Induction of Supramolecular Chirality in the Self-Assemblies of Lipophilic Pyrimidine Derivatives by Choice of the Amino Acid-Based Chiral Spacer

A new family of supramolecular organogelators, based on chiral amino acid derivatives of 2,4,6-trichloro-pyrimidine-5-carbaldehyde, has been synthesized. L-alanine was incorporated as a spacer between the pyrimidine core and long hydrocarbon tails to compare the effect of chirality and hydrogen bonding to that of the achiral analogue. The role of aromatic moiety on the chiral spacer was also investigated by introducing L-phenyl alanine moieties. The presence of intermolecular hydrogen-bonding leading to the chiral self-assembly was probed by concentration-dependent FTIR and UV/Vis spectroscopies, in addition to circular dichroism (CD) studies. Temperature and concentration-dependent CD spectroscopy ascribed to the formation of -sheet-type H-bonded networks. The morphology and the arrangements of the molecules in the freeze-dried gels were examined by scanning electron microscopy (SEM), transmission electron microscopy (TEM), atomic force microscopy (AFM), and X-ray diffraction (XRD) techniques. Calculation of the length of each molecular system by energy minimization in its extended conformation and comparison with the small-angle XRD pattern reveals that this class of gelator molecules adopts a lamellar organization. Polarized optical microscopy (POM) and differential scanning calorimetry (DSC) indicate that the solid state phase behavior of these molecules is totally dependent on the choice of their amino acid spacers. Structure-induced aggregation properties based on the H-bonding motifs and the packing of the molecule in three dimensions leading to gelation was elucidated by rheological studies. However, viscoelasticity was shown to depend only marginally on the H-bonding interactions; rather it depends on the packing of the gelators to a greater extent.

Environments of extended radio sources in the Australia Telescope Low-Brightness Survey

We present a study of the environments of extended radio sources in the Australia Telescope Low-Brightness Survey (ATLBS). The radio sources were selected from the ATLBS Extended Source Sample, which is a well defined sample containing the most extended of radio sources in the ATLBS sky survey regions. The environments were analysed using 4-m Cerro-Tololo Inter-American Observatory Blanco telescope observations carried out for ATLBS fields in the Sloan Digital Sky Survey r(') band. We have estimated the properties of the environments using smoothed density maps derived from galaxy catalogues constructed using these optical imaging data. The angular distribution of galaxy density relative to the axes of the radio sources has been quantified by defining anisotropy parameters that are estimated using a new method presented here. Examining the anisotropy parameters for a subsample of extended double radio sources that includes all sources with pronounced asymmetry in lobe extents, we find good evidence for environmental anisotropy being the dominant cause for lobe asymmetry in that higher galaxy density occurs almost always on the side of the shorter lobe, and this validates the usefulness of the method proposed and adopted here. The environmental anisotropy parameters have been used to examine and compare the environments of Fanaroff-Riley Class I (FRI) and Fanaroff-Riley Class II (FRII) radio sources in two redshift regimes (z < 0.5 and z > 0.5). Wide-angle tail sources and head-tail sources lie in the most overdense environments. The head-tail source environments (for the HT sources in our sample) display dipolar anisotropy in that higher galaxy density appears to lie in the direction of the tails. Excluding the head-tail and wide-angle tail sources, subsamples of FRI and FRII sources from the ATLBS appear to lie in similar moderately overdense environments, with no evidence for redshift evolution in the regimes studied herein.

