Frequency-dependent nonlinear optical response and refractive index investigation of lactone-derived thermochromic compounds.

Nonlinear optical (NLO) switchable materials play a crucial role in the fields of electronics and optoelectronics. The selection of an appropriate switching approach is vital in designing such materials to enhance their NLO response. Among various approaches, thermos-switching materials have shown a 4-fold increase in NLO response compared to other photo-switching materials. In this study, we computationally investigated the geometric, electronic, and nonlinear optical properties of reversible lactone-based thermochromic compounds using the ωB97XD/6-311+G (d,p) level of theory. Molecular orbital studies are employed to analyze the electronic properties of the close and open isomers of these compounds, while time-dependent density functional theory (TD-DFT) analysis is utilized to evaluate their molecular absorption. Our findings reveal that the π-electronic conjugation-induced delocalization significantly influences the ON-OFF switchable nonlinear optical response of the lactone-based thermochromic compounds. Notably, among all compounds, the open isomer of lactone 2 exhibits the highest hyperpolarizability value (6596.69 au). Furthermore, we extended our analysis to investigate the frequency-dependent second and third-order hyperpolarizabilities. The most pronounced frequency-dependent NLO response is observed at 532 nm. Additionally, we calculated the refractive index of these thermochromic compounds to further assess their nonlinear optical response. The open isomer of lactone 1 demonstrates the highest refractive index value (3.99 × 10-14 cm2/W). Overall, our study highlights the excellent potential of reversible thermochromic compounds as NLO molecular thermos-switches for future applications.

Role of Delocalization, Asymmetric Distribution of π-Electrons and Elongated Conjugation System for Enhancement of NLO Response of Open Form of Spiropyran-Based Thermochromes.

Switchable nonlinear optical (NLO) materials have widespread applications in electronics and optoelectronics. Thermo-switches generate many times higher NLO responses as compared to photo-switches. Herein, we have investigated the geometric, electronic, and nonlinear optical properties of spiropyranes thermochromes via DFT methods. The stabilities of close and open isomers of selected spiropyranes are investigated through relative energies. Electronic properties are studied through frontier molecular orbitals (FMOs) analysis. The lower HOMO-LUMO energy gap and lower excitation energy are observed for open isomers of spiropyranes, which imparts the large first hyperpolarizability value. The delocalization of π-electrons, asymmetric distribution and elongated conjugation system are dominant factors for high hyperpolarizability values of open isomers. For deep understanding, we also analyzed the frequency-dependent hyperpolarizability and refractive index of considered thermochromes. The NLO response increased significantly with increasing frequency. Among all those compounds, the highest refractive index value is observed for the open isomer of the spiropyran 1 (1.99 × 10-17 cm2/W). Molecular absorption analysis confirmed the electronic excitation in the open isomers compared to closed isomers. The results show that reversible thermochromic compounds act as excellent NLO molecular switches and can be used to design advanced electronics.

Impulsivity, impulsive aggression and borderline personality features among violent spouses.

Objective: Spousal violence in Pakistan is under researched but still not considered as a public health problem. The current study is intended to analyze the association between multiple measures of impulsivity, impulsive aggression, and borderline personality feature among violent spouses as well as to find out the moderating role of impulsive aggression between spousal violence and borderline personality features. Methods: A cross-sectional survey research design was used for conducting the research. The sample of 300 spouses, experiencing intimate partner relationships, was taken from different cities of the Hazara division through purposive sampling. Results: Present study demonstrated a significant positive correlation of spousal violence with impulsivity (r = .708∗∗, P < .001), impulsive aggression (r = .176∗∗, P < .001), and borderline personality features (r = .605∗∗, P < .001), while impulsivity was negatively correlated with impulsive aggression (r = -.018, P < .01). Impulsive aggression moderates the relationship between spousal violence and borderline personality features. The results showed that male and female spouses were found equally impulsive and impulsively aggressive. Likewise, impulsivity, impulsive aggression, and borderline personality features were found significant predictors of violence F = (3, 296) = 106. 67, P < .001. Conclusion: Current research offers some important insights and consequences for physicians and practitioners who interact with individuals who have experienced violence. These results have significant therapeutic implications for the treatment of violent couples.

Methionine Promotes the Growth and Yield of Wheat under Water Deficit Conditions by Regulating the Antioxidant Enzymes, Reactive Oxygen Species, and Ions.

The individual application of pure and active compounds such as methionine may help to address water scarcity issues without compromising the yield of wheat. As organic plant growth stimulants, amino acids are popularly used to promote the productivity of crops. However, the influence of the exogenous application of methionine in wheat remains elusive. The present investigation was planned in order to understand the impact of methionine in wheat under drought stress. Two wheat genotypes were allowed to grow with 100% field capacity (FC) up to the three-leaf stage. Twenty-five-day-old seedlings of two wheat genotypes, Galaxy-13 and Johar-16, were subjected to 40% FC, denoted as water deficit-stress (D), along with 100% FC, called control (C), with and without L-methionine (Met; 4 mM) foliar treatment. Water deficit significantly reduced shoot length, shoot fresh and dry weights, seed yield, photosynthetic, gas exchange attributes except for transpiration rate (E), and shoot mineral ions (potassium, calcium, and phosphorus) in both genotypes. A significant increase was recorded in superoxide dismutase (SOD), catalase (CAT), hydrogen peroxide (H2O2), malondialdehyde (MDA), and sodium ions (Na+) due to water deficiency. However, foliar application of Met substantially improved the studied growth, photosynthetic, and gas exchange attributes with water deficit conditions in both genotypes. The activities of SOD, POD, and CAT were further enhanced under stress with Met application. Met improved potassium (K), calcium (Ca2+), and phosphorus (P) content. In a nutshell, the foliar application of Met effectively amended water deficit stress tolerance by reducing MDA and H2O2 content under water deficit conditions in wheat plants. Thus, we are able to deduce a positive association between Met-induced improved growth attributes and drought tolerance.

Facile Synthesis of NH-Free 5-(Hetero)Aryl-Pyrrole-2-Carboxylates by Catalytic C-H Borylation and Suzuki Coupling.

A convenient two-step preparation of NH-free 5-aryl-pyrrole-2-carboxylates is described. The synthetic route consists of catalytic borylation of commercially available pyrrole-2-carboxylate ester followed by Suzuki coupling without going through pyrrole N-H protection and deprotection steps. The resulting 5-aryl substituted pyrrole-2-carboxylates were synthesized in good- to excellent yields. This synthetic route can tolerate a variety of functional groups including those with acidic protons on the aryl bromide coupling partner. This methodology is also applicable for cross-coupling with heteroaryl bromides to yield pyrrole-thiophene, pyrrole-pyridine, and 2,3'-bi-pyrrole based bi-heteroaryls.

In silico structural and functional characterization and phylogenetic study of alkaline phosphatase in bacterium, Rhizobium leguminosarum (Frank 1879).

Phosphorus is one of the primary macronutrient of plants, which is present in soil. It is essential for normal growth and development of plants. Plants use inorganic form of phosphate but organic form can also be assimilated with the help of soil inhabiting bacteria. Alkaline phosphatase is an enzyme present in Rizobium bacteria. This enzyme is responsible for solubilization and mineralization of organic phosphate and makes it readily available for plants. In the present study, nine different strains of Rhizobium leguminosarum were selected for a detailed computational structural and functional characterization and phylogenetic studies of alkaline phosphatase. Amino acid sequences were retrieved from UniProt and saved in FASTA format for use in analysis. Phylogenetic analysis of these strains was done by using MEGA7. 3D structure prediction was performed by using online server I-Tasser. Galaxy Web and 3D Refine were used for structure refinement. The refined structures were evaluated using two validation servers, QMEAN and SAVES. Protein-protein interaction analysis was done by using STRING. For detailed functional characterization, Cofactor, Coach, RaptorX, PSORT and MEME were used. Overall quality of predicted protein models was above 80%. Refined and validated models were submitted into PMDB. Seven out of nine strains were closely related and other two were distantly related. Protein-Protein interaction showed no significant co-expression among the interaction partners.