Direct Addition of Grignard Reagents to Aliphatic Carboxylic Acids Enabled by Bulky turbo-Organomagnesium Anilides

The synthesis of ketones through addition of organometallic reagents to aliphatic carboxylic acids is a straightforward strategy that is limited to organolithium reagents. More desirable Grignard reagents can be activated and controlled with a bulky aniline-derived turbo-Hauser base. This operationally simple procedure allows the straightforward preparation of a variety of aliphatic and perfluoroalkyl ketones alike from functionalized alkyl, aryl and heteroaryl Grignard reagents.     

A sustainable method of mitigating acid corrosion of mild steel using jackfruit pectin (JP) as green inhibitor: Theoretical and electrochemical studies

This study is attempted to develop a green corrosion inhibitor from a waste material of Jack fruit (Artocarpus heterophyllus). This method is therefore quite valuable to health, environment, and economic point of view. Pectin is isolated from the jackfruit peel waste using 0.05 ?N oxalic acid and used as an inhibitor for mild steel corrosion in acidic environment as it is highly water soluble. 250–1000 ?ppm of pectin was used in this study at a temperature range of 303–323 ?K. The protection efficiency of jack fruit pectin (JP) in 0.5 ?M HCl was evaluated by conventional weight loss and electrochemical techniques. The potentiodynamic polarization results revealed that JP could effectively reduce the corrosion of mild steel in acidic medium at 1000 ?ppm concentration with an inhibition efficiency of 89.75% and corrosion rate of 2.392 mpy. The mixed type behavior of the inhibitor is identified from Tafel polarization studies. Electrochemical impedance spectroscopy (EIS) measurements suggest that the corrosion inhibition process is kinetically controlled. adsorption and kinetic behavior of the inhibitor also have been studied. Surface manifestations were followed using FESEM and AFM techniques. DFT calculations and Monte Carlo simulations were also carried out to corroborate the experimental results with theoretical outputs and succeeded to a great extent.     

On exponential stability of second order delay differential equations

We propose a new method for studying stability of second order delay differential equations. Results we obtained are of the form: the exponential stability of ordinary differential equation implies the exponential stability of the corresponding delay differential equation if the delays are small enough. We estimate this smallness through the coefficients of this delay equation. Examples demonstrate that our tests of the exponential stability are essentially better than the known ones. This method works not only for autonomous equations but also for equations with variable coefficients and delays.     

Antimicrobial silica particles loaded with quaternary ammonium polyethyleneimine network

Silica particles functionalized with quaternary ammonium groups were prepared by interpenetrating polyethylenimine (PEI) into silica particles and crosslinking with diiodopentane, followed by octyliodide alkylation and methyliodide quaternarization (S‐QA‐PEI). The synthesized S‐QA‐PEI particles were identified with a slight particle size increase of 2–3 µm. Different ratios of PEI:silica particles were prepared and analyzed. While silica particles are negatively charged, ?16.7 ± 5.11 mV, the prepared S‐QA‐PEI particles are positively charged, +50–60 mV. These particles were embedded in poly(ethylene vinyl acetate) and poly(ethylene methacrylic acid) coatings which exhibited strong antibacterial activity. Copyright © 2014 John Wiley & Sons, Ltd.     

A Tandem In Situ Peptide Cyclization through Trifluoroacetic Acid Cleavage

We present a new approach for peptide cyclization during solid phase synthesis under highly acidic conditions. Our approach involves simultaneous in situ deprotection, cyclization and trifluoroacetic acid (TFA) cleavage of the peptide, which is achieved by forming an amide bond between a lysine side chain and a succinic acid linker at the peptide N‐terminus. The reaction proceeds via a highly active succinimide intermediate, which was isolated and characterized. The structure of a model cyclic peptide was solved by NMR spectroscopy. Theoretical calculations support the proposed mechanism of cyclization. Our new methodology is applicable for the formation of macrocycles in solid‐phase synthesis of peptides and organic molecules.     

