Iminopropadienethiones, Ar=N=C=C=C=S

Aryliminopropadienethiones 9 have been generated by flash vacuum thermolysis of isoxazolones of the type 5 and characterized by mass spectrometry and matrix isolation IR spectroscopy in conjunction with DFT calculations and chemical trapping.     

Organic synthesis in water: 1,3-dipolar cycloaddition reactions at ambient temperature with aqueous suspensions of solid reactants

Huisgen cycloaddition reactions of the insoluble yellow solid, phthalazinium dicyanomethanide occurred readily for vigorously stirred aqueous suspensions when the solid dipolarophile had solubility >ca. 10⁻³ mol L⁻¹. For a solubility of ca. 10⁻⁴ mol L⁻¹, liquefaction of the dipolarophile was necessary in order to achieve reactions.     

A DIAGONAL SPLIT-CELL MODEL FOR THE OVERLAPPING YEE FDTD METHOD

In this paper, we present a nonorthogonal overlapping Yee method for solv- ing Maxwell＇s equations using the diagonal split-cell model. When material interface is presented, the diagonal split-cell model does not require permittivity averaging so that better accuracy can be achieved. Our numerical results on optical force computation show that the standard FDTD method converges linearly, while the proposed method achieves quadratic convergence and better accuracy.     

Dynamic spatial replenishment of femtosecond pulses propagating in air

We present numerical simulations of nonlinear pulse propagation in air whereby an initial pulse is formed, absorbed by plasma generation, and subsequently replenished by power from the trailing edge of the pulse. This process can occur more than once for high-power input pulses and produce the illusion of long-distance propagation of one self-guided pulse.     

Electromagnetic shocks on the optical cycle of ultrashort pulses in triple-resonance Lorentz dielectric media with subfemtosecond nonlinear electronic Debye relaxation

The dynamical evolution of an intense ultrashort sub-10-fs two-cycle optical pulse is considered as it propagates through a transparent third-order dielectric medium characterized by three resonance lines and a finite sub-fs relaxation time of the electronic nonlinearity. Numerical integration of the full Maxwell's equations incorporating triple-resonance Lorentz linear dispersion and Debye nonlinear dispersion, for a linearly polarized electromagnetic pulse centered at lambda(0)=1.24 microm in the normal dispersion region near the zero dispersion wavelength, shows the formation of shocks occurring on the optical cycle due to the generation of optical harmonics. The finite relaxation time of the nonlinear electronic response (sub-fs time scale) (i) slows down the steepening rate of the optical cycle; (ii) does not limit the generation of strongly phase matched optical harmonics, and consequently the development of infinitely sharp edges on the optical cycle producing its breaking when linear dispersion is not included; (iii) reduces the production of phase matched harmonics and consequently the sharpening of the jumps when dispersion is present, compared to the case of an instantaneous nonlinear response; and (iv) reduces the harmonic spectrum spreading and modulation at later times on the appearance of self-steepening of the electric field envelope.     

Mediation of metal chelation in cysteine-derived tetramate systems

A study of bicyclic tetramates modified with a bulky ester, which leads to steric hindrance of distal chelating atoms as a route for the alteration of metal binding ability is reported. This approach required the development of a direct method for the synthesis of different esters of cysteine from cystine, which then provided access to bicyclic tetramates by Dieckmann cyclisation. Further derivation to ketones and carboxamides by Grignard addition and transamination reactions respectively provided rapid access to a chemical library of tetramates with diverse substitution. Of interest is that bicyclic tetramate ketones and carboxamides showed different tautomeric and metal binding behaviour in solution. Significantly, in both systems, the incorporation of bulky C-5 esters at the bridging position not only reduced metal binding, but also enhanced antibacterial potencies against Gram-positive MRSA bacteria. Those tetramates with antibacterial activity which was not metal dependent showed physiochemical properties of MSA of 559–737 Ų, MW of 427–577 Da, clogP of 1.8–6.1, clogD_7.4 of −1.7 to 3.7, PSA of 83–109 Ų and relative PSA of 12–15% and were generally Lipinski rule compliant. A subset of tetramates exhibited good selectivity towards prokaryotic bacterial cells. Given that the work reported herein is synthesis-led, without the underpinning detailed mechanistic understanding of biological/biochemical mechanism, that the most active compounds occupy a small region of chemical space as defined by MW, clogP, PSA and %PSA is of interest. Overall, the bicyclic tetramate template is a promising structural motif for the development of novel antibacterial drugs, with good anti-MRSA potencies and appropriate drug-like physiochemical properties, coupled with a potential for multi-targeting mechanisms and low eukaryotic cytotoxicity.

A study of bicyclic tetramates modified with a bulky ester, which leads to steric hindrance of distal chelating atoms, is used as a route for the alteration of metal binding ability.     

Simulation of femtosecond pulse propagation in sub-micron diameter tapered fibers

Ultrashort pulse propagation and supercontinuum generation in tapered and microstructured optical fibers is usually simulated using the corrected nonlinear Schrödinger equation. One of the underlying approximations is the use of a wavelength-independent effective area or, equivalently, of a constant nonlinear coefficient . In very thin waveguide structures with strong light confinement, including silica wires and sub-micron tapered fibers and some microstructured fibers, the validity of such an approximation comes into question. In this paper we present an improved model in which all modal properties are fully taken into account as functions of the wavelength. We use comparative numerical simulation to identify certain regimes in which an improved model is needed for quantitatively correct results. PACS 02.70.Hm; 02.60.Cb; 42.65.Wi; 42.65.Re; 42.81.Pp     

Excitatory amino acids

Recent developments in the understanding of the molecular function of memory and other CNS-mediated processes have arisen from the multidisciplinary interplay of excitatory amino acid synthesis and medicinal chemistry, X-ray crystallographic structural protein analysis, molecular biology, pharmacology and physiology. This review seeks to place recent synthetic developments of EAA analogues in the wider pharmacological setting, illustrating the need for and importance of these compounds.     

Substituted diaryldiazomethanes and diazofluorenes: structure, reactivity and stability

The synthesis of several substituted diaryldiazomethanes and diazofluorenes, and an assessment of their structure, reactivity and stability, is reported.