Synthesis and characterization of polyaniline salts with phenoxy acetic acids by emulsion polymerization

Polyaniline salts have been synthesized by chemical oxidative polymerization of aniline in the presence of phenoxy acetic acid and its two derivatives using emulsion method at room temperature and characterized by different techniques such as infrared, H-1 and C-13 NMR, UV-visible spectroscopy, SEM, wide angle X-ray diffractograms and conductivity measurements. These polyaniline salts have the desirable property of high solubility for processibility in solvents such as DNIF, DMSO and a mixture of CHCl3 and acetone and they exhibit fairly good conductivity of similar to 3.0 x 10(-3) S cm(-1). The variations in solubility, conductivity and morphology with the protonating strength of the dopants are examined.

Family of Mixed-Valence Oxovanadium(IV/V) Dinuclear Entities Incorporating N4O3-Coordinating Heptadentate Ligands: Synthesis, Structure, and EPR Spectra

Dinuclear ((VVV)-V-IV) oxophenoxovanadates of general formula [V2O3L] have been synthesized in excellent yields by reacting bis(acetylacetonato)oxovanadium(IV) with H3L in a 2:1 ratio in acetone under an N-2 atmosphere. Here L3- is the deprotonated form of 2,6-bis[{{(2-hydroxybenzyl)(N',N'-(dimethylamino)ethyl)}amino}methyl]-4-methylphenol (H3L1), 2,6-bis[{{(5-methyl-2-hydroxybenzyl)(N',N'-(dimethylamino)ethyl)}amino}methyl]-4-methylphenol (H3L2) 2,6-bis[ {{(5-tert-butyl-2-hydroxybenzyl)(N',N'-(dimethylamino)ethyl)}amino}methyl]-4-methylphenoI (H3L3), 2,6-bis[{{(5-chloro-2-hydroxybenzyl)(N',N'-(dimethylamino)ethyl)}amino}methyl]-4-methylphenol (H3L4) , 2,6-bis[{{(5-bromo-2-hydroxybenzyl)(N',N'-(dimethylamino)ethyl)}amino}methyl]-4-methylphenol (H3L5), or 2,6-bis[{{(5-methoxy-2-hydroxybenzyl)(N',N'-(dimethylamino)ethyl)}amino}methyl]-4-methylphenol (H3L6). In [V2O3L1], both the metal atoms have distorted octahedral geometry. The relative disposition of two terminal V=O groups in the complex is essentially cis. The O=V...V=O torsion angle is 24.6(2)degrees. The V-O-oxo-V and V-O-phenoxo-V angles are 117.5(4) and 93.4(3)degrees, respectively. The V...V bond distance is 3.173(5) Angstrom. X-ray crystallography, IR, UV-vis, and H-1 and V-51 NMR measurements show that the mixed-valence complexes contain two indistinguishable vanadium atoms (type 111). The thermal ellipsoids of O2, O4, C10, C14, and C15 also suggests a type III complex in the solid state. EPR spectra of solid complexes at 77 K display a single line indicating the localization of the odd electron (3d(xy)(1)). Valence localization at 77 K is also consistent with the V-51 hyperfine structure of the axial EPR spectra (3d(xy)(1) ground state) of the complexes in frozen (77 K) dichloromethane solution: S = 1/2, g(parallel to) similar to 1.94, g(perpendicular to) similar to 1.98, A(parallel to) similar to 166 x 10(-4) cm(-1), and A(perpendicular to) similar to 68 x 10(-4) cm(-1). In contrast isotropic room-temperature solution spectra of the family have 15 hyperfine lines (g(iso) similar to 1.974 and A(iso) similar to 50 x 10(-4) cm(-1)) revealing that the unpaired electron is delocalized between the metal centers. Crystal data for the [V2O3L1].CH2Cl2 complex are as follows: chemical formula, C32H43O6N4C12V2; crystal system, monoclinic; space group, C2/c; a = 18.461(4), b = 17.230(3), c = 13.700(3) Angstrom; beta = 117.88(3)degrees; Z = 8.