Stripping the latex: the challenge of miniemulsion polymerization without initiator,costabilizer and surfactant

When finally processed to provide the function for which the latex was selected―binding, protecting, finishing―components such as surfactant, costabilizer or initiator become generally useless, not to say detrimental. In this study, we show that miniemulsion photopolymerization provides a suitable method to create latex without the apparent addition of these three compounds. Indeed, UV-driven monomer self-initiation can create initiating radicals without the aid of initiator, the fast in situ photogenerated polymer can hinder Ostwald ripening with the assistance of external costabilizer, and finally, UV-transparent clay can replace conventional surfactant to ensure colloidal stabilization. Each strategy has been developed individually before being combined together to end up with a unique miniemulsion procedure free of initiator, costabilizer and surfactant. Such approach paves the way to a simplified and environmentally improved pathway towards aqueous polymer dispersions.     

Mechanism of Formation of Cadmium Oxalate Liesegang Rings

Qualitative and semiquantitative study of the Liesegang rings formed by the reaction of oxalic acid and cadmium chloride in the acidic range of pH in silica hydrogel is made. The behaviour of Jablczynski's space constant and Morce-Pierce's time constant at various temperatures, pH and concentration of outer electrolyte is studied. The possible mechanisms for the above observed behaviour are suggested. The deviations from Isemura's general obserations are interprerted by considering two particular aspects, viz., comparatively larger crystals constituting the rings and the irreversibility of inner and outer electrolytes.     

Synthesis,characterization, and crystal structures of two new divalent metal complexes of N,N'-bis(phosphonomethyl)-1,10-diaza-18-crown-6: a hydrogen-bonded 1D array and a 3D network with a large channel

Reaction of N,N'-bis(phosphonomethyl)-1,10-diaza-18-crown-6 (H(4)L) with copper(II) acetate in 1:1 ethanol/water mixed solvents afforded a new crystal-engineered supramolecular metal phosphonate, Cu(H(2)L) (complex 1). By reaction of the same ligand with cadmium(II) nitrate in a 2:1 (M/L) ratio in methanol, a cadmium(II) complex with a 3D network structure was isolated, Cd(2.75)(L)(H(2)O)(7) x 1.5NO(3) x 7H(2)O x MeOH (complex 2). The copper(II) complex crystallized in the monoclinic space group P2(1)/c, with a =10.125(4), b = 14.103(6), and c = 14.537(6) A, beta = 91.049(8) degrees, V = 2075.4(16) A(3), and Z = 2. The Cu(II) ions in complex 1 are 6-coordinated by two phosphonate oxygen atoms, two nitrogen, and two oxygen atoms from the crown ether ring. Their coordination geometry can be described as Jahn-Teller-distorted octahedral, with elongated Cu-O(crown) distances (2.634(4) and 2.671(4) A for Cu(1) and Cu(2), respectively). The other two crown oxygen atoms remain uncoordinated. Neighboring two Cu(H(2)L) units are further interlinked via a pair of strong hydrogen bonds between uncoordinated phosphonate oxygen atoms, resulting in a one-dimensional supramolecular array along the a axis. The cadmium(II) complex is tetragonal, P4(2)/n (No. 86) with a = 20.8150(9) and c = 18.5846(12) A, V = 8052.0(7) A(3), and Z = 8. Among four cadmium(II) atoms in an asymmetric unit, one is 8-coordinated by four chelating phosphonate groups, the second one is 8-coordinated by 6 coordination atoms from a crown ring and two oxygen atoms from two phosphonate groups, the third Cd(II) atom is octahedrally coordinated by three aqua ligands and three phosphonate oxygen atoms from three phosphonate groups, and the fourth one is 6-coordinated by four aqua ligands and two oxygen atoms from two phosphonate groups in a distorted octahedral geometry. These cadmium atoms are interconnected by bridging phosphonate tetrahedra in such a way as to form large channels along the c direction, in which the lattice water molecules, methanol solvent, and nitrate anions reside. The effect of extent of deprotonation of phosphonic acids on the type of complex formed is also discussed.