Binding Energy Values Research Articles

The In Vitro Cytotoxic Potential of Biosynthesized Silver Nanoparticles in MIA PaCa-2 Cells Supported with an In Silico Study

Pancreatic cancer affects many people and is quite aggressive. Metallic nanoparticles may be an alternative treatment for this disease. In this work, the antiproliferative activity of biosynthesized silver nanoparticles was evaluated. Stenocereus queretaroensis peel extract was used as a reducing agent for nanoparticle synthesis; the characterization was carried out using spectroscopic techniques, X-ray diffraction, and microscopy. The antiproliferative effect was evaluated in the MIA PaCa-2 pancreatic tumoral cell line, and a molecular docking test was run with the STAT3 protein. The results obtained show that it was possible to synthesize silver nanoparticles from the plant extract, which was confirmed through characterization studies. The average size of the nanoparticles was measured to be 48.8 nm, and they predominantly exhibited a spherical shape. The antiproliferative effect was demonstrated in the pancreatic cell line, with an IC50 value of 15.66 µg/mL. The molecular docking analysis predicted a strong interaction with the STAT3 protein, with a binding energy value of −6.47 obtained. With these results, it is concluded that biosynthesized silver nanoparticles inhibit pancreatic tumor cell growth and may represent an innovative cancer treatment.

Flavin mononucleotide, a potent inhibitor of insulin-degrading enzyme: an in-silico study

Diabetes Mellitus is a metabolic disorder which has affected over 476 million people globally with projections indicating a further increase in this number. Despite the availability of treatment therapies, maintaining optimal blood glucose levels remains a critical task. During literature survey, we came across Insulin degrading enzyme (IDE) which is responsible for insulin degradation in the body and inhibition of this enzyme could increase the bioavailability of insulin in the body. Therefore, a library of phytoconstituents isolated from anti-diabetic plants was prepared and screened against the IDE by using various in silico tools. This screening suggested Flavin mononucleotide (derivative of Vitamin B12) to possess the highest affinity towards IDE which interacted with a binding energy value of −332.686 kcal/mol. Moreover, molecular dynamic simulations and MMGBSA studies confirms the stability of Compound Flavin mononucleotide-IDE complex for at least 200 ns. These findings suggest that Compound Flavin mononucleotide has ability to halt the activity of this enzyme, but this study also underscores the need for confirming the anti-diabetic action of Flavin mononucleotide via in vitro assay and subsequent in vivo studies.

Palladium catalysed cross coupling reactions on 2,3-isoxazol-17α-ethynyltestosterone, their anti-cancer activity, molecular docking studies and ADMET analysis

In the current study, the Sonogashira coupling reaction of danazol with aryl halides was carried out, yielding new aryl substituted danazol derivatives. The synthetic compounds were examined for anti-cancer potential on the HeLa human cervical cancer cell line, and they showed promising cytotoxic action. Synthesized compounds 2, 4 and 5 inhibited the growth of HeLa cervical cancer cells, potentially making them effective anti-cancer drugs in the future. Furthermore, molecular docking studies were performed to evaluate the inhibitory impact of danazol derivatives on the Human Papillomavirus (HPV) target protein (1F9F). The docking results showed a significant inhibitory action against the cervical cancer protein (1F9F). The binding energy (ΔG) values of 1, 2, 3, 4 and 5 against the protein 1F9F were −8.01, −8.70, −9.43, −9.58 and −9.75 kcal/mol, indicating a high affinity of the synthesized compounds to bind with the HPV target proteins compared to their parent compound danazol (1). ADMET analyses of all derivatives have also been carried out

Cinnamic acid and its derivatives on dipeptidyl peptidase 4: structure-activity relationship and mechanism of inhibition

