Kinetics of the reaction of OH radicals with a series of esters under simulated conditions at 295 K

The rate constants of the isopropyl acetate, n-propyl acetate, isopropenyl acetate, n-propenyl acetate, n-butyl acetate, and ethyl butyrate reactions with OH radicals were determined in purified air under atmospheric conditions, at 750 torr and (295 ± 2) K. A relative rate experimental method was used; n-heptane, n-octane, and n-nonane were the reference compounds, with, respectively, rate constants for the reaction with OH of 7.12 × 10⁻¹², 8.42 × 10⁻¹², and 9.70 × 10⁻¹² molecule⁻¹ cm³s⁻¹. The following rate constants were obtained in units of 10⁻¹² molecule⁻¹ cm³s⁻¹; isopropyl acetate, (3.12 ± 0.29); n-propyl acetate, (1.97 ± 0.24); isopropenyl acetate, (62.53 ± 1.24); n-propenyl acetate, (24.57 ± 0.24); n-butyl acetate, (3.29 ± 0.35); and ethyl butyrate, (4.37 ± 0.42). Tertiary butyl acetate has a low reactivity with OH radicals (<1 × 10⁻¹² molecule⁻¹ cm³s⁻¹). © 1996 John Wiley & Sons, Inc.     

Major flavonoid components of heartsease (<Emphasis Type="Italic">Viola tricolor</Emphasis> L.) and their antioxidant activities

Sephadex LH-20 column chromatography was used to separate flavonoid components in a heartsease methanol extract. One of the main components was identified by NMR as violanthin (6-C-glucosyl-8-C-rhamnosylapigenin). As a first approximation, the other main flavonoid component was considered to be rutin (3-O-rhamnoglucosylquercetin), based on comprehensive comparison of retention times and UV spectra of reference molecules, as well as molecular mass and fragmentation patterns obtained by mass spectrometry. The minor flavonoids were separated by polyamide column and analyzed by LC-MS. The antioxidant capacity of different flavonoid fractions was determined using both Trolox equivalent antioxidant capacity (TEAC) and 2,2-diphenyl-1-picrylhydrazyl (DPPH) in vitro antioxidant assays. The highest electron-donor capacity was found for the major flavonoid component (rutin), whereas one minor component-rich flavonoid fraction exhibited the highest hydrogen-donor activity.     

Highly Efficient Trityl-Nitroxide Biradicals for Biomolecular High-Field Dynamic Nuclear Polarization

Dynamic nuclear polarization (DNP) is a powerful method to enhance the sensitivity of solid-state magnetic nuclear resonance (ssNMR) spectroscopy. However, its biomolecular applications at high magnetic fields (preferably>14 T) have so far been limited by the intrinsically low efficiency of polarizing agents and sample preparation aspects. Herein, we report a new class of trityl-nitroxide biradicals, dubbed SNAPols that combine high DNP efficiency with greatly enhanced hydrophilicity. SNAPol-1, the best compound in the series, shows DNP enhancement factors at 18.8 T of more than 100 in small molecules and globular proteins and also exhibits strong DNP enhancements in membrane proteins and cellular preparations. By integrating optimal sensitivity and high resolution, we expect widespread applications of this new polarizing agent in high-field DNP/ssNMR spectroscopy, especially for complex biomolecules.     

Noncovalent cross-links in context with other structural and functional elements of proteins

Proteins are heteropolymers with evolutionary selected native sequences of residues. These native sequences code for unique and stable 3D structures indispensable for biochemical activity and for proteolysis resistance, the latter which guarantees an appropriate lifetime for the protein in the protease rich cellular environment. Cross-links between residues close in space but far in the primary structure are required to maintain the folded structure of proteins. Some of these cross-links are covalent, most frequently disulfide bonds, but the majority of the cross-links are sets of cooperative noncovalent long-range interactions. In this paper we focus on special clusters of noncovalent long-range interactions: the Stabilization Centers (SCs). The relation between the SCs and secondary structural elements as well as the relation between SCs and functionally important regions of proteins are presented to show a detailed picture of these clusters, which are believed to be primarily responsible for major aspects of protein stability.     

Steam distillation-solid-phase microextraction for the detection of Ephedra sinica in herbal preparations

A new method involving concurrent solid-phase microextraction combined with continuous hydrodistillation of essential oil was developed. This new methodology allowed for the detection by GC-MS of very small amounts of a diagnostic peak for the authentication of Ephedra sinica, in a short period of time and using only small sample sizes. This diagnostic peak was identified as 4-vinylanisole, and elucidated from the chromatographic profile allowed for the identification of a sample as E. sinica among other species investigated in this study. To the best of our knowledge this is the first report on using continuous solid-phase microextraction coupled to hydrodistillation for the investigation of essential oil components, and the first report of 4-vinylanisole as a marker compound for E. sinica. A total of 46 collections representing 21 species of Ephedra were studied.     

Synthesis and characterization of hyperbranched mesoporous silica SBA-15

Branched mesoporous silica SBA-15 materials have been prepared in a simple process using non-ionic surfactant in acidic conditions in the presence of metal ions.     

Fully transitive -groups with finite first Ulm subgroup

An abelian -group is called (fully) transitive if for all with ( ) there exists an automorphism (endomorphism) of which maps onto . It is a long-standing problem of A. L. S. Corner whether there exist non-transitive but fully transitive -groups with finite first Ulm subgroup. In this paper we restrict ourselves to -groups of type , this is to say -groups satisfying . We show that the answer to Corner's question is no if is finite and is of type .

     

TissueDistributionDBs: a repository of organism-specific tissue-distribution profiles

Tissue-distribution profiles are crucial for understanding the characteristics of cells and tissues in terms of their differential expression of genes. Most of the currently available resources for tissue-distribution profiles are either specialized for a few particular organisms, tissue types and disease stages or do not consider the “tissue ontology” levels for the calculation of the tissue-distribution profiles. Therefore, we have developed “TissueDistributionDBs”, a repository of tissue-distribution profiles based on the expressed sequence tags (ESTs) data extracted from the UniGene database by employing “Tissue Ontology” available at BRENDA. To overcome the occurrence of the natural language variations in the EST’s source tissue-type terms, we have generated a “tissue synonym library” and standardized these tissue-type terms by cross-referencing to the controlled vocabulary for tissue-type terms available at BRENDA “Tissue Ontology”. Furthermore, we have provided a quantitative expression for genes among the tissue types at various anatomical levels by constructing “tissue slims”. Concurrently, the expression among tissue types is used for tissue-distribution calculations. The resulting output profiles can be queried by the Sequence Retrieval System (SRS) and are currently available for 20 different model organisms. We benchmarked our database system against the Swissprot database using a set of 40 different tissue types. This database system is useful for the understanding of the tissue-specific expression patterns of genes, which have implications for the identification of possible new therapeutic drug targets, in gene discovery, and in the design and analysis of micro-arrays. TissueDistributionDBs can be accessed via the World Wide Web (www) at http://genius.embnet.dkfz-heidelberg.de/menu/tissue_db/.