Reactivity studies,structural characterization,and thermolysis of cubic titanosiloxanes: precursors to titanosilicate materials which catalyze olefin epoxidation

The cubic titanosiloxane [RSiO(3)Ti(OPr(i))](4) (R = 2,6-Pr(2)(i)C(6)H(3)NSiMe(3)) (1) is found to be relatively inert in its attempted reactions with alcohols and other acidic hydrogen containing compounds. The reaction of 1 with silanol (Bu(t)O)(3)SiOH however proceeds over a period of approximately 3 months to result in the hydrolysis of (Bu(t)O)(3)SiOH and yield the transesterification product [RSiO(3)Ti(OBu(t))](4) (2) rather than the expected [RSiO(3)Ti(OSi(OBu(t))(3))](4). Products 1 and 2 have been characterized by elemental analysis, thermal analysis, and spectroscopic techniques (IR, EI-MS, and NMR). The solid-state structures of both 1 and 2 have been determined by single-crystal X-ray diffraction studies. Compounds 1 and 2 are isomorphous and crystallize in a cubic space group with a central cubic Ti(4)Si(4)O(12) core. Solid state thermolysis of 1 was carried at 450, 600, 800, 900, 1000, and 1200 degrees C in air, and the resulting titanosilicate materials 1a-f were characterized by spectroscopic (IR and DR UV), powder XRD, and electron microscopic methods. While, the presence of Ti-O-Si linkages appears to be dominant in the samples prepared at lower temperatures (450-800 degrees C), phase separation of anatase and rutile forms of TiO(2) occurs at temperatures above 900 degrees C as revealed by IR spectral and PXRD studies. The presence of octahedral titanium centers was observed by DR UV spectroscopy for the samples heated at higher temperatures. The use of new titanosilicate materials as catalysts for olefin epoxidation has been investigated. The titanosilicate materials produced at temperatures below 800 degrees C with a large number of Ti-O-Si linkages (or tetrahedral titanium centers) were found to be more active catalysts compared to the materials produced above 900 degrees C. The observed conversion in the epoxidation reactions was found to be somewhat low although the selectivity of the epoxide formation over the other possible oxidized products was found to be very good.     

Potential response in the uncatalyzed bromate oscillatory system

The potential response of the platinum indicator electrode in the uncatalyzed bromate oscillator (UBO) with three different substrates, namely gallic acid (GA), pyrogallol (PG) and veratraldehyde (VA) has been analyzed. The large amplitude oscillations obtained with a Pt electrode are due to the sequential response of the indicator electrode to the varying concentration ratios of the redox couples present in the reaction mixture.     

Diglycidyl ether of bisphenol-A epoxy resin–polyether sulfone/polyether sulfone ether ketone blends: phase morphology, fracture toughness and thermo-mechanical properties

The properties of diglycidyl ether of bisphenol-A epoxy resin toughened with poly(ether sulfone ether ketone) (PESEK) and poly(ether sulfone) (PES) polymers were investigated. PESEK was synthesised by the nucleophilic substitution reaction of 4,4’-difluorobenzophenone with dihydroxydiphenylsulfone using sulfolane as solvent and potassium carbonate as catalyst at 230 °C. The T _g–composition behaviour of the homogeneous epoxy resin/PESEK blend was modelled using Fox, Gordon–Taylor and Kelley–Bueche equations. A single relaxation near the glass transition of epoxy resin was observed in all the blend systems. From dynamic mechanical analysis, the crosslink density of the blends was found to decrease with increase in the thermoplastic concentration. The storage modulus of the epoxy/PESEK blends was lower than that of neat resin, whilst it is higher for epoxy/PES blends up to glass transition temperature, thereafter it decreases. Scanning electron microscopic studies of the blends revealed a homogeneous morphology. The homogeneity of the blends was attributed to the similarity in chemical structure of the modifier and the cured epoxy network and due to the H-bonding interactions between the blend components. The fracture toughness of epoxy resin increased on blending with PESEK and PES. The increase in fracture toughness was due to the increase in ductility of the matrix. The thermal stability of the blends was comparable to that of neat epoxy resin.     

Monomeric, tetrameric, and polymeric copper di-tert-butyl phosphate complexes containing pyridine ancillary ligands

