Organocatalytic synthesis of novel renewable non‐isocyanate polyhydroxyurethanes

Novel fully renewable AA‐BB type non‐isocyanate polyhydroxyurethanes were synthesized by the classical reaction between a diamine and a dicyclocarbonate. Sebacic acid was first reacted with an excess of glycerol carbonate, in presence of DCC and DMPA, leading to a renewable dicyclocarbonate monomer. Then, this monomer was reacted with several renewable diamines, in presence of 1,5,7‐triazabicyclo[4.4.0]dec‐5‐ene (TBD), as organocatalyst, to afford linear and branched polymers. The obtained materials exhibited T_g values varied from ?27 to ?8 °C, T_m values varying from 100 to 165 °C, and thermal stabilities above 200 °C. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 758–764     

A New Short Proof of the Local Index Formula and Some of Its Applications

We give a new short proof of the index formula of Atiyah and Singer based on combining Getzlers rescaling with Greiners approach of the heat kernel asymptotics. As an application we can easily compute the CM cyclic cocycle of even and odd Dirac spectral triples, and then recover the Atiyah-Singer index formula (even case) and the Atiyah-Patodi-Singer spectral flow formula (odd case).An erratum to this article can be found at     

Hydrogenation versus transfer hydrogenation of ketones: two established ruthenium systems catalyze both

The established standard ketone hydrogenation (abbreviated HY herein) precatalyst [Ru(Cl)(2)((S)-tolbinap)[(S,S)-dpen]] ((S),(S,S)-1) has turned out also to be a precatalyst for ketone transfer hydrogenation (abbreviated TRHY herein) as tested on the substrate acetophenone (3) in iPrOH under standard conditions (45 degrees C, 45 bar H(2) or Ar at atmospheric pressure). HY works at a substrate catalyst ratio (s:c) of up to 10(6) and TRHY at s:c<10(4). Both produce (R)-1-phenylethan-1-ol ((R)-4), but the ee in HY are much higher (78-83 %) than in TRHY (4-62 %). In both modes, iPrOK is needed to generate the active catalysts, and the more there is (1-4500 equiv), the faster the catalytic reactions. The ee is about constant in HY and diminishes in TRHY as more iPrOK is added. The ketone TRHY precatalyst [Ru(Cl)(2)((S,S)-cyP(2)(NH)(2))] ((S,S)-2), established at s:c=200, has also turned out to be a ketone HY precatalyst at up to s:c=10(6), again as tested on 3 in iPrOH under standard conditions. The enantioselectivity is opposite in the two modes and only high in TRHY: with (S,S)-2, one obtains (R)-4 in up to 98 % ee in TRHY as reported and (S)-4 in 20-25 % ee in HY. iPrOK is again required to generate the active catalysts in both modes, and again, the more there is, the faster the catalytic reactions. The ee in TRHY are only high when 0.5-1 equivalents iPrOK are used and diminish when more is added, while the (low) ee is again about constant in HY as more iPrOK is added (0-4500 equiv). The new [Ru(H)(Cl)((S,S)-cyP(2)(NH)(2))] isomers (S,S)-9 A and (S,S)-9 B (mixture, exact structures unknown) are also precatalysts for the TRHY and HY of 3 under the same conditions, and (R)-4 is again produced in TRHY and (S)-4 in HY, but the lower ee shows that in TRHY (S,S)-9 A/(S,S)-9 B do not lead to the same catalysts as (S,S)-2. In contrast, the ee are in accord with (S,S)-9 A/(S,S)-9 B leading to the same catalysts as (S,S)-2 in HY. The kinetic rate law for the HY of 3 in iPrOH and in benzene using (S,S)-9 A/(S,S)-9 B/iPrOK or (S,S)-9 A/(S,S)-9 B/tBuOK is consistent with a fast, reversible addition of 3 to a five-coordinate amidohydride (S,S)-11 to give an (S,S)-11-substrate complex, in competition with the rate-determining addition of H(2) to (S,S)-11 to give a dihydride [Ru(H)(2)((S,S)-cyP(2)(NH)(2))] (S,S)-10, which in turn reacts rapidly with 3 to generate (S)-4 and (S,S)-11. The established achiral ketone TRHY precatalyst [Ru(Cl)(2)(ethP(2)(NH)(2))] (12) has turned out to be also a powerful precatalyst for the HY of 3 in iPrOH at s:c=10(6) and of some other substrates. Response to the presence of iPrOK is as before, except that 12 already functions well without it at up to s:c=10(6).     

Material order‐independent interface reconstruction using power diagrams

We have developed a new, multi‐material, piecewise linear interface reconstruction method that correctly locates the position of each material in the mesh cell and matches the required volume fractions with no material ordering required. This is different from other volume tracking interface reconstruction methods in which an improper material ordering may result in materials being incorrectly located within the cell. The new method utilizes a type of weighted Voronoi diagram, known as a power diagram, to reconstruct the interface from approximate material locations derived either from a particle model or quadrature formula. It works on structured and general polygonal grids, for an arbitrary number of materials and can be naturally extended to three dimensions. Published in 2007 by John Wiley & Sons, Ltd.     

