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In studies of extragalactic radio sources with multiple compact components the determination of which components, if any, are stationary and which moving is of importance. In order to learn about the radio properties of the individual components it is also relevant to be able to register maps made at several wavelengths. Both tasks are usually not possible with VLBI because of the irrecoverable corruption of the fringe phase introduced by the propagation medium and the instrumentation. However, when two or more compact radio sources are separated by only a small angle from each other difference techniques can be used to help tackle both questions.
From five sets of VLBI observations spaced between 1972 and 1981, we estimated the positions of components of the superluminal quasar 3C 345 relative to the position of the single component of the quasar NRAO 512. The relative proper motion of the easternmost component of 3C 345, believed to be the “core”, was found to be 0.02±0.02 mas/yr. This result is consistent with the “core” being stationary and the “jet” components moving with respect to NRAO 512.
Mark III VLBI observations of the pulsars PSR 0329+54 and PSR 1133+16 were made at 2.3 GHz using antennas with diameters and locations as follows: 100m, Effelsberg, West Germany (but only for SPR 0329+54); 43m Green Bank, WV, USA; and 40m, Big Pine, CA, USA. The Mark III processor at the Haystack Observatory was “gated” to compute visibility amplitudes and phases as a function of pulsar longitude. This method allowed a) an improvement of the signal to noise ration, by as much as a factor of ten in the case of PSR 1133+16, and b) an interferometric investigation of the pulse structure.
On 1983 May 10–11 we undertook simultaneous λ3.6 and λ13 cm Mark III VLBI observations of the quasars 1038+528 A,B. Our experimental conditions (i.e., synthesized band, uv-coverage, etc.) were almost identical to those we used on 1981 March 17–18. Thus, we could make a direct comparison of the results from both epochs.
There have been many studies examining the differences between infant-directed speech (IDS) and adult-directed speech (ADS). However, investigations asking whether mothers clarify vowel articulation in IDS have reached equivocal findings. Moreover, it is unclear whether maternal speech clarification has any effect on a child's developing language skills. This study examined vowel clarification in mothers’ IDS at 0;10–11, 1;6, and 2;0, as compared to their vowel production in ADS. Relationships between vowel space, vowel duration, and vowel variability and child language outcomes at two years were also explored. Results show that vowel space and vowel duration tended to be greater in IDS than in ADS, and that one measure of vowel clarity, a mother's vowel space at 1;6, was significantly related to receptive as well as expressive child language outcomes at two years of age.
The NASA/Stanford Relativity Mission (Gravity Probe B) is to test the unverified “frame-dragging” prediction of general relativity through measurements of the precessions of orbiting gyroscopes. For mission accuracy goals to be met, the proper motion of a “guide star,” whose position will be used as an inertial reference, must be determined in an extragalactic reference frame with a standard error less than 0.5 mas/yr. We discuss our VLBI observations of the current guide-star candidates (radio stars HR 1099, HR 5110, and HR 8703) and our techniques for obtaining differential astrometric positions with the needed accuracy.
We determine the relative separations of the sources in the triangle 1803+784/1928+738/2007+777 with submilliarcsecond accuracy from global 8.4 GHz VLBI observations. We remove the ionospheric contribution to the phase-delay observable using ionospheric total electron content estimates obtained from Global Positioning System (GPS) data. The triangular geometry provides a consistency check through sky closure.
The use of the DNA duplex as a molecular wire is discussed with particular attention to recent experimental findings. Experimental studies of photo-excited hole dynamics in DNA can be understood within the phenomenological hopping model. However a microscopic first principles approach requires taking into account the interaction between charge and duplex degrees of freedom. The nature of possible metallic native DNA behavior is discussed.
Cryptands and crown ethers increase the cation transport in phosphazene and alkoxyaluminate polyelectrolytes. Vibrational spectroscopy indicates that the increased conductivity originates from reduced ion pairing.
The dynamic bond percolation model was developed to deal with dynamic disorder, treating ion mobility by a percolation model in which the assignment of any site-to-site jump as allowed or forbidden changes on a timescale related to the local reorganizational dynamics of the polymer segments (the renewal time). Here we discuss the special cases of highfrequency spectra and partially crystalline electrolytes. At high frequencies, the present hopping model yields unphysical behavior (frequencyindependent response); we trace this back to the incorrect treatment of short-time dynamics, and show how it can be corrected. For partially crystalline materials, we show that a rollover feature in the spectrum, in the microwave range, can be expected when ions are trapped in isolated regions of high conductivity, such as amorphous pockets in largely crystalline PEO.
