Iron(III) Chloride–Promoted Direct Conversion of Aryl/Alkyl Cyanides to Esters

Aryl/alkyl cyanides were quickly converted into the corresponding esters in the presence of iron(III) chloride in refluxing alcohols with very good yields.     

Separation and recovery of ruthenium: a review

The chemistry of the noble metal fission product, ruthenium is very complex due to the existence of many oxidation states in addition to forming a large number of co-ordination complexes. In the PUREX process for the separation of U and Pu from the spent nuclear fuels from fast breeder reactors, owing to the high volatile nature of RuO₄ problems arise not only during the extraction stages but also in the treatment of high active liquid waste and subsequent vitrification. As this volatile RuO₄ can deposit in cooler parts, there is an increase in the radiation field due to the presence of ¹⁰⁶Ru. The problem is very acute in the reprocessing of fast reactor fuels due to the increased concentration of ruthenium in the spent fuel. In nitric acid medium Ru can exist in various nitroso nitrate complexes and nitroso complexes are more stable than nitrates. The nitrates are non-extractable by the solvent TBP; however, they are extractable to a higher degree by DBP (the primary degradation product of TBP). The extractability of Ru nitrates into the solvent is inhibited by high acid content, temperature and prolonged hold-up time. Nevertheless, these factors promote the volatilization of Ru as RuO₄. The volatilization is enhanced by the addition of phosphate ions, but is suppressed by phosphite or hypophosphite ions. Thus, it would be advantageous if ruthenium is removed so that not only the purity of the product (Pu) is improved, but also the problem related to volatilisation can be resolved. High molecular weight amines (tertiary amines) capable of forming co-ordinate bonds are reported to be ideal extractants for Ru. Gas phase separation is an effective method for the recovery of Ru from catalysts, lead button and from other platinum group metals. Separation and pre-concentration of noble metals can be accomplished from non-metals by simple sorbents like coconut shell activated carbon to complicated chelating resins, aromatic polymers and zeolites. In the electro-oxidation of active Ru from nitroso salts, Pd was found to interfere and removal of Pd prior to oxidation of Ru is recommended. Redox catalysts such as Ag²⁺ and Ce⁴⁺ are found to play a prominent role in the electro-oxidation of Ru. Though, various methods and extractants are reported in the literature for the separation of Ru, R&D is being pursued for the removal of Ru during aqueous reprocessing of spent fuels using extractants and methods which are conducive to plant conditions. Hence, an exhaustive survey of literature was made and the different methods reported for the removal of Ru with emphasis towards reprocessing applications are discussed in this report as a review. Attempts made by the authors in separating Ru from simulated waste solution are also included in this review.     

Tuning the physical properties of a nematic liquid crystal elastomer actuator

In this report we demonstrate the ability to tune the physical properties of a liquid crystal elastomer (LCE) by varying the amount and type of crosslinking within the elastomer network. LCE films composed of a single mesogenic compound were capable of uniaxial contraction when thermally actuated through the nematic to isotropic phase of the material. We probed the physical properties of the LCE films while varying the amount and concentration of two crosslinking agents and measured actuation strains of 10–35%, elastic moduli of 3–14 MPa, and transition temperatures ranging between 75 and 60°C. The viscous losses of the elastomers and the estimated work capable of being produced by the films were also evaluated. The ability to tune the physical properties of the LCE films allows for a wide range of applications including robotics, microelectromechanical systems (MEMS), shape‐changing membranes, and/or microfluidics.     

