Comparison of algorithms and databases for matching unknown mass spectra

The most used algorithms for the identification of electron-ionization mass spectra are INCOS and probability based matching (PBM). For unknown spectra of high purity, ～75% of rank 1 answers are correct for both algorithms, matched against the National Institute of Standards and Technology 62,235 spectrum database. With matching criteria that retrieve 50% of the possible correct answers from the Wiley 228,998 spectrum database, 54% of the PBM and 42% of the INCOS answers are correct; for 85% purity unknowns, 48% and 27% are correct. For an unknown spectrum of two compounds, neither was reported in the first three INCOS answers; eight of the first ten PBM answers identify both components.     

Synthesis and Characterization of Calix[4]arene Functionalized Poly(ethylene glycol) Derivatives

Calix[4]arenes with both ligating and methoxy poly(ethylene glycol) groups appended have been synthesized using several approaches, involving the formation of sulfonyl ester groups on the wide rim, Schiff base derivatives on the narrow rim, and thioether groups on both the wide and narrow rims. These new derivatives have been characterized by a combination of infrared and ¹H NMR spectroscopy. Compounds 10 and 11 are insoluble in both water and aqueous poly(ethylene glycol), but the other new compounds are soluble.     

Keyhole limpet hemocyanin (KLH): a biomedical review

In this review we present a broad survey of fundamental scientific and medically applied studies on keyhole limpet hemocyanin (KLH). Commencing with the biochemistry of KLH, information on the biosynthesis and biological role of this copper-containing respiratory protein in the marine gastropod Megathura crenulata is provided. The established methods for the purification of the two isoforms of KLH (KLH1 and KLH2) are then covered, followed by detailed accounts of the molecular mass determination, functional unit (FU) structure, carbohydrate content, immunological analysis and recent aspects of the molecular genetics of KLH. The transmission electron microscope (TEM) has contributed significantly to the understanding of KLH structure, primarily from negatively stained images. We give a brief account of TEM studies on the native KLH oligomers, the experimental manipulation of the oligomeric states, together with immunolabelling data and studies on subunit reassociation. The field of cellular immunology has provided much relevant biomedical information on KLH and has led to the expansion of use of KLH in experimental immunology and clinically as an immunotherapeutic agent; this area is presented in some detail. The major clinical use of KLH is specifically for the treatment of bladder carcinoma, with efficacy probably due to a cross-reacting carbohydrate epitope. KLH also has considerable possibilities for the treatment of other carcinomas, in particular the epithelially derived adenocarciomas, when used as a carrier for carcinoma ganglioside and mucin-like epitopes. The widespread use of KLH as a hapten carrier and generalised vaccine component represent other major on-going aspects of KLH research, together with its use for the diagnosis of Schistosomiasis, drug assay and the treatment of drug addiction. Immune competence testing, assessment of stress and the understanding of inflammatory conditions are other areas where KLH is also making a useful contribution to medical research.     

Bioconversion of mixed solids waste to ethanol

A mixed solids waste (MSW) feedstock, comprising construction lumber waste (35% oven-dry basis), alm ond treeprunings (20%), wheat straw (20%), office waste paper (12.5%), and newsprint (12.5%), was converted to ethanol via dilute-acid pretreatment followed by enzymatic hydrolysis and yeast fermentation. The MSW was pretreated with dilute sulfuricacid (0.4% w/w) at 210°C for 3 min in a 4-L stea mexplosion reactor, then washed with water to recover the solubilized hemicellulose. The digestibility of water-washed, pretreated MSW was 90% in batch enzymatic hydrolysis at 66 FPU/g cellulose. Using an enzyme-recycle bioreactor system, greater than 90% cellulose hydrolysis was achieved at a net enzyme loading of about 10 FPU/g cellulose. Enzyme recycling using mebrane filtration and a fed-batch fermentation technique is a promising option for significantly reducing the cost of enzyme in cellulose hydrolysis. The hexosesugars were readily fermentable using a Saccharomyces cerevisiae yeast strain that was adapted to the hydrolysate. Solid residue after enzyme digestion was subjected to various furnace experiments designed to assess the fouling and slagging characteristics. Results of these analyses suggest the residue to be of a low to moderate slagging and fouling type if burned by itself.     

Fluorine-19 Solid-State NMR Magic-Angle-Turning Experiments Using Multiple-Pulse Homonuclear Decoupling

For compounds giving “crowded” 1-dimensional magic-angle-spinning spectra, information about the local atomic environment in the form of the chemical shift anisotropy (CSA) is sacrificed for high resolution of the less informative isotropic chemical shift. Magic-angle-turning (MAT) NMR pulse sequences preserve the CSA information by correlating it to the isotropic chemical shift in a 2-dimensional experiment. For low natural abundance nuclei such as ¹³C and ¹⁵N and under ¹H heteronuclear dipolar decoupling conditions, the dominant NMR interaction is the chemical shift. For abundant nuclei such as ¹H, ¹⁹F, and ³¹P, the homonuclear dipolar interaction becomes a significant contribution to the observed linewidth in both F₁ and F₂ dimensions. We incorporate MREV8 homonuclear multiple-pulse decoupling sequences into the MAT experiment to give a multiple-pulse MAT (MP-MAT) experiment in which the homonuclear dipolar interaction is suppressed while maintaining the chemical shift information. Extensive use of computer simulation using GAMMA has guided the pulse sequence development. In particular, we show how the MREV8 pulses can be incorporated into a quadrature-detected sequence such as MAT. The MP-MAT technique is demonstrated for a model two-site system containing a mixture of silver trifluoroacetate and calcium difluoride. The resolution in the isotropic evolution dimension is improved by faster sample spinning, shorter MREV8 cycle times in the evolution dimension, and modifications of the MAT component of the pulse sequence.