Polymerization of a Photocleavable Monomer Using Visible Light

The polymerization of the photocleavable monomer, o‐nitrobenzyl methacrylate (NBMA), is investigated using photoinduced electron/energy transfer reversible addition‐fragmentation chain transfer polymerization. The polymerizations under visible red (λ _max = 635 nm, 0.7 mW cm⁻²) and yellow (λ _max = 560 nm, 9.7 mW cm⁻²) light are performed and demonstrate rational evidence of a controlled/living radical polymerization process. Well‐defined poly(o‐nitrobenzyl methacrylate) (PNBMA) homopolymers with good control over the molecular weight and polymer dispersity are successfully synthesized by varying the irradiation time and/or targeted degree of polymerization. Chain extension of a poly(oligo(ethylene glycol) methyl ether methacrylate) macro‐chain transfer agent with NBMA is carried out to fabricate photocleavable amphiphilic block copolymers (BCP). Finally, these self‐assembled BCP rapidly dissemble under UV light suggesting the photoresponsive character of NBMA is not altered during the polymerization under yellow or red light. Such photoresponsive polymers can be potentially used for the remote‐controlled delivery of therapeutic compounds.

     

A new reversed-phase liquid chromatographic/tandem mass spectrometric method for analysis of underivatised amino acids: evaluation for the diagnosis and the management of inherited disorders of amino acid metabolism

Seventy-six compounds of biological interest for the diagnosis of inherited disorders of amino acids (AA) metabolism have previously been demonstrated to be detectable in positive mode electrospray ionisation tandem mass spectrometry (ESI-MS/MS), after separation by ion-pairing reversed-phase liquid chromatography (RPLC). The separation method used tridecafluoroheptanoic acid as ion-pairing agent, and a gradient of acetonitrile for the elution of the most retained compounds. This method had previously been demonstrated to be suitable for the qualitative diagnosis of many AA disorders, and for the quantitative measurement of 16 AA in biological fluids, using their stable isotope labelled (SIL) AA as internal standard. For quantification of the other AA, an internal standard was chosen among the available SIL-AA, as close as possible to the analyte to be measured, in terms of structural analogy, and of retention time in the chromatographic system. The performances of the quantitative analysis of the other AA to be measured are reported here. They show validated results for several AA, allowing their accurate quantification, with another SIL-AA as internal standard. For some other AA, quantitative results were not accurate, allowing only semi-quantitative or qualitative determination for these parameters.     

Reducible and finite Dehn fillings

We show that the distance between a finite filling slope anda reducible filling slope on the boundary of a hyperbolic knotmanifold is one.     

Hydrogenation of substituted aromatic aldehydes: nucleophilic trapping of the reaction intermediate, application to the efficient synthesis of methylene linked flavanol dimers

The synthesis of dimeric flavanols is the consequence of the possible trapping of the reaction intermediates generated in the course of the reductive hydrogenation of substituted benzaldehydes. The scope of this reaction is investigated.     

New methods in predictive metabolism

Molecular Diversity -     

PAC studies of hydrogen diffusion in amorphous hydrides of binary metallic alloys

The diffusive motions of hydrogen in amorphous Zr₂Ni hydrides were observed by¹⁸¹Ta PAC relaxation measurements. The comparison with the experimental data obtained for crystalline Zr₂Ni hydride lead to the conclusion that hydrogen loading induce a short-range ordering into the amorphous structure. The absence of a large distribution of activation energies may be a consequence of such ordering and/or of collective effects in the hydrogen diffusion processes Affiliated to the Centre National de la Recherche Scientifique.     

Temperature spectra from a turbulent thermal plume by ultrasound scattering

This paper reports the results of a study on temperature inhomogeneities conducted on a thermal plume by using ultrasound scattering as a non-intrusive measurement technique. The plume rises from a metallic disk which can be heated up to 800 °C. The working fluid is air at atmospheric pressure. In the measurement technique, an incoming ultrasound wave is emitted towards the thermal plume. The incident wave is scattered because of non-linear couplings with the flow instabilities present in the measurement region. The scattered wave carries information about those flow instabilities. The technique allows for the retrieving of this information. The shape of the obtained spectrum of temperature fluctuations as a function of wave vector modulus is consistent with previous theoretical analysis. Three qualitatively different regions were identified: first, a production region characterized by a q² law; secondly, a region with behavior as per q⁻³ associated with a buoyancy region and; finally, a dissipation region associated with a q⁻⁷ law. These spectral regions characterize the energy transfers mechanisms among the length scales of flow investigated here. A coefficient of anisotropy γ was defined to analyze anisotropic features of the flow.     

Drug discovery using very large numbers of patents. General strategy with extensive use of match and edit operations

A patent data base of 6.7 million compounds generated by a very high performance computer (Blue Gene) requires new techniques for exploitation when extensive use of chemical similarity is involved. Such exploitation includes the taxonomic classification of chemical themes, and data mining to assess mutual information between themes and companies. Importantly, we also launch candidates that evolve by “natural selection” as failure of partial match against the patent data base and their ability to bind to the protein target appropriately, by simulation on Blue Gene. An unusual feature of our method is that algorithms and workflows rely on dynamic interaction between match-and-edit instructions, which in practice are regular expressions. Similarity testing by these uses SMILES strings and, less frequently, graph or connectivity representations. Examining how this performs in high throughput, we note that chemical similarity and novelty are human concepts that largely have meaning by utility in specific contexts. For some purposes, mutual information involving chemical themes might be a better concept.