Dipeptidyl peptidase 4 (DPP4), which breaks down glucagon-like peptide 1 (GLP-1), is closely associated with glucose metabolism, and the inhibition of this enzyme is one of the important targets for the treatment of diabetes. Traditionally cinnamon and bitter melon have been in wide use in diabetes treatment, and cinnamic acid (CIA) as its main ingredient is expected to be an ideal DPP4 inhibitor. In vitro inhibition experiments showed that CIA had the lowest IC50 (33.56 ± 1.13 mM) compared to the other substances in the study, suggesting that it was more effective in inhibiting DPP4. Analyses showed that adding hydroxyl and methyl groups to CIA's aromatic ring reduced its effect on DPP4; CIA and its derivatives were inhibited in a mixed way. With the exception of ferulic acid (FA), CIA and its derivatives quenched the fluorescence of DPP4 via a static quenching mechanism. Thermodynamic parameters show that that the binding of CIA (the most inhibitory compound) to DPP4 was spontaneous and driven by hydrogen bonding. Atomic force microscopy and circular dichroism spectroscopy analyses reveal that upon binding with DPP4, CIA underwent a conformational change. Molecular docking results highlight , while introducing hydroxyl and methoxy groups on the aromatic ring, the superior binding capacity of CIA diminished. The study confirms that CIA is an ideal inhibitor with the highest absolute value of binding energy (-5.8) and the lowest IC50 compared to other substances. By clarifying the inhibition mechanism of DPP4,the study thus provides dietary guidance for diabetic patients.

P-type ZnO:N thin films deposited at room temperature on different substrates for p-channel Thin Film Transistor fabrication

A series of ZnO:N thin films were deposited by means of reactive pulsed laser deposition at room temperature on SiO2 glass slides, quartz, Al2O3, polyimide, silicon, and thermally oxidized SiO2. The p-type conductivity was confirmed by Hall effect-Van der Pauw measurements, with electrical parameters varying depending on the substrate deposition as follow: hole concentration between 2.4×1018 - 3.8×1017 cm-3, resistivity between 0.5 - 4 Ωcm, and mobility between 2 - 8 cm2V-1s-1. In situ X-ray photoelectron spectroscopy revealed identical binding energy values of the ZnO:N thin films across all substrates; the relative atomic concentrations varied between 49-53.8 at.%, 44-49 at.% and 2-2.4 at.% for zinc, oxygen and nitrogen respectively, due to over-quantification related to zinc particle splashing. Scanning electron microscopy confirmed a surface roughness of the films below 2 nm. Several wide and defect-related emissions were found by Cathodoluminescence; but the film deposited on quartz exhibited a unique, intense, and narrow blue band, the deconvolution of which revealed peaks at wavelengths of 430 nm and 461 nm. A growth rate of 14 nm/hour, and an etching rate of 2 nm/sec were found; these parameters were confirmed with the fabrication of smooth-walled ZnO:N thin films microstructures using photolithography. Finally, Thin Film Transistors (TFT) were fabricated. The devices exhibited low, but clear field effect current amplification, with a Ion/Ioff = 10. The feasibility of using room-temperature deposited p-type ZnO:N thin films for p-channel TFT fabrication was demonstrated.

Design, synthesis, structural characterization, cytotoxicity and computational studies of Usnic acid derivative as potential anti-breast cancer agent against MCF7 and T47D cell lines

Development of novel inhibitors is necessary to counteract the rising prevalence of breast cancer (BC) in women in recent years, as evidenced by the side-effect profiles of a few clinically approved inhibitors. In this study, the usnic acid derivative (UA1) was synthesized due to the effectiveness of usnic acid (UA) against BC cell line. Furthermore, the structure of synthesized compound was determined using FT-IR, 1H-NMR, 13C-NMR, HSQC, and HMBC spectroscopic techniques. The anticancer potential of UA1 was assessed using the MTT assay on two different cell lines of BC including MCF7 and T47D. To ascertain the binding affinity and stability of the docking complex, further procedures included the in silico molecular docking, molecular dynamic simulation, principal component analysis, and binding free energy experiments. The cytotoxicity results show that the UA1 exhibits strong antitumor activities and comparable effects against BC cell lines with the IC50 values of 9.21µM for MCF7 cell and 14.8µM for T47D cell, respectively, where the positive control cisplatin showed the IC50 values of 8.95µM for MCF7 cell and 10.9µM for T47D cell. Additionally, the molecular docking results of UA1 showed that it interacts strongly into the active site of target protein. Molecular dynamics simulation results also revealed that the docking complex was formed stability with the RMSD and RMSF values of 0.50nm and 0.19nm, respectively. According to the PCA analysis, the target protein displays good conformational space behaviour when bound with UA1. Furthermore, the UA1 showed the free binding energy value of -18.52kcal/mol with the target protein, which indicating that UA1 may prevent BC.

