Surfactant coated graphitic carbon based stationary phases for anion-exchange chromatography.

Separations of common inorganic anions were carried out on three different surfactant coated media using carbonate/bicarbonate eluents with suppressed conductivity detection. Graphitic carbon columns (porous graphitic carbon and carbon-clad zirconia) packed with 3 microm particles have been converted into anion-exchange stationary phases by equilibration with the cationic surfactants: didodecyldimethylammonium bromide (DDAB); cetyltrimethylammonium bromide (CTAB); and cetylpyridinium chloride (CPC). Additionally, an ethylene-bridged silica column was studied with CPC coatings.

Stereoselective synthesis of 2-deoxy-furanosides from 2,3-anhydro-furanosyl thioglycosides.

The stereocontrolled synthesis of 2-thiotolyl-furanosides from 2,3-anhydro-furanosyl thioglycosides through a rearrangement-glycosylation process is reported. The efficiency of this reaction is high, providing 70-95% yields of the products. Treatment of the resulting 2-deoxy-2-thiotolyl-glycosides with hydrogen and Raney nickel affords the corresponding 2-deoxy-furanosides with a 1,3-syn relationship.

Synthesis of the 'primer-adaptor' trisaccharide moiety of Escherichia coli O8, O9, and O9a lipopolysaccharide.

Described is the synthesis of the trisaccharide alpha-D-Manp-(1-->3)-alpha-D-Manp-(1-->3)-beta-D-GlcpNAcO(CH2)8N3, the glycan portion of which corresponds to the 'adaptor-primer' moiety linking the O-chain and core oligosaccharide in the lipopolysaccharide of several Escherichia coli and Klebsiella pneumoniae serotypes. This report represents the first synthesis of this trisaccharide motif, and in the route involved, a key step is a [2+1] coupling of a protected Manp-(1-->3)-alpha-D-Manp glycosyl donor with a GlcpNAc acceptor. The azido group was included in the target to facilitate future preparation of neoglycoconjugates.

Domino electrocyclization/azide-capture/schmidt rearrangement of dienones: one-step synthesis of dihydropyridones from simple building blocks.

Simple 1,4-dien-3-ones undergo Lewis acid-catalyzed Nazarov electrocyclization and intermolecular trapping by various azides to furnish 3,4-dihydropyridin-2-ones in moderate to good yields. The reaction is proposed to proceed via nucleophilic trapping of the 2-oxidocyclopentenyl intermediate, followed by Schmidt-type rearrangement to give a transient 1,4-dipole. In unsymmetrical examples, complete regioselectivity in favor of attack on the less substituted side was observed.

Off-line coupling of preparative capillary zone electrophoresis with microwave-assisted acid hydrolysis and matrix-assisted laser desorption ionization mass spectrometry for protein sequencing.

An off-line coupling of capillary electrophoresis (CE) with microwave-assisted acid hydrolysis/matrix-assisted laser desorption ionization mass spectrometry (MAAH/MALDI) has been developed for protein identification and characterization. Preparative scale protein separations enable collection of 10-50 pmol of purified cytochrome c for subsequent sequencing using MAAH/MALDI. To reduce protein adsorption onto the silica surface, the cationic surfactant-based coatings, dimethylditetradecylammonium bromide and dimethyldioctadecylammonium bromide, are employed.

Synthesis of the docosanasaccharide arabinan domain of mycobacterial arabinogalactan and a proposed octadecasaccharide biosynthetic precursor.

Two major components of the cell wall in mycobacteria, including Mycobacterium tuberculosis, the causative agent of tuberculosis (TB), are polysaccharides containing arabinofuranose residues. In one of these polysaccharides, arabinogalactan, this arabinan domain consists of three identical motifs of 22 arabinofuranose residues, which are in turn attached to an underlying galactofuranan backbone. Recent studies have proposed that this docosanasaccharide motif, and a structurally related arabinan present in another cell wall polysaccharide, lipoarabinomannan, are biosynthesized from a common octadecasaccharide precursor.

Developments in ion chromatography using monolithic columns.

The focus of this review is on current status and on-going developments in ion chromatography (IC) using monolithic phases. The use and potential of both silica and polymeric monoliths in IC is discussed, with silica monoliths achieving efficiencies upwards of 10(5) plates/m for inorganic ions in a few minutes or less. Ion exchange capacity can be introduced onto the monolithic columns through the addition of ion interaction reagents to the eluent, coating of the monolith with ionic surfactants or polyelectrolyte latexes, and covalent bonding.

Synthesis of deoxy and methoxy analogs of octyl alpha-D-mannopyranosyl-(1-->6)-alpha-D-mannopyranoside as probes for mycobacterial lipoarabinomannan biosynthesis.

