Determination of shikimate in crude plant extracts by micellar electrokinetic capillary chromatography

A method based on micellar electrokinetic capillary chromatography (MECC) has been developed for the determination of shikimate in water and crude plant extracts. The analytes are separated in a cholate-taurine buffer by MECC at pH 7.3 and measured by direct UV detection at 206 nm. Shikimate showed linearity up to 12.5 mM, with a squared correlation coefficient (r(2)) of 0.9997. The method has concentration limit of detection (cLOD) and concentration limit of quantification (cLOQ) at 24.4 and 67.8 microM, respectively, corresponding to detection in the femtomol range. The number of theoretical plates (N) was estimated to 245,000 for the optimized system using a capillary with an effective length of 560 mm. The method was tested on plant samples by measuring the shikimate content in leaves of rapeseed plants grown in hydroponic solutions containing the herbicide glyphosate, a well-known inhibitor of the shikimate pathway. In crude extracts of these plants, shikimate was found to accumulate in the leaves, confirming earlier reports of shikimate as a potential biomarker for glyphosate treatment. The method now developed was also able to detect shikimate-3-phosphate, but this compound was not accumulated in glyphosate inhibited plants as found for shikimate.     

Saturated and unsaturated nickelalactones with N-heterocyclic carbene ligands: Synthesis and structures

Monomeric and dimeric nickelalactones with N-heterocyclic carbene ligands [(py)(im^mes)Ni(CH₂CH₂COO)] (1), [(im^mes)Ni(CH₂CH₂COO)]₂ (2), [(im^t-but)Ni(C(Et)C(Et)-COO)]₂ (3), [(im^mes)Ni(C(Et)C(Et)-COO)]₂ (4), and [(im^mes)Ni(CH₂C(CH₃)C(CH₃)-CH₂-COO)] (5) (im^mes: 1,3-dimesityimidazol-2-ylidene; im^t-but: 1,3-di-t-butylimidazol-2-ylidene) were synthesized and investigated by ¹H, ¹³C NMR and IR spectroscopic measurements. The solid-state structures of 1-3 and 5 were also elucidated by X-ray diffraction analyses of single crystals. In the compounds the Ni(II) ion has square-planar geometry. The metal centers in the dimers 2 and 3 are bridged by two endocyclic oxygen donor atoms of the carboxylate groups resulting in Ni₂O₂-four-membered rings. Reaction of with 2,3-dimethylbutadiene and CO₂ resulted in an oxidative coupling of the two dienes followed by insertion of CO₂ to form the dimeric complex 6. The X-ray structure of 6 shows two substituted heptenoic acid dianions which connect the two Ni(II) centers. Each nickel atom is surrounded by a η³-allyl group, a monodentate carboxylate group and an im^mes ligand.     

Palladium mediated activation of C-F bonds in 2,4,6-trifluoropyrimidine: Synthesis and structure of palladium pyrimidyloxy and pyrimidinone derivatives

[PdMe₂(dcpm)] (1) reacts with 2,4,6-trifluoropyrimidine in the presence of water to give the palladium derivative [PdMe{4-C₄N₂F₂H(O)}(dcpm)] (2). When additional triethylamine is present complex [PdMe(2-OC₄N₂F₂H)(dcpm)] (4) in addition to 2 is formed. Compound 2 converts slowly into the binuclear complex [Pd{4-C₄N₂F₂H(O)}(μ-dcpm)]₂ (5). The molecular structure of 5 was determined by X-ray crystallography. The palladium-palladium distance is 2.5898(3) Å.     

Mapping of the habenulo-interpeduncular pathway in living mice using manganese-enhanced 3D MRI

This magnetic resonance imaging (MRI) study describes mapping of the habenulo-interpeduncular pathway in living mice based on manganese-induced contrast. Six hours after intracerebroventricular microinjection of MnCl2, T1-weighted 3D MRI (2.35 T) at 117 mum isotropic resolution revealed a continuous pattern of anterograde labeling from the habenula via the fasciculus retroflexus to the interpeduncular nucleus. Alternatively, the less invasive systemic administration of MnCl2 allowed for monitoring of the dynamic uptake pattern of respective neural components with even higher reproducibility across animals. Time courses covered the range from 42 min to 24 h after injection. In conclusion, manganese-enhanced MRI may open new ways for functional assessments of the habenulo-interpeduncular system in animal models with cognitive impairment.     

Illuminating the BOLD signal: combined fMRI-fNIRS studies

Functional magnetic resonance imaging (fMRI) is currently combined with electrophysiological methods to identify the relationship between neuronal activity and the blood oxygenation level-dependent (BOLD) signal. Several processes like neuronal activity, synaptic activity, vascular dilation, blood volume and oxygenation changes underlie both response modalities, that is, the electrophysiological signal and the vascular response. However, accessing single process relationships is absolutely mandatory when aiming at a deeper understanding of neurovascular coupling and necessitates studies on the individual building blocks of the vascular response. Combined fMRI and functional near-infrared spectroscopy studies have been performed to validate the correlation of the BOLD signal to the hemodynamic changes in the brain. Here we review the current status of the integration of both technologies and judge these studies in the light of recent findings on neurovascular coupling.     

Modelling of macroscopical transient frost processes and microscopical driving forces

The artificial saturation phenomenon due to freeze–thaw cycles is described by a multi–phase and multiscale model [1,2,3] formulated within the Theory of Porous Media, [4]. It represents partially saturated concrete as a mixture of 5 interacting constituents φ^α, namely the solid skeleton φ^s, the bulk water φ^l, the pore volume occupied by vapour φ^v, the ice φⁱ and the gel water phase φ^p. Most relevant for the model is the distinction between two length scales and their characteristic time scales. The boundary is marked where macroscopic bulk conditions change to surface physics and chemistry. Surface physics and chemistry acting on the nano–scale affect fundamental properties of concrete and consequently the durability of concrete against freeze–thaw. At the macroscopic scale the model describes transient conditions (i.e. water–uptake, heat transport, volume dilatation of 9%, phase change of first order considering hysteresis) which are characterized by a relatively long time period to reach equilibrium in contrast to the processes modelled on the microstructure. At the microscopic scale the model represents the nanoscopic CSH–gel system consisting of solid CSH and water as a linked system of both components basing on the concept of the “Solid–Liquid Gel System” [5]. In the constribution the numerical results of the model are presented with focus on the evaluation of the process zone during the penetration of the melting front into the matrix. (© 2008 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim)