Molecular Electrostatic Potential Analysis Research Articles

Efficient removal of tetracycline by a novel bimetallic nickel/copper-loaded biochar: The crucial roles of π-π interaction and complexation

The development of a novel type of high-efficient biochar (BC) is important for the removal of tetracycline (TC). In this study, a bimetallic nickel/copper-loaded BC (Ni/Cu-BC) was synthesized, which had not been used for TC removal and lacked research on its safety and stability. The adsorption process was more likely to be monolayer chemical adsorption from the experiment. The density functional theory (DFT) calculation revealed that the interaction energy (Eads), energy gap (Eg) and dipole moment (P(D)) confirmed that the bimetallic loading improved the adsorption strength of the BC to TC. Moreover, the distribution of Ni/Cu-BC surface charge was considerably different from BC after bimetallic loading, and local polarization occurred according to the analysis of molecular surface electrostatic potential (ESP). It was demonstrated that the π-π interaction and complexation played a crucial role in the removal of TC. Finally, the functional groups of Ni/Cu-BC in removal were in the following order: CO > CC > NH2 > MO > CO. This study proves that Ni/Cu-BC is a novel, high-efficient, safe and reusable adsorbent. Overall, this study provides a new perspective on the design of BC and develops its environmental applications.

Engineering green MOF-based superhydrophobic sponge for efficiently synchronous removal of microplastics and pesticides from high-salinity water.

Microplastics (MPs) and pesticides are becoming an intractable environmental issue due to their wide spreading and non-degradable nature, posing serious threat to ecosystem and human health. To settle such dilemma, this work reasonably designed a superhydrophobic MOF-based coated sponge (ODSOSS/TiO2/Ni-MOF/PDA@Sponge) through the combination of an environmentally friendly in-situ supersaturated coprecipitation and polysesiloxane modification method. Among them, (I) the introduction of polydopamine (PDA) not only improves the adhesion between coatings and sponge, but also enhances the growth of MOF structure through complexation. (II) The obtained Ni-MOF shows large-area microscale anthemy structure with multilayered flaky texture, forming heterogeneously hierarchical structure with the deposited TiO2 nanoparticles, which promotes photodegradation ability of TiO2 owing to great specific surface area of Ni-MOF. (III) The high specific large area Ni-MOF supplies sufficient action sites for linkage of PDA and polysesiloxane molecules with unique nanocage-like structure, thus further greatly increasing adsorption force for various pollutants. (IV) The superhydrophobicity protect the porous channels of MOF from contamination of various absorbed pollutants, while TiO2 nanoparticles effectively photodegrade the absorbed organic pollutants, endowing the sponge superior recyclability. The superhydrophobic sponge selectively rapidly and synchronously adsorbs various MPs (maintained almost 100% after 60 cycles) and pesticides (adsorption rates 71.6%-95.1%) from high-salinity water. The large-area sponge (9cm×6cm×1cm) simultaneously removes almost 100% MPs (40mg/L), Sudan Ⅲ (10mg/L), kerosene (30mL/L), and four pesticides (10mg/L) within 1min. Particularly, four pesticides are quickly photocatalytic degraded by the coated sponge. The free radical capture trials show that hydroxyl radicals (·OH) are the main active species of pesticide degradation. Furthermore, we reveal the negative centers where pesticide molecules are most vulnerable to ·OH attack, on basis of the charge distribution and molecular electrostatic potential (MEP) analysis. The adsorption mechanisms are carefully clarified through theoretical calculation and experimental data. This work not only provide an effective superhydrophobic candidate for MPs and pesticides removal in a broad applicable scope (especially in high-salinity wastewater), but also opens a new strategy for environmental remediation.

