Phosphatidylserine reversibly binds Cu2+ with extremely high affinity.

Phosphatidylserine reversibly binds Cu2+ with extremely high affinity.
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DOI:
10.1021/ja212138e
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发表时间:
2012-05-09
影响因子:
15
通讯作者:
Cremer, Paul S.
Cremer, Paul S.
中科院分区:
化学1区
文献类型:
--
作者:
Monson, Christopher F.;Cong, Xiao;Robison, Aaron D.;Pace, Hudson P.;Liu, Chunming;Poyton, Matthew F.;Cremer, Paul S.

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磷脂酰丝氨酸(PS)嵌入在支撑脂质双层(slb)中,与溶液中的Cu2+具有非常高的亲和力。事实上,平衡解离常数在飞摩尔范围内。所得到的络合物以1:2的Cu2+与PS的比例形成,并以可逆和ph依赖的方式熄灭了广谱的脂质结合荧光团。在酸性pH值下,荧光团几乎完全未淬灭,而在碱性pH值下,荧光团明显淬灭(85-90%)。发生转变的pH值取决于PS的浓度,范围约为pH 5至8。在低Cu2+浓度和碱性pH值下,猝灭动力学缓慢(长达数小时),而在降低pH值时,不猝灭反应的速度要快几个数量级。这与在碱性pH下扩散有限的络合物形成,但在酸性条件下快速解离相一致。在某些情况下,Cu2+与PS的紧密结合可能产生生理后果。
Phosphatidylserine (PS) embedded within supported lipid bilayers (SLBs) was found to bind Cu2+ from solution with extraordinarily high affinity. In fact, the equilibrium dissociation constant was in the femtomolar range. The resulting complex formed in a 1:2 Cu2+ to PS ratio and quenches a broad spectrum of lipid-bound fluorophores in a reversible and pH-dependent fashion. At acidic pH values, the fluorophores were almost completely unquenched, while at basic pH values significant quenching (85–90%) was observed. The pH at which the transition occurred was dependent on the PS concentration and ranged from approximately pH 5 to 8. The quenching kinetics was slow at low Cu2+ concentrations and basic values pH (up to several hours), while the unquenching reaction was orders of magnitude more rapid upon lowering the pH. This was consistent with diffusion limited complex formation at basic pH, but rapid dissociation under acidic conditions. The tight binding of Cu2+ to PS may have physiological consequences under certain circumstances.
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