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Ca2+和La3+在双层膜上的吸附:用滴定热分析法测量吸附焓和结合常数。

Adsorption of Ca2+ and La3+ to bilayer membranes: measurement of the adsorption enthalpy and binding constant with titration calorimetry.

作者信息

Lehrmann R, Seelig J

机构信息

Department of Biophysical Chemistry, Biocenter of the University of Basel, Switzerland.

出版信息

Biochim Biophys Acta. 1994 Jan 3;1189(1):89-95. doi: 10.1016/0005-2736(94)90284-4.

DOI:10.1016/0005-2736(94)90284-4
PMID:8305464
Abstract

The adsorption of Ca2+ and La3+ ions to the surface of lipid bilayer membranes was studied with high sensitivity titration calorimetry. Ca2+ adsorbs to mixed phosphatidylcholine/phosphatidylglycerol membranes with a reaction enthalpy of delta H approximately 0.1-0.2 kcal/mol. La3+ binds to sonified phosphatidylcholine vesicles with a reaction enthalpy of delta H approximately +1.8 kcal/mol. Adsorption of La3+ to phosphatidylcholine bilayers imparts a net positive charge to the membrane surface which makes the binding of further La3+ increasingly more difficult. From the decreasing amplitudes in the calorimetric titration experiment a La3+ adsorption constant of K approximately (4.1 +/- 1.1) x 10(3) M-1 was evaluated. Electrostatic effects were corrected for by means of the Gouy-Chapman theory. The adsorption constant of Ca2+ was determined previously as K approximately 10-20 M-1 using the same binding model. Since the reaction enthalpies of Ca2+ and La3+ adsorption are endothermic, the adsorption of both metal ions to the membrane surface is driven by a distinct change in entropy.

摘要

采用高灵敏度滴定热法研究了Ca2+和La3+离子在脂质双分子层膜表面的吸附情况。Ca2+吸附到混合磷脂酰胆碱/磷脂酰甘油膜上,反应焓ΔH约为0.1 - 0.2 kcal/mol。La3+与超声处理的磷脂酰胆碱囊泡结合,反应焓ΔH约为 +1.8 kcal/mol。La3+吸附到磷脂酰胆碱双分子层上会使膜表面带上净正电荷,这使得进一步吸附La3+变得越来越困难。从量热滴定实验中逐渐减小的幅度,评估出La3+的吸附常数K约为(4.1 ± 1.1)×10³ M⁻¹。借助古依 - 查普曼理论校正了静电效应。使用相同的结合模型,先前测定Ca2+的吸附常数K约为10⁻²⁰ M⁻¹。由于Ca2+和La3+吸附的反应焓是吸热的,两种金属离子在膜表面的吸附是由熵的显著变化驱动的。

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