Organic–inorganic polypyrrole‐surface modified SiO2 hybrid nanocomposites: a facile and green synthetic approach

Organic–inorganic hybrid nanocomposites composed of conductive polypyrrole (PPy) and surface modified silica (SiO₂) were successfully prepared through an in situ chemical oxidative polymerization in supercritical carbon dioxide (scCO₂). SiO₂ nanoparticles were surface modified using 3‐methacryloxypropyltrimethoxysilane (MPTMS) in order to disperse well in the medium. Transmission electron microscopy (TEM) and scanning electron microscopy (SEM) showed that the SiO₂ nanoparticles were encapsulated into the polymer. UV‐visible spectra of the diluted colloidal dispersions of PPy/SiO₂ hybrid nanocomposites were similar to those of PPy system. Fourier transform infrared spectroscopy (FT‐IR) suggested the strong interaction between PPy and SiO₂. Surface characterizations of nanocomposites were described by X‐ray photoelectron spectroscopy (XPS). The nanocomposites synthesized in scCO₂ have been shown to possess higher electrical conductivity and thermal stability. Copyright © 2009 John Wiley & Sons, Ltd.     

Optical properties of magnetically doped cholesterics

We have computed the optical diffraction pattern for linearly polarized light incident normal to the twist axis (phase grating mode) of a magnetically doped cholesteric (ferrocholesteric). The intrinsic Faraday rotation of the magnetic grains results in extra orders of diffraction. Also we find diffraction for any azimuth of the incident vibration. Further, using the Jones N matrices we have worked out the optical properties for light propagation along the twist axis on the very low wavelength side of the reflection band. We find that the medium behaves very differently from a normal cholesteric.     

Microwave-promoted efficient synthesis of spiroindenotetrahydropyridine derivatives via a catalyst- and solvent-free pseudo one-pot five-component tandem Knoevenagel/aza-Diels–Alder reaction

A microwave-assisted, one-pot pseudo five-component reaction strategy has been developed for the synthesis of some novel spiroindenotetrahydropyridine derivatives from 1,3-indanedione, an aromatic aldehyde, and ammonium acetate under catalyst- and solvent-free conditions via tandem Knoevenagel/aza-Diels–Alder reaction.     

Synthesis of graphene oxide-poly(2-hydroxyethyl methacrylate) composite by dispersion polymerization in supercritical CO2: adsorption behavior for the removal of organic dye

The use of a biocompatible and thermoresponsive polymer, poly(2-hydroxyethyl methacrylate) (PHEMA) grafted onto the surface of graphene oxide (GO) as an adsorbent for the removal of a cationic dye (methylene blue [MB]) from an aqueous solution is examined in this work. GO–PHEMA forms a hydrogel in water thus overcoming the problem faced by carbon-based adsorbent materials during post-treatment (i.e., separation of adsorbent from the aqueous phase). The GO–PHEMA composite was synthesized using a green approach through dispersion polymerization in supercritical CO₂. The successful preparation of this composite was confirmed by a series of characterization techniques. The adsorption behavior of the composite toward MB such as the effect of the adsorbent dosage, pH, contact time, dye concentration, and recyclability were observed. In addition, the adsorption isotherm, kinetics and thermodynamics were investigated. According to the experimental data, the adsorption parameters were found to fit well into the Freundlich adsorption isotherm with a correlation coefficient of 0.975 and a maximum predicted adsorption capacity of 39.41 mg g^?1 at 25 °C. The adsorption kinetics studies showed that the adsorption behavior followed a pseudo-second-order reaction. On the other hand, the thermodynamics studies showed that the adsorption of MB on GO–PHEMA composite followed spontaneous and endothermic adsorption process with an efficient adsorption temperature at 45 °C. The experimental results also showed that the GO–PHEMA composite could remove 99.8% of the dye in 45 min. Therefore, GO–PHEMA composite is a favorable green adsorbent for environmental applications.     

Synthesis of polystyrene/SiO2 composite microparticles by dispersion polymerization in supercritical fluid

A novel synthetic route to prepare polystyrene/SiO₂ composite microparticles in supercritical carbon dioxide (scCO₂) is presented. Silica particles with the size of 130 nm which were surface-modified with 3-(trimethoxysilyl) propyl methacrylate were used as seeds in the dispersion polymerization of styrene in the presence of a polymeric stabilizer, poly(1,1-dihydroheptafluorobutyl methacrylate-co-diisopropylaminoethyl methacrylate) to produce dry composite particles. The transmission electron microscopy analysis revealed that the composite microspheres contained several silica particles.     