The reaction of di-tert-butyl phosphate (((t)BuO)(2)P(O)(OH), dtbp-H) with copper acetate in the presence of pyridine (py) and 2,4,6-trimethylpyridine (collidine) has been investigated. Copper acetate reacts with dtbp-H in a reaction medium containing pyridine, DMSO, THF, and CH(3)OH to yield a one-dimensional polymeric complex [Cu(dtbp)(2)(py)(2)(mu-OH(2))](n) (1) as blue hollow crystalline tubes. The copper atoms in 1 are octahedral and are surrounded by two terminal phosphate ligands, two pyridine molecules, and two bridging water molecules. The mu-OH(2) ligands that are present along the elongated Jahn-Teller axis are responsible for the formation of the one-dimensional polymeric structure. Recrystallization of 1 in a DMSO/THF/CH(3)OH mixture results in the reorganization of the polymer and its conversion to a more stable tetranuclear copper cluster [Cu(4)(mu(3)-OH)(2)(dtbp)(6)(py)(2)] (2) in about 60% yield. The molecular structure of 2 is made up of a tetranuclear core [Cu(4)(mu(3)-OH)(2)] which is surrounded by six bidentate bridging dtbp ligands. While two of the copper atoms are pentacoordinate with a tbp geometry, the other two copper atoms exhibit a pseudooctahedral geometry with five normal Cu-O bonds and an elongated Cu-O linkage. The pentacoordinate copper centers bear an axial pyridine ligand. The short Cu.Cu nonbonded distances in the tetranuclear core of 2 lead to magnetic ordering at low temperature with an antiferromagnetic coupling at approximately 20 K (J(P) = -44 cm(-1), J(c) = -66 cm(-1), g = 2.25, and rho = 0.8%). When the reaction between di-tert-butyl phosphate (dtbp-H) and copper acetate was carried out in the presence of collidine, large dark-blue crystals of monomeric copper complex [Cu(dtbp)(2)(collidine)(2)] (3) formed as the only product. A single-crystal X-ray diffraction study of 3 reveals a slightly distorted square-planar geometry around the copper atom. Thermogravimetric analysis of 1-3 revealed a facile decomposition of the coordinated ligands and dtbp to produce a copper phosphate material around 500 degrees C. An independent solid-state thermolysis of all the three complexes in bulk at 500-510 degrees C for 2 days produced copper pyrophosphate Cu(2)P(2)O(7) along with small quantities of Cu(PO(3))(2) as revealed by DR-UV spectroscopic and PXRD studies.     

Magnetic properties of carbon nanosheets

Two-dimensional carbon nanosheets have been fabricated using inductively coupled radio frequency plasma-enhanced chemical vapour deposition. The structural properties of the nanosheets have been characterised using atomic force microscopy, scanning electron microscopy and X-ray diffractometer. The magnetisation of the samples was studied using vibrating sample magnetometer. The magnetisation of the nanosheets was found to be diamagnetic for fast synthesis processes (30 and 60 min). On the other hand, the nanosheets exhibited a weak ferromagnetic response for the slow (120 min) synthesis process. Energy dispersive spectrometry and atomic absorption spectroscopy confirmed that the magnetisation exhibited by the carbon nanosheets was an intrinsic property and that it was not due to contamination from the substrate. Raman spectroscopy studies revealed that the ferromagnetic carbon nanosheets have a higher ratio (1.20) of graphite peak (I _G) to disordered peak (I _D) than normally expected (0.75–0.90). Available data indicated that the magnetisation was due to the presence of structural disorders.     

Patterning Flexible Substrates Using Surface Relief Structures in Azobenzene Functionalized Polymer Films

A novel method for maskless micro-patterning of polymeric substrates is presented. First, an azobenzene functionalized polymer film is spin-coated on a Poly (ethylene terephthalate) (PET) sheet. Then surface relief structures are optically inscribed on the polymer film by interference of laser beams. The patterned azobenzene functionalized film is then etched in the plasma chamber such that the gratings are transferred to the PET substrate. Finally, any remaining azobenzene functionalized polymer is dissolved away using an appropriate solvent. This method of patterning can be broadly applied to a variety of flexible/polymeric substrates and the resolution is not limited by the substrate thermo-mechanical properties.     

Horseradish Peroxidase Catalyzed Synthesis of Polycardanol Microcapsules

Polymers synthesized from naturally derived monomers are valuable since they decrease the reliance on petroleum based feed stocks. Cashew nut shell oil (CNSL) is a side-product from processing of edible Cashew nuts of Annacardium occidentale. One of the major components of CNSL is cardanol, which is a phenol derivative having an unsaturated pentadecyl substituent in the ‘meta’ position with varying amount of unsaturation (no double bonds to three double bonds). The substituent in the meta position can also be hydrogenated to yield completely saturated hydrogenated cardanol. Cardanol can be utilized to stabilize the dispersions of oil in water and vice versa since it displays amphiphilic behavior owing to the phenolic head and the C15 aliphatic tail. Here we report the horseradish peroxidase (HRP) catalyzed polymerization of cardanol at oil water interface to obtain polycardanol microcapsules. A synthetic analogue of hydrogenated cardanol, 3-pentadecylphenol (3PDP), was also oxidatively polymerized at the oil-water interface to obtain Poly(3-pentadecylphenol) microcapsules.     

Synthesis of Main‐Chain Liquid‐Crystalline Polyesters Containing Diphenyl Mesogens by Chemo‐Enzymatic Route †

Main‐chain thermotropic liquid‐crystalline polyesters containing rigid biphenyl mesogens and flexible spacers were synthesized by chemo‐enzymatic route. The enzyme‐catalyzed polymerization showed high regio‐ and chemo‐ selectivity, and is environmentally friendly. The resulting polyesters were characterized with ¹H‐NMR, ¹³C‐NMR, gel permeation chromatography (GPC), differential scanning calorimetry (DSC), and polarized light optical microscopy (POM).