Isothermal Titration Calorimetry: Application of the Gibbs-Duhem Equation to the Study of the Relationship Between Forward and Reverse Titrations

被引:5
作者
Grolier, Jean-Pierre E. [1 ]
del Rio, Jose Manuel [2 ]
机构
[1] Inst Chem Clermont Ferrand UMR 6296, F-63177 Aubiere, France
[2] Mexican Inst Petr, Gerencia Herramientas & Sistemas Pozos & Instalac, Mexico City 07730, DF, Mexico
关键词
Isothermal titration calorimetry; Forward titration; Reverse titration; Thermodynamics; Partial enthalpy; Ligand binding; Diluted solutions; BINDING; RECOGNITION;
D O I
10.1007/s10953-014-0243-7
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
In this work we rigorously demonstrate that, in dilute solutions, the partial enthalpy of interaction of the ligand can be measured by a forward titration and that the partial enthalpy of interaction of the macromolecule with the ligand can be calculated from the Gibbs-Duhem equation. Using a reverse titration, it is possible to experimentally obtain the partial enthalpy of interaction of the macromolecule and to calculate that of the ligand. Based on this fact, we propose a thermodynamic criterion to experimentally discern when the forward process is equal to or different from the reverse process: they are equal (or different) if the interaction partial enthalpies obtained experimentally are equal to (or different from) those calculated from the Gibbs-Duhem equation. The above criterion is applied to four systems taken from the literature. The first system features the interaction between a bilayer and a surfactant. The second system features a binding interaction with two binding sites that are equivalent and independent. The final two systems feature binding interactions with two non-equivalent binding sites.
引用
收藏
页码:987 / 1003
页数:17
相关论文
共 18 条
[1]  
Blandamer MJ, 1998, BIOCALORIMETRY, P5
[2]   Titration microcalorimetry [J].
Blandamer, MJ ;
Cullis, PM ;
Engberts, JBFN .
JOURNAL OF THE CHEMICAL SOCIETY-FARADAY TRANSACTIONS, 1998, 94 (16) :2261-2267
[3]   Structural and thermodynamic dissection of specific mannan recognition by a carbohydrate binding module, TmCBM27 [J].
Boraston, AB ;
Revett, TJ ;
Boraston, CM ;
Nurizzo, D ;
Davies, GJ .
STRUCTURE, 2003, 11 (06) :665-675
[4]   Advances in understanding the molecular basis of plant cell wall polysaccharide recognition by carbohydrate-binding modules [J].
Gilbert, Harry J. ;
Knox, J. Paul ;
Boraston, Alisdair B. .
CURRENT OPINION IN STRUCTURAL BIOLOGY, 2013, 23 (05) :669-677
[5]   Isothermal titration calorimetry: A thermodynamic interpretation of measurements [J].
Grolier, Jean-Pierre E. ;
Manuel del Rio, Jose .
JOURNAL OF CHEMICAL THERMODYNAMICS, 2012, 55 :193-202
[6]   On the Physical Meaning of the Isothermal Titration Calorimetry Measurements in Calorimeters with Full Cells [J].
Grolier, Jean-Pierre E. ;
Manuel del Rio, Jose .
INTERNATIONAL JOURNAL OF MOLECULAR SCIENCES, 2009, 10 (12) :5296-5325
[7]   APPLICATION OF ISOTHERMAL TITRATION CALORIMETRY FOR DETECTING LIPID-MEMBRANE SOLUBILIZATION [J].
HEERKLOTZ, H ;
LANTZSCH, G ;
BINDER, H ;
KLOSE, G ;
BLUME, A .
CHEMICAL PHYSICS LETTERS, 1995, 235 (5-6) :517-520
[8]   Titration calorimetry of surfactant-membrane partitioning and membrane solubilization [J].
Heerklotz, H ;
Seelig, J .
BIOCHIMICA ET BIOPHYSICA ACTA-BIOMEMBRANES, 2000, 1508 (1-2) :69-85
[9]   Excess enthalpies of mixing in phospholipid-additive membranes [J].
Heerklotz, HH ;
Binder, H ;
Schmiedel, H .
JOURNAL OF PHYSICAL CHEMISTRY B, 1998, 102 (27) :5363-5368
[10]   Differential Binding Models for Isothermal Titration Calorimetry: Moving beyond the Wiseman Isotherm [J].
Herrera, Isaac ;
Winnik, Mitchell A. .
JOURNAL OF PHYSICAL CHEMISTRY B, 2013, 117 (29) :8659-8672