Electrostatic Terms Research Articles

The barrier to internal rotation in silabutenes: A density functional theory study

The potential energy surfaces (PESs) for internal were systematically investigated by using DFT with the B3LYP function. QTAIM, NBO, NEDA and BLW-ED were employed to study the origin of rotational barriers. The silabutenes with M1 = C–M2–M3 skeleton preferred the ac conformer and the M1 = Si–M2–M3 skeletons have the sp conformer. Silabutenes including SiSi double bond have three stable conformers, two different ac conformer and one gauche conformer. Internal rotation barriers (0.38–2.47 kcal/mol) vary with bond lengths (SiC, SiSi, CC), decomposed into steric, electrostatic, and hyperconjugation terms using NSA, NEDA, and NBO. A linear correlation (R2 = 0.78) links barrier heights to energetic differences between stable and metastable conformers. Understanding these factors aids in predicting and rationalizing rotational barriers in silabutenes, crucial for their chemical behavior and applications.

Recurrent Supramolecular Patterns in a Series of Salts of Heterocyclic Polyamines and Heterocyclic Dicarboxylic Acids: Synthesis, Single-Crystal X-ray Structure, Hirshfeld Surface Analysis, Energy Framework, and Quantum Chemical Calculations

A series of novel salts based on aromatic polyamines and 2,3-pyrazinedicarboxylic acid, such as C10H12N6O5 (1), C10H9ClN6O4 (2), C11H10N8O4 (3), and C14H17N16O5.5 (4) or 3,4-thiophenedicarboxylic acid, such as C10H10N4O4S (5), C10H9ClN4O4S (6), and C10H10N4O4S2 (7), were synthesized and characterized by single-crystal X-ray diffraction. All compounds crystallize in a monoclinic space group. The structure was subjected to complex Hirshfeld surface analysis, molecular electrostatic potential, enrichment ratio, and energy framework calculations. The influence of different cations on the packing of 3-carboxypyrazine-2-carboxylate and 4-carboxythiophene-3-carboxylate anions in the crystal lattice was studied. O…H/H…O interactions are the main contributor in all crystals. In addition, in a series of pyrazine-containing structures, N(C)…H/H…N(C) interactions have relevance, while in a series of thiophene-based compounds, C…H/H…C and S…H(O)/H(O)…S. In addition, Cl-based interactions are observed in compound 2. According to the enrichment ratio calculations, O…H/H…O and C…C are the most preferable interactions in all structures. The energy frameworks are dominated by the dispersive contribution, only in compound 3 is the electrostatic term dominant. The analyzed structures reveal intra- and intermolecular recurrent supramolecular synthons. In both series of crystals, the robust H-bonded centrosymmetric dimer R22(8) as homo- or as heterosynthon (in compounds 2, 3, 6, and 7) and the intramolecular synthon S(7) generated by O-H…O interactions (in compounds 2, 6, and 7) are present. The supramolecular patterns formed by π…π (C…C) and C-O(Cl,S)…C are also noticeable. Notably, a dual synthon linking the supramolecular chain via π…π interactions and the homosynthon R22(8) via N-H…N interactions is visible in both series of new salts. A library of H-bonding motifs at diverse levels of supramolecular architecture is provided. We extended the analysis of intramolecular H-bonding motifs to similar structures deposited in the Cambridge Structural Database. Another important feature is the existence of an intramolecular O…H…O bridge between two neighboring carboxylic groups as substituents in anions in compounds 3 and 5. In this context, we performed quantum theory of atoms-in-molecule calculations to reveal more details.

Theoretical description of hydride-hydride interactions in selected hydrogen storage materials.

The high content of hydride-hydride contacts Hδ-···δ-H in hydrogen storage materials appears to be relevant for hydrogen formation. At present time there is no consensus whether these contacts are attractive or repulsive. Accordingly, the main goal of this article is to shed light on physical factors which constitute homopolar hydride-hydride interactions Hδ-···δ-H in selected transition metal complexes i.e. HCoL4, L = CO,PPh3,PH3. In order to achieve this goal, the charge and energy decomposition ETS-NOCV approach along with the Interacting Quantum Atoms (IQA) and reduced density gradient (NCI) are applied for the bonded adducts L4CoH···HCoL4. Based on DFT and correlated methods it has been shown, that hydride-hydride interactions might be attractive and even far stronger than classical hydrogen bonds. The stability of the adducts is increased by phosphine ligand installation: overall Hδ-···δ-H bonding energy changes in the order: CO << PPh3 ~ PH3. It has been revealed that depending on monomer's conformations Hδ-···δ-H bonds are dominated by charge delocalization or London dispersion forces and the electrostatic term is also relevant. It is finally determined by IQA energy decomposition, that diatomic hydride-hydride interaction CoH···HCo is chameleon-like, namely, it is attractive in CO4CoH···HCoCO4, whereas the repulsion is unveiled in (CO)3(PPh3)CoH···HCo(CO)3(PPh3).