Microwave assisted green synthesis, Single crystal XRD, DFT, Hirshfeld surface analysis, Antibiofilm, Anti-inflammatory activity and Molecular docking study of 4-(4-Fluorophenyl)-5-methyl-1,3-thiazole-2-amine

The title compound 4-(4-Fluorophenyl)-5-methyl-1,3-thiazole-2-amine was synthesized by the green microwave irradiation method and the structure was confirmed by spectroscopic techniques. Single crystal X-ray diffraction study was performed to investigate the crystal structure of the title compound. Further, the molecular structure was optimized by density functional theory (DFT) calculations using the B3LYP/6-311G++ (d, p) basic set and compared with X-ray diffraction data. DFT optimized structure, geometrical parameters and IR spectra of the title compound showed excellent correlations with the experimental results. The chemical reactivity and stability of the title compound were studied by molecular electrostatic potential (MEP) and Frontier molecular orbitals (FMOs) analysis. Intermolecular interactions of the title compound were analyzed by Hirschfeld surfaces and 2D-fingerprint plots. In vitro, antibiofilm activity against C. albicans, suggests a potential biofilm inhibitor (MIC 12.5 μg/ml). A molecular docking study of the title compound with the active sights of the target protein (PDB:5TZ1) justifies the results of the antibiofilm activity whereas a drug-likeness pharmacokinetic study is used to analyze the safety and efficiency of the drug. Furthermore, the Anti-inflammatory activity study of the title compound indicates significant (82.63%) inhibition of protein denaturation.

A DFT and QTAIM insight into ethylene oxide adsorption on the surfaces of pure and metal-decorated inorganic fullerene-like nanoclusters

In this industrial era, the use of low-dimensional nanomaterials as gas sensors for environmental monitoring has received enormous interest. To develop an effective sensing method for ethylene oxide (EO), DFT computations are conducted using method ωB97X-D and B3LYP with 6-31G(d,p) basis set to evaluate the adsorption behavior of ethylene oxide gas on the surfaces of pristine, as well as Scandium and Titanium decorated B12N12, Al12N12, and Al12P12 nanocages. Several properties like structural, physical, and electronic are studied methodically to better understand the sensing behavior. Scandium-decorated aluminum phosphate and boron nitride nanocages were shown to perform better in terms of adsorption properties. The short recovery time observed in this study is beneficial for the repetitive use of the gas sensor. The Natural Bond Orbital and molecular electrostatic potential analysis demonstrated a substantial quantity of charge transfer from adsorbate to adsorbents. The bandgap alternation after adsorption shows an influence of adsorption on electronic properties. The interactions of adsorbate and adsorbents are further studied using the ultraviolet–visible predicted spectrum, and quantum theory of atoms in molecules all of which yielded promising findings.

In vitro and in silico perspectives on the activation of antioxidant responsive element by citrus-derived flavonoids.

Oxidative stress plays an essential role in the pathogenesis of chronic diseases. Disrupting the Keap1-Nrf2 pathway by binding Keap1 is identified as a potential strategy to prevent oxidative stress-related chronic diseases. Therefore, of special interest is the utilization of dietary antioxidations from citrus, including narirutin, naringenin, hesperetin, hesperidin, naringin, neohesperidin dihydrochalcone, neohesperidin, and nobiletin, has been exploited as a prospective way to treat or prevent several human pathologies as Keap1-Nrf2 inhibitors for modulation of antioxidant properties. To probe into the structural foundation of the molecular identification of citrus-derived antioxidations, we calculated the antioxidant responsive element activation ability of citrus-derived flavonoids after binding with Keap1. Also, the quantum chemistry properties and binding mode were performed theoretically with frontier molecular orbitals, molecular electrostatic potential analysis, molecular docking, and absorption, distribution, metabolism, excretion (ADME) calculation. Experimental findings combining computational assays revealed that the tested citrus-derived flavonoids can be grouped into strong agonists and weak agonists. The citrus-derived antioxidations were well housed in the bound zone of Keap1 via stable hydrogen bonding and hydrophobic interaction. Eventually, three of eight antioxidations were identified after ADME and physicochemical evaluations. The citrus-derived flavonoids were identified as potential dietary antioxidants of the Keap1-Nrf2 interaction, and can be used to improve oxidative stress-related chronic diseases.

