One-pot hydrosilylation-protodesilylation of functionalized diarylalkynes: a highly selective access to Z-stilbenes. Application to the synthesis of combretastatin A-4

An efficient stereoselective synthesis of Z-stilbenes has been developed from diarylalkynes via a new hydrosilylation-protodesilylation process. The scope and limitation of this method is presented to stereoselectively prepare a wide range of (Z)-stilbenes in a one-pot way is presented. A concise application to the preparation of combretastatin A-4 (CA-4), a vascular targeting agent inhibitor of tubulin polymerisation is described.     

Synthesis of racemic nitramine, isonitramine and sibirine

Condensation of enol ether 6 with methyl vinyl ketone led easily to ketoaldehyde 7 whose cyclisation afforded the azaspiranic enone 8, a key intermediate for the synthesis of the title alkaloids.     

Novel Pentaheterocycles. First General Synthesis Entry to Functionalized Derivatives of Pyrido[2,3-f:6,5-f'']di[1,2,4]triazolo[4,3-a] pyrimidin-5(1H)-ones

Summary. Thirteen derivatives of the novel title ring system were synthesized via a two-step procedure that utilizes hydrazonoyl chlorides and pyridodipyrimidinones as starting materials. The mechanism and regiochemistry of the reactions studied are discussed and the compounds prepared were characterized by alternate synthesis, spectra (mass, IR, ¹H and ¹³C NMR), and elemental analyses.     

Alkylation en catalyse par transfert de phase d'une série d'acridanone-9 substituées: Compétition entre O- et N-alkylation

Substituted acridanones were alkylated under phase transfer catalysis conditions. In so doing, a mixture of O- and N-alkyl derivatives was prepared. Orientation of the reaction products depends upon the alkylating agent but not on the position of the substituent. Hence, HSAB principles can explain this orientation.     

Regiocontrol of the palladium-catalyzed tin hydride addition to Z-enynols: remarkable Z-directing effects

Palladium-catalyzed hydrostannation of substituted Z- and E-enynols is discussed and compared. The regioselectivity of the H-Sn bond addition was found to be controlled by the geometry of the double bond (Z- or syn-directing effect) rather than the nature of its substituents. Exclusively alpha-vinyl stannanes were obtained from Z-enynols having various substituents on the double bond regardless of their electronic, steric, or chelating natures.     

On the nature of antimicrobial activity: a model for protegrin-1 pores

We conducted over 150 ns of simulation of a protegrin-1 octamer pore in a lipid bilayer composed of palmitoyloleoyl-phosphatidylethanolamine (POPE) and palmitoyloleoyl-phosphatidylglycerol (POPG) lipids mimicking the inner membrane of a bacterial cell. The simulations improve on a model of a pore proposed from recent NMR experiments and provide a coherent understanding of the molecular mechanism of antimicrobial activity. Although lipids tilt somewhat toward the peptides, the simulated protegrin-1 pore more closely follows the barrel-stave model than the toroidal-pore model. The movement of ions is investigated through the pore. The pore selectively allows negatively charged chloride ions to pass through at an average rate of one ion every two nanoseconds. Only two events are observed of sodium ions crossing through the pore. The potential of mean force is calculated for the water and both ion types. It is determined that the chloride ions move through the pore with ease, similarly to the water molecules with the exception of a zone of restricted movement midway through the pore. In bacteria, ions moving through the pore will compromise the integrity of the transmembrane potential. Without the transmembrane potential as a countermeasure, water will readily flow inside the higher osmolality cytoplasm. We determine that the diffusivity of water through a single PG-1 pore is sufficient to cause fast cell death by osmotic lysis.     