Molecular Docking: Study of Chalcone Derivatives from Boesenbergia pandurata Targeting Estrogen Receptor Alpha (ER–a) for Breast Cancer

The increasing number of cancer patients and the challenge of multidrug resistance (MDR) demand more effective drugs, which can be developed by modifying compounds derived from natural resources, such as the flavonoid-rich temu kunci rhizome (Boesenbergia pandurata (Roxb.) Schlecht.). This study aims to predict the cytotoxicity and toxicity of 20 Pinostrobin derivatives and 19 Chalcone derivatives as potential anticancer candidates. Estrogen receptor alpha (ER-α), a validated cancer therapy target, was used for molecular docking in in silico tests using Molecular Graphics Laboratory (MGL) Tools (including, AutoDock Vina, AutoDock Tools 4.1, and Python 2.5.2) and PyRx Program. Toxicity was predicted using the pkCSM program and Protox online tool. The docking process involved binding the compounds to ER-α (PDB IDs 6CHZ and 3ERT), with the binding energy indicating activity; lower binding energy values suggest greater cytotoxic potential and stronger ligand-receptor interactions. The results showed that Chalcone derivatives from temu kunci exhibited lower toxicity and higher cytotoxic activity compared to Pinostrobin derivatives and the reference compound, Tamoxifen (TAM). Notably, Bis-3-chlorobenzyloxychalcone and Bis-2-chlorobenzyloxychalcone demonstrated the highest predicted cytotoxic activity. In conclusion, Chalcone derivatives are promising candidates for further development as more effective anticancer drugs, especially those that outperform Tamoxifen. These findings highlight the potential of natural compounds, particularly Chalcone derivatives, in combating cancer while addressing the growing challenge of MDR in clinical treatments.

Riddelline from Tamarix articulate as a potential anti-bacterial lead compound for novel antibiotics discovery: A comprehensive computational and toxicological studies.

Tamarix articulate from the Tamaricaece family is a halophytic plant. This plant is commonly called Athal or Tamarix in different Arabic and Asian countries. Due to the high load of polyphenolic phytochemicals, the plant has been used as a therapeutic option against several diseases for decades. The plant is an anti-inflammatory, anti-bacterial, anti-viral, anti-cancer, anti-oxidant, and anti-inflammatory. In this work, the 222 phytochemical compounds of T. articulate from our previous study are used in different bioinformatic and biophysics techniques to explore their biological potency against different anti-bacterial, anti-cancer and anti-viral targets. By doing so, it was found that Riddelline ranked as the best binding molecule of biological macromolecules selected herein in particular the bacterial targets. The binding energy value of the compound for the KdsA enzyme was -14.64 kcal/mol, KdsB (-13.09 kcal/mol), MurC (-13.67 kcal/mol), MurD (-13.54 kcal/mol), MurF (-14.20 kcal/mol), Polo-like kinase 1 (Plk1) (-12.34 kcal/mol), Bcl-2 protein (-13.39 kcal/mol), SARS-CoV-2 main protease enzyme (-12.67 kcal/mol), and Human T cell leukemia virus protease (-13.67 kcal/mol). The mean Rg value of KdsA-Riddelline complex and KdsA-FPE complex is 32.67 Å, and average RMSD of KdsA-Riddelline complex and KdsA-FPE complex is 2.31 Å, respectively. The binding energy complexes was found to be dominated by van der Waals (-71.98 kcal/mol for KdsA-Riddelline complex and -65.09 kcal/mol for KdsA-FPE complex). The lead compound was also unveiled to show favorable druglike properties and pharmacokinetics. Together, the data suggest the good anti-bacterial activities of the T. articulate phytochemicals and thus can be subjected to experimental in vitro and in vivo investigations.

