Metallopolymers based on a polyazomethine ligand containing rigid oxadiazole and flexible tetramethyldisiloxane units

Soluble, easily processable polymer–metal complexes with improved optical and dielectric properties for optoelectronic functional materials were obtained. For this, a new polyazomethine (PAZ2) was prepared by the reaction of a siloxane dialdehyde and bis(formyl‐p‐phenoxymethyl) tetramethyldisiloxane with 2,5‐bis(p‐aminophenyl)‐1,3,4‐oxadiazole, and it was used as a ligand for Cu(II), Co(II), and Zn(II) ions on the basis of the presence of the electron‐donor nitrogen atoms from the azomethine group and oxadiazole ring. The structure of the PAZ2 was determined by spectral [Fourier transform infrared (FTIR) and ¹H‐NMR spectroscopy] techniques. The metal complexation was proven by FTIR spectroscopy, and the silicon‐to‐metal ratios in the complexes were established by energy‐dispersive X‐ray fluorescence. The new materials were characterized by gel permeation chromatography, thermogravimetric analysis, and differential scanning calorimetry. The optical properties of PAZ2 and the derived metal complexes were studied by ultraviolet–visible and fluorescence spectroscopies. PAZ2 shows fluorescence emission, and it was significantly enhanced by metal complexation. The emission was enhanced by protonation; this behavior is useful, especially for sensors. The electrical properties were investigated by dielectric spectroscopy at various frequencies and temperatures, and this emphasized the existence of dipolar relaxations. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41631.     

Synthesis and characterization of a titanium phosphate-tellurite glass for Faraday rotators

This work is focused on investigation of thermal, structural, optical, magnetic, and magneto-optical properties of novel titanium phosphate-tellurite glass applied as Faraday rotators. The glass belonging to the system 35Li₂O–10Al₂O₃–5TiO₂–45P₂O₅–5TeO₂ was prepared by a nonconventional wet route of raw materials processing, followed by melting-quenching-annealing steps. Some important physical properties of the investigated glass have been measured and calculated, providing knowledge related to glass compactness, electronic structure, glass forming capability, etc. XRD analysis evidenced an amorphous network structure of the investigated glass. The optical absorption in the Vis domain is mainly due to Ti³⁺ ions and Te₂ clusters formed during the glass melting process. A relatively low optical absorption is noticed over 600 nm that activates a significant Faraday magneto-optical effect. Photoluminescence bands in the blue, red, and infrared domains are observed, caused by Te₂ clusters formed during the glass melting process. The magnetization in dependency on applied magnetic field reveals a complex behavior of the glass, depending on temperature. Thus, it is found a ferromagnetic behavior up to 2000 Oe, a paramagnetic component up to 40 000 Oe, followed by a diamagnetic one over 40 000 Oe. Faraday rotation angle and Verdet constant values in the visible domain are correlated with the reduced TeO₂ content of the glass.     

Nanofiltration membranes for ionic liquid recovery

Nanofiltration membranes have been developed by interfacial polymerization using base PES ultrafiltration membranes. By varying the concentration of the reactive monomers present as well as the reaction conditions, the structure of the polymerized barrier layer has been modified. Here, the ability to concentrate low molecular weight sugars while allowing dissolved ionic liquids in aqueous solution to be recovered in the permeate has been investigated for application in biomass hydrolysis. The results obtained here indicate that the selectivity for 1-butyl-3-methylimidazoliumchloride (BmimCl) over glucose can be as high as 36.6. The membrane permeance was 2.31 L m^?2 h^?1 bar^?1.     

π-ELECTRON CONTENTS OF RINGS IN THE DOUBLE-HEXAGONAL-CHAIN HOMOLOGOUS SERIES (PYRENE,ANTHANTHRENE AND OTHER ACENOACENES)

Abstract

Recently three methods for calculating the π-electron content of rings of benzenoid hydrocarbons were put forward: one based on the consideration of Kekuléstructural formulas, and the other two based on an analogous treatment of the Clar aromatic sextet formulas. These three methods are applied to the homologous series consisting of two condensed acene chains (whose first members are pyrene, anthanthrene, peri-naphthacenonaphthacene, …), leading to basically identical results. In contrast to acenes (in which the partition of π-electrons into rings is uniform), in the double-hexagonal-chain species the partition of π-electrons is highly non-uniform. The electron content monotonically decreases, in opposite directions, along the two acene chains, being maximal in the least annelated rings. Some other generally valid regularities in the π-electron properties of the double–hexagonal–chain benzenoids are also pointed out.     

