Exploration of nonlinear optical properties of 4-methyl-4H-1,2,4-triazol-3-yl)thio)-N-phenylpropanamide based derivatives: experimental and DFT approach.

Triazoles, nitrogen-containing heterocycles, have gained attention for their applications in medicinal chemistry, drug discovery, agrochemicals, and material sciences. In the current study, we synthesized novel derivatives of N-substituted 2-((5-(3-bromophenyl)-4-methyl-4H-1,2,4-triazol-3-yl)thio)-N-phenylpropanamide and conducted a comprehensive investigation using density functional theory (DFT). These novel structural hybrids of 1,2,4-triazole were synthesized through the multi-step chemical modifications of 3-bromobenzoic acid (1). Initially, compound 1 was converted into its methyl-3-bromobenzoate (2) which was then transformed into 3-bromobenzohydrazide (3). The final step involved the cyclization of compound 3, producing its 1,2,4-triazole derivative (4). This intermediate was then coupled with different electrophiles, resulting in the formation of the final derivatives (7a-7c). Additionally, the characterization of these triazole-based compounds (7a, 7b, and 7c) were carried out using techniques such as IR, HNMR, and UV-visible spectroscopy to understand their structural and spectroscopic properties. The DFT study utilized M06/6-311G(d,p) functional to investigate geometrical parameters, HOMO-LUMO energies, natural bond orbital analyses, transition density matrix (TDM), density of states, and nonlinear optical (NLO) properties. The FMO analysis revealed that compound 7c exhibited the lowest band gap value (4.618 eV). Notably, compound 7c exhibited significant linear polarizability (4.195 > × 10-23) and first and second hyperpolarizabilities (6.317 > × 10-30, 4.314 × 10-35), signifying its potential for nonlinear optical applications. These NLO characteristics imply that each of our compounds, especially 7c, plays a crucial part in fabricating materials showing promising NLO properties for optoelectronic applications.

Quantum chemical framework for tailoring N/B doped phenalene derivatives to achieve high performance nonlinear optical materials.

Nonlinear optical (NLO) response materials are among the smartest materials of the era and are employed to modulate the phase and frequency of the laser. The present study presents a quantum chemical framework for tailoring nitrogen/boron doped derivatives of Dihydrodibenzo [de,op]pentacene through terminal and central core modifications. The derivatives of these compounds have been designed by introducing various π-conjugated connectors as well as B/N heteroatoms in the phenalene rings. Density functional theory (DFT) methods are used to optimize the ground state molecular geometries of designed compounds, represented as 1 to 4 (phenalene derivatives) and 1-BN to 4-BN (B/N doped phenalene derivatives) at the M06-2X/6-311G* level of theory. The highest value of 116.9 × 10-24 esu and 240.2 × 10-24 esu for isotropic and anisotropic linear polarizability is shown by compound 4. Among the designed compounds, 4-BN has achieved the highest γ amplitude of 1858 × 10-36 esu owing to its unique molecular structural design. Further analysis of electronic parameters, such as electron density difference (EDD) maps, the density of states, electrostatic potentials, transition density matrix (TDM) analysis, and frontier molecular orbitals analysis (FMOs), demonstrated the more effective intramolecular charge transfer (ICT) for the best compounds, resulting in a good NLO response. The compounds were also analyzed for their potential in photovoltaic applications based on factors such as open circuit voltage values determined to be between (0.14 eV and 1.82 eV), and light harvesting efficiency (0.425-0.909).

Computational prediction for designing novel ketonic derivatives as potential inhibitors for breast cancer: A trade-off between drug likeness and inhibition potency.

