Stearate anions were successfully intercalated into the layered double hydroxide Mg4Al2(OH)12CO3.3H2O (LDH-CO3) by several methods to form LDH-SA. The intercalation method which involved the acid-base reaction between emulsified stearic acid (SA) and the carbonate anions in aqueous media was studied for the first time. This method led to the formation of more LDH-SA than well known methods such as melting the carboxylic acid in the presence of the LDH, allowing the interlayer region to swell in the presence of glycerol and reconstructing the calcined LDH in the presence of aqueous sodium stearate. Other literature methods involve ion-exchange of Cl- in LDH-Cl with stearate in aqueous sodium stearate, usually under N2 atmosphere. The methods developed in this study are more industrially viable because the more easily produced LDH-CO3 is used and no N2 atmosphere is necessary. The LDH-SA was successfully used to intercalate sodium polyvinyl sulphonate by an ion exchange with the intercalated stearate, without the need for a N2 atmosphere. This method of production could be useful for the production of nanocomposites in general, for example anionic polymer chains (such as DNA) and anionic clays. The same intercalation reaction was allowed to take place in situ during the formation of dextrin-alginate-glycerol film solutions in water-ethanol media. The stearate intercalated as a bilayer in the interlayer region of the LDH. The SA to LDH ratio was varied from 100% SA to 100% LDH. Around the middle of the series a minimum water vapour permeability (WVP) was obtained, which corresponded to an 80% reduction in WVP in comparison to the reference (blank) film. Around the middle of the series a maximum increase in Young’s modulus, corresponding to a 213% increase in comparison to the blank film, was obtained. Around the middle of the series a reduction in the intensity of the basal reflection and interlayer distance showed that some exfoliation (delamination) took place. / Thesis (PhD (Chemistry))--University of Pretoria, 2008. / Chemistry / unrestricted

No description available.

Background: Pulsed amperometric detection is a relatively new method for detection of ions and especially non-electrolytes such as carbohydrates in aqueous solutions. Pulsed amperometric detection relies on a redox reaction while electrochemical impedance simply measures the real and capacitive resistant of the solution. There is a correlation between the real impedance of a solution and the ionic strength of the solution. Method: This work explores measuring real impedance of pure water as a function of temperature from 25.0 to 60.0 °C to determine the relationship between impedance and temperature. Maintaining temperature at 25.0 °C, solutions of sodium chloride, potassium carbonate, sodium sulfate acetate and bicarbonate have been measured using impedance spectroscopy. Results: Regression analysis shows that measuring anions using impedance spectroscopy and simple stainless steel cylinders that detection limits at the parts per trillion (ppt) level are possible. There was no statistical difference when comparing impedance values of the same concentration of acetate and chloride in solution, showing real impedance is not dependent on ion size. However, ions with higher charge do result in lower impedance measurements. Conclusions: This work establishes the use of simple, small, robust stainless steel cylinders and impedance measurements following separation for the identification and quantification of ions in solution.

The general theme of this dissertation concerns how the locality of an anionic moiety, be it a weakly coordinating anion or an anionic ligand, affect the spectroscopic and structural properties of organotransition metal complexes. Probing the columbic interactions between traditional and novel weakly coordinating anions with transition metal complexes, enables synthetic chemists to select anions that can improve catalytic transformations, impart stability of reactive intermediates, or develop new mechanistic insights. Additionally, presented herein is the manifestation of a new class of luminescent copper complexes which bear a weakly coordinating anionic N-heterocyclic carbene ligand.Firstly, a qualitative scale of coordinating ability is prepared by pairing traditional anions and weakly-coordinating anions with [Pd(IPr)(C(O)C9H6N)]+. NMR, IR, Computation, %Vbur, and X-ray crystallographic techniques are used to study the solution and solid-state interactions of these salts. During this study, a novel anion, denoted IMP- is prepared where two B(C6F5) groups are bridged by a phenyl imidazole core. Ultimately, it was found that sterics dictate coordinating ability observed by NMR and %Vbur, while IR and computation show the electronic effects of anion coordination. Continuing our understanding of the interplay between cation and anion, anionic Au(I) complexes are synthesized and paired with the same palladium cation in our first investigation. The framework of these Au(I) anions features a weakly coordinating N-heterocyclic carbene ligand that bears a borate moiety of the NHC backbone. Facile dissociation of a dimethyl sulfide ligand with metal alkoxide/phenoxides/thiophenoxides affords sodium or potassium salts. With these anions in hand, ion pairs are isolated in polar solvents and in the solid state. Au anions reside in the outer sphere of the palladium cation; like that of weakly coordinating anions such as BArF4-. Lastly, Luminescent group 11 organometallic complexes featuring N-heterocyclic carbene (NHC) ligands offer a swath of applications; catalytic transformations in organic chemistry to inorganic material uses in light emitting technologies. Conventional complexes are of the type NHC-M-X, where M is Cu, Ag, or Au and X represents anionic ligands that are often prone to hydrolysis. In this dissertation, Cu(I) complexes featuring this N- heterocyclic carbene ligand bearing a weakly coordinating anionic substituent (WCA-NHC) are prepared. (WCA-NHC)-M-L are air and moisture stable and differ from conventional NHC-M-X in that the metal can be supported by 2 datively-bound ligands. Initial computation reveals a change in dipole of (WCA-NHC)-Cu-PR3 charge transfer compared to that of reported NHC-M-X. By exchanging triphenylphosphine for diphenyl-2-pyridyl phosphine, we can change the emission wavelength by about 200 nm. / Chemistry

No description available.

<p> This project proposal is focused on the development of a novel class of Viscosity Index improvers. A bench-top method for living anionic polymerization has been set up and tested in many aspects. A new difulvene derivative, 1,4-di(6'-6'-methyl-fulvyl)benzene, was synthesized. The living anionic polymer chain was terminated on this difulvene. Cyclopentadiene groups were formed in the middle of the macromolecule chain during the termination. A doubled molecular weight of polystyrene was obtained after the termination. The cyclopentadienes were then changed to other functional groups by Diels-Alder reaction with dimethyl acetylenedicarboxylate, ozonolysis of double bonds, and bromination and reaction with amine. The infrared spectra and nuclear magnetic resonance spectra of the resulting polymers showed new peaks for the new attached groups.</p> / Thesis / Master of Science (MSc)

<p> The alkali metal dichromates show extensive polymorphism. The crystal structures of the polymorphs α-Na2Cr2O7, β-Na2Cr2O7, β1-Rb2Cr2O7 and P21/c NaRbCr2O7 have been determined with x-ray methods. Crystal data were determined for β2-Rb2Cr2O7, P1 Cs2Cr2O7 and the P21/c NaCsCr2O7.</p> <p> The dichromate ions found in this work have been compared with the dichromate ions found in other crystal structure determinations. The anions are described in terms of the bridging oxygen angles b and the torsion angles α1 and α2. Many of the dichromate ions are close to having C2v symmetry with values for α1 and α2 close to zero and bridging angles of around 124°. But there is a number of dichromates with α1 = -α2 and 0°<|α|<60° for which the bridging angle varies between 131° to 141°.</p> <p> The structures determined in this work are discussed as part of a unified description of thortveitite like and dichromate like structures in terms of layers of Y2O7 anions. In terms of this description and Brown and Calvo's classification a structure is proposed for the β2Rb2Cr2O7, while for the structure of NaCsCr2O7 it is suggested that it is isostructural to that of P21/c NaRbCr2O7. The phase transition of α-Na2Cr2O7 to β-Na2Cr2O7 is considered and it is suggested that a twisting thermal mode plays an important role in this as well as in other transitions.</p> / Thesis / Doctor of Philosophy (PhD)

京都大学 / 新制・課程博士 / 博士(工学) / 甲第24628号 / 工博第5134号 / 新制||工||1981(附属図書館) / 京都大学大学院工学研究科物質エネルギー化学専攻 / (主査)教授 陰山 洋, 教授 阿部 竜, 教授 藤原 哲晶 / 学位規則第4条第1項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DFAM

Several new families of organic acceptors that are candidates as building blocks of molecule-based ferrimagnets were synthesized and characterized. These families include fluorodicyanostilbenes, a tetrachlorodicyanostilbene, naphthyltricyanoethylenes, bromophenyltricyanoethylenes, and an anthryltricyanoethylene. The magnetic networks were synthesized by reacting each acceptor with V(CO)6. The magnets synthesized in this study were characterized using a SQUID magnetometer, elemental analysis, and infrared spectroscopy. Although some combinations failed to yield magnetically ordered materials, others exhibited ordering temperatures in the range of 95 K – 260 K. The ordering temperatures and saturation magnetizations were compared among families of acceptors and correlated with individual properties of the acceptors such as reduction potential and structure. / Doctor of Philosophy / Several new families of organic molecules have been created and examined for use as building blocks of molecule-based magnets. These families include fluorodicyanostilbenes, a tetrachlorodicyanostilbene, naphthyltricyanoethylenes, bromophenyltricyanoethylenes, and an anthryltricyanoethylene. The 3-D magnetic scaffoldings were created by combining an individual organic molecule in one of the families listed above with vanadium. The magnets created in this study were examined using a SQUID magnetometer, elemental analysis, and infrared spectroscopy. Some of the combinations of the organic molecules with vanadium failed to result in a 3-D magnetic scaffolding and showed no magnetic properties. Others showed magnetic properties in the below certain temperatures in the range of 95 K – 260 K. The magnetic properties were compared among families of molecules and correlated with individual properties of each molecule such as electronic effects and structure.

The mean quadratic elongation, < A >, is used to measure the distortions of close packed arrays of anions in crystals. It is also used to trace how such distortions vary with temperature (T) and pressure (P). A calculation of < ..\ > for arrays of anions in materials that adopt the rutile and olivine structure-types shows that the arrays exhibit increased distortions with increasing P whereas those in materials that adopt the dolomite structure-type exhibit a decrease in distortion. On the other hand, the close packed arrays in the dolomite and calcite structure-types become more distorted with increasing T. The array of oxide anions in rutile show an increased distortion while those in stishovite show a decreased distortion with increasing T. An analysis of apparent bulk moduli and linear thermal expansion coefficients calculated for the constituent polyhedra shows that the distortion of a material with a close packed structure is governed by its unoccupied as well as its occupied polyhedra. It also indicates that the rearrangement of the anions in such materials induced by an increase in P is governed by the apparent bulk moduli of its constituent polyhedra rather than by a tendency of the anions to adopt a more perfect close packed array. / Master of Science