Preparation and characterization of novel semi‐interpenetrating 2‐hydroxyethyl methacrylate‐g‐chitosan copolymeric microspheres for sustained release of indomethacin

A novel semi‐interpenetrating (semi‐IPN) graft copolymer of 2‐hydroxyethyl methacrylate (HEMA) with chitosan (CS) has been prepared in the form of microspheres, using water‐in‐oil (W/O) emulsion technique. Microspheres were characterized by Fourier transform infrared spectroscopy (FTIR), differential scanning calorimetry (DSC), and X‐ray diffractometry (X‐RD) to confirm the crosslinking and polymorphism of indomethacin (IDM). The X‐RD and DSC techniques indicated a molecular‐level dispersion of IDM in the IPN matrix. Scanning electron micrographs (SEM) taken at the cross section of the microspheres have shown rough surfaces around the microspheres. The sustained release characteristics of the matrices for IDM, an anti‐inflammatory drug, were investigated in pH 7.4 media. Particle size and size distribution of the microspheres were studied by laser light diffraction particle size analyzer. The drug was released in a sustained manner for up to 12 h. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci, 2006     

ZnO–SnO2 nanocubes for fluorescence sensing and dye degradation applications

ZnO–SnO₂ nanocubes were used as promising material for efficient sensing of p-nitrophenol and faster photocatalytic degradations of dyes like methyl orange (MO), methylene Blue (MB) and acid orange 74 (AO74). ZnO–SnO₂ nanocubes were prepared by the facile solution process at 50 °C using Zn(NO₃)₂·6H₂O and SnCl₂·2H₂O as a precursor in the presence of ethylenediammine. The synthesized material was examined for its morphological, structural, crystalline, optical, vibrational, and compositional studies by using field emission scanning electron microscopy (FESEM), X-ray diffraction (XRD), Fourier Transform Infrared (FTIR) spectroscopy, X-ray photoelectron spectroscopy (XPS) and photoluminescence spectroscopy. FESEM studies revealed the formation of well-defined ZnO–SnO₂ nanocubes where the structural examinations revealed the formation of a crystalline tetragonal rutile phase for SnO₂ with some crystal sites doped with Zn. The as-synthesized nanocubes were explored for their photocatalytic activities towards three different dye viz. MO, MB, and AO74. Practically, complete degradation of AO74 was seen within 4 minutes of photo-irradiation in the presence of 0.05 g ZnO–SnO₂ nanocubes. However, 97.17% and 41.63% degradations were observed for MB and MO within 15 and 60 minutes, respectively. All the dye degradation processes followed the pseudo-first-order kinetic model. Moreover, the as-synthesized nanocubes were utilized to fabricate highly sensitive and selective fluorescent chemical sensor for the detection of p-nitrophenol (PNP). ZnO–SnO₂ nanocubes showed a very low detection limit of 4.09 μM for the detection of PNP as calculated according to the 3σ IUPAC criteria. Further, the as-synthesized ZnO–SnO₂ nanotubes were found to be highly selective for p-nitrophenol as compared to the other two isomers.     

Synthetic and Biological Studies of Sesquiterpene Polygodial: Activity of 9‐Epipolygodial against Drug‐Resistant Cancer Cells

Polygodial, a terpenoid dialdehyde isolated from Polygonum hydropiper L., is a known agonist of the transient receptor potential vanilloid 1 (TRPV1). In this investigation a series of polygodial analogues were prepared and investigated for TRPV1‐agonist and anticancer activities. These experiments led to the identification of 9‐epipolygodial, which has antiproliferative potency significantly exceeding that of polygodial. 9‐Epipolygodial was found to maintain potency against apoptosis‐resistant cancer cells as well as those displaying the multidrug‐resistant (MDR) phenotype. In addition, the chemical feasibility for the previously proposed mechanism of action of polygodial, involving the formation of a Paal–Knorr pyrrole with a lysine residue on the target protein, was demonstrated by the synthesis of a stable polygodial pyrrole derivative. These studies reveal rich chemical and biological properties associated with polygodial and its direct derivatives. These compounds should inspire further work in this area aimed at the development of new pharmacological agents, or the exploration of novel mechanisms of covalent modification of biological molecules with natural products.     

