Carbocyclen aus Monosacchariden. III. Zur Diastereoselektivität der Bildung von Cyclopentanderivaten. Umsetzungen in der Galactosereihe

Carbocycles from monosaccharides. III. Concerning the diastereoselective formation of cyclopentane derivatives. Transformations in the galactose series. The diastereoselectivity of the intramolecular nitrone-olefine cycloaddition of 1 , 3 and 4 (Scheme 1), yielding only 2 , 5 and 6 but none of the isomers 8 , 9 and 10 is explained by assuming a kinetic control and postulating that the relative activation energies of the two relevant transition states in the cyclization of e.g. 1 can be estimated from the conformers A and B , the latter being destabilized by a synperiplanar arrangement of the nitrone function and the 2-alkoxy-group (Scheme 2). It is further postulated, that this destabilization is responsible for the formation of (2,3)-trans configurated products. Since 2 , 5 and 6 are presumably thermodynamically more stable than 8 , 9 and 10 , a case was investigated, where the cycloaddition can either give thermodynamically less stable (2,3)-trans-product such as 12 or a thermodynamically more stable (2,3)-cis-product such as 13. 12 and 13 could both be formed from the aldehyde 25 via the nitrone 11 (Schemes 3 and 5). Treatment of the galactoside 16 first with Zn in aqueous butanol (forming among other products 25 and its 2-debenzyl-oxy-derivative) and then with N-Methyldroxylamine yielded the isoxazolidines 12 (72%), 13 (2%) and 27 (7%) (Schemes 4 and 6). Similarily, the anomeric silylated galactosides 17 and 23 gave 29 (78% from 17 , 77% from 23 ) and 27 (5% and 3%). Upon desilylation, 29 gave 32 , which was converted into 12 . The structure of the isoxazolidines was unambiguously deduced from their NMR. spectra and those of their derivatives 33 and 34 . Compound 32 was further transformed into its deoxyderivative 36 . The high diastereoselectivity of the cycloaddition restricts the number of diastereomeric, pentasubstituted cyclopentanes available by this method. However, cyclization of the 2-Hydroxy-aldehyde 37 (Scheme 8) gave the kinetically less favoured isomer 40 in a higher proportion, showing the differential influence of hydrogen-bonds on the relevant activation energies. Thermolysis of 32 gave 40 (79%) and 41 (11%). The structure of 41 was deduced from its NMR. spectra and those of its derivatives 42 and 43 . Thermolysis of 29 gave, after desilylation, 41 (42%), 40 (22%) and 32 (13%) and thermolysis of 6 lead to a 25 : 75 equilibrium with 44 (combined yield 90%). These transformations illustrate means leading to additional isomers and are in agreement with the proposed explanation of the diastereoselectivity in question.     

Simultaneous determination of SO(2), NO and NO(2) in air by differential pulse polarography

The method of Garber and Wilson for SO(2) determination has been tested on real samples of air. The results demonstrate the possibility of simultaneous determination of SO(2), NO and NO(2) in the sample. Detection limits as low as 7 mul/m(3) for SO(2) and about 50 mul/m(3) for nitric oxides can be reached.     

Functionalization of Si(111) surfaces with alkyl chains terminated by electrochemically polymerizable thienyl units

A Si(111) surface has been derivatized with a thiophene-terminated alkyl monolayer which was subsequently photoanodically oxidized in the presence of thiophene to yield a strongly adherent and smooth conducting film.     

Telomerization of vinylidene fluoride with alkyl (or aryl) trifluoromethanethiosulfonates

The photochemical‐induced telomerization of vinylidene fluoride (VDF) with cyclohexyl (or phenyl) trifluoromethanethiosulfonate (CF₃SO₂SR), leading to CF₃(VDF)_nSR telomers, where R stands for cyclohexyl or phenyl, is presented. These sulfurated transfer agents were synthesized by the reaction between sodium triflinate (CF₃SO₂Na) and disulfide in the presence of bromine. ¹⁹F NMR spectroscopy enabled an assessment of the average degrees of telomerization (DP_n) of these telomers with a neat CF₃ end group as the label. These DP_n values increased for higher [VDF]₀/[CF₃SO₂SR]₀ initial molar ratios. Interestingly, the normal/reversed ratio of VDF units in these telomers was low. Finally, the cotelomerization of VDF and hexafluoropropylene with these transfer agents was successfully achieved, leading to original ω‐CF₃ fluoroelastomers, the thermal properties of which were investigated. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 4538–4549, 2002     

Protein unfolding and refolding under force: methodologies for nanomechanics.

An increasing number of inter- and intramolecular interactions can nowadays be probed using single-molecule manipulation techniques. Protein unfolding and refolding is the most representative--though complex--of these interactions. Herein, we review the main modes of performing a force unfolding experiment: the velocity clamp and the new force clamp mode. We also compare some of the physical aspects behind the two most frequently used single-molecule manipulation instrumentations: optical tweezers and atomic force microscopes.     