Physicochemical studies on the gelation of hen egg yolk; separation of gelling protein components from yolk plasma

A study of the component(s) in egg yolk responsible for gelation of yolk on freezing and thawing has shown that granule-free yolk plasma, obtained by high-speed centrifugation of yolk, has the capacity to gel. As with the whole yolk, gelation of yolk plasma on freezing and thawing could be inhibited by additives such as sugars, sodium chloride, proteolytic enzymes, and phospholipase-A. Phospholipase-C, which induces gelation of whole yolk at room temperature, has a similar effect on yolk plasma. Yolk plasma has been separated into aggregating (gelling) and soluble fractions by delipidation, using formic acid. Each of these fractions consists of three or four protein components, as observed by gel filtration, ultracentrifugation, and agar electrophoresis. The proteins are glycoproteins and contain bound hexoses, hexosamine, and sialic acid. The gelation of yolk has been attributed to the interactions between protein molecules following disruption of lipid-protein bonds.

Dielectric, pyroelectric and ferroelectric properties of Bi4Ti2.98Nb0.01Ta0.01O12 ceramics

The electrical conductivity and electrical relaxation for ferroelectric Bi4Ti2.98Nb0.01Ta0.01O12 (BTNT) ceramics have been reported in the frequency range 0.1 Hz to 1 MHz and in the 300-550 degrees C temperature range. The electrical data was analyzed in the framework of the dielectric as well as the electric modulus formalisms. The bulk dc conductivity at various temperatures was extracted from the electrical relaxation data. The activation energy associated with the electrical relaxation determined from the electric modulus spectra was found to be 0.93 +/- 0.03 eV, close to that of the activation energy for dc conductivity (1.03 +/- 0.02 eV). It suggests that the movements of oxygen ions are responsible for both ionic conduction as well as the relaxation process. The pyroelectric coefficient was found to be 12 mu C m(-2) K-1 at room temperature which is higher than that of the reported value of pyroelectric coefficient for undoped Bi4Ti3O12 ceramics. (C) 2010 Elsevier B.V. All rights reserved.

ESR study of diabrium copper formate tetrahydrate—Part I

ESR investigations on dilute single crystals of dibarium copper formate tetrahydrate, at room temperature and 90° K. have been described. A general method used for the evaluation of theg-tensor in this triclinic crystal, which contains only one ion in the unit cell, has been discussed. A detailed account of the evaluation of the quadrupole interaction is given. Expressions for the positions of the hyperfine levels of the lowest Kramer’s doublet of the Cu++ ion in the magnetic field have been worked out for the case when B and Q are of similar magnitude.

Raman spectra of ferro-electric crystals Part IV. Lithium hydrazinium sulphate (LiN2H5SO4)

The Raman spectrum of lithium hydrazinium sulphate has been recorded both in the single crystal form and in aqueous solutions. The crystal exhibits thirty-eight Raman lines having the frequency shifts 52, 70, 104, 146, 174, 220, 260, 302, 350, 454, 470, 610, 630, 715, 977, 1094, 1115, 1132, 1177, 1191, 1260, 1444, 1493, 1577, 1630, 1670, 2205, 2484, 2553, 2655, 2734, 2848, 2894, 2939, 3028, 3132, 3290 and 3330 cm.−1 The aqueous solution gave rise to six Raman lines at 452, 980, 1050–1200, 1260, 1425 and 1570 cm.−1 apart from a maximum at 180 cm.−1 in the ‘wing’ accompanying the Rayleigh line. The observed Raman lines have been assigned as arising from the vibrations of the SO4 ion, N2H5+ ion, Li-O4 group, hydrogen bond and the lattice. The influence of the hydrogen bond on the N-H stretching vibrations has been pointed out. The various features of the observed spectrum strongly support the hypothesis that the NH3 group in the crystal is rotating around the N-N axis at room temperature.