A panel of analogs of the disaccharide alpha-D-Manp-(1-->6)-alpha-D-Manp-OOctyl, a known acceptor substrate for a polyprenol monophosphomannose-dependent alpha-(1-->6)-mannosyltransferase involved in the assembly of the alpha-(1-->6)-linked mannan core of mycobacterial lipoarabinomannan, has been synthesized. Described are synthetic routes to the target deoxy and methoxy analogs in which one of the hydroxyl groups of the parent disaccharide has been modified. All glycosylation reactions involved the use of octyl glycoside acceptors and thioglycoside donors using iodonium-ion activation, and the stereochemistry of the mannopyranoside bond formed was established by measurement of the 1J(C-1,H-1).

Determination of glyphosate using off-line ion exchange preconcentration and capillary electrophoresis-laser induced fluorescence detection.

An enrichment method for the herbicide glyphosate is presented based on ion exchange solid phase extraction (SPE) technique. A 200-mul micro-pipette tip packed with 50mg of Bio-Rad AG1-X8 anion exchanger beads was used for offline extraction of glyphosate from 50ml of spiked river water sample. The retained glyphosate was eluted with 10mM HCl and then converted quantitatively to the corresponding amine (glycine) using hypochlorite.

The influence of membrane electrode assembly water content on the performance of a polymer electrolyte membrane fuel cell as investigated by 1H NMR microscopy.

The relation between the performance of a self-humidifying H(2)/O(2) polymer electrolyte membrane fuel cell and the amount and distribution of water as observed using (1)H NMR microscopy was investigated. The integrated (1)H NMR image signal intensity (proportional to water content) from the region of the polymer electrolyte membrane between the catalyst layers was found to correlate well with the power output of the fuel cell. Several examples are provided which demonstrate the sensitivity of the (1)H NMR image intensity to the operating conditions of the fuel cell.

Solid-state 129Xe and 131Xe NMR study of the perxenate anion XeO(6)4-.

Results of the first solid-state 131Xe NMR study of xenon-containing compounds are presented. The two NMR-active isotopes of xenon, 129Xe (I=1/2) and 131Xe (I=3/2), are exploited to characterize the xenon magnetic shielding and quadrupolar interactions for two sodium perxenate salts, Na4XeO6.xH2O (x=0, 2), at an applied magnetic field strength of 11.

Synthesis of daunorubicin analogues containing truncated aromatic cores and unnatural monosaccharide residues.

The anthracycline antibiotics daunorubicin and doxorubicin have been used widely as anticancer drugs, but their cardiotoxicity limits their clinical use. We describe here the preparation of a small panel of daunorubicin analogues in which the anthraquinone core is replaced with simpler aromatic moieties that lack a quinone functionality. The targets consist of a functionalized 1,2,3,4-tetrahydro-naphthalene or 1,2,3,4-tetrahydro-anthracene core bound to one of three monosaccharides: daunosamine, acosamine, or 4-amino-2,3,6-trideoxy-l-threo-hexopyranose.

Semipermanent capillary coatings in mixed organic-water solvents for CE.

This report describes the creation of semipermanent capillary coatings that are compatible with organic-water solvent systems in CE. The coatings are created by simply rinsing the fused-silica capillary with long double-chain cationic surfactants, such as dimethyl-ditetradecyl ammonium bromide (2C(14)DAB), dihexadecyldimethyl ammonium bromide (2C(16)DAB), and dimethyldioctadecyl ammonium bromide (2C(18)DAB). These surfactants generate semipermanent bilayer coatings on the capillary surface, which display a high degree of stability in buffers containing up to 60% v/v of organic solvents, such as methanol and ACN.

Ion chromatography on a latex-coated silica monolith column.

A silica monolith column (Merck Chromolith, 100 mm x 4.6 mm) has been coated with Dionex AS9-SC latex nanoparticles to convert the column into an anion-exchange stationary phase. For comparison purposes, a reversed-phase silica monolith was also converted into an anion-exchange column by coating with the cationic surfactant didodecyldimethylammonium bromide (DDAB).

Synthesis and biological evaluation of nucleoside dicarboxylates as potential mimics of nucleoside diphosphates.

A series of nucleotide analogues wherein the diphosphate moiety has been replaced by a dicarboxylate were synthesized and tested for inhibitory activity against nucleoside diphosphate (NDP) kinase as well as several pathogenic bacterial strains.

Synthesis of a pentasaccharide fragment of varianose, a cell wall polysaccharide from Penicillium varians.

