Rapid Assembly of Functionalised Spirocyclic Indolines by Palladium‐Catalysed Dearomatising Diallylation of Indoles with Allyl Acetate

Herein, we report the application of allyl acetate to the palladium‐catalysed dearomatising diallylation of indoles. The reaction can be carried out by using a readily available palladium catalyst at room temperature, and can be applied to a wide range of substituted indoles to provide access to the corresponding 3,3‐diallylindolinines. These compounds are versatile synthetic intermediates that readily undergo Ugi reactions or proline‐catalysed asymmetric Mannich reactions. Alternatively, acylation of the 3,3‐diallylindolinines with an acid chloride or a chloroformate, followed by treatment with aluminium chloride, enables 2,3‐diallylindoles to be prepared. By using ring‐closing metathesis, functionalised spirocyclic indoline scaffolds can be accessed from the Ugi products, and a dihydrocarbazole can be prepared from the corresponding 2,3‐diallylindole.     

Currents and Super-Operator Product Expansionsof N = 4 Super-W Algebra

The currents and the super-operators product expansions of theN = 4 super-Walgebra are obtained. The generators of this extended conformal algebra consistof the stress-tensor superfield J and the primary superfields _±v ^q of integer orhalf-integer conformal weight and Cartan–Weylcharge q. The algorithm forderiving the N = 4 super-W algebra is given for particular cases. Explicit formsof the operator product algebra for different values of are given.     

Scatter Search and Genetic Algorithms for MAX-SAT Problems

In this paper, both scatter search (SS) and genetic algorithms (GAs) are studied for the NP-Hard optimization variant of the satisfiability problem, namely MAX-SAT. First, we investigate a new selection strategy based on both fitness and diversity to choose individuals to participate in the reproduction phase of a genetic algorithm. The resulting algorithm is enhanced in two ways leading to two genetic algorithm variants: the first one uses a uniform crossover. The second one uses a specific crossover operator (to MAX-SAT). The crossover operator is combined with an improved stochastic local search (SLS). The crossover operator is used to identify promising regions while the stochastic local search performs an intensified search of solutions around these regions. Secondly, we propose a scatter search variant for MAX-SAT. Both the SS and the GAs implementations share the solution selection strategy, the improved SLS method and the combination operator. Experiments on several instances from MAX-SAT libraries are performed to show and compare the effectiveness of our approaches. The computational experiments show that both (SS) and (GAs) with a stochastic local search (SLS) improvement technique outperform a classical genetic algorithm (without SLS). The two metaheuristics are able of balancing search diversification and intensification which leads to good results. In general, the specific genetic algorithm with a (SLS) improvement technique and a specific combination method provides competitive results and finds solutions of a higher quality than a scatter search.     

Critical microphase properties of crosslinked polymer blends with quenched random impurities

We extend published works dealing with microphase separation in crosslinked polymer blends to the case where these are surrounded by random impurities. To study their influence on critical microphase properties, from a static and kinetics point of view, we first assume that the (real) disorder caused by impurities is quenched. Second, the replica theory is used to study such critical properties, upon the impurities concentration and their interaction strength. More precisely, we compute the spinodal temperature and structure factor. We find that the spinodal temperature is shifted towards its lower and higher values, for attractive and repulsive impurities, respectively. The obtained expression for the static structure factor suggests that, contrarily to repulsive impurities, the crosslinked mixture scatters better in the presence of attractive ones. Thereafter, the study is extended to kinetics of microphase separation, when the mixture is impregnated by small random impurities. Kinetics is investigated through the growth rate, and in particular, we demonstrate that the latter is increased by the presence of repulsive impurities. This is natural, since these play a stabilizer role. Finally, the discussion is extended to crosslinked polymer blends immersed in a good solvent, which induces drastic changes of the critical microphase properties.     

Field-theoretical Renormalization-Group approach to critical dynamics of crosslinked polymer blends

We consider a crosslinked polymer blend that may undergo a microphase separation. When the temperature is changed from an initial value towards a final one very close to the spinodal point, the mixture is out equilibrium. The aim is the study of dynamics at a given time t, before the system reaches its final equilibrium state. The dynamics is investigated through the structure factor, S(q, t), which is a function of the wave vector q, temperature T, time t, and reticulation dose D. To determine the phase behavior of this dynamic structure factor, we start from a generalized Langevin equation (model C) solved by the time composition fluctuation. Beside the standard de Gennes Hamiltonian, this equation incorporates a Gaussian local noise, ζ. First, by averaging over ζ, we get an effective Hamiltonian. Second, we renormalize this dynamic field theory and write a Renormalization-Group equation for the dynamic structure factor. Third, solving this equation yields the behavior of S(q, t), in space of relevant parameters. As result, S(q, t) depends on three kinds of lengths, which are the wavelength q ⁻¹, a time length scale R(t) ∼ t ^1/z , and the mesh size ξ ^*. The scale R(t) is interpreted as the size of growing microdomains at time t. When R(t) becomes of the order of ξ ^*, the dynamics is stopped. The final time, t ^*, then scales as t ^* ∼ ξ ^{* z}, with the dynamic exponent z = 6−η. Here, η is the usual Ising critical exponent. Since the final size of microdomains ξ ^* is very small (few nanometers), the dynamics is of short time. Finally, all these results we obtained from renormalization theory are compared to those we stated in some recent work using a scaling argument.     

