Preparation of porous clay minerals with organic-inorganic hybrid pillars using solvent-extraction route

A microporous clay mineral with organic-inorganic hybrid pillars was synthesized using a hydrochloric acid (HCl)/ethanol extraction method after intercalation of tetraethoxysilane (TEOS) or TEOS/methyltriethoxysilane (MTS) into the cetyltrimetylammonium ion (CTA)-exchanged vermiculite. The products retained their layered structure, due to the formation of stable pillars by the polymerization of hydrolyzed TEOS and MTS during the HCl/ethanol treatment. The BET surface areas, which increased to above 500 m2g(-1) with an increase in the HCl concentration up to 0.4 moldm(-3), are nearly equal to that of the calcined product obtained by the conventional method. However, the pore sizes of HCl/ethanol-treated materials were narrower than those of the calcined product, owing to the formation of the polysiloxane networks in the gallery. A water adsorption study showed that the product treated with a TEOS/MTS mixture had a hydrophobic surface as a result of the successful incorporation of methyl groups at the surface of the pillars. This novel method is advantageous for the synthesis of organophilic pillared clays with different kinds of organic materials in the interlayers.     

Crystal structures of V3S4 and V5S8

Crystal structures of the ordered phases of V₃S₄ and V₅S₈ were refined with single crystal data. Both are monoclinic. Chemical compositions, space groups and lattice constants are as follows: VS_1.47, $\text{I2}\text{m}$ (No. 12), a = 5.831(1), b = 3.267(1), c = 11.317(2)Å, β = 91.78(1)° and VS_1.64, $\text{F}\text{2}\text{m}$ (No. 12), a = 11.396(11), b = 6.645(7), c = 11.293(4), Å, β = 91.45(6)°. In both structures, short metal-metal bonds were found between the layers as well as within them. In comparison with the structure of Fe₇S₈, the stability of NiAs-type structure was discussed based on the detailed metal-sulfur distances.     

Effects of gamma-irradiation on CO2 fixation and

To investigate the possibility of ¹⁴CO₂ fixation using microorganisms in a high-dose area, the photosynthetic activity (specific production rate: SPR) and cellular proliferation (colony forming unit: CFU) of Euglena gracilis Z irradiated with gamma-rays at a dose of 0 to 500 Gy were determined. The dose responses of SPR and CFU suggested that it was possible to operate a CO₂ fixation system of Euglena up to 100 Gy. Even at a dose of 500 Gy, about half of the photosynthetic activity under non-irradiated condition was considered possible.     

Analysis of phenothiazines in human body fluids using disk solid-phase extraction and liquid chromatography

Seven phenothiazine derivatives, perazine, perphenazine, prochlorperazine, propericiazine, thioproperazine, trifluoperazine, and flupentixol, have been found to be extractable from human plasma and urine samples using disk solid-phase extraction (SPE) with an Empore C18 cartridge. Human plasma and urine (1 mL each) containing the 7 phenothiazine derivatives were mixed with 2 mL of 0.1M NaOH and 7 mL distilled water and then poured into the disk SPE cartridges. The drugs were eluted with 1 mL chloroform- acetonitrile (8 + 2) and determined by liquid chromatography with ammonium formate/formic acid-acetonitrile gradient elution. The detection was performed by ultraviolet absorption at 250 nm. The separation of the 7 phenothiazine derivatives from each other and from impurities was generally satisfactory using a SymmetryShield RP8 column (150 x 2.1 mm id, 3.5 microm particle size). The recoveries of the 7 phenothiazine derivatives spiked into plasma and urine samples were 64.0-89.9% and 65.1-92.1%, respectively. Regression equations for the 7 phenothiazine derivatives showed excellent linearity, with detection limits of 0.021-0.30 microg/mL for plasma and 0.017-0.30 microg/mL for urine. The within-day and day-to-day coefficients of variation for both samples were commonly below 9.0 and 14.9%, respectively.     

Surface modification by calcium ions—Effect on chromatographic properties of silica

Summary A liquid chromatographic method incorporating column-switching and fluorimetric detection for the determination of triamterene in untreated urine, is described. The urine samples (5 L) were directly introduced onto an Hypersil ODS-C18, 30 m (20 mm×2.1 mm I.D.) pre-column. Polar urinary compounds were removed by flushing the pre-column with water for 1 min, and the analyte was then switched onto an HP-LiChrospher RP C18,5 m (125 mm×4mm ID) analytical column using an acetonitrile/phosphate buffer gradient elution. Fluorescence detection was performed at 230 nm excitation and 430 nm emission wavelengths. The recovery of drug was 102±2% in the 0.10–20.0 g/mL concentration range, the limit of detection being 5 ng/mL. A validation of the usefulness of this procedure was accomplished by analysing urine extracts obtained from real samples.Hypersil ODS is not a product of Merck, Germany. Please give supplier (p. 5).     

