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.

Heterocyclic Donor Moiety Effect on Optical Nonlinearity Behavior of Chrysene-Based Chromophores with Push-Pull Configuration via the Quantum Chemical Approach.

Organic-based nonlinear optical (NLO) materials may be used in many optical-electronic systems and other next-generation defense technologies. With the importance of NLO materials, a series of push-pull architecture (D-π-A) derivatives (DTMD2-DTMD6) were devised from DTMR1 through structural alteration of different efficient donor heterocyclic groups. Density functional theory-based computations were executed at the MPW1PW91/6-31G(d,p) level to explore the NLO behavior of the derivatives. To investigate the optoelectronic behavior of the said compounds, various analyses like the frontier molecular orbital (FMO), global reactivity parameters, density of state (DOS), absorption spectra (UV-vis), natural bond orbital, and transition density matrix (TDM) were performed. The derivatives have a smaller band gap (2.156-1.492 eV) and a larger bathochromic shift (λmax = 692.838-969.605 nm) as compared to the reference chromophore (ΔE = 2.306 eV and λmax = 677.949 nm). FMO analysis revealed substantial charge conduction out of the donor toward the acceptor via a spacer that was also shown by TDM and DOS analyses. All derivatives showed promising NLO results, with the maximum amplitude of linear polarizability ⟨α⟩ and first (ßtotal) and second (γtotal) hyperpolarizabilities over their reference chromophore. DTMD2 contained the highest ßtotal (7.220 × 10-27 esu) and γtotal (1.720 × 10-31 esu) values corresponding with the reduced band gap (1.492 eV), representing potential futures for a large NLO amplitude. This structural modification through the use of various donors has played a significant part in achieving promising NLO behavior in the modified compounds.

Quantum Chemical Exploration of A-π1-D1-π2-D2-Type Compounds for the Exploration of Chemical Reactivity, Optoelectronic, and Third-order Nonlinear Optical Properties.

Organic compounds exhibit significant nonlinear optical (NLO) properties and can be utilized in various areas like optical parameters, fiber optics, and optical communication. Herein, a series of chromophores (DBTD1-DBTD6) with an A-π1-D1-π2-D2 framework was derived from a prepared compound (DBTR) by varying the structure of π-spacer and terminal acceptor. The DBTR and its investigated compounds were optimized at the M06/6-311G(d,p) level of theory. Frontier molecular orbitals (FMOs), nonlinear optical (NLO) properties, global reactivity parameters (GRPs), natural bonding orbital (NBO), transition density matrix (TDM), molecular electrostatic potential (MEP), and natural population analysis (NPA) were accomplished at the abovementioned level to describe the NLO findings. DBTD6 has the lowermost band gap (2.131 eV) among all of the derived compounds. The decreasing order of highest occupied molecular orbital-lowest unoccupied molecular orbital (HOMO-LUMO) energy gap values was DBTR > DBTD1 > DBTD2 > DBTD3 > DBTD4 > DBTD5 > DBTD6. The NBO analysis was carried out to describe noncovalent interactions such as conjugative interactions and electron delocalization. From all of the examined substances, DBTD5 showed the highest λmax value at 593.425 nm (in the gaseous phase) and 630.578 nm (in chloroform solvent). Moreover, the ßtot and ⟨γ⟩ amplitudes of DBTD5 were noticed to be relatively greater at 1.140 × 10-27 and 1.331 × 10-32 esu, respectively. So, these outcomes disclosed that DBTD5 depicted the highest linear and nonlinear properties in comparison to the other designed compounds, which underlines that it could make a significant contribution to hi-tech NLO devices.

Photophysical and biological aspects of α, ß-unsaturated ketones: Experimental and in silico approach.