Quantum mechanical approaches and molecular docking studies of platinum based anticancer drugs Satraplatin and picoplatin structures

The structures of the anticancer drug compounds satraplatin and picoplatin are optimized, and theoretical studies done by Density Functional Theory (DFT) to investigate the optical properties, global chemical descriptors, and band gap were calculated using the obtained Frontier molecular orbital values. The theoretically obtained data of the platinum drugs found to possess low energy gap values and low chemical hardness with high chemical softness describe that the compounds are chemically stable and most reactive. Using the molecular docking process, the binding mechanisms of the satraplatin and picoplatin drugs with cancer DNA structures were studied, and the results were analyzed. For the two drug compounds examined, satraplatin has shown the least binding energies at −5.06kcal/mol compared to picoplatin at −2.69 kcal/mol, and conformations with root mean square deviation (RMSD) values by DNA structures are less than or equal to 2.00 Å in targeting the specific DNA target residues of the reference bound ligand. The grid box was generated using the selective grid parameters using the Autodock 4.2 program. The drug molecules found to have the least binding energy value with the lowest inhibition constant implicate the good docking score towards the DNA structure by the docking studies. DFT studies also show good structural properties and chemical reactivity. From the obtained results, satraplatin and picoplatin were found to have good chemical descriptors and good binding affinity and are best suited for biological molecular targets.

Screening of Optimal Phytoconstituents through in silico Docking, Toxicity, Pharmacokinetic, and Molecular Dynamics Approach for Fighting against Polycystic Ovarian Syndrome.

Polycystic ovarian syndrome (PCOS) is a hormonal disorder caused by excessive secretion of male sex hormones in females. Herbal remedies for PCOS are lightning up as they bypass the adverse effects and are profoundly safe on prolonged usage. The present study included a selection of 34 herbs pursuing biological effects on the uterus, and their major chemical constituents were subjected to a series of in silico techniques using different software. The proteins contributing majorly to the hormonal functions like Human cytochrome P450 CYP17A1 (3RUK), Progesterone (1E3K), and estrogen receptor (1X7R) were selected for the study. Molecular docking studies were performed using AutoDock 1.5.7. The pharmacokinetic properties were predicted using the SwissADME online tool, while toxicity parameters were assessed with OSIRIS toxicity explorer and pkCSM. Molecular dynamics simulations and free energy calculations were performed using the Schrödinger suite. Constituents with a basic steroidal nucleus demonstrated high binding energy values. An analysis of all the in silico techniques showed that Sarsasapogenin from Asparagus racemosus exhibited strong binding energies of -10.88 kcal/mol, -10.51 kcal/mol, and -9.79 kcal/mol with the selected specific proteins. In molecular dynamics simulations, Sarsasapogenin displayed ideal stability, with RMSD fluctuations below 3 Å and RMSF slightly higher than the corresponding peak of apoprotein. Additionally, it showed a favorable druglikeness profile and non-toxic effects across all screened parameters. From the list of the selected constituents, sarsasapogenin was found to be ideal, and further research on it for targeting PCOS is expected to yield promising results.

In silico drug encapsulation using 2-hydroxypropyl-β-CD, tyrosine kinase and tyrosinase inhibition of dinuclear Cu(II) carboxylate complexes

In recent years, copper carboxylate complexes have garnered significant interest for biological applications. This study focuses on 20 Cu(II) carboxylate complexes selected from our previous research. Due to the hydrophobic nature of these complexes, the 2-hydroxypropyl-β-cyclodextrin (2HPβCD) was employed as a carrier to reduce toxicity and increase solubility for controlling drug delivery. Monte Carlo calculations were performed to confirm the interaction between the optimized structures of Cu(II) complexes and 2HPβCD, forming a host-guest system. All the structures were simulated and optimized using DFT-D calculations in Material Studio 2017. The results indicated that a neutral medium is more favorable for the adsorption of these complexes into 2HPβCD. More negative binding energy values suggested strong and energetically favorable adsorption on 2HPβCD. Complexes 4, 5, and 7 exhibited the highest interaction, making them excellent candidates for drug delivery systems. DFT-D calculations were also used to investigate the release of complexes, revealing that complexes 5, 14, and 19 were difficult to release due to their lowest energy. In contrast, complexes 8, 9, and 16 were found to be most efficient to release due to weak non-covalent interactions with 2HPβCD as we can predict from binding energy obtained by DFT-D. No specific trend was observed in the interaction of the complexes with 2HPβCD. Additionally, the effects of these complexes on c-kit tyrosine kinase and Mushroom tyrosinase were studied by molecular docking. The results demonstrated that all the complexes interacted with the active site of respective receptors through hydrophobic interactions. Complexes containing 1,10-phenanthroline and 2,2-bipyrdine were identified as having a strong, spontaneous binding ability with receptors.

Pyrethroids and reproductive function: some endocrine disrupting perspectives from molecular simulations.

Pyrethroids are widely used insecticides with huge applications for household as well as agricultural purposes and contribute to improved product quality and higher yields. In recent decades, the demand for pyrethroids has increased significantly due to advantages such as broad-spectrum efficacy, high insecticidal potential, and lower pest resistance. However, several studies have suggested that human exposure to pyrethroids leads to reproductive problems. Sex hormone-binding globulin (SHBG) is an important hormone transport protein regulating the availability of steroids at their target site. The aim of our study was to investigate the structural interactions of commonly used pyrethroids, cypermethrin and deltamethrin, with ligand binding pocket of SHBG. Cypermethrin and deltamethrin were docked into the steroid binding pocket of SHBG using Schrodinger's induced fit docking (IFD) followed by molecular dynamics (MD) simulation studies. The resultant SHBG-pyrethroid complexes from IFD experiments were subjected to structural analysis including the molecular interactions followed by binding energy estimation. The analysis revealed that both the ligands were tightly bound in the SHBG pocket with high percentage of commonality among the SHBG residues between the indicated pyrethroid ligands and the SHBG native ligand, dihydrotestosterone (DHT). The estimated binding energy values for cypermethrin were less but close to the values calculated for the SHBG native ligand, DHT. However, the estimated binding energy values for deltamethrin were higher compared to the values calculated for SHBG native ligand, DHT. Furthermore, the MD simulation results also revealed the higher stability of SHBG-deltamethrin than SHBG-cypermethrin complex. To sum up, the results suggested that deltamethrin has a greater capability than cypermethrin to prevent sex steroid hormone from binding to SHBG, even though both pyrethroids have this ability. Consequently, this might hamper the circulatory transport of sex steroid hormones and their availability at the target site, subsequently interfering with reproductive function.

Exploring the interplay between Porphyromonas gingivalis KGP gingipain, herpes virus MicroRNA-6, and Icp4 transcript in periodontitis: Computational and clinical insights.

Porphyromonas gingivalis, a major pathogen in periodontitis, produces KGP (Lys-gingipain), a cysteine protease that enhances bacterial virulence by promoting tissue invasion and immune evasion. Recent studies highlight microRNAs' role in viral latency, potentially affecting lytic replication through host mechanisms. Herpes virus (HSV) establishes latency via interactions between microRNA-6 (miRH-6) and the ICP4 transcription factor in neural ganglia. This suggests a potential link between periodontitis and HSV-induced latency. This study aims to identify and validate the insilico inhibitory interaction of P. gingivalis KGP with ICP4 transcripts and correlate the presence of viral latency-associated transcript micro-RNA-6 with periodontitis. Computational docking analysis was performed to investigate the potential interaction between ICP4 and KGP gingipain. The binding energy and RMSD ligand values were calculated to determine the interaction's strength. Ten patients with recurrent clinical attachment loss despite conventional therapy were included in the clinical study. Subgingival tissue samples were collected post-phase I therapy, and HSV microRNA-6 presence was detected via polymerase chain reaction and confirmed through gel electrophoresis. Computational docking identified the ICP4-KGP gingipain complex with the lowest binding energy (-288.29 kJ mol^1) and an RMSD ligand of 1.5 Angstroms, indicating strong interaction potential. Gel electrophoresis confirmed miRH-6 presence in all samples. The identification of miRNA-6 in periodontitis patients and the strong interaction potential between P. gingivalis KGP gingipain and ICP4 transcripts indicate a possible link between bacterial virulence factors and viral latency dynamics in periodontal tissues. These results highlight the complex interplay between oral pathogens, viral microRNAs, and host immune responses in periodontitis.

