Molecular Origin of the Intrinsic Bending Force for Helical Morphology Observed in Chiral Amphiphilic Assemblies: Concentration and Size Dependence

The formation of the helical morphology in monolayers and bilayers of chiral amphiphilic assemblies is believed to be driven at least partly by the interactions at the chiral centers of the amphiphiles. However, a detailed microscopic understanding of these interactions and their relation with the helix formation is still not clear. In this article a study of the molecular origin of the chirality-driven helix formation is presented by calculating, for the first time, the effective pair potential between a pair of chiral molecules. This effective potential depends on the relative sizes of the groups attached to the two chiral centers, on the orientation of the amphiphile molecules, and also on the distance between them. We find that for the mirror-image isomers (in the racemic modification) the minimum energy conformation is a nearly parallel alignment of the molecules. On the other hand, the same for a pair of molecules of one kind of enantiomer favors a tilt angle between them, thus leading to the formation of a helical morphology of the aggregate. The tilt angle is determined by the size of the groups attached to the chiral centers of the pair of molecules considered and in many cases predicted it to be close to 45 degrees. The present study, therefore, provides a molecular origin of the intrinsic bending force, suggested by Helfrich (J. Chem. Phys. 1986, 85, 1085-1087), to be responsible for the formation of helical structure. This effective potential may explain many of the existing experimental results, such as the size and the concentration dependence of the formation of helical morphology. It is further found that the elastic forces can significantly modify the pitch predicted by the chiral interactions alone and that the modified real pitch is close to the experimentally observed value. The present study is expected to provide a starting point for future microscopic studies.

Comparative study of filter-bank mean-energy distance for automated segmentation of speech signals

This paper describes a method of automated segmentation of speech assuming the signal is continuously time varying rather than the traditional short time stationary model. It has been shown that this representation gives comparable if not marginally better results than the other techniques for automated segmentation. A formulation of the 'Bach' (music semitonal) frequency scale filter-bank is proposed. A comparative study has been made of the performances using Mel, Bark and Bach scale filter banks considering this model. The preliminary results show up to 80 % matches within 20 ms of the manually segmented data, without any information of the content of the text and without any language dependence. 'Bach' filters are seen to marginally outperform the other filters.

Correlations between frequency of infra-red active vibrational modes and copper-oxygen distance in copper oxides. Application to superconductors

The infra-red spectra of a large number of ternary Cu(II) oxides with at least a quasi square-planar coordination of oxygen around the copper ions have been studied. The frequency of the bands with the highest frequency,v max, is found to correlate extremely well with the shortest Cu–O distance.v max increases at an impressive rate of sim20 cm–1 per 0.01 Å when the Cu–O distance becomes less than 1.97 Å, which is the Cu2+–O2– distance in square-planar CuO4 complexes as obtained from empirical ionic radii considerations. The marked sensitivity may be used as a ldquotitrationrdquo procedure not only to assign bands but also to obtain diagnostic information about local coordination in compounds derived, for example, from the YBa2Cu3O7–d structure such as LaCaBaCu3O7–d . The only example where this correlation fails is in the two-layer non-superconducting oxides derived from La2(Ca, Sr)Cu2O6. The significance of this result is discussed. The marked dependence of frequency on the bond-distance is qualitatively examined in terms of an increased electron-phonon coupling to account for the observed tendency of the superconducting transition temperature to go through a maximum as the average basal plane Cu–O distance is decreased.

Structure and superconducting properties of Tl1?yPbyY1?xCaxSr2Cu2O7star, open: Dependence of Tc on hole concentration

Structure and superconducting properties of Tl1?yPbyY1?xCaxSr2Cu2O7 (y=0.0, 0.1, 0.25 and 0.5) , derived from the parent insulator TlYSr2Cu2O7, have been investigated for different values of x. XANES studies show Pb to be in the 4+ state while Tl is in the 3+ state, suggesting thereby that in this series, (x?y) approximately corresponds to the hole concentration. The in-plane Cu---O distance decreases with increase in x for all values of y. The apical Cu---O distance as well as the Tl(Pb)---O(2) distance show anomalies at x=0.5 in the series with y=0.25; at this composition, Tc also reaches a maximum. In general, the composition (value of x) at which the Tc of Tl1?yPbyY1?xCaxSr2Cu2O7 reaches a maximum depends on the Pb content and the maximum Tc itself increases with increase in y, reaching a value of 105 K at y=0.5. More interestingly, a maximum Tc occurs at an (x?y) value of not, vert, similar0.25, which is close to the hole concentration at maximum Tc in other cuprate superconductors containing two CuO2 layers.

