The major objectives of my research is the application of ab initio an DFT methods for studying different reaction mechanisms and the quantitative description of reactivity of the organic systems.
My first project I started as part of my PhD thesis: The reaction mechanisms and the reactivity of secondary amides in the alkaline hydrolysis reaction. The main reason is the elucidation of the connection between the structure and the reactivity of the amides in this reaction. The reaction mechanism was thoroughly studied with the help of quantum chemical calculation and kinetical experiments for determining the rate constants and enthalpies/Gibbs free energies of activation for group of secondary amides. As a result a new descriptor of reactivity for organic reactions was proposed – the electrostatic potential at the nuclei (EPN). The proposed descriptor not only describes quantitatively the theoretically estimated energy barriers, but also gives excellent correlation with the experimentally determined rate constants for the studied amines.
In a recent paper of our group a computational approach for the evaluation of σI and σR substituent constants have been outlined. They are based on correlations between theoretically evaluated electrostatic potential at nuclei (EPN) values for the carbon atoms (VC) in substituted benzene and bicyclo[2,2,2]octane derivatives containing the same polar group at position.
The current projects I’m involved in concern the mechanism of the ring-opening polymerization of lactide by different metal alkoxides, and the kinetic and mechanism study of some biologically active carbamates.
D. Cheshmedzhieva, I. Angelova, S. Ilieva, G. Georgiev, B. Galabov “Initiation of Ring-Opening Polymerization of Lactide: The Effect of Metal Alkoxide Catalyst” Theor. Comp. Chem. 8 (2012) 995.
V. Nikolova, D. Cheshmedzhieva, S. Ilieva, B. Galabov “The Nature of Intramolecular Interactions Determining the σ−Constants for Aromatic Systems” J. Mol. Struct. (Jaan Laane special issue) 31 (2012) 1023.
D. Cheshmedzhieva, V. Dimitrova, B. Hadjieva, S. Ilieva “Rationalizing IR intensities in terms of electronic parameters” J. Mol. Struct. (Boris Galabov special issue) 69 (2012) 1009.
D. Cheshmedzhieva, P. Ivanova, S. Stoyanov, D. Tasheva, I. Ivanov, S. Ilieva “Absorption and fluorescence properties of novel 1,8-naphtalimide hydrazones for enzyme activity localization” Phys. Chem. Chem. Phys. 13 (2011) 18530.
D. Nalbantova, D. Cheshmedzhieva, S. Ilieva, B. Hadjieva, B. Galabov “Reactivity of phenyl N-phenylcarbamates in the alkaline hydrolysis reaction” J. Phys. Org. Chem. 24 (2011) 1166.
D. Cheshmedzhieva, S. Ilieva, B. Galabov “Computational evaluation of σI and σR substituent constants“ J. Mol. Struct. 976 (2010) 427.
S. Ilieva, D.Cheshmedzhieva, D. Tasheva “The Origin of Diastereoselectivity in the Michael Addition Reaction: a Computational Study of the Interaction Between CH-acidic Schiff Base and α,β-Unsaturated Ketones“ Tetrahedron 66 (2010) 5168.
D. Cheshmedzhieva, S. Ilieva, B. Hadjieva and B. Galabov “The Mechanism of alkaline Hydrolysis of Amides. A Comparative Computational and Experimental Study of the Hydrolysis of N-Methylacetamide, N-Methylbenzamide and Acetanilide“ J. Phys. Org. Chem. 22 (2009) 619.
D. Cheshmedzhieva, S. Ilieva, B. Hadjieva, T. Trayanova, B. Galabov “Reactivity of Acetanilides in the Alkaline Hydrolysis Reaction: Theory vs. Experiment“ Mol. Phys. 107 (2009) 1187.
B. Hadjieva, S. Ilieva, D. Cheshmedzhieva, B. Galabov “Conformation of some biologically active aromatic urea“ Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, 61 (2005) 1321.
D. Cheshmedzhieva, S. Ilieva, B. Galabov “Computational study of alkaline hydrolysis of acetanilide“ J. Mol. Struct. (THEOCHEM) 681, 105 (2004).
M. G. Bogdanov, I. S. Todorov, P. G. Manolova, D. V. Cheshmedzhieva, M. D. Palamareva “Configuration and conformational equilibrium of (±)-trans-1-oxo-3-thiophen-2-yl-isochroman-4-carboxylic acid methyl ester“ Tetrahedron Letters, 45 (2004) 8383.
B. Galabov, D. Cheshmedzhieva, S. Ilieva, B. Hadjieva “Computational study of N-phenylacetamides in alkali hydrolysis reaction“ J. Phys. Chem. A 108 (2004) 11457.