Morphology and oxygen sensor response of luminescent Ir-labeled poly(dimethylsiloxane)/polystyrene polymer blend films

Polymer films consisting of a linear poly(dimethylsiloxane) end-functionalized with a luminescent Ir(III) complex (Ir-PDMS), blended with polystyrene (PS), function as optical oxygen sensors. The sensor response arises by quenching of the luminescence from the Ir(III) chromophore by oxygen that permeates into the polymer film. The morphology and luminescence oxygen sensor properties of blend films consisting of Ir-PDMS and PS have been characterized by fluorescence microscopy, atomic force microscopy, and scanning electron microscopy. The investigations demonstrate that microscale phase segregation occurs in the films. In blends that contain a relatively small amount of Ir-PDMS in PS (ca. 10 wt %), the Ir-PDMS exists as circular domains, with diameters ranging from 2 to 5 mum, surrounded by the majority PS phase. For larger weight fractions of Ir-PDMS in the blends, the film morphology becomes bicontinuous. A novel epifluorescence microscopy method is applied that allows the construction of Stern-Volmer quenching images that quantify the oxygen sensor response of the blend films with micrometer spatial resolution. These images provide a map of the oxygen permeability of the polymer blend films with a spatial resolution of ca. 1 mum. The results of this investigation show that the micrometer-sized Ir-PMDS domains display a 2-3-fold higher oxygen sensor response compared to the surrounding PS matrix. This result is consistent with the fact that PDMS is considerably more gas permeable compared to PS. The relationship of the microscale morphology of the blends to their performance as macroscale optical oxygen sensors is discussed.     

A practical synthesis of kifunensine analogues as inhibitors of endoplasmic reticulum alpha-mannosidase I

[reaction: see text] A practical synthesis of the potent class I alpha-mannosidase inhibitor kifunensine (1) beginning from the inexpensive and readily available starting material L-ascorbic acid (15) is described. The protected amino-alcohol ((2R,3R,4R,5R)-5-amino-2,3:4,6-diisopropylidenedioxyhexanol, 11) served as a key intermediate from which several N-1 substituted kifunensine analogues (including N-methyl, N-cyclohexyl, and N-bis(hydroxymethyl)methyl) and 2-desoxakifunensine analogues (including N-H and N-methyl) were prepared and screened for inhibition of human endoplasmic reticulum alpha-mannosidase I (ER Man I) and mouse Golgi alpha-mannosidase IA (Golgi Man IA). In addition, several pseudodisaccharide kifunensine analogues in which a mannose residue was tethered to N-1 of kifunensine via a two-, three-, or four-carbon linker and an affinity-bound kifunensine analogue were also prepared and evaluated for biological activity. While the synthesized N-1 kifunesine analogues were found to be less potent inhibitors of Class I alpha-mannosidases than kifuensine itself, the bis(hydroxymethyl)methylkifunensine analogue 6 was shown to selectively inhibit ER Man I over Golgi Man IA.     

Plane wave source with minimal harmonic distortion for investigating nonlinear acoustic properties

The objective of this investigation is to introduce and validate a practical ultrasound source to be used in the investigation of the nonlinear material properties of liquids and soft tissues studied in vitro. Methods based on the progressive distortion of finite amplitude ultrasonic waves in the low megahertz frequency range are most easily implemented under the assumption of plane wave propagation. However, achieving an approximately planar ultrasonic field over substantial propagation distances can be challenging. Furthermore, undesired harmonic distortion of the ultrasonic field prior to insonification of the specified region of interest represents another serious limitation. This paper introduces an approach based on the use of the ultrasonic field emanating from a stainless-steel delay line. Both simulation and direct experimental measurement demonstrate that such a field exhibits relatively planar wave fronts to a good approximation (such that a 3-mm-diam receiver would be exposed to no more than 3 dB of loss across its face) and is free from the significant harmonic distortion that would occur in a conventional water path.     

An Isserlis’ Theorem for Mixed Gaussian Variables: Application to the Auto-Bispectral Density

This work derives a version of Isserlis’ theorem for the specific case of four mixed-Gaussian random variables. The theorem is then used to derive an expression for the auto-bispectral density for quadratically nonlinear systems driven with mixed-Gaussian iid noise. C.C. Olson is a NRC Postdoctoral Research Associate.     

Passive combination of multiple beams in an optical fiber via stimulated Brillouin scattering

We demonstrate passive combination of multiple beams in an optical fiber via stimulated Brillouin scattering (SBS). Four off-axis beams are combined in a long multimode optical fiber using a novel all-optical mount. The combined beam has the high spatial coherence properties of the LP(01) mode owing to the beam cleanup properties of SBS. The threshold for SBS when off-axis pumps are used is shown to be a factor of 13 times higher than for on-axis pump beams. We propose this method would improve the brightness of an array of fiber amplifiers.     

Transient spike adding in the presence of equilibria

Many models of neuronal activity exhibit complex oscillations in response to an input from other neurons in a network or to an input from a stimulus. We consider the effect of a single short stimulus on a simple model designed to mimic some features of neuronal dynamics. We focus on the transient response induced by the stimulus, particularly on the spike-adding behaviour of the response. Our main goal is to explain how the transient response is affected by the presence of unstable equilibria. We also investigate the dependence of the number of spikes on the amplitude and duration of the stimulus. In our analysis, we use numerical continuation methods and exploit the presence of different time scales in the model.     

In situ study of self-ion irradiation damage in W and W–5Re at 500 °C

In situ self-ion irradiations (150?keV?W⁺) have been carried out on W and W–5Re at 500?°C, with doses ranging from 10¹⁶ to 10¹⁸ W⁺m^?2 (～1.0?dpa). Early damage formation (10¹⁶W⁺m^?2) was observed in both materials. Black–white contrast experiments and image simulations using the TEMACI software suggested that vacancy loops were formed within individual cascades, and thus, the loop nucleation mechanism is likely to be ‘cascade collapse’. Dynamic observations showed the nucleation and growth of interstitial loops at higher doses, and that elastic loop interactions may involve changes in loop Burgers vector. Elastic interactions may also promote loop reactions such as absorption or coalescence or loop string formation. Loops in both W and W–5Re remained stable after annealing at 500?°C. One-dimensional hopping of loops (b?=?1/2 ?111>) was only seen in W. At the final dose (10¹⁸W⁺m^?2), a slightly denser damage microstructure was seen in W–5Re. Both materials had about 3–4?×?10¹⁵ loops m^?2. Detailed post-irradiation analyses were carried out for loops of size???4?nm. Both b?=?1/2 ?111? (～75%) and b?= ?100> (～25%) loops were present. Inside–outside contrast experiments were performed under safe orientations to determine the nature of loops. The interstitial-to-vacancy loop ratio turned out close to unity for 1/2 ?111? loops in W, and for both 1/2 ?111? and ?100? loops in W–5Re. However, interstitial loops were dominant for ?100? loops in W. Re seemed to restrict loop mobility, leading to a smaller average loop size and a higher number density in the W-Re alloy.