Photophysical and electrochemical redox properties of fixed distance porphyrin-quinone systems

A few fixed distance covalently linked porphyrin-quinone molecules have been synthesized in which a benzoquinone is directly attached to a meso/beta-pyrrole position of tri(phenyl/pentafluorophenyl)/tetraphenylporphyrins. The choice of fluoroarylporphyrins permit modulation of Delta G(ET) values for photoinduced electron-transfer reactions in these systems. All short distance porphyrin-quinone molecules showed efficient quenching of the porphyrin singlet excited state. The electrochemical redox data coupled with the steady-state and time-resolved singlet emission data are analysed to evaluate the dependence of Delta G(ET) values on the rate of electron transfer (k(ET)) in these systems. The meso-trifluoroarylporphyrin-quinones are found to be sensitive probes of the surrounding dielectric environment. Varying solvent polarity on the mechanism of fluorescence quenching and k(ET) values revealed that short donor-acceptor distance and the solvent dielectric relaxation properties play a dominant role. (C) 1999 Elsevier Science S.A. All rights reserved.

The theory of long distance electron transfer reactions

The rate of electron transport between distant sites was studied. The rate depends crucially on the chemical details of the donor, acceptor, and surrounding medium. These reactions involve electron tunneling through the intervening medium and are, therefore, profoundly influenced by the geometry and energetics of the intervening molecules. The dependence of rate on distance was considered for several rigid donor-acceptor "linkers" of experimental importance. Interpretation of existing experiments and predictions for new experiments were made.

The electronic and nuclear motion in molecules is correlated. A Born-Oppenheimer separation is usually employed in quantum chemistry to separate this motion. Long distance electron transfer rate calculations require the total donor wave function when the electron is very far from its binding nuclei. The Born-Oppenheimer wave functions at large electronic distance are shown to be qualitatively wrong. A model which correctly treats the coupling was proposed. The distance and energy dependence of the electron transfer rate was determined for such a model.

Photochemical electron transfer at fixed distance : a synthetic model of the photosynthetic primary process

A series of meso-phenyloctamethylporphyrins covalently bonded at the 4'phenyl position to quinones via rigid bicyclo[2.2.2]octane spacers were synthesized for the study of the dependence of electron transfer reaction rate on solvent, distance, temperature, and energy gap. A general and convergent synthesis was developed based on the condensation of ac-biladienes with masked quinonespacer-benzaldehydes. From picosecond fluorescence spectroscopy emission lifetimes were measured in seven solvents of varying polarity. Rate constants were determined to vary from 5.0x10⁹sec^-1 in N,N-dimethylformamide to 1.15x10¹⁰ Sec^-1 in benzene, and were observed to rise at most by about a factor of three with decreasing solvent polarity. Experiments at low temperature in 2-MTHF glass (77K) revealed fast, nearly temperature-independent electron transfer characterized by non-exponential fluorescence decays, in contrast to monophasic behavior in fluid solution at 298K. This example evidently represents the first photosynthetic model system not based on proteins to display nearly temperature-independent electron transfer at high temperatures (nuclear tunneling). Low temperatures appear to freeze out the rotational motion of the chromophores, and the observed nonexponential fluorescence decays may be explained as a result of electron transfer from an ensemble of rotational conformations. The nonexponentiality demonstrates the sensitivity of the electron transfer rate to the precise magnitude of the electronic matrix element, which supports the expectation that electron transfer is nonadiabatic in this system. The addition of a second bicyclooctane moiety (15 Å vs. 18 Å edge-to-edge between porphyrin and quinone) reduces the transfer rate by at least a factor of 500-1500. Porphyrinquinones with variously substituted quinones allowed an examination of the dependence of the electron transfer rate constant κ_ET on reaction driving force. The classical trend of increasing rate versus increasing exothermicity occurs from 0.7 eV≤ |ΔG^0'(R)| ≤ 1.0 eV until a maximum is reached (κ_ET = 3 x 10⁸ sec^-1 rising to 1.15 x 10¹⁰ sec^-1 in acetonitrile). The rate remains insensitive to ΔG⁰ for ~ 300 mV from 1.0 eV≤ |ΔG^0’(R)| ≤ 1.3 eV, and then slightly decreases in the most exothermic case studied (cyanoquinone, κ_ET = 5 x 10⁹ sec^-1).