Molecular dynamics simulations performed on highly concentrated Coulomb/solvent systems are used to help interpret the transport mechanism in polymer ionics. Using simple Coulomb and Lennard-Jones forces among the ions and a solvent model of a fixed dipole contained in a spherical solvent particle, we investigated the nature of ion pair formation and stability. For a model NaI system, we find that ion pairs decrease with increase in solvent dipole moment or temperature. The latter observation is at variance with experimental results on polymer electrolytes, probably because of entropy terms that do not occur with our simple solvent molecule.
The addition of I2 to PPO/MI and MEEP/MI complexes, where M - Na or Li, PPO - poly(propylene oxide), MEEP - methoxyethoxyethoxy phosphazene results in ohmic conductivity. Even in the absence of the metal iodide salt, high conductivities are observed in the polymer/I2 complexes. The presence of polyiodides in all cases is indicated by a Raman band at 170 cm.-1 The width of this peak is found to depend on the concentration of iodine and correlates with increasing conductivity at higher I2 concentrations. An additional feature of the polyiodide complexes is the apparent lack of dependence of conductivity on polymer flexibility as indicated by Tg. In most polymer electrolytes, the conductivity depends upon the glass transition, Tg, with conductivity dropping rapidly at T < Tg. By contrast, the polyiodides show only a small inflection in the conductivity around Tg and substantial conductivity below that temperature. Apparently charge transport dynamics are only weakly coupled to the dynamics of the host polymer. Variable temperature Raman spectroscopy has been employed to investigate the low temperature behavior of polyiodides in PPO/MIn systems.
Third-order optical susceptibilities (γijkl) can be efficiently analyzed for a variety of molecular structures employing perturbation theory and a PPP-SCF-SECI-DECI π-electron model Hamiltonian. The key, frequency tripling second hyperpolarizability γijkl(−3ω;ω,ω,ω) is calculated with full single and double CI. It is found that double excitations play a major role in third-order processes, and that γijkl, like the polarizability αij, is sensitive largely to the overall size (volume) of the π system, although charge transfer excitations may also contribute. The frequency dependence of v and correlations between γijkl and conjugation length are found for a series of trans polyenes.
Factors contributing to the polarizability (αij) and frequencydoubling hyperpolarizability (βijk) of 2-(p-dimethylaminophenyl)-6-(pnitrophenyl) benzo(l,2-d:4,5-d′ )blsthiazole (DNBT) are analyzed via perturbation theory and the PPP-SCF-MECI π-electron model Hamiltonian. While the observable part of β (βvec) is clearly identifiable with a small number of charge transfer excitations along the molecular dipole direction, a (and by inference, the second-order hyperpolarizability γ) is more closely related to the overall size (volume) of the π-electron cloud. As a consequence, βvec is far more sensitive to molecular distortions which affect donor-acceptor charge transfer interactions than is π. The more sensitive frequency dependence of βvec can be understood in terms of the three-photon character of this nonlinearity.
The progress of dynamically disordered hopping (DDH) in modelling charge transport in polymer electrolytes is reviewed. The DDH model successfully describes many of the salient features of polymer electrolytes, most notably, the frequency and temperature dependence of the conductivity. Furthermore, analyses and simulations based on the DDH model provide rich mechanistic information. The general picture of charge transport that emerges from the DDH model is one in which two classes of charge carriers exist in thermal equilibrium:quasi-free and bound. The quasi-free carriers dominate the conductivity response and diffuse freely over short distances (≈1Å) with longer range diffusion requiringlocal segmental motions, renewal in the language of DDH, of the polymer solvent. The bound carriers, which are likely polymer solvated ion clusters, are immobile on the time-scale of renewal and contribute relatively little to the conductivity.
