Multivariate mesoporous MOFs with regulatable hydrophilic/hydrophobic surfaces as a versatile platform for enzyme immobilization

doi:10.1016/S1872-2067(24)60020-3

Abstract

Abstract:

Zeolitic imidazole frameworks materials-8 (ZIF-8), a member of the metal-organic framework (MOFs) series, have been extensively used as a host matrix for enzyme immobilization. However, the microporous structure and hydrophobicity, as well as the protonation of the precursor 2-methylimidazole (2-MeIm) of ZIF-8, remain considerable challenges in maintaining the activity of immobilized enzymes. Here, novel multivariate mesoporous MOFs (mMOFs) with regulatable hydrophilic/hydrophobic surfaces were designed by the multivariate competitive strategy and pore modification engineering. 3-Methyl-1H-1,2,4-triazole (3-MTZ) and 5-methyltetrazole (5-MTA) were employed to partially replace 2-MeIm. These were then combined with zinc sulfate heptahydrate (soft templates) to yield mMOFs in a methanol solution. As a proof-of-concept application, we used mMOFs as carriers for enzyme immobilization and investigated the properties of the immobilized enzymes. Benefiting from their mesoporous structure, hydrophilic surface, and improved microenvironment, multivariate mMOFs exhibit a strong ability to stabilize enzyme conformation and increase enzyme activity compared with traditional ZIF-8. Our study offers an avenue for the controllable preparation of well-designed MOF structures, which will further broaden the application opportunities of MOF materials for enzyme immobilization.

Key words: Mesoporous metal-organic frameworks, Competitive ligand, Soft template, Immobilized enzyme

Yuxiao Feng, Qingqing Ma, Zichen Wang, Qunli Zhang, Lixue Zhao, Jiandong Cui, Yingjie Du, Shiru Jia. Multivariate mesoporous MOFs with regulatable hydrophilic/hydrophobic surfaces as a versatile platform for enzyme immobilization[J]. Chinese Journal of Catalysis, 2024, 60: 386-398.

×
share this article

Add to citation manager EndNote|Ris|BibTeX

URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(24)60020-3

https://www.cjcatal.com/EN/Y2024/V60/I5/386

Figures/Tables 5

Fig. 1. (a) Schematic for the preparation and properties of ZIF-8, HZIF-8, and mMOFs. (b) Schematic for synthesis process of mMOFs and mMOFs/HRP.

Fig. 2. SEM images of ZIF-8 (Scale bar 0.2 μm) (a), mMOFs before removing the template (Scale bar 2 μm) (b), mMOFs (Scale bar 2 μm) (c), surface magnification of mMOFs (Scale bar 0.5 μm) (d). TEM images of ZIF-8 (Scale 0.2 μm) (e), mMOFs before removing the template (f), mMOFs (g), surface magnification of mMOFs (h). (i) N2 adsorption-desorption isotherms of ZIF-8 and the mMOFs. (j) Pore size distributions of ZIF-8 and the mMOFs. (k) FTIR spectra of ZIF-8 and mMOFs. (l) PXRD patterns of ZIF-8 and mMOFs.

Fig. 3. (a) Recovery activity of ZIF-8/HRP, HZIF-8/HRP, mMOFs/HRP, and mMOFs. (b) Immobilization efficiency of ZIF-8/HRP, HZIF-8/HRP, and mMOFs/HRP. (c) Zeta potentials of ZIF-8, HZIF-8, mMOFs, and HRP. (d) Short-term storability of HRP, ZIF-8/HRP, HZIF-8/HRP, and mMOFs/HRP. (e) CD spectra of HRP, ZIF-8/HRP, HZIF-8/HRP and mMOFs/HRP supernatants. (f) UV-vis full wavelength scanning absorption spectra of HRP, ZIF-8/HRP, HZIF-8/HRP and mMOFs/HRP supernatants. (g) pH of 2-MeIm, 3-MTZ, 5-MTA, ZIF-8, HZIF-8 and mMOFs in water. (h) CLSM images of mMOFs/HRP (Scale bar: 10 μm). (i) EDS mapping of mMOFs/HRP (Scale bar: 2 μm).

Fig. 4. (a) EDS mapping of mMOFs/GOxHRP (Scale bar: 2 μm). (b) Schematic of the three immobilization sequences. (c) CLSM images of mMOFs/GOxHRP (HRP labeled with RhB, GOx labeled with FITC, Scale bar: 10 μm).

Fig. 5. (a) Cascade reaction activity of ZIF-8/GOxHRP, HZIF-8/GOxHRP and mMOFs/GOxHRP. (b) UV-vis spectra of the mMOFs/GOxHRP after chromogenic reaction at glucose concentrations of 10-400 μmol/L. (c) Linearity between absorbance values and glucose concentration after mMOFs/GOxHRP detection of glucose. (d) Selectivity of mMOFs/GOxHRP for 50 μmol/L glucose in comparison to 500 μM lactose, maltose, mannose, galactose, and fructose.