Convergence analysis of some first order and second order time accurate gradient schemes for semilinear second order hyperbolic equations

This work is devoted to the convergence analysis of finite volume schemes for a model of semilinear second order hyperbolic equations. The model includes for instance the so‐called Sine‐Gordon equation which appears for instance in Solid Physics (cf. Fang and Li, Adv Math (China) 42 (2013), 441–457; Liu et al., Numer Methods Partial Differ Equ 31 (2015), 670–690). We are motivated by two works. The first one is Eymard et al. (IMA J Numer Anal 30 (2010), 1009–1043) where a recent class of nonconforming finite volume meshes is introduced. The second one is Eymard et al. (Numer Math 82 (1999), 91–116) where a convergence of a finite volume scheme for semilinear elliptic equations is provided. The mesh considered in Eymard et al. (Numer Math 82 (1999), 91–116) is admissible in the sense of Eymard et al. (Elsevier, Amsterdam, 2000, 723–1020) and a convergence of a family of approximate solutions toward an exact solution when the mesh size tends to zero is proved. This article is also a continuation of our previous two works (Bradji, Numer Methods Partial Differ Equ 29 (2013), 1278–1321; Bradji, Numer Methods Partial Differ Equ 29 (2013), 1–39) which dealt with the convergence analysis of implicit finite volume schemes for the wave equation. We use as discretization in space the generic spatial mesh introduced in Eymard et al. (IMA J Numer Anal 30 (2010), 1009–1043), whereas the discretization in time is performed using a uniform mesh. Two finite volume schemes are derived using the discrete gradient of Eymard et al. (IMA J Numer Anal 30 (2010), 1009–1043). The unknowns of these two schemes are the values at the center of the control volumes, at some internal interfaces, and at the mesh points of the time discretization. The first scheme is inspired from the previous work (Bradji, Numer Methods Partial Differ Equ 29 (2013), 1–39), whereas the second one (in which the discretization in time is performed using a Newmark method) is inspired from the work (Bradji, Numer Methods Partial Differ Equ 29 (2013), 1278–1321). Under the assumption that the mesh size of the time discretization is small, we prove the existence and uniqueness of the discrete solutions. If we assume in addition to this that the exact solution is smooth, we derive and prove three error estimates for each scheme. The first error estimate is concerning an estimate for the error between a discrete gradient of the approximate solution and the gradient of the exact solution whereas the second and the third ones are concerning the estimate for the error between the exact solution and the discrete solution in the discrete seminorm of and in the norm of . The convergence rate is proved to be for the first scheme and for the second scheme, where (resp. k) is the mesh size of the spatial (resp. time) discretization. The existence, uniqueness, and convergence results stated above do not require any relation between k and . The analysis presented in this work is also applicable in the gradient schemes framework. © 2016 Wiley Periodicals, Inc. Numer Methods Partial Differential Eq 33: 5–33, 2017     

Diagnostics of the early stage of the heating of clusters by a femtosecond laser pulse from the spectra of hollow ions

Differences between X-ray argon clusters excited at the laser-cluster and laser-droplet interactions have been analyzed. X-ray spectral methods have been proposed to determine the parameters of the appearing plasma at the early stages of its evolution. It has been shown that the spectra of hollow ions are the most informative in the first moments of the heating of a cluster, whereas the diagnostics of the late stages can be performed using the conventional lines of multicharged ions.     

Continuous laser direct-writing of PbS nanoparticles inside transparent silica monoliths

Direct space-selective growth of PbS nanoparticles, embedded inside a transparent porous sol–gel derived silica matrix, has been achieved using continuous laser irradiation. Before the irradiation, the porous silica host has been soaked in a PbS precursor solution. The effect of the concentration of PbS precursors and of the incident laser power on the mean particle size was studied. Absorption spectroscopy, X-ray diffraction analysis, and TEM measurements were used to identify the PbS crystallites inside the xerogel and to estimate the average particle size. It has been shown that PbS crystallite sizes range between 3 and 13 nm depending on the PbS precursors concentration.     

Robust stability of uncertain piecewise-linear systems: LMI?approach

In this paper we propose sufficient conditions for the robust stability of time-invariant uncertain piecewise-linear systems using homogeneous polynomial Lyapunov functions. The proposed conditions are expressed in terms of linear matrix inequalities, which can be numerically determined. We solve the stabilization of piecewise uncertain linear control systems by using state piecewise-linear feedback. We propose an illustrative example to show the efficiency of the proposed approach.