Influence of photodegradation and surface modification on the graphene‐diclofenac physisorption process

Abstract

The present study provides the theoretical investigation of the mutual interaction of diclofenac and its photodegradation product with carbon materials. Because of the known weak interaction between graphene and aromatic molecules, the analyzed material surfaces are modified in order to maximize the mutual material: drug attraction. It is shown that the Stone‐Wales defects and single boron‐nitride pair doping only slightly influence the drug attraction, but the strongest impact is noticed for the introduction of the functional carboxyl group to the graphene sheet that preferably contains moreover single or double vacancies. Here, the additional stabilization with respect to the pristine graphene sheet is on the order of 7 to 10 kcal mol−1. A comparison of the adsorption of neutral acidic diclofenac molecule with its ionized form frequently applied in medical formulations shows that the negative charge accumulated on the carboxylate anion significantly increases the attraction of the drug by the graphene oxide (interaction energy changes from −27.45 to −46.33 kcal mol−1 upon ionization). Symmetry‐adapted perturbation theory applied for the decomposition of the interaction energy into the physically justified components confirms that all the investigated structures are governed by dispersion forces. Supermolecular MP2‐coupled approach with improved dispersion description allows to conclude that common density functional theory (DFT) functionals, including double hybrids with spin‐component scaling and dispersionless Pernal and Podeszwa functional, perform qualitatively well in the case of (modified‐) graphene materials, however, need to be applied with care for their boron‐nitride analogs.

Density functional theory analysis for H2S adsorption on pyridinic N- and oxidized N-doped graphenes

“…The first factor that determines the amount of the interaction energy is reported with the idea of attractive force (intermolecular force) that acts between materials caused by the transfer of charge. 75,76 Fig. 4 shows electric charges of adsorbed H 2 S and its surrounding atoms: N and O.…”

Gas Phase Computational Study of Diclofenac Adsorption on Chitosan Materials

“…On the other hand, comparison of the results of the present study to our previous study for diclofenac physisorption on graphene allows to assume that chitosan may be still a feasible adsorbent. SCS-SAPT0 interaction energies for graphene-diclofenac attraction are in the range of −16 to −11 kcal/mol, depending on the surface modification, and strong dispersion character is noticed for all of the analyzed structures [61]. Contrarily, in chitosan-diclofenac complexes, for pristine biopolymer chains interactions of the order of −30 kcal/mol are available and the supermolecular approach shows that they can increase to −40 or even −50 kcal/mol upon chitosan grafting with long alkyl substituents.…”

“…For comparison, the ranges of diclofenac-material interaction energies from Table 3 are given in the last column. For completeness, the lowest panel of Figure 18 presents the supermolecular B97-D3/jun-pVDZ energy range obtained in our previous study [61]. This range regards different structural modifications of an analyzed carbon material: from carboxylated graphene with the interaction energy toward DFH equal to −14.55 kcal/mol to a carboxylated material with double vacancies, significantly deformed from planarity, exhibiting −29.81 kcal/mol attraction toward the drug.…”

“…Supermolecular interaction energy ranges for chitosan dimers (upper panel), diclofenac:chitosan (middle panel) and diclofenac:graphene complexes[61] (lowest panel).…”

Robust Magnetized Graphene Oxide Platform for In Situ Peptide Synthesis and FRET-Based Protease Detection

“…Graphene oxide (GO) is a two-dimensional, atomically thin carbon material with good physisorption for diverse molecules, high water dispersibility, facile surface modification capability, and high biocompatibility [ 1 , 2 , 3 , 4 , 5 , 6 , 7 , 8 , 9 , 10 ]. Various chemicals can be immobilized on functionalized GO through the use of amide bonding, diazonium salts, atom transfer radical polymerization (ATRP), or click chemistry [ 11 , 12 , 13 , 14 , 15 , 16 ].…”