Thickness dependence of structure and optical properties of silver films deposited by magnetron sputtering

A series of silver films with different thickness were prepared under identical conditions by direct current magnetron sputtering. The optical properties of the silver films were measured using spectrophotometric techniques and the optical constants were calculated from reflection and transmission measurements made at near normal incidence. The results show that the optical properties and constants are affected by films' thickness. Below the critical thickness of 17 nm at which Ag film forms a continuous film, the optical properties and constants vary significantly as the thickness of films increases and then tends to a stable value which is reached at 41 nm. X-ray diffraction measurements were carried out to examine the structure and stress evolution of the Ag films as a function of films' thickness. It was found that the interplanar distance of (111) orientation decreases when the film thickness increases and tends to be close to that of bulk material. The compressive strains also decrease with increasing thickness. (C) 2007 Published by Elsevier B.V.

Extending the transmission distance of a directly modulated laser source using Bragg grating dispersion compensators

Comprehensive computer modelling has been used to investigate the dependence of dispersion penalty on transmission length in an optical communications system employing a directly modulated 2.5Gbit/s DFB laser source and an optimised fibre grating dispersion compensator. Two grating apodization schemes, tanh and Gaussian, have been compared. The 2dB dispersion penalty transmission distance is shown to be approximately 520km along standard monomode fibre after compensation with a 5cm tanh grating. This represents a great improvement over the 150km range expected for a similar uncompensated system.

Effect of polymer chain structure and chain distance on luminescent efficiency

Three kinds of PPV-based copolymers were synthesized and characterized. Their luminescent properties were investigated and discussed by PL spectrum, and time-dependence luminescent spectrum in film and solution stare. The results show that in the range of our study, the PL intensity and lifetime of luminescent decay increase with the increasing length of flexible segments and the solution diluting, indicating the tendency of the increase of luminescent efficiency.

Temperature dependence of the Raman spectra of carbon nanotubes

We report on a temperature dependence of the frequency of all the major peaks in the Raman spectra of carbon nanotubes, using different excitation laser powers at the sample. The frequency decreases with increasing temperature for all peaks, and the shifts in Raman frequencies are linear in the temperature of the sample. In comparison, a similar dependence is found in active carbon, but no shift is observed for the highly ordered pyrolytic graphite within the same range of variation in laser power. A lowering of frequency at higher temperature implies an increase in the carbon-carbon distance at higher temperature. The relatively strong temperature dependence in carbon nanotubes and active carbon may be due to the enhanced increase in carbon-carbon distance. This enhancement may originate from the heavy defects and disorder in these materials. (C) 1998 American Institute of Physics. [S0021-8979(98)05219-0].

Superluminous Supernovae as Standardizable Candles and High-Redshift Distance Probes

We investigate the use of type Ic superluminous supernovae (SLSN Ic) as standardizable candles and distance indicators. Their appeal as cosmological probes stems from their remarkable peak luminosities, hot blackbody temperatures, and bright rest-frame ultraviolet emission. We present a sample of 16 published SLSN, from redshifts 0.1 to 1.2, and calculate accurate K corrections to determine uniform magnitudes in 2 synthetic rest-frame filter bandpasses with central wavelengths at 400 nm and 520 nm. At 400 nm, we find an encouragingly low scatter in their uncorrected, raw mean magnitudes with M(400) = -21.86 ± 0.35 mag for the full sample of 16 objects. We investigate the correlation between their decline rates and peak magnitude and find that the brighter events appear to decline more slowly. In a manner similar to the Phillips relation for type Ia SNe (SNe Ia), we define a ΔM 20 decline relation. This correlates peak magnitude and decline over 20 days and can reduce the scatter in standardized peak magnitudes to ±0.22 mag. We further show that M(400) appears to have a strong color dependence. Redder objects are fainter and also become redder faster. Using this peak magnitudecolor evolution relation, a surprisingly low scatter of between ±0.08 mag and ±0.13 mag can be found in peak magnitudes, depending on sample selection. However, we caution that only 8 to 10 objects currently have enough data to test this peak magnitudecolor evolution relation. We conclude that SLSN Ic are promising distance indicators in the high-redshift universe in regimes beyond those possible with SNe Ia. Although the empirical relationships are encouraging, the unknown progenitor systems, how they may evolve with redshift, and the uncertain explosion physics are of some concern. The two major measurement uncertainties are the limited numbers of low-redshift, well-studied objects available to test these relationships and internal dust extinction in the host galaxies.

