Photobinding of Flutamide to Phospholipid Vesicles: Additional Evidence for Photoprocesses Unexpectedly Triggered by Conformational Changes in the Bilayer

It is demonstrated that irradiation of the anticancer drug flutamide (FM) in the presence of unilamellar phospholipid bilayer vesicles, chosen as a model for cell membranes, leads to an efficient photobinding process. This pathway is triggered by an unexpected hydrogen‐abstraction reaction of the excited drug by the lipid chain and provides additional evidence that the overall photochemical scenario observed in the vesicles is unusually triggered by conformational change of the drug's molecular structure upon incarceration in the ‘close‐packed' bilayer. The present investigation, beyond contributing to the general picture concerning fundamental aspects of the light‐induced processes in self‐organized assemblies, may also provide important insights for a more satisfactory understanding of the recently reported adverse photoallergic and phototoxic phenomena displayed by this anticancer drug.     

A method for Lyapunov spectrum estimation using cloned dynamics and its application to the discontinuously-excited FitzHugh–Nagumo model

This work presents a new method to calculate the Lyapunov spectrum of dynamical systems based on the time evolution of initially small disturbed copies (“clones”) of the motion equations. In this approach, it is not necessary to construct the tangent space associated with the time evolution of linearized versions of motion equations, being the Lyapunov exponents directly estimated in terms of the rate of convergence or divergence of these disturbed clones with respect to the fiducial trajectory, there being periodic correction via the Gram–Schmidt Reorthonormalization procedure. The proposed method offers the possibility of partial estimation of the Lyapunov spectrum and can also be applied to nonsmooth dynamics, since the linearization procedure is no longer required. The idea is tested for representative continuous- and discrete-time dynamical systems and validated by means of comparison with the classical method to perform this calculation. To illustrate its applicability in the nonsmooth context, the largest Lyapunov exponent of the FitzHugh–Nagumo neuronal model under discontinuous periodic excitation is calculated taking the amplitude of stimulation as control parameter. This analysis reveals some complex behaviours for this simple neuronal model, which motivates relevant discussions about the possible role of chaos in the cognitive process.     

Broadband second harmonic generation of an optical frequency comb produced by four-wave mixing in highly nonlinear fibers

We demonstrate broadband second harmonic generation of low-energy pulses produced by injecting two single-frequency lasers into a highly nonlinear fiber. Full nonlinear conversion of the corresponding spectra, consisting of broadband (∼200 nm) optical frequency combs at ∼1580 nm, were obtained by using conventional birefringence phase-matching in two BIBO crystals (2-mm and 100-μm long) with a normal incidence configuration. The crystals were not tilted and the pulses were not compressed. This broadband conversion results from the large phase-matching bandwidth of the nonlinear BIBO crystals at ∼1550 nm, but also seems to be a consequence of a fundamental comb with small spectral phase variation.     

Silyl‐Terminated Ethylene‐co‐Norbornene Copolymers by Organotitanium‐Based Catalysts

Ethylene (E) and norbornene (N) were copolymerized in the presence of PhSiH₃ as chain‐transfer agent with [Ti(η⁵:η¹‐C₅Me₄SiMe₂NBu^t)(η¹‐Me)₂] precatalyst combined with [Ph₃C][B(C₆F₅)₄]. The silane was introduced at chain‐ends of E‐co‐N copolymers with concomitant reinitiation of the growing polymer chain. The concentrations of the silane and polymer molecular weight are inversely correlated. The characteristic signals of  SiH₂Ph chain‐ends were observed by ¹H NMR. The Si heteroatom is predominantly adjacent to ethylene units in E‐co‐N copolymers with high N content.

     

Periodic Orbits and Bifurcations of the Vibrational Modes of the Ozone Molecule at High Energies

Russian Physics Journal - The study of quantum states near the dissociation threshold is necessary both to understand the formation of molecules and to explore accurately chemical reactions....     

Hybrid opto-TV image-processing system

Quantum Radiophysics Division. Translated from preprint No. 23, 1991 of the Lebedev Physics Institute, Russian Academy of Sciences, Moscow, Russia.     

Field-trial evaluation of the Q-factor penalty introduced by fiber four-wave mixing wavelength converters

The performance of tunable all-optical wavelength converters based on four-wave mixing in optical fibers is experimentally tested in a field-trial network. Two converters were built with two different fibers. The first one was made with a small variation in the zero-dispersion wavelength (ZDW) dispersion shifted fiber and the second one with a highly nonlinear fiber that presents great ZDW variations. In order to compare the tuning ranges obtained in both cases we present an experimental spectral analysis. Numerical simulations that consider the influence of both the dispersion slope and the long-scale ZDW variations of the fiber complement the experiments. The tuning bandwidth was larger in the highly nonlinear fiber case. For a set of different optical signal-to-noise ratios, the measurements of the Q-factor of the signal and those of the converted wave are our main results. These results show that the penalty imposed by the converters is different for each converted wavelength. The maximum penalty obtained for the Q-factor was ∼6 dB, but it was ?3 dB for most cases. In all experiments we used a technique based on a dynamic polarization controller in order to avoid power fluctuations in the converted wave caused by polarization induced variations in the signal.     

Spontaneous Birefringence in Layer‐by‐Layer Films of Chitosan and Azo Dye Sunset Yellow

Layer‐by‐layer (LBL) films consisting of layers of the azo dye Sunset Yellow alternated with chitosan display spontaneous birefringence, which is attributed to the film anisotropy imparted by the LBL method. This is unusual for azobenzene‐containing materials as they normally form films with randomly oriented molecules, presenting birefringence only due to photoinduced isomerization cycles. Spontaneous birefringence does not appear in cast films, but occurs for LBL films obtained under various experimental conditions.

Chemical structures of (a) Sunset Yellow and (b) chitosan.     

Circular dichroic constrained structure optimization of homoalanine peptides

This article describes a new method for peptide structure optimization within a Monte Carlo Simulated Annealing (MCSA) framework, namely the cominimization of potential energies under the constraint of a calculated Circular Dichroism (CD) spectrum. We compute potential energy as well as the CD spectrum of every structure generated within the course of the MCSA run, and cooptimize the mean deviation of this calculated spectrum to a corresponding experimental spectrum together with the potential energies of the respective structures using a modified Metropolis Criterion within the MCSA scheme. We compare the performance of this technique with two other MCSA optimization variants—first, a cominimization of potential energies and free energies of solvation; and second, the standard minimization of potential energy alone. We use homoalanines in lengths of 10 and 15, whose optimized structures are highly α‐helical, and correspondingly give α‐helix characteristic CD signals as the test peptides. This circular dichroic constrained optimization of potential energies is, compared to the other methods, highly efficient in locating α‐helical structures with lowest potential energies in both the 10 alanine and the 15 alanine peptide system, within short MCSA runs. The overall structural information embedded in the CD spectrum efficiently guides the optimization towards the native peptide structure. © 2000 John Wiley & Sons, Inc. J Comput Chem 21: 270–281, 2000