Formulation of the coupled cluster theory with localized orbitals in correlation calculations on polymers

It is shown that in the framework of coupled cluster theory both the correlation energy per unit cell and quasi-particle band structures of polymers can be computed directly from matrix elements of the excitation operator and the two-electron integrals calculated in localized orbital basis. Further, it is described how to thake advantage of the localized nature of the orbitals applied. Ab initio test calculations on a finite model system similar to the Pariser–Parr–Pople Hamiltonian are presented.     

A molecular tweezer for lysine and arginine

Lysine and arginine play a key role in numerous biological recognition processes controlling, inter alia, gene regulation, glycoprotein targeting and vesicle transport. They are also found in signaling peptide sequences responsible, e.g. for bacterial cell wall biosynthesis, Alzheimer peptide aggregation and skin regeneration. Almost none of all artificial receptor structures reported to date are selective and efficient for lysine residues in peptides or proteins. An artificial molecular tweezer is introduced which displays an exceptionally high affinity for lysine (K(a) approximately 5000 in neutral phosphate buffer). It features an electron-rich torus-shaped cavity adorned with two peripheral anionic phosphonate groups. Exquisite selectivity for arginine and lysine is achieved by threading the whole amino acid side chain through the cavity and subsequent locking by formation of a phosphonate-ammonium/guanidinium salt bridge. This pseudorotaxane-like geometry is also formed in small basic signaling peptides, which can be bound with unprecedented affinity in buffered aqueous solution. NMR titrations, NOESY and VT experiments as well as ITC measurements and Monte Carlo simulations unanimously point to an enthalpy-driven process utilizing a combination of van der Waals interactions and substantial electrostatic contributions for a conformational lock. Since DMSO and acetonitrile compete with the amino acid guest inside the cavity, a simple change in the cosolvent composition renders the whole complexation process reversible.     

Synthesis and Structure of K[Cd(O2N‐C6H4‐NNN‐C6H4‐NO2)3], an Anionic 1, 3‐Bis(4‐nitrophenyl)triazenido Complex of Cadmium

The reaction of cadmium acetate in methanol with 1, 3‐bis(4‐nitrophenyl)triazene in THF in the presence of KOH yields K[Cd(O₂NC₆H₄NNNC₆H₄NO₂)₃] in form of hexagonal prismatic, red crystals with the trigonal space group R3¯ and a = 12.229(2), c = 48.988(10) Å and Z = 6. In the anionic cadmium complexes, which are located along the threefold axis, the Cd atoms are coordinated in a trigonal prismatic arrangement by the atoms N(1) and N(3) of three triazenido ligands. The potassium cations are coordinated icosahedrally by oxygen atoms of each one nitro group of six neighbouring anionic complexes. The Cd‐N distances are 2.376(4) and 2.350(4) Å, and the K‐O distances are in the range of 2.833(6) to 3.365(6) Å.     

Pheromone, 3.Mitt.: Eine einfache Methode zur Steuerung der Reduktion von α-Alkoxy-carbonylverbindungen

Summary Enantiomerically pure 1,2-diols bearing optionallysyn oranti configurated secondary hydroxylic groups are synthesized from acetal-protected cyanohydrins. After resolution of the diastereomers the cyanohydrins are converted into -alkoxy-ketones by Grignard-reaction followed by reduction using common chelating or non-chelating agents. Among others syntheses of enantiomerically pure pheromones,endo-Brevicomin,exo-Brevicomin and Dispalure are given as examples.

Prof. Dr. Hans Berbalk zum 70. Geburtstag gewidmet     

Chip-Firing Games on Directed Graphs

We consider the following (solitary) game: each node of a directed graph contains a pile of chips. A move consists of selecting a node with at least as many chips as its outdegree, and sending one chip along each outgoing edge to its neighbors. We extend to directed graphs several results on the undirected version obtained earlier by the authors, P. Shor, and G. Tardos, and we discuss some new topics such as periodicity, reachability, and probabilistic aspects.Among the new results specifically concerning digraphs, we relate the length of the shortest period of an infinite game to the length of the longest terminating game, and also to the access time of random walks on the same graph. These questions involve a study of the Laplace operator for directed graphs. We show that for many graphs, in particular for undirected graphs, the problem whether a given position of the chips can be reached from the initial position is polynomial time solvable.Finally, we show how the basic properties of the probabilistic abacus can be derived from our results.     

