Citation: Weijie Jiang, Hang Jiang, Wei Liu, Xin Guan, Yunxing Li, Cheng Yang, To Ngai. Pickering Emulsion Templated Proteinaceous Microsphere with Bio-Stimuli Responsiveness[J]. Acta Physico-Chimica Sinica, ;2023, 39(12): 230104. doi: 10.3866/PKU.WHXB202301041 shu

Pickering Emulsion Templated Proteinaceous Microsphere with Bio-Stimuli Responsiveness

Weijie Jiang ¹ ,
Hang Jiang ^1,, ,
Wei Liu ¹ ,
Xin Guan ² ,
Yunxing Li ^1,, ,
Cheng Yang ¹ ,
To Ngai ²

1.
The Key Laboratory of Synthetic and Biological Colloids, Ministry of Education, School of Chemical and Material Engineering, Jiangnan University, Wuxi 214122, Jiangsu Province, China
2.
Department of Chemistry, The Chinese University of Hong Kong, Shatin, N. T., Hong Kong SAR, China

Corresponding author: Hang Jiang, hangjiang@jiangnan.edu.cn Yunxing Li, yunxingli@jiangnan.edu.cn
Received Date: 29 January 2023
Revised Date: 23 February 2023
Accepted Date: 23 February 2023
Available Online: 28 February 2023
Fund Project: the National Natural Science Foundation of China 22202084the Natural Science Foundation of Jiangsu Province, China BK20221059the Fundamental Research Funds for the Central Universities, China JUSRP122017

