Memory of chirality in the phthalimide photocyclization of adamantane dipeptides

Upon sensitized irradiation of N-phthalimido dipeptides containing l- or d-phenylalanine, enantioselective cyclization to diazamacrocycles takes place (ee >99%). The high optical purity of the products was explained by the memory of chirality effect. The chirality is preserved owing to the axial chirality of the biradical intermediate formed. An insight into the origin behind the enantioselective cyclization of the intermediate was given by density functional calculations. The very high enantiomeric excess in this type of photocyclization establishes it as a new method for the enantioselective synthesis of different large aza-heterocycles.     

Structure and “oxidation behavior” of W24O70, a new member of the {103} CS series of tungsten oxides

Reduced tungsten trioxide crystals WO_3?x, formed by vapor transport from a preparation with bulk composition WO_?2.90, have been studied by X-ray diffraction and electron microscopy. A single-crystal X-ray investigation showed the existence of the ordered {103} CS-structure W₂₄O₇₀, a new member of the homologous series W_nO_3n?2. Electron diffraction patterns of crystal fragments, with a few exceptions, showed the presence of the W₂₄O₇₀ phase (composition WO_2.917). Lattice images, however, indicated a fairly ordered {103} CS-phase, W₂₄O₇₀, intergrown with slabs of WO₃ giving gross compositions of the examined crystals in the range WO_2.93WO_2.96. The wide WO₃ slabs were probably formed by an oxidation process during the preparation.     

Synthesis and Complexation of 1,2-Bis[(monoaza[15]crown-5)-N-yl]glyoxime. Crystal Structure of (1,2-Bis[(monoaza[15]crown-5)-N-yl]glyoximato)palladium(II)

A new vicinal dioxime ligand with two crown-ether groups, 1,2-bis[(monoaza[15]crown-5)-N-Yl]-glyoxime(LH₂), has been prepared from cyanogen di-N-oxide and monoaza[15]crown-5. Ni(II), Pd(II), and Pt(IV) complexes of LH₂ with or without alkali-metal ions bound to macrocyclic groups have been isolated. The high affinity of [Pd(LH)₂] and [Ni(LH)₂] for the K⁺ ion is observed in solvent extraction experiments. A single-crystal X-ray structure confirms the postulated geometry of [Pd(LH)₂]- The Pd-atom of the centro-symmetric molecule has square-planar PdN₄ coordination where Pd–N distances range from 1.978(3) to 1.970(3) Å. The N–Pd–N intraligand angle is 79.9(1)^°.     

Structural characterization,thermal investigation,and liquid crystalline behavior of 4-[(4-chlorobenzyl)oxy]-3,4′-dichloroazobenzene

Using the Williamson method, a new dye 4-[(4-chlorobenzyl)oxy]-3,4′-dichloroazobenzene (CODA) with liquid crystalline properties was synthesized. The structure and the thermal behavior of CODA were investigated by means of nuclear magnetic resonance, X-ray diffraction, differential scanning calorimetry, and light polarized optical microscopy techniques. The thermophysical processes were monitored by heating–cooling cycles, but the formation of liquid crystal phases were exhibited only for small values of the cooling rates. For the first heating–cooling cycle, the melting and the solidification processes, thus the characteristic temperatures, are shifted to higher values when compared to the following cycles.     

PHOTOTRANSFORMATION OF AGGREGATED FORMS OF PROTOCHLOROPHYLLIDE IN ISOLATED ETIOPLAST INNER MEMBRANES

Abstract— Irradiation of an etioplast inner membrane fraction caused the transformation of two photoactive spectroscopically different protochlorophyllide forms into two chlorophyllide forms. A weak light flash, 6% of a saturating flash, preferentially caused the formation of a short wavelength chlorophyllide form absorbing at 672 nm and emitting at 676 nm. A saturating flash resulted in the formation of the 684 nm absorbing form of chlorophyllide with an emission maximum at 698 nm.
The circular dichroism (CD) signals of the newly formed chlorophyllide forms indicated that they are pigment aggregates of different sizes. These aggregates are probably connected to protochlorophyllide reductase and NADPH or NADP. In the absence of NADPH a decomposition of the pigment aggregates took place as revealed by a decrease in the CD-signal. A model is suggested which describes the structural changes of the pigment-protein aggregates after irradiation.     

