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Electrophoresis

Electrophoresis (from the Greek "ηλεκτροφόρηση"


meaning "to bear electrons") is the motion of
dispersed particles relative to a fluid under the
influence of a spatially uniform electric
field.[1][2][3][4][5][6][7] Electrophoresis of positively
charged particles (cations) is sometimes called
cataphoresis, while electrophoresis of negatively
charged particles (anions) is sometimes called
anaphoresis. Illustration of electrophoresis

The electrokinetic phenomenon of electrophoresis


was observed for the first time in 1807 by Russian
professors Peter Ivanovich Strakhov and Ferdinand
Frederic Reuss at Moscow State University,[8] who
noticed that the application of a constant electric
field caused clay particles dispersed in water to
migrate. It is ultimately caused by the presence of a
charged interface between the particle surface and
the surrounding fluid. It is the basis for analytical
techniques used in chemistry for separating
molecules by size, charge, or binding affinity.

Electrophoresis is used in laboratories to separate


macromolecules based on size. The technique applies
a negative charge so proteins move towards a
positive charge. Electrophoresis is used extensively
in DNA, RNA and protein analysis. Illustration of electrophoresis retardation

Contents
History
Theory
See also
References
Further reading
External links

History
Theory
Suspended particles have an electric surface charge, strongly affected by surface adsorbed species,[9] on
which an external electric field exerts an electrostatic Coulomb force. According to the double layer
theory, all surface charges in fluids are screened by a diffuse layer of ions, which has the same absolute
charge but opposite sign with respect to that of the surface charge. The electric field also exerts a force on
the ions in the diffuse layer which has direction opposite to that acting on the surface charge. This latter
force is not actually applied to the particle, but to the ions in the diffuse layer located at some distance
from the particle surface, and part of it is transferred all the way to the particle surface through viscous
stress. This part of the force is also called electrophoretic retardation force. When the electric field is
applied and the charged particle to be analyzed is at steady movement through the diffuse layer, the total
resulting force is zero :

Considering the drag on the moving particles due to the viscosity of the dispersant, in the case of low
Reynolds number and moderate electric field strength E, the drift velocity of a dispersed particle v is
simply proportional to the applied field, which leaves the electrophoretic mobility μe defined as[10]:

The most well known and widely used theory of electrophoresis was developed in 1903 by
Smoluchowski:[11]

where εr is the dielectric constant of the dispersion medium, ε0 is the permittivity of free space (C² N−1 m
−2), η is dynamic viscosity of the dispersion medium (Pa s), and ζ is zeta potential (i.e., the electrokinetic

potential of the slipping plane in the double layer, units mV or V).

The Smoluchowski theory is very powerful because it works for dispersed particles of any shape at any
concentration. It has limitations on its validity. It follows, for instance, because it does not include Debye
length κ−1 (units m). However, Debye length must be important for electrophoresis, as follows
immediately from the Figure on the right. Increasing thickness of the double layer (DL) leads to
removing the point of retardation force further from the particle surface. The thicker the DL, the smaller
the retardation force must be.

Detailed theoretical analysis proved that the Smoluchowski theory is valid only for sufficiently thin DL,
when particle radius a is much greater than the Debye length:

This model of "thin double layer" offers tremendous simplifications not only for electrophoresis theory
but for many other electrokinetic theories. This model is valid for most aqueous systems, where the
Debye length is usually only a few nanometers. It only breaks for nano-colloids in solution with ionic
strength close to water.
The Smoluchowski theory also neglects the contributions from surface conductivity. This is expressed in
modern theory as condition of small Dukhin number:

In the effort of expanding the range of validity of electrophoretic theories, the opposite asymptotic case
was considered, when Debye length is larger than particle radius:

Under this condition of a "thick double layer", Hückel[12] predicted the following relation for
electrophoretic mobility:

This model can be useful for some nanoparticles and non-polar fluids, where Debye length is much larger
than in the usual cases.

There are several analytical theories that incorporate surface conductivity and eliminate the restriction of
a small Dukhin number, pioneered by Overbeek.[13] and Booth.[14] Modern, rigorous theories valid for
any Zeta potential and often any aκ stem mostly from Dukhin–Semenikhin theory.
[15]

In the thin double layer limit, these theories confirm the numerical solution to the problem provided by
O'Brien and White.[16]

See also
Affinity electrophoresis
Electrophoretic deposition
Capillary electrophoresis
Dielectrophoresis
Electroblotting
Gel electrophoresis
Gel electrophoresis of nucleic acids
Immunoelectrophoresis
Isoelectric focusing
Isotachophoresis
Pulsed-field gel electrophoresis
Nonlinear frictiophoresis

