Experimental investigation for stability and surface properties of TiO2 and Al2O3 water-based nanofluids

Journal of Thermal Analysis and Calorimetry - Nanofluids have gained recent attention because of their potential applications in diverse engineering fields like enhancing thermal transport,...     

The separation of hypericin's enantiomers and their photophysics in chiral environments

We report the first separation of the enantiomers of hypericin. Their steady-state optical spectra and ultrafast primary photoprocesses are investigated in chiral environments. Within experimental error, there is no difference between the two enantiomers in any of the systems considered. This is consistent with the emerging picture that the rich and extended absorption spectrum of hypericin is not a result of ground-state heterogeneity. It is also consistent with the observation that the spectra and photophysics of hypericin are generally insensitive to environments in which it does not aggregate.     

Microstructure and electrical properties of BaTiO<Subscript>3</Subscript> and (Ba,Sr)TiO<Subscript>3</Subscript> ferroelectric thin films on nickel electrodes

Nickel thin films have been sputtered on standard Si/SiO₂ substrates with TiO₂ as an adhesive layer. The thermal stability of these substrates was analyzed. SEM images show an increase in grain size with annealing temperature. They were found to be stable till 800°C, beyond which the nickel layer disintegrated. These substrates were used for deposition of BaTiO₃ and (Ba,Sr)TiO₃ dielectric thin films under a reducing atmosphere. The dielectric thin films were processed with various pyrolysis and annealing temperatures in order to optimize the dielectric properties. Increased pyrolysis temperatures showed an increase in the grain size. Results on these nickelised substrates were finally compared with dielectric films deposited on platinized silicon substrates under identical conditions but crystallized in an oxygen atmosphere.     

Self-Assembly of Benzimidazole-Derived Tris-NHC Ligands and AgI-Ions to Hexanuclear Organometallic Cages and Their Unusual Transmetalation Chemistry

Multi-ligand self-assembly to attain the Ag^I-N-heterocyclic carbene (NHC)-built hexanuclear organometallic cages of composition [Ag₆( 3 a , b )₄](PF₆)₆ from the reaction of benzimidazole-derived tris(azolium) salts [H₃- 3 a , b ](PF₆)₃ with Ag₂O was achieved. The molecular structures of the cages were established by X-ray diffraction studies along with NMR and MS analyses. The existence of a single assembly in solution was supported by diffusion-ordered spectroscopy (DOSY) ¹H NMR spectra. Further, transmetalation reactions of these self-assembled complexes, [Ag₆( 3 a , b )₄](PF₆)₆, with Cu^I/Au^I-ions provided various coinage metal-NHC complexes having diverse molecular compositions, which included the first example of a hexanuclear Cu^I-dodecacarbene complex, [Cu₆( 3 b )₄](PF₆)₆.     

Coumarinyl azoimidazolyl complexes of osmium(II) hydridocarbonyls: spectroscopic and structural characterization,oxidation catalysis,photovoltaic effect and density functional theory computation

Os(II) hydridocarbonyl complexes of coumarinyl azoimidazoles, [Osh(CO)(PPh₃)₂(CZ‐4R‐R′)]^0/+ ( 3 , 4 ) (CZ‐R‐H = 2‐(coumarinyl‐6‐azo)‐4‐substituted imidazole or 1‐alkyl‐2‐(coumarinyl‐6‐azo)‐4‐substituted imidazole), were characterized from spectroscopic data and the single‐crystal X‐ray data for one of the complexes, [Osh(CO)(PPh₃)₂(CZ‐4‐Ph)] ( 3c ) (CZ‐4‐Ph = 2‐(coumarinyl‐6‐azo)‐4‐phenylimidazolate), confirmed the structure. The complexes show higher emission (quantum yield ? = 0.0163–0.16) and longer lifetime (τ = 1.4–10.3 ns) than free ligands (? = 0.0012–0.0185 and τ = 0.685–1.306 ns). Cyclic voltammetry shows quasi‐reversible metal oxidation at 0.67–0.94 V for [Os(III)/Os(II)] and 1.21–1.36 V for [Os(IV)/Os(III)] and subsequent azo reductions (?0.68 to ?0.95 V for [? N?N? ]/[? N N? ]^? and irreversible < ?1.2 V for [? N N? ]^?/[? N? N? ]^2?) of the chelated coumarinyl azoimidazole. The complexes are photostable and show better photovoltaic power conversion efficiency than free ligands. Also, the complexes were used as catalysts for the oxidation of primary/secondary alcohols to aldehydes/ketones using oxidizing agents like N‐methylmorpholine N‐oxide, t‐BuOOH and H₂O₂. Density functional theory computation was carried out from the optimized structures and the data obtained were used to interpret the electronic and photovoltaic properties. Copyright © 2016 John Wiley & Sons, Ltd.     

