Load and depth sensing indentation as a tool to monitor a gradient in the mechanical properties across a polymer coating: A study of physical and chemical aging effects

Load and depth sensing indentation has been used to characterize the elastic modulus and hardness of various polycarbonate films. This analytical technique is shown to be extremely suitable for the determination of gradients in these mechanical properties. Furthermore, it is demonstrated that such a gradient exists over a length of micrometers in chemically aged polycarbonate, but it is virtually absent in physically aged polycarbonate. From these results, it is concluded that, although the first 100 nm cannot be probed, physical aging occurs homogeneously throughout the bulk of the sample. However, chemical aging starts at the surface and moves progressively into the bulk of the material. From the study of these films, it appears that for the interpretation of these measurements, knowledge about the amount of creep occurring during the measurements and about the mechanical properties of the substrate on which these films are applied is needed. Creep can be measured with the same indenter through the application of a constant load for a period of time. Load and depth sensing indentation appears to be a powerful method for studying the physical and chemical aging of polymers. It is especially valuable for coatings and films for which conventional tensile testing is problematic. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 1628–1639, 2004     

Photoresponsive molecular tools for emerging applications of light in medicine

Light-based therapeutic and imaging modalities, which emerge in clinical applications, rely on molecular tools, such as photocleavable protecting groups and photoswitches that respond to photonic stimulus and translate it into a biological effect. However, optimisation of their key parameters (activation wavelength, band separation, fatigue resistance and half-life) is necessary to enable application in the medical field. In this perspective, we describe the applications scenarios that can be envisioned in clinical practice and then we use those scenarios to explain the necessary properties that the photoresponsive tools used to control biological function should possess, highlighted by examples from medical imaging, drug delivery and photopharmacology. We then present how the (photo)chemical parameters are currently being optimized and an outlook is given on pharmacological aspects (toxicity, solubility, and stability) of light-responsive molecules. With these interdisciplinary insights, we aim to inspire the future directions for the development of photocontrolled tools that will empower clinical applications of light.

This perspective article explores the current state of light-controlled molecular tools for medical therapy and imaging and offers an outlook on clinical application scenarios and optimisation strategies.     

DNA-based asymmetric catalysis: sequence-dependent rate acceleration and enantioselectivity

This study shows that the role of DNA in the DNA-based enantioselective Diels-Alder reaction of azachalcone with cyclopentadiene is not limited to that of a chiral scaffold. DNA in combination with the copper complex of 4,4'-dimethyl-2,2'-bipyridine (Cu-L1) gives rise to a rate acceleration of up to 2 orders of magnitude compared to Cu-L1 catalysis alone. Furthermore, both the enantioselectivity and the rate enhancement prove to be dependent on the DNA-sequence. These features are the main reasons for the efficient and enantioselective catalysis observed with salmon testes DNA/Cu-L1 in the Diels-Alder reaction. The fact that absolute levels of stereocontrol can be achieved with a simple and weak DNA-binding complex like Cu-L1 is a clear demonstration of the power of the supramolecular approach to hybrid catalysis.     

Derivations, isomorphisms, and second cohomology of generalized Witt algebras

Generalized Witt algebras, over a field of characteristic , were defined by Kawamoto about 12 years ago. Using different notations from Kawamoto's, we give an essentially equivalent definition of generalized Witt algebras over , where the ingredients are an abelian group , a vector space over , and a map which is linear in the first variable and additive in the second one. In this paper, the derivations of any generalized Witt algebra
, with the right kernel of being , are explicitly described; the isomorphisms between any two simple generalized Witt algebras are completely determined; and the second cohomology group for any simple generalized Witt algebra is computed. The derivations, the automorphisms and the second cohomology groups of some special generalized Witt algebras have been studied by several other authors as indicated in the references.

     

Numerical Simulation of Turbulent Flow in Concentric Annuli

In this paper we consider a fully developed turbulent flow in a round pipe with a small inner annulus. The diameter of the inner annulus is less than 10% of the diameter of the outer pipe. As a consequence, the surface area of the inner pipe compared to the outer pipe is small. The friction exerted by the wall on the flow is proportional to the surface area and the wall shear stress. Due to the small surface area of the inner annulus the additional stress on the flow due to the presence of the annulus may expected to be negligible. However, it will be shown that the inner annulus drastically changes the flow patterns and gives rise to unexpected scaling properties. In previous studies (Chung et al., Int J Heat Fluid Flow 23:426–440, 2002; Churchill and Chan, AIChE J 41:2513–2521, 1995) it was argued that radial position of the point of zero shear stress does not coincide with the radial location of the point of maximum axial velocity. In our direct numerical simulations we observe a coincidence of these points within the numerical accuracy of our model. It is shown that the velocity profile close to the inner annulus is logarithmic.     

A 6th order staggered compact finite difference method for the incompressible Navier–Stokes and scalar transport equations

In a previous paper we have developed a staggered compact finite difference method for the compressible Navier–Stokes equations. In this paper we will extend this method to the case of incompressible Navier–Stokes equations. In an incompressible flow conservation of mass is ensured by the well known pressure correction method  and . The advection and diffusion terms are discretized with 6th order spatial accuracy. The discrete Poisson equation, which has to be solved in the pressure correction step, has the same spatial accuracy as the advection and diffusion operators. The equations are integrated in time with a third order Adams–Bashforth method. Results are presented for a 1D advection–diffusion equation, a 2D lid driven cavity at a Reynolds number of 1000 and 10,000 and finally a 3D fully developed turbulent duct flow at a bulk Reynolds number of 5400. In all cases the methods show excellent agreement with analytical and other numerical and experimental work.