References

[1]	X. Zhang, R. Tu, Z. Lu, J. Peng, C. Hou, Z. Wang, Coord. Chem. Rev., 2021, 443, 214032.
[2]	Q. Zhu, Y. Zheng, Z. Zhang, Y. Chen, Nat. Protoc., 2023, 18, 3080-3125.
[3]	C. Suckling, K. Suckling, Chem. Soc. Rev., 1974, 3, 387-406.
[4]	C. Lin, K. Xu, R. Zheng, Y. Zheng, Chem. Commun., 2019, 55, 5697-5700.
[5]	G. Liu, Y. Xu, Y. Han, J. Wu, J. Xu, H. Meng, X. Zhang, Dalton. Trans., 2017, 46, 2114-2121.
[6]	Y. Chen, V. Lykourinou, T. Hoang, L. Ming, S. Ma, Inorg. Chem., 2012, 51, 9156-9158.
[7]	J. Lu, J. K. Wu, Y. Jiang, P. Tan, L. Zhang, Y. Lei, X. Q. Liu, L. B. Sun, Angew. Chem. Int. Ed., 2020, 59, 6428-6434.
[8]	H. Xia, N. Li, X. Zhong, Y. Jiang, Front. Bioeng. Biotechnol., 2020, 8, 695.
[9]	E. T. Hwang, M. B. Gu, Eng. Life. Sci., 2013, 13, 49-61.
[10]	H. An, J. Song, T. Wang, N. Xiao, Z. Zhang, P. Cheng, S. Ma, H. Huang, Y. Chen, Angew. Chem. Int. Ed., 2020, 59, 16964-16969.
[11]	H. R. Luckarift, J. C. Spain, R. R. Naik, M. O. Stone, Nat. Biotechnol., 2004, 22, 211-213.
[12]	M. Shinkai, H. Honda, T. Kobayashi, Biocatalysis, 1991, 5, 61-69.
[13]	H. U. Rehman, A. Aman, A. Silipo, S. A. U. Qader, A. Molinaro, A. Ansari, Food Chem., 2013, 139, 1081-1086.
[14]	X. Lian, Y. Fang, E. Joseph, Q. Wang, J. Li, S. Banerjee, C. Lollar, X. Wang, H.-C. Zhou, Chem. Soc. Rev., 2017, 46, 3386-3401.
[15]	J. Cui, Y. Feng, T. Lin, Z. Tan, C. Zhong, S. Jia, ACS Appl. Mater. Interfaces., 2017, 9, 10587-10594.
[16]	Y. Feng, H. Hu, Z. Wang, Y. Du, L. Zhong, C. Zhang, Y. Jiang, S. Jia, J. Cui, J. Colloid Interface Sci., 2021, 590, 436-445.
[17]	S. Qiu, M. Xue, G. Zhu, Chem. Soc. Rev., 2014, 43, 6116-6140.
[18]	N. K. Maddigan, O. M. Linder-Patton, P. Falcaro, C. J. Sumby, S. G. Bell, C. J. Doonan, ACS Appl. Mater. Interfaces, 2021, 13, 51867-51875.
[19]	Y. Ji, Z. Wu, P. Zhang, M. Qiao, Y. Hu, B. Shen, B. Li, X. Zhang, Biochem. Eng. J., 2021, 169, 107962.
[20]	Y. Kim, T. Yang, G. Yun, M. B. Ghasemian, J. Koo, E. Lee, S. J. Cho, K. Kim, Angew. Chem. Int. Ed., 2015, 54, 13273-13278.
[21]	J. Liang, S. Gao, J. Liu, M. Y. Zulkifli, J. Xu, J. Scott, V. Chen, J. Shi, A. Rawal, K. Liang, Angew. Chem. Int. Ed., 2021, 133, 5481-5488.
[22]	J.-P. Zhang, A.-X. Zhu, R.-B. Lin, X.-L. Qi, X.-M. Chen, Adv. Mater., 2011, 23, 1268-1271.
[23]	W. Liang, H. Xu, F. Carraro, N. K. Maddigan, Q. Li, S. G. Bell, D. M. Huang, A. Tarzia, M. B. Solomon, H. Amenitsch, L. Vaccari, C. J. Sumby, P. Falcaro, C. J. Doonan, J. Am. Chem. Soc., 2019, 141, 2348-2355.
[24]	G. Chen, X. Kou, S. Huang, L. Tong, Y. Shen, W. Zhu, F. Zhu, G. Ouyang, Angew. Chem. Int. Ed., 2020, 59, 2867-2874.
[25]	X. Wu, J. Xiong, S. Liu, M. H. Zong, W. Y. Lou, Small, 2021, 17, 2007586.
[26]	C. Hu, Y. Bai, M. Hou, Y. Wang, L. Wang, X. Cao, C.-W. Chan, H. Sun, W. Li, J. Ge, Sci. Adv., 2020, 6, eaax5785.