A validated HPLC‐PDA method for identification and quantification of two bioactive alkaloids,ephedrine and cryptolepine,in different Sida species

A simple, rapid, accurate and reproducible reverse‐phase HPLC method has been developed for the identification and quantification of two alkaloids ephedrine and cryptolepine in different extracts of Sida species using photodiode array detection. Baseline separation of the two alkaloids was achieved on a Waters RP‐18 X‐terra column (250 × 4.6 mm, 5 µm) using a solvent system consisting of a mixture of water containing 0.1% Trifluoroacetic acid (TFA) and acetonitrile in a gradient elution mode with detection at 210 and 280 nm for ephedrine and cryptolepine, respectively. The calibration curves were linear in a concentration range of 10–250 µg/mL for both the alkaloids with correlation coefficient values >0.99. The limits of detection and quantification for ephedrine and cryptolepine were 5 and 10 µg/mL and 2.5 and 5 µg/mL, respectively. Relative standard deviation values for intra‐day and inter‐day precision were 1.22 and 1.04% for ephedrine and 1.71 and 2.06% for cryptolepine, respectively. Analytical recovery ranged from 92.46 to 103.95%. The developed HPLC method was applied to identify and quantify ephedrine and cryptolepine in different extracts of Sida species. Copyright © 2013 John Wiley & Sons, Ltd.     

Assessment of the in vitro toxicity of calixarenes and a metal-seamed calixarene: a chemical pathway for clinical application

Calixarenes are known to form host–guest complexes and supramolecular nanoassemblies with well-defined architectures. However, the use of these materials in conjunction with drug moieties is still under explored. One reason is the insufficient biocompatibility studies. Our present study represents a systematic in vitro investigation of the cytotoxicity associated with C-methylresorcin[4]arene, C-methylpyrogallol[4]arene, p-phosphonated calix[8]arene and a metal-seamed calixarene–copper(II) complex, using human HEK293 and rat C6G cell lines and two different cell viability assays (MTT and CellTiter-Glo) to avoid species-biased results. All compounds showed low to moderate toxicity. The trend in the CC₅₀ values indicated that the suppression of the coordination ability and the presence of phosphonate groups decrease the overall cytotoxicity of the compounds. The results of this study not only establish calixarenes and their immediate families as potential drug carriers and drug modifiers, but also reveal a pathway for fine-tuning their toxicological behaviour by appropriate chemical modification.     

MWCNTs-ZrO2 as a reusable heterogeneous catalyst for the synthesis of N-heterocyclic scaffolds under green reaction medium

A simple, efficient, and facile heterogeneous multi-walled carbon nanotubes-zirconia nanocomposite (MWCNTs-ZrO₂) has been synthesized using natural feedstock coconut juice (água-de-coco do Ceará). The synthesized catalyst was characterized by Fourier transform infrared spectroscopy, X-ray diffraction, field emission scanning electron microscopy, and X-ray photoelectron spectroscopy analysis. The heterogeneous nanocomposite has been used for one-pot synthesis of various N-heterocyclic compounds like pyrazoles, 1,2-disubstituted benzimidazoles, 2-arylbenzazoles, and 2,3-dihydroquinazolin-4(1H)-ones under green reaction medium at room temperature. This novel method has several advantages, such as short reaction time, simple work-up, excellent yield, and green reaction conditions. The catalyst was recycled up to four times without significant loss in catalytic activity.