Local stability of a gravitating filament: a dispersion relation

Filamentary structures are ubiquitous in astrophysics and are observed at various scales. On a cosmological scale, matter is usually distributed along filaments, and filaments are also typical features of the interstellar medium. Within a cosmic filament, matter can contract and form galaxies, whereas an interstellar gas filament can clump into a series of bead-like structures that can then turn into stars. To investigate the growth of such instabilities, we derive a local dispersion relation for an idealized self-gravitating filament and study some of its properties. Our idealized picture consists of an infinite self-gravitating and rotating cylinder with pressure and density related by a polytropic equation of state. We assume no specific density distribution, treat matter as a fluid, and use hydrodynamics to derive the linearized equations that govern the local perturbations. We obtain a dispersion relation for axisymmetric perturbations and study its properties in the (kR, kz) phase space, where kR and kz are the radial and longitudinal wavenumbers, respectively. While the boundary between the stable and unstable regimes is symmetrical in kR and kz and analogous to the Jeans criterion, the most unstable mode displays an asymmetry that could constrain the shape of the structures that form within the filament. Here the results are applied to a fiducial interstellar filament, but could be extended for other astrophysical systems, such as cosmological filaments and tidal tails.

Unusual eigenvalue spectrum and relaxation in the Levy-Ornstein-Uhlenbeck process

We consider the rates of relaxation of a particle in a harmonic well, subject to Levy noise characterized by its Levy index mu. Using the propagator for this Levy-Ornstein-Uhlenbeck process (LOUP), we show that the eigenvalue spectrum of the associated Fokker-Planck operator has the form (n + m mu)nu where nu is the force constant characterizing the well, and n, m is an element of N. If mu is irrational, the eigenvalues are all nondegenerate, but rational mu can lead to degeneracy. The maximum degeneracy is shown to be 2. The left eigenfunctions of the fractional Fokker-Planck operator are very simple while the right eigenfunctions may be obtained from the lowest eigenfunction by a combination of two different step-up operators. Further, we find that the acceptable eigenfunctions should have the asymptotic behavior vertical bar x vertical bar(-n1-n2 mu) as vertical bar x vertical bar -> infinity, with n(1) and n(2) being positive integers, though this condition alone is not enough to identify them uniquely. We also assert that the rates of relaxation of LOUP are determined by the eigenvalues of the associated fractional Fokker-Planck operator and do not depend on the initial state if the moments of the initial distribution are all finite. If the initial distribution has fat tails, for which the higher moments diverge, one can have nonspectral relaxation, as pointed out by Toenjes et al. Phys. Rev. Lett. 110, 150602 (2013)].

On flame-turbulence interaction in constant-pressure expanding flames

In this paper we present one of the first high-speed particle image velocimetry measurements to quantify flame-turbulence interaction in centrally-ignited constant-pressure premixed flames expanding in nearisotropic turbulence. Measurements of mean flow velocity and rms of fluctuating flow velocity are provided over a range of conditions both in the presence and absence of the flame. The distributions of stretch rate contributions from different terms such as tangential straining, normal straining and curvature are also provided. It is found that the normal straining displays non-Gaussian pdf tails whereas the tangential straining shows near Gaussian behavior. We have further tracked the motion of the edge points that reside and co-move with the edge of the flame kernel during its evolution in time, and found that within the measurement conditions, on average the persistence time scales of stretch due to pure curvature exceed that due to tangential straining by at least a factor of two. (C) 2014 The Combustion Institute. Published by Elsevier Inc. All rights reserved.

Electron transfer statistics and thermal fluctuations in molecular junctions

We derive analytical expressions for probability distribution function (PDF) for electron transport in a simple model of quantum junction in presence of thermal fluctuations. Our approach is based on the large deviation theory combined with the generating function method. For large number of electrons transferred, the PDF is found to decay exponentially in the tails with different rates due to applied bias. This asymmetry in the PDF is related to the fluctuation theorem. Statistics of fluctuations are analyzed in terms of the Fano factor. Thermal fluctuations play a quantitative role in determining the statistics of electron transfer; they tend to suppress the average current while enhancing the fluctuations in particle transfer. This gives rise to both bunching and antibunching phenomena as determined by the Fano factor. The thermal fluctuations and shot noise compete with each other and determine the net (effective) statistics of particle transfer. Exact analytical expression is obtained for delay time distribution. The optimal values of the delay time between successive electron transfers can be lowered below the corresponding shot noise values by tuning the thermal effects. (C) 2015 AIP Publishing LLC.

