Structure evolution in the PbO-ZrO2-TiO2 sol-gel system: Part I — Characterization of prehydrolyzed precursors

In this investigation, several spectroscopic and analytical techniques were used to determine the chemical compositions and structures of the lead, zirconium, titanium, and Pb-(Zr, Ti) alkoxides involved in the sol-gel synthesis of PZT thin films. These techniques included ¹H, ¹³C, and ²⁰⁷Pb NMR; FT-IR; gas chromatography; Karl Fischer titration; and number-average molecular weights (M _n ) determined by cryoscopy. It was found that the titanium precursor had a M _n of 548 and a formula of [Ti(OCH₂CH₂OCH₃)₄]_1.6; the zirconium precursor had a M _n of 1015 and a formula of [Zr(OCH₂CH₂OCH₃)₄]_2.6; and the lead precursor had a formula Pb₆(OOCCH₃)₅(OCH₂CH₂OCH₃)₇. 4 H₂O and a molecular weight of 2131 (M _n =2113). It was observed that residual water from the incomplete dehydration of lead acetate trihydrate coupled with released water due to the esterification of acetic acid caused M-O-M (M=Pb, Zr, Ti) bonds in the Pb-(Zr, Ti) alkoxide. Two possible isomeric structures of the Pb-(Zr, Ti) alkoxide have been proposed. They are both cyclic and have a formula of Pb₂MMO₂(OR)₈(ROH)₂, (MM=Zr and/or Ti) and a molecular weight of 1336 (M _n =1386).     

Characterization of long-chain carboxylic esters with CH3OBOCH 3 + in a small fourier-transform ion cyclotron resonance mass spectrometer

The usefulness of CH₃OBOCH ₃ ⁺ as a chemical ionization reagent was examined by allowing the ion to react with carboxylic esters of various chain lengths in a small Fourier-transform ion cyclotron resonance mass spectrometer equipped with a permanent magnet. CH₃OBOCH ₃ ⁺ is a strong electrophile and readily abstracts an oxygen-containing group from the carboxylic esters. Long-chain esters exclusively lose the alkoxide moiety to give the acylium ion. The same reaction was observed for saturated, unsaturated, branched and cyclic esters. In each case, the acylium ion reacts further with a neutral ester molecule by proton transfer to yield the protonated ester as a secondary product. This remarkably simple product distribution reveals the molecular weight of the ester, the chain length of its acid moiety, and the degree of unsaturation in the acid and alcohol moieties.     

Formation of Cyclic Oligomers in Concentrated Aqueous Solutions of Formaldehyde

An MNDO calculation gave the formation enthalpies of the components of equilibrium mixtures in concentrated aqueous acid solutions of formaldehyde. The results of this study suggest that intramolecular cyclization of linear oligomers with 5 and 9 CH₂O units, respectively, is the most plausible mechanism of formation of cyclic oligomers of formaldehyde — trioxane and tetraoxane. Ring protonation by the hydroxonium ion with ring opening is the most energetically favorable route of cyclic acetal decomposition.     

Polymorphism of Acrylic and Methacrylic Acid Esters Containing Long Fluorocarbon Chains and Their Polymerizability

The molecular aggregation of acrylic and methacrylic acid esters containing long-fluorocarbon chains: 2-(perfluoroalkyl)ethyl acrylate (FF_nEA) and 2-(perfluoroalkyl)ethyl methacrylate (FF_nEMA) (F(CF₂)_nCH₂CH₂OCOC(X)=CH₂, where X=H, CH₃ and n=6, 8, 10) was investigated by differential scanning calorimetry (DSC) and temperature controlled X-ray powder diffraction measurement. These compounds exhibited some characteristic polymorphic behaviors depending on the length of fluorocarbon chain and the -position methyl group. The solid-state polymerization by -ray irradiation was studied for these compounds in the various crystal forms. In the solid-state polymerization, highest polymerizability was observed in the crystal form that exists in the highest temperature region for each compound.This revised version was published online in November 2005 with corrections to the Cover Date.     

