Zur Empfindlichkeit von Festkörperspurdetektoren

Es werden verschiedene Festkörperspurdetektor-Materialien hinsichtlich ihrer Empfindlichkeit gegenüber Bestrahlung mit α-Teilchen und zum Teil auch gegenüber Protonen und Deuteronen verglichen. Die speziell für den Einsutz als Festkörperspurdetektor hergestellten Zellulosenitrat-Folien wurden als empfindlichste Detektoren ermittelt.     

The collagen type I segment long spacing (SLS) and fibrillar forms: Formation by ATP and sulphonated diazo dyes

The collagen type I segment long spacing (SLS) crystallite is a well-ordered rod-like molecular aggregate, ∼300 nm in length, which is produced in vitro under mildly acidic conditions (pH 2.5–3.5) in the presence of 1 mM ATP. The formation of the SLS crystallite amplifies the inherent linear structural features of individual collagen heterotrimers, due to the punctate linear distribution and summation of the bulkier amino acid side chains along the length of individual collagen heterotrimers. This can be correlated structurally with the 67 nm D-banded collagen fibril that is found in vivo, and formed in vitro. Although first described many years ago, the range of conditions required for ATP-induced SLS crystallite formation from acid-soluble collagen have not been explored extensively. Consequently, we have addressed biochemical parameters such as the ATP concentration, pH, speed of formation and stability so as to provide a more complete structural understanding of the SLS crystallite. Treatment of collagen type I with 1 mM ATP at neutral and higher pH (6.0–9.0) also induced the formation of D-banded fibrils. Contrary to previous studies, we have shown that the polysulphonated diazo dyes Direct red (Sirius red) and Evans blue, but not Congo red and Methyl blue, can also induce the formation of SLS-like aggregates of collagen, but under markedly different ionic conditions to those employed in the presence of ATP. Specifically, pre-formed D-banded collagen fibrils, prepared in a higher than the usual physiological NaCl concentration (e.g. 500 mM NaCl, 20 mM Tris-HCl pH7.4 or x3 PBS), readily form SLS aggregates when treated with 0.1 mM Direct red and Evans blue, but this did not occur at lower NaCl concentrations. These new data are discussed in relation to the anion (Cl⁻) and polyanion (phosphate and sulphonate) binding by the collagen heterotrimer and their likely role in collagen fibrillogenesis and SLS formation.     

Variation of the temperature‐dependent substituent effects with solvent in alkaline hydrolysis of substituted phenyl and alkyl benzoates and phenyl tosylates

The second‐order rate constants k for the alkaline hydrolysis of eight substituted alkyl benzoates have been measured spectrophotometrically in aqueous 5.3 M NaClO₄ and 0.5 M n‐Bu₄NBr at various temperatures. Variation of the substituent effect with temperature in alkaline hydrolysis of ortho‐, meta‐, and para‐substituted phenyl benzoates, phenyl tosylates, and alkyl benzoates in various solvents (water, aqueous 0.5 M Bu₄NBr, 80% (v/v) DMSO, 2.25 M Bu₄NBr, and 5.3 M NaClO₄) was studied. The susceptibility to temperature variation of the meta and para polar substituent effect, the ortho inductive effect, and the alkyl polar effect for various media showed good correlation with the solvent electrophilicity, E_S, which characterizes the hydrogen‐bond donating power of the solvent. The variation of the temperature‐dependent ortho inductive effect with solvent hydrogen‐bond donor capacity (electrophilicity) was found to be nearly twice smaller than that for meta and para polar effect. The temperature‐dependent alkyl polar substituent effect was found to vary with E_S nearly by the same extent as the polar effect of meta and para substituents. The dependences of the ρ values (altogether 109 values of ρ) on the (1/T) term for various media were found to cross nearly at the same isosolvent temperature (1/β_isosolv ≈ 2 × 10^?3) for meta‐, para‐, ortho‐, and alkyl‐substituted esters. At T = β_isosolv the difference (ρ)_S ? (ρ)_Water becomes zero for all polar substituent effects in all media considered and the additional inductive effect from the ortho position (compared with para derivatives) disappears for all solvents studied. Copyright © 2007 John Wiley & Sons, Ltd.     

Iron(III) Chloride–Promoted Direct Conversion of Aryl/Alkyl Cyanides to Esters

Aryl/alkyl cyanides were quickly converted into the corresponding esters in the presence of iron(III) chloride in refluxing alcohols with very good yields.     

