Design of Liquid Crystal Materials Based on Palmitate, Oleate, and Linoleate Derivatives for Optoelectronic Applications.

Herein, liquid crystalline derivatives based on palmitate, oleate, and linoleate moieties with azomethine cores were synthesized, and their physical, chemical, optical, and photophysical properties were investigated in detail. The mesomorphic activity of these materials was examined through polarized optical microscopy (POM) and differential scanning calorimetry (DSC). The observed results revealed that the stability of the thermal mesophase depends on the terminal polar as well as on the fatty long-chain substituents. Purely smectogenic phases were detected in all three terminal side chains. A eutectic composition with a low melting temperature and a broad smectic A range was found by constructing a binary phase diagram and addressing it in terms of the mesomorphic temperature range. The energy bandgap of the palmitate-based derivative (Ia) was determined as 3.95 eV and slightly increased to 4.01 eV and 4.05 eV for the oleate (Ib) and linoleate (Ic) derivatives, respectively. The optical constants (n, κ, εr, and εi) were extracted from the fitting of measured spectroscopic ellipsometer data. The steady-state spectra of these samples exhibited a broad emission in the range 400-580 nm, which was found to be blue shifted to 462 nm for both Ib and Ic derivatives. The average fluorescence decay lifetime of the Ia derivative was found to be 598 ps, which became faster for the Ib and Ic derivatives and slower for the sample with a chloride end polar group.

Synthesis, Crystal Structure, Quantum Chemical Analysis, Electrochemical Behavior, and Antibacterial and Photocatalytic Activity of Co Complex with Pyridoxal-(S-Methyl)-isothiosemicarbazone Ligand.

New complex Co(III) with ligand Pyridoxal-S-methyl-isothiosemicarbazone, (PLITSC) was synthesized. X-ray analysis showed the bis-ligand octahedral structure of the cobalt complex [Co(PLITSC-H)2]BrNO3·CH3OH (compound 1). The intermolecular interactions governing the crystal structure were described by the Hirsfeld surface analysis. The structure of compound 1 and the corresponding Zn complex (([Zn(PLTSC)(H2O)2]SO4·H2O)) were optimized at the B3LYP/6-31 + G (d,p)/LanL2DZ level of theory, and the applicability was assessed by comparison with the crystallographic structure. The natural bond orbital analysis was used for the discussion on the stability of formed compounds. The antibacterial activity of obtained complexes towards S. aureus and E. coli was determined, along with the effect of compound 1 on the formation of free radical species. Activity of compound 1 towards the removal of methylene blue was also investigated. The voltammograms of these compounds showed the reduction of metal ions, as well as the catalyzed reduction of CO2 in acidic media.

Biophysical, Biochemical, and Molecular Docking Investigations of Anti-Glycating, Antioxidant, and Protein Structural Stability Potential of Garlic.

Garlic has been reported to inhibit protein glycation, a process that underlies several disease processes, including chronic complications of diabetes mellitus. Biophysical, biochemical, and molecular docking investigations were conducted to assess anti-glycating, antioxidant, and protein structural protection activities of garlic. Results from spectral (UV and fluorescence) and circular dichroism (CD) analysis helped ascertain protein conformation and secondary structure protection against glycation to a significant extent. Further, garlic showed heat-induced protein denaturation inhibition activity (52.17%). It also inhibited glycation, advanced glycation end products (AGEs) formation as well as lent human serum albumin (HSA) protein structural stability, as revealed by reduction in browning intensity (65.23%), decrease in protein aggregation index (67.77%), and overall reduction in cross amyloid structure formation (33.26%) compared with positive controls (100%). The significant antioxidant nature of garlic was revealed by FRAP assay (58.23%) and DPPH assay (66.18%). Using molecular docking analysis, some of the important garlic metabolites were investigated for their interactions with the HSA molecule. Molecular docking analysis showed quercetin, a phenolic compound present in garlic, appears to be the most promising inhibitor of glucose interaction with the HSA molecule. Our findings show that garlic can prevent oxidative stress and glycation-induced biomolecular damage and that it can potentially be used in the treatment of several health conditions, including diabetes and other inflammatory diseases.

Induced Nematic Phase of New Synthesized Laterally Fluorinated Azo/Ester Derivatives.

