Cationic molybdenum oxo alkylidenes stabilized by N-heterocyclic carbenes: from molecular systems to efficient supported metathesis catalysts

Cationic d⁰ group 6 olefin metathesis catalysts have been recently shown to display in most instances superior activity in comparison to their neutral congeners. Furthermore, their catalytic performance is greatly improved upon immobilization on silica. In this context, we have developed the new family of molecular cationic molybdenum oxo alkylidene complexes stabilized by N-heterocyclic carbenes of the general formula [Mo(O)(CHCMe₃)(IMes)(OR)[X⁻]] (IMes = 1,3-dimesitylimidazol-2-ylidene; R = 1,3-dimesityl-C₆H₃, C₆F₅; X⁻ = B(3,5-(CF₃)₂C₆H₃)₄⁻, B(Ar^F)₄, tetrakis(perfluoro-t-butoxy)aluminate (PFTA)). Immobilization of [Mo(O)(CHCMe₃)(IMes)(O-1,3-dimesityl-C₆H₃)⁺B(Ar^F)₄⁻] on silica via surface organometallic chemistry yields an active alkene metathesis catalyst that shows the highest productivity towards terminal olefins amongst all existing molybdenum oxo alkylidene catalysts.

The first cationic molybdenum oxo complexes were synthesized and immobilized on partially dehydroxylated silica. Vastly enhanced catalytic activity for terminal olefins was found compared to their neutral congeners.     

Easy and effective method to produce functionalized particles for cellular uptake

In this contribution, a versatile approach for the synthesis of functionalized particles for drug delivery is presented, using two nonaggressive standardized procedures. The first procedure considered is the functionalization of an azido‐terminated α‐norbornenyl poly(ethylene oxide) (PEO) macromonomer with an alkyne‐containing active molecule via the copper catalyzed azide alkyne cycloaddition, click type reaction. The functionalized macromonomer is then polymerized by Ring‐Opening Metathesis Polymerization (ROMP) in dispersion to form functionalized particles. The second procedure consists in synthesizing particles by ROMP in dispersed media of norbornene with azido‐terminated α‐norbornenyl PEO macromonomer. The ROMP was initiated by the first generation Grubbs catalyst. Such functionalized core‐shell particles have stealthy properties due to their PEO shell and can be viewed as universal nanocarriers on which any alkyne‐modified active molecule can be grafted by click chemistry. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2013     

First announcement the 20th annual international conference on infrared and millimeter waves

First announcement the 20th annual international conference on infrared and millimeter waves     

An SIS waveguide heterodyne receiver for 600 HGz-635 GHz

A waveguide SIS heterodyne receiver using a Nb/AlO_X/Nb junction has been built for astronomical observations of molecular transitions in the frequency range 600 GHz - 635 GHz, and has been successfully used at the Caltech Submillimeter Observatory (CSO). We report double sideband (DSB) receiver noise temperatures as low as 245 K at 600 GHz -610 GHz, and near 300 K over the rest of the bandwidth. These results confirm that SIS quasiparticle mixers work well at submillimeter-wave frequencies corresponding to photon energies of at least 90% of the superconductor energy gap. In addition, we have systematically investigated the effect on the receiver performance of the overlap between first-order and second-order photon steps of opposite sign at these frequencies. The receiver noise increases by as much as 40% in the region of overlap. We infer potential limitations for operating submillimeter-wave Nb/AlO_x/Nb mixers.     

Optimal mappings with minimum number of connected components in tree-to-tree comparison problems

In this paper we consider the problem of finding a minimum cost mapping between two unordered trees which induces a graph with a minimum number of connected components. The proposed algorithm is based on the generalization of an algorithm for computing an edit distance between trees, and it solves the stated problem in sequential time precisely in O(|T₁|×|T₂|×(degT₁+degT₂)×log₂(degT₁+degT₂)).     

Amplitude des oscillations d'ondes solitaires généralisées

Various physical systems of dispersive waves admit solutions in the form of generalized solitary waves. Such waves result from the resonance between a long localized wave and short periodic oscillations. Many estimates (rigorous and numerical) have been given for the amplitude of the ripples in the tail of the generalized solitary wave when its central part has a sech² shape. This Note provides estimates (not yet rigorous) for the ripple amplitude when the central part is flat and wide. To cite this article: C. Fochesato, F. Dias, C. R. Acad. Sci. Paris, Ser. I 337 (2003).     

Graphs with only caterpillars as spanning trees

A connected graph G is caterpillar-pure if each spanning tree of G is a caterpillar. The caterpillar-pure graphs are fully characterized. Loosely speaking they are strings or necklaces of so-called pearls, except for a number of small exceptional cases. An upper bound for the number of edges in terms of the order is given for caterpillar-pure graphs, and those which attain the upper bound are characterized.     

Superdeformed bands in195Tl

Two superdeformed (SD) bands have been found and assigned to¹⁹⁵Tl on the basis of excitation function and cross bombardment results. The two bands are almost identical in transition energies to those observed in¹⁹³Tl. They are signature partners with a splitting, presumably due to the proton i_13/2 (=5/2) orbital, characteristic of all known SD bands in the thallium isotopes. Their alignments relative to the¹⁹³Tl bands were found to be zero.On leave from Comision National de Energia Atomica 1429 Buenos Aires, Argentina.