Catalytic cyclopropanation of olefins using copper(I) diphosphinoamines

Catalytic cyclopropanation reactions of olefins with ethyl diazoacetate were carried out using copper(I) diphosphinoamine (PPh2)(2)N(R) (R = Pr-i, H, Ph and -CH2-C6H4-CH=CH2) complexes at 40 degrees C in chloroform. High yields of the cyclopropanes were obtained in all cases. The rate of the reaction was influenced by the nuclearity of the complex and the binding mode of the ligand which was either bridging or chelating. Comparison of isostructural complexes shows that the rate follows the order R = Pr-i > H > Ph, where R is the substituent on the N. However, cyclopropane formation versus dimerization of the carbene, and trans to cis ratios of cyclopropane was similar in all cases. The nearly identical selectivity for different products formed was indicative of a common catalytic intermediate. A labile "copper-olefin" complex which does not involve the phosphine or the counterion is the most likely candidate. The differences in the reaction rates for different complexes are attributed to differences in the concentration of the catalytically active species which are in equilibrium with the catalytically inactive copper-phosphinoamine complex. To test the hypothesis a diphosphinoamine polymer complexed to copper(I) was used as a heterogeneous catalyst. Leaching of copper(I) and deactivation of the catalyst confirmed the proposed mechanism. (C) 2008 Elsevier B. V. All rights reserved.

Implantation Induced Hardening of Nanocrystalline Titanium Thin Films

Formation of nanocrystalline TiN at low temperatures was demonstrated by combining Pulsed Laser Deposition (PLD) and ion implantation techniques. The Ti films of nominal thickness similar to 250 nm were deposited at a substrate temperature of 200 degrees C by ablating a high pure titanium target in UHV conditions using a nanosecond pulsed Nd:YAG laser operating at 1064 nm. These films were implanted with 100 keV N+ ions with fluence ranging from 1.0 x 10(16) ions/cm(2) to 1.0 x 10(17) ions/cm(2). The structural, compositional and morphological evolutions were tracked using Transmission Electron Microscopy (TEM), Secondary Ion Mass Spectrometry (SIMS) and Atomic Force Microscopy (AFM), respectively. TEM analysis revealed that the as-deposited titanium film is an fcc phase. With increasing ion fluence, its structure becomes amorphous phase before precipitation of nanocrystalline fcc TiN phase. Compositional depth profiles obtained from SIMS have shown the extent of nitrogen concentration gradient in the implantation zone. Both as-deposited and ion implanted films showed much higher hardness as compared to the bulk titanium. AFM studies revealed a gradual increase in surface roughness leading to surface patterning with increase in ion fluence.

Dielectric anomaly in Li-doped zinc oxide thin films grown by sol-gel route

Sol-gel route was employed to grow polycrystalline thin films of Li-doped ZnO thin films (Zn1-xLixO, x=0.15). Polycrystalline films were obtained at a growth temperature of 400-500 degrees C. Ferroelectricity in Zn0.85Li0.15O was verified by examining the temperature variation of the real and imaginary parts of dielectric constant, and from the C-V measurements. The phase transition temperature was found to be 330 K. The room-temperature dielectric constant and dissipation factor were 15.5 and 0.09 respectively, at a frequency of 100 kHz. The films exhibited well-defined hysteresis loop, and the values of spontaneous polarization (P-s) and coercive field were 0.15 mu C/cm(2) and 20 kV/cm, respectively, confirming the presence of ferroelectricity.

P-T evolution of Glenelg eclogites, NW Scotland: Did they experience ultrahigh-pressure metamorphism?

Eclogites and their retrogressed equivalents from the eastern unit of the Glenelg-Attadale Inlier in NW Scotland preserve much microstructural evidence that indicates that very high-pressure/temperature eclogite facies conditions were reached, and followed by decompression and hydration during exhumation. Rutile exsolution in garnet and quartz exsolution in omphacite and titanite formed through mineral reactions during high P-T peak metamorphism. Isochemical phase diagrams modeled for samples from three different locations indicate that the outer part of the eastern unit preserves a peak metamorphic condition of c. 850-1000 degrees C at 18-25 kbar, whereas the central part has a similar pressure (c. 23 kbar), but a lower temperature (c. 670 degrees C). Due to the limitations in the phase diagram calculations the estimated P-T conditions represent the minimum conditions attained by the peak metamorphic assemblage, and the pre-exsoived peak assemblage probably stabilized at a higher pressure. This observation is strongly supported by the presence of exsolution microstructures. The present results demonstrate that the eastern unit experienced very high P-T conditions during peak metamorphism and a tight clockwise P-T trajectory and provide the first indication of possible ultrahigh-pressure metamorphism in the Glenelg eclogites. (C) 2009 Elsevier B.V. All rights reserved.

