Spectrophotometric study of interaction of 2,3-dichloro-5,6-dicyano-1,4-benzoquinone with diaza-18-crown-6 and diaza-15-crown-5 in acetonitrile and chloroform solutions

Interactions of diaza-18-crown-6 and diaza-15-crown-5, as electron donors, with 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ), as an electron acceptor, have been investigated spectrophotometrically in acetonitrile and chloroform solutions. The results indicated immediate formation of an electron donor-electron acceptor complex DA: [reaction in text] which is followed by two relatively slow consecutive reactions: [reaction in text]. The pseudo-first-order rate constants for the formation of the ionic intermediate and the final product have been evaluated at various temperatures by computer fitting of the absorbance time data to appropriate equations. The formation constants of the resulting DA complexes have also been determined. The influences of both the azacrown's structure and the solvent properties on the formation of DA complexes and the rates of subsequent reactions are discussed.     

The Padé-Rayleigh-Ritz method for solving large hermitian eigenproblems

We make use of the Padé approximants and the Krylov sequencex, Ax,,...,A ^m–1 x in the projection methods to compute a few Ritz values of a large hermitian matrixA of ordern. This process consists in approaching the poles ofR _x()=((I–A)^–1 x,x), the mean value of the resolvant ofA, by those of [m–1/m]_Rx(), where [m–1/m]_Rx() is the Padé approximant of orderm of the functionR _x(). This is equivalent to approaching some eigenvalues ofA by the roots of the polynomial of degreem of the denominator of [m–1/m]_Rx(). This projection method, called the Padé-Rayleigh-Ritz (PRR) method, provides a simple way to determine the minimum polynomial ofx in the Krylov subspace methods for the symmetrical case. The numerical stability of the PRR method can be ensured if the projection subspacem is sufficiently small. The mainly expensive portion of this method is its projection phase, which is composed of the matrix-vector multiplications and, consequently, is well suited for parallel computing. This is also true when the matrices are sparse, as recently demonstrated, especially on massively parallel machines. This paper points out a relationship between the PRR and Lanczos methods and presents a theoretical comparison between them with regard to stability and parallelism. We then try to justify the use of this method under some assumptions.     

Intramolecular charge-transfer interactions in pi-extended tetrathiafulvalene derivatives

New electron-donor (D)-electron-acceptor (A) TTF architectures are presented in which two electron-donating 1,3-dithiole moieties are connected by a pi bridge to the weak electron-accepting quinoxaline moiety (D-pi-A compounds 9a and 9b and also two 1,3-dithiole-2-ylidene moieties are connected by a pi bridge to the electron-accepting thieno[3,4-b]quinoxaline bridge (D-pi-A-pi-D compounds 12a-c). There are through-bond intramolecular charge-transfer (ICT) interactions, predicted in theoretical calculations, and confirmed by UV-vis spectroscopy and cyclic voltammetry measurements. This work constitutes the first use of quinoxalines as electron-accepting moieties in D-pi-A compounds.     

Conductance study of ammonium complexes with several crown ethers and cryptands in nitrobenzene,acetonitrile and dimethylformamide solutions

The formation of ammonium complexes with several crown ethers and cryptands in nitrobenzene, acetonitrile and dimethylformamide solutions was investigated by conductometry at 25°C. Stability constants of the resulting 1:1 complexes sere determined from the molar conductance-mole ratio data and found to vary in the order DC18C6>18C6>DB30C10>DB21C7>DB24C8>DB18C6>15C5>B15C5>12C4, in the case of crown complexes, and in the order C222>C221>C211>C22>C21 for the ammonium cryptates. The stabilities of the complexes varied inversely with the Gutmann donicity of the solvents. Influences of the number of members in the macrocycle, nature of the substituents in the polyether ring, cavity size and dimensionality, conformations of the free and complexed ligands and number of N⁺–H bonds available for hydrogen bonding are discussed.     

