Application of ceramic carbon materials for solid-phase extraction of organic compounds

Ceramic carbon materials were developed as new sorbents for solid-phase extraction of organic compounds using chlorpromazine as a representative. The macroporosity and heterogeneity of ceramic carbon materials allow extracting a large amount of chlorpromazine over a short time. Thus, the highly sensitive and selective determination of chlorpromazine in urine sample was achieved by differential pulse voltammograms after only 1-min extraction. The total analysis time was less than 3 min. In comparison with other electrochemical and electrochemi-luminescent methods following 1-min extraction, the proposed method improved sensitivity by about 2 and 1 order of magnitude, respectively. The fast extraction, diversity, and conductivity of ceramic carbon materials make them promising sorbents for various solid-phase extractions, such as solid-phase microextraction, thin-film microextraction, and electrochemically controlled solidphase extraction. The preliminary applications of ceramic carbon materials in chromatography were also studied.

Enhanced thermal stability of zinc-based titanate (dielectric) ceramics prepared by the modified sol-gel route

A multi-component substitution of Co and Ni was incorporated into ZnTiO3 to form pure hexagonal Zn1-x(Co1/2Ni1/2)xTiO(3) (x = 0,0.8,0.9,1.0) dielectric ceramic powders by a modified sol-gel route, following heat treatments at 600 degrees C for 3 h and at 800 degrees C for 6 h. Differential scanning calorimetry measurements revealed that the order of increasing thermal stability of solid solution compound Zn1-x(Co1/2Ni1/2)(x)TiO3 was ZnTiO3 (945 degrees C), Zn0.1Ni0.9TiO3 (1346 degrees C), Zn-0.1(Co1/2Ni1/2)(0.9)TiO3 (1390 degrees C), and Zn0.1Co0.9TiO3 (> 1400 degrees C). Both the dielectric constant and loss tangent reached a maximum at x = 0.8 and then decreased with solubility, x, and measurement frequency.

Synthesis, structural characterization and electrical property of new oxide ion conductors: La3MMo2O12 (M = In, Ga and Al)

New series of oxides, La3MMo2O12 (M = In, Ga and Al), have been prepared by the solid-state reaction. The composition and elemental distribution were analyzed by the energy-dispersive X-ray (EDX) analysis. As determined by the X-ray diffraction (XRD), these compounds have similar crystal structures that can be indexed on a monoclinic cell at room temperature. AC impedance spectra and the DC electrical conductivity measurements in various atmospheres indicate that they are oxide ion conductors with ionic conductivities between 10(-2) and 10(-3) S/cm at 800 degrees C. The conductivity decreases in the order of La3GaMo2O12 > La3AlMo2O12 > La3InMo2O12, implying that the effect of cell volume and polarization associated with In3+, Ga3+ and Al3+ play an important role in the anion transport of these materials. The reversible phase transition was observed in all these compounds as confirmed by the differential thermal analysis (DTA) and dilatometric measurements.

Separation of scandium, yttrium and lanthanum in high-performance centrifugal partition chromatography with S-octyl phenyloxy acetic acid

Separation of scandium(III), yttrium(III) and lanthanum(III) was performed by high-performance centrifugal partition chromatography (HPCPC) employing the stationary phase of S-octyl phenyloxy acetic acid (CA-12). The liquid-liquid extraction behavior of CA-12 for Sc(III), Y(III) and La(III), the acidity of aqueous phase, and the operation conditions of HPCPC were examined. The retention volume (V-R) increased with the order of Y(III), La(III) and Sc(III) accompanied with the elution of the mobile phase in different pH, which is lowered from 4.6 to 2.1.

Copolymerization of carbon dioxide and propylene oxide with neodymium trichloroacetate-based coordination catalyst

The copolymerizations of carbon dioxide (CO2) and propylene oxide (PO) were performed using new ternary rare-earth catalyst, It was found that the rare-earth coordination catalyst consisting of Nd(CCl3COO)(3), ZnEt2 and glycerine was very effective for the copolymerization of PO with CO2. The effects of the relative molar ratio and addition order of the catalyst components, copolymerization reaction time, and operating pressure as well as temperature on the copolymerization were systematically investigated. At an appropriate combination of all variables, the yield could be as high as 6875 g/mol Nd per hour at 90 degreesC in a 8 h reaction period.

