Search

Additive engineering plays an important role in realizing high efficiency organic solar cells (OSCs). The introduction or residual of additives usually increases the energetic disorder of the active layer, which in turn causes a significant reduction of the open-circuit voltage (V OC). Herein, this work proposes a novel additive design approach, that is, using the highly electronegative groups trifluoromethyl and trifluoromethoxy to replace one bromine atom of 1,3,5-tribromobenzene (TBB) to obtain 3,5-Dibromobenzotrifluoride (DBTF) and 3,5-Dibromo-triffluoromethoxybenzene (DBOF). This series of additives can induce strong π-π coupling with acceptor, modulating molecular crystallization and orderly stacking, and thus reducing the non-radiative energy loss and energetic disorder of the OSCs. Furthermore, DBTF and DBOF have good volatility and can be removed from the active layer without any post-processing. Consequently, a high power conversion efficiency (PCE) of 18.78 % is obtained in D18: Y6-based OSCs and a remarkable PCE of 19.19 % is realized in D18-Cl/ Y6-based OSCs. Compared with the OSCs without or with conventional TBB additives, the DBOF-treated OSCs effectively suppress the reduction of V OC while enhancing PCE. This work provides guidance for the design and synthesis of additives with selectivity, auto-removability, and the ability to reduce the energetic disorder of the OSCs. [Display omitted] • A new additive selection strategy is proposed which can simultaneously improve the V OC , J SC , FF and PCE of OSCs. • The additives can selectively form π-π interactions with acceptor, optimize the micro-structure of acceptor. • The volatile liquid additives can be completely removed from the active layer without any post-treatment. • The optimized device obtained a high PCE of 19.19 %. [ABSTRACT FROM AUTHOR]

[Display omitted] • Three conformations, labeled A, B, and C were obtained from the interaction of XCN with CH 3 NH 2. • Conformation A is stabilized by cyclic TB-HB, while conformations B and C are stabilized by linear TB and XB interactions. • The halogen ligand belonging to the XCN played a key role in the interaction energy. • Conformation C is significantly more stable compared to the other two conformations. • MEP, EDA, QTAIM, NBO, and NCI were used to analyze the complexes. In this study, quantum calculations were conducted to investigate the nature, formation mechanism, and properties of complexes resulting from the interaction between methylamine (MA) and halogen cyanide molecules (XCN, X = F, Cl, Br, and I). Three types of complexes were formed from the interaction of MA with XCN, characterized as Tetrel bond-hydrogen bond (TB-HB), Tetrel bond (TB), and Halogen bond (XB), denoted by symbols A, B, and C, respectively. The data obtained from the interaction energy indicated that complexes with structure C are significantly more stable compared to the other two structures. Molecular electrostatic potential map (MEP) analysis revealed that the size of the σ-hole of the halogen atom ligand plays a crucial role in the stability of structure C complexes. To further evaluate the properties of the resulting complexes, various analyses were conducted, including Molecular electrostatic potential map (MEP), Geometry optimization, Spectroscopy, Interaction energy (SE), Natural bond orbital (NBO), Atoms in molecules (AIM), Non-covalent interaction index (NCI), and Energy decomposition analysis (EDA). [ABSTRACT FROM AUTHOR]

Pterostilbene (Pte) is a dietary phenolic compound derived from plants that offers numerous physiological advantages. Nonetheless, its low water solubility and limited oral bioavailability restrict its bioactivity. To address these limitations, nanoparticles were prepared using anti-solvent precipitation method. Optimal nanoparticles were achieved at a 10:1 mass ratio of whey protein isolate (WPI) to Pte, resulting in a particle size of 104.54 nm, a polydispersity index of 0.42, and an impressive encapsulation efficiency of Pte at 85.02%. The water solubility of Pte in the nanoparticles was found to be 53.14 times higher than that of free Pte and remained stable under various environmental conditions. Furthermore, the DPPH and ABTS+ free radical scavenging activities of the nanoparticles were maximized at 55.58% and 92.97%, respectively. Pte release from WPI-Pte nanoparticles was well-fitted to Korsmeyer-Peppas model and followed a non-Fickian mechanism controlled by both diffusion and erosion. This environmentally friendly, straightforward, and efficient approach shows promise for large-scale production of Pte products with amplified health benefits. [Display omitted] • Pte had a 53.14-fold increase in its water solubility complexed with WPI. • WPI-Pte had better antioxidant activity, thermal and photostability than that of Pte. • Pte release from WPI-Pte (in SGF) was well-fitted to Korsmeyer-Peppas model. • Pte followed a non-Fickian mechanism controlled by both diffusion and erosion. [ABSTRACT FROM AUTHOR]