Hydrogen bond ferroelectric liquid crystal for tripartite temperature sensor: Experimental and computational (DFT) studies

The mesogenic behavior and electronic properties of hydrogen bond ferroelectric liquid crystal (HBFLC) complex are studied using experimental and theoretical techniques. HBFLC complex is synthesized from mesogenic 4-hexyloxy benzoic acid (6O BA) as the proton donor and nonmesogenic chiral DL-tartaric acid (DLTA) as the proton acceptor through intermolecular hydrogen bonding. Molecular geometry of DLTA+6O BA HBFLC complex is optimized by density functional theory (DFT) calculation. An interesting observation is that polarizing optical microscope (POM) study confirms that the HBFLC complex exhibits thermochromic behavior in chiral nematic (N[Formula: see text] along with induced nontitled smectic G* phases. Another noteworthy observation is the manifestation of tripartite temperature stages. Fourier-transform infrared spectroscopy (FTIR) and natural bond orbital (NBO) analysis elucidate the intermolecular hydrogen bond between mesogenic (6O BA) and nonmesogenic (DLTA) compounds. Further, frontier molecular orbital (FMO) study and electrostatic potential (ESP) analysis explore the reactivity sites, intermolecular charge transfer and electronic behavior of HBFLC complex.

A novel salt- and organic solvent-tolerant phosphite dehydrogenase from Cyanothece sp. ATCC 51142.

Phosphite dehydrogenase (PtxD) is a promising enzyme for NAD(P)H regeneration. To expand the usability of PtxD, we cloned, expressed, and analyzed PtxD from the marine cyanobacterium Cyanothece sp. ATCC 51142 (Ct-PtxD). Ct-PtxD exhibited maximum activity at pH 9.0°C and 50°C and high stability over a wide pH range of 6.0-10.0. Compared to previously reported PtxDs, Ct-PtxD showed increased resistance to salt ions such as Na+, K+, and NH4 +. It also exhibited high tolerance to organic solvents such as ethanol, dimethylformamide, and methanol when bound to its preferred cofactor, NAD+. Remarkably, these organic solvents enhanced the Ct-PtxD activity while inhibiting the PtxD activity of Ralstonia sp. 4506 (Rs-PtxD) at concentrations ranging from 10% to 30%. Molecular electrostatic potential analysis showed that the NAD+-binding site of Ct-PtxD was rich in positively charged residues, which may attract the negatively charged pyrophosphate group of NAD+ under high-salt conditions. Amino acid composition analysis revealed that Ct-PtxD contained fewer hydrophobic amino acids than other PtxD enzymes, which reduced the hydrophobicity and increased the hydration of protein surface under low water activity. We also demonstrated that the NADH regeneration system using Ct-PtxD is useful for the coupled chiral conversion of trimethylpyruvic acid into L-tert-leucine using leucine dehydrogenase under high ammonium conditions, which is less supported by the Rs-PtxD enzyme. These results imply that Ct-PtxD might be a potential candidate for NAD(P)H regeneration in industrial applications under the reaction conditions containing salt and organic solvent.

Shedding light into the biological activity of aminopterin, via molecular structural, docking, and molecular dynamics analyses

