Determination of mono-, di-, and oligosaccharides by capillary electrophoresis with capacitively coupled contactless conductivity detection.

Saccharides and chitooligosaccharides can be separated in electrophoretic conditions by raising the pH of the medium, which renders the corresponding alcoholate forms. These anionic species can be separated and detected with capacitively coupled contactless conductivity detection as negative peaks because of their low mobilities when compared to the hydroxyl mobility, which is the main co-ion in the background electrolyte. Three methods for different matrixes are presented in this chapter.

High-voltage power supplies to capillary and microchip electrophoresis.

Over the past years, the development of capillary electrophoresis (CE) and microchip electrophoresis (ME) systems has grown due to instrumental simplicity and wide application. In both CE and ME, the application of a high voltage (HV) is a crucial step in the electrokinetic (EK) injection and separation processes. Particularly on ME devices, EK injection is often performed with three different modes: gated, pinched, and unpinched. In all these cases, different potential values may be applied to one or multiple channels to control the injection of small sample volumes as well as the separation process. For this reason, the construction of reliable HV power supplies (HVPS) is required. This review covers the advances of the development of commercial and laboratory-built HVPS for CE and ME. Moreover, it intends to be a guide for new developers of electrophoresis instrumentation.

Investigating the formation and the properties of monoalkyl carbonates in aqueous medium using capillary electrophoresis with capacitively coupled contactless conductivity detection.

Although alkyl carbonic acids (ACAs) and their salts are referred to as instable species in aqueous medium, we demonstrate that a monoalkyl carbonate (MAC) can in fact be easily formed from bicarbonate and an alcohol even in the presence of a high amount of water. A CE system with two capacitively coupled contactless conductivity detectors (C4Ds) was used to obtain different parameters about these species and their reactions. Based on the mobilities obtained for a series of alcohols ranging from 1 to 5 carbons, the coefficients of diffusion and the hydrodynamic radii were calculated. When compared with the equivalent carboxylates, MACs have radii systematically smaller. Although the precise pK(a) values of the ACAs could not be obtained, because of the fast decomposition in acid medium, it was possible, for the first time, to show that they are below 4.0. This result suggests that the acidity of an ACA is quite similar to the first hydrogen of H2CO3. Using a new approach to indirectly calibrate the C4D, the kinetic constants and the equilibrium constants of formation were also obtained. The results suggest that the increase in the chain length makes the MACs less stable and more inert.

Monitoring the electroosmotic flow in capillary electrophoresis using contactless conductivity detection and thermal marks.

The fundamental aspects and the capillary electrophoresis usage of thermal marks are presented. The so-called thermal mark is a perturbation of the electrolyte concentration generated by a punctual heating of the capillary while the separation electric field is maintained. The heating pulse is obtained by powering tungsten filaments or surface mount device resistors with 5 V during a few tens to hundreds of milliseconds. In the proposed model, the variation of the transport numbers with the rising temperature leads to the formation of low- and high-concentration regions during the heating. After cooling down, the initial mobilities of the species are restored and these regions (the thermal mark) migrate chiefly due to the electroosmotic flow (EOF). The mark may be recorded with a conductivity detector as part of a usual electropherogram and be used to index the analyte peaks and thus compensate for variations of the EOF. In a favorable case, 10 mmol/L KCl solution, the theory suggests that the error in the measurement of EOF mobility by this mean is only -6.5 x 10(-7) cm2 V-1 s-1. The method was applied to the analysis of alkaline ions in egg white, and the relative standard deviations of the corrected mobilities of these ions were smaller than 1%. This is a challenging matrix, because albumin reduces the EOF to 20% of its initial value after 11 runs. The combination of thermal mark, electrolysis separated, and contactless conductivity detection allowed the measurement of the EOF of a silica capillary with unbuffered KCl solution with constant ionic strength. The overall approach is advantageous, because one can easily control the chemical composition of the solution in contact with the inner surface of the capillary.