Edman-Abbau als analytische methode in der ‘Solid phase’-Peptidsynthese. Vorläufige Mitteilung

The systematic analysis of solid phase peptide synthesis by Edman degradation becomes possible by the development of a technique (high pressure liquid chromatography) for the determination of phenylthiohydantoins in trace amounts. By its qualitative beside the quantitative results the degradation method offers the possibility to follow formation and propagation of failure sequences over more than one synthetic cycle. Scope and limitations of the method are discussed.     

Molecular dynamics study of the hydration of lanthanum(III) and europium(III) including many-body effects

Lanthanides complexes are widely used as contrast agents in magnetic resonance imaging (MRI) and are involved in many fields such as organic synthesis, catalysis, and nuclear waste management. The complexation of the ion by the solvent or an organic ligand and the resulting properties (for example the relaxivity in MRI) are mainly governed by the structure and dynamics of the coordination shells. All of the MD approaches already carried out for the lanthanide(III) hydration failed due to the lack of accurate representation of many-body effects. We present the first molecular dynamics simulation including these effects that accounts for the experimental results from a structural and dynamic (water exchange rate) point of view.     

Intermolecular interactions: basis set and intramolecular correlation effects on semiempirical methods. Application to (C2H2)2, (C2H2)3 and (C2H4)2

A detailed study of the intrinsic consistency of the semiempirical method of P. Claverie namely, the effects of the basis set and intramolecular correlation on the multipole distributions of molecular subunits and the influence of the electronic population of each atom in the molecular subunit on its van der Waals radius, is performed on some van der Waals dimers. The validity, limits of this model and the appropriate way to use it is established. In particular, the dependence of the geometry and the interaction energy on the basis set chosen and the intramolecular correlation shows that the multipole distribution involved in the calculation of the electrostatic and polarization terms must be derived from a correlated wave function within an extended basis set. Associated to non local methods for finding stationary points, the method of P. Claverie reproduce reliably the intermolecular geometrical parameters observed for the equilibrium structures and the transition states of the dimer and trimer of acetylene. In addition, a study of the equilibrium structures of the ethylene dimer is presented, the aim of being to clarify the considerable uncertainty in their number and their geometry.     

Characterization of Asx Turn Types and Their Connate Relationship with β-Turns

Models of asparagine-containing dipeptides specifically designed to favor intrinsic folding into an Asx turn were characterized both theoretically, by using quantum chemistry, and experimentally, by using laser spectroscopy in the gas phase. Both approaches provided evidence for the spontaneous folding of both the Asn-Ala and Asn-Gly dipeptide models into the most stable Asx turn, a conformation stabilized by a C10 H-bond that was very similar to a type II’ β-turn. In parallel, analysis of Asx turns implicating asparagine in crystallized protein structures in the Protein Data Bank revealed a sequence-dependent behavior. In Asn-Ala sequences, the Asx turn was found in conjunction with a type I β-turn for which the first of the four defining residues was Asn. The observation that the Asx turn in these structures is mostly of type II’ (i. e., its most stable innate structure) suggests that this motif might foster the formation and/or enhance the stability of the backbone β-turn. In contrast, the Asx turns observed in Asn-Gly sequences extensively adopted a type II Asx-turn structure, thus suggesting that their formation should be ascribed to other factors, such as hydration. The fact that the Asx turn in a Asn-Gly sequence is also often found in combination with a hydrated β-bulge supports the premise that a Asn-Gly sequence might efficiently promote the formation of the β-bulge secondary structure.     

Neutron activation analysis for determination of trace elements in sediments in the Sea of Galilee,Israel

The feasibility of applying both thermal and epithermal neutron activation analysis for simultaneous determinations of elemental composition in sediments, collected from the Sea of Galilee (Kineret Lake), Israel, during 1988–1993, was experimentally investigated. In the present work, the concentrations of 30 elements (Al, Ba, Br, Ca, Ce, Co, Cs, Cr, Eu, Fe, Hf, K, La, Lu, Mg, Mn, Na, Nd, Rb, Sc, Si, Sr, Ta, Tb, Th, Ti, U, V, Yb and Zn) in sediments were determined. The validity of the method was checked by analyzing the U.S. NBS Standard Reference Material SRM-1633a; the elemental content found agreed well with the published certified data. Aluminium was determined by reactor neutron activation analysis (RNAA) taking into account the contribution of silicon to the total²⁸Al activity by the²⁸Si(n,p)²⁸Al reaction. Measurements of irradiated mixtures of Si and Al showed that the dependence of log SiAl mass ratio vs. log cadmium ratio (R _Cd) of²⁸Al is almost linear. The data can be analyzed more accurately by a parabolic correlation (log Si:Al mass ratio vs logR _Cd). The concentrations of fission radionuclide¹³⁷Cs, an activation radionuclide¹³⁴Cs (derived from Chernobyl accident) and the naturally occuring radionuclides⁴⁰K,²²⁶Ra and²³²Th in sediments were also measured by -ray spectrometry using Marinelli (Reentrant) Beaker-Sample Containers.     

Imino-Bridged heterocycles. V . Synthesis of 6,11-dimethyl-1 1H-benzo[5,6]cyclohepta[1,2-c]pyridin-6,11-imine by a regiospecific amide to olefin cyclization

Attempted utilization of sulfenimines 6a,b to prepare tertiary carbinamines as intermediates to the desired 6,11-dimethyl-11H-benzo[5,6]cyclohepta[1,2-c]pyridin-6,11-imine system ( 10 ) instead gave products resulting from nitrogen-sulfur bond cleavage. The preparation and use of the corresponding sulfonimine 8 , however, led to 10 through a regiospecific base-catalyzed reaction.