Electrochemical Sensing of Paracetamol Using Functionalized MWCNTs: Integrating Computational and Experimental Methods

An electrochemical sensing platform for the detection of paracetamol is proposed in this work. The sensor (Asp‐MWCNTs/IL/ITO) is based on Indium Tin Oxide (ITO) electrode loaded with asparagine functionalised Multi Walled Carbon Nanotubes (MWCNTs) and Ionic Liquid (IL). Initially, in‐silico studies were performed to check the favourable interaction of the drug with the nanocomposite. The potential energy surface of Asp‐MWCNTs and paracetamol complexes were explored using density functional theory and single‐point energy coupled cluster calculations. The analysis of non‐covalent interactions showed hydrogen bonding interactions predominantly stabilising the complex. The interaction process between Asp‐MWCNTs and paracetamol is spontaneous due to negative value of binding energy (‐0.75 eV). The functionalised MWCNTs were characterised through different techniques. Asp‐MWCNTs/IL/ITO electrode showed good sensitivity with a linear range from 20 – 300 μgL−1 and limit of detection of 0.0194 μM for paracetamol in phosphate buffer as supporting electrolyte. The sensor showed excellent repeatability and reproducibility with a relative standard deviation of 1.45% at 60 μgL−1 concentration. The chemical functionalization resulted in providing extra stability as it retained 95% of its signal response even after 45 days. The sensor’s applicability was tested in real water samples with the help of spiking study which showed good recovery >95%.”

Anti-quorum sensing and anti-biofilm activities of Pasteurella multocida strains

A total of 52 Pasteurella multocida strains of capsular serogroups (A, B and D) were screened for anti-quorum sensing activity against Chromobacterium violaceum. Of which, 12 strains of serogroups A were found to possess anti-quorum sensing activity. Inhibition activity was highest for strain NIVEDIPm9 and lowest for strain NIVEDIPm30 based on zone of pigment inhibition. Further, cell free extract of NIVEDIPm9 strain showed highest anti-biofilm activity in reference E. coli strain and concentration dependent degradation activity of C6-AHL molecule. In whole genome sequence annotation of NIVEDIPm9 strain predicted the presence of four metallo-β-lactamases (MBL) fold metallo-hydrolase proteins. In docking studies, MBL1 and MBL3 proteins showed high binding affinity with autoinduce signalling molecules AHL compound of OH-C10, binding energy value were −6.3 and −6.2 kcal/mol. Interaction study of VAF and quorum sensing molecules showed that OmpA and HgbA proteins were stimulated by all the ten molecules (C4-AHLs, C6-AHLs, C10-AHLs, C14-AHLs, 3-oxo-C10-AHLs, 3OH-C10-HSL, C8-HSL, C10-HSL, C12-HSL, C14-HSL), while toxA gene was stimulated by OH-C10-AHL molecule, sodC gene was stimulated by none. In conclusion, we described the anti-quorum sensing activities of diverse P. multocida strains causing Pasteurellosis in livestock.

In silico analysis of quercetin and its derivatives as potential TRPC6-targeted treatments for diabetic neuropathy