Amine-Templated Aluminoborates Exhibiting Graphite and Diamond Nets

A solvothermal reaction of Al2O3, H3BO3, pyridine, and H2O at 180 degrees C/7 days in the presence of organic amine molecules gave rise to four new aluminoborates, [(C6H18N2)(AlB6O13H3)], I; [(C5H16N2) (AlB5O10)]center dot 2H(2)O, II; [(C5H16N2)-(AlB5O10)], III; and [(C5H17N3)(AlB5O10)] center dot H2O, IV, with two- and three-dimensional structures. All the structures have been formed by the connectivity involving Al3+ ions and [B5O10] cyclic pentaborate units. In 1, the 3-connected trigonal nodes form a layer that resembles a graphite structure has been observed. The compounds II, III, and IV, have 4-connected nodes that forms a diamond related three-dimensional structure. The formation of solvatomorphs in II and III is noteworthy and has been observed first time in a family of amine template aluminoborates. A comparison of the various aluminoborate structures reveals subtle relationships between the organic amines (length of the amines) and the final framework structures. The compounds have been characterized using a variety of techniques including IR, second-order optical behavior, and MAS NMR studies.

High energy oxygen ion induced modifications in lead based perovskite thin films

The lead based ferroelectric PbZr0.53Ti0.47O3 (PZT), (Pb0.90La0.10)TiO3 (PLT10) and (Pb0.80La0.20)TiO3 (PLT20) thin films, prepared by pulsed laser ablation technique, were studied for their response to the 70 MeV oxygen ion irradiation. The dielectric analysis, capacitance-voltage (C- V) and DC leakage current measurements were performed before and after the irradiation to high-energy oxygen ions. The irradiation produced considerable changes in the dielectric, C-V, leakage characteristics and induced some amount of amorphization. The PZT films showed partial recrystallization after a thermal annealing at 400 degrees C for 10 min. The phase transition temperature [T-c] of PLT20 increased from 115 degrees C to 120 degrees C. The DC conductivity measurements showed a shift in the onset of non-linear conduction region. The current density decreased by two orders of magnitude after irradiation. After annealing the irradiated films at a temperature of 400 degrees C for 10 min, the films partially regained the dielectric and electrical properties. The results are discussed in terms of the irradiation-induced amorphization, the pinning of the ferroelectric domains by trapped charges and the thermal annealing of the defects generated during the irradiation. (C) 2007 Elsevier B.V. All rights reserved.

Immobilization of Aspergillus oryzae alpha-galactosidase in gelatin and its application in removal of flatulence-inducing sugars in soymilk

Raffinose oligosaccharides (RO) are the major factors responsible for flatulence following ingestion of soybean-derived products. Removal of RO from seeds or soymilk would then have a positive impact on the acceptance of soy-based foods. In this study, alpha-galactosidase from Aspergillus oryzae was entrapped in gelatin using formaldehyde as the hardener. The immobilization yield was 64.3% under the optimum conditions of immobilization. The immobilized alpha-galactosidase showed a shift in optimum pH from 4.8 to 5.4 in acetate buffer. The optimum temperature also shifted from 50 degrees C to 57 degrees C compared with soluble enzyme. Immobilized alpha-galactosidase was used in batch, repeated batch and continuous mode to degrade RO present in soymilk. In the repeated batch, 45% reduction of RO was obtained in the fourth cycle. The performance of immobilized alpha-galactosidase was tested in a fluidized bed reactor at different flow rates and 86% reduction of RO in soymilk was obtained at 25 ml h(-1) flow rate. The study revealed that immobilized alpha-galactosidase in continuous mode is efficient in reduction of RO present in soymilk.