In this study, the structural and anticancer properties of aminopterin, as well as its antiviral characteristics, were elucidated. The preferred conformations of the title molecule were investigated with semiempirical AM1 method, and the obtained the lowest energy conformer was then optimized by using density functional (DFT/B3LYP) method with 6-311++G(d,p) as basis set. The vibrational frequencies of the optimized structure were calculated by the same level of theory and were compared with the experimental values. The vibrational assignments were performed based on the computed potential energy distribution (PED) of the vibrational modes. The molecular electrostatic potential (MEP) and frontier molecular orbitals (HOMO, LUMO) analyses were carried out for the optimized structure and the chemical reactivity has been scrutinized. To enlighten the biological activity of aminopterin as anticancer and anti-COVID-19 agents, aminopterin was docked into DNA, αIIBβ3 and α5β1integrins, human dihydrofolate reductase, main protease (Mpro) of SARS-CoV-2 and SARS-CoV-2/ACE2 complex receptor. The binding mechanisms of aminopterin with the receptors were clarified. The molecular docking results revealed the strong interaction of the aminopterin with DNA (−8.2 kcal/mol), αIIBβ3 and α5β1 integrins (−9.0 and −10.8 kcal/mol, respectively), human dihydrofolate reductase (−9.7 kcal/mol), Mpro of SARS-CoV-2 (−6.7 kcal/mol), and SARS-CoV-2/ACE2 complex receptor (−8.1 kcal/mol). Moreover, after molecular docking calculations, top-scoring ligand-receptor complexes of the aminopterin with SARS-CoV-2 enzymes (6M03 and 6M0J) were subjected to 50 ns all-atom MD simulations to investigate the ligand-receptor interactions in more detail, and to determine the binding free energies accurately. The predicted results indicate that the aminopterin may significantly inhibit SARS-CoV-2 infection. Thus, in this study, as both anticancer and anti-COVID-19 agents, the versatility of the biological activity of aminopterin was shown. Communicated by Ramaswamy H. Sarma

Synthesis of 1-Piperoylpiperidine Investigated Through Spectroscopy, Quantum Computation, Pharmaceutical Activity, Docking and MD Simulation Against Breast Cancer

1-Piperoylpiperidine (1-PIP) was crystallized as a single unit by a slow evaporation process, and it was examined using XRD and FT-IR spectroscopy. The centrosymmetric monoclinic structure is confirmed by XRD. The functional groups were determined by experimental FT-IR range from 4000 to 400 cm−1. Density functional theory was used to do calculations on quantum chemistry on B3LYP/6-311++G (d,p) theory. The vibrational wavenumbers were calculated, and experimentally obtained were assigned and compared. The molecule’s reactivity and kinetic stability are revealed via molecular orbital research. The Mulliken atomic charge distribution and molecular electrostatic potential analyses provide additional evidence of the molecule’s reactive site. The electronic spectrum was computed through TD-DFT and the electronic transition was attained at π→π*. The molecule’s bioactivity is shown by the natural bond orbital analysis. The efficiency and contribution of interactions between various atoms were evaluated using the Hirshfeld analysis. The DPPH assay was performed to access the antioxidant ability of 1-PIP. The disk diffusion test exhibited the antibacterial efficiency of 1-PIP molecule. The safety profile of 1-PIP was confirmed through physiochemical and pharmacokinetic predictions. In silico docking evaluation was performed for 1-PIP against 10 breast cancer-aided proteins and the higher binding affinity was recorded for NAMPT, which was further investigated through molecular dynamic (MD) simulation. MD simulation for a time period of 50 ns confirmed the stability of 1-PIP bounded NAMPT structure.

Novel Fluorinated Biphenyl Compounds Synthesized via Pd(0)-Catalyzed Reactions: Experimental and Computational Studies.

