Ab-initio calculations of structural,electronic,and optical properties of Zn_3(VO_4)_2

The structural, electronic, and optical properties of Zn_3(VO_4)_2 are investigated using full potential linearized augmented plane wave(FP-LAPW) method within the framework of density functional theory(DFT). Various approaches are adopted to treat the exchange and correlation potential energy such as generalized gradient approximation(GGA),GGA+U, and the Tran–Blaha modified Becke–Johnson(TB-mBJ) potential. The calculated band gap of 3.424 eV by TB-mBJ is found to be close to the experimental result(3.3 eV). The optical anisotropy is analyzed through optical constants,such as dielectric function and absorption coefficient along parallel and perpendicular crystal orientations. The absorption coefficient reveals high absorption(1.5 × 10~(6) cm~(-1)) of photons in the ultraviolet region.     

Mechanistic Insights into a Sustainable Mechanochemical Synthesis of Ettringite

Mechanochemistry offers an environmentally benign and facile synthesis method for a variety of cement paste constituents. In addition, these methods can be used to selectively tune the properties of cement components. The mineral ettringite is an important component of cementitious materials and has additional technological potential due to its ion exchange properties. Synthesis of ettringite via mechanochemistry is an environmentally friendly alternative to conventional wet-chemical synthesis established in industry. This contribution explores the mechanism of a two-step mechanochemical synthesis of ettringite, which was previously found to greatly improve the reaction conversion as compared with one-pot synthesis. The crystallinity of Al(OH)₃ was found to decrease during the first stage of this mechanochemical synthesis. This was correlated to a significant decrease in the particle size of Al(OH)₃ in this stage. No other significant changes were found for the other components, suggesting that mechanochemical activation of Al(OH)₃ is responsible for the enhanced formation of ettringite by the two-step approach. The environmentally friendly approach developed for ettringite synthesis offers a versatile synthetic strategy, which can be applied to synthesise further cementitious materials.     

Tuning the Triplet Excited State of Bis(dipyrrin) Zinc(II) Complexes: Symmetry Breaking Charge Transfer Architecture with Exceptionally Long Lived Triplet State for Upconversion

Zinc(II) bis(dipyrrin) complexes, which feature intense visible absorption and efficient symmetry breaking charge transfer (SBCT) are outstanding candidates for photovoltaics but their short lived triplet states limit applications in several areas. Herein we demonstrate that triplet excited state dynamics of bis(dipyrrin) complexes can be efficiently tuned by attaching electron donating aryl moieties at the 5,5′-position of the complexes. For the first time, a long lived triplet excited state (τ_T=296 μs) along with efficient ISC ability (Φ_Δ=71 %) was observed for zinc(II) bis(dipyrrin) complexes, formed via SBCT. The results revealed that molecular geometry and energy gap between the charge transfer (CT) state and triplet energy levels strongly control the triplet excited state properties of the complexes. An efficient triplet–triplet annihilation upconversion system was devised for the first time using a SBCT architecture as triplet photosensitizer, reaching a high upconversion quantum yield of 6.2 %. Our findings provide a blueprint for the development of triplet photosensitizers based on earth abundant metal complexes with long lived triplet state for revolutionary photochemical applications.     

Transferred multipolar atom model for 10β,17β‐dihydroxy‐17α‐methylestr‐4‐en‐3‐one dihydrate obtained from the biotransformation of methyloestrenolone

Biotransformation is the structural modification of compounds using enzymes as the catalysts and it plays a key role in the synthesis of pharmaceutically important compounds. 10β,17β‐Dihydroxy‐17α‐methylestr‐4‐en‐3‐one dihydrate, C₁₉H₂₈O₃·2H₂O, was obtained from the fungal biotransformation of methyloestrenolone. The structure was refined using the classical independent atom model (IAM) and a transferred multipolar atom model using the ELMAM2 database. The results from the two refinements have been compared. The ELMAM2 refinement has been found to be superior in terms of the refinement statistics. It has been shown that certain electron‐density‐derived properties can be calculated on the basis of the transferred parameters for crystals which diffract to ordinary resolution.     