In this work, four fluorinated α, ß-unsaturated ketones named as 3-(3-bromophenyl)-1-(3-(trifluoromethyl)phenyl)prop-2-en-1-one (1), 3-(4-methoxyphenyl)-1-(3-(trifluoromethyl)phenyl) prop-2-en-1-one (2), 3-(3-bromo-5-chloro-2-hydroxyphenyl)-1-(3-(trifluoromethyl)phenyl) prop-2-en-1-one (3) and 3-(2-hydroxy-5-methylphenyl)-1-(3-(trifluoromethyl)phenyl)prop-2-en-1-one (4) were synthesized by Claisen-Schmidt reaction. The synthesized molecules were then characterized through ultraviolet-visible spectroscopy (UV-Vis), Fourier transform infrared (FTIR), 1 H-NMR, 13 C-NMR, and mass spectrometry. The antioxidant potential, Urease inhibition, and interaction of compounds 1-4 with Salmon sperm DNA were experimentally explored and supported by molecular docking studies. The synthesized compounds strongly interact with SS-DNA through intercalative mode. It was noticed that compound 1 served as potent Urease inhibitor while compound 4 as better antioxidant among synthesized compounds. Moreover, frontier molecular orbitals, nonlinear optical (NLO) properties, natural bond orbitals, molecular electrostatic potential, natural population analysis, and photophysical properties of synthesized compounds were accomplished through density functional theory and time-dependent density functional theory. The band gap of all the compounds have been worked out using Taucs method. In addition to that, a precise comparative account of UV and IR data obtained from theoretical and experimental findings showed good agreement between theoretical and experimental data. The findings of our studies reflected that compounds 1-4 possess better NLO properties than Urea standard and the band gap data also reflected their prospective use towards optoelectronic materials. The better NLO behavior of compounds was attributed to the noncentrosymmetric structure of synthesized compounds.

Toward Efficient Bactericidal and Dye Degradation Performance of Strontium- and Starch-Doped Fe2O3 Nanostructures: In Silico Molecular Docking Studies.

In this study, various concentrations of strontium (Sr) into a fixed amount of starch (St) and Fe2O3 nanostructures (NSs) were synthesized with the co-precipitation approach to evaluate the antibacterial and photocatalytic properties of the concerned NSs. The study aimed to synthesize nanorods of Fe2O3 with co-precipitation to enhance the bactericidal behavior with dopant-dependent Fe2O3. Advanced techniques were utilized to investigate the structural characteristics, morphological properties, optical absorption and emission, and elemental composition properties of synthesized samples. Measurements via X-ray diffraction confirmed the rhombohedral structure for Fe2O3. Fourier-transform infrared analysis explored the vibrational and rotational modes of the O-H functional group and the C=C and Fe-O functional groups. The energy band gap of the synthesized samples was observed in the range of 2.78-3.15 eV, which indicates that the blue shift in the absorption spectra of Fe2O3 and Sr/St-Fe2O3 was identified with UV-vis spectroscopy. The emission spectra were obtained through photoluminescence spectroscopy, and the elements in the materials were determined using energy-dispersive X-ray spectroscopy analysis. High-resolution transmission electron microscopy micrographs showed NSs that exhibit nanorods (NRs), and upon doping, agglomeration of NRs and nanoparticles was observed. Efficient degradations of methylene blue increased the photocatalytic activity in the implantation of Sr/St on Fe2O3 NRs. The antibacterial potential for Escherichia coli and Staphylococcus aureus was measured against ciprofloxacin. E. coli bacteria exhibit inhibition zones of 3.55 and 4.60 mm at low and high doses, respectively. S. aureus shows the measurement of inhibition zones for low and high doses of prepared samples at 0.47 and 2.40 mm, respectively. The prepared nanocatalyst showed remarkable antibacterial action against E. coli bacteria rather than S. aureus at high and low doses compared to ciprofloxacin. The best-docked conformation of the dihydrofolate reductase enzyme against E. coli for Sr/St-Fe2O3 showed H-bonding interactions with Ile-94, Tyr-100, Tyr-111, Trp-30, ASP-27, Thr-113, and Ala-6.