Magnetic/Conducting Hybrid Compound Composed of 1-D Chain [Mn2Cl5(EtOH)]∞ and BEDT-TTF Stacking Layer

An assembled compound (BEDT-TTF)₂[Mn₂Cl₅(EtOH)] (1) consisting of two structural lattices of Mn(II)-Cl one-dimensional (1-D) chains and bis(ethylenedithio)tetrathiafulvalene (BEDT-TTF) stacking layers was synthesized by electrochemical crystallization. Compound 1 crystallized in triclinic space group P-1 (#2) with a=13.1628(5) Å, b=20.3985(9) Å, c=7.4966(3) Å, α=98.3498(8)°, β=104.980(1)°, γ=74.602(2)°, V=1868.3(1) ų, and Z=2. The 1-D chains and the stacking layers are aligned along the c-axis of the unit cell. The 1-D chain is described as [Mn₂Cl₅(EtOH)]_∞⁻ in which two Mn(II) ions and four Cl⁻ ions form a ladder-like chain with Kagomé (cuboidal) sublattices, and the remaining Cl⁻ ion and an ethanol molecule cap the edge-positioned Mn(II) ions of the chains. The BEDT-TTF molecules are packed between the Mn-Cl chains (ac-plane), the intermolecular S·S contacts of which are approximately found in the range 3.440(2)-3.599(2) Å. The packing feature of BEDT-TTF molecules is very similar to that of (BEDT-TTF)₂ClO₄(TCE)_0.5 (TCE=1,1,2-trichloroethane) (J. Am. Chem. Soc., 105, 297 (1983)). Regarding the electronic state of each BEDT-TTF molecule, Raman spectroscopic analysis and ESR study revealed the presence of half-valence BEDT-TTF molecules (charge delocalization) in 1. Magnetic measurements clearly demonstrated that the paramagnetic spins on the 1-D chain [Mn₂Cl₅(EtOH)]_∞⁻ arrange antiferromagnetically in the low-temperature region. Additionally, 1 exhibits metallic conductivity in the temperature range 2.0-300 K (σ=21 S cm⁻¹ at 300 K and 1719 S cm⁻¹ at 2.0 K), due to the contribution of the stacked BEDT-TTFs. Consequently, these peculiarities that correspond to antiferromagnetic/metallic conductivity demonstrate the “bi-functionality” of 1.     

Electronic structures of zinc and palladium tetraazaporphyrin derivatives controlled by fused benzo rings

Zinc and palladium tetracyclic aromatic complexes lying structurally between tetraazaporphyrin (TAP) and phthalocyanine (Pc), that is, monobenzo-, adjacently dibenzo-, oppositely dibenzo-, and tribenzo-fused TAPs, have been prepared, and their electronic structures investigated by electronic absorption, magnetic circular dichroism (MCD), fluorescence, phosphorescence, and time-resolved electron paramagnetic resonance (TREPR) spectroscopy, as well as cyclic voltammetry. The last-named indicated that the first oxidation potentials shift to more negative values with increasing number of the fused benzo rings, but also suggested that the first reduction potential apparently has no correlation with the size and symmetry of the pi-conjugated systems. However, this latter behavior is reasonably interpreted by the finding that the effect of the fused benzo rings on destabilization of the LUMO depends on the orbital to which they are fused (i.e., whether it is an egx or egy orbital), since the LUMOs of TAP complexes are degenerate with D4h symmetry. The energy splitting of the LUMOs, that is, DeltaLUMO, was evaluated experimentally for the first time by analyzing the relationship between the first reduction potential and the size and shape of the pi-conjugated system. Electronic absorption and MCD measurements indicate that the lowest excited singlet states are split in the case of the low-symmetry TAP derivatives, although these excited states are degenerate for Pc and TAP with D4h symmetry. These energy splittings DeltaE(SS) correlate well with the DeltaLUMO values. To investigate the electronic structures in the lowest excited triplet state, zero-field splitting (zfs) was analyzed by time-resolved EPR (TREPR) spectroscopy. The energy splitting in the lowest excited triplet state, DeltaE(TT) was quantitatively evaluated from the temperature dependence of the zfs or spin-orbit coupling of the Pd complexes. Consequently, it is demonstrated that DeltaLUMO, DeltaE(SS), and DeltaE(TT) values exhibiting a mutually good relationship can be determined experimentally.     

DTA study of the chlorination of fly ash and bauxite in the presence of carbon

The chlorination processes of fly ash and bauxite in the presence of carbon were studied by means of a gas-flow type DTA, X-ray analysis and SEM observation, and the reactivity of Al-compounds as their constituents was compared. In the case of fly ash, the exothermic peak due to the formation of AlCl₃ (mainly) and FeCl₃ appeared at about 790–920°C. The reactivity of Al estimated from the DTA peak temperature depended on the particle size, carbon content and preparation temperature of fly ash, and was much lower than that of bauxite. Fractional conversion of Al was about 60–70%, when fly ash (?300 mesh) was heated up to 900°C in Cl₂ at 5°C min^?1 of heating rate. In the case of bauxite, two exothermic peaks due to the chlorination of Fe and Al appeared at about 270 and 490°C, respectively. The chlorination of Al was completed at 550°C under the above conditions.