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T J Gilligan

Publications and source records attributed to T J Gilligan.

4 recordsLinked to original sources

Dual-mode cooperative binding of adenosine 5'-triphosphate to poly(L-lysine).

Equilibrium dialysis of adenosine triphosphate interacting with polylysine at low polymer concentration yield Scatchard exhibiting an apparent non-cooperative binding mode superimposed on a positively cooperative one. The same behavior has been reported in the literature for various mononucleotides and basic poly(amino acids). It is pointed out here that both modes must not be considered as independent but to be mutually exclusive. Applying a pertinent theoretical approach yields higher degrees of cooperativity than obtained for mutual independence. Another necessary modification in the analysis of data takes into account that one ligand interacts with more than one equivalent binding contact (i.e., an elementary charge here). This leads to a further enhancement of the actual cooperativity. Increasing the polymer concentration in the binding experiments reveals a cooperative effect also in the first binding mode. This is physically interpreted and theoretically analyzed in terms of bound dimers stabilized by base stacking.

Adenosine Triphosphate↗

The self-association of adenosine-5'-triphosphate studied by circular dichroism at low ionic strengths.

The self-association of adenosine-5'-triphosphate (ATP) was studied as a function of pH, additional counterions, concentration and temperature. Circular dichroism measurements were employed as a measure of the base-stacking. The self-association of ATP is pH dependent with the protonation of the adenine ring helping stabilize the association. Highly charged counterions alter this aggregation. At pH 2.8 and 20 degrees C, a dimerization constant of 88 M-1 is obtained, while an isodesmic model leads to an equilibrium constant of 158 M-1. With increasing pH, the association constants decrease. At pH 2.8 there is a very strong temperature dependence of the CD amplitude. These results indicate the existence of additional electrostatic stabilization for the stacking of the adenine rings. At acidic pHs, models are proposed to explain this high degree of stability and a calculation of the approximate electrostatic contribution to the aggregation shows it to be of the proper magnitude.

Adenosine Triphosphate↗