Solvation Enthalpies and Free Energies for Organic Solvents through a Dense Neural Network: A Generalized-Born Approach

A dense artificial neural network, ESE-ΔH-DNN, with two hidden layers for calculating both solvation free energies ΔG°solv and enthalpies ΔH°solv for neutral solutes in organic solvents is proposed. The input features are generalized-Born-type monatomic and pair electrostatic terms, the molecular volume, and atomic surface areas of the solute, as well as five easily available properties of the solvent. ESE-ΔH-DNN is quite accurate for ΔG°solv, with an RMSE (root mean square error) below 0.6 kcal/mol and an MAE (mean absolute error) well below 0.4 kcal/mol. It performs particularly well for alkane, aromatic, ester, and ketone solvents. ESE-ΔH-DNN also exhibits a fairly good accuracy for ΔH°solv prediction, with an RMSE below 1 kcal/mol and an MAE of about 0.6 kcal/mol.

Anion-Carbonyl Interactions.

Presented herein is the exploration of a novel non-covalent anion-carbonyl (X-···C═O) interaction using aromatic imides as receptors and halides as lone pair donors. Combined theoretical calculations and experimental methods including 13C NMR, IR, and crystallographic analyses were performed to provide the physical origin and experimental evidence of anion-carbonyl interactions. The EDA analysis (energy decomposition analysis) based on DFT calculation indicates that electrostatic terms are the dominant contributions for the binding energy while electron delocalization also significantly contributes alongside the electrostatic attraction. Orbital interaction (n → π*) involving the delocalization of halide lone pairs on the carbonyl antibonding orbitals was visualized with NBO (Natural Bond Orbital) analysis. 13C NMR and IR spectra demonstrated upfield chemical shifts and red-shift frequency of hosts upon the addition of halides, reflecting the effect of orbital overlap between the halide lone pairs and π* of carbonyl (n → π* contribution). The anion-carbonyl interactions were directly revealed by X-ray structural analysis of anion and benzene triimide complexes.

Calculating structure factors of protein solutions by atomistic modeling of protein-protein interactions

We present a method, FMAPS(q), for calculating the structure factor, S(q), of a protein solution, by extending our fast Fourier transform-based modeling of atomistic protein-protein interactions (FMAP) approach. The interaction energy consists of steric, nonpolar attractive, and electrostatic terms that are additive among all pairs of atoms between two protein molecules. In the present version, we invoke the free-rotation approximation, such that the structure factor is given by the Fourier transform of the protein center-center distribution function gC(R). At low protein concentrations, gC(R) can be approximated as e−βW(R), where W(R) is the potential of mean force along the center-center distance R. We calculate W(R) using FMAPB2, a member of the FMAP class of methods that is specialized for the second virial coefficient [Qin and Zhou, J Phys Chem B 123 (2019) 8203–8215]. For higher protein concentrations, we obtain S(q) by a modified random-phase approximation, which is a perturbation around the steric-only energy function. Without adjusting any parameters, the calculated structure factors for lysozyme and bovine serum albumin at various ionic strengths, temperatures, and protein concentrations are all in reasonable agreement with those measured by small-angle X-ray or neutron scattering. This initial success motivates further developments, including removing approximations and parameterizing the interaction energy function.

The molecular interaction of six single-stranded DNA aptamers to cardiac troponin I revealed by docking and molecular dynamics simulation.

