MCM-Enzyme-Supramolecular Hydrogel Hybrid as a Fluorescence Sensing Material for Polyanions of Biological Significance
MCM-Enzyme-Supramolecular Hydrogel Hybrid as a Fluorescence Sensing Material for Polyanions of Biological Significance
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DOI：
10.1021/ja900500j
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发表时间：
2009-04-15
影响因子：
15
通讯作者：
Hamachi, Itaru
中科院分区：
文献类型：
--
作者：
Wada, Atsuhiko;Tamaru, Shun-ichi;Hamachi, Itaru
聚阴离子具有广泛的生物活性，是重要的传感靶点。我们报道了一种新型的多阴离子选择性荧光传感系统，该系统由超分子水凝胶、酶和氨基乙基修饰的mcm41型介孔二氧化硅颗粒（NH2-MCM41）包封阴离子荧光染料的杂化材料组成。NH2-MCM41的多阴离子交换能力与半湿超分子水凝胶基质的合理结合成功地产生了三个不同的结构域；即阳离子纳米孔、疏水纳米/微纤维和水体凝胶相，它们彼此正交。NH2-MCM41的阴离子选择性探针释放与酶促反应促进探针易位的耦合使得荧光共振能量转移型传感在杂化材料中对多阴离子如肝素、硫酸软骨素、八硫酸蔗糖等进行传感。凝胶基质中嵌入的磷酸酶（碱性磷酸酶或酸性磷酸酶）催化的酶促去磷酸化也有助于提高对多硫酸盐的感知选择性。很明显，这些材料的正交结构域的形成和保持荧光染料在三个结构域之间的迁移性对于该系统提供的快速和方便的传感至关重要。
Polyanions are important sensing targets because of their wide variety of biological activities. We report a novel polyanion-selective fluorescence sensing system composed of a hybrid material of supramolecular hydrogel, enzymes, and aminoethyl-modified MCM41-type mesoporous silica particles (NH2-MCM41) encapsulating anionic fluorescent dyes. The rational combination of the polyanion-exchange ability of NH2-MCM41 and semi-wet supramolecular hydrogel matrix successfully produced three distinct domains; namely, cationic nanopores, hydrophobic nano/microfibers, and aqueous bulk gel phase, which are orthogonal to each other. The coupling of anion-selective probe release from NH2-MCM41 with translocation of the probe facilitated by enzymatic reaction enabled fluorescence resonance energy transfer-type sensing in the hybrid materials for polyanions such as heparin, chondroitin sulfate, sucrose octasulfate, and so forth. The enzymatic dephosphorylation catalyzed by phosphatase (alkaline phosphatase or acid phosphatase) that is embedded in gel matrix with retention of activity also contributed to improving the sensing selectivity toward polysulfates relative to polyphosphates. It is clear that the orthogonal domain formation of these materials and maintaining the mobility of the fluorescent dyes between the three domains are crucial for the rapid and convenient sensing provided by this system.