Pressure and temperature dependence of the reaction of vinyl radical with ethylene

This work reports measurements of absolute rate coefficients and Rice-Ramsperger-Kassel-Marcus (RRKM) master equation simulations of the C2H3+C2H4 reaction. Direct kinetic studies were performed over a temperature range of 300-700 K and pressures of 20 and 133 mbar. Vinyl radicals (H2C=CH) were generated by laser photolysis of vinyl iodide (C2H3I) at 266 nm, and time-resolved absorption spectroscopy was used to probe vinyl radicals through absorption at 423.2 nm. Measurements at 20 mbar are in good agreement with previous determinations at higher temperature. A weighted three-parameter Arrhenius fit to the experimental rate constant at 133 mbar, with the temperature exponent fixed, gives k=(7+/-1)x10(-14) cm3 molecule(-1) s(-1) (T/298 K)2 exp[-(1430+/-70) K/T]. RRKM master equation simulations, based on G3 calculations of stationary points on the C4H7 potential energy surface, were carried out to predict rate coefficients and product branching fractions. The predicted branching to 1-methylallyl product is relatively small under the conditions of the present experiments but increases as the pressure is lowered. Analysis of end products of 248 nm photolysis of vinyl iodide/ethylene mixtures at total pressures between 27 and 933 mbar provides no direct evidence for participation of 1-methylallyl.     

Generation of 3.5 nJ femtosecond pulses from a continuous-wave laser without mode locking

Using time-lens compression in a loop configuration, we generate 516 fs pulses at 3.5 nJ pulse energy from a continuous-wave 1.55 mum source without mode locking. Just as a spatial lens can expand or focus a beam in space, so can a time-lens broaden or compress a pulse in time. By placing a time-lens in a loop, we maximize the efficiency of bandwidth generation by using one time-lens driven at low power to emulate a stack of many lenses. Our system is compact, is all fiber, and allows large tuning of the repetition rate and continuous tuning of the pulse width and center wavelength.     

A tilting procedure to enhance compositional contrast and reduce residual diffraction contrast in energy-filtered TEM imaging of planar interfaces

This paper systematically demonstrates that energy-filtered transmission electron microscope (EFTEM) images of a planar interface between two single crystals have increased compositional contrast and decreased residual diffraction contrast when the sample is oriented so that the electron beam is parallel to the interface, but not directly on a zone axis. This off-axis orientation reduces diffraction contrast in the unfiltered (and zero-loss) image, which in turn, reduces residual diffraction contrast in single energy-filtered TEM (EFTEM) images, thickness maps, jump-ratio images, and elemental maps. Most importantly, this procedure produces EFTEM images that are more directly interpretable and, in most cases, possess superior spatial resolution compared to EFTEM images acquired directly on a zone axis.     

On the role of glottis-interior sources in the production of voiced sound

The voice source is dominated by aeroacoustic sources downstream of the glottis. In this paper an investigation is made of the contribution to voiced speech of secondary sources within the glottis. The acoustic waveform is ultimately determined by the volume velocity of air at the glottis, which is controlled by vocal fold vibration, pressure forcing from the lungs, and unsteady backreactions from the sound and from the supraglottal air jet. The theory of aerodynamic sound is applied to study the influence on the fine details of the acoustic waveform of "potential flow" added-mass-type glottal sources, glottis friction, and vorticity either in the glottis-wall boundary layer or in the portion of the free jet shear layer within the glottis. These sources govern predominantly the high frequency content of the sound when the glottis is near closure. A detailed analysis performed for a canonical, cylindrical glottis of rectangular cross section indicates that glottis-interior boundary/shear layer vortex sources and the surface frictional source are of comparable importance; the influence of the potential flow source is about an order of magnitude smaller.     

A note on the UV behaviour of maximally supersymmetric Yang–Mills theories

The question of whether BPS invariants are protected in maximally supersymmetric Yang–Mills theories is investigated from the point of view of algebraic renormalisation theory. The protected invariants are those whose cohomology type differs from that of the action. It is confirmed that one-half BPS invariants (F⁴$F^4$) are indeed protected while the double-trace one-quarter BPS invariant (d²F⁴$d^2{F}^4$) is not protected at two loops in D=7$D=7$, but is protected at three loops in D=6$D=6$ in agreement with recent calculations. Non-BPS invariants, i.e. full superspace integrals, are also shown to be unprotected.     

Toric degeneration of branching algebras

For each classical symmetric pair (G,H), there is a naturally defined multi-graded algebra , called the branching algebra for (G,H), which encodes the branching rule from G to H. This algebra has a natural family of subalgebras, depending on integer parameters. For a certain range of the parameters, the subalgebras have a particularly simple structure and are called stable branching algebras.In this paper, we show that the stable branching algebras for eight out of the ten families of classical symmetric pairs are flat deformations of the semigroup algebras of explicitly described lattice cones.     

