Anion relay chemistry: an effective tactic for diversity oriented synthesis

An effective one-flask multicomponent linchpin coupling protocol employing the concept of anion relay chemistry (ARC) was developed. This concept calls for addition of an anion (5) to an epoxide (6), bearing on a distal carbon a trialkyl silyl group and an anion stabilizing group (ASG), to furnish upon epoxide ring opening oxyanion 7. Addition of HMPA or other polar solvents to trigger a solvent controlled 1,4-Brook rearrangement then leads to a new distal anion (8), which in turn is available to react with a variety of second electrophiles.     

Bright‐Dark Rogue Waves

During the last two decades, revealing mechanisms of origin waves with anomalous amplitude (rogue waves) have been in the focus of researchers from different fields ranging from oceanography to laser physics. Mode‐locked lasers, as a test bed system, provide a unique opportunity to collect more data on rogue waves in the form of random pulses (soliton rain) and to clarify the mechanisms of rogue‐wave emergence caused by soliton–soliton and soliton–dispersive wave interactions. Here, for the first time, for an Er‐doped mode‐locked laser, a new type of vector rogue waves is demonstrated experimentally and theoretically, which is driven by desynchronization of the orthogonal linear states of polarization, so leading to output power oscillations in the form of anomalous spikes‐dips (bright‐dark rogue waves). The results can pave the way to unlocking the universal nature of the origin of rogue waves and thus can be of interest to the broad scientific community.     

Multiphase thermoplastic hybrid for controlled release of antimicrobial essential oils in active packaging film

Active packaging, a new technology concept in the field of food packaging, has been introduced in recent years in order to provide quality and safety, as well as extend the shelf life of food products. Antimicrobial (AM) agents can be incorporated directly into the active packaging and migrate in a controlled manner to the headspace between the food and the package, inhibiting bacteria growth on the food surface. Naturally derived AM agent, such as essential oils (EOs), has received considerable attention for food preservation purposes, because of their effective AM activity against various bacteria and fungi. In the present study, AM active film systems based on polypropylene/polyamide blends, montmorillonite nanoclays, and thymol EO were produced to investigate the feasibility of controlling the release rate of thymol from food packaging systems. Selective localization of thymol in a specific phase in the system that derives from thermodynamic affinity was assumed to be useful in controlling its migration rate from the film to the headspace. EO retention in the film under two different time conditions was measured by spectroscopic analysis. The release rate of EO was determined using Gas chromatography technique and analyzed by diffusion model approach. Inhibition of bacterial growth was periodically tested for Listeria and Escherichia coli bacteria. This study confirms the thermodynamic affinity of polyamide phase with thymol that has a positive effect in retaining the EO. Results show controlled AM behavior of the active packaging films, based on various blend compositions. Copyright © 2016 John Wiley & Sons, Ltd.     

On network form and function

Moving from the observation that drainage network configurations minimizing total energy dissipation are stationary solutions of the general equation describing landscape evolution, we review theoretical and observational evidence on river patterns and their scale-invariant structure. Exact results complemented by numerical annealing of the basic equation in the presence of additive noise suggest that configurations at (or very close to) the global minimum of energy dissipation differ from dynamically accessible states, which have rather different scaling properties and conform much better to natural forms. Thus we argue that, at least in the fluvial landscape, Nature works through imperfect searches for dynamically accessible optimal configurations. We also show that optimal networks are spanning loopless configurations only under precise physical requirements. This is stated in a form applicable to generic networks, suggesting that other branching structures occurring in Nature (e.g. scale-free and looping) may possibly arise through optimality to selective pressures. Indeed, we show that this is the case.     

Improved methods for thermal rearrangement of alicyclic α-hydroxyimines to α-aminoketones: synthesis of ketamine analogues as antisepsis candidates

Ketamine is an analgesic/anesthetic drug, which, in combination with other drugs, has been used as anesthetic for over 40 years. Ketamine induces its analgesic activities by blocking the N-methyl-D-aspartate (NMDA) receptor in the central nervous system (CNS). We have reported that low doses of ketamine administrated to patients before incision significantly reduced post-operative inflammation as reflected by reduced interleukin-6 (IL-6) sera-levels. Our data demonstrated in a rat model of Gram-negative bacterial-sepsis that if we inject a low dose of ketamine following bacterial inoculation we reduce mortality from approximately 75% to 25%. Similar to what we have observed in operated patients, the levels of TNF-α and IL-6 in ketamine-treated rats were significantly lower than in septic animals not treated with ketamine. On the base of these results, we have designed and synthesized series of new analogues of ketamine applying a thermal rearrangement of alicyclic α-hydroxyimines to a-aminoketones in parallel arrays. One of the analogues (compound 6e) displayed high activity in down-regulating the levels of IL-6 and TNF-α in vivo as compared to ketamine.     