Metal Complexes with Macrocyclic Ligands. Part XLI. Nickel(II) and copper(II) complexes with mono-N-functionalized dithiadiazamacrocycles

Three N₂S₂ macrocycles ( 3, 10, 12 ) carrying an amino group as a pendant arm have been synthesized and their complexation properties towards Ni²⁺ and Cu²⁺ studied. The crystal structures of the Cu²⁺ complexes with 10-methyl-1,4-dithia-7,10-diazacyclododecane-7-ethanamine ( 3 ) and 11-methyl-1,4-dithia-8,11-diazacyclotetradecane-8-ethanamine ( 10 ) show that, in both cases, the Cu²⁺ is pentacoordinated by the four donor atoms of the macrocycle and the amino group of the side chain. In aqueous solution, however, two forms of the complexes with stoichiometries [MLH] and [ML] (M = Cu²⁺ or Ni²⁺) have been observed. In [MLH], the amino group is protonated and does not bind to the metal ion, whereas in [ML] the amino group is bound, and a pentacoordinated geometry results. The pK_a values for the equilibrium [ML] + H⁺?[MLH]⁺ decrease in the order 12 > 10 > 3 , indicating that the 2-aminoethyl side chain binds better to the Cu²⁺ than the 3-aminopropyl side chain. Cyclic voltammetry for the Cu²⁺/Cu⁺ pair shows that the 2-aminoethyl pendant arm stabilizes the Cu²⁺ oxidation state, when the metal ion is in the 14-membered ring ( 10 ), whereas it stabilizes Cu⁺ for the 12-membered macrocycle ( 3 ).     

Structure and reactivity of a sulfoximine-stabilized chiral dilithiocarbanion

The synthesis and X-ray analysis of a racemic dilithiated S-ethyl-N-methyl-S-phenylsulfoximine cluster 2 with N,N,N′,N′-tetramethylethane-1,2-diamine (TMEDA) as coordinating solvent is presented. The lithium complex 2 consists of a mixed tetrameric mono- and dilithio salt. Unexpectedly, a separation of the enantiomers in mono-and dilithiated antipodes with respect to the chirality center on the S-atom is observed. Dilithiation of S-ethyl-N-methyl-S-phenylsulfoximine ( 1 ) affords a chiral dinucleophile which undergoes highly regie- and stereoselective alkylation reactions with bis-electrophiles.     

Rodriguez-type Representation for the Eigenfunctions of Durrmeyer-type Operators

In this paper we consider a generalization of different variants of Durrmeyer- type modifications of Baskakov and Meyer- König and Zeller operators. We prove a general result concerning the commutativity of these operators with certain differential operators. Prom this result a Rodriguez- type formula for the eigenfunctions follows as a corollary.     

Large eddy simulation of compressible channel flow

Astract The present study is a contribution to the analysis of wall-bounded compressible flows, including a special focus on wall modeling for compressible turbulent boundary layer in a plane channel. large eddy simulation (LES) of fully developed isothermal channel flows at Re = 3,000 and Re = 4,880 with a sufficient mesh refinement at the wall are carried out in the Mach number range 0.3 ≤ M ≤ 3 for two different source term formulations: first the classical extension of the incompressible configuration by Coleman et al. (J. Fluid Mech. 305:159–183, 1995), second a formulation presently derived to model both streamwise pressure drop and streamwise internal energy loss in a spatially developed compressible channel flow. It is shown that the second formulation is consistent with the spatial problem and yields a much stronger cooling effect at the wall than the classical formulation. Based on the present LES data bank, compressibility and low Reynolds number effects are analysed in terms of coherent structure and statistics. A study of the universality of the structure of the turbulence in non-hypersonic compressible boundary layers (M≤5) is performed in reference to Bradshaw (Annu. Rev. Fluid. Mech. 9:33–54, 1977). An improvement of the van Driest transformation is proposed; it accounts for both density and viscosity changes in the wall layer. Consistently, a new integral wall scaling (y ^c+) which accounts for strong temperature gradients at the wall is developed for the present non-adiabatic compressible flow. The modification of the strong Reynolds analogy proposed by Huang et al. (J. Fluid Mech. 305:185–218, 1995) to model the correlation between velocity and temperature for non-adiabatic wall layers is assessed on the basis of a Crocco–Busemann relation specific to channel flow. The key role of the mixing turbulent Prandtl number Pr _m is pointed out. Results show very good agreement for both source formulations although each of them involve a very different amount of energy transfer at the wall. The present work was performed within the framework of the French–German research initiative “large eddy simulation of complex flows’ (UR 507). The computing resources were provided by IDRIS-France. The authors gratefully acknowledge the financial support from the Centre National de la Recherche Scientifique (CNRS), the Centre d’été Mathématique de Recherche Avancée en Calcul Scientifique (CEMRACS) and the Direction Générale de l’Armement (DGA/D4S).