Synthesis and Mesophase Properties of Intraanular Functionized Shape-persistent Macrocycles Containing Dibenzo [fg,op] naphthacenes

IntroductionDiscotic liquid crystals can exhibit both columnarand nematic mesophases. The columnar mesophaseshave wider potential applications to conducting andphotoconducting systems, optical data storage, light-emitting diodes, photovoltaic solar cells,…     

Transfer Operators and State Spaces for Discrete Multidimensional Linear Systems

This paper treats multidimensional discrete input-output systems from the constructive point of view. We adapt and improve recursive algorithms, derived earlier by E. Zerz and the second author from standard Gröbner basis algorithms, for the solution of the canonical Cauchy problem for linear systems of partial difference equations with constant coefficients on the lattices N = ^r1 × ^r2. These recursive algorithms, in turn, furnish four other solution methods for the initial value problem, namely by transfer operators, by canonical Kalman global state equations, by parametrizations of controllable systems and, for systems with proper transfer matrix and left bounded input signals, by convolution with the transfer matrix. In the 2D-case N = ² the last method was studied by S. Zampieri. Minimally embedded systems are studied and give rise to especially simple Kalman equations. The latter also imply a useful characterization of the characteristic or polar variety of the system by eigenvalue spectra. For N = ^r we define reachability of a system and prove that controllability implies reachability, but not conversely. Moreover we solve, in full generality, the modelling problem which was introduced and partially solved by F. Pauer and S. Zampieri. Various algorithms have been implemented by the first author in axiom, and examples are demonstrated by means of computer generated pictures. Related work on state space representations has been done by the Padovian and Groningian system theory schools.     

Self-diffusion in core-shell composite 12CO2/13CO2 nanoparticles

A new technique for the generation of multilayered molecular nanoparticles is presented. Core-shell composite nanoparticles of CO(2) with varied composition have been investigated by Fourier-transform infrared spectroscopy over 600 s at 78 K. The isotopically different zones of the particles turned out to have completely different spectra in the nu(3) region: a tub structure (mantle) and a head-and-shoulders structure (core). From the aggregation behavior of both components the particle formation time was found to be 0.1 s. Low-temperature self-diffusion of airborne molecular nanoparticles has been monitored for the first time. The self-diffusion coefficient for (12)CO(2)/(13)CO2 nanocomposites at 78 K was determined from the time evolution of the nu(1) + nu(3) combination band to about 7 x 10(-20) m(2)/s. The work represents a major advance toward nanoengineering of molecular nanoparticles at low temperatures.     

An axiomatic semantics for nested concurrency

We give transformation rules for the concurrent parts of Hoare's language CSP, transforming concurrent CSP programs into nondeterministic, sequential programs.On the basis of these transformations we define an axiomatic semantics for CSP with nested concurrency.This axiomatic system includes a rule for binary, associative process composition, enabling modular verification dealing with parts of concurrent systems as well as full programs.The proof system is fully abstract, in the sense that the internal structure of processes is irrelevant in the specification inasmuch it is not externally observable.An outline of a verification of a recursive, concurrent sorter is given as an example.     

Nanopatterns of molecular spoked wheels as giant homologues of benzene tricarboxylic acids

Molecular spoked wheels with D_3h and C_s symmetry are synthesized by Vollhardt trimerization of C_2v-symmetric dumbbell structures with central acetylene units and subsequent intramolecular ring closure. Scanning tunneling microscopy of the D_3h-symmetric species at the solid/liquid interface on graphite reveals triporous chiral honeycomb nanopatterns in which the alkoxy side chains dominate the packing over the carboxylic acid groups, which remain unpaired. In contrast, C_s-symmetric isomers partially allow for pairing of the carboxylic acids, which therefore act as a probe for the reduced alkoxy chain nanopattern stabilization. This observation also reflects the adsorbate substrate symmetry mismatch, which leads to an increase of nanopattern complexity and unexpected templating of alkoxy side chains along the graphite armchair directions. State-of-the-art GFN-FF calculations confirm the overall structure of this packing and attribute the unusual side-chain orientation to a steric constraint in a confined environment. These calculations go far beyond conventional simple space-filling models and are therefore particularly suitable for this special case of molecular packing.

Scanning tunneling microscopy investigations of phenylene-based molecular spoked wheels with D_3h and C_s symmetries on graphite show the competitive or complementary effects of carboxylic acid groups and alkoxy chains on the nanopattern formation.     

Identification, cloning and characterization of a novel 47 kDa murine PKA C subunit homologous to human and bovine Cβ2

Background  

Two main genes encoding the catalytic subunits Cα and Cβ of cyclic AMP dependent protein kinase (PKA) have been identified in all vertebrates examined. The murine, bovine and human Cβ genes encode several splice variants, including the splice variant Cβ2. In mouse Cβ2 has a relative molecular mass of 38 kDa and is only expressed in the brain. In human and bovine Cβ2 has a relative molecular mass of 47 kDa and is mainly expressed in lymphoid tissues.     

Shape-persistent linear, kinked, and cyclic oligo(phenylene-ethynylene-butadiynylene)s: self-assembled monolayers

Shape-persistent rigid phenylene-ethynylene-butadiynylenes form lamellar self-assembled monolayers (SAMs) at the HOPG/TCB interface, which were studied by scanning tunneling microscopy (STM) with submolecular resolution. Substitution of the terminating acetylene functions with polar cyanopropyldimethylsilyl groups leads to 2D phase separation and defined rod-rod interactions, which determine the packing distances between the rigid rods. The results stimulated the connection of rigid rods via septiarylene clamp units. They covalently link two rigid rod units and define the intramolecular rod-rod distance that matches the alkoxy substituent chain lengths. The systems can be described as half-ring structures of two rigid rods connected via a rotatable joint unit. These acetylene-terminated half-ring structures were also oligomerized under Cu and Pd catalysis to yield defined acyclic and cyclic oligomers. Detailed STM studies decoded the molecular origin of the surface patterning of such systems. The dodecyloxy side chains are adsorbed along the HOPG main axes and, together with the alkoxy backbone angle, determine the adsorption direction of the adlayers.     

The proapoptotic G41S mutation to human cytochrome c alters the heme electronic structure and increases the electron self-exchange rate

The naturally occurring G41S mutation to human (Hs) cytochrome (cyt) c enhances apoptotic activity based upon previous in vitro and in vivo studies, but the molecular mechanism underlying this enhancement remains unknown. Here, X-ray crystallography, nuclear magnetic resonance (NMR) spectroscopy, and density functional theory (DFT) calculations have been used to identify the structural and electronic differences between wild-type (WT) and G41S Hs cyt c. S41 is part of the hydrogen bonding network for propionate 7 of heme pyrrole ring A in the X-ray structure of G41S Hs cyt c and, compared to WT, G41S Hs cyt c has increased spin density on pyrrole ring C and a faster electron self-exchange rate. DFT calculations illustrate an electronic mechanism where structural changes near ring A can result in electronic changes at ring C. Since ring C is part of the solvent-exposed protein surface, we propose that this heme electronic structure change may ultimately be responsible for the enhanced proapoptotic activity of G41S Hs cyt c.