Bio-stimuli-responsive microspheres, which can encapsulate and release actives in response to physiological triggers, have attracted increasing attention in pharmaceutical, cosmetic, food biotechnology, and agricultural industries. However, most microspheres are based on synthetic polymers and suffer from a lack of biocompatibility due to the residues of harsh organic solvents or crosslinkers used in the synthesis process. Herein, we develop a simple and sustainable method for the construction of proteinaceous microspheres templated from Pickering double emulsions. Specifically, silica nanoparticles with a diameter of 100 nm were synthesized by Stöber method and modified by reacting with dichlorodimethylsilane. The Pickering emulsions are stabilized by hydrophobic silica nanoparticles, while zein protein is dissolved in the middle phase. Subsequent ethanol removal from the emulsion template precipitated the protein skeleton. First, we stained the aqueous ethanol phase with rhodamine B and the oil phase with pyrene to demonstrate the formation of double emulsions by confocal laser scanning microscopy (CLSM). The morphology of microspheres and silica nanoparticles was characterized by scanning electron microscopy (SEM). The obtained microspheres showed high sphericity and uniformity. In addition to acting as particulate stabilizers, the silica nanoparticles could improve the mechanical strength and monodispersity of microspheres. Herein, fluorescein isothiocyanate (FITC)-labeled dextran was chosen as the model active for encapsulation into microspheres. The CLSM images showed that it was uniformly dispersed in the microspheres and had no effect on the structure of the microspheres. Next, we investigated the pH tolerance of the microspheres. Through optical microscope, it was noted that the structure was intact under pH 3–11, and thus, it has a high resistance. Finally, we investigated the bio-stimuli-responsive behavior of microspheres. Zein is rich in sulfur-containing amino acids, which can form intra- and inter-molecular disulfide bonds. Because disulfide bonds can be reduced by glutathione (GSH) and the protein itself has enzymatic hydrolysis characteristics, the proteinaceous microspheres can be triggered release in response to GSH and protease. The release profiles of FITC-dextran from microspheres at different concentrations of GSH and protease were evaluated by fluorescence spectrophotometer. The decomposition behavior of microspheres under certain concentrations of GSH and protease was further verified by CLSM and SEM. To conclude, excellent stability and tunability of emulsion templates render the resulting proteinaceous microspheres with adjustable structures. Meanwhile, the proteinaceous microspheres have high encapsulation efficiency of model actives and have shown excellent bio-stimuli-responsiveness to protease and glutathione.
- Bio-stimuli-responsive,
- Proteinaceous microsphere,
- Pickering emulsion,
- Protease,
- Glutathione
1. [1]
  Kiser, P. F.; Wilson, G.; Needham, D. Nature 1998, 394, 459. doi: 10.1038/28822 doi: 10.1038/28822
2. [2]
  Caldorera-Moore, M. E.; Liechty, W. B.; Peppas, N. A. Acc. Chem. Res. 2011, 44, 1061. doi: 10.1021/ar2001777 doi: 10.1021/ar2001777
3. [3]
  Kureha, T.; Aoki, D.; Hiroshige, S.; Iijima, K.; Aoki, D.; Takata, T.; Suzuki, D. Angew. Chem. Int. Ed. 2017, 56, 15393. doi: 10.1002/anie.201709633 doi: 10.1002/anie.201709633
4. [4]
  Zhao, C.; Tian, S.; Liu, Q.; Xiu, K.; Lei, I.; Wang, Z.; Ma, P. X. Adv. Funct. Mater. 2020, 30 (21). doi: 10.1002/adfm.202000776 doi: 10.1002/adfm.202000776
5. [5]
  Ruan, L.; Su, M.; Qin, X.; Ruan, Q.; Lang, W.; Wu, M.; Chen, Y.; Lv, Q. Mater. Today Bio 2022, 16, 100394. doi: 10.1016/j.mtbio.2022.100394 doi: 10.1016/j.mtbio.2022.100394
6. [6]
  Rosenblum, D.; Joshi, N.; Tao, W.; Karp, J. M.; Peer, D. Nat. Commun. 2018, 9, 1410. doi: 10.1038/s41467-018-03705-y doi: 10.1038/s41467-018-03705-y
7. [7]
  Lu, Y.; Aimetti, A. A.; Langer, R.; Gu, Z. Nat. Rev. Mater. 2016, 2, 16075. doi: 10.1038/natrevmats.2016.75 doi: 10.1038/natrevmats.2016.75
8. [8]
  Wu, C.; Schwibbert, K.; Achazi, K.; Landsberger, P.; Gorbushina, A.; Haag, R. Biomacromolecules 2017, 18, 210. doi: 10.1021/acs.biomac.6b01527 doi: 10.1021/acs.biomac.6b01527
