Short and efficient access to imidazo[1,2-a]pyrrolo[3,2-c]pyridine derivatives

Access to N-protected or N-free imidazo[1,2-a]pyrrolo[3,2-c]pyridine derivatives as potential antiviral compounds was achieved in good yields from N-protected 7-amino-8-halo-2-methylimidazo[1,2-a]pyridines by catalytic coupling of terminal acetylenes under mild conditions using [PdCl₂(PPh₃)₂] or [Cu(Phen)(PPh₃)₂]NO₃.     

Structure du radical cyano-vinyle CH2=Ċ-CN Etude expérimentale et théorique

Résumé Tout d'abord, on montre par RPE que le radical CH₂=-CN possède à basse température une structure instable pliée et à température plus élevée une structure stable linéaire. Un calcul théorique sur ce radical ainsi que sur le radical butatriényle est en bon accord avec les résultats expérimentaux.

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The structure of the Cyano-Vinyl Radical CH₂=-CN experimental and theoretical study

First, it is shown by ESR that the radical CH₂=-CN at low temperature presents an unstable bent structure and at higher temperature a stable linear structure. A theoretical calculation on this radical and on the butatrienyl one is in good agreement with the experimental results.

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Zusammenfassung Aus ESR Messungen wird gefolgert, daß das Radikal CH₂=-CN bei tiefer Temperatur in einer instabilen gebogenen Struktur und bei höherer Temperatur in einer stabilen linearen Struktur vorliegt. Theoretische Berechnungen stehen sowohl für dieses als auch für das Butatrienyl-Radikal in guter Übereinstimmung mit experimentellen Daten.

     

Numerical and analytical modelling of the MHD buoyancy-driven flow in a Bridgman crystal growth configuration

We present analytical and numerical models of magnetohydrodynamic(MHD) buoyancy-driven flow within the liquid pool of a horizontal Bridgman crystal growth furnace, under the influence of a uniform vertical magnetic field B₀. A horizontal differentially heated cylinder, whose aspect ratio (radius to length) is small enough for a fully developed regime to be established in the central core, is considered. With Hartmann layers remaining electrically inactive, a modified Rayleigh number Ra_G, which is the ration of the ordinary Rayleigh number to the square of the Hartmann number, is found to control the MHD reorganisation of the flow. This modified Rayleigh number is a measure of the importance of thermal convection relative to diffusion if velocity is estimated from the balance between the torques of buoyancy and the Laplace force. When Ra_G is much smaller than unity (quasi-diffusive regime), an analytical modelling of the flow, based on a power series of Ra_G, demonstrates that this balance requires secondary vortices within vertical mid-planes of the cylinder, both within the core flow and near the end walls. A 3-D numerical calculation of the flow provides evidence of the transition from a convective MHD flow (when Ra_G is still of the order of unity) to the quasi-diffusive flow, analytically studied. Indeed, this transition takes the form of a rather complex 3-D MHD organisation of the flow which is due to the nonuniformity of the axial temperature gradient along the cylinder.     

Electron transport through high-κ dielectric barriers: A non-equilibrium Green’s function (NEGF) study

We present a simulation study of the coherent transport of electrons through high permittivity (high-κ) dielectric barriers using the non-equilibrium Green’s function (NEGF) formalism. Calculation and useful formula are established for a one-dimensional grid using a finite-difference scheme and an effective-mass depending on the position along the grid. A numerical simulation code is used to investigate the tunneling properties and the transmission coefficient of different metal–insulator–metal structures with stacked dielectrics and to compare single- or two-layer high-κ dielectric stacks in terms of tunneling transmission coefficient and local density-of-states. We particularly highlight the influence of wave-function reflections against barrier discontinuity on the transmission coefficient, especially in two-layer high-κ dielectric stacks.     

Synthesis and evaluation of new phosphonated δ-lactam and glutarimide derivatives as angiotensin converting enzyme inhibitors

An efficient synthesis of new γ,δ-insaturated δ-lactam and glutarimide derivatives bearing a phosphonomethyl group from a common allylphosphonate precursor is described. Our approach is based on a two-step procedure involving the preparation of phosphonated-1,5-ketoester and −1,5-diester followed by an amidation–heterocyclization sequence. The first step proceeds via Michael's addition of ethyl acetoacetate and diethyl malonate on an allylphosphonate starting material. The second step consists of a base-promoted intramolecular amidation-cyclization sequence with primary amines, which accounts for the construction of δ-lactams and glutarimide skeletons. We performed the evaluation of angiotensin I-converting enzyme (ACE) inhibition using an in vitro enzyme assay on six new compounds. Five compounds showed potent ACE inhibitory activity, with IC₅₀ values ranging from 0.02 to 0.27 mg/ml. Compared with Captopril, used as a reference drug, two new glutarimide derivatives exhibited higher efficiency ACE inhibition activity.     

