The effect of processing method on dry sliding performance of polyimides at high load/high velocity conditions

Polyimides can be processed by sintering or injection moulding, depending on their molecular structure. Raman spectroscopy shows differences in imide I (CO stretch), imide II (CNC axial vibration) and imide III (CNC transverse vibration) bands for both polyimide types, indicating that (i) further imidisation happens during sintering, while being amorphous and (ii) crystallisation happens during melt processing. Thermogravimetric analysis indicates no glass transition or melting temperatures until degradation at 592 °C after sintering, while moulded polyimides show a glass transition temperature at 250 °C. A dehydration reaction at 180 °C will importantly influence the sliding properties of both sintered and injection moulded polyimides. For sintered polyimide, friction and wear in cylinder-on-plate tests is mechanically controlled and mainly determined by normal loads. Overload for sintered polyimides is due to brittleness above 150 N, as also observed in debris morphology. For moulded polyimide, both normal loads and sliding velocity cause a decrease in friction and increase in wear. Overload for moulded polyimide is thermo-mechanically controlled. Sliding stability is controlled by smooth transfer, which is influenced by thermal action, plastic deformation or shear and promoted by elongation at break. Overload conditions are further discussed in relation to deformation of the Hertz line contact, recovery after sliding and the pv-limit (contact pressure × sliding velocity) related to frictional heating.     

Characterization of a new tailoring domain in polyketide biogenesis: the amine transferase domain of MycA in the mycosubtilin gene cluster

We report the expression and characterization of a truncated form of MycA from the Mycosubtilin gene cluster from Bacillus subtilis. The MycA fragment contains a new amino transferase (AMT) tailoring domain, allowing the first detailed study of a PLP-dependent enzyme operating in cis within the PKS and NRPS biosynthetic paradigm. As the AMT domain acts on covalently bound beta-ketothioesters, and is therefore a single-turnover system, electrospray ionization-Fourier transform mass spectrometry (ESI-FTMS) was used to observe the amine-transfer reaction both for amine donor substrate specificity and to regiospecifically determine enzyme-bound intermediates. We confirm the function of the AMT domain, dissect the mechanistic steps of amine transfer, identify the preferred amine source, and localize the beta-ketothioester substrate during amine transfer.     

Boxlike filter response based on complementary photonic bandgaps in two-dimensional microresonator arrays

We propose that a boxlike filter response can be obtained by utilizing complementary photonic bandgap properties of the column and row configurations in two-dimensional microresonator arrays. The filters are fabricated using deep-UV lithography in silicon-on-insulator technology. The observed sidelobes reduction is approximately 10 dB, and the usable bandwidth can be as high as 500-750 GHz.     

Generalised expressions for the association and dissociation rate constants of molecules with multiple binding sites

ABSTRACT

Many proteins exhibit multiple binding patches. A patch may harbour a key chemical modification site, but may also simply act as a trap for the binding to another site. Here we consider the scenario in which one molecule (enzyme) binds another molecule (substrate) which contains two sites. We present microscopic expressions for the rate at which the enzyme binds to a particular site on the substrate, both for the scenario in which the enzyme directly binds the site without first visiting the other site, and for the case in which it may visit the other site an arbitrary number of times before binding to the site of interest. We also present the expressions for the corresponding dissociation reactions. These expressions can be used to compute in a single rare-event simulation of the dissociation pathway not only both the intrinsic and effective dissociation rate constants but also both association rate constants.     

Conformational analysis of 1,2-difluoroethane, an ab-initio investigation

Contrary to expectation, the gauche conformer of 1,2-difluoroethane is more stable than the trans conformer in the gas phase. In order to understand the underlying causes of the “gauche effect”, a complete geometry relaxation was performed for the gauche and trans conformers of 1,2-difluoroethane with the 4-21G, 4-31G and 4-31G** basis sets. The 4-31G** optimized geometry of the gauche conformer compares well with the experimental values obtained from a number of electron-diffraction studies. A correction for the correlation energy, calculated by means of second-order Møller—Plesset perturbation theory with the 6-31G** basis set, proves to be essential to obtain a correct estimate of the energy difference between the gauche and trans conformers 1,2-difluoroethane.     

The modal interpretation of quantum mechanics and its generalization to density operators

We generalize the modal interpretation of quantum mechanics so that it may be applied to composite systems represented by arbitrary density operators. We discuss the interpretation these density operators receive and relate this to the discussion about the interpretation of proper and improper mixtures in the standard interpretation.     

Numerical study of the flow in a three-dimensional thermally driven cavity

Solutions for the fully compressible Navier–Stokes equations are presented for the flow and temperature fields in a cubic cavity with large horizontal temperature differences. The ideal-gas approximation for air is assumed and viscosity is computed using Sutherland's law. The three-dimensional case forms an extension of previous studies performed on a two-dimensional square cavity. The influence of imposed boundary conditions in the third dimension is investigated as a numerical experiment. Comparison is made between convergence rates in case of periodic and free-slip boundary conditions. Results with no-slip boundary conditions are presented as well. The effect of the Rayleigh number is studied.     

Computation of symbolic dynamics for one-dimensional maps

In this paper we design and implement rigorous algorithms for computing symbolic dynamics for piecewise-monotone-continuous maps of the interval. The algorithms are based on computing forwards and backwards approximations of the boundary, discontinuity and critical points. We explain how to handle the discontinuities in the symbolic dynamics which occur when the computed partition element boundaries are not disjoint. The method is applied to compute the symbolic dynamics and entropy bounds for the return map of the singular limit of a switching system with hysteresis and the forced Van der Pol equation.