The first synthesis of 3-deoxyoripavine and its utilization in the preparation of 10-deoxyaporphines and cyprodime

The synthesis of 3-deoxyoripavine (7) was realized as a novel and promising intermediate towards the synthesis of the important class of dopaminergic and/or serotonergic 10-deoxyaporphines and the special pharmacological tool µ opioid antagonist cyprodime. Generally, the preparation of these valuable biologically active compounds was achieved in remarkable yields.      

Ferroelectric smectic meso-phase formed by banana-shaped achiral liquid crystals

A new banana-shaped achiral molecule, 1,3-phenylene bis[4-(3-chloro-4-n-octyloxyphenyliminomethyl)benzoate] (PBCOB) has been synthesized, and its ferroelectric properties and homeotropic alignment investigated. The presence of a lateral chloro-substituent in the Schiff 's base moiety prevents the regular stacking of molecules and results in lowering the transition temperature and the degree of crystallinity of the switchable banana phase. Their smectic mesophases, including a switchable banana phase B₇, were characterized by differential scanning calorimetry, X-ray scattering and polarizing optical microscopy. Both the left- and right-handed helical domains are spontaneously formed upon cooling from the isotropic liquid to the switchable banana phase B₇. By X-ray study, the smectic phases showed a layer spacing of 38.1 Å, compatible with the end-to-end distance of the molecule with a bent conformation. Significantly, the smectic B7 phase exhibited a periodicity of 292 Å that corresponds to a helical structure with periodicity about 7.5 times 38.1 Å. The spontaneous polarization for PBCOB is about 50 nCcm^-2 and shows a temperature dependence. The ferroelectric lyomesophase of PBCOB showed a ferroelectric electro-optical switching range extending more than 50°C, switchable at room temperature.     

Enantioselective Liquid Chromatographic Separations Using Macrocyclic Glycopeptide-Based Chiral Selectors

Numerous chemical compounds of high practical importance, such as drugs, fertilizers, and food additives are being commercialized as racemic mixtures, although in most cases only one of the isomers possesses the desirable properties. As our understanding of the biological actions of chiral compounds has improved, the investigation of the pharmacological and toxicological properties has become more and more important. Chirality has become a major issue in the pharmaceutical industry; therefore, there is a continuous demand to extend the available analytical methods for enantiomeric separations and enhance their efficiency. Direct liquid chromatography methods based on the application of chiral stationary phases have become a very sophisticated field of enantiomeric separations by now. Hundreds of chiral stationary phases have been commercialized so far. Among these, macrocyclic glycopeptide-based chiral selectors have proved to be an exceptionally useful class of chiral selectors for the separation of enantiomers of biological and pharmacological importance. This review focuses on direct liquid chromatography-based enantiomer separations, applying macrocyclic glycopeptide-based chiral selectors. Special attention is paid to the characterization of the physico-chemical properties of these macrocyclic glycopeptide antibiotics providing detailed information on their applications published recently.     

Dielectric Spectroscopy of Ferronematics Based on 6CHBT Liquid Crystal

In our study, the dielectric behaviour of the rod-like liquid crystal (6CHBT) doped with magnetic nanoparticles of spherical shape was investigated by means of dielectric spectroscopy in the frequency range from 20 Hz to 2 MHz. A low frequency dielectric dispersion in the nematic and isotropic phases of the pure liquid crystal (LC) has been assigned to the space charge polarization. After doping the host LC with the magnetic nano particles, a nearly Debye-like relaxation process was observed with the temperature dependence obeying the Arrhenius law. Considering a possible electric double layer formation on the particle surfaces, the detected relaxation process in the doped LC can be associated with the electric double layer polarization. The experimental results point out that in the measured frequency range the space charge and interfacial effects constitute the main dielectric response. Any anchoring effects were not observed and are therefore expected to appear in higher frequencies.     

Age-Related Absorption of the Human Lens in the Near-Ultraviolet Range

The purpose of the present study was to determine the age dependence of the ultraviolet (UV) absorption of the different parts of the human crystalline lens. Cryostat sections of human cadaveric lenses (60 μm) were cut. The UV absorbance of nine samples, derived from different parts of the lens, was determined using a Shimadzu scanning spectrophotometer. The absorbance of the anterior and posterior lens capsules was measured separately. The absorption coefficients were calculated from the measured absorbance and values taken at 280 as well as at 360 nm were compared statistically. ANCOVA analysis of the values taken at 280 and at 360 nm wavelengths shows that correlation between the absorption coefficients and age can be found only in the case of the posterior layers. These results suggest a differential age-dependent increase of the UV absorption of the posterior layers compared to the anterior ones and can be related to the differential protein expression in the anterior and posterior parts. Posterior crystalline lens capsules have higher absorption coefficients than the anterior ones regardless of age.     