Solubility and Stability of Peroxo Solvates KF·nH2O2 in Organic and Aqueous-Organic Media

The solubility and stability of the peroxo solvates KF·nH₂O₂ (n 1) and disinfectants based on them was studied in organic and aqueous-organic solvents. Polyhydric alcohols (glycerol and ethylene glycol) and Tosol (commercial antifreeze) were used as solvents.     

End-Functionalized polymers by living cationic polymerization. IV. Poly(vinyl ethers) with acidic or basic terminal groups by functional initiator method

Carboxylic acid or primary amine-terminated poly(isobutyl vinyl ethers) were synthesized by living cationic polymerizations with functionalized initiators (CH₃CHIO? CH₂CH₂ ? X; X: that are the adducts of the corresponding vinyl ethers (CH₂ ? CH ? OCH₂CH₂? X) with hydrogen iodide. In the presence of iodine, these initiators induced living cationic polymerization of isobutyl vinyl ether to give polymers with the α-end group of X originating from the initiators. The polymer molecular weights were regulated by the monomer to initiator feed ratio and the molecular weight distributions were very narrow (M _w/M _n ≤ 1.15). Subsequent deprotection of the terminal group X led to polymers with a terminal carboxylic acid or primary amine. ¹H- and ¹³C-NMR analyses showed that the end functionalities of these polymers were all close to unity.     

A Simple Way of Synthesis of Bisethylthiopolymethylene Sulfides EtS(CH2S)nEt

Two methods of synthesis of bisethylthiopolymethylene sulfides RS(CH₂S) _n R (R = Et, n 1) are developed. Both approaches are based on the reductive cleavage of the S-S bonds in diethyl polysulfides or a mixture of diethyl polysulfides with elementary sulfur by the system: hydrazine hydrate-base. Subsequent alkylation of the formed thiolate anions with dichloromethane leads to the formation of mixtures of oligomeric bisethylthiopolymethylene sulfides with a predominance of compounds with n = 1, 2.     

Spinnability and rheological properties of sols derived from Si(OC2H5)4 and Zr(O-nC3H7)4 solutions

The shape of the polymers in the mixed alkoxide solutions of Si(OC₂H₅)₄ and Zr(n-OC₃H₇)₄ with various water contents (1, 2, 4, and 8 in molar ratio to alkoxide, r) and catalysts was examined by rheological measurements, and its relation with fiber drawing behavior of the solutions was described. It was found that fibers could be drawn in the viscosity range 1–100 P from the acid-catalyzed solutions with lower water contents of the molar ratio H₂O/alkoxide, r2. On the other hand, no fiber could be drawn from the acid-catalyzed solutions including a large amount of water (r4) and the base-catalyzed solutions.The relation between the intrinsic viscosity [] and the number average molecular weight M_n, namely []=KM _n ^a , has shown that the acid-catalyzed spinnable solutions (r=1 and 2) have linear polymers where the exponent a's are about 0.56 and 0.81, whereas non-spinnable solutions (r=4 and 8) have three dimensional network polymers or spherical particles where the exponent a's are 0.41–0.51 and 0.35.     

Effect of pressure on the solubility of naphthalene in water at 25°C

Solubility of naphthalene in water was measured at 25°C and pressures up to 200 MPa. The solubility decreased with increasing pressure. From the pressure coefficient of the solubility, the volume change V accompanying the dissolution was estimated as 13.8±0.4 cm ³ -mol ^–1 . Further we estimated the volume change V _CH accompanying hydrophobic hydration as –0.1±0.6 cm ³ -mol ^–1 using the V value, the molar volume of crystalline naphthalene, and the partial molar volume of naphthalene in n-heptane. This V _CH is much larger (i.e., less negative) than that for hydrophobic hydration of alkyl-chain compounds and suggests that the hydration structure of naphthalene differs from that of alkyl-chain compounds.     

