微过氧化物酶-8与Eu3+相互作用的机理

用紫外-可见(UV-Vis)吸收光谱和电化学方法研究Eu3+与微过氧化物酶-8(MP-8)相互作用的机理,发现Eu3+优先与MP-8中血红素基团的2个丙酸基的羧基氧发生强的配位作用,导致MP-8分子中血红素基团的非平面性、暴露程度和电化学可逆性的增加.过剩的Eu3+与MP-8分子中肽链上的含氧基团发生弱的相互作用,对血红素基团结构的影响较小.

Interaction Mechanism Between Microperoxidase-8 and Eu3+

The interaction mechanism of microperoxidase-8 (MP-8) and Eu 3+ was determined by using UV-Vis absorption spectroscopic and electrochemical techniques. The study of the UV-Vis absorption spectra indicated that when Eu 3+ is added into the MP-8 solution, the Sored band shifts to the red direction and its absorbance decreases. The difference between the absorbance of the Soret band of the MP-8 solution without and with Eu 3+ increases linearly with increasing the molar ratio of Eu 3+ to MP-8 when the molar ratio is less than 3. When the molar ratio is larger than 3, the difference decreases with increasing the molar ratio. Their extension lines intersect at the molar ratio of 2. The electrochemical study showed that after MP-8 was added into the Eu 3+ solution with the molar ratio of 10, the area of the anodic or cathodic peak of Eu 3+ decreases about 20% comparing with that before adding MP-8. All the UV-Vis absorption spectroscopic and elelctrochemical results illustrated that Eu 3+ ions would coordinate strongly with carboxy oxygen of two propionic acid groups of the heme group in an MP-8 molecule, leading to an increase in the non-planarity of the porphyrin ring, greater exposure degree of the heme group, and better reversibility of the electrochemical reaction of the MP-8 molecule. The excessive Eu 3+ ions weakly interact with the oxygen-contained groups in the peptide chain, resulting in a slight alteration of the structure of the prophyrin group.