End Capping Ring-Opening Olefin Metathesis Polymerization Polymers with Vinyl Lactones

The selective placement of a functional group at the chain end of a ring-opening metathesis polymer using ruthenium carbene initiators has been a significant limitation. Here we demonstrate a highly effective and facile end-capping technique for ROMP with living ruthenium carbene chain ends using single-turnover olefin metathesis substrates. Vinylene carbonate and 3H-furanone are introduced as functionalization and termination agents for the ruthenium-initiated ring-opening metathesis polymerization. This leads directly to the formation of functional polymer end groups without further chemical transformation steps. Aldehyde and carboxylic acid end groups can be introduced by this new method which involves the decomposition of acyl carbenes to ruthenium carbides. The high degrees of chain-end functionality obtained are supported by ^1H NMR spectroscopy, MALDI-ToF mass spectrometry, and end-group derivatization

Application of the RMF mass model to the r-process and the influence of mass uncertainties

A new mass table calculated by the relativistic mean field approach with the state-dependent BCS method for the pairing correlation is applied for the first time to study r-process nucleosynthesis. The solar r-process abundance is well reproduced within a waiting-point approximation approach. Using an exponential fitting procedure to find the required astrophysical conditions, the influence of mass uncertainty is investigated. R-process calculations using the FRDM, ETFSI-Q and HFB-13 mass tables have been used for that purpose. It is found that the nuclear physical uncertainty can significantly influence the deduced astrophysical conditions for the r-process site. In addition, the influence of the shell closure and shape transition have been examined in detail in the r-process simulations.Comment: to be published in Phys. Rev. C, 22 pages, 9 figure

Phase shift experiments identifying Kramers doublets in a chaotic superconducting microwave billiard of threefold symmetry

The spectral properties of a two-dimensional microwave billiard showing threefold symmetry have been studied with a new experimental technique. This method is based on the behavior of the eigenmodes under variation of a phase shift between two input channels, which strongly depends on the symmetries of the eigenfunctions. Thereby a complete set of 108 Kramers doublets has been identified by a simple and purely experimental method. This set clearly shows Gaussian unitary ensemble statistics, although the system is time-reversal invariant.Comment: RevTex 4, 5 figure

Sacrificial Synthesis of Hydroxy-Functionalized ROMP Polymers: An Efficiency Study

We present here a ^1H NMR spectroscopy study of the kinetics of the ROMP macroinitiation of poly(exo-N-phenyl-2,3-norbornene dicarboximide) with various dioxepine derivatives and Grubbs first generation ruthenium initiators. We have recently demonstrated that this so-called “sacrificial block copolymer” approach yields hydroxy-functionalized ROMP polymers with high end-group functionality. This study shows that the substituents on the dioxepine are important for functionalization efficiency, in the order phenyl > isopropyl > methyl. Addition of triphenylphosphine to the ruthenium carbene initiator resulted in lower k_i/k_p (rate of initiation/rate of propagation) values for the macroinitiation than in the absence of triphenylphosphine. We demonstrate that the value of k_i/k_p for macroinitiations can be estimated for new sacrificial monomers by analyzing one or two functionalization reactions. This provides an easy tool for the rapid screening and evaluation of new sacrificial monomers

Sacrificial Synthesis of Hydroxy-Functionalized ROMP Polymers: An Efficiency Study

We present here a ^1H NMR spectroscopy study of the kinetics of the ROMP macroinitiation of poly(exo-N-phenyl-2,3-norbornene dicarboximide) with various dioxepine derivatives and Grubbs first generation ruthenium initiators. We have recently demonstrated that this so-called “sacrificial block copolymer” approach yields hydroxy-functionalized ROMP polymers with high end-group functionality. This study shows that the substituents on the dioxepine are important for functionalization efficiency, in the order phenyl > isopropyl > methyl. Addition of triphenylphosphine to the ruthenium carbene initiator resulted in lower k_i/k_p (rate of initiation/rate of propagation) values for the macroinitiation than in the absence of triphenylphosphine. We demonstrate that the value of k_i/k_p for macroinitiations can be estimated for new sacrificial monomers by analyzing one or two functionalization reactions. This provides an easy tool for the rapid screening and evaluation of new sacrificial monomers

Porphyrin synthesis from ALA derivatives for photodynamic therapy. In vitro and in vivo studies

The aim of this work was to test in vitro and in vivo the efficacy of the derivatives of 5-aminolevulinic acid (ALA): hexyl-ALA (He-ALA), undecanoyl-ALA and R,S-2-(hydroximethyl)tetrahydropyranyl-ALA (THP-ALA) as pro-photosensitising agents. The compounds were assayed in a cell line derived from a murine mammary tumour, in tumour explants and after injection of the cells into mice. In vitro, undecanoyl-ALA and THP-ALA did not improve ALA efficacy in terms of porphyrin synthesis. On the other hand, half of the amount of ALA is required to obtain the same plateau amount of photosensitiser from He-ALA. However, this plateau value cannot be surpassed in spite of the four-times higher accumulation of ALA/He-ALA from the ALA derivative. This shows that He-ALA conversion to porphyrins but not He-ALA entry to the cells is limiting. Employing ionic exchange chromatography, we found that 80% of total uptake was He-ALA whereas only 20% was ALA. This suggests that the esterases, probably themselves regulated by the heme pathway, are limiting the conversion of ALA derivatives into porphyrins. A similar situation occurs with THP-ALA. Tumour explant porphyrin results correlate well with cell line data. However, i.p. injection of ALA derivatives to mice resulted in a lower porphyrin concentration in the tumour when compared to the administration of equimolar amounts of ALA, indicating that there should be retention of ALA derivatives either within the blood vessels in the initial phase of distribution and/or within the capillaries of the tumour. © 2004 Cancer Research UK.Fil: Perotti, C.. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Houssay. Centro de Investigaciones sobre Porfirinas y Porfirias. Universidad de Buenos Aires. Centro de Investigaciones sobre Porfirinas y Porfirias; ArgentinaFil: Fukuda, Haydee. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Houssay. Centro de Investigaciones sobre Porfirinas y Porfirias. Universidad de Buenos Aires. Centro de Investigaciones sobre Porfirinas y Porfirias; ArgentinaFil: Di Venosa, Gabriela Mariana. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Houssay. Centro de Investigaciones sobre Porfirinas y Porfirias. Universidad de Buenos Aires. Centro de Investigaciones sobre Porfirinas y Porfirias; ArgentinaFil: MacRobert, A.J.. No especifíca;Fil: Batlle, Alcira María del C.. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Houssay. Centro de Investigaciones sobre Porfirinas y Porfirias. Universidad de Buenos Aires. Centro de Investigaciones sobre Porfirinas y Porfirias; ArgentinaFil: Casas, Adriana Gabriela. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Houssay. Centro de Investigaciones sobre Porfirinas y Porfirias. Universidad de Buenos Aires. Centro de Investigaciones sobre Porfirinas y Porfirias; Argentin