Absolute Configuration of 3-Substituted 1-Azabicyclo[2.2.1]heptanes

The l-azabicyclo[2.2.1]heptan-3-exo-ol ( 2 ) was resolved by fractional crystallisation of its hydrogen tartrate salts. The enantiomers (+)- and (?)- 2 were oxidised to the ketones (?)- 4 and (+)- 4 , respectively (Scheme). CD spectroscopy suggested that (?)- 4 possesses the (1R,4S)-configuration. This absolute configuration was confirmed by single-crystal X-ray diffraction of the derivative (+)-(1R,4R)-3-(1,3-dithian-2-ylidene)-1-azabicyclo [2.2.1]-heptane ((+)- 5 ).     

Analysis of nitriles at low parts per million levels by capillary gas chromatography

Two methods have been developed for the determination of trace levels of acetonitrile and propionitrile in light naphthas. One involves clean-up and preconcentration by medium pressure liquid chromatography (MPLC) in which nitriles are concentrated ten-fold while the complex hydrocarbon matris is removed. The concentrated solution is then analyzed by high resolution GC with flame ionization detection. The second method involves direct injection of samples into a capillary GC equipped with chemiluminescence nitrogen detection. The results and repeatability obtained from both methods are comparable. Preconcentration enables identification by GC-MS and simultaneous analysis of other polar species, with no need for selective detectors. Direct analysis is, on the other hand, much less time-consuming and requires less sample.     

Red Blood Cell Stiffness and Adhesion Are Species-Specific Properties Strongly Affected by Temperature and Medium Changes in Single Cell Force Spectroscopy

Besides human red blood cells (RBC), a standard model used in AFM-single cell force spectroscopy (SCFS), little is known about apparent Young’s modulus (Ea) or adhesion of animal RBCs displaying distinct cellular features. To close this knowledge gap, we probed chicken, horse, camel, and human fetal RBCs and compared data with human adults serving as a repository for future studies. Additionally, we assessed how measurements are affected under physiological conditions (species-specific temperature in autologous plasma vs. 25 °C in aqueous NaCl solution). In all RBC types, Ea decreased with increasing temperature irrespective of the suspension medium. In mammalian RBCs, adhesion increased with elevated temperatures and scaled with reported membrane sialic acid concentrations. In chicken only adhesion decreased with higher temperature, which we attribute to the lower AE-1 concentration allowing more membrane undulations. Ea decreased further in plasma at every test temperature, and adhesion was completely abolished, pointing to functional cell enlargement by adsorption of plasma components. This halo elevated RBC size by several hundreds of nanometers, blunted the thermal input, and will affect the coupling of RBCs with the flowing plasma. The study evidences the presence of a RBC surface layer and discusses the tremendous effects when RBCs are probed at physiological conditions.     

Density of the Set of Generators of Wavelet Systems

Given a function ψ in the affine (wavelet) system generated by ψ, associated to an invertible matrix a and a lattice Γ, is the collection of functions In this paper we prove that the set of functions generating affine systems that are a Riesz basis of ${\cal L}^2({\Bbb R}^d)$ is dense in We also prove that a stronger result is true for affine systems that are a frame of In this case we show that the generators associated to a fixed but arbitrary dilation are a dense set. Furthermore, we analyze the orthogonal case in which we prove that the set of generators of orthogonal (not necessarily complete) affine systems, that are compactly supported in frequency, are dense in the unit sphere of with the induced metric. As a byproduct we introduce the p-Grammian of a function and prove a convergence result of this Grammian as a function of the lattice. This result gives insight in the problem of oversampling of affine systems.     

Euler discretization for a class of nonlinear optimal control problems with control appearing linearly

We investigate Euler discretization for a class of optimal control problems with a nonlinear cost functional of Mayer type, a nonlinear system equation with control appearing linearly and constraints defined by lower and upper bounds for the controls. Under the assumption that the cost functional satisfies a growth condition we prove for the discrete solutions Hölder type error estimates w.r.t. the mesh size of the discretization. If a stronger second-order optimality condition is satisfied the order of convergence can be improved. Numerical experiments confirm the theoretical findings.     

Variational particle number approach for rational compound design

Within density functional theory, a variational particle number approach for rational compound design (RCD) is presented. An expression for RCD is obtained in terms of minimization of a suitably defined energy penalty functional whose gradients are the nuclear and the electronic chemical potential. Using combined quantum and molecular mechanics, a nonpeptidic anticancer drug candidate is designed.     

Electrochemical characterization of screen-printed carbonaceous electrodes for the determination of peroxidase activity in novel screen-printed flow-through modules

A novel totally screen-printed flow-through cell for immunoanalysis is presented. It contained screen-printed carbonaceous electrodes, which allowed the determination of peroxidase activity through the electrochemical reduction of p-benzoquinone. As different electrode materials differ strongly in their electrochemical properties, electrodes resulting from various screen-printable carbonaceous pastes were characterized using the hydroquinone/ p-benzoquinone redox couple. For most of the electrodes, cyclic voltammogram peak separations of between 550 and 670 mV were observed indicating only quasi-reversible electrochemical behavior. This was confirmed by variation of the peak separation with scan rate. Heterogeneous electron transfer rates of ca. 0.5 - 1 x 10(-3) cm s(-1) and electrochemical activation energies of ca. 20 kJ mol(-1) were found. These flow-through cells were not only applied to electrochemical peroxidase activity determinations but also, in combination with a separate detector, as affinity reactors. After biotinylation of screen-printed layers, streptavidin and then biotinylated peroxidase could be bound. However, as signals were only 10-20% of those obtained with a column filled with biotinylated glass beads, only the screen-printed electrochemical detector was applied to the detection of antibodies against the African Swine Fever Virus.     

A one-step route to 4-hydroxy-2,3-diaryl-3,4-dihydro-1 (2 )-isoquinolones

A new procedure for the synthesis of 2,3-diaryl-3,4-dihydro-4-hydroxy-1 (2 )-isoquinolones is described in which the -isomer predominates. Dehydration leads to 2,4-diarylisocarbostyrils.