[Display omitted] • Molecular packing and supramolecular geometry of Cu(II)-catecholase is significant. • The systems are excellent catalyst with reversibly oxygen binding with lesser-known packing pattern. • Cu(II)system with variable auxiliary groups are reported with detailed NCI. • Supramolecular arrangement of these systems are reported. • The study enables the interaction efficacy of catecholase with macromolecules. Understanding of molecular packing is one of the favorable modes to study the mechanistic behavior of a supramolecular system. The present study aims in analyzing the molecular packing and supramolecular arrangement of Cu+2-catecholase system [C 13 H 13 BrCuN 4 O 2 (System A) , C 14 H 17 BrCuN 4 O 3 (System B) , and C 20 H 36 Cl 2 Cu 2 N 4 O 11 ((System C)] with variable auxiliary groups. These systems are well studied for their reversible binding with oxygen and catalytic property towards oxidation of ortho -diphenol. The primary novelty of such study is elucidating the architecture of auxiliary part of the system whose influence is studied but not understood in terms of the molecular packing. The respective supramolecular arrangement of the Cu (II) systems having such auxiliary part is reported herein which illustrates the interaction efficacy with macromolecules like proteins. The respective non covalent interactions (NCI) of aforementioned three antiferromagnetic Cu (II) species are reported using Hirsfeld analyses which also helps in the correlation of structure–property interaction. [ABSTRACT FROM AUTHOR]

[Display omitted] • Graphyne is explored as a carrier for Purinethol drug. • Graphyne has significant therapeutic potential as a drug carrier. • The DFT calculation was used to study the interaction of the drug Purinethol with graphdiyne. • The adhesion energy of the Purinethol drug on the graphydine surface was calculated at about −1.87 eV. Within this piece of research, DFT calculations were undertaken in order to investigate the drug-loading performance of graphyne for Purinethol. In order to evaluate the possibility of using graphyne as a carrier, the energetic, geometrical and optimized attributes of graphyne, Purinethol, and the complex of graphyne and Purinethol were investigated. We investigated three sites, namely a, b and c, in the structures of Purinethol for its interaction with graphyne. The most suitable interaction was the one in which sulfur and nitrogen atoms were involved. Purinethol had an interaction with graphyne with the adhesion-energy of −1.87 eV in the gaseous phase. The non-covalent interaction analysis was performed to explore the interaction of graphyne with Purinethol. Based on the analysis results, the interaction forces of the complex of graphyne and Purinethol were weak. The HOMO-LUMO analysis and charge-decomposition analysis were performed to describe the charge transported from Purinethol to graphyne during the formation of graphyne and Purinethol. The results demonstrated the possibility of using graphyne as a suitable carrier for Purinethol. The theoretical results obtained within this work can inspire researchers to find novel 2D nanomaterials for drug delivery purposes. [ABSTRACT FROM AUTHOR]

Conductive hydrogel-based electronic skins (e-skins) have attracted great attentions in health monitoring, human-machine interactions, and soft devices. Yet, broad challenges still remain in manufacturing of high-performance units, ingenious assembly of devices and developing of multimodal applications. Here, a typical strategy of combined covalent crosslinking and dynamic non-covalent interaction (multiple hydrogen bonds and electrostatic complexation) is used to prepare the ultra-durable polyacrylic acid (PAA)/ chitosan (CS)/ Ti 3 C 2 T x (MXene) conductive hydrogel. It exhibits matched modulus for human skin, subtle mechanical hysteresis behavior (η=0.27% of 200% stretch, energy loss coefficient), great fatigue-resistant stability (>99%, 400% strain), robust interface adhesion (∼30 kPa) and essential biocompatibility. Benefited of such high performance, a series of hydrogel-based devices are further assembled to demonstrate the multi-mode and multi-scenario applications, including the strain and temperature sensors, triboelectric nanogenerator. Clearly, thereby this work provides a new toolbox for the rational design of high-performance hybrid hydrogel, and points out a general route for further hydrogel-based device assembly and multimodal applications. [Display omitted] • Conductive hydrogel is well-designed through interpenetrating molecular networks and hydrogen bond engineering. • Conductive hydrogel has high adhesion, skin-matched modulus, hysteresis-free and fatigue-resistant features. • Hydrogel electrode supports strain and temperature sensing, and TENG applications. [ABSTRACT FROM AUTHOR]

[Display omitted] • Pure and metal-doped C 3 N nanosheets were introduced for the drug delivery system. • The Al atom, the attributes of PC 3 NNS changed, thereby increasing the adhesion process of Cis-P. • The NCI and RDG analysis were performed to examination the main interactions. This research focuses on investigating how a targeted drug delivery system (DDS) can improve distribution and bioavailability of a drug on tumor cells. Specifically, study examines the use of pristine and Al-doped graphitic carbon nitride (C 3 N) sheets as the delivery system. By employing density functional theory (DFT), researchers analyze interaction between anticancer drug cisplatin (Cis) and sheets. Results demonstrate that doping process modifies characteristics of pristine sheets, leading to improved adsorption of anticancer drugs. Al-doped sheet exhibits a cohesive energy within range of 4.96 eV, indicating its high stability. Present work has uncovered that adsorption of Cis drug over pristine C 3 N sheet is weak, with low adsorption energy (E ads) values of approximately −3.26 eV and −2.19 eV in a gaseous (aqueous) phase, respectively. However, E ads is significantly enhanced by approximately 85.92 % through introduction of Al doping in pristine C 3 N sheet. Primary interactions within the complexes are examined employing non-covalent interaction (NCI) analysis, utilizing a reduced density gradient (RDG) map. Cis@Al-C 3 N complex reveals that non-covalent interactions have a significant role in drug adsorption. Moreover, NCI indicates van der Waals interactions exert a substantial impact on interaction between carrier sheets and anticancer drug. Present investigation sets foundation for future research focusing on utilization of doped C 3 N sheets as effective drug carriers in targeted DDSs, potentially benefiting a wide range of drugs. [ABSTRACT FROM AUTHOR]

[Display omitted] • The interaction of VCM with BNNS, BNAlNS, and BNGaNS are studied. • To study the adsorption processes, the results of an NBO analysis are analyzed. • To unravel the nature of intermolecular interactions a QTAIM analysis is applied. • NCI analysis were performed to consider the non-covalent interactions. Utilizing density functional theory, an investigation was conducted to scrutinize the nature of interactions between the vinyl chloride and the pristine, Al-, and Ga-doped boron nitride nanosheets. A range of functionals, namely B3LYP-D3, PBE0, ωB97XD, and M06-2X, were meticulously selected for all structural configurations. Each functional was harmoniously coupled with the 6-311G(d) basis functions. In-depth analysis of the electronic sructure was accomplished through a comprehensive examination of the total density of state. Furthermore, the examination encompassed the application of quantum theory of atoms in molecules, natural bond orbitals, and non-covalent interaction approaches to elucidate the underlying nature of the gas-nanosheet interactions. Remarkably, the insertion of dopant atoms into the nanosheets resulted in a striking alteration of the location of the HOMO-LUMO energy gap. Among all the adsorbents, Ga-doped system emerged as the preeminent material, exhibiting superior potential for deployment in the creation of sensors or gas removal apparatuses. [ABSTRACT FROM AUTHOR]

