Published online 7 January 2005
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Kinetics of tetramolecular quadruplexes
Laboratoire de Biophysique, Muséum National d'Histoire Naturelle USM503 INSERM U565, CNRS UMR 5153, 43 rue Cuvier, 75231 Paris Cedex 05, France
*To whom correspondence should be addressed. Tel: +33 1 40 79 36 89; Fax: +33 1 40 79 37 05; Email: mergny{at}vnumail.com
Received October 21, 2004. Revised December 7, 2004. Accepted December 7, 2004.
The melting of tetramolecular DNA or RNA quadruplexes is kinetically irreversible. However, rather than being a hindrance, this kinetic inertia allows us to study association and dissociation processes independently. From a kinetic point of view, the association reaction is fourth order in monomer and the dissociation first order in quadruplex. The association rate constant k on, expressed in M–3·s–1 decreases with increasing temperature, reflecting a negative activation energy (E on) for the sequences presented here. Association is favored by an increase in monocation concentration. The first-order dissociation process is temperature dependent, with a very positive activation energy E off, but nearly ionic strength independent. General rules may be drawn up for various DNA and RNA sequence motifs, involving 3–6 consecutive guanines and 0–5 protruding bases. RNA quadruplexes are more stable than their DNA counterparts as a result of both faster association and slower dissociation. In most cases, no dissociation is found for G-tracts of 5 guanines or more in sodium, 4 guanines or more in potassium. The data collected here allow us to predict the amount of time required for 50% (or 90%) quadruplex formation as a function of strand sequence and concentration, temperature and ionic strength.
Present address: Barbara Saccà, Laboratoire de Biophysique de l'ADN, Institut Pasteur, 25 rue du Dr Roux, 75724 Paris Cedex 15, France
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