Background: Diabetic neuropathy is a condition that arises as a complication of diabetes mellitus and often causes pain in patient. Quercetin and its derivatives have antinociceptive activity, making them potential agents for relieving the pain associated with diabetic neuropathy. Objective: This study aims to analyze the interactions between quercetin and its eight derivatives with canonical transient receptor potential channels 6 (TRPC6) as protein target. Method: The TRPC6 structure (PDB ID: 6UZ8) was prepared and validated with redocked to native ligand R0D using Autodock 4.2.6, with the established grid box and grid center settings. The test compounds were then optimized and docked using the same grid box and grid center settings as in the validation process, followed by visualization and analysis of the docking results. Results: The compound with the best affinity for TRPC6 was tamarixetin, with a binding energy value of -3.27 kcal/mol, close to the binding energy value of the native ligand, which was -4.22 kcal/mol. The amino acid residues interacting with tamarixetin at the active site were 702-Asn, 705-Tyr, 706-Val, and 709-Gly. This indicates that tamarixetin and the native ligand bind to the same active site amino acids, resulting in a similar affinity to the native ligand in inhibiting TRPC6. Conclusion: A total of eight quercetin derivatives were predicted to have TRPC6 antagonistic activity against diabetic neuropathy, with tamarixetin exhibiting the highest affinity compared to the other quercetin derivatives.

Designing plausible catalysts for synthesis of zingerone from vanillin and acetone via aldol condensation reaction on O-terminated M3C2-MXenes

Herein, high-performance O-terminated M3C2 MXene catalysts were screened for the synthesis of zingerone using vanillin and acetone. The electrochemical and electronic properties of O-terminated ordered MXenes in the form of M3C2O2(H) [M = Ti, V, and Cr (3d); Zr, Nb, and Mo (4d); and Hf, Ta, and W (5d)] were investigated using first principle density functional theory (DFT) calculations. These calculations revealed 37 stable candidates based on their negative binding energy values of ΔG*H and three O-terminated M3C2 MXene candidates with superior zingerone synthesis activity than pure precious metal (platinum), a UL > −0.4 V can guarantee high activity and low energy consumption during zingerone synthesis. Ti3C2O (FCC)), Hf3C2O2 (HCPFCC), and Nb3C2O2 (HCPHCP) exhibited higher catalytic activity than other candidates, and their performances were competitive for zingerone synthesis, with low limiting potentials of −0.37, −0.27, and −0.35 V, respectively. Zingerone synthesis via the protolysis reaction between vanillin and acetone includes two paths, i.e., induced protolysis and direct protolysis via the aldol condensation reaction. Multiple descriptors were used to evaluate and screen promising candidates for the synthesis of zingerone. For example, ΔG(*vanillin*acetone), and Bader charge, and d-band center analyses revealed the origin of zingerone synthesis activity based on binding energy and electronic structure. Importantly, binding energy and electronic structure have a strong intrinsic linear scaling relationship that can be used to screen for the optimal catalyst by controlling the scaling relationship between the intermediate binding energy and electronic properties. Indicating a scaling relationship and volcano plot were established based on ΔG(*vanillin+*acetone) and ΔG[*zingiberone] depending on Limiting potential (UL). Finally, we proposed a method for directly inducing protolysis during the aldol condensation reaction, which may be widely applicable to different biomass-derived carbonyl compounds, yielding chemicals and medicinal compounds through biomass valorization.

On the Versatility of the sp-, sp 2-, and sp 3-Hybridized Chalcogen-Bearing Molecules To Engage in Type I Chalcogen···Chalcogen Interactions: A Quantum Mechanical Investigation of Like···Like and Unlike Complexes.

The predilection of sp-, sp 2-, and sp 3-hybridized chalcogen-bearing molecules to engage in type I chalcogen···chalcogen interactions was comparatively unveiled in like···like/unlike CY···YC, YCY···YCY, and F2Y···YF2 (where Y = O, S, and Se) complexes, respectively. Upon the optimized monomers, a potential energy surface (PES) scan was conducted to pinpoint the most favorable complexes. The energetic findings unveiled the ability of the investigated systems to engage in the interactions under study with binding energy values ranging from -0.36 to -2.33 kcal/mol. Notably, binding energies were disclosed to align in the posterior sequence; sp 2- (i.e., YCY···YCY) > sp- (i.e., CY···YC) > sp 3- (i.e., F2Y···YF2) hybridized complexes, except the like···like oxygen-bearing complexes. Instead, the highest negative binding energy values were detected for the OCO···OCO followed by those of the F2O···OF2 and CO···OC complexes. Furthermore, the like···like selenium-bearing complexes demonstrated the most considerable binding energies compared to the other investigated complexes. Remarkably, the quantum theory of atoms in molecules and noncovalent interaction index analyses revealed the highly directional and closed-shell nature of the investigated chalcogen···chalcogen interactions. Symmetry adapted-perturbation theory findings outlined the dispersion forces as the commanding forces for all the studied complexes. These observations will provide convincing justifications for the nature of chalcogens within type I chalcogen···chalcogen interactions, leading to increased progress in various domains regarding drug design and materials science.