References
1. Lyklema, J. (1995). Fundamentals of Interface and Colloid Science. 2. p. 3.208.
2. Hunter, R.J. (1989). Foundations of Colloid Science. Oxford University Press.
3. Dukhin, S.S.; Derjaguin, B.V. (1974). Electrokinetic Phenomena. J. Wiley and Sons.
4. Russel, W.B.; Saville, D.A.; Schowalter, W.R. (1989). Colloidal Dispersions. Cambridge
University Press.
5. Kruyt, H.R. (1952). Colloid Science. Volume 1, Irreversible systems. Elsevier.
6. Dukhin, A.S.; Goetz, P.J. (2017). Characterization of liquids, nano- and micro- particulates
and porous bodies using Ultrasound (https://www.elsevier.com/books/characterization-of-liq
uids-dispersions-emulsions-and-porous-materials-using-ultrasound/dukhin/978-0-444-6390
8-0). Elsevier. ISBN 978-0-444-63908-0.
7. Anderson, J L (January 1989). "Colloid Transport by Interfacial Forces". Annual Review of
Fluid Mechanics. 21 (1): 61–99. Bibcode:1989AnRFM..21...61A (https://ui.adsabs.harvard.e
du/abs/1989AnRFM..21...61A). doi:10.1146/annurev.fl.21.010189.000425 (https://doi.org/1
0.1146%2Fannurev.fl.21.010189.000425). ISSN 0066-4189 (https://www.worldcat.org/issn/0
066-4189).
8. Reuss, F.F. (1809). "Sur un nouvel effet de l'électricité galvanique". Mémoires de la Société
Impériale des Naturalistes de Moscou. 2: 327–37.
9. Hanaor, D.A.H.; Michelazzi, M.; Leonelli, C.; Sorrell, C.C. (2012). "The effects of carboxylic
acids on the aqueous dispersion and electrophoretic deposition of ZrO2". Journal of the
European Ceramic Society. 32 (1): 235–244. arXiv:1303.2754 (https://arxiv.org/abs/1303.27
54). doi:10.1016/j.jeurceramsoc.2011.08.015 (https://doi.org/10.1016%2Fj.jeurceramsoc.20
11.08.015).
10. Anodic Aqueous electrophoretic Deposition of Titanium Dioxide Using Carboxylic Acids as
Dispersing Agents (https://arxiv.org/ftp/arxiv/papers/1303/1303.2742.pdf) Journal of the
European Ceramic Society, 31(6), 1041-1047, 2011
11. von Smoluchowski, M. (1903). "Contribution à la théorie de l'endosmose électrique et de
quelques phénomènes corrélatifs". Bull. Int. Acad. Sci. Cracovie. 184.
12. Hückel, E. (1924). "Die kataphorese der kugel". Phys. Z. 25: 204.
13. Overbeek, J.Th.G (1943). "Theory of electrophoresis — The relaxation effect". Koll. Bith.:
287.
14. Booth, F. (1948). "Theory of Electrokinetic Effects". Nature. 161 (4081): 83–86.
Bibcode:1948Natur.161...83B (https://ui.adsabs.harvard.edu/abs/1948Natur.161...83B).
doi:10.1038/161083a0 (https://doi.org/10.1038%2F161083a0). PMID 18898334 (https://ww
w.ncbi.nlm.nih.gov/pubmed/18898334).
15. Dukhin, S.S. and Semenikhin N.V. "Theory of double layer polarization and its effect on
electrophoresis", Koll.Zhur. USSR, volume 32, page 366, 1970.
16. O'Brien, R.W.; L.R. White (1978). "Electrophoretic mobility of a spherical colloidal particle".
J. Chem. Soc. Faraday Trans. 2 (74): 1607. doi:10.1039/F29787401607 (https://doi.org/10.1
039%2FF29787401607).

Further reading
Voet and Voet (1990). Biochemistry (https://archive.org/details/biochemistry00voet). John
Wiley & Sons.
Jahn, G.C.; D.W. Hall; S.G. Zam (1986). "A comparison of the life cycles of two
Amblyospora (Microspora: Amblyosporidae) in the mosquitoes Culex salinarius and Culex
tarsalis Coquillett". J. Florida Anti-Mosquito Assoc. 57: 24–27.
Khattak, M.N.; R.C. Matthews (1993). "Genetic relatedness of Bordetella species as
determined by macrorestriction digests resolved by pulsed-field gel electrophoresis". Int. J.
Syst. Bacteriol. 43 (4): 659–64. doi:10.1099/00207713-43-4-659 (https://doi.org/10.1099%2
F00207713-43-4-659). PMID 8240949 (https://www.ncbi.nlm.nih.gov/pubmed/8240949).
Barz, D.P.J.; P. Ehrhard (2005). "Model and verification of electrokinetic flow and transport
in a micro-electrophoresis device". Lab Chip. 5 (9): 949–958. doi:10.1039/b503696h (http
s://doi.org/10.1039%2Fb503696h). PMID 16100579 (https://www.ncbi.nlm.nih.gov/pubmed/
16100579).
Shim, J.; P. Dutta; C.F. Ivory (2007). "Modeling and simulation of IEF in 2-D
microgeometries". Electrophoresis. 28 (4): 527–586. doi:10.1002/elps.200600402 (https://d
oi.org/10.1002%2Felps.200600402).

External links
List of relative mobilities (http://web.med.unsw.edu.au/phbsoft/mobility_listings.htm)

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