Citation: Zou Houbing, Ettelaie Rammile, Yan Shuai, Xue Nan, Yang Hengquan. Solvent-Induced Inversion of Pickering Emulsions for In Situ Recycling of Enzyme Biocatalysts[J]. Acta Physico-Chimica Sinica, ;2020, 36(10): 191000. doi: 10.3866/PKU.WHXB201910006 shu

Solvent-Induced Inversion of Pickering Emulsions for In Situ Recycling of Enzyme Biocatalysts

1.
School of Chemistry and Chemical Engineering, Shanxi University, Taiyuan 030006, P. R. China
2.
Food Colloids Group, School of Food Science and Nutrition, University of Leeds, Leeds LS2 9JT, United Kingdom

Corresponding author: Ettelaie Rammile, R.Ettelaie@food.leeds.ac.uk Yang Hengquan, hqyang@sxu.edu.cn
Received Date: 7 October 2019
Revised Date: 29 November 2019
Available Online: 12 December 2019
Fund Project: the National Natural Science Foundation of China U1510105the National Natural Science Foundation of China 21573136the National Natural Science Foundation of China 21703128The project was supported by the National Natural Science Foundation of China (21703128, U1510105, 21733009, 21573136)the National Natural Science Foundation of China 21733009

Separation and recycling of catalysts are crucial for realizing the objectives of sustainable and green chemistry but remain a great challenge, especially for enzyme biocatalysts. In this work, we report a new solvent-induced reversible inversion of Pickering emulsions stabilized by Janus mesosilica nanosheets (JMSNs), which is then utilized as a strategy for the in situ separation and recycling of enzymes. The interfacial active solid particle JMSNs is carefully characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), nitrogen sorption experiments, Fourier transform infrared (FT-IR) spectroscopy, and thermogravimetric analysis (TGA).The JMSNs are demonstrated to show order-oriented mesochannels with a large specific surface area, and the hydrophobic octylgroup is selectively modified on one side of the nanosheets. Furthermore, the inversion is found to be a fast process that is strongly dependent on the interfacial activity of the solid emulsifier JMSNs. Such a phase inversion is also a general process that can be realized in various oil/water phasic systems, including ethyl acetate-water, octane-water, and cyclohexane-water systems. By carefully analyzing the capacity of JMSNs with different surface wettabilities for phase inversion, a triphase contact angle (θ) close to 90° and a critical oil-water ratio of 1 : 2 are identified as the key factors to achieve solvent-induced phase inversion via a catastrophic phase inversion mechanism. Importantly, this reversible phase inversion is suitable for the separation and recycling of enzyme biocatalysts that are sensitive to changes in the reaction medium. Specifically, during the reaction, the organic substrates are dissolved in the oil droplets and the water-soluble catalysts are dispersed in the water phase, while a majority of the product is released into the upper oil phase and the