A mild deprotection strategy for allyl-protecting groups and its implications in sequence specific dendrimer synthesis

A mild deprotection strategy for allyl ethers under basic conditions in the presence of a palladium catalyst is described. Under these conditions, aryl allyl ethers can be cleaved selectively in the presence of alkyl allyl ethers. These conditions are also effective in the deprotection of allyloxycarbonyl groups. The utility of the current methodology in sequence specific dendrimer synthesis is demonstrated.     

Kinetics of thermal degradation of poly(-caprolactone)

The thermal degradation/modification dynamics of poly(-caprolactone) (PCL) was investigated in a thermogravimetric analyzer under non-isothermal and isothermal conditions. The time evolution of the molecular weight distribution during degradation was studied using gel permeation chromatography. Experimental molecular weight evolution and weight loss profile were modeled using continuous distribution kinetics. The degradation exhibited distinctly different behavior under non-isothermal and isothermal heating. Under non-isothermal heating, the mass of the polymer remained constant at initial stages with rapid degradation at longer times. The Friedman and Chang methods of analysis showed a 3-fold change (from 18 to 55–62 kcal mol⁻¹) in the activation energy from low temperatures to high temperatures during degradation. This suggested the governing mechanism changes during degradation and was explained using two parallel mechanisms (random chain scission and specific chain end scission) without invoking the sequential reaction mechanisms. Under isothermal heating, the polymer degraded by pure unzipping of specific products from the chain end.     

High‐mobility solution‐processed zinc oxide thin films on silicon nitride

A high effective electron mobility of 33 cm² V^–1 s^–1 was achieved in solution‐processed undoped zinc oxide (ZnO) thin films. The introduction of silicon nitride (Si₃N₄) as growth substrate resulted in a mobility improvement by a factor of 2.5 with respect to the commonly used silicon oxide (SiO₂). The solution‐processed ZnO thin films grown on Si₃N₄, prepared by low‐pressure chemical vapor deposition, revealed bigger grain sizes, lower strain and better crystalline quality in comparison to the films grown on thermal SiO₂. These results show that the nucleation and growth mechanisms of solution‐processed films are substrate dependent and affect the final film structure accordingly. The substantial difference in electron mobilities suggests that, in addition to the grain morphology and crystalline structure effects, defect chemistry is a contributing factor that also depends on the particular substrate. In this respect, interface trap densities measured in high‐κ HfO₂/ZnO MOSCAPs were about ten times lower in those fabricated on Si₃N₄ substrates. (© 2014 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)

     

Rh2(OAc)4 catalyzed substrate selective [4+2]/[2+2] cycloaddition of acylketenes: a highly chemo- and regioselective synthesis of spiro(oxindolyl)oxazinones and β-lactams

A rhodium(II) catalyzed [4+2]/[2+2] cycloaddition reaction of N-protected isatin-3-arylimine with acylketene derived from α-diazocarbonyl compounds has been achieved for the first time for the preparation of a novel class of spiro(oxindolyl)oxazinone and spiro(oxindolyl)-β-lactam derivatives.     

Electrochemical Method for the Preparation of Dibromomethyl,Bis(bromomethyl), and Bis(dibromomethyl) Arenes

Electrochemical bromination of alkyl aromatic compounds by two-phase electrolysis yields the corresponding α, α-dibrominated products. The reaction has been carried out in a single-compartment electrochemical cell using aqueous sodium bromide (40–50%), containing a catalytic amount of HBr as electrolyte, and chloroform, containing an alkyl aromatic compound, as the organic phase with a Pt plate as anode at 10–15°C. Two-phase electrolysis results in high yields (70–90%) of dibromomethyl, bis(bromomethyl), and bis(dibromomethyl) arenes, depending upon the charge passed.     

Relaxor behavior of K0.5La0.5Bi2Ta2O9 ceramics

Potassium lanthanum bismuth tantalate (K_0.5La_0.5Bi₂Ta₂O₉), a new relaxor ferroelectric was synthesized via the solid-state reaction route. X-ray structural studies along with Rietveld refinement confirmed it to be an n=2 member of the Aurivillius family of oxides and the refined lattice parameters are , and . The appearance of 1/2{h00} and 1/2{hk0} type superlattice reflections in the electron diffraction patterns reflected the presence of ordered polar regions. A broad dielectric peak associated with frequency dependent dielectric maximum temperature was observed. The value of the diffuseness parameter γ=1.93, obtained from the fit of a modified Curie-Weiss law established the relaxor nature of the title compound. The dielectric relaxation obeyed the Vogel-Fulcher relation wherein and . The relaxor behavior was attributed to the local polar ordering on A-sites.     

Direct observation of ferroelectric domain switching in varying electric field regimes using in situ TEM

In situ Transmission Electron Microscopy (TEM) techniques can potentially fill in gaps in the current understanding interfacial phenomena in complex oxides. Select multiferroic oxide materials, such as BiFeO(3) (BFO), exhibit ferroelectric and magnetic order, and the two order parameters are coupled through a quantum-mechanical exchange interaction. The magneto-electric coupling in BFO allows control of the ferroelectric and magnetic domain structures via applied electric fields. Because of these unique properties, BFO and other magneto-electric multiferroics constitute a promising class of materials for incorporation into devices such as high-density ferroelectric and magnetoresistive memories, spin valves, and magnetic field sensors. The magneto-electric coupling in BFO is mediated by volatile ferroelastically switched domains that make it difficult to incorporate this material into devices. To facilitate device integration, an understanding of the microstructural factors that affect ferroelastic relaxation and ferroelectric domain switching must be developed. In this article, a method of viewing ferroelectric (and ferroelastic) domain dynamics using in situ biasing in TEM is presented. The evolution of ferroelastically switched ferroelectric domains in BFO thin films during many switching cycles is investigated. Evidence of partial domain nucleation, propagation, and switching even at applied electric fields below the estimated coercive field is revealed. Our observations indicate that the occurrence of ferroelastic relaxation in switched domains and the stability of these domains is influenced the applied field as well as the BFO microstructure. These biasing experiments provide a real time view of the complex dynamics of domain switching and complement scanning probe techniques. Quantitative information about domain switching under bias in ferroelectric and multiferroic materials can be extracted from in situ TEM to provide a predictive tool for future device development.     

Transformation of hydrophobic surface into superhydrophobic surface by interfacial flower like silver films

Fabrication of superhydrophobic surface was achieved by electroless deposition of silver film and subsequent immersion into a mixture of stearic acid and cysteamine. The resultant superhydrophobic surface with flower and fall‐leaves like structure showed lotus leaf effect with the water contact angle of about 154° making copper surface water repellant. Copyright © 2014 John Wiley & Sons, Ltd.     

Catalytic deactivation of gold surface as a consequence of Prussian blue electrodeposition and removal

It is shown that the gold surface is catalytically deactivated and smoothened upon removal of the Prussian blue (PB)–gold nanocomposite formed on the gold surface. Atomic force microscopy proves surface smoothening after PB removal. The voltammetric responses of Ru(NH₃)₆Cl₃ on the smoothened surface remain unaffected, but the reactions that involve multistep and inner-sphere electron transfer are affected on the smoothened surface as exemplified by hydroquinone, ferrous oxalate redox reactions, and oxygen reduction. These effects are attributed to catalytic deactivation as a consequence of removal of the active sites.