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The Nature of Interactions in Nicotinamide Crystal

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The Nature of Interactions in Nicotinamide Crystal Journal of Molecular Graphics and Modelling 51 (2014) 73–78 Contents lists available at ScienceDirect Journal of Molecular Graphics and Modelling journa l homepage: www.elsevier.com/locate/JMGM The nature of interactions in nicotinamide crystal a,∗ b,∗∗ Tomasz Misiaszek , Zaneta˙ Czyznikowska˙ a Institute of Physical and Theoretical Chemistry, Wrocław University of Technology, Wyb. Wyspianskiego´ 27, 50-370 Wrocław, Poland b Department of Inorganic Chemistry, Wrocław Medical University, Borowska 211, 50-556 Wrocław, Poland a r a t i c b s t l e i n f o r a c t Article history: In this study, we analyze the nature of intermolecular interactions in nicotinamide complexes appearing Accepted 17 April 2014 in conformations found in the crystal structure, including many-body effects. In doing so, we employ Available online 26 April 2014 symmetry-adapted perturbation theory based on density functional theory description of monomers, and we perform the many-body variational–perturbational interaction energy decomposition. The prin- Keywords: cipal finding of this study is that the stability of nicotinamide complexes is a complicated interplay of Nicotinamide crystal four (large in magnitude) interaction-energy components, i.e. induction, dispersion, electrostatic and Intermolecular interactions exchange repulsion. However, the last two contributions cancel each other out to a large extent. In the Density functional theory case of considered three-body complexes, the nonadditivity effects are found to be not important. Based Symmetry-adapted perturbation theory on the results of topological analysis of charge densities we characterized also the properties of short H · · · H contact and identified it as a weak noncovalent closed shell interaction. © 2014 Elsevier Inc. All rights reserved. 1. Introduction It is worth mentioning that nicotinamide exhibits ability to inhibit the oxidative damage. It was confirmed in the case of injury induced Nicotinamide (NAm) molecule appears to be very important by reactive oxygen species whose presence can lead to oxidation of precursor of many coenzymes responsible for redox processes protein and lipid peroxidation. Interestingly, the protective effect in liver, brain and erythrocytes. Its physiological functions were was bigger than in the case of tocopherol and ascorbic acid [8]. Due recognized already in the mid-1930s, when Warburg and Chris- to its particular importance, nicotinamide is the subject of many tian isolated nicotinamide (NAm) from the hydrogen-transporting studies concerning its physico-chemical properties. The recent sub- coenzymes NAD(H) and NADP(H), giving the first clue to its ject of interest is also the ability of nicotinamide to form co-crystals importance in metabolism [1]. About one decade later Elvehjem because of its well-known hydrogen-bonding moieties in the struc- discovered its nutritional significance [2]. Since then NAm has been ture. The presence of two nitrogens of pyridine and amide enables used successfully for the treatment of several deficiency conditions. to create reliable syntons with many active pharmaceutical ingre- One of the examples is the supplementation with NAm in the case of dients [9–12]. Co-crystal can be defined as a crystalline structure clinical depression. It has been shown that NAm enhances the effect composed of two or more different components in a stoichio- of tryptophan in supporting of brain serotonin levels [3]. Nicotin- metric composition stabilized by strong and directional hydrogen amide was also found to protect high-risk children from progres- bonds, – stacking and electrostatic interactions [13]. Although sion of clinical insulin-dependent diabetes. It was assumed that the co-crystals are known for a long time, it seems that their potential effect of nicotinamide involves the support of pancreatic cell func- is not fully exploited. Due to the diversity of crystal forms, active tion through the support of both NAD+ and DNA-protective enzyme pharmaceutical ingredients (AIP) and ability to improve their prop- poly(ADP-ribose) polymerase activity [4–6]. The study of Ieraci erties in clinical practice these are very attractive and challenging and Herrera on the ethanol-induced apoptotic neurodegeneration issues of pharmaceutical sciences. Indeed, co-crystal formation is showed protective effect of NAm. Such properties of nicotinamide an attractive route to modifications of physicochemical solid state can be used to prevent the damage in fetal alcohol syndrome [7]. properties such as stability, solubility and bioavailability without breaking or formation of covalent bonds [14–17]. It is proved that co-crystalization with nicotinamide can improve tableting behav- ∗ ior, dissolution performance and hygroscopic properties of drugs Corresponding author. Tel.: +48 713203606. ∗∗ [18]. So far, several co-crystaline structures of nicotinamide with Corresponding author. Tel.: +48 717840330. different AIPs have been determined. It is worth to mention here E-mail addresses: [email protected] (T. Misiaszek), [email protected] (Zaneta˙ Czyznikowska).