Polymorphism in yttrium molybdate Y2Mo3O12

Yttrium molybdate (Y₂Mo₃O₁₂) has been prepared by non-hydrolytic sol–gel chemistry. The phase evolution upon heating was investigated using in situ and ex situ heat treatments combined with powder X-ray diffraction. This method has led to the isolation of two orthorhombic phases with different atomic connectivity. Yttrium adopts 6- and 7-coordinate sites in the Pbcn and Pba2 structures, respectively. Cocrystallization of both phases was observed in a narrow temperature range, suggesting that crystallization kinetics play a major role in phase formation. It was found that the Pba2 phase is the stable polymorph below 550 °C, and converts to Pbcn at higher temperatures.     

Dithiafulvene (1,3-dithiole): Monomers and polymers

Monomers and polymers of 2-benzylidene-1,3-dithioles (dithiafulvenes) were synthesized. Polymerization of substituted dithiafulvenes with diacid chlorides, p-phenylene diisocyanate, or terephthalaldehyde yielded yellow polymers with inherent viscosities ranging from 0.10 to 0.21 dL/g.     

Investigation of the mechanism of pH-mediated stacking of anions for the analysis of physiological samples by capillary electrophoresis

Capillary electrophoresis has been widely used for the analysis of physiological samples such as plasma and microdialysate. However, sample destacking can occur during the analysis of these high-ionic strength samples, resulting in poor separation efficiency and reduced sensitivity. A technique termed pH-mediated stacking of anions (base stacking) has previously been developed to analyze microdialysate samples and achieve on-line preconcentration of analytes by following sample injection with an injection of sodium hydroxide. In this work, the mechanism of base stacking was investigated. Peak efficiency was shown to be a function of background electrolyte and sample ionic strength. Analytes representing several classes of compounds with a wide range of mobilities were used to study the effects of multiple parameters on sample stacking. The length of hydroxide injection required for stacking was shown to be dependent on analyte mobility and the type of amine background electrolyte used. Combinations of electrokinetic and hydrodynamic injections of sample and hydroxide were examined and it was concluded that although stacking could be achieved with several injection modes, electrokinetic injection of both sample and hydroxide was most effective for sample stacking. The mechanism of pH-mediated stacking for each of these modes is presented.     

Hydroxynorleucine as a glycosyl acceptor is an efficient means for introducing amino acid functionality into complex carbohydrates

A new approach to the synthesis of biologically relevant glycosyl amino acids using a non-natural amino acid as the glycosyl acceptor is described. The procedure involves a glycosylation reaction of a suitable carbohydrate donor with Fmoc-l-hydroxynorleucine benzyl ester. This reaction results in the direct incorporation of the amino acid moiety. The acceptor can be used for the preparation of α- or β-O-linked glycosides depending upon the nature of the glycosyl donor. This method has been applied in the synthesis of six different tumor-associated carbohydrate antigens.     

Psammaplins from the sponge Pseudoceratina purpurea: inhibition of both histone deacetylase and DNA methyltransferase

Four novel bisulfide bromotyrosine derivatives, psammaplins E (9), F (10), G (11), and H (12), and two new bromotyrosine derivatives, psammaplins I (13) and J (14), were isolated from the sponge Pseudoceratina purpurea, along with known psammaplins A (4), B (6), C (7), and D (8) and bisaprasin (5). The structures of psammaplins E (9) and F (10), which each contain an oxalyl group rarely found in marine organisms, were determined by spectroscopic analysis. Compounds 4, 5, and 10 are potent histone deacetylase inhibitors and also show mild cytotoxicity. Furthermore, compounds 4, 5, and 11 are potent DNA methyltransferase inhibitors. The biogenetic pathway previously proposed for the psammaplins class is also revisited.     

The interaction of organosilanes with triphenylmethyl tetrafluoroborate

Under mild conditions, Ph₃CBF₄ readily fluorinates the SiH bond(s) of trialkylsilanes and dialkylsilanes. The use of this reagent in the successful fluorination of HSiMe₂CH₂Fe(CO)₂Cp suggests that the reaction can be used to fluorinate silicon compounds that possibly would not survive more vigorous fluorination reactions. A convenient preparation of diorganofluorosilanes that have both hydrogen and fluorine bonded to silicon is described.     

Electrolyte and pH effects on Pb(II)-calcite sorption processes: the role of the PbCO0 (3aq) complex

Batch sorption experiments were conducted under conditions of ambient temperature and atmospheric PCO2g to determine the effects of electrolyte type, ionic strength, and pH on Pb(II) interactions with calcite. For 0.15 M nitrate and chloride solutions at pH 8.2, no significant effect of electrolyte type on Pb sorption was observed. Varying ionic strength from 0.15 to 0.5 M produced little effect on Pb sorption in nitrate compared to chloride solutions in which Pb uptake decreased with increasing ionic strength. For a pH range of 7.3-9.4 in 0.15-0.2 M nitrate solutions, Pb sorption increased from pH 7.3 to 8.5 with a subsequent decrease in uptake out to pH 9.4. The trends in electrolyte and pH experiments correlate well with those for PbCO0(3aq) speciation, indicating that this metal-ligand complex in solution dictates Pb sorption in the system under investigation.     

Comprehensive two-dimensional gas chromatography analysis of high-ethanol containing motor fuels

A comprehensive 2-D GC (GC x GC) instrument equipped with a flow-switching modulator was used to determine the concentration of ethanol and eight other alcohols in a retail pump sample of E85 fuel. E85 is a mixture of ethanol and gasoline where the ethanol concentration can range from 70 to 85 vol%. The increased peak capacity and selectivity generated by GC x GC analysis allowed the alcohols to be fully resolved from the gasoline hydrocarbons. GC x GC analysis was compared to the performance obtained with the standard analytical method for determining ethanol in fuel ethanol (ASTM D5501) and the standard method for determining oxygenate concentrations in gasoline (ASTM D4815). The GC x GC analysis required 14 min while the combined ASTM D5501 and ASTM D4815 analyses required more than 60 min. The ethanol concentration obtained by GC x GC was in excellent agreement with the value obtained by the D5501 method. Poorer agreement was observed between the GC x GC and D4815 concentrations for the other alcohols present in E85. In all cases, the differences could be attributed to deficiencies in the D4815 method that led to coelutions between the alcohols and gasoline hydrocarbons.