Cardiac troponin I (cTnI) is a cardiac biomarker for diagnosing ischemic heart disease and acute myocardial infarction. Current biochemical assays use antibodies (Abs) due to their high specificity and sensitivity. However, there are some limitations, such as the high-cost production of Abs due to complex instruments, reagents, and steps; the variability of Abs quality from batch to batch; the low stability at high temperatures; and the difficulty of chemical modification. Aptamer overcomes the limitations of antibodies, such as relatively lower cost, high reproducibility, high stability, and ease of being chemically modified. Aptamers are three-dimensional architectures of single-stranded RNA or DNA that bind to targets such as proteins. Six aptamers (Tro1-Tro6) with higher binding affinity than an antibody have been identified, but the molecular interaction has not been studied. In this study, six DNA aptamers were modeled and docked to cTnI protein. Molecular docking revealed that the interaction between all aptamer and cTnI happened in the similar cTnI region. The interaction between aptamer and cTnI involved hydrophobic interaction, hydrogen bonds, π-cation interactions, π-stack interactions, and salt-bridge formation. The calculated binding energy of all complexes was negative, which means that the complex formation was thermodynamically favorable. The electrostatic energy term was the main driving force of the interaction between all aptamer and cTnI. This study could be used to predict the behavior of further modified aptamer to improve aptamer performance.

Molecular Hydrogen Acts as a Hydrogen Bond Proton Acceptor: From Protonated Betaine Tagging to the Weakest Hydrogen Bond.

In an attempt to gain further insights into the intermolecular interactions implied by Rizzo's group's cautionary tale related to molecular tagging in infrared multiple photon dissociation (IRMPD) spectroscopy with molecular messengers [Masson, A. . J. Chem. Phys. 2015, 143, 104313], in the present study, we provide an in-depth analysis of the noncovalent interaction between the molecular hydrogen and protonated betaine molecule in the gas phase. We aim to shed some new light on the fundamental issues concerning the wide diapason of hydrogen-bonding-type intermolecular interactions, with a wide variety of proton acceptors. We demonstrate that in the course of tagging the protonated betaine with molecular hydrogen from the OH group side, it is the σ bond of molecular hydrogen that plays the role of hydrogen-bonding proton acceptor. The tagging thus induces a small yet significant red shift of the protonated betaine O-H stretching mode. We investigate the performance of a wide range of density functional theory (DFT) functionals for the calculation of anharmonic vibrational frequency shifts of the studied system, which are essential for the correct interpretation of the experimental IRMPD data. For an accurate prediction of the OH stretching frequency shifts, specifically designed functionals such as Handy's group HCTH/407 should be applied. The empirical dispersion correction enhances the systematic overestimation of the anharmonic frequency shift, characteristic of the most widely used DFT functionals. Combining the full-wave function approach with the charge field perturbation and natural bond orbital (NBO) deletion analyses, we demonstrate that the frequency shift in the OH-tagged structure is governed by the σHH → σ*OH intermolecular charge transfer. This interaction stabilizes the OH-tagged dimer as well, in contrast to the dipole-quadrupole electrostatic interaction energy term. Topological analysis of the electron density reveals the presence of an intermolecular bond critical point with a positive value of the density Laplacian very close to the lower limit for hydrogen bonds. NCI analyses demonstrate that the OH···H2 interaction is weaker than the intramolecular CH···O one within the protonated betaine molecule, with the through of reduced density gradient appearing at less negative sign(λ2)·ρ values. Analyzing the O-H stretching vibrational potential with the second-generation absolutely localized molecular orbitals energy decomposition analysis (ALMO-EDA 2) revealed that in the case of betaineH(+) tagged from the OH group side, the permanent electrostatics (ΔEelec), polarization (ΔEpol), and charge-transfer (ΔEct) contributions to the total intermolecular interaction energy contribute favorably to the weak hydrogen bond formation and to the red shift of the fundamental O-H stretching frequency, the ΔEct contribution being the most significant in the last context. The Pauli repulsion term, on the other hand, favors an O-H stretching frequency blue shift as a consequence of the vibrational confinement effects.

Do electrostatic interactions make a difference in physics-based AutoDock4 scoring function?

Physics-based scoring function AutoDock4 is one of the most successfully applied tools in the area of structure-based drug design. However, current scoring functions are still far from being perfect. In a recent work highlighting the strengths and deficiencies of current scoring functions, we discovered that the residual error of ΔGbind predictions made by AutoDock4 is highly correlated to the presence of formally charged fragments in a ligand. In this work, we study how the use of the high-quality atomic charges, applied for contemporary force fields calculation, affects the quality of the experimental ΔGbind prediction by means of AutoDock4. We initially expected that the previously found discrepancy could be attributed to the Gasteiger charges used within AutoDock4. We show that AutoDock4 is, surprisingly, not sensitive to the charges used, and the use of QC-derived atomic charges does not lead to any statistical improvements. We also briefly discuss the role of the explicit empirical hydrogen bond term along with the electrostatic term.

