Mechanistic Studies of the Radical S‐Adenosylmethionine Enzyme DesII with TDP‐D‐Fucose

DesII is a radical S‐adenosylmethionine (SAM) enzyme that catalyzes the C4‐deamination of TDP‐4‐amino‐4,6‐dideoxyglucose through a C3 radical intermediate. However, if the C4 amino group is replaced with a hydroxy group (to give TDP‐quinovose), the hydroxy group at C3 is oxidized to a ketone with no C4‐dehydration. It is hypothesized that hyperconjugation between the C4 C? N/O bond and the partially filled p orbital at C3 of the radical intermediate modulates the degree to which elimination competes with dehydrogenation. To investigate this hypothesis, the reaction of DesII with the C4‐epimer of TDP‐quinovose (TDP‐fucose) was examined. The reaction primarily results in the formation of TDP‐6‐deoxygulose and likely regeneration of TDP‐fucose. The remainder of the substrate radical partitions roughly equally between C3‐dehydrogenation and C4‐dehydration. Thus, changing the stereochemistry at C4 permits a more balanced competition between elimination and dehydrogenation.     

Ortho‐Quinone Methides as Reactive Intermediates in Asymmetric Brønsted Acid Catalyzed Cycloadditions with Unactivated Alkenes by Exclusive Activation of the Electrophile

An efficient method for the highly enantioselective synthesis of chiral chromanes bearing multiple stereogenic centers was developed. A chiral BINOL‐based N‐triflylphosphoramide proved to be an effective catalyst for the in situ generation of ortho‐quinone methides (o‐QMs) and their subsequent cycloaddition reaction with unactivated alkenes provided chromanes with excellent diastereo‐ and enantioselectivity.     

Microstructures réalisant toute compressibilité ou conductivité encadrée par les bornes de Hashin et Shtrikman

The conductivity or bulk modulus of an isotropic composite consisting of two well-ordered isotropic phases is situated between the lower and upper bounds of Hashin and Shtrikman. This work is concerned with the construction of two new microstructures capable of realizing every conductivity or bulk modulus comprised between these bounds. The two microstructures obtained, appearing to be simpler than those presented in the literature to achieve the same purpose, have the property that the variation of the corresponding conductivity or bulk modulus is strictly monotone with respect to the geometric parameter characterizing them. To cite this article: Q.-C. He, H.L. Quang, C. R. Mecanique 333 (2005).     

Active dielectric metasurface based on phase‐change medium

We propose all‐dielectric metasurfaces that can be actively re‐configured using the phase‐change material Ge₂Sb₂Te₅ (GST) alloy. With selectively controlled phase transitions on the composing GST elements, metasurfaces can be tailored to exhibit varied functionalities. Using phase‐change GST rod as the basic building block, we have modelled metamolecules with tunable optical response when phase change occurs on select constituent GST rods. Tunable gradient metasurfaces can be realized with variable supercell period consisting of different patterns of the GST rods in their amorphous and crystalline states. Simulation results indicate a range of functions can be delivered, including multilevel signal modulating, near‐field coupling of GST rods, and anomalous reflection angle controlling. This work opens up a new space in exploring active meta‐devices with broader applications that cannot be achieved in their passive counterparts with permanent properties once fabricated.

     

An experimental technique for measuringtransient natural/forced convective heatfluxes in a vertical channel

A series of systematic experiments for measuring transient natural andforced convected heat fluxes in a one-sided heated vertical channel have beenconducted. The total heat input in transient natural and forced experiments iscomposed of four kinds modes: radiative heat loss, conductiveheat lossm, thermal capacity of the plate, and convective heat transfer in thetest channel. In the transient periods, the generalized correlations for estimatingtransient convective heat flux are proposed in natural and forced convectionexperiments. By using the proposed q_c^″ distributions, satisfactory agreementsare achieved between the transient Nu_x predictions and experimentaldata.     

Uniform strain fields and exact results in an elastoplastic fibre-reinforced composite

This work is concerned with a two-phase material consisting of an elastoplastic matrix reinforced by linearly elastic fibres. It is first shown that uniform strain fields can be generated in this heterogeneous material. A return-mapping based algorithm is then proposed and used to find uniform strain loading paths. With the help of uniform strain fields, exact results, independent of the transverse geometry and arrangement of the fibres, are derived for the effective elastic properties and for the effective initial and current yield surfaces. To cite this article: Q.-C. He, H. Le Quang, C. R. Mecanique 332 (2004).     

Nouvelle approche numerique des solutions de la couche limite laminaire incompressible en regime non-stationnaire autour d'une paroi cylindrique elliptique mise en impulsion brutale

The equations of the unsteady incompressible laminar boundary layers about circular and elliptic cylinders started impulsively from rest are solved, after an original coordinate transformation, with the help of a semi-implicit difference scheme linearly stable without conditions. The knowledge of the phenomenon results only from that of the flow characteristics at the initial time; this makes mandatory the use of an analytical method of the Blasius type. When the ratio of the semi-axes of the elliptic cylinder becomes infinite, the present method gives the solution of the stagnation flow.When the flow presents a separation point in the steady state (circular cylinder), a criterion for stopping computation is proposed. It may be noted that to obtain the stagnation flow, we can continue the computations as far as possible and a steady solution is found with excellent accuracy.     

Cyclic orbifolds of lattice vertex operator algebras having group-like fusions

Letters in Mathematical Physics - Let L be an even (positive definite) lattice and $$g\in O(L)$$. In this article, we prove that the orbifold vertex operator algebra $$V_{L}^{{\hat{g}}}$$ has...     

Regularized gap functions and error bounds for split mixed vector quasivariational inequality problems

In this paper, we consider a class of split mixed vector quasivariational inequality problems in real Hilbert spaces and establish new gap functions by using the method of the nonlinear scalarization function. Further, we obtain some error bounds for the underlying split mixed vector quasivariational inequality problems in terms of regularized gap functions. Finally, we give some examples to illustrate our results. The results obtained in this paper are new.