Five new difluorinated biphenyl compounds, 4'-(tert-butyl)-3,4-difluoro-1,1'-biphenyl (TBDFBP), 1-(3',4'-difluoro-[1,1'-biphenyl]-4-yl)ethanone (DFBPE), 3',4'-difluoro-2,5-dimethoxy-1,1'-biphenyl (DFDMBP), 3,4-difluoro-3'-nitro-1,1'-biphenyl (DFNBP), and (3',4'-difluoro-[1,1'-biphenyl]-3-yl)(methyl)sulfane (DFBPMS), have been successfully synthesized by the well-known Suzuki-Miyaura coupling with excellent yields averaging 78%. UV-visible, Fourier transform infrared ,and 13C NMR and 1H NMR spectroscopies along with single-crystal X-ray diffraction (SC-XRD) analysis (for TBDFBP and DFBPE) were used for the structure elucidation of the synthesized compounds. The SC-XRD results demonstrated the crystal systems of the studied compounds, TBDFBP and DFBPE, to be monoclinic, and their space groups were found to be P21/c. Also, a detailed density functional theory study was performed. The calculated structures for TBDFBP and DFBPE were found to agree quite well with the experimental results. The natural bonding orbital charge analysis suggested that molecules of these compounds should interact quite noticeably with each other in the solid phase and with polar solvent molecules. Molecular electrostatic potential analysis suggests that accumulation of positive and negative potential implies possibility of quite significant dipole-dipole intermolecular interactions in crystals of these compounds, as well as quite strong interactions with polar solvent molecules. The global reactivity parameters analysis suggests all compounds to be quite stable in redox reactions, with the compound DFNBP being relatively more reactive and the compounds TBDFBP and DFDMBP being relatively more stable.

Effect of functional group position in co-formers and solvent on cocrystal polymorphism/stoichiomorphism: a case study

In recent years, there has been an increase in the number of reports on cocrystal polymorphism and stoichiomorphism. However, the research on the factors that influence these phenomena is limited. Herein, picolinamide (PAM), nicotinamide (NAM), and isonicotinamide (INA) were selected as co-formers to form multicomponent solids with 4-chloro-3-sulfamoylbenzoic acid (CSBA). Six new cocrystal forms of CSBA were discovered and their crystal structures were determined. It was found that PAM and NAM can only form one cocrystal with CSBA, while INA can form up to four cocrystals, including both cocrystal polymorphism and stoichiomorphism. Molecular electrostatic potential analysis and crystal structure analysis showed that the functional group position of PAM limited the diversity of cocrystal synthons, while the lattice energy limited the diversity of cocrystal synthons when NAM acted as a co-former. Only INA was not subject to these restrictions when forming cocrystals. Finally, the influence of solvents on cocrystals was illustrated by determining the ternary phase diagrams. The mechanism of two similar solvents, ethyl acetate and acetone, controlling the crystallization of cocrystal polymorphism was analyzed by molecular simulations.

Molecular docking/dynamics simulations, MEP analysis, and pharmacokinetics prediction of some withangulatin A derivatives as allosteric glutaminase C inhibitors in breast cancer

The current study aims to understand the binding mechanism and intermolecular interactions of the novel Withangulatin A derivatives towards the allosteric site of Glutaminase C (GAC) using in silico analysis. The molecular docking and dynamics simulation results revealed that compounds L5, L8, L13, and L18 show high affinity toward the allosteric pocket of the GAC (PDB:3UO9), as confirmed by the high negative score values and hydrogen bonds. We found that these compounds interact with the most important residues and suggest a similar binding mechanism to the native compound (BPTES) and the clinical trial drug (CB-839). The combination of molecular electrostatic potential (MEP) analysis and molecular docking/dynamics studies confirms that the favorable reactive sites of these compounds establish many hydrogen bonds with active site residues of the target. Finally, pharmacokinetics prediction showed that L8 and L13 present the best ADMET profile among the selected compounds, and they share similar properties with the clinical compound CB-839. The obtained results in this investigation demonstrate that these two Withangulatin A derivatives might be used for further development as new allosteric GAC inhibitors for treating TNBC.

Theoretical insight of hydrochlorothiazide and aspirin adsorption on potassium and phosphorus doped carbon nanostructure as polypill prototype

Simultaneous adsorption of drugs on a novel carrier is a challenge for cardiovascular polypill design. The Density Functional Theory (DFT) calculations have been carried out to provide a possible mechanism associated with hydrochlorothiazide and aspirin adsorption on potassium- and phosphor- doped eighteen carbon nanostructure. The energetically most stable geometries are determined. The electronic structure of both molecules, as well as the doping nanostructure, before and after adsorption of the drugs, is studied. The molecular electrostatic potential analysis is presented and the orbital hybridizing is searched by the density of states plots. The results provide a direction for the further experiments in terms of through the recognition of binding trends and how the binding interaction change by modifying the surface.

