Discrete, Amorphous Physical Models

Discrete models of physical phenomena are an attractive alternative to continuous models such as partial differential equations. In discrete models, such as cellular automata, space is treated as having finitely many locations per unit volume, and physical processes are modelled by rules that depend on a small number of nearby locations. Such models depend critically on a regular (crystalline) lattice, as well as the global synchronization of all sites. We should ask, on the grounds of minimalism, whether the global synchronization and crystalline lattice are inherent in any discrete formulation. Is it possible to do without these conditions and still have a useful physical model? Or are they somehow fundamental? We will answer this question by presenting a class of models that are “extremely local” in the sense that the update rule does not depend on synchronization with the other sites, or on knowledge of the lattice geometry. All interactions involve only a single pair of sites. The models have the further advantage that they exactly conserved the analog of quantities such as momentum and energy which are conserved in physics. An example model of waves is given, and evidence is given that it agrees well qualitatively and quantitatively with continuous differential equations.     

Proton and α sequential emission in the 16O + 58Ni deep inelastic reaction: A semi-classical approach

The 132 MeV ¹⁶O + ⁵⁸Ni reaction has been experimentally investigated by using coincident charged particle techniques. A closed-form theoretical approach, describing in a simple picture the non-equilibrium component and the evaporative one of the angular correlation between light particles and reaction residues emitted in a peripheral heavy-ion collision, is applied — in the hypotesis of a sequential process — to the (C,N,O)-α and (C,N,O)-p differential multiplicities for the ¹⁶O + ⁵⁸Ni at 8.25 MeV/A deep inelastic collision. From this analysis some reaction mechanism information is deduced.     

Determining reliable edge isopachic data from interior thermoelastic measurements

The maximum stresses in a plane-stressed component typically occur on the boundary. However, it is generally difficult to obtain reliable experimental data at an edge and thermoelastic stress analysis is no exception. The inability to measure reliable edge isopachic stresses has caused many previous thermoelastic stress analyses to be more qualitative than quantitative. This paper develops and implements an effective iterative least-squares method for calculating reliable edge isopachic stresses from measured interior values. The method is based upon the plane-stress isotropic compatibility equation. A regularization scheme is employed to minimize the sensitivity to measurement error and to improve the stability of the algorithm by controlling the rate of convergence. An illustrative example with actual measured thermoelastic data is included. The processes thermoelastically determined results compare well with those obtained using strain gages.Paper was presented at the 1994 SEM Spring Conference held in Baltimore, MD on June 6–8.     

Specific CLK inhibitors from a novel chemotype for regulation of alternative splicing

There is a growing recognition of the importance of protein kinases in the control of alternative splicing. To define the underlying regulatory mechanisms, highly selective inhibitors are needed. Here, we report the discovery and characterization of the dichloroindolyl enaminonitrile KH-CB19, a potent and highly specific inhibitor of the CDC2-like kinase isoforms 1 and 4 (CLK1/CLK4). Cocrystal structures of KH-CB19 with CLK1 and CLK3 revealed a non-ATP mimetic binding mode, conformational changes in helix αC and the phosphate binding loop and halogen bonding to the kinase hinge region. KH-CB19 effectively suppressed phosphorylation of SR (serine/arginine) proteins in cells, consistent with its expected mechanism of action. Chemical inhibition of CLK1/CLK4 generated a unique pattern of splicing factor dephosphorylation and had at low nM concentration a profound effect on splicing of the two tissue factor isoforms flTF (full-length TF) and asHTF (alternatively spliced human TF).     

Colorimetrische Bestimmung des Aluminiumgehaltes von Magnesiumlegierungen

Ohne Zusammenfassung     

Backbone-controlled LUMO energy induces intramolecular C–H activation in ortho-bis-9-borafluorene-substituted phenyl and o-carboranyl compounds leading to novel 9,10-diboraanthracene derivatives

The choice of backbone linker for two ortho-bis-(9-borafluorene)s has a great influence on the LUMO located at the boron centers and, therefore, the reactivity of the respective compounds. Herein, we report the room temperature rearrangement of 1,2-bis-(9-borafluorenyl)-ortho-carborane, C₂B₁₀H₁₀-1,2-[B(C₁₂H₈)]₂ ([2a]) featuring o-carborane as the inorganic three-dimensional backbone and the synthesis of 1,2-bis-(9-borafluorenyl)benzene, C₆H₄-1,2-[B(C₁₂H₈)]₂ (2b), its phenylene analog. DFT calculations on the transition state for the rearrangement support an intramolecular C–H bond activation process via an S_EAr-like mechanism in [2a], and predicted that the same rearrangement would take place in 2b, but at elevated temperatures, which indeed proved to be the case. The rearrangement gives access to 3a and 3b as dibora-benzo[a]fluoroanthene isomers, a form of diboron polycyclic aromatic hydrocarbon (PAH) that had yet to be explored. The isolated compounds 2b, 3a, and 3b were fully characterized by NMR, HRMS, cyclic voltammetry (CV), single-crystal X-ray diffraction analysis, and photophysical measurements, supported by DFT and TD-DFT calculations.

The backbone linker for two ortho-bis-(9-borafluorene)s influences the LUMO at the boron centers and the reactivity of the respective compounds.     

Ring Expansions of Boroles with Diazo Compounds: Steric Control of C or N Insertion and Aromatic/Nonaromatic Products

Access to novel imine‐substituted 1,2‐azaborinines, as well as highly arylated boracyclohexa‐3,5‐dienes has been developed by ring expansion of boroles with diazoalkanes with varying degrees of steric bulk. The formation of a diazoalkane intermediate is also discussed for the reaction of ortho‐brominated p‐tolyl‐azide with 1,2,3,4,5‐pentaphenylborole. Structural details as well as UV/Vis spectroscopic and cyclic voltammetric data are provided. These boron‐containing heterocycles have the potential to serve as building blocks for boron‐containing materials.