Sofie P. Pasilis

Atmospheric pressure surface sampling/ionization techniques for direct coupling of planar separations with mass spectrometry.

Planar separations, which include thin layer chromatography and gel electrophoresis, are in widespread use as important and powerful tools for conducting separations of complex mixtures. To increase the utility of planar separations, new methods are needed that allow in situ characterization of the individual components of the separated mixtures. A large number of atmospheric pressure surface sampling and ionization techniques for use with mass spectrometry have emerged in the past several years, and several have been investigated as a means for mass spectrometric read-out of planar separations. In this article, we review the atmospheric pressure surface sampling and ionization techniques that have been used for the read-out of planar separation media. For each technique, we briefly explain the operational basics and discuss the analyte type for which it is appropriate and some specific applications from the literature.

Isolation and structure elucidation of highly antioxidative 3,8″-linked biflavanones and flavanone-C-glycosides from Garcinia buchananii bark.

The aim of this study was to identify antioxidants from Garcinia buchananii bark extract using hydrogen peroxide scavenging and oxygen radical absorbance capacity (ORAC) assays. LC-MS/MS analysis, 1D- and 2D-NMR, and circular dichroism (CD) spectroscopy led to the unequivocal identification of the major antioxidative molecules as a series of three 3,8″-linked biflavanones and two flavanone-C-glycosides. Besides the previously reported (2R,3R,2″R,3″R)-naringenin-C-3/C-8″ dihydroquercetin linked biflavanone (GB-2; 4) and (2R,3S,2″R,3″R)-manniflavanone (3), whose stereochemistry has been revised, the antioxidants identified for the first time in Garcinia buchananii were (2R,3R)-taxifolin-6-C-β-D-glucopyranoside (1), (2R,3R)-aromadendrin-6-C-β-D-glucopyranoside (2), and the new compound (2R,3S,2″S)-buchananiflavanone (5). The H₂O₂ scavenging and the ORAC assays demonstrated that these natural products have an extraordinarily high antioxidative power, especially (2R,3S,2″R,3″R)-manniflavanone (3) and GB-2 (4), with EC₅₀ values of 2.8 and 2.2 μM, respectively, and 13.73 and 12.10 μmol TE/ μmol. These findings demonstrate that G. buchananii bark extract is a rich natural source of antioxidants.

5-HT3 and 5-HT4 receptors contribute to the anti-motility effects of Garcinia buchananii bark extract in the guinea-pig distal colon

Background  Garcinia buchananii bark extract is an anti‐motility diarrhea remedy. We investigated whether G. buchananii bark extract has components that reduce gastrointestinal peristaltic activity via 5‐HT3 and 5‐HT4 receptors.

Garcinia buchananii bark extract is an effective anti-diarrheal remedy for lactose-induced diarrhea.

ETHNOPHARMACOLOGICAL RELEVANCE The extract from the stem bark of Garcinia buchananii trees is used as an anti-diarrhea remedy in sub-Saharan Africa. We tested the hypothesis that G. buchananii bark extract and its anti-motility fractions are effective treatments against lactose-induced diarrhea. MATERIALS AND METHODS A high-lactose (35%) diet was used to induce diarrhea in Wistar rats, which were then treated with either G. buchananii bark extract (0.1, 0.5, 1.0 and 5.0 g bark powder), and its anti-motility fractions isolated using preparative thin layer chromatography; termed PTLC1 (15 mg) and PTLC5 (3.8 mg) or loperamide (8.4 mg). Drug preparations were dissolved in 1L except PTCL1 and PTLC5 that were dissolved in 100mL tap water. Numerous parameters were measured in each condition including consistency, fluid and mucus content of feces, body weight, water and food consumption, urine production and bloating. RESULTS Diarrheic rats produced watery or loose, mucuoid, sticky, feces. Fluids constituted 86% of stool mass compared with only 42% for control rats fed standard chow. Compared with controls, diarrheic rats produced more urine, lost weight and had bloated ceca and colons. All doses of the extract, its anti-motility fractions and loperamide individually stopped diarrhea within 6-24 h of administration, whilst significantly reducing mucus and fecal fluid content, urine production and intestinal bloating. Rats treated with 0.1g extract, PTLC1 and PTLC5 gained weight, whilst PTLC5 also increased water intake. CONCLUSIONS Garcinia buchananii extract and its anti-motility fractions are effective remedies against lactose-induced diarrhea. The extract contains compounds that reverse weight loss, promote food and water intake, supporting the notion that characterization of the compounds could lead to new therapies against diarrheal diseases.

Probing uranyl(VI) speciation in the presence of amidoxime ligands using electrospray ionization mass spectrometry

RATIONALE Extraction processes using poly(acrylamidoxime) resins are being developed to extract uranium from seawater. The main complexing agents in these resins are thought to be 2,6-dihydroxyiminopiperidine (DHIP) and N(1),N(5)-dihydroxypentanediimidamide (DHPD), which form strong complexes with uranyl(VI) at the pH of seawater. It is important to understand uranyl(VI) speciation in the presence of these and similar amidoxime ligands to understand factors affecting uranyl(VI) adsorption to the poly(acrylamidoxime) resins. METHODS Experiments were carried out in positive ion mode on a quadrupole ion trap mass spectrometer equipped with an electrospray ionization source. The ligands investigated were DHIP, DHPD, and N(1),N(2)-dihydroxyethanediimidamide (DHED). DHED and DHPD differ only in the number of carbons separating the oxime groups. The effects on the mass spectra of changes in uranyl(VI):ligand ratio, pH, and ligand type were examined. RESULTS DHIP binds uranyl(VI) more effectively than DHPD or DHED in the pH range investigated, forming ions derived from solution-phase species with uranyl(VI):DHIP stoichiometries of 1:1, 1:2, and 2:3. The 2:3 uranyl(VI):DHIP complex appears to be a previously undescribed solution species. Ions related to uranyl(VI):DHPD complexes were detected in very low abundance. DHED is a more effective complexing agent for uranyl(VI) than DHPD, forming ions having uranyl(VI):DHED stoichiometries of 1:1, 1:2, 1:3, and 2:3. CONCLUSIONS This study presents a first look at the solution chemistry of uranyl(VI)-amidoxime complexes using electrospray ionization mass spectrometry. The appearance of previously undescribed solution species suggests that the uranyl-amidoxime system is a rich and relatively complex one, requiring a more in-depth investigation.

Modern Atmospheric Pressure Surface Sampling/Ionization Techniques in Mass Spectrometry

Over the last few years, there has been a rapid increase in atmospheric pressure surface sampling/ionization techniques for mass spectrometry, dramatically expanding the range of sample types that can be analyzed. The growth in this field of mass spectrometry has also resulted in a plethora of new acronyms. In this article, the various techniques are first sorted into four major categories based on the method used for analyte desorption and then subcategorized by the ionization method. The underlying principles of operation are explained and some representative applications are described.