Doubly photoresponsive and water‐soluble block copolymers: Synthesis and thermosensitivity

We report the synthesis and investigation of a new type of photoresponsive block copolymers (BCPs). They were designed to comprise two water‐soluble polymers containing two different photoisomerizable moieties (either azobenzene and spiropyran or two different azobenzenes), with the two constituting blocks that, when separated, exhibit a lower critical solution temperature (LCST) in water and can shift their LCST in opposite directions upon photoisomerization (decrease of LCST for one polymer and increase for the other). A variety of such doubly photoresponsive BCPs were synthesized using either azobenzene‐ or spiropyran‐containing poly(N,N‐dimethylacrylamide) (PDMA), poly(N‐isopropylacrylamide) (PNIPAM) and poly[methoxydi(ethylene glycol) methacrylate] (PDEGMMA). Their thermal phase transition behaviors in aqueous solution before and after simultaneous photoreactions on the two blocks were investigated in comparison with their constituting blocks, by means of solution transmittance (turbidity) and variable‐temperature ¹H NMR measurements. The results show that BCPs displayed a single LCST whose shift upon two photoisomerizations appeared to be determined by the competing and opposing photoinduced effects on the two blocks. Moreover, optically controlling the relative photoisomerization degrees of trans azobenzene‐to‐cis azobenzene and spiropyran‐to‐merocyanine could be used to tune the LCST of BCP solution. This study demonstrates the potential of exploring a more complex photoreaction scheme to optically control the solution properties of water‐soluble thermosensitive BCPs. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 4055–4066, 2010     

Selection of kernel functions used in a new constitutive equation for viscoelastic fluids

A selection of kernel functions is given to be used in a new integral constitutive equation proposed by Piau whereby the deviatoric stress is calculated from the integral of the history of the past intrinsic rate of rotation and rate of deformation tensors through a representation theorem. Piau has demonstrated the objectivity of a frame moving with a given particle whose axis are directed along the eigenvectors of the rate of deformation tensor. The use of such a framework provides a new approach in the attempt to reduce the computational difficulties associated with conventional constitutive equations written in co-deformational or co-rotational reference frames.The shear and primary normal-stress material functions and the extensional (elongational) stress growth function are defined for the proposed integral constitutive equation. These material functions are used to calculate the kernel functions using steady state, stress relaxation and stress growth data of Attané in simple shear flow for monodisperse polystyrene solutions. The shear and extensional stress growth data of Meissner for a polyethylene melt are also used to show the flexibility of the rheological model.The material functions are first written in terms of five monotonically decreasing functions of the time lag between the past and the present time. Then kernel functions are chosen such that when substituted in the new integral constitutive equation they yield the functions used to describe the data. A further condition imposed on the normalized kernel functions is that they be decreasing functions of time lag.     

Synthesis of luminescent heterometallic bis-lanthanide complexes via selective, sequential metallation

A modular synthetic method for the differential incorporation of two lanthanide ions into a single molecular scaffold is reported; the mixed bimetallic Tb/Eu complex displays an interesting solvent polarity-dependent ratiometric luminescence.     

Bicomplex Quantum Mechanics: II. The Hilbert Space

Using the bicomplex numbers

Random sampling of bandlimited signals on graphs

We study the problem of sampling k-bandlimited signals on graphs. We propose two sampling strategies that consist in selecting a small subset of nodes at random. The first strategy is non-adaptive, i.e., independent of the graph structure, and its performance depends on a parameter called the graph coherence. On the contrary, the second strategy is adaptive but yields optimal results. Indeed, no more than $O(k\log ?(k))$ measurements are sufficient to ensure an accurate and stable recovery of all k-bandlimited signals. This second strategy is based on a careful choice of the sampling distribution, which can be estimated quickly. Then, we propose a computationally efficient decoder to reconstruct k-bandlimited signals from their samples. We prove that it yields accurate reconstructions and that it is also stable to noise. Finally, we conduct several experiments to test these techniques.     

Solid-phase synthesis of phenolic steroids: from optimization studies to a convenient procedure for combinatorial synthesis of biologically relevant estradiol derivatives

During the course of our studies on therapeutic agents for the treatment of breast cancer, we became interested in the solid-phase combinatorial synthesis of estradiol derivatives that contain a functionalized side chain at either position 16 beta or 7 alpha. Both types of compounds have already demonstrated inhibitory activity toward both biosynthesis and action of estradiol. As a first step, two versatile precursors bearing an azidoalkyl side chain at either position 16 beta or 7 alpha of estradiol were synthesized using standard solution-phase methods. Afterward, the effectiveness of five linkers to attach the phenolic function of these estradiol derivatives to a polystyrene resin was investigated; they were benzylic ether (Merrifield), 4-alkoxy-benzylic ethers (Wang, Sheppard), tetrahydropyranyl ether (Ellman), benzoic ester, and o-nitrobenzyl ether. To test the linker in a synthetic context, a short sequence of reactions, including reduction of the azide and acylation of the corresponding amine, was performed on the polymer-bound estradiol derivative. While all of the tested linkers proved effective in attaching the phenol functionality of the precursor, only the o-nitrobenzyl ether photolabile linker enabled the release of the final products in acceptable purities. Consequently, this linker was used to perform successfully the solid-phase synthesis of four different classes of estradiol derivatives in acceptable yields and excellent purities. This study was preliminary to the combinatorial synthesis of larger libraries of biologically relevant estradiol derivatives.     

Fluctuations about hydrodynamic nonequilibrium steady states

Using an extension of the Langevin method, we calculate the fluctuations of a fluid about a stationary state held away from global thermal equilibrium by a temperature gradient or shear flow. In the former case, the Brillouin peaks in the light scattering spectrum acquire an asymmetry that is qualitatively similat to earlier results but different in detail.