Comments on single-mass models of vocal fold vibration

Proposed mechanisms for single-mass oscillation in the vocal tract are examined critically. There are two areas that distinguish single-mass models: in the sophistication of the air flow modeling near the oscillator and whether or not oscillation depends on acoustic feedback. Two recent models that do not depend on acoustic feedback are examined in detail. One model that depends on changing flow separation points is extended with approximate calculations.     

Removal of zero-quantum peaks from 1D selective TOCSY and NOESY spectra

Selective 1D TOCSY and NOESY experiments are widely used for structure determination. However, they often give distorted peak shapes owing to coherence transfer though zero-quantum coherence (ZQ) which cannot be suppressed by conventional phase cycling or pulse-field gradients. This paper demonstrates that ZQ contributions can be removed from selective 1D spectra by introducing a ZQ evolution time, as previously demonstrated for 2D NOESY spectra by Wang et al. [A three-dimensional method for the separation of zero-quantum coherence and NOE in NOESY spectra, J. Magn. Reson. A 102 (1993) 116-121]. This approach is simple to implement and robust, and is not demanding of spectrometer hardware. Using a new approach to phase cycling described here, spectra can be acquired in a similar time to spectra without a ZQ evolution time.     

Tri-partite complex for axonal transport drug delivery achieves pharmacological effect

Background

Targeted delivery of pharmaceutical agents into selected populations of CNS (Central Nervous System) neurons is an extremely compelling goal. Currently, systemic methods are generally used for delivery of pain medications, anti-virals for treatment of dermatomal infections, anti-spasmodics, and neuroprotectants. Systemic side effects or undesirable effects on parts of the CNS that are not involved in the pathology limit efficacy and limit clinical utility for many classes of pharmaceuticals. Axonal transport from the periphery offers a possible selective route, but there has been little progress towards design of agents that can accomplish targeted delivery via this intraneural route. To achieve this goal, we developed a tripartite molecular construction concept involving an axonal transport facilitator molecule, a polymer linker, and a large number of drug molecules conjugated to the linker, then sought to evaluate its neurobiology and pharmacological behavior.

Results

We developed chemical synthesis methodologies for assembling these tripartite complexes using a variety of axonal transport facilitators including nerve growth factor, wheat germ agglutinin, and synthetic facilitators derived from phage display work. Loading of up to 100 drug molecules per complex was achieved. Conjugation methods were used that allowed the drugs to be released in active form inside the cell body after transport. Intramuscular and intradermal injection proved effective for introducing pharmacologically effective doses into selected populations of CNS neurons. Pharmacological efficacy with gabapentin in a paw withdrawal latency model revealed a ten fold increase in half life and a 300 fold decrease in necessary dose relative to systemic administration for gabapentin when the drug was delivered by axonal transport using the tripartite vehicle.

Conclusion

Specific targeting of selected subpopulations of CNS neurons for drug delivery by axonal transport holds great promise. The data shown here provide a basic framework for the intraneural pharmacology of this tripartite complex. The pharmacologically efficacious drug delivery demonstrated here verify the fundamental feasibility of using axonal transport for targeted drug delivery.     

Flow and oxygenation dependent (FLOOD) contrast MR imaging to monitor the response of rat tumors to carbogen breathing

Gradient recalled echo (GRE) images are sensitive to both paramagnetic deoxyhaemoglobin concentration (via T2*) and flow (via T1*). Large GRE signal intensity increases have been observed in subcutaneous tumors during carbogen (5% carbon dioxide, 95% oxygen) breathing. We term this combined effect flow and oxygenation-dependent (FLOOD) contrast. We have now used both spin echo (SE) and GRE images to evaluate how changes in relaxation times and flow contribute to image intensity contrast changes. T1-weighted images, with and without outer slice suppression, and calculated T2, T2* and "flow" maps, were obtained for subcutaneous GH3 prolactinomas in rats during air and carbogen breathing. T1-weighted images showed bright features that increased in size, intensity and number with carbogen breathing. H&E stained histological sections confirmed them to be large blood vessels. Apparent T1 and T2 images were fairly homogeneous with average relaxation times of 850 ms and 37 ms, respectively, during air breathing, with increases of 2% for T1 and 11% for T2 during carbogen breathing. The apparent T2* over all tumors was very heterogeneous, with values between 9 and 23 ms and localized increases of up to 75% during carbogen breathing. Synthesised "flow" maps also showed heterogeneity, and regions of maximum increase in flow did not always coincide with maximum increases in T2*. Carbogen breathing caused a threefold increase in arterial rat blood PaO2, and typically a 50% increase in tumor blood volume as measured by 51Cr-labelled RBC uptake. The T2* increase is therefore due to a decrease in blood deoxyhaemoglobin concentration with the magnitude of the FLOOD response being determined by the vascular density and responsiveness to blood flow modifiers. FLOOD contrast may therefore be of value in assessing the magnitude and heterogeneity of response of individual tumors to blood flow modifiers for both chemotherapy, antiangiogenesis therapy in particular, and radiotherapy.