51 resultados para chromatographic separation
Resumo:
Recently, we demonstrated the possibility to extend the range of capillary electrophoresis (CE) applications to the separation of non-water-soluble synthetic polymers. This work focuses on the control of the electro-osmotic flow (EOF) and on the limitation of the solute adsorption in nonaqueous electrolytes. For these purposes, different strategies were investigated. For the initial, a viscous additive (ethylene glycol or glycerol) was used in the electrolyte in order to decrease the EOF magnitude and, possibly, to compete with solute adsorption. A second strategy was to modify, before separation, the fused-silica capillary wall by the adsorption of poly(ethylene oxide) (PEO) via hydrogen bonding. The influence of the molecular mass of the adsorbed PEO on the EOF magnitude and direction was studied in electrolytes based on methanol/acetonitrile mixtures containing ammonium ions. For PEO molecular masses above 1000 g/mol, reversed (anodic) EOF were reported in accordance with previous results obtained with PEO covalently bonded capillaries. The influence of the nature and the concentration of the background electrolyte cation on the EOF magnitude and direction were also investigated. A third strategy consisted in modifying the capillary wall by the adsorption of a cationic polyelectrolyte layer. Advantageously, this polyelectrolyte layer suppressed the adsorption of the polymer solutes onto the capillary wall. The results obtained in this work confirm the high potential and the versatility of CE for the characterization of ionizable organic polymers in nonaqueous media.
Resumo:
The rhythm created by spacing a series of brief tones in a regular pattern can be disguised by interleaving identical distractors at irregular intervals. The disguised rhythm can be unmasked if the distractors are allocated to a separate stream from the rhythm by integration with temporally overlapping captors. Listeners identified which of 2 rhythms was presented, and the accuracy and rated clarity of their judgment was used to estimate the fusion of the distractors and captors. The extent of fusion depended primarily on onset asynchrony and degree of temporal overlap. Harmonic relations had some influence, but only an extreme difference in spatial location was effective (dichotic presentation). Both preattentive and attentionally driven processes governed performance. (PsycINFO Database Record (c) 2012 APA, all rights reserved)
Resumo:
This paper describes the horizontal deflection behaviour of the streams of particles in paramagnetic fluids under a high-gradient superconducting magnetic field, which is the continued work on the exploration of particle magneto-Archimedes levitation. Based on the previous work on the horizontal deflection of a single particle, a glass box and collector had been designed to observe the movement of particle group in paramagnetic fluids. To get the exact separation efficiency, the method of "sink-float" involved the high density fluid polytungstate (dense medium separation) and MLA (Mineral Liberation Analyser) was performed. It was found that the particles were deflected and settled at certain positions on the container floor due to the combined forces of gravity and magneto-Archimedes forces as well as a lateral buoyancy (displacement) force. Mineral particles with different densities and susceptibilities could be deflected to different positions, thus producing groups of similar types of particles. The work described here, although in its infancy, could form the basis of new approach of separating particles based on a combination of susceptibility and density. © 2014 Elsevier B.V.
Resumo:
Uniform thin-films of polymer blends can be produced through spin-coating, which is used on an industrial scale for the production of light emitting diodes, and more recently organic photovoltaic devices. Here, we present the results of the direct observation, and control, over the phase separation of polystyrene and poly(9,9′-dioctylfluorene) during spin-coating using high speed stroboscopic fluorescence microscopy. This new approach, imaging the fluorescence, from a blend of fluorescent + non-fluorescent polymers allows for intensity to be directly mapped to composition, providing a direct determination of composition fluctuations during the spin-coating process. We have studied the compositional development and corresponding structural development for a range of compositions, which produce a range of different phase separated morphologies. We initially observe domains formed by spinodal decomposition, coarsening via Ostwald Ripening until an interfacial instability causes break-up of the bicontinuous morphology. Ostwald ripening continues, and depending upon composition a bicontinuous morphology is re-established. By observing compositional and morphological development in real-time, we are able to direct and control morphological structure development through control of the spin coating parameters via in situ feedback. © 2013 The Royal Society of Chemistry.
Resumo:
In this paper, we investigate the use of manifold learning techniques to enhance the separation properties of standard graph kernels. The idea stems from the observation that when we perform multidimensional scaling on the distance matrices extracted from the kernels, the resulting data tends to be clustered along a curve that wraps around the embedding space, a behavior that suggests that long range distances are not estimated accurately, resulting in an increased curvature of the embedding space. Hence, we propose to use a number of manifold learning techniques to compute a low-dimensional embedding of the graphs in an attempt to unfold the embedding manifold, and increase the class separation. We perform an extensive experimental evaluation on a number of standard graph datasets using the shortest-path (Borgwardt and Kriegel, 2005), graphlet (Shervashidze et al., 2009), random walk (Kashima et al., 2003) and Weisfeiler-Lehman (Shervashidze et al., 2011) kernels. We observe the most significant improvement in the case of the graphlet kernel, which fits with the observation that neglecting the locational information of the substructures leads to a stronger curvature of the embedding manifold. On the other hand, the Weisfeiler-Lehman kernel partially mitigates the locality problem by using the node labels information, and thus does not clearly benefit from the manifold learning. Interestingly, our experiments also show that the unfolding of the space seems to reduce the performance gap between the examined kernels.
Resumo:
Background: Recent morpho-functional evidence pointed out that abnormalities in the thalamus could play a major role in the expression of migraine neurophysiological and clinical correlates. Whether this phenomenon is primary or secondary to its functional disconnection from the brainstem remains to be determined. We used a Functional Source Separation algorithm of EEG signal to extract the activity of the different neuronal pools recruited at different latencies along the somatosensory pathway in interictal migraine without aura (MO) patients. Methods: Twenty MO patients and 20 healthy volunteers (HV) underwent EEG recording. Four ad-hoc functional constraints, two sub-cortical (FS14 at brainstem and FS16 at thalamic level) and two cortical (FS20 radial and FS22 tangential parietal sources), were used to extract the activity of successive stages of somatosensory information processing in response to the separate left and right median nerve electric stimulation. A band-pass digital filter (450-750 Hz) was applied offline in order to extract high-frequency oscillatory (HFO) activity from the broadband EEG signal. Results: In both stimulated sides, significant reduced sub-cortical brainstem (FS14) and thalamic (FS16) HFO activations characterized MO patients when compared with HV. No difference emerged in the two cortical HFO activations between the two groups. Conclusions: Present results are the first neurophysiological evidence supporting the hypothesis that a functional disconnection of the thalamus from the subcortical monoaminergic system may underline the interictal cortical abnormal information processing in migraine. Further studies are needed to investigate the precise directional connectivity across the entire primary subcortical and cortical somatosensory pathway in interictal MO. Written informed consent to publication was obtained from the patient(s).