Competitive adsorption of an anionic and a nonionic surfactant on polystyrene latex particles as monitored by small x-ray scattering

Adsorption of the anionic surfactant sodium dodecylsulfate (SDS) as well as competitive adsorption of SDS with the nonionic surfactant Triton X-405 on a polystyrene latex has been examined by the use of small-angle x-ray scattering (SAXS). Since the latex particles only have a low contrast towards water whereas the electron densities of the added surfactants are rather high, their gradual adsorption can be monitored with good sensitivity. The particles covered with SDS have been investigated by the contrast variation method. A distinct core-shell structure has been observed. After maximum coverage of the surface is reached, the additional surfactant forms free micelles. The analysis presented here allows the simultaneous investigation of the covered particles and the free micelles. This is due to their respective characteristic scattering contributions in different angular ranges. Information on the competitive adsorption could be obtained by analyzing the structure of the coated particles and the composition of the free mixed micelles. The adsorption is shown to be an equilibrium process where adsorption of the nonionic component is found to be much stronger than of the SDS molecules.     

Structural Comparison of Oligoribonucleotides and Their 2′-Deoxy-2′-fluoro Analogs by heteronuclear NMR spectroscopy

1-(2′-Deoxy-2′-fluororibofuranosyl)pyrimidines were synthesized and incorporated into an RNA oligonucleotide to give 5′-r[C_fGC_f(U_fU_fC_fG)GC_fG]-3′ (C_f: short form of C = 2′-deoxy-2′-fluorocytidine; U_f: short form of U = 2′-deoxy-2′-fluorouridine). The oligomer was investigated by means of UV, CD, and NMR spectroscopy to address the question of how F-labels can substitute ¹³C-labels in the ribose ring. Through-space (NOE) and through-bond (scalar couplings) experiments were performed that make use of the ameliorated chemical-shift dispersion induced by ¹⁹F as an alternative heteronucleus. A comparison of the structures of fluorinated vs. unmodified oligomer is given. It turns out that the fluorinated oligonucleotide exists in a 14:3 equilibrium between a hairpin and a duplex conformation, in contrast to the unmodified oligonucleotide which predominantly adopts the hairpin conformation. Furthermore, the fluorinated hairpin structure adopts two distinct conformations that differ in the sugar conformation of the U and C nucleoside units, as detected by the ¹⁹F-NMR chemical shifts. The role of the 2′-OH group as stabilizing element in RNA secondary structure is discussed.     

Four-jet production in e+e−-annihilation

We investigate the four-jet production processes $e^{+}{e}^{?}\to q\overline{q}ggand{e}^{+}{e}^{?}\to q\overline{q}q\overline{q}$ in lowest order QCD perturbation theory. We estimate that four-jet events should be detectable at a rate of about 5% at the highest PETRA energy. The acoplanarity distribution is calculated and compared to nonperturbative effects.     

16, 18O induced transfer reactions on122, 120Sn

The reactions¹²⁰Sn+72 MeV¹⁸O and¹²²Sn+74 MeV¹⁶O were investigated with time of-flightE-E-telescopes. Data are presented for all quasi-elastic reaction channels. The two neutron stripping and pickup reactions (¹⁸O,¹⁶O), (¹⁸O,²⁰O) and (¹⁶O,¹⁸O) are analyzed in detail. It is shown that these heavy ion induced two neutron transfer reactions proceed with essentially the same type of selectivity as the corresponding light ion induced reactions. The differential cross sections for transfer reactions leaving the^{120, 122}Sn nuclei in their 2⁺ first excited states are shown to be influenced by interference effects due to additional inelastic excitations.     

BINOL-derived diphosphoramidites bearing unsymmetrical 1,2-diamine link and their application in asymmetric catalysis

New P,P-bidentate diastereomeric diphosphoramidite chiral ligands with mixed stereogenic elements and a C₁ backbone symmetry have been prepared from (S_a)- and (R_a)-1,1′-binaphthyl-2,2′-diol (BINOL) and (S)-N-benzyl-1-(pyrrolidin-2-yl)methanamine and are fully characterized. The use of these ligands provides up to 84% ee in the Pd-catalyzed asymmetric allylic substitution of (E)-1,3-diphenylallyl acetate and up to 95% ee in the Rh-catalyzed asymmetric hydrogenation of α-dehydrocarboxylic acid esters. The results indicate that the catalytic performance is highly affected by the axial chirality of the binaphthyl moieties of the ligand and the nature of the solvent.