A DFT investigation of the host–guest interactions between boron-based aromatic systems and β-cyclodextrin

Abstract

Density-functional theory calculations including dispersion at BLYP-D3(BJ)/def2-SVP level of theory were performed for a series of systems based on cyclodextrin complexation with boron-based aromatic compounds. Elaborated investigations were carried out using different quantum chemical parameters such as computed complexation energies, theoretical association constants and natural bond orbital (NBO) analysis. Several configurations and inclusion modes were considered in this work. The calculated complexation energies were consistent with the experimental classification of these systems on the basis of occurring interactions. Reduced density gradient (RDG) and independent gradient model (IGM) approaches determined the nature and strength of non-covalent interactions which played a central role in the formation of the complexes. Thus, phenylboronic acid (PBA) and benzoxaborole (Bxb) act mainly as hydrogen-bonded complexes with β-cyclodextrin, while mainly Van der Waals (vdW) interactions stabilize both catechol (PhBcat) and pinacol esters of phenylboronic acid (PhBpin) complexes. The ferroceneboronic acid (FcBA) exhibits a mixture of H-bonds and vdW interactions with β-cyclodextrin.

A Dispersion Corrected DFT Investigation of the Inclusion Complexation of Dexamethasone with β-Cyclodextrin and Molecular Docking Study of Its Potential Activity against COVID-19

“…As can be seen in Table 2, the intermolecular hydrogen bonds mainly occurred between oxygen lone-pair electron-donating orbitals (LP) and σ* (BD*) O-H antibonding orbitals. The strongest H-bonds with higher stabilization energies (63.39, 19.87, 37.66, and 19.41 kJ/mol) were found to correspond to the shortest H-bonds (1.80, 1.79, 1.79, and 1.90 Å), and these interactions were found to be associated with the blue discs of the IGM isosurface that indicate the presence of the intermolecular hydrogen bonds, therefore confirming the role of hydrogen-bonding interaction [33,41] in the formation and stabilization of the Dex@β-CD complex. It is worth noting the presence of a weak hydrogen bond (10.67 kJ/mol) corresponding to the interaction between the lone-pair electron-donating orbitals LP(3) of fluorine (F148) and the anti-bonding orbital of the O45-H59 bond of β-CD.…”

Modifying Enzymatic Substrate Binding within a Metal–Organic Capsule for Supramolecular Catalysis

“…The DFT calculations about the structure of host–guest complex species were carried out using the Orca program (version 4.2.0) with Gaussian 09 quantum computational package. The host–guest structure geometries of the resulting configurations were fully optimized at BLYP-D3/def2-SVP level of theory, , which combined with Becke–Johnson (BJ) damping function dispersion correction D3­(BJ) and the def2-SVP basis set. − A geometrical counterpoise correction scheme (gCP) to the def2-SVP for the intra- and intermolecular basis set superposition error was applied . The resolution of the identity (RI) approximation was used to improve the computational efficiency of our large-scale calculations .…”

Three-in-one: exploration of co-encapsulation of cabazitaxel, bicalutamide and chlorin e6 in new mixed cyclodextrin-crosslinked polymers

“…Being the polymer a large molecule the computational DFT study has been conducted on a model consisting of the drug encapsulated by either 1 or 2bCyD units chosen as the pbCyD seems the most promising for the drug delivery purpose. In previous works, DFT methods have been extensively used to study the inclusion process of drugs in bCyD, [52][53][54][55][56] with the inclusion of the dispersion correction method. 57 In these works, calculations of the interaction energy (IE), binding free energy, natural bond orbital (NBO) and natural population analysis (NPA) were used to investigate the inclusion process, while the non-covalent interaction method (NCI) 58 or independent gradient model (IGM) analysis 49 were employed to study indepth the non-covalent interaction in the host guest complex.…”