A new series of laterally fluorinated mesomorphic compounds, namely 2-fluoro-4-((4-(alkyloxy)phenyl)diazenyl)phenyl 4-substitutedbenzoate (Inx) were prepared and evaluated for their mesophase behavior. The synthesized series constitutes five members that possess different terminally attached polar groups (X). Their molecular structures were confirmed by elemental analyses and both FT-IR and NMR spectroscopy. Examination of the prepared derivatives was conducted via experimental and theoretical tools. Mesomorphic investigations were carried by polarized optical microscopy (POM) and differential scanning calorimetry (DSC). DSC and POM measurements indicated that except for the un-substituted analogue, all other derivatives were purely nematogenic, possessing their nematic (N) mesophase enantiotropically. This is to say that insertions of terminal polar substituents on their mesogenic structures induced the N phase. In addition, the location of lateral and terminal polar moieties played a considerable role in achieving good thermal N stability. Computational calculations were investigated to determine the deduced optimized molecular structures. Theoretical data indicated that both size and polarity of the terminal substituent (X) have essential impact on the thermal parameters and optical properties of possible geometries.

Biologically Active α-Amino Amide Analogs and γδ T Cells-A Unique Anticancer Approach for Leukemia.

Advanced stage cancers are aggressive and difficult to treat with mono-therapeutics, substantially decreasing patient survival rates. Hence, there is an urgent need to develop unique therapeutic approaches to treat cancer with superior potency and efficacy. This study investigates a new approach to develop a potent combinational therapy to treat advanced stage leukemia. Biologically active α-amino amide analogs (RS)-N-(2-(cyclohexylamino)-2-oxo-1-phenylethyl)-N-phenylpropiolamide (α-AAA-A) and (RS)-N-(2-(cyclohexylamino)-2-oxo-1-phenylethyl)-N-phenylbut2-enamide (α-AAA-B) were synthesized using linear Ugi multicomponent reaction. Cytotoxicities and IC50 values of α-AAA-A and α-AAA-B against leukemia cancer cell lines (HL-60 and K562) were analyzed though MTT assay. Cytotoxic assay analyzed percent killing of leukemia cell lines due to the effect of γδ T cells alone or in combination with α-AAA-A or α-AAA-B. Synthesized biologically active molecule α-AAA-A exhibited increased cytotoxicity of HL-60 (54%) and K562 (44%) compared with α-AAA-B (44% and 36% respectively). Similarly, α-AAA-A showed low IC50 values for HL-60 (1.61 ± 0.11 µM) and K562 (3.01 ± 0.14 µM) compared to α-AAA-B (3.12 ± 0.15 µM and 6.21 ± 0.17 µM respectively). Additive effect of amide analogs and γδ T cells showed significantly high leukemia cancer cell killing as compared to γδ T cells alone. A unique combinational therapy with γδ T cells and biologically active anti-cancer molecules (α-AAA-A/B), concomitantly may be a promising cancer therapy.

Synthetic, Mesomorphic, and DFT Investigations of New Nematogenic Polar Naphthyl Benzoate Ester Derivatives.

Four new non-symmetrical derivatives based on central naphthalene moiety, 4-((4-(alkoxy)phenyl) diazenyl)naphthalen-1-yl 4-substitutedbenzoate (In/x), were prepared, and their properties were investigated experimentally and theoretically. The synthesized materials bear two wing groups: an alkoxy chain of differing proportionate length (n = 6 and 16 carbons) and one terminal attached to a polar group, X. Their molecular structures were elucidated via elemental analyses and FT-IR and NMR spectroscopy. Differential scanning calorimetry (DSC) and polarized optical microscopy (POM) were carried out to evaluate their mesomorphic properties. The results of the experimental investigations revealed that all the synthesized analogues possess only an enantiotropic nematic (N) mesophase with a high thermal stability and broad range. Density functional theory (DFT) calculations were in accordance with the experimental investigations and revealed that all prepared materials are to be linear and planar. Moreover, the rigidity of the molecule increased when an extra fused ring was inserted into the center of the structural shape, so its thermal and geometrical parameters were affected. Energy gap predictions confirmed that the I16/c derivative is more reactive than other compounds.

Optimization of methods for peripheral blood mononuclear cells isolation and expansion of human gamma delta T cells.