[27]	Y. Feng, R. Shi, M. Yang, Y. Zheng, Z. Zhang, Y. Chen, Angew. Chem. Int. Ed., 2023, 62, e202302436.
[28]	H. Li, X. Lu, Q. Lu, Y. Liu, X. Cao, Y. Lu, X. He, K. Chen, P. Ouyang, W. Tan, Chem. Commun., 2020, 56, 4724-4727.
[29]	Y. Feng, Y. Du, G. Kuang, L. Zhong, H. Hu, S. Jia, J. Cui, J. Colloid Interface Sci., 2022, 610, 709-718.
[30]	Y. Xu, Y. Liu, H. Han, Z. Ma, Chem. Mater., 2022, 34, 4242-4247.
[31]	N. Singh, S. Ahmed, A. Fakim, S. Qutub, O. Alahmed, O. El Tall, O. Shekhah, M. Eddaoudi, N. M. Khashab, Chem. Sci., 2020, 11, 11280-11284.
[32]	X. Wu, J. Ge, C. Yang, M. Hou, Z. Liu, Chem. Commun., 2015, 51, 13408-13411.
[33]	I. Alemzadeh, S. Nejati, J. Hazard. Mater., 2009, 166, 1082-1086.
[34]	C. Hou, Y. Wang, Q. Ding, L. Jiang, M. Li, W. Zhu, D. Pan, H. Zhu, M. Liu, Nanoscale, 2015, 7, 18770-18779.
[35]	K. Y. Cho, H. An, X. H. Do, K. Choi, H. G. Yoon, H.-K. Jeong, J. S. Lee, K.-Y. Baek, J. Mater. Chem. A, 2018, 6, 18912-18919.
[36]	Y. R. Lee, X. H. Do, K. Y. Cho, K. Jeong, K.-Y. Baek, ACS Appl. Nano Mater., 2020, 3, 9852-9861.
[37]	B. Ji, G. Yi, K. Zhang, Y. Zhang, Y. Gui, D. Gao, J. Zeng, L. Wang, Z. Xia, Q. Fu, Anal. Chem., 2020, 92, 15655-15662.
[38]	H. Jing, C. Wang, Y. Zhang, P. Wang, R. Li, RSC Adv., 2014, 4, 54454-54462.
[39]	X. Wang, J. Liu, S. Leong, X. Lin, J. Wei, B. Kong, Y. Xu, Z.-X. Low, J. Yao, H. Wang, ACS Appl. Mater. Interfaces, 2016, 8, 9080-9087.
[40]	H. Gao, W. Wei, L. Dong, G. Feng, X. Jiang, R. Wu, Z. Lin, W. Li, Crystals, 2017, 7, 99.
[41]	X. Wu, H. Yue, Y. Zhang, X. Gao, X. Li, L. Wang, Y. Cao, M. Hou, H. An, L. Zhang, Nat. Commun., 2019, 10, 5165.
[42]	H. Zhu, X. Li, Z. He, Y. Chen, J.-J. Zhu, Anal. Chem., 2022, 94, 6827-6832.
[43]	Y.-M. Li, J. Yuan, H. Ren, C.-Y. Ji, Y. Tao, Y. Wu, L.-Y. Chou, Y.-B. Zhang, L. Cheng, J. Am. Chem. Soc., 2021, 143, 15378-15390.
[44]	K. Gawlitza, R. Georgieva, N. Tavraz, J. Keller, R. von Klitzing, Langmuir, 2013, 29, 16002-16009.
[45]	H. Xia, X. Zhong, Z. Li, Y. Jiang, J. Colloid Interface Sci., 2019, 533, 1-8.
[46]	S. A. Mohamed, A. L. Al-Malki, T. A. Kumosani, R. M. El-Shishtawy, Int. J. Biol. Macromol., 2013, 60, 295-300.
[47]	J. A. John, M. S. Samuel, E. Selvarajan, Fuel, 2023, 333, 126364.
[48]	Y. Zhang, J. Zhu, J. Hou, S. Yi, B. Van der Bruggen, Y. Zhang, J. Membrane. Sci. Lett., 2022, 2, 100031.
[49]	J. Mehta, N. Bhardwaj, S. K. Bhardwaj, K.-H. Kim, A. Deep, Coord. Chem. Rev., 2016, 322, 30-40.
[50]	J. Liang, K. Liang, Chem. Rec., 2020, 20, 1100-1116.
[51]	R. Ahmad, J. Shanahan, S. Rizaldo, D. S. Kissel, K. L. Stone, Catalysts, 2020, 10, 499.
[52]	M. Khan, S. Park, J. Colloid Interface Sci., 2015, 457, 281-288.
[53]	T. Man, C. Xu, X.-Y. Liu, D. Li, C.-K. Tsung, H. Pei, Y. Wan, L. Li, Nat. Commun., 2022, 13, 305.
[54]	Y. Zhang, L. Xu, J. Ge, Nano Lett., 2022, 22, 5029-5036.