Synthesis of novel dispiro-oxindoles via 1,3-dipolar cycloaddition reactions of azomethine ylides

The 1,3-dipolar cycloaddition of 1-allyl-5-haloisatin derivatives as dipolarophiles with the azomethine ylides generated in situ from N-allylisatin and l-proline to furnish novel dispiro-oxindoles has been investigated. The structures and relative stereochemistry of both types of cycloadducts were confirmed by single crystal X-ray diffraction, ¹H and ¹³C NMR spectroscopy and mass spectrometry.     

A search for kinase inhibitors and antibacterial agents: bromopyrrolo-2-aminoimidazoles from a deep-water Great Australian Bight sponge, Axinella sp.

Biological screening of a deep-water Great Australian Bight marine sponge, Axinella sp., detected inhibition against the neurodegenerative disease kinase targets CDK5/p25, CK1δ, and GSK3β, as well as significant levels of antibacterial activity. Chemical fractionation returned 18 secondary metabolites identified by detailed spectroscopic analysis as three new bromopyrrolo-2-aminoimidazoles, 14-O-sulfate massadine (1), 14-O-methyl massadine (2), and 3-O-methyl massadine chloride (3), together with the known metabolites massadine chloride (4), massadine (5), stylissadine B (6), axinellamines A-C (7-9), hymenin (10), stevensine (also known as odiline) (11), tauroacidin A (12), hymenidin (13), taurodispacamide A (14), oroidin (15), debromohymenialdisine (16), hymenialdisine (17), and aldisin (18). Armed with this focused natural product chemical diversity library, we re-established that 16 and 17 were nM kinase inhibitors, and determined that 3, 6, and 12-15 were sub μM antibacterials.     

Antimicrobial agents as photostabilizers for rigid poly(vinyl chloride)

Some amide derivatives of ethylene glycol‐bis(2‐aminoethylether)‐N,N,N^′,N^′‐tetraacetic acid (EGTA) have been prepared via their coupling with different aniline derivatives: amino, methyl, chloro, and hydroxy aniline. The EGTA amide derivatives were characterized, and their antimicrobial activities were evaluated. These antimicrobial agents have been investigated as photostabilizers for rigid poly(vinyl chloride) (PVC), suspension PVC, with a K value of 70. Their stabilizing efficiencies were evaluated by determining the percentage of weight loss, the intrinsic viscosities, as well as the amount of formed gel of the photodegraded PVC. The extent of discoloration and the change in the mechanical properties of the photodegraded polymer were also evaluated. The applied materials reduced the loss in weight that resulted from HCl evolution during photodegradation. Both viscosity and gel content measurements showed also a decrease in their values during the degradation process. The decrease in the percentage of gel formation upon applying the investigated photostabilizers reflects the lowering in extent of cross‐linking of the polymer, which implies preserving the mechanical properties of PVC. The extent of discoloration was also improved in the presence of the investigated compounds. The results have proved a greater stabilizing efficiencies of the antimicrobial EGTA amide derivatives than that of the phenyl salicylate ultraviolet (UV) absorber, which is commonly used as an industrial stabilizer. A radical mechanism was proposed to account for the stabilizing action of the investigated products. Copyright © 2011 John Wiley & Sons, Ltd.     

Communication: Probing non-equilibrium vibrational relaxation pathways of highly excited C≡N stretching modes following ultrafast back-electron transfer

Fifth-order nonlinear visible-infrared spectroscopy is used to probe coherent and incoherent vibrational energy relaxation dynamics of highly excited vibrational modes indirectly populated via ultrafast photoinduced back-electron transfer in a trinuclear cyano-bridged mixed-valence complex. The flow of excess energy deposited into four C≡N stretching (ν(CN)) modes of the molecule is monitored by performing an IR pump-probe experiment as a function of the photochemical reaction (τ(vis)). Our results provide experimental evidence that the nuclear motions of the molecule are both coherently and incoherently coupled to the electronic charge transfer process. We observe that intramolecular vibrational relaxation dynamics among the highly excited ν(CN) modes change significantly en route to equilibrium. The experiment also measures a 7 cm(-1) shift in the frequency of a ～57 cm(-1) oscillation reflecting a modulation of the coupling between the probed high-frequency ν(CN) modes for τ(vis) < 500 fs.     

