Tank treading and unbinding of deformable vesicles in shear flow: determination of the lift force

Deformation and tank-treading motion of flaccid vesicles in a linear shear flow close to a wall are quantitatively studied by light microscopy. Velocities of bounded vesicles obey Goldman's law established for rigid spheres. A progressive tilt and a transition of unbinding of vesicles are evidenced upon increasing the shear rate, gamma;. These observations disclose the existence of a viscous lift force, F(l), depending on the viscosity eta of the fluid, the radius R of the vesicle, its distance h from the substrate, and a monotonous decreasing function f(1-v) of the reduced volume v, in the following manner: F(l) = eta(gamma)(R(3)/h)f(1-v). This relation is valid for vesicles both close to and farther from the substrate.     

Construction of discrete series for classical -adic groups

The classification of irreducible square integrable representations of classical -adic groups is completed in this paper, under a natural local assumption. Further, this classification gives a parameterization of irreducible tempered representations of these groups. Therefore, it implies a classification of the non-unitary duals of these groups (modulo cuspidal data). The classification of irreducible square integrable representations is directly related to the parameterization of irreducible square integrable representations in terms of dual objects, which is predicted by Langlands program.

     

Frequency-to-electrode allocation and speech perception with cochlear implants

The hypothesis was investigated that selectively increasing the discrimination of low-frequency information (below 2600 Hz) by altering the frequency-to-electrode allocation would improve speech perception by cochlear implantees. Two experimental conditions were compared, both utilizing ten electrode positions selected based on maximal discrimination. A fixed frequency range (200-10513 Hz) was allocated either relatively evenly across the ten electrodes, or so that nine of the ten positions were allocated to the frequencies up to 2600 Hz. Two additional conditions utilizing all available electrode positions (15-18 electrodes) were assessed: one with each subject's usual frequency-to-electrode allocation; and the other using the same analysis filters as the other experimental conditions. Seven users of the Nucleus CI22 implant wore processors mapped with each experimental condition for 2-week periods away from the laboratory, followed by assessment of perception of words in quiet and sentences in noise. Performance with both ten-electrode maps was significantly poorer than with both full-electrode maps on at least one measure. Performance with the map allocating nine out of ten electrodes to low frequencies was equivalent to that with the full-electrode maps for vowel perception and sentences in noise, but was worse for consonant perception. Performance with the evenly allocated ten-electrode map was equivalent to that with the full-electrode maps for consonant perception, but worse for vowel perception and sentences in noise. Comparison of the two full-electrode maps showed that subjects could fully adapt to frequency shifts up to ratio changes of 1.3, given 2 weeks' experience. Future research is needed to investigate whether speech perception may be improved by the manipulation of frequency-to-electrode allocation in maps which have a full complement of electrodes in Nucleus implants.     

Synthesis and metabolism of the first thia-bilirubin

A symmetrical C(10)-thiabilirubin analogue, 8,12-bis(2-carboxyethyl)-2,3,17,18-tetraethyl-7,13-dimethyl-10-thia-(21H,23H,24H)-bilin-1,19-dione (1), was synthesized from 8-(2-carboxyethyl)-2,3-diethyl-7-methyl-10H-dipyrrin-1-one in one step by reaction with sulfur dichloride. The thia-rubin exhibited the expected IR, UV-vis, and NMR spectroscopic properties, which are rather similar to those of mesobilirubin-XIIIalpha. Like bilirubin and mesobilirubin, 1 adopts an intramolecularly hydrogen-bonded conformation, shaped like a ridge-tile but with a steeper pitch. The longer C-S bond lengths and smaller bond angles at C-S-C, as compared to C-CH(2)-C, lead to an interplanar angle between the two dipyrrinones of only 74 degrees -or considerably less than that of bilirubin (approximately 100 degrees). On normal- and reversed-phase chromatography, 1 is substantially less polar than bilirubin. Despite this conformational distortion, 1 is metabolized in normal rats to acyl glucuronides, which are secreted into bile. In mutant (Gunn) rats lacking bilirubin glucuronosyl transferase, 1 (like bilirubin) was not excreted in bile.     