Antipyrine complexes of titanium(IV), zirconium(iv), thorium(IV) and uranium(VI) perchlorates

Antipyrine complexes of TiO2+, ZrO2+, Zr4+, Th4+ and UO2+2 perchlorates with molecular formulae TiO(Apy)4(ClO4)2, ZrO(Apy)3(ClO4)2, Zr(Apy)6(ClO4)4, Th(Apy)7(ClO4)4 and UO2(Apy)5(ClO4)2 have been prepared and characterized. The complexes are stable in air at room temperature and decompose exothermally at ~3OO °C. The i.r. study indicates the bonding of the antipyrine to the metal ion through its carbonyl oxygen. The nature of the bonding of the perchlorate and the stereochemistry of the complexes are discussed in the light of infrared spectra, conductivity in solvents of different polarity, and molecular weight measurements. From the UO2+2 group frequencies, the force constant K and rU-o are found to be 6.29 × 105 dynes/ cm-1 and 1.74 Å, respectively.

A simple miniature furnace for routine collection of single crystal x-ray data up to 1000°C on the Hilger and Watts linear diffractometer

A miniature furnace suitable for routine collection of x-ray data up to 1000°C from single crystals on the Hilger and Watts linear diffractometer, without restricting the normally allowed region of reciprocal space on the diffractometer, is described. The crystal is heated primarily by radiation from a surrounding current-heated, stationary platinum coil wound on a silica bracket. The coil is split at its middle to provide a 4 mm gap for crystal mounting and x-irradiation. The crystal, mounted on a standard goniometer head, can be rotated and centred freely, as in the room temperature case. There is no need for any radiation shields or water-cooling arrangement. Investigations up to 1500°C are possible with slight modifications of the furnace.

Some sulphoxide complexes of iron

Diphenyl sulphoxide(DPSO) and dimethyl sulphoxide(DMSO) complexes of iron(II) having the composition [Fe(DPSO)6](ClO4)2, Fe(DPSO)2Cl2, Fe(DPSO)3Br2, Fe(DPSO)4I2, [Fe (DMSO)3Cl2]. DMSO and [Fe(DMSO)3Br2]. DMSO and DPSO complexes of iron(III), Fe(DPSO)2 Cl3 have been prepared and their physico-chemical properties studied. Their magnetic moments at room temperature show them to be spin-free complexes. The i.r. spectra reveal that oxygen is the donor atom in all the complexes. The electronic spectra of iron(II) complexes indicate octahedral coordination for the metal ion. A salt like structure [Fe(DPSO)4Cl2][FeCl4], is suggested for the iron (III) complex, where the cationic species has distorted octahedral structure while the anionic species has tetrahedral structure.

Electron spin resonance in cupric acid fluoride

The electron spin resonance in undiluted single crystals of cupric acid fluoride has been investigated at room temperature with microwaves of frequency 9625 Mc/s. The anisotropy in the g value has been measured in three orthogonal planes. The principal g values gave gshort parallel = 2.410 ± 0.010, gperpendicular = 2.090 ± 0.010. The linewidth shows anisotropy with orientation. The exchange frequency has been estimated to be approximately 0.08 cm-1.The powdered specimen shows asymmetry in the line shape.

Infra-red absorption bands of co-ordinated water in titanium complexes

ORANGE red and amorphous peroxy-titanium complexes of oxalic, malonic and maleic acids1-3, when vacuum-dried, have co-ordinated water molecules firmly bonded to the central titanium atom as shown in formula (I). The peroxy-oxygen from these compounds is slowly lost even at room temperature because of the strained peroxy-group3,4. The compounds, when kept at 95°-100°C. for about three days, give deperoxygenated compounds of the type (II). However, a sample of peroxy-titanium oxalate sealed in a glass tube lost all its peroxy-oxygen in about four years and gave a white crystalline basic oxalate (II). The amorphous nature of the compounds may be due to random hydrogen bonding in the complexes. The crystallinity observed in one of the deperoxygenated titanyl oxalates may be due to the rearrangement of the molecules during ageing for more than four years. The infra-red absorption of these compounds was studied to find out the effect of co-ordination and hydrogen bonding on the infra-red bands of the free water.