The drag exerted by an oblate rotating atmosphere on an artificial satellite

A theory is formulated for the motion of an artificial satellite under the joint effects of Earth oblateness and atmospheric drag. The Hamilton ' s equations of motion are derived including the zonal harmonics of the geopotential up to J4 and the drag accelerations. The atmospheric model is an oblate rotating model in which the atmospheric rotation lags behind that of the Earth as the increasing distance from the Earth. The drag free problem is first solved via two canonical transformations to eliminate in succession the short and long period terms. An operator D is then defined and used to formulate the drag acceleration in terms of the double primed variables expressing the solution of the drag-free problem.     

Statistical and Mathematical Investigations for Determining the Binding Constants of Micelle with Reactants Molecules from Kinetic Data

Binding constants between reactants molecules with micelles are considered to be important parameters particularly in micellar catalysis area. Recently, we developed a statistical method based on multiple linear regression for determining those parameters from kinetic data (Phys. Chem. Liq. 2008, 46, 34–46). In the present work, we derived further two statistical equations from the same original equation using also multiple linear regression method. A substantial difference has been found between the results of those equations and with that of the recently published one. This strongly indicates that the statistical procedures are not valid for such a purpose, that is, the available statistical and graphical methods in the literature are also not suitable for such treatment. A mathematical procedure using iterative method for evaluating the binding constants is introduced. An equation for such treatment has also been derived from the same original equation, and a computer program for this purpose has been written. Application of the developed method to the kinetic data has been found to be quite successful. It has been concluded that the presented mathematical method is simple, reliable, and accurate.     

Nonlinear instability of charged liquid jets: Effect of interfacial charge relaxation

A linear and nonlinear study has been made of cylindrical interface, carrying a uniform surface charge in the presence of a finite rate of charge relaxation, is investigated by using multiple scales method. The linear stability flow is analyzed by deriving a dispersion relation for the growth waves, and solving it analytically and numerically to find marginal stability curves. We investigate the electric charge relaxation effects on the stability of the flow by considering various limiting cases. We also examine the effects of finite charge relaxation times in axisymmetric and nonaxisymmetric modes. In the nonlinear approach, it is shown that the evolution of the amplitude is governed by a Ginzburg–Landau equation. There is also obtained a nonlinear modified Schrödinger equation describing the evolution of wave packets for small charge relaxation time. Further, the classic Schrödinger equation is obtained when the influence of relaxation time charge is neglected. On the other hand, the complex amplitude of quasi-monochromatic standing waves near the cutoff wavenumber is governed by a similarly type of nonlinear Schrödinger equation in which the roles of time and space are interchanged. This equation makes it possible to estimate the nonlinear effect on the cutoff wavenumber. The nonlinear theory, when used to investigate the stability of charged liquid jet, appears accurately to predict a new unstable regions. The effects of the surface charge and charge relaxation on the stability are identified. The various stability criteria are discussed both analytically and numerically and the stability diagrams are obtained.     

Existence results for some partial functional differential equations with state-dependent delay

In this paper, we establish sufficient conditions for the existence of solutions for some partial functional differential equations with state-dependent delay; we assume that the linear part is not necessarily densely defined and satisfies the well-known Hille–Yosida conditions. Our approach is based on a nonlinear alternative of Leray–Schauder type and integrated semigroup theory. An application is provided to a reaction–diffusion equation with state-dependent delay.     

Additional stringy sources for electric dipole moments

We show that string models with low energy supersymmetry which accommodate the fermion mass hierarchy generally give nonuniversal soft trilinear couplings (A terms). In conjunction with the apparently large Cabibbo-Kobayashi-Maskawa (CKM) phase, this results in large fermion electric dipole moments (EDMs) even in the absence of CP violating phases in the supersymmetry breaking auxiliary fields and the micro term. Nonobservation of the EDMs therefore implies that strings select special flavor and/or supersymmetry breaking patterns.