Preparation of 1,2exo- and 1,2endo-Diiodo-bicyclo[2.2.1]heptane

1,2 exo-Diiodo-norbornane ( 4 ) was prepared from norcamphor hydrazone by oxidative iodination and subsequent rearrangement of the 2,2-diiodo-bicyclo [2.2.1]heptane ( 2 ). The stable α-iodohydrazone 11 was obtained from 1-iodo-bicyclo[2.2.1]heptan-2-one ( 10 ), which itself was prepared from 1-iodo-norbornene ( 5 ). Subsequent treatment of 11 with iodine lead to 1,2,2-triiodo-norbornane ( 12 ) and l,2-diiodo-norborn-2-ene ( 13 ). 1,2 endo-Diiodo-norbornane ( 14 ) was obtained by stereoselective reduction of 12 with tribtityltinhydride or by reaction of 13 with diimide.     

Conductivity anisotropy ofn-type silicon in the range of warm and hot carriers

The electric conductivity ofn-type silicon was measured as a function of the field intensity in different crystallographic directions at temperatures between 78 and 275 °K. From the data at medium fields (range of warm carriers) the coefficientsβ ₀ andγ ₀ ofSchmidt-Tiedemann's anisotropy theory were determined. Especially at low temperatures these coefficients are different for lightly and heavily doped crystals. The differences can be explained by the influence of ionized impurity scattering in addition to lattice scattering. The repopulation of the energy valleys of the conduction band as a function of the field intensity was calculated from the ratioγ ₀/β ₀ and — in the range of hot carriers — from the conductivities measured in <001> and <111> directions. A maximum increase of population of a cool valley was found to be between 0.5 and 1.2 of the zero-field population, depending on the particular sample, the field intensity being about 0.5 kV/cm and the lattice temperature 89 °K.     

Podospermic acid, 1,3,5-tri-O-(7,8-dihydrocaffeoyl)quinic acid from Podospermum laciniatum (Asteraceae)

A phytochemical investigation of Podospermum laciniatum (L.) DC. (Asteraceae) yielded the new quinic acid derivative podospermic acid (1,3,5-tridihydrocaffeoylquinic acid), which was named after the genus it was isolated from. The structure was established by HR mass spectrometry and extensive 1D and 2D NMR spectroscopy. Podospermic acid is the first naturally occurring dihydrocaffeoylquinic acid derivative. The chemosystematic impact and the radical scavenging activity of the new compound are discussed briefly.     

Tyrolobibenzyls – Novel Secondary Metabolites from Scorzonera humilis

Tyrolobibenzyls A ( 2 ), B ( 3 ), and C ( 4 ) were isolated from Scorzonera humilis (Asteraceae) of Tyrolean origin. Compounds 2 and 3 possess a unique phenylethyl‐benzofuran backbone and represent a new class of natural compounds. Structural assignments are based on 1D and 2D NMR as well as MS data. Furthermore, peracetylated derivatives of compounds 3 and 4 were synthesized. Pharmacological evaluation of these compounds by the [³H]thymidine assay showed no pronounced cytotoxicity.     

Phenolic Compounds from Scorzonera tomentosa L.

From the subaerial parts of S. tomentosa L. (Asteraceae), two new dihydroisocoumarins, compounds 1 and 2 , a new phthalide, 3 , and a new stilbene derivative, 4 , were isolated, together with four known compounds, (±)‐hydrangenol ( 5 ), (?)‐hydrangenol 4′‐O‐β‐glucoside ( 6 ), (±)‐hydramacrophyllol A ( 7 ), and (±)‐hydramacrophyllol B ( 8 ). All secondary metabolites were identified on the basis of physicochemical, spectroscopic, and mass‐spectrometric data. The known compounds 5 – 8 were isolated for the first time from this species.     

Recirculation—a novel approach to quantify interstitial analytes in living tissue by combining a sensor with open-flow microperfusion

We report a novel approach to quantify interstitial analytes in living tissue by combining open-flow microperfusion (OFM) with a sensor and the re-circulation method. OFM is based on the unrestricted exchange of molecules between the interstitial fluid (ISF) and a perfusion medium through macroscopic perforations that enables direct access to the ISF. By re-circulating the perfusate and monitoring the changes of the analytes’ concentration with a sensor, the absolute analyte concentration in the ISF can be calculated. In order to validate the new concept, the absolute electrical conductivity of the ISF was identified in six subjects to be 1.33?±?0.08 S/m (coefficient of variation CV?=?6 %), showing the robustness of this approach. The most striking feature of this procedure is the possibility to monitor several compounds simultaneously by applying different sensors which will allow not only the determination of the concentration of a single substance in vivo but also the simultaneous dynamics of different analytes. This will open new fields in analytical chemistry, pharmacology, as well as clinical experimental research.     

13-Chloro-3-O-β-d-glucopyranosylsolstitialin from Leontodon palisae: the first genuine chlorinated sesquiterpene lactone glucoside

Apart from a number of known sesquiterpenoids, a novel chlorinated sesquiterpene lactone glucoside--13-chloro-3-O-β-d-glucopyranosylsolstitialin--has been isolated from the Southwestern European plant Leontodon palisae (Asteraceae, tribe Lactuceae). The structure has been established by high resolution mass spectrometry and 1D as well as 2D NMR spectroscopy. The compound represents the first naturally occurring chlorinated sesquiterpene lactone glucoside. The cytotoxicity of the new compound and related ones was evaluated using the MTT assay.