Studies on thermotropic main chain liquid crystalline segmented polyurethanes I. Synthesis and properties of polyurethanes from high aspect ratio mesogenic diol as chain extender

Thermotropic main chain liquid crystalline polyurethanes were prepared from 4-{[4-(6-hydroxyhexyloxy)phenylimino]methyl}benzoic acid 4-{[4-(6-hydroxyhexyloxy)phenylimino]methyl}phenyl ester (mesogenic diol) and 1,6-hexamethylene di-isocyanate. The effects of partial replacement of the mesogenic diol by 20-50 mol% of poly(tetramethylene oxide)glycol (PTMG) of varying molecular mass (M _n =650, 1000, 2000) on the liquid crystalline properties were studied. Structural characterization was carried out by FTIR spectroscopy and the molecular mass distribution was determined by GPC. Differential scanning calorimetry and hot stage polarizing optical microscopy were used to study the mesomorphic properties. It was observed that the partial replacement of the mesogenic diol by PTMG of varying molecular masses influenced the phase transitions and the occurrence of mesophase textures. When the molecular mass of PTMG was enhanced, a higher content of mesogenic agent was needed to obtain liquid crystalline properties.     

Electrospun Porous NiCo2O4 Nanotubes as Advanced Electrodes for Electrochemical Capacitors

Novel, porous NiCo₂O₄ nanotubes (NCO‐NTs) are prepared by a single‐spinneret electrospinning technique followed by calcination in air. The obtained NCO‐NTs display a one‐dimensional architecture with a porous structure and hollow interiors. The effect of precursor concentration on the morphologies of the products is investigated. Due to their unique structure, the prepared NCO‐NT electrode exhibits a high specific capacitance (1647 F g^?1 at 1 A g^?1), excellent rate capability (77.3 % capacity retention at 25 A g^?1), and outstanding cycling stability (6.4 % loss after 3000 cycles), which indicates it has great potential for high‐performance electrochemical capacitors. The desirable enhanced capacitive performance of NCO‐NTs can be attributed to the relatively large specific surface area of these porous and hollow one‐dimensional nanostructures.     

Carbon‐Coated LiTi2(PO4)3: An Ideal Insertion Host for Lithium‐Ion and Sodium‐Ion Batteries

We report the extraordinary performance of carbon‐coated sodium super ion conductor (NASICON)‐type LiTi₂(PO₄)₃ as an ideal host matrix for reversible insertion of both Li and Na ions. The NASICON‐type compound was prepared by means of a Pechini‐type polymerizable complex method and was subsequently carbon coated. Several characterization techniques such as XRD, thermogravimetric analysis (TGA), field‐emission (FE) SEM, TEM, and Raman analysis were used to study the physicochemical properties. Both guest species underwent a two‐phase insertion mechanism during the charge/discharge process that was clearly evidenced from galvanostatic and cyclic voltammetric studies. Unlike that of Li (≈1.5 moles of Li), Na insertion exhibits better reversibility (≈1.59 moles of Na) while experiencing a slightly higher capacity fade (≈8 % higher than Li) and polarization (780 mV) than Li. However, excellent rate capability profiles were noted for Na insertion relative to its counterpart Li. Overall, the Na insertion properties were found to be superior relative to Li insertion, which makes carbon‐coated NASICON‐type LiTi₂(PO₄)₃ hosts attractive for the development of next‐generation batteries.     

Correction to: Effects of environmental factors on key kinetic parameters relevant to pitting corrosion

Journal of Solid State Electrochemistry -     

Quasi Monte Carlo-based isotropic distribution of gradient directions for improved reconstruction quality of 3D EPR imaging

In continuous wave (CW) electron paramagnetic resonance imaging (EPRI), high quality of reconstructed image along with fast and reliable data acquisition is highly desirable for many biological applications. An accurate representation of uniform distribution of projection data is necessary to ensure high reconstruction quality. The current techniques for data acquisition suffer from nonuniformities or local anisotropies in the distribution of projection data and present a poor approximation of a true uniform and isotropic distribution. In this work, we have implemented a technique based on Quasi-Monte Carlo method to acquire projections with more uniform and isotropic distribution of data over a 3D acquisition space. The proposed technique exhibits improvements in the reconstruction quality in terms of both mean-square-error and visual judgment. The effectiveness of the suggested technique is demonstrated using computer simulations and 3D EPRI experiments. The technique is robust and exhibits consistent performance for different object configurations and orientations.