClZlS’i ;ri01,