In situ synthesis of monolithic stationary phases for electrochromatographic separations: study of polymerization conditions

Acrylate-based monolithic capillary columns were prepared from fused-silica capillaries using UV photopolymerization. The effect of the pretreatment of the capillary wall surface before polymerization was investigated and several procedures were compared. The columns were characterization by van Deemter curves and SEM imaging. The results indicated that a pre-silanization of the capillary wall in order to introduce methacrylate groups at the wall surface gave similar efficiencies but more homogeneous structures than when the silanization agent was introduced in the polymerization mixture. The conditioning of the capillary before silanization, especially the conditions of basic rinsing was also an important factor. The effect of the dose of UV light that was applied for the polymerization had also been investigated. The results demonstrated that the irradiation energy is a critical parameter. The minimum energy threshold required to obtain a suitable monolith was 3 J/cm(2) and the maximum was around 12 J/cm(2). A higher energy destroys the monolith. Within the convenient range of energy, the columns had the same efficiency and a good structure as seen by SEM imaging. Using the optimized procedure for the pretreatment and an adequate energy, the column-to-column repeatability was found good (n = 12). The repeatability was obtained for the plate height at two velocity values, the retention factor and the electroosmotic mobility with RSD values below 10.     

Validation and evaluation of a high performance liquid chromatographic method for the determination of aluminium in wine

A new method is reported for the determination of aluminium in wine by HPLC, involving derivatisation with 8-hydroxyquinoline (oxine) in the presence of micelles resulting in the formation of a fluorescent derivative. The complex is separated on a C18 column using a mobile phase of oxine - SDS - 35% acetonitrile, in a pH 7 buffer. The method was validated in the range 0.125-2 mg/l in a synthetic wine. The method was applied to the determination of aluminium in white, rosé and red wines and results compared with those obtained by atomic absorption (GFAA). Aluminium concentrations found by HPLC in white wines were greater than those found in red wines. Further investigation using a polyphenol-enriched white wine revealed a statistically significant inverse relationship between wine polyphenol content and the aluminium concentration determined by HPLC. The method may therefore be envisaged for the determination of unbound aluminium in wine.     

Characterization of hemoglobin Würzburg (alpha2beta2 4(A1)Thr-->Asn), a new electrophoretically silent variant, by mass spectrometry and molecular modeling studies

The first hemoglobin (Hb) variant carrying a mutation at beta4 was identified as beta4(A1)Thr-->Asn or Hb Würzburg and constituted 38% of the total hemoglobin. It showed a slightly elevated oxygen affinity and a slightly decreased cooperativity index (n50 = 2.3 versus n50 = 2.8). The analysis of the electrostatic potential showed an increased negative charge at the site of the mutation with a displacement of beta6(A3)Glu by 1.3A. The replacement of threonine by asparagine seems to stabilize the R conformation. This may explain partially both the high affinity and the reduction in cooperativity.     

Bacillibactin-mediated iron transport in Bacillus subtilis

The hexadentate triscatecholamide bacillibactin delivers iron to Bacillus subtilis and is structurally similar to enterobactin, although in a more oblate conformation. B. subtilis uses two partially overlapping permeases (1 and 2) to acquire iron from its endogenous siderophores (bacillibactin and itoic acid). Enterobactin and bacillibactin have opposite metal chiralities, different affinity for ferric ion, and dissimilar iron transport behaviors. The solution thermodynamic stability of ferric bacillibactin has been investigated through potentiometric and spectrophotometric titrations. The addition of a glycine to the catechol chelating arms causes a destabilization of the ferric complex of bacillibactin compared to ferric enterobactin. B. subtilis appears to express a separate receptor for enterobactin (permease 3), although enterobactin can also be transported through the permease for bacillibactin (permease 2).     

The case of the missing delay lines: synthetic delays obtained by cross-channel phase interaction

Temporal models of pitch and harmonic segregation call for delays of up to 30 ms to cover the full range of existence of musical pitch. To date there is little anatomical or physiological evidence for delays that long. We propose a mechanism by which delays may be synthesized from cross-channel phase interaction. Phases of adjacent cochlear filter channels are shifted by an amount proportional to frequency and then combined as a weighted sum to approximate a delay. Synthetic delays may be used by pitch perception models such as autocorrelation, segregation models such as harmonic cancellation, and binaural processing models to explain sensitivity to large interaural delays. The maximum duration of synthetic delays is limited by the duration of the impulse responses of cochlear filters, itself inversely proportional to cochlear filter bandwidth. Maximum delay is thus frequency dependent. This may explain the fact, puzzling for temporal pitch models such as autocorrelation, that pitch is more salient and easy to discriminate for complex tones that contain resolved partials.     

Decentralized harmonic active vibration control of a flexible plate using piezoelectric actuator-sensor pairs

We have investigated decentralized active control of periodic panel vibration using multiple pairs combining PZT actuators and PVDF sensors distributed on the panel. By contrast with centralized MIMO controllers used to actively control the vibrations or the sound radiation of extended structures, decentralized control using independent local control loops only requires identification of the diagonal terms in the plant matrix. However, it is difficult to a priori predict the global stability of such decentralized control. In this study, the general situation of noncollocated actuator-sensor pairs was considered. Frequency domain gradient and Newton-Raphson adaptation of decentralized control were analyzed, both in terms of performance and stability conditions. The stability conditions are especially derived in terms of the adaptation coefficient and a control effort weighting coefficient. Simulations and experimental results are presented in the case of a simply supported panel with four PZT-PVDF pairs distributed on it. Decentralized vibration control is shown to be highly dependent on the frequency, but can be as effective as a fully centralized control even when the plant matrix is not diagonal-dominant or is not strictly positive real (not dissipative).     

How does crystalline substrate plasticity modify thin film buckling?

We report experimental atomic force microscopy observations and analytical modeling of buckling structures of thin films deposited on single crystal substrates. The formation of straight-sided blisters just above the step structures resulting from the dislocations emergence has been observed and explained in the framework of the F?ppl-von Karman theory of thin plates. A critical step height above which the buckling may occur has been determined and the asymmetry of the resulting blisters has been explained. Finally, the new buckling criterion has been compared with the classical one in the plane case and allows us to explain the blisters localization on step structures.     

Mode-coupling control in resonant devices: Application to solid-state ring lasers

We report the theoretical and experimental investigation of the effects of mode coupling in a resonant macroscopic quantum device, in the case of a solid-state ring laser. This is achieved by introducing an additional coupling source whose interplay with the already-existing nonlinear effects ensures the coexistence of two counterpropagating cavity modes yielding a rotation-sensitive beat note. The determination of the condition for rotation sensing, both theoretically and experimentally, allows a quantitative study of the role of various mode-coupling mechanisms, in particular, the gain-induced mode coupling. We point out the connection between our work and the theoretical work on mode coupling in superfluid devices. This work opens up the possibility of new types of active rotation sensors.     

Theory and simulation of wave phase conjugation

This paper briefly presents the general analytical solution for the resonant modes in 1D active magneto acoustic phase conjugators in contact with passive media of arbitrary impedance. The first non-resonant but amplified modes are also derived. All results are successfully compared with direct numerical simulations.     

Localization Properties of the Chalker–Coddington Model

The Chalker–Coddington quantum network percolation model is numerically pertinent to the understanding of the delocalization transition of the quantum Hall effect. We study the model restricted to a cylinder of perimeter 2M. We prove first that the Lyapunov exponents are simple and in particular that the localization length is finite; secondly, that this implies spectral localization. Thirdly, we prove a Thouless formula and compute the mean Lyapunov exponent, which is independent of M.