Silica aerogel–iron oxide nanocomposites: recoverable catalysts for the oxidation of alcohols with hydrogen peroxide

Various aerogels of silica gel doped with Fe₂O₃ were prepared by sol–gel method. They were calcined to produce nanoparticle solids. The nanosized mixed oxides were active in the oxidation of alcohols and produced carbonyl compounds in very good to excellent yields using hydrogen peroxide.     

Synthesis of a new smart temperature responsive glycopolymer via click-polymerisation

A novel temperature responsive water-soluble glycopolymer was synthesised via copper wire-catalysed click-polymerisation. Di-hydroxyl terminated poly(ethylene glycol) was quantitatively alkyne end-capped to yield di-alkyne terminated poly(ethylene glycol) (DAT-PEG). 2,3,4,2′,3′,4′-hexa-O-acetyl-6,6′-diazido-6,6′-dideoxy-α,α-D-trehalose (HADADT) was prepared from the di hydrated α,α-D-Trehalose by tosylation/acetylation followed by azidation. Click-polymerisation reaction between DAT-PEG and HADADT was successfully carried out to produce an alternating glycopolymer with triazole rings as linkers in high yield. All the intermediates as well as the glycopolymer were fully characterised by NMR, MS, IR, SEC, TGA and DSC. The cloud point of the aqueous solution of glycopolymer was investigated by optical microscopy and UV–vis spectroscopy. The LCST was found to be within physiological range of about 39 °C, known as fever temperature.     

Synthesis and photochemical properties of novel pentamethylated norbornadiene containing polyimides

A novel pentamethylated norbornadiene (NBD) based dianhydride, α,α′‐bis‐(3,4,5,6,7‐pentamethylcyclopenta‐2,4‐dienyl)meta‐xylene‐1,2‐dianhydride (3), was prepared from α,α′‐bis‐(pentamethylcyclopentadienyl)meta‐xylene (1) and acetylene dicarboxylic acid. The bis‐adduct formed via Diels–Alder reaction afforded tetra‐acid (2), which was chemically cyclodehydrated to lead the targeted dianhydride (3). New polyimides containing NBD moieties in the main chain were prepared from the dianhydride monomer (3) and various aromatic diamines. The chemical structure of the polymers was confirmed by both ¹H and ¹³C NMR analysis. Their Molecular weights were also measured by SEC. All of these polyimides are soluble at room temperature in common organic solvents, such as chloroform, dichloromethane, THF, DMSO, DMF, and NMP, and show good thermal stabilities. The photochemical isomerization of the NBD into quadricyclane (QC) was investigated by UV/vis spectrophotometry from polymer films using visible sunlight as irradiation source. It was found that the kinetic rate of the conversion NBD‐QC which proceeded smoothly is a first kinetic order. The stored energies released by the transformation of QC groups into NBD ones of the irradiated polymer films were also evaluated by DSC measurement and were found to be around 90 kJ mol^?1. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Atmospheric plasma treatment of pre‐electrospinning polymer solution: A feasible method to improve electrospinnability

The electrospinnability of polyethylene oxide (PEO) was manipulated by atmospheric plasma treatment of pre‐electrospinning solutions. Conductivity, viscosity, and surface tension of PEO solutions increased after plasma treatment, and the plasma effect remained longer when the solution concentrate increased. Both untreated and treated solutions were then electrospun, and the morphology of the resultant nanofibers was observed by SEM. Atmospheric plasma treatment improved the electrospinnability of PEO solutions and led to less beads and finer diameter distribution in the resultant nanofibers. Additionally, plasma treatment of the pre‐electrospinning solutions affected the crystal structure of resultant nanofibers. These results suggest that atmospheric plasma treatment is a feasible approach to improve the electrospinnability of polymer solutions and can used to control the structure of electrospun nanofibers. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2011     

Investigating the effect of nanolayered silicates on blend segmental dynamics and minor component relaxation behavior in poly(ethylene oxide)/poly(methyl methacrylate) miscible blends