Human Vg9/Vδ2 T cells (γδ T cells) are immune surveillance cells both in innate and adaptive immunity and are a possible target for anticancer therapies, which can induce immune responses in a variety of cancers. Small non-peptide antigens such as zoledronate can do activation and expansion of T cells in vitro. It is evident that for adoptive cancer therapies, large numbers of functional cells are needed into cancer patients. Hence, optimization of methods needs to be carried out for the efficient expansion of these T cells. Standardization of peripheral blood mononuclear cells (PBMCs) isolation was devised. Cytokines (interleukin 2 (IL-2) and interleukin 15 (IL-15)) and zoledronate were also standardized for different concentrations. It was found that an increased number of PBMCs were recovered when washing was done at 1100 revolution per minute (rpm). Significantly high expansion fold was (2524 ± 787 expansion fold) achieved when stimulation of PBMCs was done with 1 µM of zoledronate and both cytokines IL-2 and IL-15 supported the expansion and survival of cells at the concentrations of 100 IU/ml and 10 ng/ml respectively. 14-day cultures showed highly pure (91.6 ± 5.1%) and live (96.5 ± 2.5%) expanded γδ T cells. This study aimed to standardize an easy to manipulate technique for the expansion of γδ T cells, giving a higher yield.

Fabrication of Reproducible and Selective Ammonia Vapor Sensor-Pellet of Polypyrrole/Cerium Oxide Nanocomposite for Prompt Detection at Room Temperature.

Polypyrrole (PPy) and polypyrrole/cerium oxide nanocomposite (PPy/CeO2) were prepared by the chemical oxidative method in an aqueous medium using anhydrous ferric chloride (FeCl3) as an oxidant. The successful formulation of materials was confirmed by Fourier transform infrared spectroscopy (FT-IR), X-ray diffraction (XRD), thermogravimetric analysis (TGA), scanning electron microscopy (SEM), and transmittance electron microscopy (TEM). A four-in-line probe device was used for studying DC electrical conductivity and ammonia vapor sensing properties of PPy and PPy/CeO2. The significant improvement in both the conductivity and sensing parameters of PPy/CeO2 compared to pristine PPy reveals some synergistic/electronic interaction between PPy and cerium oxide nanoparticles (CeO2 NPs) working at molecular levels. The initial conductivity (i.e., conductivity at room temperature) was found to be 0.152 Scm-1 and 1.295 Scm-1 for PPy and PPy/CeO2, respectively. Also, PPy/CeO2 showed much better conductivity retention than pristine PPy under both the isothermal and cyclic ageing conditions. Ammonia vapor sensing was carried out at different concentration (0.01, 0.03, 0.05, 0.1, 0.2, 0.3, 0.4, and 0.5 vol %). The sensing response of PPy/CeO2 varied with varying concentrations. At 0.5 vol % ammonia concentration, the % sensing response of PPy and PPy/CeO2 sensor was found to be 39.1% and 93.4%, respectively. The sensing efficiency of the PPy/CeO2 sensor was also evaluated at 0.4. 0.3, 0.2, 0.1, 0.05, 0.03, and 0.01 vol % ammonia concentration in terms of % sensing response, response/recovery time, reversibility, selectivity as well as stability at room temperature.

Enhanced Photocatalytic Activity of Cu2O Cabbage/RGO Nanocomposites under Visible Light Irradiation.

Towards the utilization of Cu2O nanomaterial for the degradation of industrial dye pollutants such as methylene blue and methyl orange, the graphene-incorporated Cu2O nanocomposites (GCC) were developed via a precipitation method. Using Hummers method, the grapheme oxide (GO) was initially synthesized. The varying weight percentages (1-4 wt %) of GO was incorporated along with the precipitation of Cu2O catalyst. Various characterization techniques such as Fourier-transform infra-red (FT-IR), X-ray diffraction (XRD), UV-visible diffused reflectance (UV-DRS), Raman spectroscopy, thermo gravimetric analysis (TGA), energy-dispersive X-ray analysis (EDX), and electro chemical impedance (EIS) were followed for characterization. The cabbage-like morphology of the developed Cu2O and its composites were ascertained from field-emission scanning electron microscopy (FESEM) and high-resolution transmission electron microscopy (HR-TEM). In addition, the growth mechanism was also proposed. The results infer that 2 wt % GO-incorporated Cu2O composites shows the highest value of degradation efficiency (97.9% and 96.1%) for MB and MO at 160 and 220 min, respectively. Further, its catalytic performance over visible region (red shift) was also enhanced to an appreciable extent, when compared with that of other samples.