Ethynylbenzene monolayers on gold: a metal-molecule binding motif derived from a hydrocarbon

Exposure of a Au(111) surface to ethynylbenzene in solution leads to the formation of a bound monolayer. A chemisorption process occurs to give a stable layer consisting of oxygen-containing hydrocarbon species. Ethynylbenzene itself does not oxidize under the deposition conditions indicating that the gold surface facilitates the oxidation process. Calculations show that ethynylbenzene and its oxidation products phenylacetic acid and phenyloxirane have positive binding energies to the gold surface. 1,4-Diethynylbenzene also binds to Au(111) and anchors gold nanoparticles deposited from solution to form dense, semiregular arrays.     

Characterization of the amorphous phase of polyacetylene by thermally stimulated currents

The Thermally Stimulated Current (TSC) Spectroscopy has shown that cis-polyacetylene can be considered as a semi-crystalline polymer. Indeed a relaxation mode obeying a compensation law has been observed: it is the dielectric manifestation of the glass transition. Upon oxidation, two TSC peaks have been observed. They have been associated with two diffusion processes revealing the existence of two amorphous phases: - the intrafibrillar amorphous phase located between crystallites inside the fibrils, - the interfibrillar amorphous phase situated between the fibrils and so much more exposed to oxygen.     

Novel multiparametric approach to elucidate the surface amine-silanization reaction profile on fluorescent silica nanoparticles

This Article addresses the important issue of the characterization of surface functional groups for optical bioassay applications. We use a model system consisting of spherical dye-doped silica nanoparticles (NPs) that have been functionalized with amine groups whereby the encapsulated cyanine-based near-infrared dye fluorescence acts as a probe of the NP surface environment. This facilitates the identification of the optimum deposition parameters for the formation of a stable ordered amine monolayer and also elucidates the functionalization profile of the amine-silanization process. Specifically, we use a novel approach where the techniques of fluorescence correlation spectroscopy (FCS) and fluorescence lifetime measurement (FL) are used in conjunction with the more conventional analytical techniques of zeta potential measurement and Fourier transfer infrared spectroscopy (FTIR). The dynamics of the ordering of the amine layer in different stages of the reaction have been characterized by FTIR, FL, and FCS. The results indicate an optimum reaction time for the formation of a stable amine layer, which is optimized for further biomolecular conjugation, whereas extended reaction times lead to a disordered cross-linked layer. The results have been validated using an immunoglobulin (IgG) plate-based direct binding assay where the maximum number of IgG-conjugated aminated NPs were captured by immobilized anti-IgG antibodies for the NP sample corresponding to the optimized amine-silanization condition. Importantly, these results point to the potential of FCS and FL as useful analytical tools in diverse fields such as characterization of surface functionalization.     

Solvation effects on the valence tautomeric transition of a cobalt complex in the solid state

A detailed investigation of a valence tautomeric (VT) transition for the new complex [Co(III)(3,5-DBCat)(3,5-DBSQ)(py)?]/[Co(II)(3,5-DBSQ)?(py)?] (1) is reported, where 3,5-DBCatH? is 3,5-di-tert-butyl-catechol, 3,5-DBSQH is 3,5-di-tert-butyl-semiquinone and py is pyridine. Complex 1 exists as a mixture of the two valence tautomers, with the relative proportion of each depending on the external conditions. Three differently solvated forms of the complex have been synthesized and variable temperature structural and magnetic investigations of one of these, 1·0.5py, reveals that this compound undergoes a thermally-induced VT transition from the [Co(III)(3,5-DBCat)(3,5-DBSQ)(py)?] tautomer at temperatures below 150 K to a 1 : 1 mixture of the two tautomers at temperatures above 300 K. The VT transition may also be photo-induced at 9 K, affording a similar mixture of the two tautomers. In both cases the incomplete transition is attributed to the presence of π-π stacking interactions between the pyridine molecules of solvation and one of the two crystallographically independent complex molecules, which inhibits the expansion of this molecule that would accompany a VT transition. Studies on alternatively solvated forms 1·2MeCN and 1·1.67hexane also suggest a significant dependence of the VT transition on solvation-induced packing effects and/or intermolecular interactions.