enzyme catalyst is confined inside the water droplets in the bottom layer after phase inversion. The perpendicular mesochannels of JMSNs provide a highly accessible reaction interface, and their excellent interfacial activity allows for more than 10 rounds of consecutive phase inversions by simply adjusting the ratio of oil to water in the system. Using the enzymatic hydrolysis kinetic resolution of racemic acetate as an example, our Pickering emulsion system shows not only a 3-fold enhanced activity but also excellent recyclability. Because no sensitive chemical reagents are used in this phase inversion process, the intrinsic activities of the catalysts can be preserved even after seven cycles. The current study provides an alternative strategy for the separation and recycling of enzymes, in addition to revealing a new innovative application for Janus-type nanoparticles.
- Janus nanosheet,
- Emulsion inversion,
- Mesoporous silica,
- Catalyst recycling,
- Enzyme catalysis,
- Kinetic resolution reaction
1. [1]
  Gladysz, J. A. Recoverable and Recyclable Catalysts; Wiley: Chichester, 2009; pp. 1–14.
2. [2]
  Cole-Hamilton, D. J. Science 2003, 299, 1702. doi: 10.1126/science.1081881 doi: 10.1126/science.1081881
3. [3]
  Dioumaev, V. K.; Bullock, R. M. Nature 2003, 424, 530. doi: 10.1038/nature01856 doi: 10.1038/nature01856
4. [4]
  Ikegami, S.; Hamamoto, H. Chem. Rev. 2009, 109, 583. doi: 10.1021/cr800481x doi: 10.1021/cr800481x
5. [5]
  Molnár, A.; Papp, A. Coord. Chem. Rev. 2017, 349, 1. doi: 10.1016/j.ccr.2017.08.011 doi: 10.1016/j.ccr.2017.08.011
6. [6]
  Rudroff, F.; Mihovilovic, M. D.; Groger, H.; Snajdrova, R.; Iding, H.; Bornscheuer, U. T. Nat. Catal. 2018, 1, 12. doi: 10.1038/s41929-017-0010-4 doi: 10.1038/s41929-017-0010-4
7. [7]
  Zhang, M.; Ettelaie, R.; Yan, T.; Zhang, S. J.; Cheng, F. Q.; Binks, B. P.; Yang, H. Q. J. Am. Chem. Soc. 2017, 139, 17387. doi: 10.1021/jacs.7b07731 doi: 10.1021/jacs.7b07731
8. [8]
  Gao, J.; Ou, X.; Xu, P.; Zong, M.; Lou, W. Chin. J. Catal. 2018, 39, 937. doi: 10.1016/S1872-2067(18)63033-5 doi: 10.1016/S1872-2067(18)63033-5
9. [9]
  Desset, S. L.; Cole-Hamilton, D. J. Angew. Chem. Int. Ed. 2009, 48, 1472. doi: 10.1002/anie.200804729 doi: 10.1002/anie.200804729
10. [10]
  Mokhadinyana, M.; Desset, S. L.; Williams, D. B. G.; Cole-Hamilton, D. J. Angew. Chem. Int. Ed. 2012, 51, 1648. doi: 10.1002/anie.201108200 doi: 10.1002/anie.201108200
11. [11]
  Brunsch, Y.; Behr, A. Angew. Chem. Int. Ed. 2013, 52, 1586. doi: 10.1002/anie.201208667 doi: 10.1002/anie.201208667
12. [12]
  Crossley, S.; Faria, J.; Shen, M.; Resasco, D. E. Science 2010, 327, 68. doi: 10.1126/science.1180769 doi: 10.1126/science.1180769
13. [13]
  Pera-Titus, M.; Leclercq, L.; Clacens, J. M.; Campo, F. D.; Nardello-Rataj, V. Angew. Chem. Int. Ed. 2015, 54, 2006. doi: 10.1002/anie.201402069 doi: 10.1002/anie.201402069
14. [14]
  Yang, H. Q.; Fu, L. M.; Wei, L. J.; Liang, J. F.; J. Am. Chem. Soc. 2015, 137, 1362. doi: 10.1021/ja512337z doi: 10.1021/ja512337z