New Nitro-Laterally Substituted Azomethine Derivatives; Synthesis, Mesomorphic and Computational Characterizations.

Two new homologues series, based on two rings of the azomethine central group bearing the terminal alkoxy group of various chain lengths, were prepared. The alkoxy chain length varied between 6 and 16 carbons. The other terminal wing in the first series was the F atom, and the compound is named N-4-florobenzylidene-4-(alkoxy)benzenamine (In). The second group of compounds included a lateral NO2 substituent in addition to the terminal F atom, named N-(4-fluoro-3-nitrobenzylidene)-4-(alkyloxy)aniline (IIn). Mesomorphic and optical properties were carried out via differential scanning calorimetry (DSC) and polarized optical microscopy (POM). Elemental analyses, FT-IR, and NMR spectroscopy were carried out to elucidate the molecular structures of the synthesized groups. Mesomorphic investigations indicated that all the synthesized homologues (In) were monomorphic, possessing the smectic A (SmA) phase monotropically, while the second group (IIn) members were non-mesomorphic. The experimental data indicated that the formation of the mesophase is affected by the protrusion of the lateral nitro group. The disruption of the mesophase in the second group was attributed to the increase of its molecular width, which affects its lateral intermolecular interactions. The computational simulations were in agreement with the experimental data. On the other hand, the location of NO2 group within the molecular geometry increased the melting temperature of the molecule, and thus, affected their thermal and physical properties. By discussing the estimated parameters, it was found that the molecular architecture, the dipole moment, and the polarizability of the investigated compounds are highly affected by the electronic nature and position of the terminal and lateral substituents as well as their volumes.

Combinational therapeutics to combat cancer.

Mono-therapeutics is rarely effective as a treatment option, which limits the survival of patients in advanced grade aggressive cancers. Combinational therapeutics (multiple drugs for multiple targets) to combat cancer is gaining momentum in recent years. Hence, it is of interest to document known data for combinational therapeutics in cancer treatment. An amalgamation of therapeutic agents enhances the efficacy and potency of the therapy. Combinational therapy can potentially target multiple pathways that are necessary for the cancer cells to proliferate, and/or target molecules, which may help cancer to become more aggressive and metastasize. In this review, we discuss combinational therapeutics, which include human γδ T cells in combinations with biologically active anti-cancer molecules, which synergistically may produce promising combinational therapeutics.

Glycation and Oxidative Stress Increase Autoantibodies in the Elderly.

Aging causes gradual changes in free radicals, antioxidants, and immune-imbalance in the elderly. This study aims to understand links among aging, gluco-oxidative stress, and autoantibodies in asymptomatic individuals. In vitro glycation of human serum albumin (Gly-HSA) induces appreciable biochemical changes. Significant inhibition of advanced glycation end products (AGEs) formation was achieved using garlic extract (53.75%) and epigallocatechin-3-gallate from green tea (72.5%). Increased amounts of serum carbonyl content (2.42 ± 0.5) and pentosidine (0.0321 ± 0.0029) were detected in IV-S (S represent smokers) vs. IV group individuals. Direct binding ELISA results exhibited significantly high autoantibodies against Gly-HSA in group IV-S (0.55 ± 0.054; p < 0.001) and III-S (0.40 ± 0.044; p < 0.01) individuals as compared to the age matched subjects who were non-smokers (group IV and III). Moreover, high average percent inhibition (51.3 ± 4.1%) was obtained against Gly-HSA in IV-S group individuals. Apparent association constant was found to be high for serum immunoglobulin-G (IgG) from group IV-S (1.18 × 10-6 M) vs. serum IgG from IV group (3.32 × 10-7 M). Aging induced gluco-oxidative stress and AGEs formation may generate neo-epitopes on blood-proteins, contributing to production of autoantibodies in the elderly, especially smokers. Use of anti-glycation natural products may reduce age-related pathophysiological changes.