Electrokinetic electrophoresis

IMPELLING FORCE / Gravitational (ultracentrifugation) Electrokinetic (electrophoresis) Hydrodynamic (chromatography)... 

This chapter introduces the basic concepts and principles of capillary electrophoresis (CE), presenting some background on electrophoresis and capillary electrophesis and describing the components of the system. The two main types of CE, capillary zone and micellar electrokinetic electrophoresis, are described, and a selection strategy, based on the two types of separation, electrophoretic migration and electroosmosis, is presented. 

Berli CLA (2013) The appanmt hydrodynamic slip of polymer solutimis and its implications in electrokinetics. Electrophoresis 34 5) 622-630... 

The most familiar type of electrokinetic experiment consists of setting up a potential gradient in a solution containing charged particles and determining their rate of motion. If the particles are small molecular ions, the phenomenon is called ionic conductance, if they are larger units, such as protein molecules, or colloidal particles, it is called electrophoresis. 

In particular, in polar solvents, the surface of a colloidal particle tends to be charged. As will be discussed in section C2.6.4.2, this has a large influence on particle interactions. A few key concepts are introduced here. For more details, see [32] (eh 13), [33] (eh 7), [36] (eh 4) and [34] (eh 12). The presence of these surface charges gives rise to a number of electrokinetic phenomena, in particular electrophoresis. 

Injecting the Sample The mechanism by which samples are introduced in capillary electrophoresis is quite different from that used in GC or HPLC. Two types of injection are commonly used hydrodynamic injection and electrokinetic injection. In both cases the capillary tube is filled with buffer solution. One end of the capillary tube is placed in the destination reservoir, and the other is placed in the sample vial. 

The last set of experiments provides examples of the application of capillary electrophoresis. These experiments encompass a variety of different types of samples and include examples of capillary zone electrophoresis and micellar electrokinetic chromatography. 

Electrokinetics. The first mathematical description of electrophoresis balanced the electrical body force on the charge in the diffuse layer with the viscous forces in the diffuse layer that work against motion (6). Using this force balance, an equation for the velocity, U, of a particle in an electric field... 

There are four related electrokinetic phenomena which are generally defined as follows electrophoresis—the movement of a charged surface (i.e., suspended particle) relative to astationaiy hquid induced by an applied ectrical field, sedimentation potential— the electric field which is crested when charged particles move relative to a stationary hquid, electroosmosis—the movement of a liquid relative to a stationaiy charged surface (i.e., capiUaty wall), and streaming potential—the electric field which is created when liquid is made to flow relative to a stationary charged surface. The effects summarized by Eq. (22-26) form the basis of these electrokinetic phenomena. 

Electroosmotic flow (EOE) is thus the mechanism by which liquids are moved from one end of the sepai ation capillai y to the other, obviating the need for mechanical pumps and valves. This makes this technique very amenable to miniaturization, as it is fai simpler to make an electrical contact to a chip via a wire immersed in a reservoir than to make a robust connection to a pump. More important, however, is that all the basic fluidic manipulations that a chemist requires for microchip electrophoresis, or any other liquid handling for that matter, have been adapted to electrokinetic microfluidic chips. 

S. Terabe, Electrokinetic cliromatography an interface between electrophoresis and chromatography . Trends Anal. Chem. 8 129-134 (1989). 

Hoyt, JJ Wolfer, WG, Boundary Element Modeling of Electrokinetically Driven Fluid Flow in Two-Dimensional Microchaimels, Electrophoresis 19, 2432, 1998. 

Overbeek, JTG Bijsterbosch, BH, The Electrical Double Layer and the Theory of Electrophoresis. In Electrokinetic Separation Methods Righetti, PG van Oss, CJ Vanderhoff, JW, eds. Elsevier/North-Holland Biomedical Press , 1979 1. 

WORTH c c, wiESSLER M and SCHMITZ o J (2000) Analysis of catechins and caffeine in tea extracts by micellar electrokinetic chromatography . Electrophoresis, 21 (17), 3634-... 

CE was recently used for anthocyanin analysis because of its excellent resolution. This technique has different modes capillary zone electrophoresis (CZE), capillary gel electrophoresis (CGE), micellar electrokinetic chromatography (MEKC), capillary electrochromatography (CEC), capillary isoelectric focusing (CIEE), and capillary isotachophoresis (CITP)."° CZE is the most popular method for anthocyanin... 

Capillary electrophoresis is increasingly used in food analysis due to its separation performance combined with the short time of analysis. - CapiUary electrophoresis recently applied to colorant measurements includes technical variants such as capillary zone electrophoresis (CZE) and micellar electrokinetic chromatography. ... 

Huang, H.Y, Determination of food colorants by microemulsion electrokinetic chromatography, Electrophoresis, 26, 867, 2005. 

Klampfl, C.W., Solvent effects in microemulsion electrokinetic chromatography. Electrophoresis, 24, 1537, 2003. 

Four different electrokinetic processes are known. Two of them, electroosmosis and electrophoresis, were described in 1809 by Ferdinand Friedrich Renss, a professor at the University of Moscow. The schematic of a cell appropriate for realizing and studying electroosmosis is shown in Fig. 31.1a. An electrolyte solution in a U-shaped cell is divided in two parts by a porous diaphragm. Auxiliary electrodes are placed in each of the half-cells to set up an electric held in the solution. Under the inhuence of this held, the solution starts to how through the diaphragm in the direction of one of the electrodes. The how continues until a hydrostahc pressure differential (height of liquid column) has been built up between the two cell parts which is such as to compensate the electroosmotic force. 

The electrokinetic processes can actually be observed only when one of the phases is highly disperse (i.e., with electrolyte in the fine capillaries of a porous solid in the cases of electroosmosis and streaming potentials), with finely divided particles in the cases of electrophoresis and sedimentation potentials (we are concerned here with degrees of dispersion where the particles retain the properties of an individual phase, not of particles molecularly dispersed, such as individual molecules or ions). These processes are of great importance in particular for colloidal systems. 

S. L, Carlucci, A., Bregni, C., Kenndler, E. Comparison of the retention charaderi sties of different pseudostationary phases for microemulsion and micellar electrokinetic chromatography of betamethasone and derivatives. Electrophoresis 2003, 24, 984-991. 

Ostergaard, J., Hansen, S. H., Larsen, C., Schou, C., Heegaard, N. H. Determination of octanol-water partition coefficients for carbonate esters and other small organic molecules by microemulsion electrokinetic chromatography. Electrophoresis 2003, 24, 1038-1045. 

Huie, C. W. Recent applications of microemulsion electrokinetic chromatography. Electrophoresis 2006, 27, 60-75. 

A variety of formats and options for different types of applications are possible in CE, such as micellar electrokinetic chromatography (MEKC), isotachophoresis (ITP), and capillary gel electrophoresis (CGE). The main applications for CE concern biochemical applications, but CE can also be useful in pesticide methods. The main problem with CE for residue analysis of small molecules has been the low sensitivity of detection in the narrow capillary used in the separation. With the development of extended detection pathlengths and special optics, absorbance detection can give reasonably low detection limits in clean samples. However, complex samples can be very difficult to analyze using capillary electrophoresis/ultraviolet detection (CE/UV). CE with laser-induced fluorescence detection can provide an extraordinarily low LOQ, but the analytes must be fluorescent with excitation peaks at common laser wavelengths for this approach to work. Derivatization of the analytes with appropriate fluorescent labels may be possible, as is done in biochemical applications, but pesticide analysis has not been such an important application to utilize such an approach. 

Interfacial Electrokinetics and Electrophoresis, edited by Angel V. Delgado... 

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