Magnesium(I) Reduction of Aluminum(III) Hydride Complexes: Generation of Mixed Valence Aluminum (AlI/Al0) Hydride Cluster Compounds, [Al6H8(NR3)2{Mg(β-diketiminate)}4]**

Reduction of a range of amido- and aryloxy-aluminum dihydride complexes, e.g. [AlH₂(NR₃){N(SiMe₃)₂}] (NR₃=NMe₃ or N-methylpiperidine (NMP)), with β-diketiminato dimagnesium(I) reagents, [{(^ArNacnac)Mg}₂] (^ArNacnac=[HC(MeCNAr)₂]⁻, Ar=mesityl (Mes) or 2,6-xylyl (Xyl)), have afforded deep red mixed valence aluminum hydride cluster compounds, [Al₆H₈(NR₃)₂{Mg(^ArNacnac)}₄], which have an average Al oxidation state of +0.66, the lowest for any well-defined aluminum hydride compound. In the solid-state, the clusters are shown to have distorted octahedral Al₆ cores, having zero-valent Al axial sites and mono-valent AlH₂⁻ equatorial units. Several novel by-products were isolated from the reactions that gave the clusters, including the Mg−Al bonded magnesio-aluminate complexes, [(^ArNacnac)(Me₃N)Mg−Al(μ-H)₃[{Mg(^ArNacnac)}₂(μ-H)]]. Computational analyses of one aluminum hydride cluster revealed its Al₆ core to be electronically delocalized, and to possess one unoccupied, and six occupied, skeletal molecular orbitals.     

Synthesis of polyaniline/Q-CdSe composite via ultrasonically assisted dynamic inverse emulsion polymerization

In this communication, polyaniline/CdSe quantum dots (PANI/Q-CdSe) composite was successfully synthesized via in situ ultrasonically assisted dynamic inverse emulsion polymerization. The synthesized PANI-coated Q-CdSe composite was characterized by field emission transmission electron microscopy showed that the CdSe quantum dots have an average size of around ca. 5 nm were dispersed in the PANI matrix. X-ray diffraction, Fourier transform infrared spectrum (FT-IR) and UV-visible spectrum were used to characterize the structure of the obtained PANI/Q-CdSe composite. FT-IR spectra indicated that the polymer was highly doped and existed in conducting emeraldine salt form. The obtained PANI/Q-CdSe composite showed significant improvement in the thermal behavior as indicated by TGA thermograph. The presented dynamic polymerization process is very fast and produces stable colloidal dispersion. This approach provides a one-step, simple, general, and inexpensive method for the preparation of PANI/Q-CdSe composite.     

B(C6F5)3 catalyzed synthesis of dihydropyrano[3,2-b]chromenediones under solvent-free conditions

Abstract

A simple, efficient, solventless, and one step, B(C₆F₅)₃ catalyzed, synthesis of dihydropyrano[3,2-b]chromenediones from dimedone, aldehyde and kojic acid is described. This protocol proceeds smoothly, accommodates aromatic as well as heteroaromatic aldehydes and gives dihydropyrano[3,2-b]chromenediones in excellent yield.     

Native Fluorescence and Time Resolved Fluorescence Spectroscopic Characterization of Normal and Malignant Oral Tissues Under UV Excitation—an In Vitro Study

The present work aims to investigates the native fluorescence and time resolved fluorescence spectroscopic characterization of oral tissues under UV excitation. The fluorescence emission spectra of oral tissues at 280 nm excitation were obtained. From the spectra, it was observed that the alteration in the biochemical and morphological changes present in tissues. Subsequently, the Full width at Half Maximum (FWHM) of every individual spectra of 20 normal and 40 malignant subjects were calculated. The student’s t-test analysis reveals that the data were statistically significant (p?=?0.001). The fluorescence excitation spectra at 350 nm emission of malignant tissues confirms the alteration in protein fluorescence with respect to normal counterpart. To quantify the observed spectral differences, the two ratio variables R₁?=?I₂₇₅/I₃₁₀ and R₂?=?I₃₁₀/I₃₂₈ were introduced in the excitation spectra. Among them, the Linear Discriminant Analysis (LDA) of R₁ reveals better classification with 86.4 % specificity and 82.5 % sensitivity. The fluorescence decay kinetics of oral tissues was obtained at 350 nm emission and it was found that the decay kinetics was triple exponential. Then the ROC analysis of fractional amplitudes and component lifetime reveals that the average lifetime shows 77 % sensitivity and 70 % specificity with the cut off value 4.85 ns. Briefly, the average lifetime exhibits better statistical significance when compared to fractional amplitudes and component lifetimes.