In Silico Designing of Thieno[2,3-b]thiophene Core-Based Highly Conjugated, Fused-Ring, Near-Infrared Sensitive Non-fullerene Acceptors for Organic Solar Cells.

The performance of organic solar cells (OSCs) has been improving steadily over the last few years, owing to the optimization of device fabrication, fine-tuning of morphology, and thin-film processing. Thiophene core containing fused ring-type non-fullerene acceptors (NFAs) achieved significant proficiency for highly efficient OSCs. Quantum chemical computations are utilized herein with the motive of suggesting new NIR sensitive, highly efficient low-band gap materials for OSCs. A series of extended conjugated A-π-D-π-A architectured novel fused-ring NFAs (FUIC-1-FUIC-6) containing thieno[2,3-b]thiophene-based donor core are proposed by substituting the end-capped units of synthesized molecule F10IC. Different properties including frontier molecular orbital analysis, density of states analysis, transition density matrix analysis, excitation energy, reorganizational energies of both holes (λh) and electrons (λe), and open-circuit voltage (V oc) were performed employing the density functional theory approach. Charge transfer analysis of the best-designed molecule with the donor complex was analyzed to comprehend the efficiency of novel constructed molecules (FUIC-1-FUIC-6) and compared with the reference. End-caped acceptor alteration induces the reduction of the energy gap between HOMO-LUMO (1.88 eV), tunes the energy levels, longer absorption in the visible and near-infrared regions, larger V oc, smaller reorganizational energies, and binding energy values in designed structures (FUIC-1-FUIC-6) in comparison to reference (FUIC). The designed molecules show the best agreement with the PTBT-T donor polymer blend and cause the highest charge from the HOMO to the LUMO orbital. Our findings predicted that thieno[2,3-b] thiophene-based newly designed molecules would be efficient NFAs with outstanding photovoltaic characteristics and can be used in future applications of OSCs.

Comprehensive Comparative Analysis of the GATA Transcription Factors in Four Rosaceae Species and Phytohormonal Response in Chinese Pear (Pyrus bretschneideri) Fruit.

The GATA gene family is one of the most important transcription factors (TFs). It extensively exists in plants, contributes to diverse biological processes such as the development process, and responds to environmental stress. Although the GATA gene family has been comprehensively and systematically studied in many species, less is known about GATA genes in Chinese pears (Pyrus bretschneideri). In the current study, the GATA gene family in the four Rosaceae genomes was identified, its structural characteristics identified, and a comparative analysis of its properties was carried out. Ninety-two encoded GATA proteins were authenticated in the four Rosaceae genomes (Pyrus bretschneideri, Prunus avium, Prunus mume, and Prunus persica) and categorized into four subfamilies (Ⅰ-Ⅳ) according to phylogeny. The majority of GATA genes contained one to two introns and conserved motif composition analysis revealed their functional divergence. Whole-genome duplications (WGDs) and dispersed duplication (DSD) played a key role in the expansion of the GATA gene family. The microarray indicated that, among P. bretschneideri, P. avium, P. mume and P. persica, GATA duplicated regions were more conserved between Pyrus bretschneideri and Prunus persica with 32 orthologous genes pairs. The physicochemical parameters, duplication patterns, non-synonymous (ka), and synonymous mutation rate (ks) and GO annotation ontology were performed using different bioinformatics tools. cis-elements respond to various phytohormones, abiotic/biotic stress, and light-responsive were found in the promoter regions of GATA genes which were induced via stimuli. Furthermore, subcellular localization of the PbGATA22 gene product was investigated, showing that it was present in the nucleus of tobacco (Nicotiana tabacum) epidermal cells. Finally, in silico analysis was performed on various organs (bud, leaf, stem, ovary, petal, and sepal) and different developmental stages of fruit. Subsequently, the expression profiles of PbGATA genes were extensively expressed under exogenous hormonal treatments of SA (salicylic acid), MeJA (methyl jasmonate), and ABA (abscisic acid) indicating that play important role in hormone signaling pathways. A comprehensive analysis of GATA transcription factors was performed through systematic biological approaches and comparative genomics to establish a theoretical base for further structural and functional investigations in Rosaceae species.