Co-liposomes of redox-active alkyl-ferrocene modified low MW branched PEI and DOPE for efficacious gene delivery in serum

Herein, we present six new lipopolymers based on low molecular weight, branched polyethylenimine (BPEI 800 Da) which are hydrophobically modified using ferrocene terminated alkyl tails of variable lengths. The effects of degree of grafting, spacer length and the redox state of ferrocene in the lipopolymers on the self assembly properties were investigated in detail by TEM, AFM, DLS and zeta potential measurements. The assemblies displayed an oxidation induced increase in the size of the aggregates. The co-liposomes comprising the lipopolymer and a helper lipid, 1,2-dioleoyl phosphatidyl ethanolamine (DOPE), showed excellent gene (pDNA) delivery capability in a serum containing environment in two cancer cell lines (HeLa and U251 cells). Optimized formulations showed remarkably higher transfection activity than BPEI (25 kDa) and were also significantly better than a commercial transfection reagent, Lipofectamine 2000 as evidenced from both the luciferase activity and GFP expression analysis. Oxidation of ferrocene in the lipopolymers led to drastically reduced levels of gene transfection which was substantiated by reduced cellular internalization of fluorescently labelled pDNA as detected using confocal microscopy and flow cytometry. Moreover, the transfection inactive oxidized lipopolyplexes could be turned transfection active by exposure to ascorbic acid (AA) in cell culture medium during transfection. Endocytosis inhibition experiments showed that gene expression mediated by reduced formulations involved both clathrin and caveolae mediated pathways while the oxidized formulations were routed via the caveolae. Cytotoxicity assays revealed no obvious toxicity for the lipopolyplexes in the range of optimized transfection levels in both the cell lines studied. Overall, we have exploited the redox activity of ferrocene in branched PEI-based efficient polymeric gene carriers whose differential transfection activities could be harnessed for spatial or temporal cellular transfections.

Descending from infinity: Convergence of tailed distributions

We investigate the relaxation of long-tailed distributions under stochastic dynamics that do not support such tails. Linear relaxation is found to be a borderline case in which long tails are exponentially suppressed in time but not eliminated. Relaxation stronger than linear suppresses long tails immediately, but may lead to strong transient peaks in the probability distribution. We also find that a delta-function initial distribution under stronger than linear decay displays not one but two different regimes of diffusive spreading.

Handling large variations in mechanics: Some applications

There is a need to use probability distributions with power-law decaying tails to describe the large variations exhibited by some of the physical phenomena. The Weierstrass Random Walk (WRW) shows promise for modeling such phenomena. The theory of anomalous diffusion is now well established. It has found number of applications in Physics, Chemistry and Biology. However, its applications are limited in structural mechanics in general, and structural engineering in particular. The aim of this paper is to present some mathematical preliminaries related to WRW that would help in possible applications. In the limiting case, it represents a diffusion process whose evolution is governed by a fractional partial differential equation. Three applications of superdiffusion processes in mechanics, illustrating their effectiveness in handling large variations, are presented.

Atomistic Simulation of Stacked Nucleosome Core Particles: Tail Bridging, the H4 Tail, and Effect of Hydrophobic Forces

