Two-photon absorption and third-order nonlinear optical characterization of pyrrolo-tetrathiafulvalene derivatives

To provide an insight into the third-order nonlinear optical (NLO) behaviour of a series of tetrathiafulvalene (TTF)-based molecules, the third-order NLO properties and two-photon absorption characterizations have been theoretically investigated by means of the time-dependent Hartree–Fock method. According to ab-initio calculation results, the examined molecules exhibit second hyperpolarizabilities $(\gamma )$ with non-zero values, implying microscopic third-order optical nonlinearity. Our computed results are also in good agreement with the previous experimental observations on the title compounds.     

Spatially confined redox chemistry in periodic mesoporous hydridosilica-nanosilver grown in reducing nanopores

Periodic mesoporous hydridosilica, PMHS, is shown for the first time to function as both a host and a mild reducing agent toward noble metal ions. In this archetypical study, PMHS microspheres react with aqueous Ag(I) solutions to form Ag(0) nanoparticles housed in different pore locations of the mesostructure. The dominant reductive nucleation and growth process involves SiH groups located within the pore walls and yields molecular scale Ag(0) nanoclusters trapped and stabilized in the pore walls of the PMHS microspheres that emit orange-red photoluminescence. Lesser processes initiated with pore surface SiH groups produce some larger spherical and worm-shaped Ag(0) nanoparticles within the pore voids and on the outer surfaces of the PMHS microspheres. The intrinsic reducing power demonstrated in this work for the pore walls of PMHS speaks well for a new genre of chemistry that benefits from the mesoscopic confinement of Si-H groups.     

C labelled internal standards-A solution to minimize ion suppression effects in liquid chromatography–tandem mass spectrometry analyses of drugs in biological samples?

Liquid chromatography-tandem mass spectrometry (LC-MS/MS) is frequently used to identify and quantify drugs in human biological samples due to the high selectivity and sensitivity of this technique. However, ion suppression effects caused by co-eluting compounds: drugs, metabolites, matrix components, impurities and degradation products, are a major concern. Stable isotope labelled internal standards (SIL ISs), usually deuterium ((2)H) labelled, are often used to compensate for these effects. In many LC separations the retention times of (2)H labelled ISs and their analogues will differ. Ultra performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS) is increasingly being used for bio-analysis. With the better chromatographic resolution provided with sub 2 μm particles, larger separation between analytes and their (2)H labelled analogues can be expected, which might reduce the benefits of the SIL IS. There is a greater difference in physico-chemical properties between hydrogen isotopes than between isotopes of other elements. (13)C, (15)N and (18)O labelled ISs are more similar to their analytes than (2)H labelled ISs and thereby expected to behave more similarly in chromatographic separations. In this study we have investigated the use of (13)C and (2)H labelled ISs for the determination of amphetamine and methamphetamine by UPLC-MS/MS. The (13)C labelled ISs were co eluting with their analytes under different chromatographic conditions while the (2)H labelled ISs and their analytes were slightly separated. An improved ability to compensate for ion suppression effects were observed when the (13)C labelled ISs were used. Furthermore, an UPLC-MS/MS method for determination of amphetamine and methamphetamine in urine using (13)C labelled ISs has been developed and validated. Unfortunately, there are few (13)C labelled ISs commercial available today. If more (13)C labelled ISs become commercial available they may well be the coming solution to minimize ion suppression/enhancement effects in LC-MS/MS analyses of drugs in biological samples.     

Electron spin resonance studies of anisotropy in semiconducting polymeric films

X‐band electron spin resonance was employed to study the structural anisotropy in several polythiophene derivatives. Because of the dominating homogeneous width, the obtained absorption spectra were Lorentzian‐shaped. Information about the structural anisotropy was obtained from the position and width of the absorption peak. Qualitatively, the anisotropy was in full agreement with earlier results from X‐ray diffraction, including a flip in molecular orientation with respect to the film substrate between solution‐cast and spin‐cast films. With the Monte Carlo technique, the spectra were fitted with a biaxial g tensor, an anisotropy parameter S, and an intrinsic width σ. The simulations showed that g could be treated as pseudo‐uniaxial, with the unique axis along the side chains rather than along the ring normal. Closed‐form analytical expressions relating g to the anisotropy were obtained and used for a quantitative assessment of the molecular anisotropy. Because the molecular g tensor for these materials was not known, a known value of S for one of the samples obtained by X‐ray diffraction was used for normalization. Fairly consistent values were obtained for both g and S. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 3011–3025, 2003     

Continuity, proof systems and the theory of transfinite computations

 We use the theory of domains with totality to construct some logics generalizing ω-logic and β-logic and we prove a completenes theorem for these logics. The key application is E-logic, the logic related to the functional ³ E. We prove a compactness theorem for sets of sentences semicomputable in ³ E. Received: 21 January 1998 / Published online: 2 September 2002     

Total objects in inductively defined types

Coherence-spaces and domains with totality are used to give interpretations of inductively defined types. A category of coherence spaces with totality is defined and the closure of positive inductive type constructors is analysed within this category. Type streams are introduced as a generalisation of types defined by strictly positive inductive definition. A semantical analysis of type streams with continuous recursion theorems is established. A hierarchy of domains with totality defined by positive induction is defined, and density for a sub-hierarchy is proved. Received March 27, 1995     

Wave simulations of Gray‐Scott reaction‐diffusion system

In this work, we study the numerical simulation of the one‐dimensional reaction‐diffusion system known as the Gray‐Scott model. This model is responsible for the spatial pattern formation, which we often meet in nature as the result of some chemical reactions. We have used the trigonometric quartic B‐spline (T4B) functions for space discretization with the Crank‐Nicolson method for time integration to integrate the nonlinear reaction‐diffusion equation into a system of algebraic equations. The solutions of the Gray‐Scott model are presented with different wave simulations. Test problems are chosen from the literature to illustrate the stationary waves, pulse‐splitting waves, and self‐replicating waves.     

Three‐dimensional internal gravity‐capillary waves in finite depth

We consider three‐dimensional inviscid‐irrotational flow in a two‐layer fluid under the effects of gravity and surface tension, where the upper fluid is bounded above by a rigid lid and the lower fluid is bounded below by a flat bottom. We use a spatial dynamics approach and formulate the steady Euler equations as an infinite‐dimensional Hamiltonian system, where an unbounded spatial direction x is considered as a time‐like coordinate. In addition, we consider wave motions that are periodic in another direction z. By analyzing the dispersion relation, we detect several bifurcation scenarios, two of which we study further: a type of 00(is)(iκ₀) resonance and a Hamiltonian Hopf bifurcation. The bifurcations are investigated by performing a center‐manifold reduction, which yields a finite‐dimensional Hamiltonian system. For this finite‐dimensional system, we establish the existence of periodic and homoclinic orbits, which correspond to, respectively, doubly periodic travelling waves and oblique travelling waves with a dark or bright solitary wave profile in the x direction. The former are obtained using a variational Lyapunov‐Schmidt reduction and the latter by first applying a normal form transformation and then studying the resulting canonical system of equations.     

Application of homogenization theory related to Stokes flow in porous media

We consider applications, illustration and concrete numerical treatments of some homogenization results on Stokes flow in porous media. In particular, we compute the global permeability tensor corresponding to an unidirectional array of circular fibers for several volume-fractions. A 3-dimensional problem is also considered.