The first synthesis of an oligosaccharide fragment of varianose, a polysaccharide produced by Penicillium varians, is reported. The target pentasaccharide features both alpha- and beta-galactofuranoside residues and the alpha-galactofuranoside residue is hindered, being substituted on adjacent oxygens (O1 and O2), both of which are cis to the two-carbon side chain at C4. Key features of the synthesis include a novel method for the selective protection of the C3 hydroxyl group of galactofuranosyl residues via an epoxide formation/opening sequence, the introduction of the alpha-d-galactofuranosyl residue using a 2,3-anhydrosugar donor, and the use of the 1-benzenesulfinylpiperidine/trifluoromethanesulfonic anhydride activation method for the addition of an alpha-D-glucopyranosyl residue to a hindered hydroxyl group in an advanced tetrasaccharide intermediate.

2,3-Anhydrosugars in glycoside bond synthesis. Application to alpha-D-galactofuranosides.

We report here the use of 2,3-anhydro-D-gulofuranosyl thioglycosides and glycosyl sulfoxides in the synthesis of alpha-D-galactofuranosidic bonds, which are present in a range of bacterial and fungal glycoconjugates. This two-step method involves a stereoselective glycosylation in which a 2,3-anhydro-alpha-D-gulofuranoside is obtained either as the sole or as the major product, followed by a regioselective opening of the epoxide ring using lithium benzylate in the presence of (-)-sparteine. In exploring the scope of the method, donors protected at O5 and O6 with an isopropylidene acetal, benzyl ethers, or benzoate esters were studied.

A combined experimental and quantum chemistry study of selenium chemical shift tensors.

A comprehensive investigation of selenium chemical shift tensors is presented. Experimentally determined chemical shift tensors were obtained from solid-state 77Se NMR spectra for several organic, organometallic, or inorganic selenium-containing compounds. The first reported indirect spin-spin coupling between selenium and chlorine is observed for Ph(2)SeCl(2) where 1J(77Se,35Cl)iso is 110 Hz.

Construction of fused bis(pyran) units from enones via a hydrosilylation-dihydroxylation-acetalization-reduction sequence.

HWE coupling of two simple bifunctional fragments provides enones that can be subjected to a four-step sequence to furnish trans-fused bis(pyrans) in good overall yield.

Insights into the distribution of water in a self-humidifying H2/O2 proton-exchange membrane fuel cell using 1H NMR microscopy.

Proton ((1)H) NMR microscopy is used to investigate in-situ the distribution of water throughout a self-humidifying proton-exchange membrane fuel cell, PEMFC, operating at ambient temperature and pressure on dry H(2)(g) and O(2)(g). The results provide the first experimental images of the in-plane distribution of water within the PEM of a membrane electrode assembly in an operating fuel cell. The effect of gas flow configuration on the distribution of water in the PEM and cathode flow field is investigated, revealing that the counter-flow configurations yield a more uniform distribution of water throughout the PEM.

Sensitivity enhancement of NMR spectra of half-integer spin quadrupolar nuclei in solids using hyperbolic secant pulses.

The experimental factors influencing the enhancements achievable for the central NMR transition, m(I)=1/2-->m(I)=-1/2, of spin-3/2 and spin-5/2 nuclei in the solid state using hyperbolic secant, HS, pulses for population transfer are investigated. In the case of powder samples spinning at the magic angle, it is found that the spinning frequency, the bandwidth and the frequency offset of the HS pulse play a crucial role in determining the maximum enhancements. Specifically, the bandwidth must be set to the spinning frequency for maximum signal enhancements.

Synthesis of 2-deoxy-2-fluoro analogs of polyprenyl beta-D-arabinofuranosyl phosphates.

Described is the synthesis of polyprenyl 2-deoxy-2-fluoro-beta-D-arabinofuranosyl phosphate derivatives, including an analog of decaprenyl beta-D-arabinofuranosyl phosphate, the donor species used by the arabinosyltransferases involved in mycobacterial cell-wall biosynthesis. The targets were synthesized via a route involving the synthesis of a protected beta-D-arabinofuranosyl phosphate derivative, its coupling with a polyprenyl trichloroacetimidate, and then deprotection of the resulting product. The use of arabinofuranosyl phosphates with the monosaccharide hydroxyl groups protected as either silyl ethers or benzoate esters was explored.

Preparative capillary zone electrophoresis using a dynamic coated wide-bore capillary.

Preparative capillary zone electrophoresis separations of cytochrome c from bovine and horse heart are performed efficiently in a surfactant-coated capillary. The surfactant, dimethylditetradecylammonium bromide (2C(14)DAB), effectively eliminated protein adsorption from the capillary surface, such that symmetrical peaks with efficiencies of 0.7 million plates/m were observed in 50-microm id capillaries when low concentrations of protein were injected.