Rhodium(II) catalyzed highly diastereoselective synthesis of conformationally restricted dispiro[1,3-dioxolane]bisoxindoles

Synthesis of conformationally restricted dispiro- and bis-dispiro-1,3-dioxolanes via three-component reaction of diazoamides, ketoamides/diketones, and aromatic/heteroaromatic aldehydes in the presence of rhodium(II) acetate dimer catalyst at room temperature involving carbonyl ylides is demonstrated with diastereoselectivity. Synthesis of macrocyclic dispiro-1,3-dioxolanes via intramolecular carbonyl ylide is also delineated in high yield. The conformationally restricted symmetrical as well as unsymmetrical dispiro-1,3-dioxolanes were obtained under mild conditions in a highly diastereo- and regioselective manner.     

Analysis of recognition of fructose by imprinted polymers

Binding of fructose to the fructose imprinted polymer (MIP(Frc)) and pinacol imprinted polymer (control) were studied both in batch and a flow through mode. The influence of the cross-linkers ethylene glycol dimethacrylate (EDMA) and trimethylolpropane trimethacrylate (TRIM) on the binding characteristics was analysed. TRIM cross-linked MIPs showed a lower (unspecific) binding for the control polymer (pinacol imprinted) and higher binding of fructose as compared with the EDMA-MIPs. Furthermore interactions of a TRIM cross-linked molecularly imprinted polymer against fructose and its corresponding template were studied using a thermistor. Label-free detection of fructose was realised in the range of 0.5-10mM. The difference in enthalpy changes between specific binding of fructose to boronic acid moieties of the MIP and non-specific binding to the matrix leads to an 18-fold higher apparent imprinting factor than batch binding studies. Cross-reactivity studies using MIP sensor indicate that the interaction of fructose to MIP generates higher signal than disaccharides. The studies described in this paper demonstrate the potential of direct characterisation of molecular binding events.     

Thermodynamics of hypoelasticity

A thermodynamic framework for hypoelasticity is constructed based on a modified Gibbs Function which depends on the stress deviator and specific volume. In the hypoelastic equations considered here, the stress deviator is obtained from a rate equation involving the corotational derivative and coefficients which depend on the invariants of the stress deviator as well as specific volume. Non-negative entropy production is enforced, leading to a non-dissipative condition in the sense that entropy is produced only by heat transfer. The resulting conditions lead to relations among the coefficients in the rate equation. These relations underdetermine the coefficients, so that there is leeway in specifying these coefficients. An example of a set of rate equations which satisfy the thermodynamics is presented.     

Shear flows of a new class of power-law fluids

We consider the flow of a class of incompressible fluids which are constitutively defined by the symmetric part of the velocity gradient being a function, which can be non-monotone, of the deviator of the stress tensor. These models are generalizations of the stress power-law models introduced and studied by J. Málek, V. Pr??a, K.R. Rajagopal: Generalizations of the Navier-Stokes fluid from a new perspective. Int. J. Eng. Sci. 48 (2010), 1907–1924. We discuss a potential application of the new models and then consider some simple boundary-value problems, namely steady planar Couette and Poiseuille flows with no-slip and slip boundary conditions. We show that these problems can have more than one solution and that the multiplicity of the solutions depends on the values of the model parameters as well as the choice of boundary conditions.     

Start-up flows of second grade fluids in domains with one finite dimension

A number of unidirectional transient flows of a second grade fluid in a domain with one finite dimension are studied. The method of integral transforms (Fourier, Hankel or Laplace) is applied to obtain exact solutions. A general theorem on start-up flows for second grade fluids is presented that allows us to determine unidirectional flows of second grade fluids once the corresponding solution is known within the context of the Navier-Stokes theory. In the process of obtaining solutions for the fluid of second grade, we find several new exact solutions within the context of the classical Navier-Stokes theory.     

Competition Between Radial Expansion and Thickening in the Enlargement of an Intracranial Saccular Aneurysm

Rupture of intracranial saccular aneurysms is the leading cause of spontaneous subarachnoid hemorrhage, which results in significant morbidity and mortality. Although many have suggested that saccular aneurysms enlarge and rupture due to mechanical instabilities, our recent nonlinear analyses suggest that at least certain classes of aneurysms do not exhibit a quasi-static limit point instability or dynamic instabilities in response to periodic loading. Based on an increased understanding of the ubiquitous role of growth and remodeling within the vasculature and recent histopathological data on saccular aneurysms, it is hypothesized that a stress-mediated regulation of collagen turnover causes their enlargement. There is a need, however, for a theoretical framework to explore this and competing hypotheses. In this paper, we present a 2-D constrained mixture model for growth and remodeling of an ellipsoidally shaped saccular aneurysm and numerically simulate enlargement and changes in material symmetry in the aneurysmal wall. Results suggest that ellipsoidal aneurysms tend toward spherical shapes, and a competition between radial expansion and wall thickening plays a critical role in determining the stability of an enlarging lesion.