Molecularly imprinted polystyrene–titania hybrids with both ionic and π–π interactions: a case study with pyrenebutyric acid

We present hybrid films consisting of a composite prepared from polystyrene (PS) and titanium dioxide (titania; TiO₂) and molecularly imprinted with 1-pyrenebutyric acid (PBA). The interaction of PBA with the polymer is shown to occur via binding of the carboxylic group to TiO₂ and hydrophobic interaction of the pyrene moiety with the PS network. We investigated the effects of the PS fraction on morphology, imprinting properties, and guest binding. The template could be completely removed by incubating the films in an acetonitrile solution of pyrene, which is due to the stronger π–π interaction between PBA and pyrene than the interaction between PBA and its binding site. A guest binding study with pyrene, 1-aminopyrene, pyrenemethanol, and anthracene-9-carboxylic acid showed that the hybrid films possessed selectivity and much higher binding capacity for PBA. This study demonstrates the first case of clear PS-assisted imprinting, where the π–π interaction of the template with a linear (non-crosslinked) polymer creates selective binding sites and enhances the binding capacity. This is a driving force for guest binding in addition to the interaction of the template/analyte with TiO₂. All molecularly imprinted films displayed better binding, repeatability and reversibility compared to the respective non-imprinted films.

Discotic Liquid Crystals of Transition Metal Complexes VI. Monotropic Lamella Mesomorphism of Tetrakis(N-Alkyldithiolato)Dinickel(II) and Bis(N-Alkylxanthato)Nickel(II) Complexes

Abstract

It was found that each of the tetrakis(n-alkyldithiolato)dinickel(II), (C_n-DTA)₄-Ni₂, complexes where n-alkyl is n-pentyl through n-dodecyl, exhibits a broken-fan texture on cooling from an isotropic liquid, and that the phase gave a characteristic lamella structure X-ray diffraction powder pattern. Furthermore, the infrared spectrum of this phase is more similar to that of the isotropic liquid than that of the crystal. Therefore, the phase can be described as a monotropic lamella mesophase. Interestingly, each of the complexes of bis(n-alkylxanthato)nickel(II), (C_n-Xan)₂Ni, (n = 5, 7, 9, 11) exhibits double (triple) melting behavior via the isotropic liquid, whereas each of the complexes of (C_n-Xan)₂Ni (n = 4, 6, 8, 10, 12) shows ordinary single melting behavior. Such unique double melting accompanied by an even-odd effect appears to be the first example of this in the long chain substituted compounds. Each of the complexes of (C_n-Xan)₂ Ni (n = 9, 11, 12) has a monotropic lamella mesophase exhibiting a large broken fan texture.     

Influence of lateral methyl and terminal substituents on the mesophase behaviour of four rings azo-ester liquid crystal compounds

ABSTRACT

The effect of introducing a lateral methyl substitution into the previously investigated laterally neat four-ring analogues, 4-substituted phenylazo phenyl 4?-(4?-alkoxyphenylazo) benzoates (In_a–e), on their mesophase behaviour was investigated for the newly prepared five homologous series of 4-substituted phenylazo phenyl 4?-(3?-methyl-4?-alkoxyphenylazo) benzoates (IIn_a–e). Within each homologous series, the alkoxy group varies between 6, 8, 10, 12, 14, and 16 carbons, while the substituent, X, is a polar group that alternatively changes between the electron-donating (CH₃O and CH₃) groups, and the electron-withdrawing (Br and NO₂) groups, including the unsubstituted homologues (IIn_c). Their mesophase stabilities were determined by DSC and phases identified by PLM. The results showed that independent of the alkoxy-chain length or the polarity of the substituent X, the nematic phase is predominant with relatively high stability and wide temperature ranges. All compounds show a good thermal stability in the mesophases domain, except the nitro and Br substituted derivatives bearing short alkoxy chain length. Comparison of the mesophase behaviour was also made between the present series and corresponding three-ring laterally CH_3-substituted azo/ester analogues. UV-vis absorption spectra revealed that derivatives with electron donating or an electron withdrawing groups exhibited redshifts of the π→π* transition compared with unsubstituded derivative.     

