JBM  Vol.7 No.5 , May 2019
MOFzyme: FJU-21 with Intrinsic High Protease-Like Activity for Hydrolysis of Proteins
In this work, metal-organic frameworks (MOFs) FJU-21 was synthesized by solvothermal method. The crystal structure of FJU-21 was characterized by XRD and BET and it was applied to the catalytic hydrolysis of bovine serum albumin. The effects of reaction pH, temperature and reaction time on the catalytic activity of FJU-21 were studied. FJU-21 were found to possess an intrinsic enzyme mimicking activity similar to that found in trypsin. The Michaelis constant (Km) of the artificial protease (0.18 × 10-3 - 0.20 × 10-3 M-1) was about 15-fold lower than that free trypsin (2.7 × 10-3 M-1) and about 3-fold lower than that of soluble Cu(II) oxacyclen (0.54 × 10-3 M-1). The Kcat of FJU-21 is 102 times higher than that of soluble Cu(II) oxacyclen catalysts and, indicating a much higher affinity of BSA for FJU-21 surface. FJU-21 could be reused for eleven times without losing in its activity.
Cite this paper: Li, L. , Li, B. , Chen, D. , Zhao, J. , Yang, D. , Ma, D. , Jiang, L. , Yang, Y. , Li, Y. , Wang, J. (2019) MOFzyme: FJU-21 with Intrinsic High Protease-Like Activity for Hydrolysis of Proteins. Journal of Biosciences and Medicines, 7, 222-230. doi: 10.4236/jbm.2019.75024.

[1]   Wulff, G. (2002) Enzyme-Like Catalysis by Molecularly Imprinted Polymers. Chemical Reviews, 102, 1-28.

[2]   Shoji, E. and Freund, M.S. (2002) Potentiometric Saccharide Detection Based on the pKa Changes of Poly (Aniline Boronic Acid). Journal of the American Chemical Society, 124, 12486-12493.

[3]   Marinescu, L.G. and Bols, M. (2010) Very High Rate Eenhancement of Benzyl Alcohol Oxidation by an Artificial Enzyme. Angewandte Chemie, 45, 4590-4593.

[4]   Günter, W., Chong, B. and Ute, K. (2010) Soluble Single-Molecule Nanogels of Controlled Structure as a Matrix for Efficient Artificial Enzymes. Angewandte Chemie, 45, 2955-2958.

[5]   Ali, S.S., Hardt, J.I., Quick, K.L., Kimhan, J.S., Erlanger, B.F., Huang, T.T., et al. (2004) A Biologically Effective Fullerene (C60) Derivative with Superoxide Dismutase Mimetic Properties. Free Radical Biology & Medicine, 37, 1191-1202.

[6]   Pasquato, L., Rancan, F., Scrimin, P., Mancin, F. and Frigeri, C. (2000) N-Methylimidazole-Functionalized Gold Nanoparticles as Catalysts for Cleavage of A Carboxylic Acid Ester. Chemical Communications, 22, 2253-2254.

[7]   Comotti, M., Pina, C.D., Matarrese, R. and Rossi, M. (2004) The Catalytic Activity of “Naked” Gold Particles. Angewandte Chemie International Edition, 43, 5812-5815.

[8]   Seal, S. (2006) Rare Earth Nanoparticles Prevent Retinal Degeneration Induced by Intracellular Peroxides. Nature Nanotechnology, 1, 142-150.

[9]   Gao, L., Zhuang, J., Nie, L., Zhang, J., Zhang, Y., Gu, N., et al. (2007) Intrinsic Peroxidase-Like Activity of Ferromagnetic Nanoparticles. Nature Nanotechnology, 2, 577-583.

[10]   Wei, H. and Wang, E. (2008) Fe3O4 Magnetic Nanoparticles as Peroxidase Mimetics and Their Applications in H2O2 and Glucose Detection. Analytical Chemistry, 80, 2250-2254.

[11]   Fan, K., Cao, C., Pan, Y., Lu, D., Yang, D., Feng, J., et al. (2012) Magnetoferritin Nanoparticles for Targeting and Visualizing Tumour Tissues. Nature Nanotechnology, 7, 459.

