RESUMEN
A new HPLC stationary phase has been synthesized based on the ionic liquid n-butylimidazolium bromide. Imidazolium was covalently immobilized on a silica substrate through an n-alkyl tether and the retention characteristics of the resulting stationary phase were evaluated systematically. Using 28 small aromatic test solutes and reversed phase conditions, the linear solvation energy relationship approach was successfully used to characterize this new phase. The retention characteristics of the test solutes show remarkable similarity with phenyl stationary phases, despite the presence of a positive charge on the new imidazolium phase. Operated in the reversed phase mode, this new stationary phase shows considerable promise for the separation of neutral solutes and points to the potential for a truly multi-modal stationary phase.
Asunto(s)
Imidazoles/química , Cromatografía Líquida de Alta Presión/métodos , Hidrocarburos Aromáticos/química , Imidazoles/síntesis química , Modelos Lineales , Sensibilidad y Especificidad , Dióxido de Silicio/química , Factores de TiempoRESUMEN
The simulation of the optical response in spectroelectrochemical sensing has been investigated. The sensor consists of a sensing film coated on an optically transparent electrode (OTE). The mode of detection is attenuated total reflection. Only species that partition into the sensing film, undergo electrochemistry at the potentials applied to the OTE, and have changes in their absorbance at the wavelength of light propagated within the glass substrate of the OTE can be sensed. A fundamental question arises regarding the excitation potential waveforms employed to initiate the electrochemical changes observed. Historically, selection has been based solely upon the effectiveness of the waveform to quickly electrolyze any analyte observable by the optical detection method employed. In this report, additional requirements by which the waveform should be selected for use in a remote sensing configuration are discussed. The effectiveness of explicit finite difference simulation as a tool for investigating the applicability of three different excitation potential waveforms (square, triangle, sinusoid) is demonstrated. The simulated response is compared to experimental results obtained from a prototype sensing platform consisting of an indium tin oxide OTE coated with a cation-selective, sol-gel-derived Nafion composite film designed for the detection of a model analyte, tris(2,2'-bipyridyl)ruthenium(II) chloride. Using a diffusion coefficient determined from experimental data (5.8 x 10(-11) cm2 s for 5 x 10(-6) M Ru(bipy)3(2+)), the simulator program was able to accurately predict the magnitude of the absorbance change for each potential waveform (0.497 for square, 0.403 for triangular, and 0.421 for sinusoid), but underestimated the number of cycles required to approach steady state. The simulator program predicted 2 (square), 3 (triangle), and 5 cycles (sinusoid), while 5 (square), 15 (triangle), and 10 (sinusoid) cycles were observed experimentally.
RESUMEN
A qualitative informational similarity technique has been used to describe the informational orthogonality of projected two-dimensional (2-D) chromatographic separations of complex mixtures from their one-dimensional 1-D separations. The reversed-phase liquid chromatography (RPLC), supercritical fluid chromatography (SFC), gas-liquid chromatography (GLC), and micellar electrokinetic capillary chromatography (MECC) retention behavior of up to 46 solutes of varying molecular properties was studied by 2-D range-scaled retention time plots and information entropy calculations. One hundred five combinations of technique/stationary phase pairs were used to simulate the 2-D chromatographic analyses. The informational entropy of one and two dimensions, the mutual information, the synentropy or "cross information", and the informational similarity were calculated to describe the informational orthogonality. In addition, pattern descriptors were used to qualitatively describe the 2-D peak distribution. With the solutes tested, informational orthogonality, zero informational similarity, was observed with MECC-SDS/SFC-C1, MECC-SDS/SFC-Carbowax, MECC-TTAB/SFC-Carbowax, HPLC-C18/GLC-DB-5, HPLC-PBD/SFC-phenyl, SFC-Carbowax/GLC-DB5, and HPLC-phenyl/SFC-phenyl 2-D chromatographic systems. Conversely, with the solutes tested, informational nonorthogonal behavior described by range-scaled retention time plots to moderate to severe band overlap and data clustering was observed with 2-D chromatographic systems with high informational similarity and moderate to high degrees of synentropy. These results should prove useful for predicting complementary 2-D techniques as well as for choosing a second separation technique for confirmation of separation or peak purity.
Asunto(s)
Cromatografía/estadística & datos numéricos , Indicadores y Reactivos , Teoría de la Información , TermodinámicaRESUMEN
Visualization of immobilized antibodies can be achieved with scanning electrochemical microscopy (SECM) by saturation of the antigen binding sites with an alkaline phosphatase-antigen conjugate, which catalyzes hydrolysis of the redox-inactive 4-aminophenyl phosphate to the redox-active 4-aminophenol (PAP). PAP was detected in the collection mode at an amperometric SECM tip. The tip current reflects the density of active binding sites in the immobilized antibody layer. The application of this approach for immunosensing research has been demonstrated with the optimization of a covalent immobilization procedure of antibodies on glass. The special advantages and present limitations of the procedures are discussed.
Asunto(s)
Anticuerpos Monoclonales/química , Sitios de Unión de Anticuerpos , Microscopía Electrónica de Rastreo , Propiedades de SuperficieRESUMEN
A new method for the fabrication and polymer modification of microelectrodes is described. These electrodes are constructed by heat sealing the electroactive material in dual shrink/melt poly(tetrafluoroethylene) (PTFE) under vacuum. The PTFE shield may be activated to provide a support upon which polymers of interest may be grafted. gamma-Irradiation was used to graft polymerize styrene to the surface. The poly-(styrene) was subsequently sulfonated with chlorosulfonic acid to form poly(styrenesulfonate). Scanning electron microscopy and Raman microspectroscopy provide evidence that the poly-(styrenesulfonate) film has been formed and extends over the electrode material. Voltammetry indicates that hexaammine-ruthenium(III) cation is preconcentrated and stabilized via an association with the polymer film.
Asunto(s)
Rayos gamma , Microelectrodos , Poliestirenos/química , Politetrafluoroetileno/química , Resinas de Intercambio de Catión/química , Microscopía Electrónica de Rastreo , Espectrometría RamanRESUMEN
We have integrated a commercially available microprogrammable state machine (Tecmag PULSkit) for use as a magnetic resonance pulse programmer. Providing the capability for active research environment imaging protocols, it features timing resolution of 100 nsec, ten 16-bit loop counters, and individually addressable look-up tables. This integration involved hardware and software integration with a VAX 11/750 at several levels. Hardware: Each of the three gradient channels employs three digital-to-analog converters (DACs). An 8-bit, 4-quadrant, multiplying DAC generates the gradient waveform shape. A 12-bit DAC generates the multiplying DAC scaling voltage, controlling gradient amplitude and sign. A third 12-bit DAC produces a gradient offset (shim) voltage. An eddy current compensation network is present for each gradient channel. Software: The software design philosophy was to create a flexible interface (interactive window environment), while not constraining complex manipulation of the hardware (direct use of the pulse-sequence compiler primitives and microprogramming). The software levels include (a) pulse-sequence microprogramming, (b) pulse-sequence compiler, (c) interactive parameter specification, and (d) canned pulse-sequence microcode library.