Three-dimensional representation of metastable peaks at high mass resolution

Isobaric daughter ions formed from a common metastable ion have been analysed at high mass resolution. A three-dimensional representation is used to summarize the data for competitive CO and C₂H₄ losses and competitive CHO˙ and C₂H₅˙ losses from metastable molecular ions of cyclohexanone.     

Rearrangements in chemical ionization mass spectra

Rearrangements reported in the literature for positive ions formed by chemical ionization are briefly reviewed, with particular emphasis on illustrative examples of hydrogen and skeletal rearrangements.     

Non-hemolytic α-AApeptides as antimicrobial peptidomimetics

We report a new class of peptide mimetics, α-AApeptides, that display broad-spectrum activity against both Gram-negative and Gram-positive bacteria and fungi. With non-hemolytic activity, resistance to protease hydrolysis, and easy sequence programmability, α-AApeptides may emerge as a novel class of antibiotics.     

Esmodil: an acetylcholine mimetic resurfaces in a Southern Australian marine sponge Raspailia (Raspailia) sp

Bioassay directed fractionation of a Raspailia (Raspailia) sp. (Order Poecilosclerida; Family Raspailiidae) collected during scientific trawling operations off the Northern Rottnest Shelf yielded as nematocidal agents the known metabolites, phorboxazoles A (1) and B (2). Further examination revealed the new natural product but known synthetic compound, esmodil (3). The structure for 3 was confirmed by spectroscopic analysis and total synthesis.     

Fungal upgrading of wheat straw for straw-thermoplastics production

Combining biologic pretreatment with storage is an innovative approach for improving feedstock characteristics and cost, but the magnitude of responses of such systems to upsets is unknown. Unsterile wheat straw stems were upgraded for 12 wk with Pleurotus ostreatus at constant temperature to estimate the variation in final compositions with variations in initial moisture and inoculum. Degradation rates and conversions increased with both moisture and inoculum. A regression analysis indicated that system performance was quite stable with respect to inoculum and moisture content after 6 wk of treatment. Scale-up by 150× indicated that system stability and final straw composition are sensitive to inoculum source, history, and inoculation method. Comparative testing of straw-thermoplastic composites produced from upgraded stems is under way.     

Phase behaviour of the ternary system {poly(ε-caprolactone) + carbon dioxide + dichloromethane}

Recently, production of biocompatible and biodegradable polymer microparticles has been a matter of growing interest in pharmaceutical and food areas such as drug or active compounds delivery. To conduct production of microparticles, polymeric particle coating, impregnation of active compounds in polymeric films, the knowledge of phase behaviour involving the biodegradable polymer in supercritical carbon dioxide in the presence of a modifier may be needed to allow developing new industrial applications. In this sense, the aim of this work was to investigate the phase behaviour of the ternary system formed by the biodegradable polymer poly(ε-caprolactone) in (carbon dioxide + dichloromethane). Experimental phase transition (bubble and cloud point) values were obtained by applying the static-synthetic method using a variable-volume view cell over the temperature range of (303 to 343) K and pressures up to 21 MPa, in the CO₂ overall composition range of (25–46) wt%, while polymer concentrations studied were (1, 3, 5, and 7) wt%. For the system investigated, depending on the polymer concentration, vapour–liquid, liquid–liquid, and vapour–liquid–liquid phase transitions were verified.     

Sequencing of sulfonic acid derivatized peptides by electrospray mass spectrometry

We report the application of nanoelectrospray ionization tandem mass spectrometry (nES-MS/MS) and capillary LC/microelectrospray MS/MS (cLC/&mgr;ES-MS/MS) for sequencing sulfonic acid derivatized tryptic peptides. These derivatives were specifically prepared to facilitate low-energy charge-site-initiated fragmentation of C-terminal arginine-containing peptides, and to enhance the selective detection of a single series of y-type fragment ions. Both singly and doubly protonated peptides were analyzed by MS/MS and the results were compared with those from their derivatized counterparts. Model peptides and peptides from tryptic digests of gel-isolated proteins were analyzed. Derivatized singly protonated peptides fragment in the same way by nES-MS/MS as they do by post-source decay matrix-assisted laser desorption/ionization mass spectrometry (PSD-MALDI-MS). They produce fragment ion spectra dominated by y-ions, and the simplified spectra are readily interpreted de novo. Doubly protonated peptides fragment in much the same way as their non-derivatized doubly protonated counterparts. The fragmentation of doubly protonated derivatives is especially useful for sequencing peptides that possess a proline residue near the N-terminus of the molecule. The singly protonated forms of these proline-containing derivatives often show enhanced fragmentation on the N-terminal side of the proline and considerably reduced fragmentation on the C-terminal side. In addition, sulfonic acid derivatization increases the in-source fragmentation of arginine-containing peptides. This could be useful for sequence verification and sequence tagging for use in single stage mass spectrometry. Copyright 2000 John Wiley & Sons, Ltd.     

Assessment of silver and gold substrates for the detection of amphetamine sulfate by surface enhanced Raman scattering (SERS)

Methods of detection of amphetamine sulfate using surface enhanced Raman scattering (SERS) from colloidal suspensions and vapour deposited films of both silver and gold are compared. Different aggregating agents are required to produce effective SERS from silver and gold colloidal suspensions. Gold colloid and vapour deposited gold films give weaker scattering than the equivalent silver substrates when high concentrations of drug are analysed but they also give lower detection limits, suggesting a smaller surface enhancement but stronger surface adsorption. A 10(-5) mol dm(-3) solution (the final concentration after addition of colloid was 10(-6) mol dm(-3)) of amphetamine sulfate was detected from gold colloid with an RSD of 5.4%. 25 microl of the same solution could be detected on a roughened gold film. The intensities of the spectra varied across the film surface resulting in relatively high RSDs. The precision was improved by averaging the scattering from several points on the surface. An attempt to improve the detection limit and precision by concentrating a suspension of gold colloid and amphetamine sulfate in aluminium wells did not give effective quantitation. Thus, positive identification and semi-quantitative estimation of amphetamine sulfate can be made quickly and easily using SERS from suspended gold colloid with the appropriate aggregating agents.     

Benzene–kaolinite interaction properties

In this work, we present a theoretical study of interaction of benzene with kaolinite and an analysis of the vibrational spectra, electrostatic potential maps, and self consistent field (SCF) orbitals. B3LYP and MP2 benzene–kaolinite results indicate a preferential interaction of benzene on kaolinite octahedral surface. Population analysis indicates that the atoms modified their charges when the monoaromatic molecule and clay mineral are close to tetrahedral and octahedral surface of kaolinite, which suggests that the adsorbed molecule becomes slightly positive. Infrared vibrational data show the reduction in the band frequencies related to the kaolinite external hydroxyls, indicating a weak interaction of benzene with clay mineral. It also was verified, from the potential electrostatic maps, a change in electron density in both benzene and kaolinite. Electron localization function analysis was also carried out for this interaction. © 2011 Wiley Periodicals, Inc.