Highly biocompatible and water-dispersible, amine functionalized magnetite nanoparticles, prepared by a low temperature, air-assisted polyol process: a new platform for bio-separation and diagnostics

A low temperature polyol process, based on glycolaldehyde mediated partial reduction of FeCl3 center dot 6H(2)O at 120 degrees C in the presence of sodium acetate as an alkali source and 2,2'-(ethylenedioxy)-bis-(ethylamine) as an electrostatic stabilizer has been used for the gram-scale preparation of biocompatible, water-dispersible, amine functionalized magnetite nanoparticles (MNPs) with an average diameter of 6 +/- 0.75 nm. With a reasonably high magnetization (37.8 e.m.u.) and amine groups on the outer surface of the nanoparticles, we demonstrated the magnetic separation and concentration implications of these ultrasmall particles in immunoassay. MRI studies indicated that these nanoparticles had the desired relaxivity for T-2 contrast enhancement in vivo. In vitro biocompatibility, cell uptake and MR imaging studies established that these nanoparticles were safe in clinical dosages and by virtue of their ultrasmall sizes and positively charged surfaces could be easily internalized by cancer cells. All these positive attributes make these functional nanoparticles a promising platform for further in vitro and in vivo evaluations.

Dielectric properties of Poly(vinylidene fluoride)/CaCu3Ti4O12 composites

The possibility of obtaining relatively high dielectric constant polymer-ceramic composite by incorporating the giant dielectric constant material, CaCu3Ti4O12 (CCTO) in a Poly(vinylidene fluoride) (PVDF) polymer matrix by melt mixing and hot pressing process was demonstrated. The structure, morphology and dielectric properties of the composites were characterized using X-ray diffraction, Thermal analysis. scanning electron microscope, and impedance analyzer. The effective dielectric constant a(epsilon(eff)) of the composite increased with increase in the volume fraction of CCTO at all the frequencies(100 Hz-1 MHz) under study. The dielectric loss did not show any variation up to 40% loading of CCTO, but showed an increasing trend beyond 40%. The room temperature dielectric constant as high as 95 at 100 Hz has been realized for the composite with 55 vol.% of CCTO, which has increased to about 190 at 150 degrees C. Theoretical models like Maxwell's, Clausius-Mossotti, Effective medium theory, logarithmic law and Yamada were employed to rationalize the dielectric behaviour of the composite and discussed. (C) 2010 Published by Elsevier Ltd.

'Wet N2O oxidation' process and interface state density characterization of nanoscale nitrided SiO2 for flash memory application

In this paper we first present the 'wet N2O' furnace oxidation process to grow nitrided tunnel oxides in the thickness range 6 to 8 nm on silicon at a temperature of 800 degrees C. Electrical characteristics of MOS capacitors and MOSFETs fabricated using this oxide as gate oxide have been evaluated and the superior features of this oxide are ascertained The frequency response of the interface states, before and after subjecting the MOSFET gate oxide to constant current stress, is studied using a simple analytical model developed in this work.

Influence of surfactant and annealing temperature on optical properties of sol-gel derived nano-crystalline TiO2 thin films

Titanium dioxide thin films have been synthesized by sol-gel spin coating technique on glass and silicon substrates with and without surfactant polyethylene glycol (PEG). XRD and SEM results confirm the presence of nano-crystalline (anatase) phase at an annealing temperature of 300 degrees C. The influence of surfactant and annealing temperature on optical properties of TiO2 thin films has been studied. Optical constants and film thickness were estimated by Swanepoel's (envelope) method and by ellipsometric measurements in the visible spectral range. The optical transmittance and reflectance were found to decrease with an increase in PEG percentage. Refractive index of the films decreased and film thickness increased with the increase in percentage of surfactant. The refractive index of the un-doped TiO2 films was estimated at different annealing temperatures and it has increased with the increasing annealing temperature. The optical band gap of pure TiO2 films was estimated by Tauc's method at different annealing temperature. (C) 2010 Elsevier B.V. All rights reserved.