High-performance liquid chromatographic evaluation of Med 15 and its metabolites Med 5 and tolmetin in rat plasma.

A simple and reliable high-performance liquid chromatographic method is described for the quantitative analysis of the new non-steroidal anti-inflammatory agent Med 15 and its metabolites Med 5 and tolmetin in rat plasma. After selective extraction the three analytes and an internal standard (p-phenyl-phenol) were separated on a reversed-phase Ultrasphere 5 micron column using potassium dihydrogenphosphate (0.05 M)-acetonitrile (52:48) (pH 4.7) as the mobile phase. The analytes were detected at 313 nm; the sensitivity of the method proved to be 0.05 microgram/ml for all three compounds. The method has been applied to investigate Med 15 pharmacokinetics in rats.     

Adhesion Behaviour of Organically-Modified Silicate Coatings on Stainless Steel

The mechanical properties of organically modified silicate coatings on stainless steel substrates were investigated, using nano-indentation and simultaneous in situ microtensile testing/optical microscopy. The load-displacement response and fracture behaviour is examined to ascertain the effects of different organic groups on the film properties and adhesion characteristics. The relationship between the morphology and mechanical properties of the films is discussed, and it is demonstrated that the mechanical response of the coatings is significantly influenced by the nature of the organic group attached to the ormocer precursor.     

A theoretical model for the Gla-TSR-EGF-1 region of the anticoagulant cofactor protein S: From biostructural pathology to specie

Protein S (PS), which functions as a species-specific anticoagulant cofactor to activated protein C (APC), is a mosaic protein that interacts with the phospholipid membrane via its -carboxyglutamate-rich (Gla) module. This module is followed by the thrombin-sensitive region (TSR), sensitive to thrombin cleavage, four epidermal growth factor (EGF)-like modules and a last region referred to as the sex hormone binding globulin (SHBG) domain. Of these, the TSR and the first EGF-like regions have been shown to be important for the species-specific interaction with APC. Difficulties in crystallising PS have so far hindered its study at the atomic level. Here, we report theoretical models for the Gla and EGF-1 modules of human PS constructed using prothrombin and factor X experimental structures. The TSR was built interactively. Analysis of the model linked with the large body of biochemical literature on PS and related proteins leads to suggestions that (i) the TSR stabilises the calcium-loaded Gla module through hydrophobic and ionic interactions and its conformation depends on the presence of the Gla module; (ii) the TSR does not form a calcium binding site but is protected from thrombin cleavage in the calcium-loaded form owing to short secondary structure elements and close contact with the Gla module; (iii) the PS missense mutations in this region are consistent with the structural data, except in one case which needs further investigation; and (iv) the two PS faces involving regions of residues Arg⁴⁹–Gln⁵²–Lys⁹⁷ (TSR-EGF-1) and Thr¹⁰³–Pro¹⁰⁶ (EGF-1) may be involved in species-specific interactions with APC as they are richer in nonconservative substitution when comparing human and bovine protein S. This preliminary model helps to plan future experiments and the resulting data will be used to further validate and optimise the present structure.     

Synthesis and properties of fluorinated telechelic macromolecular diols prepared by radical grafting of fluorinated thiols onto hydroxyl-terminated polybutadienes

The radical grafting of C_nF_{2n +1} CH₂CH₂SH (n = 6,8) onto the double bonds of hydroxyl-terminated liquid polybutadienes (HTPBD) was studied. Various methods for investigating the amount of grafting (titration of residual thiol and fluorine analysis) were used and compared. The nature and the amount of the initiator, the quantity of thiol, the temperature and the time of the reaction. the solvent, and the microstructure of HTPBD were optimized. The kinetic aspect showed that the thiol disappeared according to a first-norder law. A method using up to 100% of grafting fluorinated mercaptan was described and standards were set up with fluorine contents of 5–59% to evaluate the physicochemical properties of these thioether group-containing polymers: solubility, refractive index, intrinsic and dynamic viscosities, and thermal characteristics (glass transition and decomposition temperatures). Finally, the surface properties of these standards showed improvements of surface energy as low as 9 mN m^?1 for a totally saturated fluorinated HTPBD. © 1993 John Wiley & Sons, Inc.     

Indecomposable representations of the algebra su(2,1)

Representations of the Lie algebra sl(3) with highest weight are analyzed. Invariant subspaces of indecomposable representations are determined. We study the decomposition of these representations with respect to the subalgebras su(2) and su(1,1) (in their obvious imbedding in su(2,1)).For special cases this decomposition gives indecomposable non multiplicity free representations (indecomposable pairs) with highest weight. These were discussed in [1] and appear also in the decomposition so(3,2) su(1,1) of the Rac representation, [7].