Self-assembly of bidentate ligands for combinatorial homogeneous catalysis: asymmetric rhodium-catalyzed hydrogenation

The first chiral ligand library based on self-assembly through complementary hydrogen-bonding was realized. From a 10 x 4 ligand library, catalysts that show excellent activity and enantioselectivity for the asymmetric rhodium-catalyzed hydrogenation have been identified.     

Transient rheological behaviour of poly-para-henylenetherephthalamide (PpPTA) in sulphuric acid

Nearly all the available information on the transient flow behaviour of liquid crystalline polymers has been obtained on model systems, especially on solutions of polybenzylglutamate (PBG) and hydroxypropylcellulose (HPC). The assessment of rheological models has been based almost entirely on these model systems. It is not clear how much of the available theoretical and experimental knowledge can be applied to systems of industrial relevance, which have quite different molecular structures. Here, an industrial lyotropic system, poly(p-phenylenetherephthalamide) (PpPTA) in sulphuric acid (TWARON from AKZO), is investigated. Various techniques to study transient behaviour are used, these include measurements of transient shear and normal stresses after sudden changes in shear rate, dynamic moduli and stress relaxation after cessation of flow and elastic recoil. At all shear rates studied the PpPTA solution is shear thinning, and the first normal stress difference remains positive. For the stress transients a strain scaling applies reasonably well as it did in model systems. The moduli increase with time upon cessation of flow, indicating that the molecules become less oriented in the previous flow direction. This particular behaviour is similar to that of HPC. Transients also resemble more closely those of HPC rather than those of PBG. This latter difference might be attributed to the higher flexibility of HPC and PpPTA chains as compared with PBG molecules.     

Swelling instability of surface-attached gels as a model of soft tissue growth under geometric constraints

The purpose of this work is to provide a theoretical analysis of the mechanical behavior of the growth of soft materials under geometrical constraints. In particular, we focus on the swelling of a gel layer clamped to a substrate, which is still the subject of many experimental tests. Because the constrained swelling process induces compressive stresses, all these experiments exhibit surface instabilities, which ultimately lead to cusp formation. Our model is based on fixing a neo-Hookean constitutive energy together with the incompressibility requirement for a volumetric, homogeneous mass addition. Our approach is developed mostly, but not uniquely, in the plane strain configuration. We show how the standard equilibrium equations from continuum mechanics have a similarity with the two-dimensional Stokes flows, and we use a nonlinear stream function for the exact treatment of the incompressibility constraint. A free energy approach allows the extension both to arbitrary hyperelastic strain energies and to additional interactions, such as surface energies. We find that, at constant volumetric growth, the threshold for a wavy instability is completely governed by the amount of growth. Nevertheless, the determination of the wavelength at threshold, which scales with the initial thickness of the gel layer, requires the coupling with a surface effect. Our findings, which are valid in proximity of the threshold, are compared to experimental results. The proposed treatment can be extended to weakly nonlinearities within the aim of the theory of bifurcations.     

An efficient catalytic system for cyclocarbonylation of terpenes into lactones

Three different kinds of representative monoterpenic alcohol are involved in the palladium‐catalysed cyclocarbonylation reaction. Lactone formation is shown to occur when cyclic ( 1 ), tertiary ( 3 ) and primary allylic alcohol ( 7 ) functions are reacted, in the presence of CO with [HPd(SnCl₃)L₂] as the active catalytic species. Good yields and selectivities can easily be reached for isopulegol ( 1 ), and dihydromyrcenol ( 3 ). However, more modest results are obtained for the functionalization of geraniol into the original lactone ( 9 ). This lactone can be largely favoured by using a basic chelating diphosphine ligand such as 1,4‐bis(diphenylphosphino)butane. Copyright © 2005 John Wiley & Sons, Ltd.     

SSPaQ: A Subtractive Segmentation Approach for the Exhaustive Parallel Quantification of the Extent of Protein Modification at Every Possible Site

Protein modifications, whether chemically induced or post-translational (PTMs), play an essential role for the biological activity of proteins. Understanding biological processes and alterations thereof will rely on the quantification of these modifications on individual residues. Here we present SSPaQ, a subtractive method for the parallel quantification of the extent of modification at each possible site of a protein. The method combines uniform isotopic labeling and proteolysis with MS, followed by a segmentation approach, a powerful tool to refine the quantification of the degree of modification of a peptide to a segment containing a single modifiable amino acid. The strength of this strategy resides in: (1) quantification of all modifiable sites in a protein without prior knowledge of the type(s) of modified residues; (2) insensitivity to changes in the solubility and ionization efficiency of peptides upon modification; and (3) detection of missed cleavages caused by the modification for mitigation. The SSPaQ method was applied to quantify modifications resulting from the interaction of human phosphatidyl ethanolamine binding protein 1 (hPEBP1), a metastasis suppressor gene product, with locostatin, a covalent ligand and antimigratory compound with demonstrated activity towards hPEBP1. Locostatin is shown to react with several residues of the protein. SSPaQ can more generally be applied to induced modification in the context of drugs that covalently bind their target protein. With an alternate front-end protocol, it could also be applied to the quantification of protein PTMs, provided a removal tool is available for that PTM.

Open image in new window

Graphical Abstract ?

     

Synthèse et Propriétés d'Alkylidénehydrazono-2 Méthyl-3 Dihydro-2,3 Benzothiazoles

The synthesis and the spectral properties of 2-alkylidenehydrazono-3-methyl-2,3-dihydrobenzothiazoles are reported. In the mass spectra of each of these compounds, the main fragmentation implies the breaking of the ?N? -N?bond of the azine.     

Self-induced generation of an off-axis frequency shifted radiation from atoms

The transient resonant linear response at wavelength λ_a of an N two-level atom vapor driven by a strong pulse with wavelength λ_f = λ_a - |Δλ| is shown to promote an emission of radiation peaked at wavelength λ_c = λ_a + |Δλ| in a conical shell around the propagation axis of the incident beam. In the limit of weak excitation, i.e. for an incident Rabi frequency much smaller than the detuning, the cone angle is found to be equal to 2λμ(2N/ch|Δλ|)^{$\text{1}\text{2}$} where μ is the transition dipole moment.     

Comments on “theory of oscillatory oxidation of carbon monoxide over platinum” by R.E. Lagos,B.S. Sales and H. Suhl

The position of the thermochemical surface oscillation (TCSO) model applied to the CO oxidation on supported Pt pellets is tentatively specified.     

Diterpenic skeleton transformations : alumina catalysed rearrangements of epoxides

The 8,14 β-epoxide of methyl sandaracopimarate undergoes new rearrangements on contact with active alumina, yielding labdane and another compound having the cycloisopimarane skeleton.