Unlike simple molecular screening, a combined hybrid computational methodology has been applied which includes quantum chemical methods, molecular docking, and molecular dynamics simulations to design some novel ketonic derivatives. The current study contains the derivatives of an experimental ligand which are designed as a trade-off between drug likeness and inhibition strength. We investigate the interaction of various newly designed ketonic compounds with the breast cancer receptor known as the Estrogen Receptor Alpha (ERα). The molecular structures of all newly designed ligands were studied quantum chemically in terms of their fully optimized structures, 3-D molecular orbital distributions, global chemical descriptors, molecular electrostatic potentials and energies of frontier molecular orbitals (FMOs). All ligands under study show good binding affinities with the ERα protein. The ligands CMR2 and CMR4 exhibit improved molecular docking interactions. The intermolecular interactions indicate that CMR4 demonstrates better hydrophobic and hydrogen bonding interactions with protein (ERα). Furthermore, molecular dynamics simulations were conducted on ligands and reference drugs interacting with the ERα protein over a time span of 120 nanoseconds. The molecular dynamics results are interpreted in terms of ligand-protein stability and flexible behaviour based on their respective values of RMSD, RMSF, H-bonds, the radius of gyration, and SASA graphs. To analyse ligand-protein interactions throughout the entire 120 ns trajectory, a more advanced MM/PBSA method is utilized, where six selected ligands (CMR1, CMR2, CMR3, CMR4, CMR5 and CMR9) illustrate promising results for inhibition of the ERα receptor as assessed through MM/BBSA analysis. The CMR9 has the highest MM/BBSA binding free energy (-14.46 kcal/mol). The ADMET analysis reveals that CMR4 has maximum intestinal absorption (6.68) and clearance rate (0.1). All the compounds are non-toxic and safe to use. These findings indicate the potential of involving different computational techniques to design the ligand structures and to study the ligand-protein interactions for better understanding and achieving more potent synthetic inhibitors for breast cancer.

Comparative catalytic reduction and degradation with biodegradable sodium alginate based nanocomposite: Zinc oxide/N-doped carbon nitride/sodium alginate.

Sodium alginate (SA) is a biodegradable macromolecule which is used to synthesize nanocomposites and their further use as catalysis. Zinc oxide (ZnO) and nitrogen doped carbon nitride (ND-C3N4) nanoparticles are prepared using solvothermal and hydrothermal methods, respectively. ZnO/ND-C3N4/SA nanocomposites are successfully synthesized by employing in-situ polymerization. The presence of essential functional groups is confirmed by Fourier transform infrared (FTIR) spectroscopic analysis. Controlled spherical morphology for ZnO nanoparticles, with an average diameter of ∼52 nm, is shown by Scanning electron microscopic (SEM) analysis, while rice-like grain structure with an average grain size ∼62 nm is exhibited by ND-C3N4 nanoparticles. The presence of required elements is confirmed by Energy dispersive X-ray spectroscopic (EDX) analysis. The crystalline nature of nanocomposites is verified by X-ray diffraction spectroscopic (XRD) analysis. The investigation of the catalytic efficiency for degradation and reduction of various organic dyes is carried out on nanoparticles and nanocomposites. Thorough examination and comparison of parameters, such as apparent rate constant (kapp), reduction time, percentage reduction, reduced concentration and half-life, are conducted for all substrates. The nanocomposites show greater efficiency than nanoparticles in both reactions: catalytic reduction and catalytic degradation.

Exploration of high-performance triptycene-based thermally activated delayed fluorescence materials via structural alteration of donor fragment.

The utilization of thermally activated delayed fluorescence (TADF) materials in highly proficient organic light-emitting diodes (OLEDs) has attracted much attention. Based on TADF material TPA-QNX(CN)2, a series of three-dimensional donor-acceptor (D-A) triptycenes have been designed via structural modification of D-fragment. The influences of different D-fragments with various electron-donating strengths on the singlet-triplet energy gap (ΔEST), emission wavelength (λem), and electron/hole reorganization energy (λe/λh) are extensively studied by applying density functional theory (DFT) coupled with time-dependent density functional theory (TD-DFT). The computed results imply that as the electron-donating strength of the D-fragments increases, the ΔEST value decreases and λem is red-shifted for the molecules using the same acceptor units. Analogously, the 1CT‒3CT state splitting (ΔEST (CT)) is also decreased by enlarging the twist angle (ß) between the phenyl ring and alternative D-fragment. Therefore, efficient color tuning within a broad emission range (434-610 nm), as well as small ΔEST (CT) values (0.01-0.05 eV), has been accomplished by structural modification of the D-fragments. The greater electron-donating strength, the smaller ΔEST, and the smaller λh for PPXZ-QNX(CN)2 make it the best candidate among all the designed molecules.

Recent advances in synthesis and characterization of iron-nickel bimetallic nanoparticles and their applications as photo-catalyst and fuel additive.