Non-covalent interaction is believed to play a vital role in stabilizing various complex chemical species. Herein, we have undertaken a theoretical study to understand the nature and extent of non-covalent interaction between the aromatic surfaces of benzene and its substituted derivatives with hydrogen bond donors as well as lone pair containing molecules. Molecular electrostatic potential (MESP) calculation has been used to identify the attractive zones of the aromatic surface. Symmetry adopted perturbation theory (SAPT) calculations reveal that the stability of these interactions is dominated by both electrostatic as well as dispersion interaction. Non-covalent interaction plot (NCI) analysis provided the qualitative visualization of the interaction while quantum theory of atoms in molecules (QTAIM) proved the existence of this interaction through the formation of bond and cage critical points. [ABSTRACT FROM AUTHOR]

An accurate long-range corrected density functional theory (CAM-B3LYP) is used to optimize hydroxycarbamide (HC) with pristine/Fe-doped boron nitride nanotubes (Fe-BNNTs). In order to investigate the more detailed mechanism of their interactions, Natural Bond Orbital (NBO), Quantum Theory of Atoms in Molecules (QTAIM), and Frontier Molecular Orbital (FMO) calculations are implemented. Weak interactions such as hydrogen bonds and Van der Waals’ dispersion are analyzed via the non-covalent interaction index (NCI) as well as the reduced density gradient (RDG) analyses. The molecular electrostatic potential and density of state spectra for all complexes are obtained. The local reactivity of the drug molecule is studied using the Fukui function. Adsorption energies in the gas phase and solution (via IEFPCM model) are also calculated. Based upon the results, all complexes are energetically favorable, especially in the aqueous phase. The calculated results showed that Fe doping in BNNT increases drug-nanotube interaction, especially in case Fe substitutes nitrogen atom. [ABSTRACT FROM AUTHOR]

A computational analysis based on the “Atoms in Molecules” i.e. AIM formalism; of the molecular forces present within 3-Hydroxy-2-pyridin-2-yl-propenal (HPYP) has been undertaken in this contribution. The study presents a critical argument on the regulatory role(s) of hydrogen bonds (HBs) and other non-covalent interactions, viz. H···H and N···O/O···O; toward the structural features as well as global stabilization and/or destabilization of the aforesaid molecular system. Furthermore, to acquire a comprehensive account of the aromatic stabilization of the framework in the presence of the concerned non-covalent interactions; Nucleus Independent Chemical Shift (NICS) descriptor has been employed. [ABSTRACT FROM AUTHOR]

[Display omitted] • The competition between σ-hole and π-hole was evaluated. • Hydrogen interaction is the dominant interaction. • The amount of CT between orbitals participating in the interaction was evaluated. • The nature of the type of interactions was determined with QTAIM. • Electronegativity of halogens played an essential role in the strength of interaction. The interaction between phosgene and hydrohalides resulted in the formation of Hydrogen, Tetrel, and Halogen bonds, which were analyzed using MP2/aug-cc-pVTZ level quantum chemistry calculations. A combination of geometrical, spectroscopic, and energetic parameters was used to analyze the obtained complexes. The most stable complexes were made by Hydrogen, Tetrel, and Halogen bonds, respectively. The electronegativity of the halogen atom determined how strong the interactions were. Natural bond orbitals (NBO), atoms in molecules (AIM), and molecular electrostatic potentials (MEPs) were used to analyze the nature and characteristics of all three types of interactions. [ABSTRACT FROM AUTHOR]

In the light of interacting quantum atoms (IQA) and natural energy decomposition analysis (NEDA) the nature of different types of beryllium bonds is studied. IQA intra-atomic (self) energies indicate that, in most of the traditional beryllium bonds (in which the Lewis base is a lone pair donor), π -Be bonds (Lewis base is an unsaturated molecule) and also the Be–Ng (noble gases) interactions, the beryllium atom is stabilized upon complex formations. According to IQA inter-atomic energy components, the Be ⋯ Y bonds (Y is an atom in the Be-bond acceptor that is connected directly to the beryllium atom) have a dominant classical electrostatic character. However, in the IQA partitioning of total inter-molecular interactions, the contributions of non-classical (exchange–correlation) terms are non-negligible. Natural energy decomposition analysis of traditional and π -Be bonds indicate that the attractive interactions come from both the electrical and charge transfer terms. The electrical term in the Be–Ng bonds is negligibly small and the charge transfer is the most dominant contributor in the interaction energy. [ABSTRACT FROM AUTHOR]

