Reactions of d(0) tungsten alkylidyne complexes with O2 or H2O. Formation of an oxo siloxy complex through unusual silyl migrations.

(Me3SiCH2)3(Me3SiC≡)W←O=PMe3 (1), an adduct between (Me3SiCH2)3W≡CSiMe3 (2) and O=PMe3, reacts with O2 to give O=W(OSiMe3)(CH2SiMe3)3 (3) and CO2. Reaction of 2 with H2O yields 3 and the trimer [(µ-O)W(CH2SiMe3)2(=O)(THF)]3 (4). In the reaction of D2O with 2, 3-d(n) and methane isotopologues CH2D2, CHD3 and CD4 have been observed.

Trace-fiber color discrimination by electrospray ionization mass spectrometry: a tool for the analysis of dyes extracted from submillimeter nylon fibers.

The application of electrospray ionization mass spectrometry (ESI-MS) to trace-fiber color analysis is explored using acidic dyes commonly employed to color nylon-based fibers, as well as extracts from dyed nylon fibers. Qualitative information about constituent dyes and quantitative information about the relative amounts of those dyes present on a single fiber become readily available using this technique. Sample requirements for establishing the color identity of different samples (i.e., comparative trace-fiber analysis) are shown to be submillimeter. Absolute verification of dye mixture identity (beyond the comparison of molecular weights derived from ESI-MS) can be obtained by expanding the technique to include tandem mass spectrometry (ESI-MS/MS). For dyes of unknown origin, the ESI-MS/MS analyses may offer insights into the chemical structure of the compound-information not available from chromatographic techniques alone. This research demonstrates that ESI-MS is viable as a sensitive technique for distinguishing dye constituents extracted from a minute amount of trace-fiber evidence. A protocol is suggested to establish/refute the proposition that two fibers--one of which is available in minute quantity only--are of the same origin.

Characterizing the electrospray-ionization mass spectral fragmentation pattern of enzymatically derived hyaluronic acid oligomers.

Oligosaccharides derived from hyaluronic acid by action of bovine testicular hyaluronidase (BTH) (hyaluronate 4-glycanohydrolase, E.C. 3.2.1.35) were characterized by mass spectrometry (MS) with electrospray-ionization mass spectrometry (ESIMS) and compared with results obtained by matrix-assisted laser desorption/ionization. Both oligomers with an odd number and even number of sugar units with molecular masses up to 8 kDa were observed in the ESI spectra. However, the generation of odd-numbered oligomers is not consistent with the regiospecificity of the enzyme and with the MALDI results, which indicated even-numbered oligomers exclusively. In addition, a third method of characterization, high-performance anion-exchange chromatography (HPAEC), showed only even-numbered oligomers. Relative intensities of the odd-numbered oligomers demonstrated in ESIMS a cone-voltage dependence suggesting the odd-numbered oligomers resulted from collisional activation. In order to achieve results by ESI that mirror results from other techniques, the cone voltage must be kept low and precisely controlled. This study displays the usefulness and possible vulnerabilities of ESIMS when utilized for carbohydrate analysis without corroborating data from other methods of analysis.

Qualitative assessment of monomer ratios in putative ionic terpolymer samples by electrospray ionization mass spectrometry with collision-induced dissociation.

Collision-induced dissociation in the source of an electrospray (ES) mass spectrometer was employed to characterize putative samples of the ionic terpolymer poly(styrene sulfonate-co-acrylic acid-co-2-acrylamido-2-methyl-1-propanesulfonic acid). Qualitative and semi-quantitative information about the monomer content was quickly obtainable from ES spectra, and indicated that some samples contained little or none of one or two expected comonomers. For two representative samples, confirmatory nuclear magnetic resonance (NMR) data were acquired. The NMR experiments required sample clean-up (to remove additives) and long acquisition times (up to 720 min) for 13C NMR. Cleanup also improved the ES results, providing better agreement with the NMR data. However, qualitative and semi-quantitative information was obtainable by ES (but not by NMR) without the cleanup step. Full quantitation of monomer ratios would require suitable standards, but even without such standards the ES measurements provide a rapid (<1 min) means for differentiating these samples (e.g., for process or quality control).