Iron-nickel bimetallic nanoparticles (Fe-Ni BMNPs) are prepared by combining two different metals by using the bottom-up approach. The resulting material has entirely different properties as compared to both the metals. The product is examined by using different analytical instruments such as.; scanning electron microscope (SEM), transmission electron microscope (TEM), X-ray diffraction (XRD), MDIJADE, ORIGIN pro to characterize their morphology, crystallinity and elemental composition and the final data has been statistically analyzed. SEM findings show that most nanoparticles are irregular in form and range in size from 10 nm to 100 nm. The findings of the TEM verified that the particles between 10 nm and 50 nm are irregular in size shape. The products acquired utilized as a fuel additive to monitor oil effectiveness by studying various parameters. The degradation of methylene blue dye depends directly on the concentration of the nanocatalyst. Different parameters also use the freshly prepared bimetallic nanocatalyst to investigate the efficacy of the kerosene fuel. By adding a tiny quantity of the nanocatalyst, the value of the flash point and fire point is significantly reduced. The nanocatalyst does not affect the cloud point and pour point to a large extent. The bimetallic nanocatalyst therefore has very excellent catalytic characteristics.

Investigation of the adsorption properties of gemcitabine anticancer drug with metal-doped boron nitride fullerenes as a drug-delivery carrier: a DFT study.

Anticancer-drug delivery is now becoming a challenging approach for researchers as it allows controlled drug delivery near cancerous cells with minimized generic collection and the avoidance of secondary side effects. Hence in this work, the applications of nanostructures as anticancer drug-delivery carriers were widely investigated to target cancerous tissues. Based on DFT calculations, we investigated the transition metal-doped boron nitride nanostructure as a drug-delivery agent for the gemcitabine drug utilizing the B3LYP/6-31G (d, p) level of theory. In this research, the adsorption energy and electronic parameters of gemcitabine on the interaction with the metal-doped BN nanostructures were studied. It has been observed that metal doping significantly enhances the drug-delivery properties of BN nanostructures. Among the investigated nanostructures, Ni-BN has been found to be the most prominent nanostructure to transport gemcitabine with an elevated value of adsorption energy in both the gas phase (-45.79) and water media (-32.46). The interaction between gemcitabine and BN nanostructures was confirmed through frontier molecular orbitals and stabilization energy analysis. The fractional charge transfer, MEP, NCI, and NBO analyses exposed the charge transfer from drug molecule to the BN nanostructures. Transition density maps and UV-VIS spectra were also plotted to investigate the excited-state properties of the designed complexes. Thus, the present study provides an in-depth interaction mechanism of the gemcitabine drug with BN, which reveals that metal-doped BN nanostructures can be a favorable drug-delivery vehicle for the gemcitabine anticancer drug.

Excited State Complexes of Coumarin Derivatives.

Furocoumarins are the useful derivatives of coumarin, and they act as skin photosensitizing material due to their exciting exciplex states. Dendrimers also form exciplexes when they contain coumarin as core and used for light harvesting. A number of ingredients in human nutrition contain coumarins. The apiaceae family is the most common example of this class that contains carrots, celery and parsley etc. Rutaceae family is also an important food source that contains coumarins and provides citrus food. Besides fruits and vegetables, beverages like coffee, wine, black and green tea also incorporates coumarin derivatives. Few coumarin dyes show absorption and one emission peak but it can show a double amplified spontaneous emission band due to the generation of super exciplexes in coumarins. Exciplex formation of different coumarin derivatives including 7-methoxy coumarin, 7-hydroxy coumarin show wide application in synthesis of various other derivatives and they can be used as dye due to their prominent fluorescence properties. Exciplexes and excimers of coumarin are widely used in lasers. Both singlet and triplet state exciplexes are considered. Thus a comprehensive review of excited state complexes of coumarin derivatives is discussed here with emphases on the interaction and overlap of the energy levels.

Chemically Modified Quinoidal Oligothiophenes for Enhanced Linear and Third-Order Nonlinear Optical Properties.

