Key Electronic, Linear and Nonlinear Optical Properties of Designed Disubstituted Quinoline with Carbazole Compounds.

Organic materials development, especially in terms of nonlinear optical (NLO) performance, has become progressively more significant owing to their rising and promising applications in potential photonic devices. Organic moieties such as carbazole and quinoline play a vital role in charge transfer applications in optoelectronics. This study reports and characterizes the donor-acceptor-donor-π-acceptor (D-A-D-π-A) configured novel designed compounds, namely, Q3D1-Q3D3, Q4D1-Q1D2, and Q5D1. We further analyze the structure-property relationship between the quinoline-carbazole compounds for which density functional theory (DFT) and time-dependent DFT (TDDFT) calculations were performed at the B3LYP/6-311G(d,p) level to obtain the optimized geometries, natural bonding orbital (NBO), NLO analysis, electronic properties, and absorption spectra of all mentioned compounds. The computed values of λmax, 364, 360, and 361 nm for Q3, Q4, and Q5 show good agreement of their experimental values: 349, 347, and 323 nm, respectively. The designed compounds (Q3D1-Q5D1) exhibited a smaller energy gap with a maximum redshift than the reference molecules (Q3-Q5), which govern their promising NLO behavior. The NBO evaluation revealed that the extended hyperconjugation stabilizes these systems and caused a promising NLO response. The dipole polarizabilities and hyperpolarizability (ß) values of Q3D1-Q3D3, Q4D1-Q1D2, and Q5D1 exceed those of the reference Q3, Q4, and Q5 molecules. These data suggest that the NLO active compounds, Q3D1-Q3D3, Q4D1-Q1D2, and Q5D1, may find their place in future hi-tech optical devices.

Synthesis of gold and silver nanoparticles by use of arabinoglucan from Lallemantia royleana.

Highly stable gold and silver nanoparticles were synthesized by use of an arabinoglucan from Lallemantia royleana seeds without additional use of reducing or stabilizing agents. The mechanism involved the reduction potential of the hemicellulose as verified by cyclic voltammetry. The arabinoglucan used was substantially free from ferulic acid and phenolic content, suggesting the inherent reducing potential of arabinoglucan for gold and silver ions. The synthesized nanoparticles exhibited surface plasmon resonance maxima at 515 nm (gold) and 397 nm (silver) corresponding to sizes of 10 nm and 8 nm, respectively. The zeta potential values were -24.1 mV (gold) and -22.3 mV (silver). The silver nanoparticles showed potential for application in surface-enhanced Raman spectroscopy. Gold nanoparticles were found to be non-toxic, whereas silver nanoparticles exhibited dose-dependent biological activities and found to be cytotoxic against brine shrimps and HeLa cell lines and the tumours caused by A. tumefaciens.

Exploration of Noncovalent Interactions, Chemical Reactivity, and Nonlinear Optical Properties of Piperidone Derivatives: A Concise Theoretical Approach.

The organic compounds with a π-bond system lead to electric charge delocalization which enables them to reveal fascinating nonlinear optical properties. Mono-carbonyl curcuminoids also have an appealing skeleton from the conjugation view point. Interesting chemical structures of the 3,5-bis(arylidene)-N-benzenesulfonyl-4-piperidone derivatives motivated us to perform density functional theory (DFT)-based studies. Therefore, computations using the B3LYP/6-311G(d,p) functional of DFT were executed to explore geometric parameters, highest occupied molecular orbital (HOMO)-lowest unoccupied molecular orbital (LUMO) energies, and natural bond orbital (NBO) analyses. Moreover, three different functionals such as HF, B3LYP, and M06 with the 6-311G(d,p) basis set were used to investigate the average polarizability ⟨α⟩ and first hyperpolarizability (ßtot)-based properties of all compounds. A good concurrence among calculated and experimental parameters was obtained through root mean square error calculations. The molecular stability of piperidone derivatives was examined using the Hirshfeld surface and NBO analyses. Natural population analysis was also performed to obtain insights about atomic charges. Calculated HOMO-LUMO energies showed that charge transfer interactions take place within the molecules. Moreover, global reactivity parameters including electronegativity, chemical hardness, softness, ionization potential, and electrophilicity were calculated using the HOMO and LUMO energies. The average polarizability ⟨α⟩ and first hyperpolarizability (ßtot) values of all compounds were observed to be larger in magnitude at the aforesaid functional than the standard compound.

First principles study of electronic and nonlinear optical properties of A-D-π-A and D-A-D-π-A configured compounds containing novel quinoline-carbazole derivatives.

Materials with nonlinear optical (NLO) properties have significant applications in different fields, including nuclear science, biophysics, medicine, chemical dynamics, solid physics, materials science and surface interface applications. Quinoline and carbazole, owing to their electron-deficient and electron-rich character respectively, play a role in charge transfer applications in optoelectronics. Therefore, an attempt has been made herein to explore quinoline-carbazole based novel materials with highly nonlinear optical properties. Structural tailoring has been made at the donor and acceptor units of two recently synthesized quinoline-carbazole molecules (Q1, Q2) and acceptor-donor-π-acceptor (A-D-π-A) and donor-acceptor-donor-π-acceptor (D-A-D-π-A) type novel molecules Q1D1-Q1D3 and Q2D2-Q2D3 have been quantum chemically designed, respectively. Density functional theory (DFT) and time-dependent density functional theory (TDDFT) computations are performed to process the impact of acceptor and donor units on photophysical, electronic and NLO properties of selected molecules. The λ max values (321 and 319 nm) for Q1 and Q2 in DSMO were in good agreement with the experimental values (326 and 323 nm). The largest shift in absorption maximum is displayed by Q1D2 (436 nm). The designed compounds (Q1D3-Q2D3) express absorption spectra with an increased border and with a reduced band gap compared to the parent compounds (Q1 and Q2). Natural bond orbital (NBO) investigations showed that the extended hyper conjugation and strong intramolecular interaction play significant roles in stabilising these systems. All molecules expressed significant NLO responses. A large value of ß tot was elevated in Q1D2 (23 885.90 a.u.). This theoretical framework reveals the NLO response properties of novel quinoline-carbazole derivatives that can be significant for their use in advanced applications.