Investigation of ion transfer across the micro-water/nitrobenzene interface facilitated by a fullerene derivative

A functionalized fullerene derivative containing a monoaza-18-crown-6 moiety was investigated by facilitated ion (such as Li+, Na+, K+, NH4+, Mg2+, and Ca2+) transfer across the micro-water/nitrobenzene interface supported at the tip of a micropipet. The current responses were detected by cyclic voltammetry and Osteryoung square wave voltammetry, which demonstrated that the facilitated ion transfer does occur by an interfacial complexation-dissociation process. The diffusion coefficient of this compound in nitrobenzene was approximately (5.90 +/- 0.04) x 10(-7) cm(2) s(-1), which is 1 order of magnitude less than other common ionophores due to the large size of the molecule. The selectivity of this molecule toward the metal ions followed the sequence Na+ > Li+ > K+ > NH4+ > Ca2+ similar to Mg2+. In addition, this compound was also easy to form film at the water/nitrobenzene interface to inhibit the simple ion transfer of tetramethylammonium ion. However, the adsorption of this ionophore has less influence on the facilitated metal ion transfer.

Photoluminescent properties of organic film in flat optical microcavity

The microcavity is sandwiched between a quarterwavelength distributed Bragg reflector(DBR) and a metal Ag reflective mirror. A single layer of a Tris(8-quinolinolato)aluminum (Alq) film was used as the light-emitting layer. The photoluminescent properties of the optical microcavity and that of the Alq film were studied at the same excitation condition. Compared with the Alq film,the significantly narrowed spectral emission linewidth from 90 nm to 10 nm was observed, the PL emission intensity of the microcavity at the resonant mode is enhanced by the order of 1. The spectral narrowing and intensity enhancement of the microcavity is attributed to the microcavity effect.

Sintering of nanopowders of amorphous silicon nitride under ultrahigh pressure

Nanopowders of amorphous silicon nitride were densified and sintered without additives under ultrahigh pressure (1.0-5.0 GPa) between room temperature and 1600 degrees C. The powders had a mean diameter of 18 nm and contained similar to 5.0 wt% oxygen that came from air-exposure oxidation, Sintering results at different temperatures were characterized in terms of sintering density, hardness, phase structure, and grain size. It was observed that the nanopowders can be pressed to a high density (87%) even at room temperature under the high pressure. Bulk Si3N4 amorphous and crystalline ceramics (relative density: 95-98%) were obtained at temperatures slightly below the onset of crystallization (1000-1100 degrees C and above 1420 degrees C, respectively. Rapid grain growth occurred during the crystallization leading to a grain size (>160 nm) almost 1 order of magnitude greater than the starting particulate diameters, With the rise of sintering temperature, a final density was reached between 1350 and 1420 degrees C, which seemed to be independent of the pressure applied (1.0-5.0 GPa), The densification temperature observed under the high pressure is lower by 580 degrees C than that by hot isostatic pressing sintering, suggesting a significantly enhanced low-temperature sintering of the nanopowders under a high external pressure.

Hydrogen-deuterium exchange reactions of cis- and trans-cyclopropane derivatives with D2O and CD3OD in the gas phase

Gas-phase hydrogen-deuterium (H/D) exchange reactions involving four isomeric cyclopropane derivatives were investigated under chemical ionization (CI) conditions, using D2O and CD3OD as reagent gases. There are abundant ions at [M + 1](+), [M + 2](+) and [M + 3](+) in the D2O and CD3OD positive-ion CI mass spectra of the two isomer pairs 1, 2 and 3, 4, Their CI mass spectra are identical with each pair, and so are the collision-induced dissociation (CID) spectra of ions [M + 1](+), [M + 2](+) and [M + 3](+) of each of the two isomer pairs. The CID spectra of [M + 1](+) ions indicate that they have common D/H exchange reactions within each pair, which take place between molecular ions and deuterium-labeling reagents to form the [M - H + D](+) ions. Those of their [M + 2](+) ions show that they have common D/H exchange reactions within each pair, which form the [M-d1 + H](+) ions. Those of their [M + 3](+) ions show that they have common D/H exchange reactions within each pair, which take place between the [M-d1] and deuterium-labeling reagents to produce [Md-2 + H](+) for the isomer pair 1, 2 and [M-d1 + D](+) for the Isomer pair 3, 4. The number and position, and active order of the active hydrogen atoms of the isomer pairs 1, 2 and 3, 4 were determined. Copyright (C) 2000 John Wiley & Sons, Ltd.

Gas and water vapor transport through a series of novel poly(aryl ether sulfone) membranes

The permeation behavior of water vapor, H-2, CO2, O-2, N-2, and CH4 gases in a series of novel poly(aryl ether sulfone)s has been examined over a temperature range of 30-100 degreesC. These polymers include four alkyl-substituted cardo poly(aryl ether sulfone)s and four intermolecular interaction enhanced poly(aryl ether sulfone)s. Their water vapor and gas transport properties were compared to the unmodified cardo poly(aryl ether sulfone) (PES-C). It was found that the bulky alkyl substituents on the phenylene rings were advantageous for gas permeability, while the intermolecular hydrogen bonds and ionic bonds resulted in a considerable increase in gas permselectivity. The causes of the trend were interpreted according to free volume, interchain distance, and glass transition temperature, together with the respective contribution of gas solubility and diffusivity to the overall permeability. Of interest was the observation that IMPES-L, which simultaneously bears bulky isopropyl substituent and pendant carboxylic groups, displayed 377% higher O-2 permeability and 5.3% higher O-2/N-2 permselectivity than PES-C. Furthermore, sodium salt form PES-Na+ and potassium salt form PES-K+ exhibited water vapor permeability twice as high as PES-C and H2O/N-2 selectivity in 10(5) order of magnitude.

