posted on 2022-05-31, 06:29authored byLing Li, Huan Li, Lin Shi, Lili Shi, Tao Li
As
the oxidative stress is related to human aging and many diseases,
a diversity of antioxidant biomimetic enzymes to eliminate reactive
oxygen species in vivo and maintain the redox balance has attracted
intensive attention. Of particular interest are superoxide dismutase
(SOD)-mimicking artificial enzymes that bear inherent characteristics
of natural counterparts but overcome their deficiencies in thermal
and acidic stability. Inspired by the metallized active center of
natural SODs, here, we engineered different groups of metalloporphyrins
and found that Sn-metallized porphyrins can act as novel SOD mimics,
in which Sn-metallized meso-tetra(4-carboxyphenyl) porphine (Sn-TCPP)
can more effectively catalyze the disproportionation of superoxide
radical anions (•O2–) into hydrogen
peroxide and oxygen. Especially, Sn-TCPP-based metal–organic
frame nanozyme (Sn-PCN222) displays an unusually high catalytic activity
that remarkably exceeds those of commonly used counterparts. Such
unprecedented catalytic behaviors are proposed to depend on the Sn(IV)/Sn(II)
transition at the center of Sn-TCPP. In addition, the metal–organic
framework (MOF) nanozymes also display higher thermal and acidic stability
than natural SODs. Interestingly, we find that Sn-complexed methylated
tetra-(4-aminophenyl) porphyrin shows an aggregation-induced SOD activity
in an acidic environment, whereas conventional SOD mimics do not function
well in this case. Given these unique features, our reported Sn-porphyrin-based
nanozymes would be potent alternatives for natural SODs to be widely
used in clinical treatments of oxidative stress-related diseases.