Anionic graft polymerization of ethylene oxide on starch. II. Structure of the graft polymers

Starch–poly(ethylene oxide) graft polymers were prepared in DMSO at various monomer and starch alkoxide concentrations. Complimentary and varied information on the structure of the graft polymers was obtained from NMR and periodic acid oxidation of the polymers. From the NMR spectra of the graft polymers in pyridine containing a trace of HCl, which causes shifting of the resonance of the internal ? CH₂O? protons from the terminal ? CH₂OH protons, the polyethylene oxide content, the DP _n of the grafted side chains, and the efficiency of the alkoxides were calculated. With increase of the alkoxide concentration there was a small decrease in ? DP _n, and in the efficiency of the alkoxides in initiating graft polymerization. With increase of monomer concentration, there was only a small increase in ? DP _n but a large increase in the efficiency, indicating the existence of transfer reactions between the growing anions and the free hydroxyl groups on the starch. The results of he periodic acid oxidation showed that with increase of alkoxide concentration there was no significant change in the per cent oxidation of the graft polymers, but with increase of monomer, there was an increase in the participation of the secondary hydroxyl groups in initiation. This supports the NMR evidence for the existence of transfer reactions leading to ? DP _n values much lower than those calculated from [monomer]/[catalyst] ratios.     

Synthesis and characterization of some bis(cyclopentadienyl)titanium(IV) complexes with internally functionalized oximes(LH): sol–gel transformations of Cp2TiCl2, Cp2TiClL and Cp2TiL2 to nano‐sized anatase titania

Some bis(cyclopentadienyl)titanium(IV) complexes of the type [Cp₂TiCl_2?n{L}_n] {where, n = 1 or 2; L = ONC(R)Ar; R = H or CH₃ and Ar = C₅H₄N‐2, C₄H₃O‐2 or C₄H₃S‐2} have been synthesized by the metathetical reactions of Cp₂TiCl₂ with the sodium salt of internally functionalized oximes in 1:1 and 1:2 stoichiometry in anhydrous THF. All these red to brown colored solid derivatives have been characterized by elemental analyses, FT‐IR and NMR (¹H and ¹³C{¹H}) spectral studies. The FAB mass spectra of some representative derivatives indicate their monomeric nature. Oximato ligands in all the complexes appear to bind the titanium via N and O in a dihapto ( ‐N, O) manner in the solid state. Thermogravimetric curves of [Cp₂TiCl{ONC(CH₃)C₅H₄N‐2}] and [Cp₂Ti{ONC(CH₃)C₅H₄N‐2}₂] suggest the formation of hybrid materials CpTiO(Cl) and Cp₂TiO, respectively, as the final products at 900 °C under nitrogen atmosphere. Sol–gel transformations of Cp₂TiCl₂, [Cp₂TiCl{ONC(CH₃)C₅H₄N‐2}] and [Cp₂Ti{ONC(CH₃)C₅H₄N‐2}₂] yielded titania a–c, respectively, at low sintering temperature (600 °C). The powder XRD patterns, IR as well as Raman spectra of all these oxides indicate the formation of nano‐sized anatase phase. The SEM images of titania a–c indicate agglomers like surface morphologies. The absorption spectra of a–c exhibit an energy band gap in the range of 3.47–3.71 eV. Copyright © 2011 John Wiley & Sons, Ltd.     

Thermal Behaviour of Titania Based Materials: Mathematical modeling of emanation thermal analysis results

Emanation thermal analysis (ETA) was used in the characterization of microstructure changes during heating ofprecursors for the titania based materials: hydrous titania, TiO₂nH₂O (n=0.58) and hydrous titania containing 10% ruthenia,(TiO₂)_0.9(RuO₂)_0.1nH₂O (n=1.5). The precursors were heated at the constant rate 6 K min^–1 in argon flow in the range 20–1000°C. ETA results were compared with the theoretical curves simulating the temperature dependences of radon release rate, E(T). Two mathematical models were used in the simulation. The models considered either subsequent or simultaneous solid state processes (i.e. dehydration, crystallization orphase transition, resp.) during thermal treatment of titania based materials. A good agreement was found between experimental and the simulated ETA curves. The results of ETA were confirmed by XRD patterns of intermediate products of thermal treatment of the precursors.This revised version was published online in November 2005 with corrections to the Cover Date.     