15. [15]
  Zhang, M.; Wei, L. J.; Chen, H.; Du, Z. P.; Binks, B. P.; Yang, H. Q. J. Am. Chem. Soc. 2016, 138, 10173. doi: 10.1021/jacs.6b04265 doi: 10.1021/jacs.6b04265
16. [16]
  Xue, F.; Zhang, Y.; Zhang, F.; Ren, X.; Yang, H. ACS Appl. Mater. Interfaces 2017, 9, 8403. doi: 10.1021/acsami.6b16605 doi: 10.1021/acsami.6b16605
17. [17]
  Yang, T. Y.; Wei, L. J.; Jing, L. Y.; Liang, J. F.; Zhang, X. M.; Tang, M.; Monteiro, M.; Chen, Y.; Wang, Y.; Gu, S.; et al. Angew. Chem. Int. Ed. 2017, 56, 8459. doi: 10.1002/anie.201701640 doi: 10.1002/anie.201701640
18. [18]
  Kim, H.; Cho, J.; Cho, J.; Park, B.; Kim, J. ACS Appl. Mater. Interfaces 2018, 10, 1408. doi: 10.1021/acsami.7b15894 doi: 10.1021/acsami.7b15894
19. [19]
  Dai, J. Y.; Zou, H. B.; Shi, Z. Q.; Yang, H. Q.; Wang, R. W.; Zhang, Z. T.; Qiu, S. L. ACS Appl. Mater. Interfaces 2018, 10, 33474. doi: 10.1021/acsami.8b11888 doi: 10.1021/acsami.8b11888
20. [20]
  Zhao, Y. P.; Zhang, X. M.; Sanjeevi, J.; Yang, Q. H. J. Catal. 2016, 334, 52. doi: 10.1016/j.jcat.2015.11.011 doi: 10.1016/j.jcat.2015.11.011
21. [21]
  Yang, X.; Wang, Y.; Bai, R.; Ma, H.; Wang, W.; Sun, H.; Dong, Y.; Qu, F.; Tang, Q.; Guo, T.; et al. Green Chem. 2019, 21, 2229. doi: 10.1039/C8GC03573C doi: 10.1039/C8GC03573C
22. [22]
  Xue, D.; Meng, Q. B.; Song, X. -M. ACS Appl. Mater. Interfaces 2019, 11, 10967. doi: 10.1021/acsami.8b21012 doi: 10.1021/acsami.8b21012
23. [23]
  Zhang, W. J.; Fu, L. M.; Yang, H. Q. ChemSusChem 2014, 7, 391. doi: 10.1002/cssc.201301001 doi: 10.1002/cssc.201301001
24. [24]
  Wei, L. J.; Zhang, M.; Zhang, X. M.; Xin, H. C.; Yang, H. Q. ACS Sustainable Chem. Eng. 2016, 4, 6838. doi: 10.1021/acssuschemeng.6b01776 doi: 10.1021/acssuschemeng.6b01776
25. [25]
  Tu, F.; Lee, D. J. Am. Chem. Soc. 2014, 136, 9999. doi: 10.1021/ja503189r doi: 10.1021/ja503189r
26. [26]
  Liang, F. X.; Liu, B.; Cao, Z.; Yang, Z. Z. Langmuir 2018, 34, 4123. doi: 10.1021/acs.langmuir.7b02308 doi: 10.1021/acs.langmuir.7b02308
27. [27]
  Wei, P. R.; Luo, Q. M.; Edgehouse, K. J.; Hemmingsen, C. M.; Rodier, B. J.; Pentzer, E. B. ACS Appl. Mater. Interfaces 2018, 10, 21765. doi: 10.1021/acsami.8b07178 doi: 10.1021/acsami.8b07178
28. [28]
  Yang, H. Q.; Zhou, T.; Zhang, W. J. Angew. Chem. Int. Ed. 2013, 52, 7455. doi: 10.1002/anie.201300534 doi: 10.1002/anie.201300534
29. [29]
  Huang, J. P.; Yang, H. Q. Chem. Commun. 2015, 51, 7333. doi: 10.1039/C5CC01211B doi: 10.1039/C5CC01211B
30. [30]
  Hao, Y. J.; Liu, Y.; Yang, R.; Zhang, X. M.; Liu, J.; Yang, H. Q. Chin. Chem. Lett. 2018, 29, 778. doi: 10.1016/j.cclet.2018.01.010 doi: 10.1016/j.cclet.2018.01.010
31. [31]
  Chen, Z. W.; Zhou, L.; Bing, W.; Zhang, Z. J.; Li, Z. H.; Ren, J. S.; Qu, X. G. J. Am. Chem. Soc. 2014, 136, 7498. doi: 10.1021/ja503123m doi: 10.1021/ja503123m
32. [32]
  Zhang, Q.; Bai, R. X.; Guo, T.; Meng, T. ACS Appl. Mater. Interfaces 2015, 7, 18240. doi: 10.1021/acsami.5b06808 doi: 10.1021/acsami.5b06808
33. [33]