The dust environment of comet 67P/Churyumov-Gerasimenko from Rosetta OSIRIS and VLT observations in the 4.5 to 2.9 au heliocentric distance range inbound

Context. The ESA Rosetta spacecraft, currently orbiting around comet 67P/Churyumov-Gerasimenko, has already provided in situ measurements of the dust grain properties from several instruments,particularly OSIRIS and GIADA. We propose adding value to those measurements by combining them with ground-based observations of the dust tail to monitor the overall, time-dependent dust-production rate and size distribution.
Aims. To constrain the dust grain properties, we take Rosetta OSIRIS and GIADA results into account, and combine OSIRIS data during the approach phase (from late April to early June 2014) with a large data set of ground-based images that were acquired with the ESO Very Large Telescope (VLT) from February to November 2014.
Methods. A Monte Carlo dust tail code, which has already been used to characterise the dust environments of several comets and active asteroids, has been applied to retrieve the dust parameters. Key properties of the grains (density, velocity, and size distribution) were obtained from Rosetta observations: these parameters were used as input of the code to considerably reduce the number of free parameters. In this way, the overall dust mass-loss rate and its dependence on the heliocentric distance could be obtained accurately.
Results. The dust parameters derived from the inner coma measurements by OSIRIS and GIADA and from distant imaging using VLT data are consistent, except for the power index of the size-distribution function, which is α = −3, instead of α = −2, for grains smaller than 1 mm. This is possibly linked to the presence of fluffy aggregates in the coma. The onset of cometary activity occurs at approximately 4.3 AU, with a dust production rate of 0.5 kg/s, increasing up to 15 kg/s at 2.9 AU. This implies a dust-to-gas mass ratio varying between 3.8 and 6.5 for the best-fit model when combined with water-production rates from the MIRO experiment.

Assessment of surface winds over the Atlantic, Indian and Pacific Ocean sectors of the Southern Ocean in CMIP5 models: historical bias, forcing response, and state dependence

An assessment of the fifth Coupled Models Intercomparison Project (CMIP5) models’ simulation of the near-surface westerly wind jet position and strength over the Atlantic, Indian and Pacific sectors of the Southern Ocean is presented. Compared with reanalysis climatologies there is an equatorward bias of 3.7° (inter-model standard deviation of ± 2.2°) in the ensemble mean position of the zonal mean jet. The ensemble mean strength is biased slightly too weak, with the largest biases over the Pacific sector (-1.6±1.1 m/s, 27 -22%). An analysis of atmosphere-only (AMIP) experiments indicates that 41% of the zonal mean position bias comes from coupling of the ocean/ice models to the atmosphere. The response to future emissions scenarios (RCP4.5 and RCP8.5) is characterized by two phases: (i) the period of most rapid ozone recovery (2000-2049) during which there is insignificant change in summer; and (ii) the period 2050-2098 during which RCP4.5 simulations show no significant change but RCP8.5 simulations show poleward shifts (0.30, 0.19 and 0.28°/decade over the Atlantic, Indian and Pacific sectors respectively), and increases in strength (0.06, 0.08 and 0.15 m/s/decade respectively). The models with larger equatorward position biases generally show larger poleward shifts (i.e. state dependence). This inter-model relationship is strongest over the Pacific sector (r=-0.89) and insignificant over the Atlantic sector (r=-0.50). However, an assessment of jet structure shows that over the Atlantic sector jet shift is significantly correlated with jet width whereas over the Pacific sector the distance between the sub-polar and sub-tropical westerly jets appears to be more important.

Relationship between the near-Earth interplanetary field and the coronal source flux: dependence on timescale

The Ulysses spacecraft has shown that the radial component of the heliospheric magnetic field is approximately independent of latitude. This has allowed quantification of the total open solar flux from near-Earth observations of the interplanetary magnetic field. The open flux can also be estimated from photospheric magnetograms by mapping the fields up to the ‘‘coronal source surface’’ where the field is assumed to be radial and which is usually assumed to be at a heliocentric distance r = 2.5R_{S} (a mean solar radius, 1R_{S} = 6.96x10^{8} m). These two classes of open flux estimate will differ by the open flux that threads the heliospheric current sheet(s) inside Earth’s orbit at 2.5R_{S} < r < 1R{1} (where the mean Earth-Sun distance, 1R_{1} = 1 AU = 1.5 x 10^{11} m). We here use near-Earth measurements to estimate this flux and show that at sunspot minimum it causes only a very small (approximately 0.5%) systematic difference between the two types of open flux estimate, with an uncertainty that is of order ±24% in hourly values, ±16% in monthly averages, and between -6% and +2% in annual values. These fractions may be somewhat larger for sunspot maximum because of flux emerging at higher heliographic latitudes.