Hemolytic activity of polyoxyethylene cholesteryl ethers

Hemolytic activity of nonionic surfactants, polyoxyethylene cholesteryl ethers, C₂₇H₄₅O(CH₂CH₂O) _n H (Chol-E _n ,n=, 25, 30, 50) and polyoxyethylene dihydrocholeseryl ethers, C₂₇H₄₇O(CH₂CH₂O) _n H (DHChol-E _n ,n=15, 30 50) were measured, changing the concentration of surfactant and erythrocyte at 37 °C. Maximum hemolytic activity was observed in these cholesteryl derivatives with 25–30 oxyethylene units. The time course of hemolysis was also measured as a function of the concentrations of surfactant and erythrocyte. Hemolysis started after a certain induction period,, and then apparently proceeded as a first-order reaction with respect to the erythrocyte concentration. The surfactant inducing 50% hemolysis at low concentration had a small value and large rate constant. The maximum amount of adsorption without inducing hemolysis,a ₀, decreased with increasing polyoxyethylene chain length. Chol-E₂₅ has the maximum activity for the solubilization of egg yolk lecithin at 37 °C. Based on these results, the mechanism of hemolysis by these surfactants was quantitatively discussed.     

Synthesis and properties of photosensitive polyimide-nanocrystalline titania optical thin films

In this study, synthesis, morphology, and properties of high refractive index photosensitive polyimide-nanocrystalline titania hybrid materials are reported. A soluble polyimide grafted with carboxylic acid or methacrylate groups (P1) was first synthesized from 4,4′-(hexafluoroisopropylidene) diphthalic anhydride (6FDA), 3,5-diaminobenzoic acid (DABA), 4-aminobenzoic acid (4ABA), and 2-hydroxyethyl methacrylate (2HEMA). The residual carboxylic acid groups could undergo an esterification reaction with titanium butoxide to provide an organic-inorganic bonding. On the other hand, the grafted methacrylate groups rendered photosensitive property for photopatterning. A homogeneous hybrid solution was obtained through the formulation on different mole ratios of titanium butoxide/carboxylic acid, water/acid content in a mixed solvent. It was followed by spin-coating, photocuring and post-baking. The titania domain size in the hybrid materials analyzed by high resolution transmission electron microscopy (HRTEM) and X-ray diffraction (XRD) was around 4-7 nm. The prepared optically transparent films had tunable refractive index (1.583 < n < 2.029), relatively good surface planarity and high thermal stability. A fine pattern with a line width of 50 μm was produced by direct lithographic process on the hybrid films. The present study demonstrates a novel approach for preparing high refractive index hybrid photosensitive materials with patternability.     

Photocatalytic reaction on photofuel cell titania electrode

Benzoic acid-doped titania electrodes were prepared from titanium alkoxide sols containing benzoic acid in order to examine the photocatalytic reaction of the fuel material concentrated on the titania surface of a photofuel cell electrode. This doping was developed in order to understand the physicochemical processes on the titania rather than to advance the practical use of the photofuel cells. The observed photocurrent and CO₂ and H₂O productions indicated that the oxidation of the benzoic acid enhanced the generation of electricity during the UV irradiation. Benzoic acid molecules should be oxidized by oxygen molecules and holes on the titania surface. The steam treatment of the electrodes improved the benzoic acid oxidation and the photocurrent because it promoted the titania densification and enhanced the interaction between the benzoic acid and titania. The benzoic acid-doped titania is a valid model of the fuel material concentrated in the porous titania when using benzoic acid as the fuel material. The contact between the benzoic acid and titania is important in order to obtain a high photofuel electric conversion.     

Methyl and phenyl esters and thioesters of carboxylic acids as surrogate substrates for microassay of proteinase K esterase activity

The development of a microassay for proteinase K esterase activity with carboxylic acid esters is reported using novel substrates of the general formula R-C(O)-XR. Highest rates of hydrolysis have been obtained with the O-phenyl esters CH₃(CH₂)_{n = 1 – 2}-S-(CH₂)_{n = 1 – 2} C(O)-O-phenyl and their thioester analogs in studies where R, X and R have been varied. The phenol release has been measured with 4-aminoantipyrine and potassium ferricyanide to determine the rates of O-phenyl ester hydrolyses. Thioester hydrolyses have been monitored continuously with 5,5-dithio-bis (2-nitrobenzoic acid).