  Cao, Y. Y.; Wang, Z.; Zhang, S. M.; Wang, Y. P. Mater. Chem. Front. 2017, 1, 2136. doi: 10.1039/C7QM00275K doi: 10.1039/C7QM00275K
34. [34]
  Shi, Y. L.; Xiong, D. Z.; Li, Z. Y.; Wang, H. Y.; Pei, Y. C.; Chen, Y. K.; Wang, J. J. ACS Sustainable Chem. Eng. 2018, 6, 15383. doi: 10.1021/acssuschemeng.8b03808 doi: 10.1021/acssuschemeng.8b03808
35. [35]
  Binks, B. P.; Olusanya, S. O. P. Langmuir 2018, 34, 5040. doi: 10.1021/acs.langmuir.8b00715 doi: 10.1021/acs.langmuir.8b00715
36. [36]
  Binks, B. P.; Shi, H. Langmuir 2019, 35, 4046. doi:10.1021/acs.langmuir.8b04151 doi: 10.1021/acs.langmuir.8b04151
37. [37]
  Yan, S.; Zou, H. B.; Chen, S.; Xue, N.; Yang, H. Q. Chem. Commun. 2018, 54, 10455. doi: 10.1039/C8CC05967E doi: 10.1039/C8CC05967E
38. [38]
  Liang, F. X.; Shen, K.; Qu, X. Z.; Zhang, C. L.; Wang, Q.; Li, J. L.; Liu, J. G.; Yang, Z. Z. Angew. Chem. Int. Ed. 2011, 50, 2379. doi: 10.1002/anie.201007519 doi: 10.1002/anie.201007519
39. [39]
  Walther, A.; Muller, A. H. E. Chem. Rev. 2013, 113, 5194. doi: 10.1021/cr300089t doi: 10.1021/cr300089t
40. [40]
  Liang, F.; Zhang, C.; Yang, Z. Adv. Mater. 2014, 26, 6944. doi: 10.1002/adma.201305415 doi: 10.1002/adma.201305415
41. [41]
  Binks, B. P.; Fletcher, P. D. I. Langmuir 2001, 17, 4708. doi: 10.1021/la0103315 doi: 10.1021/la0103315
42. [42]
  Luo, J.; Zeng, M.; Peng, B.; Tang, Y.; Zhang, L.; Wang, P.; He, L.; Huang, D.; Wang, L.; Wang, X.; Chen, M.; Lei, S.; Lin, P.; Chen, Y.; Cheng, Z. Angew. Chem. Int. Ed. 2018, 57, 11752. doi: 10.1002/ange.201807372 doi: 10.1002/ange.201807372
43. [43]
  Finkle, P.; Draper, H. D.; Hildebrand, J. H. J. Am. Chem. Soc. 1923, 45, 2780. doi: 10.1021/ja01665a002 doi: 10.1021/ja01665a002
44. [44]
  Binks, B. P.; Lumsdon, S. O. Langmuir 2000, 16, 8622. doi: 10.1021/la000189s doi: 10.1021/la000189s
45. [45]
  Aveyard, R.; Binks, B. P.; Clint, J. H. Adv. Colloid Interface Sci. 2003, 100-102, 503. doi: 10.1016/S0001-8686(02)00069-6 doi: 10.1016/S0001-8686(02)00069-6
46. [46]
  Kumar, A.; Li, S.; Cheng, C.; Lee, D. Eng. Chem. Res. 2015, 54, 8375. doi: 10.1021/acs.iecr.5b01122 doi: 10.1021/acs.iecr.5b01122
47. [47]
  Perazzo, A.; Preziosi, V.; Guido, S. Adv. Colloid Interface Sci. 2015, 222, 581. doi: 10.1016/j.cis.2015.01.001 doi: 10.1016/j.cis.2015.01.001
48. [48]
  Wu, D. L.; Binks, B. P.; Honciuc, A. Langmuir 2018, 34, 1225. doi: 10.1021/acs.langmuir.7b02331 doi: 10.1021/acs.langmuir.7b02331
49. [49]
  Binks, B. P.; Lumsdon, S. O. Langmuir 2000, 16, 3748. doi: 10.1021/la991427q doi: 10.1021/la991427q
50. [50]
  Binks, B. P.; Lumsdon, S. O. Langmuir 2000, 16, 2539. doi: 10.1021/la991081j doi: 10.1021/la991081j
51. [51]
  Arditty, S.; Whitby, C. P.; Binks, B. P.; Schmitt, V.; Leal-Calderon, F. Eur. Phys. J. E 2003, 11, 273. doi: 10.1140/epje/i2003-10018-6 doi: 10.1140/epje/i2003-10018-6
52. [52]
  Verho, O.; Backvall, J. E. J. Am. Chem. Soc. 2015, 137, 3996. doi: 10.1021/jacs.5b01031 doi: 10.1021/jacs.5b01031
53. [53]
  Khan, A.; Bilal, M.; Rasheed, T.; Iqbal, H. Chin. J. Catal. 2018, 39, 1861. doi: 10.1016/S1872‐2067(18)63144‐4 doi: 10.1016/S1872‐2067(18)63144‐4
