Selektive Funktionalisierung von Wortmannin mit Hilfe einer Furanring-Maskierung

Wortmannin ( 1 ) and its 11-desacetoxy derivative 2 are highly susceptible to nucleophiles, which limits the possibilities of transformation. Masking the furan ring by a new method allowed selective transformations with various reagents.     

Experimental strategy for characterization of essential dynamical variables in oscillatory systems: effect of double-layer capacitance on the stability of electrochemical oscillators

An experimentally accessible algorithm for changing the time scale associated with a dynamical variable is proposed. In general, a differential controller can be applied to (a) identify the essential species in oscillatory systems and (b) explore their role in the feedback loops. Here, we report on classifying electrochemical oscillators by changing the time scale over which the electrode potential varies; the type of different electrochemical oscillators is identified based on whether the controlled modification of pseudo-capacitance induces or suppresses current oscillations.     

High temperature determination of the rate coefficient for the reaction H2O + CN → HCN + OH

The rate coefficient, k, of the reaction has been determined in the temperature range 2460–2840 K using a shock tube technique. C₂N₂? H₂O? Ar mixtures were heated behind incident shock waves and the CN and OH concentration time histories were monitored simultaneously using broad-band absorption near 388 nm (CN) and narrow-line laser absorption at 306.67 nm (OH). The rate coefficient expression providing the best fit to the data was with uncertainty limits of about ±45% in the temperature range 2460–2840 K. The rate coefficient of the reverse reaction was calculated using detailed balancing, and its extrapolation to lower temperatures was compared with previously published results.     

Investigation of solid surfaces modified by Langmuir-Blodgett monolayers using sum-frequency vibrational spectroscopy and X-ray photoelectron spectroscopy

Langmuir-Blodgett (LB) monomolecular layers of alkylhydroxamic acids and alkylphosphonic acids on copper and iron substrates have been studied by X-ray photoelectron spectroscopy (XPS) and sum-frequency vibrational spectroscopy. According to the XPS results, the structures of the hydroxamic acid and phosphonic acid Langmuir-Blodgett films are very similar: the thickness of the layer of the hydrocarbon tails is typically 1.9-2.1 nm, while the layer of headgroups is about 0.3-0.35 nm thick. The tilt angle of the carbon chains is estimated to be 20-30 degrees with respect to the sample surface normal, and the molecules are connected to the substrate via their headgroups. Analysis of the P 2p and N 1s lines indicates the presence of deprotonated headgroups. The substrate Cu 2p line includes a component which can be assigned to Cu(2+) ions in a thin Cu(OH)(2) layer. The deposition of LB layers led to significant decrease of the hydroxide-related signal, which indicates that binding of the headgroups to the surface is accompanied by the elimination of water molecules. The sum-frequency spectra also clearly indicate that well-ordered monolayers can be formed by the Langmuir-Blodgett technique. Since the non-resonant background from the metal substrates renders the analysis of the spectra more difficult, model system samples on glass were prepared. It was found that the alkyl chains of the adsorbed acids predominantly adopt the all-trans conformation and form an ordered structure. Upper limits for the mean tilt angle of the terminal methyl groups are approximately 10-20 degrees.     

Synthesis and application of a fluorous Lawesson's reagent: convenient chromatography-free product purification

[reaction: see text] A fluorous analogue of Lawesson's reagent for thionation of carbonyl compounds has been developed and its use demonstrated on a series of amides, esters, and ketones. The separation of the Lawesson's reagent-derived byproducts can be achieved by a simple fluorous solid-phase extraction.     

A mass spectrometric line for tritium analysis of water and noble gas measurements from different water amounts in the range of microlitres and millilitres

This paper describes the procedure followed for noble gas measurements for litres, millilitres and microlitres of water samples in our laboratory, including sample preparation, mass spectrometric measurement procedure, and the complete calibrations. The preparation line extracts dissolved gases from water samples of volumes of 0.2 μ l to 3 l and it separates them as noble and other chemically active gases. Our compact system handles the following measurements: (i) determination of tritium concentration of environmental water samples by the ³He ingrowth method; (ii) noble gas measurements from surface water and groundwater; and (iii) noble gas measurements from fluid inclusions of solid geological archives (e.g. speleothems). As a result, the tritium measurements have a detection limit of 0.012 TU, and the expectation value (between 1 and 20 TU) is within 0.2 % of the real concentrations with a standard deviation of 2.4 %. The reproducibility of noble gas measurements for water samples of 20–40 ml allows us to determine solubility temperatures by an uncertainty better than 0.5 °C. Moreover, noble gas measurements for tiny water amounts (in the microlitre range) show that the results of the performed calibration measurements for most noble gas isotopes occur with a deviation of less than 2 %. Theoretically, these precisions for noble gas concentrations obtained from measurements of waters samples of a few microlitres allow us to determine noble gas temperatures by an uncertainty of less than 1 °C. Here, we present the first noble gas measurements of tiny amounts of artificial water samples prepared under laboratory conditions.     

Improving the visible-light photocatalytic activity of SnO<Subscript>x</Subscript>·SiO<Subscript>2</Subscript> glass systems by introducing SnO<Subscript>x</Subscript> nanoparticles

Tin silicate glass without SnO_x nanoparticles (SiO₂·SnO_x), a silica glass containing only SnO_x nanoparticles (SiO₂·SnO_xNP) and the improved product, which combines the tin silicate glass with SnO_x nanoparticles (SiO₂·SnO_x·SnO_xNP) was prepared. For the structural analysis ¹¹⁹Sn Mössbauer spectroscopy and X-ray diffraction were applied. The ¹¹⁹Sn Mössbauer spectra showed that the SiO₂·SnO_x·SnO_xNP sample had the largest Sn^II content (12.0%). It also had an outstanding methylene blue degradation with the first-order rate value with (18?±?2) × 10^?3 min^?1 with visible light irradiation.     

Chemical properties of oxopropenyl adducts of purine and pyrimidine nucleosides and their reactivity toward amino acid cross-link formation

N2-oxopropenyldeoxyguanosine (2) forms in duplex DNA by modification of dG residues with base propenal or malondialdehyde. The pKa of 2 was estimated to be 6.9 from the pH dependence of its ring-closing to the pyrimidopurinone derivative 1. The acidity of 2 may be an important determinant of its miscoding properties and its reactivity to nucleophiles in DNA or protein. To test this hypothesis, analogous N-oxopropenyl derivatives of dA (4), dC (5), and N1-methyl-dG (6) were synthesized and their pKa's were determined by optical titration. The N-oxopropenyl derivatives of dA and dC both exhibited pKa's of 10.5, whereas the N-oxopropenyl derivative of N1-methyldG exhibited a pKa of 8.2. Cross-linking of 2, 4, 5, and 6 to N(alpha)-acetyl-lysine was explored at neutral pH. Adduct 2 did not react with N(alpha)-acetyl-lysine, whereas 4-6 readily formed cross-links. The structures of the cross-links were elucidated, and their stabilities were investigated. The results define the acidity of oxopropenyl deoxynucleosides and highlight its importance to their reactivity toward nucleophiles. This study also identifies the structures of a potential novel class of DNA-protein cross-links.