Investigating the potential of thiazolyl carbohydrazides derivatives as anti-Candida albicans agents: An intuition from molecular modelling, pharmacokinetic evaluation, and molecular docking analysis

With increasing incidences of antifungal resistance, biofilm formation, and its predilection for vulnerable populations, Candida albicans have been reported to cause a wide range of infections, from superficial skin irritations to life-threatening systemic diseases. Therefore, understanding and addressing the infections associated with Candida albicans has become an urgent imperative in the realm of global healthcare. As a result, this study employed DFT calculations at the DFT/ωB97XD/6–311++G (2d, 2p) level to optimize the geometric properties of two compounds: (Z)-N'-(4-(4-bromophenyl)-3-(4-fluorophenyl)thiazol-2(3H)-ylidene)-2-(thiophen-2-yl)thiazole-5-carbohydrazide (4-FBC) and (Z)-N'-(4-(4-bromophenyl)-3-(2-fluorophenyl)thiazol-2(3H)-ylidene)-2-(thiophen-2-yl)thiazole-5-carbohydrazide(2-FBC). Significantly, employing spectral analysis techniques such as FT-IR and NMR, the compounds were characterized and identified. Additionally, the compounds (4-FBC and 2-FBC) exhibited comparable reactivity and stability, with more promising reactivity potential in water than in the gas phase. The analysis of Molecular Electrostatic Potential (MESP) and the density of States (DOS) shed light on the electrical characteristics and intermolecular interactions occurring during chemical processes. Furthermore, the natural bond orbital (NBO) analysis provided insights into second-order perturbation energies and the presence of intense intermolecular interactions, as evident in the order of their increasing concentrated intermolecular interaction as thus: 4-FBC_gas (668.34 kcal/mol) > 4-FBC _water (563.98 kcal/mol) and 2-FBC _gas (978.64 Kcal/mol) > 2-FBC_water (696.46 Kcal/mol). The pharmacokinetics study indicated favorable intestinal absorption, low distribution, and cytotoxicity profiles, although 4-FBC required further optimization due to slower clearance, potential enzyme interactions, and immunotoxicity concerns. In addition, molecular docking analysis revealed robust binding affinities and the presence of significant conventional hydrogen bonds. The optimal binding positions (best pose) for the 4-FBC and 2-FBC complexes were determined to have binding affinities of -8.7, -8.4, -8.3 kcal/mol, and -8.6, -8.5, -8.3 kcal/mol, respectively, when interacting with 4YDE, 3DRA, and 1EAG. These findings provide strong evidence supporting the potential pharmacological suitability of 4-FBC and 2-FBC compounds as effective choices for inhibiting and treating Candida albicans.

Studies on thiophene-thiazole-carbohydrazides as methicillin-resistant staphylococcus aureus (MRSA) agents: Insight from DFT and Molecular docking simulation

Methicillin-resistant Staphylococcus aureus (MRSA) is an increasingly common bacterial infection that poses a serious threat to human health. MRSA is resistant to many common antibiotics, making it particularly difficult to treat. To address this issue, the density functional theory (DFT) approach was employed in this study to examine thiophene- and thiazole-containing carbohydrazides for their biological activities. Quantitative experimental and spectroscopic results were obtained and compared to the theoretical. The FMO reactivity parameters revealed superior biological activity and reactivity of compound 6 G in gas phase, polar and non-polar solvents according to the data. Additionally, molecular electrostatic potential (MESP) analysis and non-covalent interaction (NCI) indicated that compound 6F contained more weak and steric repulsion interactions, while compound 6 G featured minimal van der Waals forces of attraction. Also, compound 6 G had the highest stabilization energy in the NBO analysis which show a better donor - acceptor charge transfer and electron delocalization. Molecular docking analyses with standard drugs showed higher binding affinities for compound 6 G with 3VSL than with CIPRO. The in-silico analysis suggests that 6F and 6 G have great bioactivity for tackling MRSA.