54. [54]
  Engstrom, K.; Johnston, E.; Verho, O.; Gustafson, K.; Shakeri, M.; Tai, C.; Backvall, J. Angew. Chem. Int. Ed. 2013, 52, 14006. doi: 10.1002/anie.201306487 doi: 10.1002/anie.201306487
1. [1]
  Wantong Zhang , Zixing Xu , Guofei Dai , Zhijian Li , Chunhui Deng . Removal of Microcystin-LR in lake water sample by hydrophilic mesoporous silica composites under high-throughput MALDI-TOF MS detection platform. Chinese Chemical Letters, 2024, 35(5): 109135-. doi: 10.1016/j.cclet.2023.109135
2. [2]
  Liliang Chu , Xiaoyan Zhang , Jianing Li , Xuelei Deng , Miao Wu , Ya Cheng , Weiping Zhu , Xuhong Qian , Yunpeng Bai . Continuous-flow synthesis of polysubstituted γ-butyrolactones via enzymatic cascade catalysis. Chinese Chemical Letters, 2024, 35(4): 108896-. doi: 10.1016/j.cclet.2023.108896
3. [3]
  Yujuan Zhao , Zaiwang Zhao . Monolayer mesoporous nanosheets with surface asymmetry via a dual-emulsion-directed monomicelle assembly. Chinese Journal of Structural Chemistry, 2024, 43(2): 100238-100238. doi: 10.1016/j.cjsc.2024.100238
4. [4]
  Zhaomin Tang , Qian He , Jianren Zhou , Shuang Yan , Li Jiang , Yudong Wang , Chenxing Yao , Huangzhao Wei , Keda Yang , Jiajia Wang . Active-transporting of charge-reversal Cu(Ⅱ)-doped mesoporous silica nanoagents for antitumor chemo/chemodynamic therapy. Chinese Chemical Letters, 2024, 35(7): 109742-. doi: 10.1016/j.cclet.2024.109742
5. [5]
  Ruilong Geng , Lingzi Peng , Chang Guo . Dynamic kinetic stereodivergent transformations of propargylic ammonium salts via dual nickel and copper catalysis. Chinese Chemical Letters, 2024, 35(8): 109433-. doi: 10.1016/j.cclet.2023.109433
6. [6]
  Mengli Xu , Zhenmin Xu , Zhenfeng Bian . Achieving Ullmann coupling reaction via photothermal synergy with ultrafine Pd nanoclusters supported on mesoporous TiO2. Chinese Journal of Structural Chemistry, 2024, 43(7): 100305-100305. doi: 10.1016/j.cjsc.2024.100305
7. [7]
  Baokang Geng , Xiang Chu , Li Liu , Lingling Zhang , Shuaishuai Zhang , Xiao Wang , Shuyan Song , Hongjie Zhang . High-efficiency PdNi single-atom alloy catalyst toward cross-coupling reaction. Chinese Chemical Letters, 2024, 35(7): 108924-. doi: 10.1016/j.cclet.2023.108924
8. [8]
  Ling Tang , Yan Wan , Yangming Lin . Lowering the kinetic barrier via enhancing electrophilicity of surface oxygen to boost acidic oxygen evolution reaction. Chinese Journal of Structural Chemistry, 2024, 43(11): 100345-100345. doi: 10.1016/j.cjsc.2024.100345
9. [9]
  Peng Wang , Daijie Deng , Suqin Wu , Li Xu . Cobalt-based deep eutectic solvent modified nitrogen-doped carbon catalyst for boosting oxygen reduction reaction in zinc-air batteries. Chinese Journal of Structural Chemistry, 2024, 43(1): 100199-100199. doi: 10.1016/j.cjsc.2023.100199
10. [10]
  Conghui Wang , Lei Xu , Zhenhua Jia , Teck-Peng Loh . Recent applications of macrocycles in supramolecular catalysis. Chinese Chemical Letters, 2024, 35(4): 109075-. doi: 10.1016/j.cclet.2023.109075