Efficient Synthesis, SC-XRD, and Theoretical Studies of O-Benzenesulfonylated Pyrimidines: Role of Noncovalent Interaction Influence in Their Supramolecular Network.

Crystalline organic compounds, 2-amino-6-methylpyrimidin-4-yl benzenesulfonate (AMPBS) and 2,6-diaminopyrimidin-4-yl benzenesulfonate (DAPBS), were prepared via O-benzenesulfonylation of 2-amino-6-methylpyrimidin-4-ol 1 and 2,6-diaminopyrimidin-4-ol 2, respectively. The structural interpretations were achieved unambiguously by single-crystal X-ray diffraction (SC-XRD) analysis. The Hirshfeld surface study showed that C-H···O, N-H···N, and especially C-H···C hydrogen bond interactions are the key contributors to the intermolecular stabilization in the crystal. Density functional theory (DFT) studies were used to obtain a better understanding of natural bond orbitals (NBOs) and nonlinear optical (NLO) analysis for AMPBS and DAPBS at the B3LYP/6-311G(d,p) level. The time-dependent density functional theory (TD-DFT)/CAM-B3LYP/6-311G(d,p) level was employed for frontier molecular orbital analysis of both compounds. DFT-based vibrations for C-H, C=N, N-H, and stretching for C-C were found to be in good agreement with the experimental data. Overall, the theoretical findings were acquired in correspondence to the SC-XRD-based parameters. Intracharge transfer occurred in AMPBS and DAPBS compounds, which was evaluated through FMO activity. Global reactivity indices had been acquired utilizing energies of HOMO-LUMO orbitals. Overall, the theoretical findings related to AMPBS and DAPBS consist of promising correspondence to experimental findings. The theoretical-based study also exhibited that both AMPBS and DAPBS compounds contain promising NLO features.

Sinus of valsalva aneurysm rupturing into main pulmonary artery: A rare paediatric cardiac emergency.

Congenital Sinus of Valsalva aneurysm is a rare congenital cardiac disease. Most common site of origin is the right sinus. It ruptures into right ventricle or right atrium most of the times. Only in less than 2% of the cases it ruptures into the pulmonary artery. We report a rare case of right sinus of valsalva aneurysm rupturing into pulmonary artery.

Processed foods as an integral part of universal salt iodization programs: a review of global experience and analyses of Bangladesh and Pakistan.

BACKGROUND: Despite the reference to salt for food processing in the original definition of universal salt iodization (USI), national USI programs often do not explicitly address food industry salt. This may affect program impact and sustainability, given the increasing consumption of processed foods in developing countries. OBJECTIVE: To review experience of the use of iodized salt in the food industry globally, and analyze the market context in Bangladesh and Pakistan to test whether this experience may be applicable to inform improved national USI programming in developing countries. METHODS: A review of relevant international experience was undertaken. In Bangladesh and Pakistan, local rural market surveys were carried out. In Bangladesh, structured face-to-face interviews with bakers and indepth interviews with processed food wholesalers and retailers were conducted. In Pakistan, face-to-face structured interviews were conducted with food retailers and food labels were checked. RESULTS: Experience from industrialized countries reveals impact resulting from the use of iodized salt in the food industry. In Bangladesh and Pakistan, bread, biscuits, and snacks containing salt are increasingly available in rural areas. In Bangladesh, the majority of bakers surveyed claimed to use iodized salt. In Pakistan, 6 of 362 unique product labels listed iodized salt. CONCLUSIONS: Successful experience from developed countries needs to be adapted to the developing country context. The increasing availability of processed foods in rural Bangladesh and Pakistan provides an opportunity to increase iodine intake. However, the impact of this intervention remains to be quantified. To develop better national USI programs, further data are required on processed food consumption across population groups, iodine contents of food products, and the contribution of processed foods to iodine nutrition.