The effect of preparation conditions on the catalyst Nd(P-507)(3)/H2O/Al(i-Bu)(3) for the polymerization of styrene

The catalyst system neodymium phosphonate Nd(P-507)(3)/H2O/Al(i-Bu)(3) for the polymerization of styrene was examined. Effects of the addition order of the catalyst components, catalyst aging time and aging temperature on the catalyst activity and the polymer characteristics were investigated. The catalyst activity for isospecific polymerization of styrene increases with aging time and reaches the maximum with a catalyst aged for 45 min at 70 degrees C. The aging time that the catalyst needs to reach the highest activity for isospecific polymerization decreases with increasing aging temperature. The preformed catalyst and the in situ catalyst were compared with respect to the kinetic behavior of the styrene polymerization and the polymer characteristics.

Interaction of scopolamine and cholesterol with sphingomyelin bilayers by FT-Raman spectroscopy

The interaction of scopolamine and cholesterol with sphingomyelin bilayers has been investigated by FT-Raman spectroscopy in head-group region (600-1000 cm(-1)), the C-C stretching (1000-1200 cm(-1)), CH2 deformation (1400-1500 cm(-1)) and the C-H stretching (2800-3000 cm(-1)) mode regions. The results indicate that scopolamine and cholesterol do not change the conformation of O-C-C-N+ backbone in the choline group of sphingomyelin bilayers, the polar headgroup is still extending parallel to the bilayer surface and O-C-C-N+ group is still in its gauche conformer. Scopolamine and cholesterol lower the order of the interface, the interchain, CH2 crystal lattices and the lateral chain-chain packing, and increase their fluidity.

NMR titration and molecular model MOPAC calculation of protonation processes of two MRI ligands

The protonation process of two DTPA bis(amide) derivatives, DTPA-BDMA and DTPA-BDEA, was studied by using H-1 NMR titration and MOPAC calculation. Their protonation process was proposed in the order of the central amine, the terminal amines, the central carboxyl, the terminal carboxyl, the other terminal carboxyl and central amine. During the protonation of the terminal amine, there existed a large fraction of proton transfer from the central amine to the other terminal amine.

Self-assembly of the pre-formed inclusion complexes between cyclodextrins and alkanethiols on gold electrodes

A new kind of self-assembled monolayer (SAM) formed in aqueous solution through the pre-formed inclusion complexes (abbreviated CD . C-n) between alpha-, beta-cyclodextrins (CDs) and alkanethiols (CH3(CH2)(n-1)SH, n = 10, 14 and 18) was prepared successfully on gold electrodes. High-resolution H-1 NMR was used to confirm the formation of CD . C-n. X-ray photoelectron spectroscopy, cyclic voltammetry and chronoamperometry were used to characterize the resulting SAMs (denoted as M-CD . Cn). It was found that M-CD . Cn were more stable against repeated potential cycling in 0.5 M H2SO4 than SAMs of CH3(CH2)(n-1)SH (denoted as M-Cn), with a relative sequence of Mbeta-CD . Cn > Malpha-CD . Cn > M-Cn. In addition, an order of blocking the electron transfer between gold electrodes and redox couples (both Fe(CN)(6)(3-) and Ru(NH3)(6)(3+)) in solution, M-CD . C10 > M-CD . C14 > M-CD . C18, was observed. A plausible explanation is provided to elucidate some of the observations. (C) 1997 Elsevier Science S.A.

Electrochemical and spectroelectrochemical study of (OEP)Co in the presence of acrylonitrile, ethanol, N,N-dimethylformamide and dimethylsulfoxide in dichloroethane solution

The ligand effects of acrylonitrile, EtOH, DMF and DMSO on the electrochemical oxidation reactions of (OEP)Co were investigated by CV monitored electrochemical titration and in - situ thin - layer spectroelectrochemical method. The formation constants of (OEP)Co(III) with these molecules were calculated. The magnitude of the values shows the order of acrylonitrile of these molecules. However, the Co(II) center does not show any coordination with any of these molecules. It was also find that the ring cation radicals of the Co(III) can form one or two axial bindings with these molecules.