In vitro study of chitosan-based multi-responsive hydrogels as drug release vehicles: a preclinical study.

Systematic administration of painkillers and anti-inflammatory drugs is routinely employed to minimize pain and bodily disorders. Controlled drug delivery has the potential to improve the outcomes of disorders by providing sustained exposure to efficacious drug concentrations. Herein, we report the fabrication of multi-responsive hydrogels using reactive and functional polymers such as chitosan and polyvinyl pyrrolidone by varying the concentration of a cleavable crosslinker, tetraethyl orthosilicate. The swelling indices of the hydrogels were evaluated in distilled water, solutions with different pH values and different electrolytes. FTIR, WAXRD and TGA were conducted to investigate the structures, crystallinities and thermal stabilities of the prepared multi-responsive hydrogels, respectively. The ultimate tensile strength and elongations at break of the fabricated hydrogels were investigated to assess their mechanical stability. Optical microscopy, biodegradation, antimicrobial and cytotoxicity analyses were further carried out to verify the magnified crosslinked and porous structures, biodegradabilities, biocompatibilities and toxic behaviour of the as-prepared hydrogels, respectively. Drug release analysis was conducted to evaluate their release behaviour in PBS, SGF, SIF and electrolyte solutions. The overall results indicate the successful development of novel, non-toxic and sustained drug deliverable hydrogels, which can be considered as a paramount success towards the fabrication of controlled drug delivery systems.

Electrochemical treatment of 2, 4-dichlorophenol using a nanostructured 3D-porous Ti/Sb-SnO2-Gr anode: Reaction kinetics, mechanism, and continuous operation.

2, 4-dichlorophenol (2, 4-DCP) is considered to be a highly toxic, mutagenic, and possibly carcinogenic pollutant. This study is focused on the electrochemical oxidation of 2, 4-DCP on nanostructured 3D-porous Ti/Sb-SnO2-Gr anodes, with the aim of presenting a comprehensive elucidation of mineralization process through the investigation of influential kinetics, the reactivity of hydroxyl radical's and analysis of intermediates. High efficiency was achieved at pH of 3 using Na2SO4 electrolytes at a current density of 30 mA cm-2. Under the optimized conditions, a maximum removal of 2, 4-DCP of up to 99.9% was reached, whereas a TOC removal of 81% was recorded with the lowest ECTOC (0.49 kW h g-1) within 40 min of electrolysis. To explore the stability of the 3D-Ti/Sb-SnO2-Gr electrodes, a continuous electrochemical operation was established, and the consistent mineralization results indicated the effectiveness of the 3D-Ti/Sb-SnO2-Gr system concerning its durability and practical utilization. EPR studies demonstrated the abundant generation of OH radicals on 3D-Ti/Sb-SnO2-Gr, resulting in fast recalcitrant pollutant incineration. From dechlorination and the reactivity of the OH radicals, several intermediates including six cyclic byproducts and three aliphatic carboxylic acids were detected, and two possible degradation pathways were proposed that justify the complete mineralization of 2, 4-DCP.

Nanostructured 3D-porous graphene hydrogel based Ti/Sb-SnO2-Gr electrode with enhanced electrocatalytic activity.

Nanostructured highly porous 3D-Ti/Sb-SnO2-Gr electrode, based on 3D porous graphene hydrogel was fabricated via a fast-evaporation technique through layer by layer (LBL) deposition. The 3D pores are uniformly distributed on the high fidelity of substrate with pore sizes of 7-12 nm, as confirmed by SEM analysis. Compared to Ti/Sb-SnO2 electrode, the fabricated 3D porous electrode possesses high oxygen evolution potential (2.40 V), smaller charge transfer resistance (29.40 Ω cm-2), higher porosity (0.90), enhanced roughness factor (181), and larger voltammetric charge value (57.4 mC cm-2). Electrocatalytic oxidation of Rhodamine B (RhB) was employed to evaluate the efficiency of the fabricated 3D-Ti/Sb-SnO2-Gr anode. The results show that the electrochemical reaction follows pseudo first order kinetics with rate constant (k) value of 4.93 × 10-2 min-1, which is about 3.91 times higher compared to flat Ti/Sb-SnO2. The fabricated electrode demonstrates better stability and low specific energy consumption signifying its potential usage in electrocatalysis.

Facile Synthesis of Defective TiO2-x Nanocrystals with High Surface Area and Tailoring Bandgap for Visible-light Photocatalysis.

A facile hydrothermal approach has been developed to prepare defective TiO2-x nanocrystals using Ti(III)-salt as a precursor and L-ascorbic acid as reductant and structure direction agent. The prepared TiO2-x nanocrystals are composed of a highly crystallized TiO2 core and a disordered TiO2-x outer layer, possessing high surface area, controlled oxygen vacancy concentration and tunable bandgap via simply adjusting the amount of added L-ascorbic acid. The defective TiO2-x shows high photocatalytic efficiency in methylene blue and phenol degradation as well as in hydrogen evolution under visible light, underlining the significance of the present strategy for structural and bandgap manipulation in TiO2-based photocatalysis.