˙ that in advance prediction if co-crystalization would be successful http://dx.doi.org/10.1016/j.jmgm.2014.04.007 1093-3263/© 2014 Elsevier Inc. All rights reserved. 74 T. Misiaszek, Zaneta˙ Czyznikowska˙ / Journal of Molecular Graphics and Modelling 51 (2014) 73–78 or not is still hardly possible [19]. Therefore, it is necessary to carry all of its components are basis set superposition error free due out plenty of experiments under many conditions with different to the counterpoise correction. At the MP2 level of theory, the techniques in order to propose active form of co-crystals. total intermolecular interaction energy of a 3-body complex can The knowledge about the non-covalent forces that cause the be decomposed in the following way [25,26]: stabilization of a molecular crystals is one of the most important MP2 HF (12) (20) (2) (2) E = E + + + E + E (3) and useful elements in crystal engineering, especially in control el,r disp exch-del,2 exch-del,3 of the stoichiometry and composition of co-crystals [20–22]. This (20) (12) forms the basis for the present study, which reports on the results where disp is the second order dispersion interaction; el,r of quantum-chemical calculations of the intermolecular interac- describes the electron correlation correction to the first order elec- tions in nicotinamide crystals, including many-body effects. The trostatic interaction and the remaining electron correlation effects (2) HF structures were taken from Cambridge Crystal Structure Database E are encompassed in the ex term. E is the intermolecular (CSD). In doing so, we aim at providing a better understanding of interaction energy at the HF level of theory: the nature of binding forces in the molecular crystal to elucidate EHF = (10) HL HL HF HF + + + E + E what might further contribute to the development of a strategy el exch,2 exch,3 del,2 del,3 (4) to predict and design the pharmaceutically relevant properties of (10) co-crystals involving nicotinamide. Additionally, we have investi- el is the electrostatic interactions of unperturbed monomer HL E gated the hydrogen bonds by means of periodic DFT calculations charge densities; ex stands for the associated exchange and atoms in molecule (AIM) theory. repulsion and Edel is the delocalization component. Moreover variational–perturbational scheme was applied in order to estimate 2. Computational methods the 2-body interactions in the considered crystal. All calculations of the decomposition of intermolecular interaction energy at the 2.1. DFT-SAPT calculations MP2/aug-cc-pVDZ level of theory were performed using the mod- ified version of the GAMESS US package [27–31]. In the present study, the components of the intermolecular interaction energy were obtained within the DFT-SAPT framework, 2.3. Atoms in molecules method which combines Kohn–Sham formulation of density functional theory (DFT) and symmetry-adapted intermolecular perturbation In the present study, the topological properties of electron den- theory, as implemented in the MOLPRO package [23]. In this sity in the considered complexes were assigned using the Quantum approach the total intermolecular interaction energy E is deter- int Theory of Atoms in Molecules (QTAIM) of Bader [32,33]. (1) E mined as a sum of first-order electrostatic energy el , second-order We estimated the properties of bond critical points (BCPs) local- (2) (2) (1) induction E , dispersion E and the exchange counterparts E , ized at the bond path linking the interacting species, especially the ind disp exch 2 (2) (2) electronic density at BCP, (rBCP), and its Laplacian, ∇ (rBCP). It E E exch-ind, exch-disp, respectively: 2 is known that negative values of ∇ (rBCP) imply concentration of (1) (1) (2) (2) (2) (2) electronic charge in the intermolecular region and its magnitude E = E + E + E + E + E + E int el exch ind exch-ind disp exch-disp (1) yields the information about the strength of interactions of consid- (2) ered systems. The positive values of Laplacian, in turn, correspond E The intramolecular charge-transfer contribution is included in ind, to the reduction of electronic charge in the intermolecular region. while the exchange terms describe the repulsive effects of electron The local kinetic G(rBCP), potential V(rBCP) and total H(rBCP) exchange between subsystems [24]. We estimated also the ı(HF) energy densities, estimated at the bond critical point can be also correction: useful in analysis of the weak intermolecular interactions. The HF (1) (1) (2) (2) ı = E − E − E − E + E electronic energy density of the local charge distribution may be (HF) int el (HF) exch(HF) ind(HF) exch-ind(HF) (2) calculated as the sum of the local kinetic and potential energy den- This contribution provides an estimation of higher-order induc- sities: tion and exchange-induction effects, that might be of particular H importance for hydrogen-bonded stabilized systems. All DFT-SAPT (rBCP) = G(rBCP) + V(rBCP) (5) calculations were performed assuming LPBE0AC exchange- The AIM calculations were performed using the AIM2000 program correlation potential with a hybrid xc kernel containing 25% of [34].
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