An attractive and challenging approach to the construction of robust, thin film materials with large second-order optical nonlinearities is the covalent self-assembly of aligned arrays of high-β molecular chromophores into multilayer superlattices. In this paper, we describe the dispersion of second harmonic generation (SHG) in a self-assembled (SA) monolayer containing a stilbazolium chromophore. The frequency-dependent measurements were performed on 25 Å thick monolayers on glass using a tunable (0.4–2 μm) light source based on optical parametric amplification (OPA). The SHG spectrum contains a clear two-photon resonance at hω = 1.3eV. The maximum in the second-order susceptibility coincides with a low energy chromophore-centered charge-transfer excitation at 480 nm. The experimental SHG dispersion values compare favorably with theoretical results computed using a sum-over-states (SOS) formalism. However, the measured values exhibit a somewhat broader band response than the theoretical curve, and the origin of this behavior is discussed.
We present microscopic study of electronic and transport properties of single molecules sandwiched between two metallic contacts using Green's function based modeling approach within both ab initio and self-consistent semi-empirical framework. The methods are applied to thiol-based organic molecules and finite-size single-wall carbon nanotubes respectively. Results on electrostatics, transmission and current-voltage characteristics are presented.
Amine-functionalized thin films were prepared by plasma induced deposition of allylamine. Radio frequency (rf) plasma polymerization was carried out under both continuous wave (CW) and pulsed plasma conditions to control the film chemistry, all other process variables being held constant. Using plasma polymerized films for subsequent grafting reactions or for direct biomedical applications usually involves exposure of the films to a solvent environment. It was the major focus of this work to investigate both the chemical and physical effects of solvents on plasma polymerized allylamine films. Film properties were determined using Fourier Transform Infrared Spectroscopy (FTIR), X-ray Photoelectron Spectroscopy (XPS), Waveguide Mode Spectroscopy (WaMS) and Surface Plasmon Spectroscopy (SPS). WaMS provided an ideal opportunity to study the complex swelling and drying behaviour of these films by allowing a simultaneous study of the changes in film thickness and refractive index. Although the amine groups of the monomer were increasingly retained in the films as the RF duty cycle was lowered, a larger amount of oxygen was also found to be incorporated upon exposure to air. Extraction in ethanol led to a decrease in film thickness, especially for the films produced at low duty cycles, but appeared to have little effect on the film composition, as measured by XPS and FTIR.
Coatings of biologically active molecules on synthetic ”bulk“materials are of much interest for biomedical applications since they can in principle elicit specific, predictable. controlled responses of the host environment to an implanted device. However, issues such as shelf life. storage conditions, biological safety, and enzymatic attack in the biological environment must be considered; synthetic proteins may offer advantages. In this study we investigated the covalent immobilization onto polymeric materials of synthetic proteins which possess some properties that mimic those of the natural protein collagen, particularly the ability to form triple helical structures, and thus may provide similar bio-responses while avoiding enzymatic degradation. In order to perform immobilization of these collagen-like molecules (CLMs) under mild reaction conditions, the bulk materials are first equipped with suitable surface groups using rf plasma methods. Plasma polymer interlayers offer advantages as versatile reactive platforms for the immobilization of proteins and other biologically active molecules. Application of a thin plasma polymer coating from an aldehyde monomer is particularly suitable as it enables direct immobilization of CLMs by reaction with their terminal amine groups, using reductive amination chemistry. An alternative route is via plasma polymer layers that contain carboxylic acid groups and using carbodiimnide chemistry. A third route makes use of alkylamme plasma polymer interlayers, which are less process sensitive than aldehyde and acid plasma coatings. A layer of poly-carboxylic acid compounds such as carboxylic acid terminated PAMAM-starburst dendrimers or carboxymethylated dextran is then attached by carbodiimide chemistry onto the amine plasma layer. Amine-terminated CLMs can then be immobilized onto the poly-carboxylic acid layer. Surface analytical methods have been used to characterize the immobilization steps and to assess the surface coverage. Initial cell attachment and growth assays indicate that the biological performance of the CLMs depends on their amino acid sequence.
A cylindrically-configured plasma treatment system in Radio Frequency Glow Discharges fed with ammonia was used to modify the internal surface of ePTFE arterial prostheses. The effects of RF-power on the surface chemical composition were characterized by XPS. Results show that the treatment at 20 W, for 250 seconds and under an ammonia pressure of 300 mtorr yielded a good compromise between ablation and substitution phenomena on the surface. With this treatment, fluorine content was decreased, while up to 20 % of the surface atoms were substituted by nitrogen.