Chitosan/poly(dimethylaminoethylmethacrylate-co-hydroxyethylacrylate) based semi-IPN hydrogels and silver nanocomposites: Synthesis,evaluation of amoxicillin release studies,and antibacterial studies

To fabricate new smart materials that can deliver both the pharmaceutically active molecules and metal nanoparticles, we have formulated chitosan-based semi-IPN hydrogels and their silver nanocomposites (Ag NCs) along with amoxicillin (AMX). Semi-IPN hydrogels and their Ag NCs were synthesized from chitosan, dimethylamino ethyl methacrylate and 2-hydroxyethyl methacrylate via simple-free radical polymerization method and reducing with NaBH₄. The resultant formulations were evaluated for in vitro release of AMX, anti-bacterial studies and DNA cleavage studies. The hydrogels with AMX-derived silver nanoparticles (Ag NPs) show better ability to cleave DNA and anti-microbial activity than individual AMX and Ag NPs.     

Ethanol dehydration activity on hydrothermally stable LaPxOy catalysts synthesized using CTAB template

Nanocrystalline LaP_xO_y with various starting P to La ratios from 0.5 to 2.0 catalysts were prepared by a sol?Cgel method using cetyl trimethylammonium bromide (CTAB) as template. The catalysts were thoroughly characterized by N₂ physisorption, powder X-ray diffraction (XRD), temperature programmed desorption (TPD) of NH₃, solid state ³¹P and ¹H nuclear magnetic resonance (NMR), and transmission electron microscopy (TEM) techniques. XRD results indicate the presence of predominantly monazite LaPO₄ with minor amounts of (??3.0 wt%) rhabdophane LaPO₄ phase in the samples with starting P/La ratios of 1.0 and 1.5. NH₃-TPD results show an increasing trend in the total acidity with increase in P/La ratio. These catalysts were tested in the selective ethanol dehydration in the temperature range between 250 and 400?°C. The catalyst activity (??mol/h/m²) is increased with P/La ratio and the catalyst with highest P/La ratio of 2.0 exhibiting the highest ethanol dehydration activity. The ethanol conversion increased with reaction temperature, reaching 100% at 350?°C and remains unchanged at higher temperatures. On the other hand, the ethylene selectivity is also increased up to 350?°C and then decreased with further increase of reaction temperature. At a P/La ratio of 2, the CTAB templated LaP_xO_y catalyst showed higher catalytic activities compared to the LaP_xO_y by hydrothermal method without any template.     

Tailor-made fumed silica-based nano-composite polymer electrolytes consisting of BmImTFSI ionic liquid

In this work, nano-sized fumed silica (SiO₂) was embedded in poly(methyl methacrylate) (PMMA)?Cpoly(vinyl chloride) (PVC) blend with 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl imide) (BmImTFSI) as ionic liquid. These composite polymer electrolytes (CPEs) were prepared by solution casting technique. The samples followed Arrhenius behavior in the temperature-dependence of ionic conductivity and further proved the ionic hopping mechanism in the polymer electrolyte. It is suggested the formation of three-dimensional polymer network among the aggregates weakens the interaction of polar group of the polymer backbone and initiates the ionic decoupling process. The mobile ions from adjacent sites would occupy this vacant site and reform the interactive bond with the polymer backbone whereby the ionic hopping mechanism is generated. The activation energy (E _a) is further determined. The higher the ionic conductivity, the lower the activation energy. The maximum ionic conductivity of (8.26?±?0.02) mScm^?1 was achieved at 80?°C upon inclusion of 8 wt% of SiO₂. X-ray diffraction (XRD) analysis revealed the higher amorphous region with increasing SiO₂ mass loadings. The coherence length is further determined by using Debye?CScherrer equation. Higher amorphous region in the polymer matrix is conferred by showing the lower coherent length. Scanning electron microscopy (SEM) was applied to examine the morphology of polymer electrolytes. Based on the differential scanning calorimetry (DSC) study, glass transition temperature (T _g) and melting temperature (T _m) were decreased. Highly flexible polymer chain is produced when the T _g was lowered down. On the other hand, thermal stability of polymer electrolytes was increased by SiO₂ dispersion, as depicted in thermogravimetric analysis (TGA).     

