Application of direct on-line coupling of HPLC and SFC with 1HNMR spectroscopy for the investigation of monomeric acrylates

The separation of monomeric acrylates was performed with High Performance Liquid Chromatography (HPLC) and Supercritical Fluid Chromatography (SFC). A direct on-line structural assignment of all compounds by continuous-flow ¹HNMR spectroscopy is possible with both separation techniques. The direct SFC-NMR coupling offers the advantage that the recorded continuous-flow ¹HNMR spectrum is not obscured by solvent signals.     

The Carbon Zip Reaction: A Method for Expanding Carbocycles

A general method for enlargement of carbocyclic rings by the so called zip reaction is given. The Michael adducts of 2-nitrocycloalkanones with 3-oxo-4-pentenoates in the presence of tetrabutylammonium fluoride give in high yield compounds with the ring enlarged by four C-atoms. By this method 7-, 8-, and 12-membered cycloalkanones were converted respectively to 11-, 12-, and 16-membered functionalized carbocycles (see Scheme 2 and 3).     

Sensitive indoor air monitoring of monoterpenes using different adsorbents and thermal desorption gas chromatography with mass-selective detection

A simple method using active trapping on adsorbents and thermal desorption followed by GC-MS analysis was developed for the indoor air monitoring of monoterpenes. The study was carried out using a dynamically generated atmosphere consisting of 11 monoterpenes: camphene, camphor, delta 3-carene, 1,8-cineol, limonene, linalool, alpha-pinene, beta-pinene, alpha-terpinene, gamma-terpinene, fenchyl alcohol. The influence of the different adsorbents Tenax TA, Tenax GR, Carbosieve SIII, Chromosorb 106 on the yield of six selected monoterpenes at indoor air concentrations was studied. The adsorbent Tenax GR gave relatively the best yields followed by Tenax TA. Detection limits of approximately 1 microgram m3 were determined with Tenax GR for most of the monoterpenes.     

Preparation and Crystal Structure of MnBiS<Subscript>2</Subscript>Br

Summary. Black single crystals of MnBiS₂Br were obtained by the reaction of stoichiometric amounts of α-MnS, Bi, S, and BiBr₃ (3:2:3:1) at 600°C for 4 weeks. The compound crystallises in the monoclinic system, space group C2/m, with a = 12.767(2), b = 3.9468(4), c = 9.574(1) ?, β = 90.87(2)°, and Z = 4. The crystal structure refinement based on 720 reflections converged at R = 0.0244 and wR2 = 0.0579, respectively. MnBiS₂Br forms a layer structure consisting of MnS₆ octahedra, MnS₂Br₄ octahedra, and BiS₃₊₂ pyramids.     

Arbitrary torsion classes and almost free abelian groups

Using the set theoretical principle ? for arbitrary large cardinals κ, arbitrary large strongly κ-free abelian groupsA are constructed such that Hom(A, G)={0} for all cotorsion-free groupsG with |G|<κ. This result will be applied to the theory of arbitrary torsion classes for Mod-Z. It allows one, in particular, to prove that the classF of cotorsion-free abelian groups is not cogenerated by aset of abelian groups. This answers a conjecture of Göbel and Wald positively. Furthermore, arbitrary many torsion classes for Mod-Z can be constructed which are not generated or not cogenerated by single abelian groups.     