[Display omitted] • The energetic, geometrical, topological and molecular orbital descriptors indicate that the chalcogen bond is stronger than the pnicogen bond. • The presence of multiple interactions in a complex reduces the strength of individual interactions, which represents a negative shared presence in the system. • The cooperativity effects for chalcogen bond are stronger than those of pnicogen bond. • Cooperativity energy indicates that the ternary and quaternary complexes is less stable than in binary complexes. • Evaluation of the aromaticity the triazine ring show that with an incerement in the numbers of non-covalent interactions, the aromaticity character of TA ring decreased. In the present study, the strength, nature and cooperativity effects of chalcogen and pnicogen bonds in a set of complexes between the triazine (TA) with SHF and PH 2 F are investigated at M06-2X/6–311++G (d, p) and CCSD/6–311++G (d, p) levels of theory. According to the results, the absolute values of complexation energies of chalcogen bonded systems are greater than the corresponding pnicogen bonded complexes. The simultaneous presence of two or three non-covalent interactions leads to negative cooperativity effects. Furthermore, the electron density values of chalcogen bonded complexes are more than their pnicogen ones, which emphasizes the stronger interactions in the former systems. Also, the Lp N → σ* X-F interaction has been attenuated in the presence of two or three interactions, which is attributed to the presence of negative cooperativity effects. Finally, the aromaticity indices values show with an increase in the number of non-covalent interactions, the TA ring aromaticity character is decreased. [ABSTRACT FROM AUTHOR]

[Display omitted] • Optimized geometries of the complexes between eight pyrimidine ring and methane were calculated using DFT technique. • SAPT0 analysis was performed to decompose the interaction energy into various physically meaningful terms. • Non-covalent index and atoms in molecule analysis were performed to visualize the non-covalent interactions between the interacting fragments in each complex. • Second order perturbation energies were calculated to investigate the orbital interactions. In the present study alkyl-π interactions between methane and the pyrimidine heterocyclic systems have been studied. Interaction energies were calculated using the B97D/def2-TZVPP level of theory. Energy decomposition analysis (EDA) using SAPT0/ jun-cc-pVTZ method revealed that the interaction energy is mainly dispersion and electrostatic with a minor contribution from induction energy. Non covalent index analysis was performed to visualize the interactions between the fragments of the studied complexes and atoms in molecule (AIM) study were done to investigate the bond critical points (BCP). The natural bond order (NBO) analyses were carried out to study the donor-acceptor orbitals and the second-order perturbation energies. Interaction energy, AIM study and NBO analysis revealed that the alkyl-π interactions involving the pyrimidine heterocyclic systems become stronger with the presence of various substituents on the pyrimidine ring. [ABSTRACT FROM AUTHOR]

[Display omitted] • Two major driving forces for the host-guest complex formation, i.e. the host-guest non-covalent interaction and the hydrophobic interaction, are found to work in opposition, i.e. if one is strengthened, the other is weakened. • The binding poses of DMCD complexes reconcile the non-covalent interaction and hydrophobic interaction superiorly. • For β-CD and its guests, the polarizability significantly decreases after the formation of the inclusion complexes. For DMCD and its guests, the formation of the inclusion complexes causes little change in the polarizability. • Compared to PM3, DFT-D3 predicts more host-guest intermolecular H-bonds and produces more accurate binding free energy in vacuum. Naphthalenes, a class of persistent organic pollutants, are difficult to remove from environment due to their low water solubility. β-cyclodextrin (β-CD) and its derivatives can encapsulate these compounds and enhance their solubility. For OH-substituted naphthalenes, several inclusion complexes with β-CD and 2,6-di-methyl-β-CD (DMCD) of varying stabilities were reported. However, the role of non-covalent interaction was not defined and the binding mechanisms remain vague. We use a molecular dynamics/quantum mechanics/continuum solvent model to explore the inclusion mechanisms of these systems. Both the measured binding modes and binding trend are well reproduced by our computations. The host-guest non-covalent interaction favors the β-CD complexes, while the hydrophobic interaction favors the DMCD complexes, and the latter plays a more important role in determining the binding trend. A correlation between the polarizability of the inclusion complex as measured by its dipole moment and hydrophobic interaction is also revealed. [ABSTRACT FROM AUTHOR]