Tobramycin and Nebramine as Pseudo‐oligosaccharide Scaffolds for the Development of Antimicrobial Cationic Amphiphiles

Antimicrobial cationic amphiphiles derived from aminoglycoside pseudo‐oligosaccharide antibiotics interfere with the structure and function of bacterial membranes and offer a promising direction for the development of novel antibiotics. Herein, we report the design and synthesis of cationic amphiphiles derived from the pseudo‐trisaccharide aminoglycoside tobramycin and its pseudo‐disaccharide segment nebramine. Antimicrobial activity, membrane selectivity, mode of action, and structure–activity relationships were studied. Several cationic amphiphiles showed marked antimicrobial activity, and one amphiphilic nebramine derivative proved effective against all of the tested strains of bacteria; furthermore, against several of the tested strains, this compound was well over an order of magnitude more potent than the parent antibiotic tobramycin, the membrane‐targeting antimicrobial peptide mixture gramicidin D, and the cationic lipopeptide polymyxin B, which are in clinical use.     

Antifungal Imidazole‐Decorated Cationic Amphiphiles with Markedly Low Hemolytic Activity

Herein we report that an imidazole‐decorated cationic amphiphile derived from the pseudo‐disaccharide nebramine has potent antifungal activity against strains of Candida glabrata pathogens. In combination with the natural bis‐benzylisoquinoline alkaloid tetrandrine the reported antifungal cationic amphiphile demonstrated synergistic antifungal activity against Candida albicans pathogens. This unique membrane disruptor caused no detectible mammalian red blood cell hemolysis at concentrations up to more than two orders of magnitude greater than its minimal inhibitory concentrations against the tested C. glabrata strains. We provide evidence that potency against C. glabrata may be associated with differences between the drug efflux pumps of C. albicans and C. glabrata. Imidazole decorated‐cationic amphiphiles show promise for the development of less toxic membrane‐disrupting antifungal drugs and drug combinations.     

Transient effects of orthogonal pipe oscillations on laminar developing incompressible flow

This paper presents a numerical study of the transient developing laminar flow of a Newtonian incompressible fluid in a straight horizontal pipe oscillating around the vertical diameter at its entrance. The flow field is influenced by the tangential and Coriolis forces, which depend on the through‐flow Reynolds number, the oscillation Reynolds number and the angular amplitude of the pipe oscillation. The impulsive start of the latter generates a transient pulsating flow, whose duration increases with axial distance. In any cross‐section, this flow consists of a pair of symmetrical counter‐rotating vortices, which are alternatively clockwise and anti‐clockwise. The circumferentially averaged friction factor and the axial pressure gradient fluctuate with time and are always larger than the corresponding values for a stationary pipe. On the other hand, local axial velocities and local wall shear stress can be smaller than the corresponding stationary pipe values during some part of the pipe oscillation. The fluctuation amplitude of these local variables increases with axial distance and can be as high as 50% of the corresponding stationary pipe value, even at short distances from the pipe entrance. Eventually, the flow field reaches a periodic regime that depends only on the axial position. The results show that the transient flow field depends on the pipe oscillation pattern (initial position and/or direction of initial movement). Copyright © 2000 John Wiley & Sons, Ltd.     

Interaction force between incompatible star-polymers in dilute solution

We consider a low-density assembly of spherical colloids, such that each is clothed by L end-grafted chemically incompatible polymer chains either of types A or B. These are assumed to be dissolved in a good common solvent. We assume that colloids are of small size to be considered as star-polymers. Two adjacent star-polymers A and B interact through a force F originating from both excluded-volume effects and chemical mismatch between unlike monomers. Using a method developed by Witten and Pincus (Macromolecules 19, 2509 (1986)) in the context of star-polymers of the same chemical nature, we determine exactly the force F as a function of the center-to-center distance h. We find that this force is the sum of two contributions F _e and F _s. The former, that results from the excluded volume, decays as F _e∼A _L h ^-1, with the L -dependent universal amplitude A _L∼L ^3/2. While the second, which comes from the chemical mismatch, decays more slowly as F _s∼χB _L h ^{-1 - τ}, where τ is a critical exponent whose value is found to be τ 0.40, and χ is the standard Flory interaction parameter. We find that the corresponding L-dependent universal amplitude is B _L∼L ^{3 + τ /2}. Theses forces are comparable near the cores of two adjacent star-polymers, i.e. for h∼h _c∼a (a is the monomer size). Finally, for two star-polymers of the same chemical nature (A or B), the force F that simply results from excluded-volume effects coincides exactly with F _e, and then the known result is recovered. Received 2 October 2000 and Received in final form 24 January 2001     

Determination of the amplitude of the repulsive-pair potential between particles clothed by end-grafted polymers

 We examine the problem of the determination of the repulsive potential between spherical particles clothed by long end-grafted flexible polymers. This potential varying with the distance according to a logarithmic law has a potential amplitude that depends on the number, L, of grafting chains per particle. The purpose of this work is to compute such a potential amplitude. The clothed particles are first regarded as star polymers with small enough diameter and the same number of arms. Then, the amplitude potential is identified to the critical exponent related to the contact probability between cores of these stars, which allows us to find a universal function for the expected potential amplitude depending on L and d-space dimension only. In two-dimensional space, conformal invariance is used to extract the potential amplitude as a function of L. For dimensions greater than 2, the potential amplitude is obtained within the framework of renormalization theory to third order in ɛ=4 − d, where d is the critical dimension of the system. To determine the best three-dimensional expression for the potential amplitude, A _L , use is made of the Padé–Borel transformation, which provides a closer form valid for small, intermediate and high values of L. This form of potential amplitude, consistent with the exact scaling asymptotic value of Witten and Pincus [(1986) Macromolecules 19:2509], allows us to find the associated prefactor. The procedure is also extended to interacting stars of different numbers of arms. Received: 4 October 1999 Accepted: 2 January 2001