11. [11]
  Wei Chen , Pieter Cnudde . A minireview to ketene chemistry in zeolite catalysis. Chinese Journal of Structural Chemistry, 2024, 43(11): 100412-100412. doi: 10.1016/j.cjsc.2024.100412
12. [12]
  Yu Mao , Yilin Liu , Xiaochen Wang , Shengyang Ni , Yi Pan , Yi Wang . Acylfluorination of enynes via phosphine and silver catalysis. Chinese Chemical Letters, 2024, 35(8): 109443-. doi: 10.1016/j.cclet.2023.109443
13. [13]
  Huan Yao , Jian Qin , Yan-Fang Wang , Song-Meng Wang , Liu-Huan Yi , Shi-Yao Li , Fangfang Du , Liu-Pan Yang , Li-Li Wang . Ultra-highly selective recognition of nucleosides over nucleotides by rational modification of tetralactam macrocycle and its application in enzyme assay. Chinese Chemical Letters, 2024, 35(6): 109154-. doi: 10.1016/j.cclet.2023.109154
14. [14]
  Yan Zou , Yin-Shuang Hu , Deng-Hui Tian , Hong Wu , Xiaoshu Lv , Guangming Jiang , Yu-Xi Huang . Tuning the membrane rejection behavior by surface wettability engineering for an effective water-in-oil emulsion separation. Chinese Chemical Letters, 2024, 35(6): 109090-. doi: 10.1016/j.cclet.2023.109090
15. [15]
  Yunan Yuan , Zhimin Luo , Jie Chen , Chaoliang He , Kai Hao , Huayu Tian . Constructing thermoresponsive PNIPAM-based microcarriers for cell culture and enzyme-free cell harvesting. Chinese Chemical Letters, 2024, 35(7): 109549-. doi: 10.1016/j.cclet.2024.109549
16. [16]
  Xinyu Huai , Jingxuan Liu , Xiang Wu . Cobalt-Doped NiMoO4 Nanosheet for High-performance Flexible Supercapacitor. Chinese Journal of Structural Chemistry, 2023, 42(10): 100158-100158. doi: 10.1016/j.cjsc.2023.100158
17. [17]
  Yue Zhang , Xiaoya Fan , Xun He , Tingyu Yan , Yongchao Yao , Dongdong Zheng , Jingxiang Zhao , Qinghai Cai , Qian Liu , Luming Li , Wei Chu , Shengjun Sun , Xuping Sun . Ambient electrosynthesis of urea from carbon dioxide and nitrate over Mo₂C nanosheet. Chinese Chemical Letters, 2024, 35(8): 109806-. doi: 10.1016/j.cclet.2024.109806
18. [18]
  Feng Cui , Fangman Chen , Xiaochun Xie , Chenyang Guo , Kai Xiao , Ziping Wu , Yinglu Chen , Junna Lu , Feixia Ruan , Chuanxu Cheng , Chao Yang , Dan Shao . Scalable production of mesoporous titanium nanoparticles through sequential flash nanocomplexation. Chinese Chemical Letters, 2024, 35(4): 108681-. doi: 10.1016/j.cclet.2023.108681
19. [19]
  Ning LI , Siyu DU , Xueyi WANG , Hui YANG , Tao ZHOU , Zhimin GUAN , Peng FEI , Hongfang MA , Shang JIANG . Preparation and efficient catalysis for olefins epoxidation of a polyoxovanadate-based hybrid. Chinese Journal of Inorganic Chemistry, 2024, 40(4): 799-808. doi: 10.11862/CJIC.20230372
20. [20]
  Uttam Pandurang Patil . Porous carbon catalysis in sustainable synthesis of functional heterocycles: An overview. Chinese Chemical Letters, 2024, 35(8): 109472-. doi: 10.1016/j.cclet.2023.109472

Get Citation

PDF

XML

Metrics

PDF Downloads(12)
Abstract views(583)
HTML views(74)

通讯作者: 陈斌, bchen63@163.com

1.
沈阳化工大学材料科学与工程学院沈阳 110142