Scaling, Optimality, and Landscape Evolution

A nonlinear model is studied which describes the evolution of a landscape under the effects of erosion and regeneration by geologic uplift by mean of a simple differential equation. The equation, already in wide use among geomorphologists and in that context obtained phenomenologically, is here derived by reparametrization invariance arguments and exactly solved in dimension d=1. Results of numerical simulations in d=2 show that the model is able to reproduce the critical scaling characterizing landscapes associated with natural river basins. We show that configurations minimizing the rate of energy dissipation (optimal channel networks) are stationary solutions of the equation describing the landscape evolution. Numerical simulations show that a careful annealing of the equation in the presence of additive noise leads to configurations very close to the global minimum of the dissipated energy, characterized by mean field exponents. We further show that if one considers generalized river network configurations in which splitting of the flow (i.e., braiding) and loops are allowed, the minimization of the dissipated energy results in spanning loopless configurations, under the constraints imposed by the continuity equations. This is stated in the form of a general theorem applicable to generic networks, suggesting that other branching structures occurring in nature may possibly arise as optimal structures minimizing a cost function.     

Axial heat conduction effects in the entrance region of circular ducts

This paper describes the transport of thermal energy within a small distance after an abrupt wall temperature change in a circular duct. In general, the axial conduction becomes significant when the Peclet number is small. The results indicate that the inclusion of axial conduction in the fluid substantially increases the wall heat flux at near the thermal inlet location. The exact series solution leads to a modified Graetz type problem. This exact solution is augmented by an asymptotic solution describing the wall heat flux near the thermal entrance location.     

Antimicrobial active packaging combining essential oils mixture: Migration and odor control study

Thymol is an essential oil (EO), known to have excellent antimicrobial (AM) properties and can potentially be used as an active agent in AM food packages. Mixing Thymol with other EOs may help to reduce the organoleptic impact of its strong odor. In the present study, the effect of thymol, carvacrol, citral, and eugenol binary mixtures on the AM activity, migration over time, and sensory properties of polypropylene (PP)/polyamide (PA)/nanoclays composite blends active package (AP) films was examined. The release of different EOs from the polymer film was found to have a direct correlation with the odor perception of thymol. Varied EOs bearing films have shown different capacity to inhibit bacterial growth over time (Escherichia coli). Lastly, the inhibition of fungal growth on food sample using EO‐loaded films was obtained for over 50 days, indicating the potential use of the developed films as active food packaging.     

Radiation from a Charge Supported in a Gravitational Field

We examine whether a charge supported statically in a gravitational field radiates, and find the answer to this question to be positive. Based on our earlier results we find that the important condition for the creation of radiation is the existence of a relative acceleration between the charge and its electric field, where such an acceleration causes the curving of the electric field and the creation of a stress force due to this curvature. This stress force is the reaction force, which creates the radiation. Later we find that this condition do exist for a charge supported statically in a gravitational field, where the electric field of the charge falls in the gravitational field, it curves, and the stress force raised in this curved field, creates electromagnetic radiation.     

Crystal and molecular structure of hydroxyjatrophone C

The structure of the title compound has been established by means of the x-ray diffraction method on a single crystal. The crystals are othorhombic, space groupP2₁2₁2₁ (No. 19) witha=10.222(4),b=10.622(2),c=16.434(3) Å,z=4. Full-matrix least squares refinement led toR=4.9%. The molecular stereochemistry, bond distances, bond angles, torsion angles, and hydrogen bond scheme have all been determined.Camille and Henry Dreyfus Teacher Scholar, 1978–1983; National Institutes of Health (National Cancer Institute) Career Development Award, 1980–1985.