Polymer–silicate nanocomposites based on poly (ethylene oxide), PEO, poly(methyl methacrylate), PMMA, and sodium montmorillonite clay were fabricated and characterized to investigate the effect of nanolayered silicates on segmental dynamics of PEO/PMMA blends. X‐ray results indicate the formation of an exfoliated morphology in the nanocomposites. At low silicate contents, an enhancement in segmental dynamics of blend nanocomposites and also PEO, minor component in blend, is observed at temperature region below blend glass transition. This result can be attributed to the improvement of the confinement effect of rigid PMMA matrix on the PEO chains by introducing a low amount of layered silicates. On the other hand, at high silicate contents, an enhancement in segmental dynamics of blend nanocomposites and PEO is observed at temperature region above blend glass transition. This behavior could be interpreted based on the reduction of monomeric friction between two polymer components, which can facilitate segmental motions of blend components in nanocomposite systems. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2011     

Empirical correlation study of dryout heat transfer at high pressure using high order neural network and feed forward neural network

A hybrid high order neural network (HHONN) and a feed forward neural network (FNN) are developed and applied to find an optimized empirical correlation for prediction of dryout (DO) heat transfer. The values predicted by the HHONN and FNN models are compared with each other and also with the previous values of empirical correlation. HONN successfully provides an efficient open-box model of nonlinear input–output mapping which provides easier understanding of data mining. By removing the hidden layers, HONN structures become simpler than FNNs and initialization of learning parameters (weights) will not be catastrophic. The RMS results show that the HHONN model has superior fitting specification for prediction of DO heat transfer problem compared to the other prediction methods.     

Hierarchical structure in polymer‐based drug delivery systems as probed by calorimetric measurements

Thermoporosimetry (TPM), a differential scanning calorimetry technique that relies on the shift of transition temperatures caused by the confinement of liquids, was applied to elucidate the complex morphology of drug‐loaded polymeric microcapsules prepared by the emulsion solvent evaporation method. For the very first time, TPM has been applied simultaneously with two liquids as structural probes. It was found that Miglyol, which dissolves the selected drug (Ibuprofen), is confined inside vesicles having a mean radius of 26.3 nm, whereas water, which is the continuous phase, is trapped inside a swollen polymeric network of Eudragit with an average mesh radius of 1.7 nm. A proposed hierarchical structure is given, which predicts that Eudragit microcapsules are formed from a collection of inert oil vesicles partitioned by polymeric Eudragit membranes swollen by water. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 48: 1939–1945, 2010     

Electrochemical genosensor based on three-dimensional DNA polymer brushes monolayers

A new approach to the three dimensional integration of short DNA strands at gold electrode surfaces via the in situ formation of DNA-acrylamide conjugates is presented. Surface initiated atom transfer radical polymerisation was employed to grow acrylamide brushes co-polymerised in the presence of acrylamide modified DNA probes. This strategy was demonstrated for the realisation of biofunctionalised thin polymer films capable of binding its complementary 105-base DNA amplicon. The synthesised brushes were characterised using atomic force microscopy, attenuated total reflectance spectroscopy and electrochemical impedance spectroscopy. Once characterised, the polymer brushes were applied to the quantitative detection of target DNA using an enzyme labelled reporter DNA probe in a sandwich-type format.     

Open Chain Chiral Macrolide Building Blocks by Opening of Deoxygenated 1,6-Anhydrosugars with 1,3-Propanedithiol

Chiral building blocks for macrolides and related natural products are obtained from 1,6-anhydrosugars by conversion of the bicyclic acetals 2 or 12 into the open chain chiral 1,3-dithianes 6 and 13. Branched precursors can be obtained by opening of the ?erný epoxide 1 with the 1,3-dithiane anion to yield 7, followed by ring opening with 1,3-propanedithiol to the bis-1,3-dithiane 8.     

Pore growth in heavy ion-irradiated PET foils using a constructed ECE unit

A well performance Electrolytic Controlled Etching (ECE) unit has been designed and constructed in our laboratory. Low electric field strength of few volts and a 2 kHz wave signals has been applied across the electrodes that confined the 9 and 12 μm thick PET foils in the ECE unit. PET foils were exposed to fission fragments (FF_S) using ²⁵²Cf source. The dependence of different measurable parameters such as FF_S fluence (Φ), applied voltage (V), etching temperature (T) and etching concentration (C) on both track etch rate (V _T) and breakthrough time (T _B) have extensively been studied using the FF_S-irradiated PET foils. Various empirical relationships connecting the results of the present work have been extracted. Moreover, the constructed ECE technique has proven to be an encouraged time saving method in the development of trusting measurements comparing with others that might involve expensive sophisticated tools.