SYNTHESES, CHARACTERIZATION, CRYSTAL STRUCTURES AND ANTIMICROBIAL PROPERTIES OF A NEW ORGANIC−INORGANIC HYBRID [4FBzTPP]2[CuBr4

This article presents a study on the synthesis and character of a new organic-inorganic hybrid [4FBzTPP]2[CuBr4](1) ([4FBzTPP]+ is 4-fluorobenzyltriphenylphosphinium) by XRD, SEM, FT-IR and UV-Vis. The XRD analysis showed that the hybrid 1 belongs to the triclinic space group P21 with b = 8.8600(10) Å, c = 16.4867(17) Å, α = 16.639(2) °, β = 96.342(4) °, V = 2415.6(5) Å3, and Z = 2. The hybrid consists of two [4FBzTPP]+ cations and one [CuBr4]2– anion, and the [CuBr4]2– exhibits a twisted tetrahedral coordination geometry with the average bond length between Cu−Br is 2.393 Å. The 3D network structure of 1 is formed by electrostatic terms and other intermolecular interactions. The hybrid material undergoes a direct optical transition and has energy gap values of 1.66 eV and 2.18 eV, indicating its potential as a semiconductor material for optical research. The hybrid material undergoes a direct optical transition and has energy gap values of 1.66 eV and 2.18 eV, showing that the hybrid material is a potential semiconductor material for optical research. In addition, the compound exhibited good antibacterial activity against E. coli and S. aureus.

The impact of chemical properties of the solid-liquid-adsorbate interfaces on the entropy-enthalpy compensation involved in adsorption.

Despite extensive studies on the thermodynamic mechanism governing molecular adsorption at the solid-water interface, a comprehensive understanding of the crucial role of interface properties in mediating the entropy-enthalpy compensation during adsorption is lacking, particularly at a quantitative level. Herein, we employed two types of surface models (hydroxyapatite and graphene) along with a series of amino acids to successfully elucidate how distinct interfacial features dictate the delicate balance between entropy and enthalpy variations. The adsorption of all amino acids on the hydroxyapatite surface is an enthalpy-dominated process, where the water-induced enthalpic component of the free energy and the surface-adsorbate electrostatic interaction term alternatively act as the driving force for adsorption in different regions of the surface. Although favorable interactions are observed between amino acids and the graphene surface, the entropy-enthalpy compensation exhibits dependence on the molecular size of the adsorbates. For small amino acids, favorable enthalpy changes predominantly determine their adsorption behavior; however, larger amino acids tend to bind more tightly with the graphene surface, which is thermodynamically dominated by the entropy variations despite the structural characteristics of amino acids. This study reveals specific entropy-enthalpy mechanisms underlying amino acid adsorption at the solid-liquid interface, providing guidance for surface design and synthesis of new biomolecules.

Insight into melting point differences of dinitroimidazoles and dinitropyrazoles from the perspective of intermolecular interactions.

Dinitroimidazole (DNI) and dinitropyrazole (DNP), along with their congeners, possess similar molecular structures but exhibit distinct melting points. To analyse and elucidate the fundamental reasons for property differences from the perspective of intermolecular interactions, we proposed a simplified approach named binding energy in clusters (BEC) in computing weak interactions within complex crystal systems. Based on the results of the symmetry-adapted perturbation theory (SAPT) calculations, an approximate estimation of the melting point range can be derived by taking into account the cumulative effect (energy of electrostatic, dispersion and induction terms) and repulsive effect (energy of exchange term) values. We have also proposed a formula for calculating the specific melting point, which indicates that stronger intermolecular interactions have a major impact on the melting point, while the distribution of weak interactions also affects the melting point. This work would provide an effective reference for molecular design and structure-performance analysis.

The Interplay between Protein Frustration and Hotspot Formation

Hotspots situated at protein-protein interfaces, allosteric and orthosteric binding sites, traditionally play a crucial role in the initial phases of drug discovery, as they are useful to identify druggable targets and guide the optimization of fragments into lead compounds. Despite the high level of protein frustration, which can be thought of as the percentage of residues that cannot independently achieve minimum energy due to tridimensional restraints, observed at those locations, limited efforts have been made to investigate any potential connection between the localized frustration and hotspots in proteins. This review paper aims to partially address this knowledge gap by proposing that the origin of hotspots is, at least in part, due to localized frustration in proteins. While there is no hard evidence to support this hypothesis, the results obtained by integrating in silico tools predicting hot spot locations, with those calculating localized protein frustration, suggest that druggable hotspots are surrounded by residues involved in frustrated contacts. Additionally, the inclusion of long-range electrostatic terms in the protein frustration calculation enables the identification of an equal to a higher number of frustrated residues. These observations indirectly suggest that localized protein frustration around druggable hotspots could guide the development of more potent leads.