Amplifying the photovoltaic properties of tetrathiafulvalenes based materials by incorporation of small acceptors: a density functional theory approach

Currently, polycyclic aromatic compounds in organic solar cells (OSCs) have gained substantial consideration in research communities due to their promising characteristics. Herein, polycyclic aromatic hydrocarbons (PAHs) core-based chromophores (TTFD1-TTFD6) were designed by structural modifications of peripheral acceptor groups into TTFR. The density functional theory (DFT) and time dependent density functional theory (TD-DFT) calculations were carried out at B3LYP/6-311G (d, p) functional to explore insights for their structural, electronic, and photonic characteristics. The structural modulation unveiled notable electronic impact on the HOMO and LUMO levels across all derivatives, leading to decreased band gaps. All the designed compounds exhibited band gap ranging from 2.246 to 1.957 eV, along with wide absorption spectra of 897.071-492.274 nm. An elevated exciton dissociation rate was observed due to the lower binding energy values (Eb = 0.381 to 0.365 eV) calculated in the derivatives compared to the reference (Eb = 0.394 eV). Furthermore, data from the transition density matrix (TDM) and density of states (DOS) also corroborated the effective charge transfer process. Comparable results of Voc for reference and designed chromophores were obtained via HOMOdonor−LUMOPC71BM. The declining Voc order values was noted as TTFD5 > TTFD6 > TTFD4 > TTFD3 > TTFD2 > TTFD1 > TTFR. Interestingly, TTFD5 was found with the smallest energy gap and highest absorption value, resulting in better charge transference among all the derivatives. The results illustrated that the modification in indenofluorene based chromophores with end-capped small acceptors proved to be a significant approach in achieving favorable photovoltaic properties.

Exploring the impact of end-capped benzothiazine-based acceptors to lead the photovoltaic properties of solar cells: A DFT/TD-DFT approach

To improve the solar cells performance, usually end-capped acceptors are used in designing of new molecules. Therefore, in this study, the side-chain and end-capped moieties were modified in reference compound (BTZR) and proposed new compounds (BTZD1-BTZD6) to augment their photovoltaic and optoelectronic properties. The density functional method was employed at the M06/6-311G(d,p) level to optimize and interpret their frontier molecular orbitals (FMOs), density of states (DOS), transition density matrix (TDM), exciton binding energy (Eb), light absorption and open circuit voltage (Voc) characteristics. Their global reactivity parameters (GRPs) were calculated via the HOMO-LUMO energy band gap. Further, it was observed that all the investigated compounds showed lower band gaps (2.975–3.160 eV) and bathochromic shifts in the visible region (482.501–504.223 nm). Various plots such as the DOS, TDM and hole-electron further confirmed the efficiency of designed chromophores. Additionally, an interface of model donor–acceptor was constructed by considering the donor polymer (PBDB-T) and designed NFAs. Significant results were obtained for Voc (1.538–1.772 V). Among the selected candidates, BTZD3 and BTZD5 were obtained as high-performance non-fullerene acceptors (NFAs). They exhibited least band gaps (2.988 and 2.975 eV) and highest λmax (504.223 and 498.606, respectively). These compounds also demonstrated the least exciton binding energy values as 0.529 and 0.488 eV, respectively. Besides this, comparative study with the standard hole transport material (HTM) spiro-OMeTAD showed a reasonable agreement, suggesting that the entitled compounds could serve as effective HTMs. Overall, the findings suggested the crucial role of end-capped modification in elevating the charge mobility and photovoltaic characteristics of BTZD1-BTZD6. This study provides a valuable insight in the development of good photovoltaic materials.