Flexible Structures Based on a Short Pitch Cholesteric Liquid Crystals

We report on the realization and characterization of electro-responsive and pressure sensitive polydimethylsiloxane (PDMS) conductive photonic structures combined with the reconfigurable properties of short pitch cholesteric liquid crystals (aligned in Grandjean configuration). By combining ion-implantation process and surface chemistry functionalization, we have overcome the insulating properties of PDMS and induced long range organization of cholesteric liquid crystals, thus controlling both diffraction and selective Bragg reflection of light by means of external perturbations (electric field, pressure). We have characterized our devices in terms of morphological, optical and electro-optical properties.     

Infinite dimensional duality and applications

The usual duality theory cannot be applied to infinite dimensional problems because the underlying constraint set mostly has an empty interior and the constraints are possibly nonlinear. In this paper we present an infinite dimensional nonlinear duality theory obtained by using new separation theorems based on the notion of quasi-relative interior, which, in all the concrete problems considered, is nonempty. We apply this theory to solve the until now unsolved problem of finding, in the infinite dimensional case, the Lagrange multipliers associated to optimization problems or to variational inequalities. As an example, we find the Lagrange multiplier associated to a general elastic–plastic torsion problem.     

Elliptic systems with nonlinearity q greater or equal than two with controlled growth. Global Hölder continuity of solutions to the Dirichlet problem

Hölder regularity up to the boundary of the solutions to the Dirichlet problem for second order elliptic systems with nonlinearity q>2 and with controlled growth is proved when n?q+2.     

Positive solutions for a quasilinear degenerate elliptic equation inR n

In questa nota proviamo un teorema di esistenza di soluzioni positive su tuttoR ⁿ della equazionediv(|Du| ^p?2Du)+f(u)=0.     

Rate constants from the reaction path Hamiltonian. I. Reactive flux simulations for dynamically correct rates

As ab initio electronic structure calculations become more accurate, inherent sources of error in classical transition state theory such as barrier recrossing and tunneling may become major sources of error in calculating rate constants. This paper introduces a general method for diabatically constructing the transverse eigensystem of a reaction path Hamiltonian in systems with many degenerate transverse frequencies. The diabatically constructed reaction path Hamiltonian yields smoothly varying coupling constants that, in turn, facilitate reactive flux calculations. As an example we compute the dynamically corrected rate constant for the chair to boat interconversion of cyclohexane, a system with 48 degrees of freedom and a number of degenerate frequencies. The transmission coefficients obtained from the reactive flux simulations agree with previous results that have been calculated using an empirical potential. Furthermore, the calculated rate constants agree with experimental values. Comparison to variational transition state theory shows that, despite finding the true bottleneck along the reaction pathway, variational transition state theory only accounts for half of the rate constant reduction due to recrossing trajectories.     

A Formal Total Synthesis of (+)-Methyl Trachyloban-18-oate and (+)-Methyl 16-Oxo-17-norkauran-18-oate: Regio- and Diastereoselective Preparation of Methyl (13S)-13-Hydroxyisoatisiren-18-oate from (−)-Abietic Acid

A novel preparation of methyl (13S)-13-hydroxyisoatisiren-18-oate ( 4 ), a key-intermediate in a synthesis of (+)-methyl trachyloban-18-oate ((+)- 1 ), from (?)-abietic acid, is described. Since (?)- 1 has been previously converted into (?)-methyl 16-oxo-17-norkauran-18-oate ((?)- 16 ), our preparation of 4 constitutes also a formal total synthesis, from (?)-abietic acid, of (+)- 16 . Key steps in this approach were the allene photoaddition to podocarp-8(14)-en-13-one ( 5 ) and the conversion of the endo-toluene-4-sulfonate 11 into the exo-benzoate 12b .     

Shear-flow-based chromatographic separations as an alternative to pressure-driven liquid chromatography

It is only by developing specially designed injection and detection systems that shear-driven chromatography can become a viable alternative to HPLC. In the present paper, a dedicated zero dead-volume injection procedure is presented with which sample volumes can be injected reproducibly in the required picoliter range. In addition, a transversal detection groove system is designed which should allow to perform on-line UV-VIS absorption measurements with path lengths in the millimeter range, with an acceptable theoretical plate loss (only 20% in a 5 cm long channel) and acting as a nearly perfect wave guide.