Determination of percolation threshold electroactivity and phase behavior study on conducting blends of thermotropic polyesters and polyaniline

The new thermotropic polyester/polyaniline (PIn/PAni) blends have been prepared by solution blend of synthesized liquid crystalline poly[4,4′‐bis (ω‐alkoxy) biphenylisophthalate]s having four and six methylene units in spacer (PI4 and PI6) with PAni doped with camphorsolfonic acid (CSA). The percolation threshold electroactivity of prepared blend films has been determined by cyclic voltammetry. The effect of the PAni concentration, solvent nature and polyester structure on the electroactivity of the blends has been investigated. The extremely low percolation threshold of prepared PIn/PAni‐CSA blends from dimethylformamide (DMF) and m‐cresol solution was 3% weight of PAni‐CSA. The amount of conducting polymer necessary to retard the formation of the liquid crystalline (LC) phase is up to 45% by weight. Phase behavior studies by differential scanning calorimetry and polarizing microscopy show that blends with 45% of conducting polymer are both liquid crystal and conductive. The morphology of the blends has been investigated by scanning electron microscopy. Copyright © 2004 John Wiley & Sons, Ltd.     

A Lead‐Selective Membrane Electrode Based Upon a Phosphorylated Hexahomotrioxacalix[3]Arene

Solvent extraction of a mixture of Pb^II, Mn^II, Fe^III, Co^II, Ni^II and Cd^II in aqueous perchlorate medium by a phosphorylated hexahomotrioxacalix[3]arene (calix‐3) in dichloromethane shows a significant selectivity towards lead ions. The ligand can also be incorporated into a membrane to provide a new lead ion‐selective electrode (Pb^II‐ISE). A plasticized PVC membrane containing 30% PVC, 53.5% ortho‐nitrophenyloctylether (NPOE), 4.5% sodium tetraphenylborate (NaTPB) and 12% ionophore was directly coated on a graphite rod. This sensor gave a good Nernstian response of 29.7 ± 0.7 mV decade^?1 over a concentration range of 1 × 10^?8 – 1 × 10^?4 M of lead ions, independent of pH in the range 3‐7, with a detection limit of 0.4 × 10^?8 M. The dynamic response time of the electrode to achieve a steady potential was very fast and found to be less than 7 s. The selectivity relative to Ag⁺, NH₄⁺, Li⁺, Na⁺, K⁺, Ca²⁺, Sr²⁺, Ba²⁺, Mn²⁺, Fe²⁺, Co²⁺, Ni²⁺, Cu²⁺, Zn²⁺, Cd²⁺, Fe³⁺, La³⁺, Sm³⁺, Dy³⁺, Er³⁺, Y³⁺ and Th⁴⁺ was examined. The electrode exhibits adequate stability with good reproducibility (with a slope of 29.6 ± 1.5 mV for 8 weeks). The characteristics of the sensor are compared with those of a tetraphosphorylated calix[4]arene (calix‐4) based Pb^II‐ISE, reported recently. The electrode was successfully used as an indicator electrode for a potentiometric titration of a lead solution using a standard solution of EDTA. The applicability of the sensor for lead ion measurements in various synthetic samples was also investigated.     

Non-covalently lactose imprinted polymers and recognition of saccharides in aqueous solutions

The aim of this work was to prepare lactose imprinted polymer and study of its selectivity for the recognition of different mono- and disaccharides. A series of molecularly imprinted polymers (MIPs) against lactose were synthesized and their binding properties were compared with a Blank non-imprinted polymer. Methacrylamide (MAAM) and ethylene glycol dimethacrylate were used as functional monomer and cross-linker, respectively. Dimethylsulfoxide was also applied as polymerization solvent. Different lactose:MAAM ratios were applied and optimized MIP was selected in a conventional batch adsorption study. The dissociation constant and maximum binding sites of polymer were determined using the Scatchard analysis. The selectivity of MIP for different mono- and disaccharides was also evaluated. The results indicated that the shape of cavity and orientation of functional monomers in binding sites and the spatial arrangement of hydroxyl groups in saccharide structure were responsible for the selectivity of lactose imprinted polymer.     

Structure and energetics of Li/Na, Li/K, and K/Na bimetallic hexamers

A systematic study of neutral mixed clusters, Li_6?x Na _x , Li_6?x K _x and K_6?x Na _x (x = 0–6), was performed within the framework of density functional theory. The aim of this work is to explore the geometry variation and the energy change of homonuclear hexamers (Li₆ and K₆) induced by impurities. It is found that the geometry of bimetallic hexamers varies with their compositions. The geometries of resulting clusters show evolution from D_4h symmetry for Li₆ to D_3h symmetry for Na₆ and K₆. The stability of bimetallic hexamers has been also explained in terms of binding energy, excess energy, the second difference in energy, and the highest occupied molecular orbital–lowest unoccupied molecular orbital (HOMO–LUMO) gaps. It is found that replacing each Li–Li bond with Li–Na or Li–K bonds decreases the cluster stability, while replacing each K–K bond by K–Na leads to stability enhancement. Examining the cluster stability, excess energy and second difference in energy reveal that among studied bimetallic hexamers, Li₂Na₄ is the most stable mixed hexamer.     

