Bimetallic Metal–Organic Framework Fe/Co-MIL-88(NH2) Exhibiting High Peroxidase-like Activity and Its Application in Detection of Extracellular Vesicles

Jiang, Qiaoshi; Xiao, Yuchen; Hong, Anh N.; Gao, Ziting; Shen, Yuyang; Fan, Qingsong; Feng, Pingyun; Zhong, Wenwan

doi:10.1021/acsami.2c12115

Bimetallic Metal–Organic Framework Fe/Co-MIL-88(NH₂) Exhibiting High Peroxidase-like Activity and Its Application in Detection of Extracellular Vesicles

Journal Article · Fri Sep 09 00:00:00 EDT 2022 · ACS Applied Materials and Interfaces

DOI:https://doi.org/10.1021/acsami.2c12115· OSTI ID:2205479

Jiang, Qiaoshi ^[1]; Xiao, Yuchen ^[2]; ^[2]; Gao, Ziting ^[2]; Shen, Yuyang ^[2]; Fan, Qingsong ^[2]; ^[2]; ^[2]

Univ. of California, Riverside, CA (United States); UC Riverside
Univ. of California, Riverside, CA (United States)

Metal–organic frameworks (MOFs) have many attractive features, including tunable composition, rigid structure, controllable pore size, and large specific surface area, and thus are highly applicable in molecular analysis. Depending on the MOF structure, a high number of un-saturated metal sites can be exposed to catalyze chemical reactions. In the present work, we report that by using both Co(II) and Fe(III) to prepare the MIL-88(NH₂) MOF, we can produce the bimetallic MOF that can catalyze the conversion of 3,3', 5,5"-tetramethylbenzidine (TMB) to a color product through reaction with H₂O₂ at a higher reaction rate than the monometallic Fe-MIL-88(NH₂). The Michaelis constants (K_m) of the catalytic reaction for TMB and H₂O₂ are 3-5 times smaller, and the catalytic constants (k_cat) are 5-10 times higher than those of the horse-radish peroxidase (HRP), supporting ultrahigh peroxidase-like activity. These values are also much more superior to those of the HRP-mimicking MOFs reported previously. Interestingly, the bimetallic MOF can be coupled with glucose oxidase (GOx) to trigger the cascade enzymatic reaction for highly sensitive detection of extracellular vesicles (EVs), a family of important biomarkers. Through conjugation to the aptamer that recognizes the marker protein on EV surface, the MOF can help isolate the EVs from biological matrices, which are subsequently labeled by GOx via antibody recognition. The cascade enzymatic reaction between MOF and GOx enables detection of EVs at a concentration as low as 7.8 × 10⁴ particles/ml. Further, the assay can be applied to monitor EV secretion by cultured cells, and also can successfully detect the different EV quantities in the sera samples collected from cancer patients and healthy controls. Overall, we prove that the bimetallic Fe/Co-MIL-88(NH₂) MOF, with its high peroxidase-activity and high biocompatibility, is a valuable tool deployable in clinical assays to facility disease diagnosis and prognosis.

View Accepted Manuscript (DOE)

Research Organization:: Univ. of California, Riverside, CA (United States)

Sponsoring Organization:: National Science Foundation (NSF); USDOE Office of Science (SC), Basic Energy Sciences (BES). Materials Sciences & Engineering Division (MSE)

Grant/Contract Number:: SC0010596

OSTI ID:: 2205479

Alternate ID(s):: OSTI ID: 1978285

Journal Information:: ACS Applied Materials and Interfaces, Journal Name: ACS Applied Materials and Interfaces Journal Issue: 37 Vol. 14; ISSN 1944-8244

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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