We report the first atomistic simulation of two stacked nucleosome core particles (NCPs), with an aim to understand, in molecular detail, how they interact, the effect of salt concentration, and how different histone tails contribute to their interaction, with a special emphasis on the H4 tail, known to have the largest stabilizing effect on the NCP-NCP interaction. We do not observe specific K16-mediated interaction between the H4 tail and the H2A-H2B acidic patch, in contrast with the findings from crystallographic studies, but find that the stacking was stable even in the absence of this interaction. We perform simulations with the H4 tail (partially/completely) removed and find that the region between LYS-16 and LYS-20 of the H4 tail holds special importance in mediating the inter-NCP interaction. Performing similar tail-clipped simulations with the H3 tail removed, we compare the roles of the H3 and H4 tails in maintaining the stacking. We discuss the relevance of our simulation results to the bilayer and other liquid-crystalline phases exhibited by NCPs in vitro and, through an analysis of the histone-histone interface, identify the interactions that could possibly stabilize the inter-NCP interaction in these columnar mesophases. Through the mechanical disruption of the stacked nucleosome system using steered molecular dynamics, we quantify the strength of inter-NCP stacking in the presence and absence of salt. We disrupt the stacking at some specific sites of internucleosomal tail-DNA contact and perform a comparative quantification of the binding strengths of various tails in stabilizing the stacking. We also examine how hydrophobic interactions may contribute to the overall stability of the stacking and find a marked difference in the role of hydrophobic forces as compared with electrostatic forces in determining the stability of the stacked nucleosome system.

Polysiloxane surfactants for the dispersion of carbon nanotubes in nonpolar organic solvents.

We develop two new amphiphilic molecules that are shown to act as efficient surfactants for carbon nanotubes in nonpolar organic solvents. The active conjugated groups, which are highly attracted to the graphene nanotube surface, are based on pyrene and porphyrin. We show that relatively short (C18) carbon tails are insufficient to provide stabilization. As our ultimate aim is to disperse and stabilize nanotubes in siloxane matrix (polymer and cross-linked elastomer), both surfactant molecules were made with long siloxane tails to facilitate solubility and steric stabilization. We show that the pyrene-siloxane surfactant is very effective in dispersing multiwall nanotubes, while the porphyrin-siloxane makes single-wall nanotubes soluble, both in petroleum ether and in siloxane matrix.

Testing the Forecasting Performance of Ibex 35 Option-implied Risk-neutral Densities

Published also as: Documento de Trabajo Banco de España 0504/2005.

Preliminary guide to the identification of the early life history stages of Gerreid fishes of the Western Central Atlantic

The family Gerreidae contains four genera and 13 species that occur in the western central North Atlantic. Adult gerreids are small to medium size fishes that are abundant in coastal waters, bays, and estuaries in tropical and warm temperate regions and sometimes occur in freshwaters. They are generally associate~ with grassy or open bottoms, but not with reefs. Gerreids are silvery fishes, with deeply forked tails, and extremely protrusible mouth that points downward when protracted. They apparently feed on bottom-dwelling organisms and at least one species (Eucinostomus gula) shows a distinct transition, during the juvenile period, from a planktivore (exclusively copepods) to a carnivore that includes a diet of almost solely polychaetes (Carr & Adams, 1973; Robins and Ray, 1987; Murdy et al., 1997). (PDF contains 10 pages)

Part 1: Longitudinal static and dynamic effects in semiconductor lasers. Part II: Spectral characteristics of passively mode-locked quantum well lasers

In the first part of this thesis a study of the effect of the longitudinal distribution of optical intensity and electron density on the static and dynamic behavior of semiconductor lasers is performed. A static model for above threshold operation of a single mode laser, consisting of multiple active and passive sections, is developed by calculating the longitudinal optical intensity distribution and electron density distribution in a self-consistent manner. Feedback from an index and gain Bragg grating is included, as well as feedback from discrete reflections at interfaces and facets. Longitudinal spatial holeburning is analyzed by including the dependence of the gain and the refractive index on the electron density. The mechanisms of spatial holeburning in quarter wave shifted DFB lasers are analyzed. A new laser structure with a uniform optical intensity distribution is introduced and an implementation is simulated, resulting in a large reduction of the longitudinal spatial holeburning effect.