High proton conductivity in a flexible, cross-linked, ultramicroporous magnesium tetraphosphonate hybrid framework

Multifunctional materials, especially those combining two or more properties of interest, are attracting immense attention due to their potential applications. MOFs, metal organic frameworks, can be regarded as multifunctional materials if they show another useful property in addition to the adsorption behavior. Here, we report a new multifunctional light hybrid, MgH(6)ODTMP·2H(2)O(DMF)(0.5) (1), which has been synthesized using the tetraphosphonic acid H(8)ODTMP, octamethylenediamine-N,N,N',N'-tetrakis(methylenephosphonic acid), by high-throughput methodology. Its crystal structure, solved by Patterson-function direct methods from synchrotron powder X-ray diffraction, was characterized by a 3D pillared open framework containing cross-linked 1D channels filled with water and DMF. Upon H(2)O and DMF removal and subsequent rehydration, MgH(6)ODTMP·2H(2)O (2) and MgH(6)ODTMP·6H(2)O (3) can be formed. These processes take place through crystalline-quasi-amorphous-crystalline transformations, during which the integrity of the framework is maintained. A water adsorption study, at constant temperature, showed that this magnesium tetraphosphonate hybrid reversibly equilibrates its lattice water content as a function of the water partial pressure. Combination of the structural study and gas adsorption characterization (N(2), CO(2), and CH(4)) indicates an ultramicroporous framework. High-pressure CO(2) adsorption data are also reported. Finally, impedance data indicates that 3 has high proton conductivity σ = 1.6 × 10(-3) S cm(-1) at T = 292 K at ~100% relative humidity with an activation energy of 0.31 eV.     

Functional polysiloxanes. I. Microstructure of poly(hydrogenmethylsiloxane‐co‐dimethylsiloxane)s obtained by cationic copolymerization

Poly(hydrogenmethylsiloxane‐co‐dimethylsiloxane)s of various compositions have been prepared by cationic ring‐opening polymerization of octamethylcyclotetrasiloxane (D₄) and 1,3,5,7‐tetramethylcyclotetrasiloxane (D) in the presence of hexamethyldisiloxane as end‐blocker or by rearrangement of poly(hydrogenmethylsiloxane) in the presence of D₄. These copolymers were examined by high resolution ¹H NMR (500.13 MHz) and ²⁹Si NMR (99.37 MHz) spectroscopies. Triad effects were observed by ¹H and up to heptad effects by ²⁹Si NMR. The chemical shifts were assigned for these stereosequences. The intensities of the triad signals were used to calculate the quantitative parameters describing the microstructure of the copolymer chains: number‐average block length (L̄) and persistence ratio (η). The values of these parameters for copolymers prepared in various experimental conditions show that the time necessary for redistribution reactions (backbiting) is much larger than the time required to establish the equilibrium between linear polymer and cyclic oligomers. However, redistribution is fast enough to prevent the formation of block copolymers even in the case of the rearrangement of poly(hydrogenmethylsiloxane) in the presence of D₄. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 826–836, 2000     

Synthese et reactivite d'organomagnesiens perfluores. V.[1] Synthese et identification de nouveaux composes perfluoroalkyles du mercure a chaine longue.

The reaction of mercuric salts HgY₂ or organic mercuric compounds R_HHgX with long chain perfluorinated Grignard reagents R_FMgBr leads to a series of new perfluoroalkyl mercury derivatives with the general formula R_FHgZ (R_F=C₄F₉, C₆F₁₃, C₈F₁₇ ; Z=R_F,R_H,Y with Y = I,Br,Cl, NO₃,OCOCH₃,OCOCF₃).The synthesis of these organomercuric compounds is described, and their spectroscopic properties are reported.     

Control of the evolution of iron peroxide intermediate in superoxide reductase from Desulfoarculus baarsii. Involvement of lysine 48 in protonation

Superoxide reductase is a nonheme iron metalloenzyme that detoxifies superoxide anion radicals O(2)(?-) in some microorganisms. Its catalytic mechanism was previously proposed to involve a single ferric iron (hydro)peroxo intermediate, which is protonated to form the reaction product H(2)O(2). Here, we show by pulse radiolysis that the mutation of the well-conserved lysine 48 into isoleucine in the SOR from Desulfoarculus baarsii dramatically affects its reaction with O(2)(?-). Although the first reaction intermediate and its decay are not affected by the mutation, H(2)O(2) is no longer the reaction product. In addition, in contrast to the wild-type SOR, the lysine mutant catalyzes a two-electron oxidation of an olefin into epoxide in the presence of H(2)O(2), suggesting the formation of iron-oxo intermediate species in this mutant. In agreement with the recent X-ray structures of the peroxide intermediates trapped in a SOR crystal, these data support the involvement of lysine 48 in the specific protonation of the proximal oxygen of the peroxide intermediate to generate H(2)O(2), thus avoiding formation of iron-oxo species, as is observed in cytochrome P450. In addition, we proposed that the first reaction intermediate observed by pulse radiolysis is a ferrous-iron superoxo species, in agreement with TD-DFT calculations of the absorption spectrum of this intermediate. A new reaction scheme for the catalytical mechanism of SOR with O(2)(?-) is presented in which ferrous iron-superoxo and ferric hydroperoxide species are reaction intermediates, and the lysine 48 plays a key role in the control of the evolution of iron peroxide intermediate to form H(2)O(2).