Molecular structure, electronic, topology and non-covalent interaction of 4-(Bis(2-chloroethyl)amino)-L-phenylalanine- Anti-blood cancer activity

In this study, it is attempted to scrutinize the global minimum energy structure of anti-blood cancer drug 4-(Bis(2-chloroethyl)amino)-L-phenylalanine (4B2CA-LPA) and functionalized density functional theory (DFT) calculations regarding their geometries, topological features of covalent, non-covalent interactions with employing Atoms in molecule (AIM) and Reduced density gradient (RDG) studies. As per the topological results, a new type of non-covalent attraction forces of hydrogen-hydrogen interaction was found in this molecule. Electrostatic potential variation as well as global reactive descriptor energy variations in the solvation phases was carried out by molecular electrostatic potential (MEP) and frontier molecular orbitals (FMOs) analysis. Moreover, the electronic excitations in liquids of 4B2CA-LPA were evaluated in UV-Vis absorptions. The local bonding electron transitions and optical properties of the compound were examined with natural bond orbital (NBO) studies. The 4B2CA-LPA molecule can serve as lead molecules for the growth of anti-blood cancer drugs. Molecular docking investigation has also been carried out to determine the ability of target molecules to bind with Hematopoietic inhibitors in blood cells.

Two Layers of Computational Screening on Silaborane‐based Clusters Filter Ca(SiB11H11CH3)2 as the Promising Electrolyte for Calcium‐Ion Batteries

AbstractCalcium‐ion batteries (CIBs) are promising energy storage systems, but the unavailability of adept electrolytes has hindered their development. In this work, a range of silaborane clusters ( ; n=5–15) were investigated using density functional theory (DFT) at ωB97XD3/6‐311+G(d,p) level of theory. The vertical detachment energy (VDE), electrochemical stability window (ESW) and binding energy (BE) of the silaboranes were computed at the same level of DFT. A methodology based on molecular electrostatic potential surface analysis was designed to locate the most suitable binding site for calcium ions on the clusters. DFT results show that the SiB11 cluster turns out to be superior to other candidates. Effect of substitution on silaboranes ( R− R=−CH3, −NCS, −CF3, −F and −Cl) was computed. −NCS and −CF3 substituted SiB11 ions were found to be the best from DFT. Ab initio molecular dynamics (AIMD) studies were performed to explore the interactions between silaborane‐based electrolytes and the Ca anode. AIMD results highlight the decomposition of −NCS and −CF3 substituted SiB11 on Ca anode. DFT and AIMD studies reveal that −CH3 substituted silaborane‐based Ca‐salt (Ca(SiB11H11CH3)2) is the promising electrolyte for CIBs.

Preparation, Crystal Structure, Supramolecular Assembly, and DFT Studies of Two Organic Salts Bearing Pyridine and Pyrimidine.

The effective preparation of two new pyrimidine- and pyridine-based organic crystalline salts with substituted acidic moieties (i.e., (Z)-4-(naphthalen-2-ylamino)-4-oxobut-2-enoic acid (DCNO) and 2-hydroxy-3,5-dinitrobenzoic acid (PCNP)) using methanol as a solvent has been reported. These molecular salts have ionic interactions that are responsible for their structural stabilization in their solid-state assemblies. The crystal structures of DCNO and PCNP were determined by the single-crystal X-ray diffraction (SCXRD) technique. The SCXRD study inferred that cations and anions are strongly packed due to N-H···O, N-H···N, and C-H···O noncovalent interactions in DCNO, whereas in PCNP, N-H···N noncovalent interactions are absent. The noncovalent interactions in both organic crystalline salts were comprehensively investigated by Hirshfeld surface analysis. Further, a detailed density functional theory (DFT) study of both compounds was performed. The optimized structures of both compounds supported the existence of the H-bonding and weak dispersion interactions in the synthesized organic crystalline salt structures. Both compounds were shown to have large and noticeably different HOMO/LUMO energy gaps. The atomic charge analysis results supported the SCXRD and HSA results, showing the formation of intermolecular noncovalent interactions in both organic crystalline salts. The results of the natural bond orbital (NBO) analysis confirmed the existence of (relatively weak) noncovalent interactions between the cation and anion moieties of their organic crystalline salts. The global reactivity parameters (GRPs) analysis showed that both organic crystalline salts' compounds should be quite thermodynamically stable and that DCNO should be less reactive than PCNP. For both compounds, the molecular electrostatic potential (MEP) analysis results support the existence of intermolecular electrostatic interactions in their organic crystalline salts.