In the present investigation, quantum chemical calculations have been performed in a systematic way to explore the optoelectronic, charge transfer, and nonlinear optical (NLO) properties of different bis(dicyanomethylene) end-functionalized quinoidal oligothiophenes. The effect of different conformations (linking modes of thiophene rings) on conformational, optoelectronic, and NLO properties are studied from the best-performed dimer to octamer. The optical and NLO properties of all the selected systems (1-7) are calculated by means of density functional theory (DFT) methods. Among all the designed compounds, the largest linear isotropic (αiso) polarizability value of 603.1 × 10-24 esu is shown by compound 7 which is ∼12, ∼16, ∼9, ∼11, ∼10, and ∼4 times larger as compared to compounds 1-6, respectively. A relative investigation is performed considering the expansion in third-order NLO polarizability as a function of size and conformational modes. Among all the investigated systems, system 7 shows the highest value of static second hyperpolarizability ⟨γ⟩ with an amplitude of 7607 × 10-36 esu at the M06/6-311G** level of theory, which is ∼521, ∼505, ∼38, ∼884, ∼185, and ∼15 times more than that of compounds 1-6, respectively. The extensively larger ⟨γ⟩ amplitude of compound 7 with higher oscillator strength and lower transition energy indicates that NLO properties are remarkably dependent upon linking modes of thiophene rings and its chain length. Furthermore, to trace the origin of higher nonlinearities, TD-DFT calculations are also performed at the same TD-M06/6-311G** level of theory. Additionally, a comprehensive understanding of the effect of structure/property relationship on the NLO polarizabilities of these investigated quinoidal oligothiophenes is obtained through the inspection of Frontier molecular orbitals, the density of states (TDOS and PDOS), and molecular electrostatic potential diagrams including the transition density matrix. Hence, the current examination will not just feature the NLO capability of entitled compounds yet additionally incite the interest of experimentalists to adequately modify the structure of these oligothiophenes for efficient optical and NLO applications.

Metal doped fullerene complexes as promising drug delivery materials against COVID-19.

An outbreak of respiratory disorder caused by coronavirus has been named as coronavirus infection 2019 (COVID-19). To find a specific treatment against this disease researchers are at the frontline. To cure COVID-19, favipiravir (FPV) has been reported as an effective drug based on its high recovery rate. Among nanomaterials, fullerene C60 has achieved enormous attention as a drug delivery vehicle due to its good bioavailability and low toxicity. Hence, in this work, we have investigated the potential of metal-doped fullerene as a drug carrier, based on DFT calculations by using M06-2X functional and 6-31G(d) basis set in water media. In this research electronic parameters and adsorption energy of FPV on interaction with metal-doped (Cr, Fe, and Ni) fullerene is studied. The charge transfer between drug and doped fullerene has been studied through electrophilicity indexes. The structural and electronic properties are explored in terms of adsorption energy through frontier molecular orbital (FMO) and density of state (DOS). It is observed that doping of fullerene C60 with Cr, Fe, and Ni metals significantly enhances the drug delivery rate and provides numerous advantages including controlled drug release at specific target sites which minimize the generic collection in vivo and reduce the side effects. Thusly, it is suggested that our designed metal-doped complexes might be efficient candidates as drug delivery materials for COVID-19 infection. Supplementary Information: The online version contains supplementary material available at 10.1007/s11696-021-01815-4.

Exploring the potential of novel phenolic compounds as potential therapeutic candidates against SARS-CoV-2, using quantum chemistry, molecular docking and dynamic studies.

In the current study, the interaction of SARS-CoV-2 protein (A and B chains of nsp13) with different recently synthesized phenolic compounds (Sreenivasulu et al., Synthetic Communications, 2020, 112-122) has been studied. The interactions have been investigated by using molecular docking, quantum chemical and molecular dynamics simulations methods. The molecular structures of all the ligands are studied quantum chemically in terms of their optimized structures, 3-D orbital distributions, global chemical descriptors, molecular electrostatic potential plots and HOMO-LUMO orbital energies. All the ligands show reasonably good binding affinities with nsp-13 protein. The ligand L2 shows to have better binding affinities to Chain A and Chain B of nsp13 protein, which are -6.7 and -6.4 kcal/mol. The study of intermolecular interactions indicates that L2 shows different hydrophobic and hydrogen bond interactions with both chains. Furthermore, molecular dynamic simulations of the nsp13-L2 complex are obtained over a time scale of 60 ns, which indicates its stability and flexibility behavior as assessed in terms of its RMSD and RMSF graphs. The ADMET analysis also shows no violation of Lipinski rule (RO5) by studied phenolic compounds. We believe that the current findings will be further confirmed by in vitro and in vivo studies of these recent phenolic compounds for their potential as inhibitors for SARS-Co-V-2 virus.

Exploring the impact of central core modifications among several push-pull configurations to enhance nonlinear optical response.

