Fluorescence patterns from supramolecular polymer assembly and disassembly for sensing metallo- and nonmetalloproteins.
Fluorescence patterns from supramolecular polymer assembly and disassembly for sensing metallo- and nonmetalloproteins.
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DOI：
10.1021/ja900579g
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发表时间：
2009-06-10
影响因子：
15
通讯作者：
Thayumanavan S
中科院分区：
文献类型：
--
作者：
González DC;Savariar EN;Thayumanavan S
当聚电解质充当抗衡离子时，表面活性剂的临界聚集浓度（CAC）会降低。当浓度介于表面活性剂和聚合物-表面活性剂复合物的 CAC 之间时，可以实现蛋白质诱导的分解。这是因为，当蛋白质竞争性地与聚电解质结合时，表面活性剂无法维持该浓度下的胶束型组装。由于这些两亲性聚集体能够非共价隔离疏水性客体分子，因此蛋白质结合诱导的分解过程也会导致客体从这些组装体中释放。我们在这里表明，不同蛋白质的荧光变化不仅取决于聚合物-表面活性剂复合物的性质，还取决于荧光传感器。有两个过程可能导致观察到的荧光变化：荧光团客体从组件的疏水内部释放或由于分析物中的互补成分而激发态猝灭。后一种机制对于金属蛋白尤其可能。我们在这里表明，在蛋白质的纳摩尔浓度下，激发态猝灭是可能的，而在微摩尔浓度下，基于拆卸的荧光减少是主要途径。
Critical aggregation concentration (CAC) of surfactants is lowered, when polyelectrolytes act as counterions. At a concentration in between the CACs of the surfactant and the polymer-surfactant complex, protein-induced disassemblies can be achieved. This is because, when proteins competitively bind to the polyelectrolytes, the surfactants are not capable of sustaining a micelle-type assembly at this concentration. Since these amphiphilic aggregates are capable of non-covalently sequestering hydrophobic guest molecules, the protein binding induced disassembly process also results in a guest release from these assemblies. We show here that the change in fluorescence with different proteins is not only dependent on the nature of the polymer-surfactant complex, but also on the fluorescent transducer. Two processes can be responsible for the observed fluorescence change: fluorophore guest release from the hydrophobic interior of the assembly or excited state quenching due to complementary components in the analyte. The latter mechanism is especially possible with metalloproteins. We show here that at nanomolar concentration of the proteins, an excited state quenching is possible while at micromolar concentrations the disassembly-based fluorescence reduction is the dominant pathway.
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影响因子：
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