A dynamic small-signal model is then developed by including the optical intensity and electron density distribution, as well as the dependence of the grating coupling coefficients on the electron density. Expressions are derived for the intensity and frequency noise spectrum, the spontaneous emission rate into the lasing mode, the linewidth enhancement factor, and the AM and FM modulation response. Different chirp components are identified in the FM response, and a new adiabatic chirp component is discovered. This new adiabatic chirp component is caused by the nonuniform longitudinal distributions, and is found to dominate at low frequencies. Distributed feedback lasers with partial gain coupling are analyzed, and it is shown how the dependence of the grating coupling coefficients on the electron density can result in an enhancement of the differential gain with an associated enhancement in modulation bandwidth and a reduction in chirp.

In the second part, spectral characteristics of passively mode-locked two-section multiple quantum well laser coupled to an external cavity are studied. Broad-band wavelength tuning using an external grating is demonstrated for the first time in passively mode-locked semiconductor lasers. A record tuning range of 26 nm is measured, with pulse widths of typically a few picosecond and time-bandwidth products of more than 10 times the transform limit. It is then demonstrated that these large time-bandwidth products are due to a strong linear upchirp, by performing pulse compression by a factor of 15 to a record pulse widths as low 320 fs.

A model for pulse propagation through a saturable medium with self-phase-modulation, due to the a-parameter, is developed for quantum well material, including the frequency dependence of the gain medium. This model is used to simulate two-section devices coupled to an external cavity. When no self-phase-modulation is present, it is found that the pulses are asymmetric with a sharper rising edge, that the pulse tails have an exponential behavior, and that the transform limit is 0.3. Inclusion of self-phase-modulation results in a linear upchirp imprinted on the pulse after each round-trip. This linear upchirp is due to a combination of self-phase-modulation in a gain section and absorption of the leading edge of the pulse in the saturable absorber.

Singularities and horizons in the collisions of gravitational waves

This thesis presents a study of the dynamical, nonlinear interaction of colliding gravitational waves, as described by classical general relativity. It is focused mainly on two fundamental questions: First, what is the general structure of the singularities and Killing-Cauchy horizons produced in the collisions of exactly plane-symmetric gravitational waves? Second, under what conditions will the collisions of almost-plane gravitational waves (waves with large but finite transverse sizes) produce singularities?

In the work on the collisions of exactly-plane waves, it is shown that Killing horizons in any plane-symmetric spacetime are unstable against small plane-symmetric perturbations. It is thus concluded that the Killing-Cauchy horizons produced by the collisions of some exactly plane gravitational waves are nongeneric, and that generic initial data for the colliding plane waves always produce "pure" spacetime singularities without such horizons. This conclusion is later proved rigorously (using the full nonlinear theory rather than perturbation theory), in connection with an analysis of the asymptotic singularity structure of a general colliding plane-wave spacetime. This analysis also proves that asymptotically the singularities created by colliding plane waves are of inhomogeneous-Kasner type; the asymptotic Kasner axes and exponents of these singularities in general depend on the spatial coordinate that runs tangentially to the singularity in the non-plane-symmetric direction.

In the work on collisions of almost-plane gravitational waves, first some general properties of single almost-plane gravitational-wave spacetimes are explored. It is shown that, by contrast with an exact plane wave, an almost-plane gravitational wave cannot have a propagation direction that is Killing; i.e., it must diffract and disperse as it propagates. It is also shown that an almost-plane wave cannot be precisely sandwiched between two null wavefronts; i.e., it must leave behind tails in the spacetime region through which it passes. Next, the occurrence of spacetime singularities in the collisions of almost-plane waves is investigated. It is proved that if two colliding, almost-plane gravitational waves are initially exactly plane-symmetric across a central region of sufficiently large but finite transverse dimensions, then their collision produces a spacetime singularity with the same local structure as in the exact-plane-wave collision. Finally, it is shown that a singularity still forms when the central regions are only approximately plane-symmetric initially. Stated more precisely, it is proved that if the colliding almost-plane waves are initially sufficiently close to being exactly plane-symmetric across a bounded central region of sufficiently large transverse dimensions, then their collision necessarily produces spacetime singularities. In this case, nothing is now known about the local and global structures of the singularities.