Ono Toshikazu, Hisaoka Yasushi, Onoda Akira, Oohora Koji, Hayashi Takashi
Department of Applied Chemistry, Graduate School of Engineering, Osaka University, Suita, 565-0871, Japan.
Department of Chemistry and Biochemistry, Center for Molecular Systems (CMS), Kyushu University, 744 Motooka, Nishi-ku, Fukuoka, 819-0395, Japan.
Chem Asian J. 2016 Apr 5;11(7):1036-42. doi: 10.1002/asia.201501415. Epub 2016 Feb 17.
A supramolecular conjugate of myoglobin (Mb) and water-soluble poly(acrylate), (PA5k and PA25k , where 5k and 25k represent the molecular weight of the polymers, respectively), is constructed on the basis of a noncovalent heme-heme pocket interaction. The modified heme with an amino group linked to the terminus of one of the heme-propionates is coupled to the side-chain carboxyl groups of poly(acrylate) activated by N-hydroxysuccinimide. The ratios of the heme-modified monomer unit and the unmodified monomer unit (m:n) in the polymer chains of Heme-PA5k and Heme-PA25k were determined to be 4.5:95.5 and 3.1:96.9, respectively. Subsequent addition of apoMb to the conjugated polymers provides Mb-connected fibrous nanostructures confirmed by atomic force microscopy. A mixture of the heme-modified polymer and dimeric apomyoglobin as a cross-linker forms a microgel in which the reconstituted myoglobin retains its native exogenous ligand binding activity.
基于非共价血红素-血红素口袋相互作用构建了肌红蛋白(Mb)与水溶性聚丙烯酸酯(PA5k和PA25k,其中5k和25k分别代表聚合物的分子量)的超分子共轭物。将带有与血红素丙酸酯之一末端相连的氨基的修饰血红素与经N-羟基琥珀酰亚胺活化的聚丙烯酸酯的侧链羧基偶联。经测定,Heme-PA5k和Heme-PA25k聚合物链中血红素修饰单体单元与未修饰单体单元的比例(m:n)分别为4.5:95.5和3.1:96.9。随后向共轭聚合物中加入脱辅基肌红蛋白,通过原子力显微镜证实形成了与Mb相连的纤维状纳米结构。血红素修饰聚合物与作为交联剂的二聚体脱辅基肌红蛋白的混合物形成一种微凝胶,其中重构的肌红蛋白保留其天然的外源配体结合活性。