A first-principles alternative to empirical solvent parameters.

The use of solvents is ubiquitous in chemistry. Empirical parameters, such as the Kamlet-Taft parameters and Gutmann donor/acceptor numbers, have long been used to predict and quantify the effects solvents have on chemical phenomena. Collectively however, such parameters are unsatisfactory, since each describes ultimately the same non-covalent solute-solvent and solute-solute interactions in completely disparate ways. Here we hypothesise that empirical solvent parameters are essentially proxy measures of the electrostatic terms that dominate solvent-solute interactions. On the basis of this hypothesis, we develop a new fundamental descriptor of these interactions, , and show that it is a self-consistent, probe-free, first principles alternative to established empirical solvent parameters.

Calculation of electrostatic free energy for the nonlinear Poisson-Boltzmann model based on the dimensionless potential

The Poisson-Boltzmann (PB) equation governing the electrostatic potential with a unit is often transformed to a normalized form for a dimensionless potential in numerical studies. To calculate the electrostatic free energy (EFE) of biological interests, a unit conversion has to be conducted, because the existing PB energy functionals are all described in terms of the original potential. To bypass this conversion, this paper proposes energy functionals in terms of the dimensionless potential for the first time in the literature, so that the normalized PB equation can be directly derived by using the Euler-Lagrange variational analysis. Moreover, alternative energy forms have been rigorously derived to avoid approximating the gradient of singular functions in the electrostatic stress term. A systematic study has been carried out to examine the surface integrals involved in alternative energy forms and their dependence on finite domain size and mesh step size, which leads to a recommendation on the EFE forms for efficient computation of protein systems. The calculation of the EFE in the regularization formulation, which is an analytical approach for treating singular charge sources of the PB equation, has also been studied. The proposed energy forms have been validated by considering smooth dielectric settings, such as diffuse interface and super-Gaussian, for which the EFE of the nonlinear PB model is found to be significantly different from that of the linearized PB model. All proposed energy functionals and EFE forms are designed such that the dimensionless potential can be simply plugged in to compute the EFE in the unit of kcal/mol, and they can also be applied in the classical sharp interface PB model.

Is there a Covalent Au(I)-Au(I) Bond in the trans-(AuX)2 (X = F, Cl, Br, I) Structure? A Post-Hartree-Fock and Density Functional Theory Study.

We present an exhaustive exploration of the driving forces dominating the interaction between gold atoms in the trans-(AuX)2, where X is a halogen ligand. This work provides insights into the nature of the gold-gold contact in the trans-(AuX)2. The geometries and energies were calculated at the MP2, CCSD(T), and DFT-D3(BJ) (B3LYP, PBE, and TPSS) levels of theory. The results show a short Au-Au distance, typical of a covalent bond, but with a weak interaction energy associated with noncovalent interactions. It is established that the physical contributions from polarization and the electronic correlation forces are the most relevant at the post-Hartree-Fock level of theory. Also, the electrostatic term is attractive but with low contribution. Finally, the Wiberg indices and NBO analysis exposed a small covalent character between the gold atoms, revealing that this contribution is insufficient to explain the stability of the dimers. It is concluded that a sum of contributions makes it possible to establish an attraction between the gold atoms in the dimers studied beyond a classical aurophilic interaction.

Influence of Protonation on the Norepinephrine Inhibiting α-Synuclein 71-82 Oligomerization.

