α-Umpolung/Michael Addition/Quaternization Tandem Reaction to provide α-Imido-β-phosphonium Propanoates with Broad Spectrum of Biological Activity.

This paper has been supported by the Kazan Federal University Strategic Academic Leadership Program ('PRIORITY-2030'). HRMS data were obtained in the CSF-SAC FRC KSC RAS by support of the State Assignment of the Federal Research Center "Kazan Scientific Center", Russian Academy of Sciences. A.

The kinetics and mechanisms of reactions in the flow systems glycine-sodium trimetaphosphate-imidazoles: the crucial role of imidazoles in prebiotic peptide syntheses.

The kinetics of oligopeptides formation in the flow systems glycine-sodium trimetaphosphate-imidazole/N-methylimidazole at thermocyclic regime has been investigated by HPLC and P NMR methods in the ranges of temperature from 45 to 90 °C and pH from 8.5 to 11.5.

Prebiotic Syntheses Under Shock in the Water - Formamide - Potassium Bicarbonate - Sodium Hydroxide System.

Syntheses under shock in nitrogen bubbled samples of the water - formamide - bicarbonate - sodium hydroxide system at pH 8.63, 9.46 and 10.

Structure of copper(II) complexes grown from ionic liquids - 1-ethyl-3-methyl-imidazolium acetate or chloride.

Crystals of four new copper(II) complexes have been grown from copper(II) acetate/chloride-1-ethyl-3-methyl-imidazolium acetate/chloride-water systems and characterized by X-ray analysis. The first complex, bis-(1-ethyl-3-methyl-imidazolium) tetra-μ-acetato-bis[chloridocuprate(II)], [Emim][Cu(CHO)Cl] () (Emim is 1-ethyl-3-methyl-imidazolium, CHN), contains [Cu(CHO)Cl] coordination anions with a paddle-wheel structure and ionic liquid cations. Two of the synthesized complexes are one-dimensional polymers, namely -poly[1-ethyl-3-methyl-imidazolium [[tetra-μ-acetato-dicuprate(II)]-μ-chlorido] monohydrate], {[Emim][Cu(CHO)Cl]·HO} (), and -poly[1-ethyl-3-methyl-imidazolium [[tetra-μ-acetato-dicuprate(II)]-μ-acetato]], {[Emim][Cu(CHO)]} ().

Hydration of copper(II) amino acids complexes.

Hydration of the copper(II) bis-complexes with glycine, serine, lysine, and aspartic acid was studied by DFT and MD simulation methods. The distances between copper(II) and water molecules in the 1st and 2nd coordination shells, the average number of water molecules and their mean residence times in the hydration shells were calculated. Good agreement was observed between the values obtained and those found by DFT and NMR relaxation methods.

Structure and Dynamics of Solvation Shells of Copper(II) Complexes with N,O-Containing Ligands.

EPR, NMR relaxation methods, and DFT calculations were jointly used to investigate the structural and dynamical characteristics of solvation shells of copper(II) complexes with iminodiacetic acid, glycylglycine, and glycyglycylglycine in comparison with the copper(II) bis-glycinate studied previously. A strong trans influence of deprotonated peptide nitrogen was revealed in EPR spectra parameters of copper(II) complexes with oligopeptides. With models of the experimental NMRD data and literature X-ray structural information, it was suggested that only one water molecule coordinates in axial position of copper(II) complexes with glycine and di- and triglycine (Cu(Gly)2, Cu(GGH(-1)), and Cu(GGGH(-2))(-)), and the copper ion in these complexes is pentacoordinated, while in the iminodiacetate complex, Cu(IDA), both apical positions can be occupied by solute molecules.

The C-H bond activation in 1-ethyl-3-methylimidazolium acetate-copper(II) acetate-water-air (dioxygen) systems.

Ionic liquid (1-ethyl-3-methylimidazolium acetate, [C2C1im][AcO])-copper(ii) diacetate monohydrate-water-air (O2) systems have been investigated by (13)C NMR, EPR, spectrophotometry, HPLC, and synthetic chemistry methods at different temperatures. The C-H bond activation of [C2C1im](+) with the formation of the unusual dication 1,1'-diethyl-3,3'-dimethyl-2,2'-biimidazolium ([(C2C1im)2](2+)) at 50 °C and 1-ethyl-3-methyl-1H-imidazol-2(3H)-one (C2C1imO) at 50-85 °C was revealed. Two new complexes with the above compounds, [(C2C1im)2][Cu(AcO)4] and Cu2(AcO)4(C2C1imO)2, were isolated from the systems and characterized by X-ray structural analysis.