2D-IR Study of a Photoswitchable Isotope-Labeled α-Helix

A series of photoswitchable, α-helical peptides were studied using two-dimensional infrared spectroscopy (2D-IR). Single-isotope labeling with 13C18O at various positions in the sequence was employed to spectrally isolate particular backbone positions. We show that a single 13C18O label can give rise to two bands along the diagonal of the 2D-IR spectrum, one of which is from an amide group that is hydrogen-bonded internally, or to a solvent molecule, and the other from a non-hydrogen-bonded amide group. The photoswitch enabled examination of both the folded and unfolded state of the helix. For most sites, unfolding of the peptide caused a shift of intensity from the hydrogen-bonded peak to the non-hydrogen-bonded peak. The relative intensity of the two diagonal peaks gives an indication of the fraction of molecules hydrogen-bonded at a certain location along the sequence. As this fraction varies quite substantially along the helix, we conclude that the helix is not uniformly folded. Furthermore, the shift in hydrogen bonding is much smaller than the change of helicity measured by CD spectroscopy, indicating that non-native hydrogen-bonded or mis-folded loops are formed in the unfolded ensemble

Optimized Discretization of Sources Imaged in Heavy-Ion Reactions

We develop the new method of optimized discretization for imaging the relative source from two particle correlation functions. In this method, the source resolution depends on the relative particle separation and is adjusted to available data and their errors. We test the method by restoring assumed pp sources and then apply the method to pp and IMF data. In reactions below 100 MeV/nucleon, significant portions of the sources extend to large distances (r > 20 fm). The results from the imaging show the inadequacy of common Gaussian source-parametrizations. We establish a simple relation between the height of the pp correlation function and the source value at short distances, and between the height and the proton freeze-out phase-space density.Comment: 36 pages (inc. 9 figures), RevTeX, uses epsf.sty. Submitted to Phys. Rev.

New Interstellar Dust Models Consistent with Extinction, Emission, and Abundance Constraints

We present new interstellar dust models which have been derived by simultaneously fitting the far-ultraviolet to near-infrared extinction, the diffuse infrared (IR) emission and, unlike previous models, the elemental abundance constraints on the dust for different interstellar medium abundances, including solar, F and G star, and B star abundances. The fitting problem is a typical ill-posed inversion problem, in which the grain size distribution is the unknown, which we solve by using the method of regularization. The dust model contains various components: PAHs, bare silicate, graphite, and amorphous carbon particles, as well as composite particles containing silicate, organic refractory material, water ice, and voids. The optical properties of these components were calculated using physical optical constants. As a special case, we reproduce the Li & Draine (2001) results, however their model requires an excessive amount of silicon, magnesium, and iron to be locked up in dust: about 50 ppm (atoms per million of H atoms), significantly more than the upper limit imposed by solar abundances of these elements, about 34, 35, and 28 ppm, respectively. A major conclusion of this paper is that there is no unique interstellar dust model that simultaneously fits the observed extinction, diffuse IR emission, and abundances constraints.Comment: 70 pages, 23 figures, accepted for publication in the Astrophysical Journal Supplemen

Variational Principles for Stellar Structure

The four equations of stellar structure are reformulated as two alternate pairs of variational principles. Different thermodynamic representations lead to the same hydromechanical equations, but the thermal equations require, not the entropy, but the temperature as the thermal field variable. Our treatment emphasizes the hydrostatic energy and the entropy production rate of luminosity produced and transported. The conceptual and calculational advantages of integral over differential formulations of stellar structure are discussed along with the difficulties in describing stellar chemical evolution by variational principles.Comment: 28 pages, LaTeX, requires AASTeX, 1 PostScript figure, revisions: erratum; accepted by Astrophysical Journa

Multiwavelength Observations of the Blazar Mrk 421 in December 2002 and January 2003