The present study explores a series of novel donor-π-acceptor (D-π-A) molecules containing 4,4'-dimethyldiphenylamine moiety as donor, 4,4'-dinitrodiphenylborane as acceptor while different π-bridges as efficient linkers between them, which comprises of (-HCCH-)n, (-Ph-)n and (-Ph ̶ HCCH-)n combinations for compounds in series 1, 2 and 3, respectively. Quantum chemical computations are applied to calculate the linear polarizability (α), first (ß) and second (γ) hyperpolarizabilities. A comparative analysis is performed considering an increase of NLO polarizabilities as a function of different π-linkers. Among the investigated compounds, 3c shows the largest first and second hyperpolarizabilities of 1378 × 10-30 and 34971 × 10-36 esu, respectively. Interestingly, an increase in NLO polarizability is observed by modifying the π-conjugated bridges and the largest NLO polarizability is observed for series 3 possessing (Ph ̶ HCCH-)n π-linker which is found due to its lower transition energy and higher oscillator strengths. Furthermore, TD-DFT investigations, frontier molecular orbitals (FMOs) and electron density difference (EDD) maps analysis have shown a more efficient intramolecular charge transfer character from donor to acceptor moieties through (Ph ̶ HCCH-)n π-linkers. The density of states (DOS) maps are showing explicit contributions of electronic states from different fragments of a molecular system where the partial contributions of (Ph ̶ HCCH-)n π-linkers is seen significant in HOMO-LUMO orbitals of all the systems in series number 3. Thus, we believe that our study will highlight the importance of different D-π-A chromophores having variant types of π-conjugation cores as discussed in the present investigation.

The effect of different aromatic conjugated bridges on optoelectronic properties of diketopyrrolopyrrole-based donor materials for organic photovoltaics.

A series of twelve Acceptor-π-Donor-π-Acceptor (A-π-D-π-A) topology-based donor molecules, where diketopyrrolopyrrole (DPP) as donor core unit is connected through furan which acts as conjugated π-bridge (CB) to aromatic derivatives (Ar) as acceptor units, have been investigated by making substitutions in acceptor units by using density functional theory(DFT) and time-dependent density functional theory (TD-DFT) for organic solar cell applications. The comparative study of optoelectronic properties indicates that thiadiazole with pyridine units containing molecules (M6b) exhibit lower energy of highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) energy levels than those of oxadiazole and pyridine containing units (M6b). Among our investigated donors, the smallest Eg of 1.60 eV was observed for both M6a and M6b with distinctive broad absorption at 843 and 857 nm, respectively. Overall, smaller electron transfer (λe) values in contrast to hole transfer (λh) demonstrate that these donor compounds would be best for λe. The calculated open circuit voltage (Voc) is 2.45 and 2.17 eV, regarding bisPCBM and PC60BM (phenyl-C61-butyric acid methyl ester) acceptors. Thus, these theoretical calculations not only endorse the deep consideration between the chemical structures and optoelectronic characteristics of the donor-acceptor systems but also suggest appropriate materials for high-performance Organic Photovoltaics (OPV). Graphical abstract.

The ratio and topology effects of benzodithiophene donor-benzooxadiazole acceptor fragments on the optoelectronic properties of donor molecules toward solar cell materials.

A series of conjugated donor molecules (DmAnSq where m = 1-4, n = 1-7 while D = benzodithiophene, A = benzooxadiazole and S denotes ethyne spacers between D and A or D and D fragments) with various ratios of D/A fragments and topologies have been designed and investigated for OPV applications. An increase in the ratio of the acceptor fragment with respect to the donor fragment decreases the LUMO energy level and narrows the Eg for the designed molecule. More vertically (C4 and C8 substituted phenyl ring positions) bonded acceptor fragments than linearly (C2 and C6 substituted thiophene ring positions) bonded fragments result in a significant red shift in the maximum absorption wavelength. While, linearly bonded fragments lead to stronger absorption bands. Molecules with D-A-D topology exhibit more significant optical and electronic characteristics than those with D-D topology. All donor molecules (m = 2-4) of the D-A-D type show lower λh values than those of 1 donor containing (DAn) molecules. D-D type molecules show only lower λe values than DAn molecules because of the presence of a second donor fragment. The charge transfer phenomenon is shape dependent. The branched or anisotropic X, H, π, n, and square shaped molecules display higher charge transfer rates than the corresponding linear isomers due to better dimensionality. On the basis of these results, we suggest that designed donor and corresponding matched acceptor molecules have potential to act as promising candidates in solar cell devices.