Modelling of θ-conditions for bisphenol—A polycarbonate single chains

Assessing conformational dimensions of macromolecules is a topic of long-standing interest. Because of its simplicity, it is attractive to investigate the chain properties in θ-conditions. Under these special conditions, the effects of excluded volume of the segments of the polymer chain vanish. The molecular chain is only subject to local constraints resulting from the bond structure and the hindrance to rotations about bonds. To model θ-conditions a contour length dependent cutoff is introduced ensuring that only nonbonded interactions of atoms of neighbouring monomeric units are taken into account for energy calculations. Using this energy model we will show that it is possible to model θ-conditions of a single bisphenol-A polycarbonate (BPA-PC) chain in vacuum by two different methods: (i) (Pseudo-) Langevin dynamics simulations and (ii) regular reassignment of randomly generated atom velocities during a molecular dynamics simulation. Both methods can be used to avoid oscillative dynamic behaviour of the chain. Calculations of the end-to-end vector and the radius of gyration of the equilibrium ensembles derived from simulations at different temperatures show good agreement with experimental data. Thus our model techniques are well suited to simulate θ-conditions with small computational expense.     

Light scattering and dielectric relaxation studies of glass forming liquids

Extended Abstract: Glass forming organic liquids and polymers exhibit long range density fluctuations with correlation length ξ in the range of 10–300 nm at temperatures above T_g (1 - 6). This follows from dynamic and static light scattering experiments revealing some unexpected features, which cannot be explained on the basis of conventional liquid state theories: (i) In static light scattering the intensity I(q → 0) is no longer proportional to the isothermal compressibility, (ii) This excess scattering I_exc shows a strong q-dependence (q = (4π/Λ.)sin(θ/2)) corresponding to a correlation length ξ in the above mentioned range, (iii) The Landau-Placzek ratio I_Rayleigh/2I_Brillouin is much too high compared with the results of light scattering theories, (iv) In photon correlation spectroscopy a new ultraslow hydrodynamic mode (Γ ˜ q²) is detected with relaxation rates Γ about 10⁻⁶ to 10⁻⁹ lower than those of the α-process at a given temperature. In order to explain these observations, a two-state fluid model is proposed, which starts from the coexistence of “liquid-like” and “aperiodic solid-like” regions within the liquids. Such ideas have been discussed many times before, so for example A.R. Ubbelohde (7) speculates about “anticrystalline” clusters in liquids. Molecular dynamics simulations of atomic liquids showed that long range orientational fluctuations appear upon supercooling (8). A preferred icosahedral ordering is observed (9) and the number of icosahedral clusters increases with decreasing temperature (10). In connection with the interpretation of the dynamics of supercooled liquids different “two-state” models have been proposed (11 - 15). For the explanation of the light scattering results we propose that the molecules in the different dynamic states (“liquid” or “solid”) aggregate during annealing of the liquid at temperatures above T_g. Experiments showed that the equilibration times can be rather long (3 - 5), but nevertheless the liquids exhibiting long range density fluctuations are in the state of lowest free energy. We claim that our observations are the first experimental proof of the existence of such different dynamic states, which have been discussed many times before. The extended secondary clusters can also be detected by ultra small angle X-ray scattering.     

Charge Reconfiguration in Isolated Quantum Dot Arrays

A high level of tunability and control over arrays of quantum dots are key ingredients toward the goal of scalable‐based qubit architectures. Increasing array size simultaneously increases the parameter space and therefore the tuning complexity. The electron reconfiguration behavior of quantum dot arrays isolated from the electron reservoirs is studied experimentally. Isolating a quantum dot array from the reservoirs does not only enable a high degree of control over the tunnel couplings but at the same time drastically simplifies the stability diagrams for small numbers of electrons trapped in the array. Experimental results on double, triple, and quadruple quantum dot arrays are presented and complementary model calculations allow the identification of all transitions observed in the experiment. Highly tunable long‐range transitions are observed in isolated triple quantum dots and evidence of higher‐order cotunneling is found for the quadruple quantum dot array.     

Application of a Viscoelastic Model to simulate the Interface of a Metal/Fibre-Reinforced Polymer Joint

A viscoelastic model with the Lemaitre-type damage is applied to simulate an interfacial adhesive zone in light weight engineering structures, like aluminum/fiber-reinforced polymer specimens. The evolution of irreversible deformation and damage progression are investigated. The joint of aluminium alloy 5754 (AA5754) and carbon fibre reinforced thermoplastic composite CF-PA66 is manufactured by means of an epoxy (1K) adhesive. The adhesive zone is considered as an interface material. The aim of the research is to study the influence of the interface geometry on the mechanical characteristics of the structure. (© 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim)     

Real-Time Multibody System Dynamic Simulation: Part I. A Modified Recursive Formulation and Topological Analysis

ABSTRACT

ABSTRACT With the advent of parallel computers and recursive dynamics formulations, multibody mechanical systems such as ground vehicles can be simulated in real time. This permits the engineer to rapidly modify design parameters, evaluate dynamic performance, and improve designs, prior to fabrication and testing. Perhaps more important, real-time simulation can be used for simulation with the operator-in-the-loop, permitting system design to be optimized for the capability of the human operator. To achieve the goal of real-time simulation, a modified recursive dynamics formulation and a topological analysis method for the formulation are presented in Part I. A parallel computational algorithm that exploits inherent parallelism in the modified recursive formulation and numerical results will be presented in Part II. By combining the topological analysis method and the parallel algorithm, an efficient general-purpose dynamic simulation method is developed for real-time simulation on shared memory parallel processors.     

An index 0 Differential-Algebraic equation formulation for multibody dynamics: Holonomic constraints

The Lagrange multiplier form of index 3 differential-algebraic equations of motion for holonomically constrained multibody systems is transformed using tangent space generalized coordinates to an index 0 form that is equivalent to an ordinary differential equation. The index 0 formulation includes embedded tolerances that assure satisfaction of position, velocity, and acceleration constraints and is solved using established explicit and implicit numerical integration methods. Numerical experiments with two spatial applications show that the formulation accurately satisfies constraints, preserves invariants due to conservation laws, and behaves as if applied to an ordinary differential equation.     

Non-Hydroxamate Zinc-Binding Groups as Warheads for Histone Deacetylases

Histone deacetylases (HDACs) remove acetyl groups from acetylated lysine residues and have a large variety of substrates and interaction partners. Therefore, it is not surprising that HDACs are involved in many diseases. Most inhibitors of zinc-dependent HDACs (HDACis) including approved drugs contain a hydroxamate as a zinc-binding group (ZBG), which is by far the biggest contributor to affinity, while chemical variation of the residual molecule is exploited to create more or less selectivity against HDAC isozymes or other metalloproteins. Hydroxamates have a propensity for nonspecificity and have recently come under considerable suspicion because of potential mutagenicity. Therefore, there are significant concerns when applying hydroxamate-containing compounds as therapeutics in chronic diseases beyond oncology due to unwanted toxic side effects. In the last years, several alternative ZBGs have been developed, which can replace the critical hydroxamate group in HDACis, while preserving high potency. Moreover, these compounds can be developed into highly selective inhibitors. This review aims at providing an overview of the progress in the field of non-hydroxamic HDACis in the time period from 2015 to present. Formally, ZBGs are clustered according to their binding mode and structural similarity to provide qualitative assessments and predictions based on available structural information.     

State reconstruction of the kicked rotor

We propose two experimentally feasible methods based on atom interferometry to measure the quantum state of the kicked rotor.