[12]   Hegg, E.L. and Burstyn, J.N. (1995) Hydrolysis of Unactivated Peptide Bonds by a Macrocyclic Copper(Ⅱ) Complex: Cu([9]anen3)cl2 Hydrolyzes Both Dipeptides and Proteins. Journal of the American Chemical Society, 117, 7015-7016.

[13]   Jang, B.B., Lee, K.P., Dalhee Min, A. and Suh, J. (1999) Immobile Artificial Metalloproteinase Containing Both Catalytic and Binding Groups. J.Am.Chem.SOC, 120, 12008-12016.

[14]   Jityuti, B., Liwporncharoenvong, T. and Buranaprapuk, A. (2013) Use of a Molybdenum(vi) Complex as Artificial Protease in Protein Photocleavage. Journal of Photochemistry & Photobiology B Biology, 126, 55-59.

[15]   Kim, H.M., Jang, B., Cheon, Y.E., Suh, M.P. and Suh, J. (2009) Proteolytic Activity of Co(Ⅲ) Complex of 1-Oxa-4,7,10-Triazacyclododecane: A New Catalytic Center for Peptide-Cleavage Agents. Journal of Biological Inorganic Chemistry, 14, 151-157.

[16]   Murray, L.J., Dincäf, M. and Long, J.R. (2009) Hydrogen Storage in Metal-Organic Frameworks. Chemical Society Reviews, 38, 1294-1314.

[17]   Li, J.R., Sculley, J. and Zhou, H.C. (2012) Metal-Organic Frameworks for Separatios. Chemical Reviews, 112, 869-932.

[18]   Lee, J.Y., Farha, O.K., Roberts, J., Scheidt, K.A., Nguyen, S.B.T. and Hupp, J.T. (2010) Cheminform Abstract: Metal-Organic Framework Materials as Catalysts. Cheminform, 40.

[19]   Li, B., Chen, D., Wang, J., Yan, Z., Jiang, L., Duan, D., et al. (2014) Mofzyme: Intrinsic Protease-Like Activity of Cu-MOF. Scientific Reports, 4, 6759.

[20]   Yao, Z., Zhang, Z., Liu, L., Li, Z., Zhou, W., Zhao, Y., et al. (2016) Extraordinary Separation of Acetylene-Containing Mixtures with Microporous Metal-Organic Frameworks with Open Donor Sites and Tunable Robustness through Control of the Helical Chain Secondary Building Units. Chemistry, 22, 5676-5683.

[21]   Kim, H., Kim, M.S., Paik, H., Chung, Y.S., Hong, I.S. and Suh, J. (2002) Effective Artificial Proteases Synthesized by Covering Silica Gel with Aldehyde and Various Other Organic Groups. Bioorganic & Medicinal Chemistry Letters, 12, 3247-3250.

[22]   Chang, E.Y., Chae, P.S., Kim, J.E., And, E.J.J. and Suh, J. (2003) Degradation of Myoglobin by Polymeric Artificial Metalloproteases Containing Catalytic Modules with Various Catalytic Group Densities: Site Selectivity in Peptide Bond Cleavage. Journal of the American Chemical Society, 125, 14580.

[23]   Feng, D., Gu, Z.Y., Li, J.R., Jiang, H.L., Wei, Z., Zhou, H.C., et al. (2012) Zirconium-Metalloporphyrin PCN-222: Mesoporous Metal-Organic Frameworks with Ultrahigh Stability as Biomimetic Catalysts. Angewandte Chemie International Edition, 51, 10307-10310.

[24]   Yoo, S.H., Lee, B.J., Kim, H. and Suh, J. (2005) Artificial Metalloprotease with Active Site Comprising Aldehyde Group and Cu(II)cyclen Complex. Journal of the American Chemical Society, 127, 9593-9602.

[25]   And, S.W.J. and Suh, J. (2008) Proteolytic Activity of Cu(II) Complex of 1-oxa-4,7,10-Triazacyclododecane. Organic Letters, 10, 481-484.

[26]   Kim, M.G., Yoo, S.H., Chei, W.S., Lee, T.Y., Kim, H.M. and Suh, J. (2010) Soluble Artificial Metalloproteases with Broad Substrate Selectivity, High Reactivity, and High Thermal and Chemical Stabilities. Journal of Biological Inorganic Chemistry Jbic A Publication of the Society of Biological Inorganic Chemistry, 15, 1023.