Production of polychlorinated biphenyls (PCBs) was banned a long time ago because of their harmful health effects but humans continue to be exposed to residual PCBs in the environment. In this study, the susceptibility of human nuclear receptors to binding by PCBs was investigated using molecular docking simulation. Findings revealed that PCBs belonging to ortho -substituted, mono- ortho -substituted and non- ortho -substituted congeners could bind to agonistic conformations of androgen (AR), estrogen (ER α and ER β), glucocorticoid (GR) and thyroid hormone (TR α and TR β) receptors as well as antagonistic conformation of androgen receptor (AR an) but only ortho -substituted and mono- ortho -substituted PCBs could bind to estrogen receptors in their antagonistic conformations (ER α an and ER β an). Further molecular docking analyses showed that PCBs mimic the modes of interaction observed for the co-crystallized ligands in the crystal structures of the affected receptors, utilizing 81%, 83%, 78%, 60%, 75%, 60%, 86%, 100% and 75% of the amino acid residues utilized by the co-crystallized ligands for binding in AR, AR an, ER α, ER α an, ER β, ER β an, GR, TR α and TR β respectively. This computational study suggests that PCBs may cause endocrine disruption via formation of non-covalent interactions with androgen, estrogen, glucocorticoid and thyroid hormone receptors. [Display omitted] • Susceptibility of 12 nuclear receptors to binding by PCBs was investigated in silico. • Steroid and thyroid hormone receptors were found to be susceptible to binding by PCBs. • PCBs may cause endocrine disruption in humans via nuclear receptor binding. [ABSTRACT FROM AUTHOR]

• Organotin(IV)-phosphoric triamide complexes including iphosphoric triamide ligand with a segment (O═)P[ N ] 3) are explored to investigate various properties by means of the DFT calculations. • The connectivities around tin center, especially Sn...O(═P) contact, in such complexes are fully analyzed by QTAIM method. • Intermolecular interactions in the crystal structures are studied by using Hirshfeld surface analysis. Different computational investigations by using help of DFT (density functional theory), QTAIM (quantum theory of atom in molecule) and HS (Hirshfeld surface) approaches are carried out to evaluate the various properties, especially Sn...O interactions, of some organotin(IV)-phosphoric triamide (OP is introduced as the phosphoric triamide ligand with a segment (O═)P[ N ] 3) complexes. Among the most important results of this study is the absence of a net Sn-O bond between Sn(IV) center and O atom of P═O group (of OP ligand) in the segment Sn(CH 3) 2 Cl 2 (OP) 2 , where no bond critical point (BCP) is found along the path connecting tin and oxygen atoms. However, a survey of other connectivities (such as Sn...C and C/Cl...O contacts) suggests a weak non-covalent interaction (with ionic in nature) for Sn...O(═P) in the studied complexes. DFT studies show that orientation of OP ligands around tin (tran s or cis) is important for the strength of Sn...O interactions; so that a slightly higher strength is found in trans (OP)-form six-coordinate complexes of 1 – 3. Furthermore, a precise exploration of the intermolecular interactions by using Hirshfeld surface analysis reveals that the H...O/O...H (for 1 – 4) and H...Cl/Cl...H (for 1 – 5) contacts are favoured. A characteristic Sn....Cl contact with a high enrichment ratio is explored in five-coordinate complex 5. Finally, the presence of normal intermolecular interactions in the crystal structures of 3 and 4 is aligned with the lower chemical reactivities of these structures. [ABSTRACT FROM AUTHOR]