Linking quinoline ring to 5-nitrofuran moiety via sulfonyl hydrazone bridge: Synthesis, structural characterization, DFT studies, and evaluation of antibacterial and antifungal activity

In the present work, we report the synthesis, structural characterization, and computational studies of (E)-N'-((5-nitrofuran-2-yl)methylene)quinoline-8-sulfonohydrazide (QNF) as a potential antimicrobial drug candidate. To design the target molecule, we utilized a molecular hybridization technique that connects two antimicrobial pharmacophores (quinoline and 5-nitrofuran rings) with a sulfonyl hydrazone moiety. QNF was synthesized by the condensation of quinoline-8-sulfonohydrazide with 5-nitrofuran-2-carbaldehyde, and characterized by various spectral techniques including single-crystal X-ray crystallography. QNF was extensively evaluated for its antibacterial and antifungal activity. The inhibition capacity of QNF on Candida albicans filamentation and biofilm formation was further investigated. Biofilm inhibition of QNF against C. albicans was supported by molecular docking studies in the binding site of agglutinin-like sequence 3 (Als3). Drug-like profile of QNF was confirmed by in silico calculation of its significant physicochemical properties. Additionally, the optimized geometrical structure, natural bond orbital calculations, frontier molecular orbital and molecular electrostatic potential analysis of QNF were carried out using the density functional theory method at the B3LYP with 6–31+G(d,p) basis set. The predictions of 1H and 13C NMR chemical shift values were performed using the gauge-independent atomic orbital method. Structural parameters and NMR values obtained experimentally were compared with the calculated values.

Theoretical designing of symmetrical non-fullerene acceptor molecules by end-capped modification for promising photovoltaic properties of organic solar cells

Non-fullerene small molecules must absorb in a broader wavelength range for achieving high efficiencies. This work presents seven indacenodithiophene core-based acceptor molecules (SJA1-SJA7) designed by structurally tailoring the pre-existed SJ-IC molecule. Detailed studies of these newly designed molecules were carried out to analyze the stabilization of energy levels, planarity, UV–Visible absorption, light-harvesting efficiency, open circuit voltage (Voc), and other photovoltaic properties. Structural modification with different acceptors resulted in the narrowing of band gap and broader absorption spectrum. All the newly reported molecules showed significant redshift having λmax values ranging from 686 nm to 722 nm in the gas phase and 742 nm to 792 nm in chloroform as compared to SJ-IC which has λmax values at 675 nm and 732 nm in gas and chloroform medium respectively. Moreover, newly presented molecules exhibited lower excitation energy values and higher oscillator strength than SJ-IC molecule which indicate effective charge transfer between frontier molecular orbitals. Improved charge mobilities were observed as newly developed molecules possessed lower internal reorganization energies. These findings were further confirmed by molecular electrostatic potential (MEP) and transition density matrix (TDM) analysis. In case of Voc, SJA7 emerged as a more proficient molecule due to its higher value (1.440 eV) than SJ-IC (1.42 eV). These results assure the remarkable improvement in optoelectronic properties of designed molecules which makes them a better choice than pre-existing SJ-IC molecule for the development of improved OSCs in the future.