The pathogenesis of Parkinson's disease (PD) is closely linked to the massive presence of Lewy vesicles and Lewy axons in the cytoplasm of neurons, mainly consisting of α-synuclein (αS). Norepinephrine (NE), whose secretion can be increased by exercise, has been demonstrated to prevent the fibrillation of αS and to break down the mature αS fibrils. In this work, we focus on the influence of protonation on the inhibitory ability of NE by using amyloid core fragment αS71-82 as a template. All-atom replica-exchange molecular dynamics simulations (accumulating to 33.6 μs) in explicit water were performed to explore the inhibitory effect of protonated and nonprotonated NE on αS oligomerization. Our results show that NE/NE+ can lead to a significant decrease in β-sheet content with increasing temperature, while isolated αS maintains relatively higher β-sheet conformations until 363 K, implying that both NE and NE+ can lower the critical temperature required for αS fibril decomposition. NE and NE+ also lead to the formation of less compact αS oligomers by preventing the backbone hydrogen bonds and the side-chain packing. The protonation would affect the binding affinity, interaction modes, and binding intensity of NE with αS. Interesting, NE and NE+ have a distinct binding free energy in the electrostatic and solvation terms, which mostly counter each other and produce a weak binding intensity with αS. Our work contributes to a better understanding of the inhibitory mechanism of NE and NE+ on αS oligomerization relevant to PD pathogenesis, which may provide clues for the design of antiamyloid medicine.

Interface Engineering of Carrier-Protein-Dependent Metabolic Pathways.

Carrier-protein-dependent metabolic pathways biosynthesize fatty acids, polyketides, and non-ribosomal peptides, producing metabolites with important pharmaceutical, environmental, and industrial properties. Recent findings demonstrate that these pathways rely on selective communication mechanisms involving protein-protein interactions (PPIs) that guide enzyme reactivity and timing. While rational design of these PPIs could enable pathway design and modification, this goal remains a challenge due to the complex nature of protein interfaces. Computational methods offer an encouraging avenue, though many score functions fail to predict experimental observables, leading to low success rates. Here, we improve upon the Rosetta score function, leveraging experimental data through iterative rounds of computational prediction and mutagenesis, to design a hybrid fatty acid-non-ribosomal peptide initiation pathway. By increasing the weight of the electrostatic score term, the computational protocol proved to be more predictive, requiring fewer rounds of iteration to identify mutants with high in vitro activity. This allowed efficient design of new PPIs between a non-ribosomal peptide synthetase adenylation domain, PltF, and a fatty acid synthase acyl carrier protein, AcpP, as validated by activity and structural studies. This method provides a promising platform for customized pathway design, establishing a standard for carrier-protein-dependent pathway engineering through PPI optimization.

Halide‐Triel Bonds between R3SiX (X=F, Cl and Br) and TrY3 (Tr=Al, B and Ga)

AbstractHalide‐triel bonds between halosilane donors and alane/borane/gallane acceptors are investigated considering 24 model complexes using quantum chemical calculations. Nature and strength of Si−X….Tr interactions (X=F, Cl, Br and Tr=Al, B, Ga) binding these complexes has been studied using Electrostatic Potential (ESP), Quantum Theory of Atoms in Molecules (QTAIM), Natural Bond Orbital (NBO), and Energy Decomposition Analysis (EDA) techniques. Basis Set Superposition Error (BSSE) corrected binding energy of the complexes ranges from −3.19 to −29.40 kcal mol−1. QTAIM parameters Laplacian and the total electron density at the Bond Critical Points (BCPs) indicate that the halide‐triel bonds studied here are largely electrostatic in nature (closed‐shell interactions); this has also been revealed through ESP analysis and EDA scheme. In addition, role of charge transfer in these halide‐triel bonds has also been established through NBO analysis. Two charge transfer orbital interactions are responsible for the primary interaction Si−X….Tr: and σ(Si−X) . EDA analysis identifies electrostatic term as the biggest contributor towards the binding of the complexes followed by the polarisation and dispersion terms in most of the complexes. Results of this study have relevance in the Si−F bond activation methodology in organic synthesis.

Alkali cations and H2 molecules on BN-doped carbon nanoflakes: Theoretical study

Non-covalent interactions of two cations (Li+ and Na+) and hydrogen molecules with coronene and hexagonal boron nitride models as well as their heterostructures (mBNC and pBNC) were studied by using a set of theoretical methods. It was shown that the shapes of boron nitride moieties in the graphene-like framework have a strong influence on the cation-π interactions. Decomposition of the interaction energy (Eint) was classified as consisting mainly of the inductive energy term (Eind), which is followed by the electrostatic term (Eel). Hydrogen adsorption, however, depends strongly on both these terms, and in the case of numerous adsorbed H2 molecules, the dispersion interactions (Edisp) are also of importance. The assessed hydrogen capacity of studied structures reaches 5.5 wt%. The present investigation explicitly shows that cation-π and, in some cases, hydrogen adsorption properties can be easily modified by a B and N atoms introduction in the carbon nanoflakes, and, hence, it establishes the route to the remarkable adsorbent materials.