Free-to-bound and bound exciton transitions at isoelectronic impurities: GaP(Zn,O)

We show, for sufficiently high temperatures and sufficiently weak majority-carrier binding energies, that the dominant radiative transition at an isoelectronic acceptor (donor) in p-type (n-type) material consists of the recombination of singly trapped minority carriers (bound by central-cell forces) with free majority carriers attracted by a Coulomb interaction. There are two reasons why the radiative recombination rate of the free-to-bound process is greater than the bound exciton process, which dominates at lower temperatures: (i) The population of free majority-carrier states greatly exceeds that of exciton states at higher temperatures, and (ii) the oscillator strength of the free-to-bound transition is greatly enhanced by the Coulomb attraction between the free carrier and the charged isoelectronic impurity. This enhancement is important for isoelectronic centers and is easily calculable from existing exciton models. We show that the free carrier attracted by a Coulomb interaction can be viewed as a continuum excited state of the bound exciton. When we apply the results of our calculations to the GaP(Zn, O) system, we find that the major part of the room-temperature luminescence from nearest-neighbor isoelectronic Zn-O complexes results from free-to-bound recombination and not exciton recombination as has been thought previously. Recent experiments on impulse excitation of luminescence in GaP(Zn, O) are reevaluated in the light of our calculations and are shown to be consistent with a strong free-to-bound transition. For deep isoelectronic centers with weakly bound majority carriers, we predict an overwhelming dominance of the free-to-bound process at 300°K.

Studies on the structure of the chromosomes - I. Allium cepa-Stain fixatives and their utility

The structure of the mitotic chromosomes of Allium cepa has been elucidated by controlling the temperature and time of exposure of fresh roots to stain fixatives. The details seen in material stained in N HCl-orcein for 8 min. at 60° C. and squashed after varying intervals of storage at room temperature were essentially similar to pictures obtained with 1% aceto-orcein and 1% aceto-orcein-N HCl (10:1) under identical conditions of handling. The chromosomes appear quadri-partite at metaphase and bi-partite at anaphase. A rare instance of the precocious assumption of a quadri-partite condition by two anaphase chromosomes is illustrated. Caduceus coiling of chromonemata was seen in chromosome bridges also. Chromosomes have material easily dissociable from the chromonemata and their removal does not affect the structural integrity of the chromosome.

Hydrolysis of elemental sulphur in a homogeneous medium

Elemental sulphur dissolved in organic solvents (such as chloroform, carbon tetrachloride and benzene) reacts rapidly and quantitatively, with aqueous alkali at room temperature, when this immiscible liquid mixture is homogenized by the addition of ethyl alcohol. The products of reaction under these experimental conditions are sulphide, thiosulphate and a small quantity of sulphite. A mechanism involving the intermediate formation and decomposition of dihydrogen sulphoxide, HSOH, is suggested for the reaction.

Ultrasonic studies in chemically active liquid media (1) aqueous solution of N2O4

Using a pulse method the ultrasonic absorption has been studied in the frequency range of 2 to 10 Mc/s in dilute aqueous solutions of nitrogen tetroxide gas at room temperature. The absorption peaks (αλ vs frequency) observed in this study are attributed to the ionic dissociation reaction of the nitrous acid into its constituent ions. The rate constants of the forward and backward reactions are calculated using the theory of Tabuchi. The variation of the logarithm of the rate constant of the bimolecular ionic reaction, namely, log10 kb, with the square root of ionic strength qualitatively follows Brönsted's theory for ionic reactions in solutions.