Conductance study of the thermodynamics of ammonium ion complexes with several crown ethers in acetonitrile solution

A conductance study concerning the interaction between ammonium ion and several crown ethers in acetonitrile solution has been carried out at different temperatures. The stability constants of the resulting 11 complexes at various temperatures were determined from the molar conductance-mole ratio data and found to vary in the order DC18C6>18C6>DB30C10>DB21C7>DB24C8>DB18C6>15C5>B15C5. The enthalpy and entropy of complexation were determined from the temperature dependence of the formation constants. The influence on the thermodynamic data of different parameters such as cavity size and dimensionality of crown ethers, nature of substituents in the polyether ring, conformations of the free and complexed ligands, solvent-ligand interaction and number of N–H bonds available for hydrogen bonding are discussed.     

Mixed Polymer‐Coated Magnetic Nanoparticles as Forward Osmosis Draw Agents of Tuned Hydrophilicity

We recently reported a polymer‐coated magnetic nanoparticle (MNP) draw agent for the forward osmosis (FO) water desalination process. The water flux was found to increase when the polymer poly(sodium acrylate) (PSA) was anchored to the MNP surface as compared to the polymer (or polyelectrolyte solution) alone, due to the polymer chains being stretched out and most of the hydrophilic groups on the polymer contributing to water flux. We herein report the use of a secondary polymer poly(N‐isopropylacrylamide) PNIPAM to manipulate the PSA polymer conformation and influence inter‐ and intrachain interactions to enhance the efficiency of the FO draw agent. These PSA–PNIPAM‐coated MNPs generated a much higher water flux of ～11.66 LMH when compared to the 100 % PSA‐coated MNPs featuring a value of ～5.32 LMH under identical FO conditions. The osmotic pressure and water flux driven by the mixed polymer‐coated MNPs were found to be a strong function of the net polymer coverage on MNPs, that is, net available hydrophilic groups. Our new draw agent demonstrates potential for use in the water industry due to its improved efficiency and cost effectiveness as it uses only ～0.062 % (w/v) of the draw agent solution.     

Fatty amides synthesized from vegetable oil as extractant of molybdenum(VI)

In this study, fatty amides (FAs) synthesized from palm olein were used to extract and separate Mo(VI) from acidic media. Effects of various parameters upon the separation of Mo(VI) from Co(II), Ni(II), Al(III) and Mn(II), including extractant concentration, metal ion concentration, contact time, diluent, and acidity, were investigated. It was found that Mo(VI) was successfully separated from the above commonly associated metal ions by stripping from the loaded organic phase. Different acidic and alkaline solutions were used. Ammonium hydroxide solution was an optimal. Extraction of Mo(VI) into the organic phase involved the formation of 1:3 complexes. This work presents the development of a low-cost and environmentally friendly extractant to recycle and recover molybdenum.     

Design,preparation and characterization of Cu/GA/Fe3O4@SiO2 nanoparticles as a catalyst for the synthesis of benzodiazepines and imidazoles

The synthesis and characterization of an efficient and reusable nanocatalyst, Cu/GA/Fe₃O₄@SiO₂, obtained by ultrasonic‐assisted grafting of guanidineacetic acid on modified Fe₃O₄@SiO₂ core–shell nanocomposite spheres and subsequent immobilization of Cu(II), are described. The catalyst was characterized by means of X‐ray diffraction, scanning and transmission electron microscopies, energy‐dispersive X‐ray spectroscopy, elemental analysis, thermogravimetric analysis, Fourier transform infrared spectroscopy, vibrating sample magnetometry and inductively coupled plasma optical emission spectrometry. The prepared nanocatalyst facilitated an efficient and straightforward friendly procedure for the synthesis of benzodiazepines and imidazoles in ethanol and under solvent‐free conditions, respectively. The nanocatalyst can be easily recovered using a magnet and reused several times without any significant loss of activity. Copyright © 2016 John Wiley & Sons, Ltd.