Thermal Stability of Periodic Mesoporous SiCO Glasses

Periodic Mesoporous Organosilicas (PMOs) with 2D-hexagonal and cubic Pm3n structures have been prepared from bis(trialkoxysilyl)ethane and cetyltrimethylammonium chloride. The two samples have been pyrolyzed under argon up to 1000 °C. Study by X-ray diffraction (synchrotron radiation) allows the thermal stability of both structures to be followed as a function of the pyrolysis temperature. While the 2D-hexagonal structure collapses after pyrolysis at 800 °C, the cubic Pm3n structure is retained up to 1000 °C. Further characterizations were performed by ²⁹Si MAS-NMR, N₂ adsorption-desorption experiments and elemental analysis. At 1000 °C, the first sample can be described as a mixture of silica and a free C phase, while the cubic one is a true SiCO glass with mixed SiC_xO_{4 – x} units (x = 0,1,2) and a very large surface area of 730 m²/g.     

Fluctuation spectrum of fluid membranes coupled to an elastic meshwork: jump of the effective surface tension at the mesh size

We identify a class of composite membranes: fluid bilayers coupled to an elastic meshwork that are such that the meshwork's energy is a function F(el)[A(xi)] not of the real microscopic membrane area A, but of a smoothed membrane's area A(xi), which corresponds to the area of the membrane coarse grained at the mesh size xi. We show that the meshwork modifies the membrane tension sigma both below and above the scale xi, inducing a steep crossover of amplitude deltasigma=dF(el)/dA(xi). The predictions of our model account for the fluctuation spectrum of red blood cell membranes coupled to their cytoskeleton. Our results indicate that the cytoskeleton might be under extensional stress, which would provide a means to regulate available membrane areas. We also predict an observable tension jump for membranes decorated with polymer "brushes."     

Three-dimensional modelling of micromachined-ultrasonic-transducer arrays operating in water

We report on the 3-D modelling of periodic arrays of capacitive micromachined ultrasonic transducers (cMUTs) operating in fluid. Specific developments have been performed to model biperiodic transducer arrays and to take into account radiation into any stratified media at the front-side as well as the back-side of the device. The model is based on a periodic finite-element-analysis/boundary-element-method (FEA/BEM). It is applied to micromachined ultrasonic transducers (MUTs), based on silicon-nitride-circular-membrane arrays on a silicon substrate, and operating in water. The spectrum characteristics of MUTs excited in phase are investigated, showing that very-large-band emission is achievable as previously demonstrated by many authors. However, other contributions are also found, depending on the excitation conditions, that do not radiate in the fluid. These contributions are identified as guided modes that could generate significant cross-talk effects. The origin and the nature of these modes is analyzed to gain insight in the actual operation of MUTs.     

Self-equivalences of stable module categories

Let P be an abelian p-group, E a cyclic -group acting freely on P and k an algebraically closed field of characteristic . In this work, we prove that every self-equivalence of the stable module category of comes from a self-equivalence of the derived category of . Work of Puig and Rickard allows us to deduce that if a block B with defect group P and inertial quotient E is Rickard equivalent to , then they are splendidly Rickard equivalent. That is, Broué's original conjecture implies Rickard's refinement of the conjecture in this case. All of this follows from a general result concerning the self-equivalences of the thick subcategory generated by the trivial module. Received January 22, 1998; in final form June 23, 1998     

Local transformations of hexahedral meshes of lower valence

The modification of conforming hexahedral meshes is difficult to perform since their structure does not allow easy local refinement or un-refinement such that the modification does not go through the boundary. In this paper we prove that the set of hex flipping transformations of Bern et al. (2002) [1] is the only possible local modification on a geometrical hex mesh of valence less than five i.e., with less than five edges per vertex. We propose a new basis of transformations that can generate sequences of local modifications on hex meshes of valence less than six. For quadrilateral meshes, we show the equivalence between modifying locally the number of quads on a mesh and the number of its internal vertices.     

Copper- or manganese-doped ZnS quantum dots as fluorescent probes for detecting folic acid in aqueous media

3-Mercaptopropionic acid-capped core/shell ZnS:Cu/ZnS and ZnS:Mn/ZnS doped quantum dots (QDs) prepared through hydrothermal methods exhibit high photoluminescence intensity as well as good photostability. These water-dispersible nanoparticles exhibit high fluorescence sensitivity to folic acid due to the high affinity of the carboxylate groups and nitrogen atoms of folic acid towards the Zn surface atoms of the doped dots. Quenching of the fluorescence intensity of the QDs allows the detection of folic acid concentrations as low as 11 μM, thus affording a very sensitive system for the sensing of this biologically active molecule in aqueous solution. The possible quenching mechanism is discussed.