Olefin epoxidation with H2O2 in the presence of Mn(II) dicarboxylate coordination polymer catalysts

Abstract  

The Mn(II) dicarboxylate coordination polymers [Mn(μ-terephthalate)(H₂O)₂] _n , [Mn(μ-oxalate)(H₂O)₂] _n , and [Mn(μ-d-(−)-tartrate)] _n were prepared in water and characterized by FT-IR spectroscopy and CHN analysis. Particles of the terephthalate catalyst were also synthesized, by reaction of terephthalic acid and MnCl₂·4H₂O by a sonochemical method. The catalytic potential of these coordination polymers as slow-release sources of catalytically active Mn species was tested in the oxidation of cyclooctene to its epoxide in acetonitrile, using hydrogen peroxide as oxygen source. For the terephthalate species the catalytic activity was found to increase with increasing dielectric constant and dipole moment of the solvent (being highest in acetonitrile), with reaction temperature to a maximum at 60 °C, and with an imidazole co-catalyst (highest activity found for a imidazole-to-catalyst molar ratio of 20:1). Good activity with more than 64% conversion in 24 h was obtained for epoxidation of cyclooctene and cyclohexene, whereas low yields only were obtained from aryl-substituted olefins. Some exo versus endo regioselectivity was found for norbornene.     

Solvent influence upon complex formation between benzo-15-crown-5 and Mg2+, Ca2+ and Sr2+ cations in some pure and binary mixed solvents using conductometric method

The complexation reactions between Mg²⁺, Ca²⁺ and Sr²⁺ cations with the macrocyclic ligand, benzo-15-crown-5 (B15C5), in pure acetonitrile, water, methanol and tetrahydrofuran and also in acetonitrile–water (AN–H₂O) and in methanol–tetrahydrofuran (MeOH–THF) binary mixtures have been studied at different temperatures using conductometric method. The conductance data show that the stoichiometry of the complexes in most cases is 1:1 [ML]. But in the case of Ca²⁺ cation a 1:2 [ML₂] complex is formed in pure THF, which shows that the stoichiometry of the complexes may be changed by the nature of the medium. The values of stability constants of complexes, which were obtained from conductometric data, show that the stability of complexes is affected by the nature and composition of the binary mixed solvents and a non-linear behavior was observed for variation of logK_f of the complexes versus the composition of the solvent systems. The results show that the selectivity order of B15C5 for the metal cations in two AN–H₂O binary solutions (mol% AN = 25.71 and 50.94) at 25 °C is: Mg²⁺ > Sr²⁺ > Ca²⁺. The values of thermodynamic parameters (ΔH _c ⁰ , ΔS _c ⁰ ) for formation of complexes were obtained from temperature dependence of stability constants of complexes using the van’t Hoff plots. The results show that the values and also the sign of these parameters are influenced by the nature and also the composition of the binary mixed solvents.     

Thermotropic polyesters. 1: Synthesis, characterization and thermal transition of poly[4,4-bis(ω-alkoxy)biphenyl isophthalate]

A new homologous series of thermotropic polyesters has been synthesized by polycondensation reaction between isophthaloyl chloride and mesogenic diols 4,4^′-bis(ω-hydroxyalkoxy)biphenyl in which the spacer length is varied from 3 to 6 methylene units. The thermal behavior of the polymers has been characterized using polarized light microscopy and differential scanning calorimetry (DSC). The odd members exhibit a smectic C (S_C) phase in a narrow temperature interval, while the even members form a smectic A (S_A) phase in a broader temperature range. All of the obtained compounds were characterized by conventional spectroscopic methods.     

Investigating the nature of intermolecular and intramolecular bonds in noble gas containing molecules

This article presents a theoretical study on a number of selected noble gas containing systems of the general formula FNgR and NgR (Ng = He, Ne, Ar, Kr, Xe and R = CH₃, CN, CCH, BO, BNH, H, BeO, and AuF). The principal structures, bond energies, spectroscopic, and electronic properties of 28 noble gas containing molecules were investigated using density functional theory at the BMK level. Quantum theory of atoms in molecules, natural bond orbital, and several other analysis methods have been used to provide more insight into the nature of noble gas bonds. Although both F? Ng and Ng? R bonds in the investigated molecules are assigned to have partially covalent and partially electrostatic nature, the covalent character is dominant in Ng? R bonds. In the second part, the intermolecular interactions between FNgR molecules and hydrogen fluoride are overviewed with emphasis on the hydrogen bonding through the fluorine side of noble gas molecule with hydrogen of HF. The calculated interaction energies were found to decrease in magnitude going down the noble gas series. For all noble gases, the strongest hydrogen bond has been observed in the case R=CH₃. On the contrary, using R=CN in the FNgR moiety weakens the interaction strength. © 2014 Wiley Periodicals, Inc.     

Substituent effect on local aromaticity in mono and di‐substituted heterocyclic analogs of naphthalene

A quantitative study on local aromaticity has been performed on a series of mono‐ and di‐substituted biheterocycles (quinoline, isoquinoline, quinoxaline, quinazoline). Three electronically based indices (PDI, ATI, and FLU) have been employed to investigate the substituent effect on the π‐electron delocalization in both heterocycle and benzenoid rings. Three typical substituents (Cl, OCH₃, and CN) with different inductive and resonance power have been selected. Generally, substituent causes a reduction in aromaticity irrespective of whether it is electron attracting or electron donating. It is shown that the maximum aromaticity exhibits a similar trend of Cl > CN > OCH₃ for all the studied rings. Moreover, it is found that the substituent situation with respect to the heteroatom has a significant influence on the aromaticity. It results from our study that in di‐substituted derivatives, irrespective of whether the two substituents form a meta or para isomer, they preferably choose the position which leads to the maximum aromaticity character. Copyright © 2009 John Wiley & Sons, Ltd.