Highly Efficient Trityl-Nitroxide Biradicals for Biomolecular High-Field Dynamic Nuclear Polarization

Dynamic nuclear polarization (DNP) is a powerful method to enhance the sensitivity of solid-state magnetic nuclear resonance (ssNMR) spectroscopy. However, its biomolecular applications at high magnetic fields (preferably>14 T) have so far been limited by the intrinsically low efficiency of polarizing agents and sample preparation aspects. Herein, we report a new class of trityl-nitroxide biradicals, dubbed SNAPols that combine high DNP efficiency with greatly enhanced hydrophilicity. SNAPol-1, the best compound in the series, shows DNP enhancement factors at 18.8 T of more than 100 in small molecules and globular proteins and also exhibits strong DNP enhancements in membrane proteins and cellular preparations. By integrating optimal sensitivity and high resolution, we expect widespread applications of this new polarizing agent in high-field DNP/ssNMR spectroscopy, especially for complex biomolecules.     

Electron delocalization and dimerization in solid C59N doped C60 fullerene

Electron spin resonance and ab initio electronic structure calculations show an intricate relation between molecular rotation and chemical bonding in the dilute solid solution. The unpaired electron of C59N is delocalized over several C60 molecules above 700 K, while at lower temperatures it remains localized within short range. The data suggest that below 350 K rigid C59N-C60 heterodimers are formed in thermodynamic equilibrium with dissociated rotating molecules. The structural fluctuations between heterodimers and dissociated molecules are accompanied by simultaneous electron spin transfer between C60 and C59N molecules. The calculation confirms that in the C59N-C60 heterodimer the spin density resides mostly on the C60 moiety, while it is almost entirely on C59N in the dissociated case.     

Infinite Volume Limit for the Stationary Distribution of Abelian Sandpile Models

We study the stationary distribution of the standard Abelian sandpile model in the box Λ_n = [-n, n] ^d ∩ ℤ ^d for d≥ 2. We show that as n→ ∞, the finite volume stationary distributions weakly converge to a translation invariant measure on allowed sandpile configurations in ℤ ^d . This allows us to define infinite volume versions of the avalanche-size distribution and related quantities. The proof is based on a mapping of the sandpile model to the uniform spanning tree due to Majumdar and Dhar, and the existence of the wired uniform spanning forest measure on ℤ ^d . In the case d > 4, we also make use of Wilson’s method. An erratum to this article is available at .     

Langmuir monolayers of bent-core molecules

A systematic study of five different, symmetric bent-core liquid crystals in Langmuir thin films at the air/water interface is presented. Both the end chains (siloxane vs hydrocarbon) and the core (more or less amphiphilic) are varied, to allow an exploration of different possible layer structures at the interface. The characterization includes systematic surface pressure isotherms, Brewster angle microscopy, and surface potential measurements. The properties of these layers are strongly dependent on the individual type of molecule: the molecules with amphiphilic end chains lie quite flat on the surface, while the molecules with hydrophobic end chains construct multilayer structures. In both cases, the three-dimensional collapse structure is reversible.     

Fehlerquellen bei der polarographischen Bestimmung von Mikrogrammengen Uran (nach der Anreicherung aus festen Proben und Wässern)

Zusammenfassung An Hand zahlreicher Analysenergebnisse konnten die Fehlerquellen bei der polarographischen Bestimmung von Mikrogrammengen Uran aus festen und flüssigen Proben beurteilt werden. Durch weitere Experimente wurden Spuren der Schwermetalle W, Mo (bzw. Pt, V und Sn) als Ursache dieser Fehler erkannt, so daß eine Anpassung der analytischen Methoden möglich war.

---

Summary On the basis of numerous analytical findings, the sources of error in the polarographic determination of microgram amounts of uranium from solid and liquid samples could be assessed. Further experiments showed that these errors were due to traces of the heavy metals W, Mo (or Pt, V, and Sn) so that it was possible to adjust the analytical methods.

---

Résumé Ayant en main de nombreux résultats d'analyse, on a pu estimer les sources d'erreurs du dosage polarographique de quantités de l'ordre du microgramme d'uranium sur des prises d'essai solides et liquides. Grâce à d'autres expériences, on a pu reconnaître la cause de ces erreurs comme étant due à des traces de métaux lourds: W, Mo (ou encore Pt, V et Sn), ce qui a rendu possible une adaptation des méthodes analytiques.