Effect of transmission fiber and amplifier noise on optical chaos synchronization

Optical chaos propagation has few constraints peculiar to itself which do not become as significant in conventional nonchaotic optical communication. We have investigated the effects of transmission fiber nonlinearities, dispersion and noise of erbium doped fiber amplifier (EDFA) on chaotic signal synchronization in lumped and distributed configuration. It is found that the effects of fiber dispersion can be easily compensated; however, the effects of fiber nonlinearity on chaos cannot be overdone and must be avoided. Three distinct configurations with different combinations of standard telecommunication fiber, dispersion compensation fiber and lumped and distributed EDF for amplification are analysed. The results are compared in terms of sync diagrams and noise figure. The chaos after propagation through distributed amplification performs better as compared to lumped amplification. Also, a new quantitative measure for the calculation of deviation in sync diagram of chaos is introduced.     

Scaling in Electrical Conductivity Measurements and Rheological Measurements of Monarch 700 Dispersions Stabilized by Polymers

For making stable dispersions of graphitic carbon black (Monarch 700), the effectiveness of three dispersants/polymers (hypermer LP1, hypermer B246, and OLOA 11000) in xylene is investigated. Hypermer LP1 (polyhydroxystearic acid) is a homopolymer and hypermer B246 (PEG 30-dipolyhydroxystearate) is a polyhydroxystearic acid/polyethylene oxide/polyhydroxystearic acid ABA block copolymer, while OLOA 11000 (polyisobutylene succinimide) has a polar head group (polyamine) attached to a hydrocarbon chain (polyisobutylene). Well-dispersed graphitic carbon black dispersions were prepared using dispersants at optimum concentrations. Percolation threshold and rheological threshold were determined by analyzing the variations in electrical conductivity and elastic modulus with concentration of carbon black. Above threshold concentration, scaling law was applied to experimental data of rheology (dynamic measurements) and electrical conductivity measurements to evaluate quality of the system. Effectiveness of polymers was investigated on the basis of value of critical exponent (t and t′, respectively) in scaling power law. Hypermer LP1 was proved to be a poor dispersant for Monarch 700 dispersions while other two polymers were found to be effective stabilizers.     

Formulation of Piperine–Chitosan-Coated Liposomes: Characterization and In Vitro Cytotoxic Evaluation

The present research work is designed to prepare and evaluate piperine liposomes and piperine–chitosan-coated liposomes for oral delivery. Piperine (PPN) is a water-insoluble bioactive compound used for different diseases. The prepared formulations were evaluated for physicochemical study, mucoadhesive study, permeation study and in vitro cytotoxic study using the MCF7 breast cancer cell line. Piperine-loaded liposomes (PLF) were prepared by the thin-film evaporation method. The selected liposomes were coated with chitosan (PLFC) by electrostatic deposition to enhance the mucoadhesive property and in vitro therapeutic efficacy. Based on the findings of the study, the prepared PPN liposomes (PLF3) and chitosan coated PPN liposomes (PLF3C1) showed a nanometric size range of 165.7 ± 7.4 to 243.4 ± 7.5, a narrow polydispersity index (>0.3) and zeta potential (−7.1 to 29.8 mV). The average encapsulation efficiency was found to be between 60 and 80% for all prepared formulations. The drug release and permeation study profile showed biphasic release behavior and enhanced PPN permeation. The in vitro antioxidant study results showed a comparable antioxidant activity with pure PPN. The anticancer study depicted that the cell viability assay of tested PLF3C2 has significantly (p < 0.001)) reduced the IC₅₀ when compared with pure PPN. The study revealed that oral chitosan-coated liposomes are a promising delivery system for the PPN and can increase the therapeutic efficacy against the breast cancer cell line.     

Convergent synthesis of carbonic anhydrase inhibiting bi-heterocyclic benzamides: Structure–activity relationship and mechanistic explorations through enzyme inhibition,kinetics, and computational studies

By using a convergent methodology, a novel series of N-arylated 4-yl-benzamides containing a bi-heterocyclic thiazole–triazole core was synthesized, and the structures of these hybrid molecules, 9a–k , were corroborated through spectral analyses. The in vitro studies of these multifunctional molecules demonstrated their potent carbonic anhydrase inhibition relative to the standard used. The kinetics mechanism was exposed by Lineweaver–Burk plots, which revealed that 9j inhibited carbonic anhydrase non-competitively by forming an enzyme-inhibitor complex. The inhibition constants K_i calculated from Dixon plots for this compound was 1.2 μM. The computational study was also persuasive with the experimental results, and these molecules disclosed good results of all scoring functions and interactions, which suggested a good binding to carbonic anhydrase. So, it was predicted from the inferred results that these molecules might be considered as promising medicinal scaffolds for various diseases related to the uncontrolled production of this enzyme.