COMMENTS ON π-ELECTRON CONJUGATION IN THE FIVE-MEMBERED RING OF BENZO-DERIVATIVES OF CORANNULENE

Cyclic conjugation in corannulene and its benzo-derivatives is studied by means of the π-electron contents and the energy effects of individual rings, with particular attention to the structural effects influencing the magnitude of cyclic conjugation in the 5-membered ring. Two main general regularities were observed: (a) the PCP effect (6-membered rings connected by a single bond to the 5-membered ring increase in it the intensity of cyclic conjugation), and (b), the linear effect (6-membered rings separated from the 5-membered ring by another 6-membered ring, but not in PCP constellation, decrease the magnitude of cyclic conjugation in the 5-membered ring).     

PARTITIONING OF π-ELECTRONS IN RINGS OF POLYCYCLIC conjugated HYDROCARBONS. PART 1: CATACONDENSED BENZENOIDS

Recently a novel view on Kekulé valence structures (or resonance structures) was reported in which their standard geometrical representation was replaced by a numerical representation obtained by assigning π-electrons associated with CC double bonds to individual benzenoid rings. In the present article, we examine in more detail the partitioning of π-electrons to benzenoid rings for cata-condensed benzenoid hydrocarbons. For special families of cata-condensed benzenoids, we offer formulas which allow one to obtain the average π-electron ring content for individual benzenoid rings of polycyclic conjugated hydrocarbons. We also show that the average π-electron ring content for individual benzenoid rings can be calculated from Pauling bond orders without a need to examine all Kekulé resonance structures of a molecule.     

Polymer-Biologically Active Principle Conjugates Obtained by Esterification of Poly(Vinyl Alcohol)

The paper deals with the study of some polymer-biologically active principle systems characterized by the controlled release of the bioactive component by hydrolyze followed by diffusion. The systems were obtained by coupling the 2-mercapto-benzotiazolyl-acetic acid and N-(m-nitrobenzoyl)-L-methionine on poly(vinyl alcohol) by means of esteric bonds in the presence of diciclohexylcarbodiimide as an activator. The influence of some coupling process parameters on the reaction efficiency was studied, such as the drug/support and activator/support ratios. The coupling products with a maximum content of biologically active compound were characterized by spectral measurements, also as regards the capacity of bioactive compound release under the conditions simulating those within the gastro-intestinal tract. The antibacterial activity of the conjugates against Staphylococcus aureus, Eschrichia coli, Sarcina lutea, and Bacillus subtilis was determined.     

l-Lactic acid biosensor based on multi-layered graphene

Pristine graphene platelets and graphene oxide were used as electrode modifiers, aiming the investigation of their electrochemical efficacy towards β-nicotinamide adenine dinucleotide (NADH). The electrochemical detection of NADH is one of the most studied areas of bioelectroanalysis because of the ubiquity of NAD(P)H-based enzymatic reactions in nature. Commercially available graphene and laboratory prepared graphene oxide were used to modify glassy carbon electrodes and the behaviour of such modified electrodes against potassium ferricyanide (III) and NADH was reported. Relying on the graphene-modified transducer, l-lactic dehydrogenase (l-LDH) was successfully immobilised in a 1 % Nafion^® membrane. The developed biosensor, working at +250 mV versus Ag/AgCl reference electrode, was used to assess l-lactic acid in four different types of yogurts, revealing an l-lactic acid concentration ranging between 0.3 and 0.6 %.     

Ion‐exchange resins. II. Acrylamide crosslinked copolymers as precursors for some ion exchangers

Crosslinked copolymers of acrylamide (AA) and ethylacrylate and some ion exchangers derived from them containing either primary amine groups, obtained by the Hofmann degradation of the amide groups, or carboxylic groups, obtained by the alkaline hydrolysis of the ester groups, were studied. Divinylbenzene and N,N′‐methylenebisacrylamide were used as crosslinkers. The starting copolymers and the corresponding ion exchangers were characterized by IR spectroscopy, swelling behavior, and thermogravimetric analysis. The ion‐exchanger properties were correlated with the crosslinker nature and the chemical reactions performed on the AA copolymers. The average molecular weight between two crosslinks, determined from the swelling data in water, was compared with that calculated on the basis of the copolymerization stoichiometry only for the carboxylic cation exchangers. In this way, the preservation of the crosslink density after the hydrolysis was revealed. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 2701–2707, 2003