We report on a multiwavelength campaign on the TeV gamma-ray blazar Markarian (Mrk) 421 performed during December 2002 and January 2003. These target of opportunity observations were initiated by the detection of X-ray and TeV gamma-ray flares with the All Sky Monitor (ASM) on board the Rossi X-ray Timing Explorer (RXTE) and the 10 m Whipple gamma-ray telescope.The campaign included observational coverage in the radio (University of Michigan Radio Astronomy Observatory), optical (Boltwood, La Palma KVA 0.6m, WIYN 0.9m), X-ray (RXTE pointed telescopes), and TeV gamma-ray (Whipple and HEGRA) bands. At TeV energies, the observations revealed several flares at intermediate flux levels, peaking between 1 and 1.5 times the flux from the Crab Nebula. While the time averaged spectrum can be fitted with a single power law of photon index Gamma =2.8, we find some evidence for spectral variability. Confirming earlier results, the campaign reveals a rather loose correlation between the X-ray and TeV gamma-ray fluxes. In one case, a very strong X-ray flare is not accompanied by a comparable TeV gamma-ray flare. Although the source flux was variable in the optical and radio bands, the sparse sampling of the optical and radio light curves does not allow us to study the correlation properties in detail. We present a simple analysis of the data with a synchrotron-self Compton model, emphasizing that models with very high Doppler factors and low magnetic fields can describe the data.Comment: Accepted for publication in the Astrophysical Journa

Two-Dimensional Spectroscopy of Extended Molecular Systems: Applications to Energy Transport and Relaxation in an α-Helix

A simulation study of the coupled dynamics of amide I and amide II vibrations in an α-helix dissolved in water shows that two-dimensional (2D) infrared spectroscopy may be used to disentangle the energy transport along the helix through each of these modes from the energy relaxation between them. Time scales for both types of processes are obtained. Using polarization-dependent 2D spectroscopy is an important ingredient in the method we propose. The method may also be applied to other two-band systems, both in the infrared (collective vibrations) and the visible (excitons) parts of the spectrum.

Ultrashort filaments of light in weakly-ionized, optically-transparent media

Modern laser sources nowadays deliver ultrashort light pulses reaching few cycles in duration, high energies beyond the Joule level and peak powers exceeding several terawatt (TW). When such pulses propagate through optically-transparent media, they first self-focus in space and grow in intensity, until they generate a tenuous plasma by photo-ionization. For free electron densities and beam intensities below their breakdown limits, these pulses evolve as self-guided objects, resulting from successive equilibria between the Kerr focusing process, the chromatic dispersion of the medium, and the defocusing action of the electron plasma. Discovered one decade ago, this self-channeling mechanism reveals a new physics, widely extending the frontiers of nonlinear optics. Implications include long-distance propagation of TW beams in the atmosphere, supercontinuum emission, pulse shortening as well as high-order harmonic generation. This review presents the landmarks of the 10-odd-year progress in this field. Particular emphasis is laid to the theoretical modeling of the propagation equations, whose physical ingredients are discussed from numerical simulations. Differences between femtosecond pulses propagating in gaseous or condensed materials are underlined. Attention is also paid to the multifilamentation instability of broad, powerful beams, breaking up the energy distribution into small-scale cells along the optical path. The robustness of the resulting filaments in adverse weathers, their large conical emission exploited for multipollutant remote sensing, nonlinear spectroscopy, and the possibility to guide electric discharges in air are finally addressed on the basis of experimental results.Comment: 50 pages, 38 figure

Exciton bimolecular annihilation dynamics in supramolecular nanostructures of conjugated oligomers

We present femtosecond transient absorption measurements on $\pi$-conjugated supramolecular assemblies in a high pump fluence regime. Oligo(\emph{p}-phenylenevinylene) monofunctionalized with ureido-\emph{s}-triazine (MOPV) self-assembles into chiral stacks in dodecane solution below 75$^{\circ}$C at a concentration of $4\times 10^{-4}$ M. We observe exciton bimolecular annihilation in MOPV stacks at high excitation fluence, indicated by the fluence-dependent decay of $1^1$B$_{u}$-exciton spectral signatures, and by the sub-linear fluence dependence of time- and wavelength-integrated photoluminescence (PL) intensity. These two characteristics are much less pronounced in MOPV solution where the phase equilibrium is shifted significantly away from supramolecular assembly, slightly below the transition temperature. A mesoscopic rate-equation model is applied to extract the bimolecular annihilation rate constant from the excitation fluence dependence of transient absorption and PL signals. The results demonstrate that the bimolecular annihilation rate is very high with a square-root dependence in time. The exciton annihilation results from a combination of fast exciton diffusion and resonance energy transfer. The supramolecular nanostructures studied here have electronic properties that are intermediate between molecular aggregates and polymeric semiconductors