UV-B EFFECTS ON TERRESTRIAL PLANTS

The potential impacts of an increase in solar UV-B radiation reaching the Earth's surface due to stratospheric ozone depletion have been investigated by several research groups during the last 15 years. Much of this research has centered on the effects of plant growth and physiology under artificial UV-B irradiation supplied to plants in growth chambers or greenhouses. Since these artificial sources do not precisely match the solar spectrum and due to the wavelength dependency of photobiol-ogical processes, weighting functions, based on action spectra for specific responses, have been developed to assess the biological effectiveness of the irradiation sources and of predicted ozone depletion. Recent experiments have also utilized artificially produced ozone cuvettes to filter natural solar radiation and simulate an environment of reduced UV-B for comparative purposes. Overall, the effectiveness of UV-B varies both among species and among cultivars of a given species. Sensitive plants often exhibit reduced growth (plant height, dry weight, leaf area, etc.), photosynthetic activity and flowering. Competitive interactions may also be altered indirectly by differential growth responses. Photosynthetic activity may be reduced by direct effects on photosynthetic enzymes, metabolic pathways or indirectly through effects on photosynthetic pigments or stomatal function. The fluence response of these changes has yet to be clearly demonstrated in most cases. Plants sensitive to UV-B may also respond by accumulating UV-absorbing compounds in their outer tissue layers, which presumably protect sensitive targets from UV damage. Several key enzymes in the biosynthetic pathways of these compounds have been shown to be specifically induced by UV-B irradiation. Few studies have documented the effects of UV-B on total plant yield under field conditions. One notable exception is a 6-yr study with soybean demonstrating harvestable yield reductions under a simulated 25% ozone depletion. These effects are further modified by prevailing microclimatic conditions. Plants tend to be less sensitive to UV-B radiation under drought or mineral deficiency, while sensitivity increases under low levels of visible light. Further studies are needed to understand the mechanisms of UV-B effects and the interactions with present stresses and future projected changes in the environment.     

Epimeric Isopavine N-Oxides from Roemeria refracta

Roemeria refracta DC. (Papaveraceae) of Turkish origin yielded two novel epimeric N-oxides, (?)-(5R, 11S,14R)-reframidine N-oxide ( = (?)-(5R, 11S,14R)-11,12-dihydro-14-methyl-11,5-(iminomethano)-5H -cyclohepta[1, 2-f: 4, 5-f′]bis[1,3]benzodioxole 14-oxide; 1 ) and (?)-(5R, 11S, 14S)-reframidine N-oxide ( = (?)-(5R, 11S, 14S)-11, 12-dihydro-14-methyl-11, 5-(iminomethano)-5H-cyclohepta[1, 2-f:4, 5-f′]bis[1, 3]benzodioxole 14-oxide; 2 ). The isolated (?)-roelactamine ( = (?)-11, 12-dihydro-14-methyl-11, 5-(iminomethano)-5H-cyclohepta[1, 2-f:4, 5-f′]bis[1, 3]benzodioxol-15-one, 4 ) is the first natural isopavinoid incorporating a lactam group. The epimeric (?)-15-(2-oxopropyl)reframidines ( = (?)-1-[11, 12-dihydro-14-methyl-11, 5-(iminomethano)-5H-cyclohepta[1, 2-f:4, 5-f′]bis[1, 3]benzodioxol-15-y1]propan-2-ones; 5/6 ) and the epimeric (?)-ethyl (reframidin-15-yl)acetates ( = (?)-ethyl [11, 12-dihydro-14-methyl-11, 5-(iminomethano)-5H-cyclohepta[1, 2-f:4, 5-f′]bis[1, 3]benzodioxol-15-y1]acetates; 7/8 ) are probably artifacts. (±)-Coclaurine ( 9 ), (±)-N-methylcoclaurine ( 10 ), (?)-roemeridine ( 11 ), and N-feruloyltyramine ( 12 ) are also isolated from R. refracta together with the previously reported bases. Specific ¹³C-NMR assignments are reported for the first time for the isopavines.     

Synthese von N-(4-Aminobutyl)-16-aza-19-nonadecanlactam und N-(4-Aminobutyl)-17-aza-20-icosanlactam (Desoxoinandenin)

Synthesis of N-(4-Aminobutyl)-16-aza-19-nonadecanelactam and N-(4-Aminobutyl)-17-aza-20-icosanelactam (Desoxoinandenine) According to Scheme 1, the two homologous macrocyclic spermidine derivatives 12 and 23 were synthesized. Key steps in both cases were two different types of ring-enlargement reactions. Compound 12 was identical with a degradation product of the naturally occurring spermidine alkaloids of inandenine-type.