Asymmetric α‐Hydroxylation of Tetralone‐Derived β‐Ketoesters by Using a Guanidine–Urea Bifunctional Organocatalyst in the Presence of Cumene Hydroperoxide

Highly enantioselective catalytic oxidation of 1‐tetralone‐derived β‐keto esters was achieved by using a guanidine–urea bifunctional organocatalyst in the presence of cumene hydroperoxide (CHP), a safe, commercially available oxidant. The α‐hydroxylation products were obtained in 99 % yield with up to 95 % enantiomeric excess (ee). The present oxidation was successfully applied to synthesize a key intermediate of the anti‐cancer agent daunorubicin ( 2 ).     

Dehydrogenative Meyer–Schuster‐Like Rearrangement: A Gold‐Catalyzed Reaction Generating an Alkyne

Easily accessible propargylic esters are converted to the inverted alkynyl ketones in an oxidative gold‐catalyzed reaction. Gagosz’s catalyst in combination with PhI(OAc)₂ is the best system for this conversion and 18 examples with yields up to 80 % are reported. The results indicate that the triple bond in the product is formed by elimination from a vinylgold intermediate. In a formal sense the new conversion overall is a dehydrogenative Meyer–Schuster rearrangement.     

Isolation,Characterization and In Silico Studies of Secondary Metabolites from the Whole Plant of Polygala inexpectata Peşmen & Erik

Polygala species are frequently used worldwide in the treatment of various diseases, such as inflammatory and autoimmune disorders as well as metabolic and neurodegenerative diseases, due to the large number of secondary metabolites they contain. The present study was performed on Polygala inexpectata, which is a narrow endemic species for the flora of Turkey, and resulted in the isolation of nine known compounds, 6,3′-disinapoyl-sucrose (1), 6-O-sinapoyl,3′-O-trimethoxy-cinnamoyl-sucrose (tenuifoliside C) (2), 3′-O-(O-methyl-feruloyl)-sucrose (3), 3′-O-(sinapoyl)-sucrose (4), 3′-O-trimethoxy-cinnamoyl-sucrose (glomeratose) (5), 3′-O-feruloyl-sucrose (sibiricose A5) (6), sinapyl alcohol 4-O-glucoside (syringin or eleutheroside B) (7), liriodendrin (8), and 7,4′-di-O-methylquercetin-3-O-β-rutinoside (ombuin 3-O-rutinoside or ombuoside) (9). The structures of the compounds were determined by the spectroscopic methods including 1D-NMR (¹H NMR, ¹³C NMR, DEPT-135), 2D-NMR (COSY, NOESY, HSQC, HMBC), and HRMS. The isolated compounds were shown in an in silico setting to be accommodated well within the inhibitor-binding pockets of myeloperoxidase and inducible nitric oxide synthase and anchored mainly through hydrogen-bonding interactions and π-effects. It is therefore plausible to suggest that the previously established anti-inflammatory properties of some Polygala-derived phytochemicals may be due, in part, to the modulation of pro-inflammatory enzyme activities.     

Current status of biodiesel development in Brazil

In recent years, the concept of producing biodiesel from renewable lipid sources has regained international attention. In Brazil, a national program was launched in 2002 to evaluate the technical, economic, and environmental competitiveness of biodiesel in relation to the commercially available diesel oil. Several research projects were initiated nationwide to investigate and/or optimize biodiesel production from renewable lipid sources and ethanol derived from sugarcane (ethyl esters). Once implemented, this program will not only decrease our dependence on petroleum derivatives but also create new market opportunities for agribusiness, opening new jobs in the countryside, improving the sustainability of our energy matrix, and helping the Brazilian government to support important actions against poverty. This article discusses the efforts to develop the Brazilian biodiesel program in the context of technical specifications as well as potential oilseed sources.     

On the thermal behaviour of acetylphenyl-hydroxyaceticacid-4-nitrobenzyl esters

The 4-nitrobenzyl ester of acetylphenylhydroxyacetic acid differs in its melting behaviour from other nitrobenzyl esters of phenylhydroxyacetic or acetylphenylhydroxyacetic acids, the racemate having a higher melting point than the enantiomers. By means of thermal analysis, IR spectroscopy and X-ray diffractometry the ester can be shown to occur in two crystalline modifications. In the process of solidification of the molten mass, at first a modification of higher energy is formed, obviously being caused by an excess of one enantiomer, which is then exothermally rearranged in the lattice of the racemate.