Designing polyethylene terephthalate‐based barrier resins

We have studied the efficiencies of commercially available barrier resins used for food packaging and beverage bottle applications and compared them with resins made using copolymer and blending approaches. The effects of various copolymer related parameters that influence oxygen barrier performance and the underlying mechanisms for these effects in PET‐based copolymers and blends were investigated. Using these approaches, it is possible to make highly effective PET‐based copolymers for gas barrier applications. Blending of PET with phenolic and other organic materials shows equivalent barrier performance in PET copolymers having comonomer levels of <8‐mole %. Reduction in oxygen permeation rates results from the reduction or elimination of short range molecular motion of polyethylene terephthalate molecules. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Improved transfection efficiency of chitosan‐DNA complexes employing reverse transfection

The present study was designed to systematically compare the conventional and reverse transfection methodologies for chitosan/DNA complexes using a low molecular weight (MW) chitosan. The hydrodynamic diameter of the complexes, measured by Dynamic Light Scattering (DLS) was found to be ～ 216 nm and TEM investigations showed spherical and compact complexes with an average size of 200 nm. The transfection efficiency of chitosan using the two methodologies was assessed by employing reporter gene coding for green fluorescent protein (GFP) and luciferase. More than 50% of HEK 293 cells were transfected when transfection done using reverse transfection strategy at pH 6.5 with 10% serum for 24 h followed by media replenishment with pH 7.4 with 10% serum for an additional 24 h period. Also, the cytotoxicity of chitosan/DNA complexes was also considerably lower than the commercially available transfection reagent lipofectamine. Our investigation concludes that maximal transgene expression levels could be achieved using reverse transfection where the chitosan/DNA complexes are pre‐incubated on the plate surface followed by plating of cells at pH 6.5 with 10% serum for 24h and media resupplemented with pH 7.4 with 10% serum for an additional 24 h period. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Oxidative Stability of Conjugated Linoleic Acid Rich Soy Oil

This study was conducted to determine the oxidative stability of conjugated linoleic acid rich soy oil (CLARSO) and the effects of conjugated linoleic acid (CLA) levels on volatile oxidation products formed during CLARSO oxidation. CLARSO oxidative stability was determined by gravimetric analysis, peroxide value, headspace oxygen analysis and p-anisidine value. Volatile oxidation compounds were analyzed by solid phase microextraction–gas chromatography with a flame ionization detector and a mass spectrometer. CLA oxidation results were highly dependent on analytical methods used and oxidation parameters measured. The gravimetric study showed a CLA concentration effect on oxidation, which was not seen in the headspace oxygen depletion and peroxide value. Volatile oxidation data indicate that CLARSO had significantly higher (p < 0.05) levels of pentanal and trans-2-heptenal than the other oils, but there was no significant difference between the amounts of any volatiles present in 8 and 15% CLARSO. This suggests that oxidation was greater in CLARSO and that CLA concentration did not affect oxidation.     

Blends of thermoplastic polyurethane (TPU) and polydimethyl siloxane rubber (PDMS), part-I: assessment of compatibility from torque rheometry and mechanical properties

Thermoplastic polyurethane (TPU) and polydimethyl siloxane rubber (PDMS) are two major polymers used extensively for biomedical applications. Blending of these polymers combines the superior mechanical properties, abrasion resistance, solvent resistance and aging resistance of TPU with chemical stability, inertness, flexibility and biocompatibility of PDMS. In the present investigation, an 80:20 blend of TPU and PDMS was selected for the preparation of an in situ compatibilized blend using ethylene methyl acrylate copolymer (EMA) as the compatibilizer. Effect of EMA on blends of ester type and ether type TPU with PDMS was studied. From the results obtained from torque rheometry, mechanical property evaluation, fourier transform infrared spectroscopy (FTIR), atomic force microscopy (AFM) and scanning electron microscopy (SEM), it was concluded that 5 wt% of compatibilizer effectively compatibilized an 80:20 blend of ester type TPU and PDMS, whereas similar blend of ether type TPU required only 2 wt% compatibilizer.