Synthesis of multiwall carbon nanotubes by chemical vapor deposition of ferrocene alone

Multiwall carbon nanotubes (MWNTs) filled with Fe nanoparticles (NPs) have been synthesized by thermal chemical vapor deposition of ferrocene alone as the precursor. The MWNTs were grown at different temperatures: 980 and 800 degrees C. Characterization of as-prepared MWNTs was done by scanning and transmission electron microscopy, and X-ray diffraction. The transmission electron microscopy study revealed that Fe NPs encapsulated in MWNTs grown at 980 and 800 degrees C are spherical and rod shaped, respectively. Room-temperature vibrating sample magnetometer studies were done on the two samples up to a field of 1T. The magnetization versus magnetic field loop reveals that the saturation magnetization for the two samples varies considerably, almost by a factor of 4.6. This indicates that Fe is present in different amounts in the MWNTs grown at the two different temperatures. (C) 2009 Elsevier Ltd. All rights reserved.

ZnO nanocrystalline thin films: a correlation of microstructural, optoelectronic properties

The compositional, structural, microstructural, dc electrical conductivity and optical properties of undoped zinc oxide films prepared by the sol-gel process using a spin-coating technique were investigated. The ZnO films were obtained by 5 cycle spin-coated and dried zinc oxide films followed by annealing in air at 600 A degrees C. The films deposited on the platinum coated silicon substrate were crystallized in a hexagonal wurtzite form. The energy-dispersive X-ray (EDX) spectrometry shows Zn and O elements in the products with an approximate molar ratio. TEM image of ZnO thin film shows that a grain of about 60-80 nm in size is really an aggregate of many small crystallites of around 10-20 nm. Electron diffraction pattern shows that the ZnO films exhibited hexagonal structure. The SEM micrograph showed that the films consist in nanocrystalline grains randomly distributed with voids in different regions. The dc conductivity found in the range of 10(-5)-10(-6) (Omega cm)(-1). The optical study showed that the spectra for all samples give the transparency in the visible range.

Optimization of the distance between source and substrate for device-grade SnS films grown by the thermal evaporation technique

Tin monosulfide (SnS) films with varying distance between the source and substrate (DSS) were prepared by the thermal evaporation technique at a temperature of 300 degrees C to investigate the effect of the DSS on the physical properties. The physical properties of the as-deposited films are strongly influenced by the variation of DSS. The thickness, Sn to S at.% ratio, grain size, and root mean square (rms) roughness of the films decreased with the increase of DSS. The films grown at DSS = 10 and 15 cm exhibited nearly single-crystalline nature with low electrical resistivity. From Hall-effect measurements, it is observed that the films grown at DSS <= 15 cm have p-type conduction and the films grown at higher distances have n-type conduction due to the variation of the Sn/S ratio. The films grown at DSS = 15 cm showed higher optical band gap of 1.36 eV as compared with the films grown at other distances. The effect of the DSS on the physical properties of SnS films is discussed and reported.

Study of (Ba3MMWO9)-M-II-W-IV (M-II = Ca, Zn; M-IV = Ti, Zr) perovskite oxides: Competition between 3C and 6H perovskite structures

We describe an investigation of (Ba3MMWO9)-M-II-W-IV oxides for M-II = Ca, Zn, and other divalent metals and M-IV = Ti, Zr. In general, a 1:2-ordered 6H (hexagonal, P6(3)/mmc) perovskite structure is stabilized at high temperatures (1300 degrees C) for all of the (Ba3MTiWO9)-Ti-II oxides investigated. An intermediate phase possessing a partially ordered 1:1 double perovskite (3C) structure with the cation distribution, Ba-2(Zn2/3Ti1/3)(W2/3Ti1/3)O-6, is obtained at 1200 degrees C for Ba3ZnTiWO9. Sr substitution for Ba in the latter stabilizes the cubic 3C structure instead of the 6H structure. A metastable Ba3CaZrWO9 that adopts the 3C (cubic, Fm (3) over barm) structure has also been synthesized by a low-temperature metathesis route. Besides yielding several new perovskite oxides that may be useful as dielectric ceramics, the present investigation provides new insights into the complex interplay of crystal chemistry (tolerance factor) and chemical bonding (anion polarization and d(0)-induced distortion of metal-oxygen octahedra) in the stabilization of 6H versus 3C perovskite structures for the (Ba3MMWO9)-M-II-W-IV series.