9. [9]
  Huang, X.; Patil, A. J.; Li, M.; Mann, S. J. Am. Chem. Soc. 2014, 136, 9225. doi: 10.1021/ja504213m doi: 10.1021/ja504213m
10. [10]
  Li, J.; Zhang, L.; Liu, Y.; Wen, J.; Wu, D.; Xu, D.; Segura, T.; Jin, J.; Lu, Y.; Wang, H. Chem. Commun. 2016, 52, 13608. doi: 10.1039/c6cc05099a doi: 10.1039/c6cc05099a
11. [11]
  Sun, Z.; Zhao, Q.; Haag, R.; Wu, C. Angew. Chem. Int. Ed. 2021, 60, 8410. doi: 10.1002/anie.202013737 doi: 10.1002/anie.202013737
12. [12]
  Ju, S.; Shin, G.; Lee, M.; Koo, J. M.; Jeon, H.; Ok, Y. S.; Hwang, D. S.; Hwang, S. Y.; Oh, D. X.; Park, J. Green Chem. 2021, 23, 6953. doi: 10.1039/d1gc01588e doi: 10.1039/d1gc01588e
13. [13]
  Jo, Y. K.; Lee, D. Small 2020, 16 (Suppl. 9), 1903736. doi: 10.1002/smll.201903736 doi: 10.1002/smll.201903736
14. [14]
  Wang, Y.; Liu, Y.; Xu, S.; Liu, H. Acta Phys. -Chim. Sin. 2019, 35, 876. doi: 10.3866/PKU.WHXB201901019
15. [15]
  Liao, Y.; Fan, Z.; Du, J. Acta Phys. -Chim. Sin. 2021, 37, 1912053. doi: 10.3866/PKU.WHXB201912053
16. [16]
  Stoppel, W. L.; Ghezzi, C. E.; McNamara, S. L.; Black, L. D., Ⅲ; Kaplan, D. L. Ann. Biomed. Eng. 2015, 43, 657. doi: 10.1007/s10439-014-1206-2 doi: 10.1007/s10439-014-1206-2
17. [17]
  Li, Y.; Maciel, D.; Rodrigues, J.; Shi, X.; Tomás, H. Chem. Rev. 2015, 115, 8564. doi: 10.1021/cr500131f doi: 10.1021/cr500131f
18. [18]
  Sun, M.; Yin, W.; Chen, J.; Wang, W.; Guo, T.; Meng, T. Green Chem. 2021, 23, 740. doi: 10.1039/d0gc02999h doi: 10.1039/d0gc02999h
19. [19]
  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
20. [20]
  Patel, A. R.; Remijn, C.; Cabero, A. -i. M.; Heussen, P. C. M.; ten Hoorn, J. W. M. S.; Velikov, K. P. Adv. Funct. Mater. 2013, 23, 4710. doi: 10.1002/adfm.201300320 doi: 10.1002/adfm.201300320
21. [21]
  Reddy, N.; Yang, Y. Trends Biotechnol. 2011, 29, 490. doi: 10.1016/j.tibtech.2011.05.003 doi: 10.1016/j.tibtech.2011.05.003
22. [22]
  Lawton, J. W. Cereal Chem. 2002, 79, 1. doi: 10.1094/CCHEM.2002.79.1.1 doi: 10.1094/CCHEM.2002.79.1.1
23. [23]
  Argos, P.; Pedersen, K.; Marks, M. D.; Larkins, B. A. J. Biol. Chem. 1982, 257, 9984. doi: 10.1016/s0021-9258(18)33974-7 doi: 10.1016/s0021-9258(18)33974-7
24. [24]
  Giteru, S. G.; Ali, M. A.; Oey, I. Food Hydrocolloids 2021, 120, 106948. doi: 10.1016/j.foodhyd.2021.106948 doi: 10.1016/j.foodhyd.2021.106948
25. [25]
  Dong, S.; Wang, J. -M.; Cheng, L. -M.; Lu, Y. -L.; Li, S. -H.; Chen, Y. J. Agric. Food Chem. 2017, 65, 7352. doi: 10.1021/acs.jafc.7b02205 doi: 10.1021/acs.jafc.7b02205
26. [26]
  Manickam, D. S.; Li, J.; Putt, D. A.; Zhou, Q. H.; Wu, C.; Lash, L. H.; Oupicky, D. J. Control. Release 2010, 141, 77. doi: 10.1016/j.jconrel.2009.08.022 doi: 10.1016/j.jconrel.2009.08.022
27. [27]
  Zhang, M.; Liu, J.; Kuang, Y.; Li, Q.; Chen, H.; Ye, H.; Guo, L.; Xu, Y.; Chen, X.; Li, C.; et al. J. Mater. Chem. B 2016, 4, 3387. doi: 10.1039/c5tb02548f doi: 10.1039/c5tb02548f
28. [28]
  Zhang, P.; Wu, J.; Xiao, F.; Zhao, D.; Luan, Y. Med. Res. Rev. 2018, 38, 1485. doi: 10.1002/med.21485 doi: 10.1002/med.21485
29. [29]
  Su, L.; Li, R.; Khan, S.; Clanton, R.; Zhang, F.; Li, Y. N.; Song, Y.; Wang, H.; Fan, J.; Hernandez, S.; et al. J. Am. Chem. Soc. 2018, 140, 1438. doi: 10.1021/jacs.7b11462 doi: 10.1021/jacs.7b11462
30. [30]
  Ding, Y.; Kang, Y.; Zhang, X. Chem. Commun. 2015, 51, 996. doi: 10.1039/c4cc05878j doi: 10.1039/c4cc05878j
31. [31]
  de la Rica, R.; Aili, D.; Stevens, M. M. Adv. Drug Delivery Rev. 2012, 64, 967. doi: 10.1016/j.addr.2012.01.002 doi: 10.1016/j.addr.2012.01.002
32. [32]
  Luo, Y.; Wang, Q. J Appl. Polym. Sci. 2014, 131, 40696. doi: 10.1002/app.40696 doi: 10.1002/app.40696
33. [33]
  Zhang, Y.; Cui, L.; Li, F.; Shi, N.; Li, C.; Yu, X.; Chen, Y.; Kong, W. Int. J. Pharm. 2016, 513, 191. doi: 10.1016/j.ijpharm.2016.09.023 doi: 10.1016/j.ijpharm.2016.09.023
34. [34]
  Jiang, H.; Hu, X.; Li, Y.; Ngai, T. Mater. Chem. Front. 2021, 5, 3897. doi: 10.1039/d0qm01010c doi: 10.1039/d0qm01010c
35. [35]
  Jiang, H.; Hu, X.; Li, Y.; Yang, C.; Ngai, T. Chem. Sci. 2021, 12, 12463. doi: 10.1039/d1sc03693a doi: 10.1039/d1sc03693a
36. [36]
  Jiang, H.; Hu, X.; Jiang, W.; Guan, X.; Li, Y.; Ngai, T. Langmuir 2022, 38, 12273. doi: 10.1021/acs.langmuir.2c01904 doi: 10.1021/acs.langmuir.2c01904
37. [37]
  Stöber, W.; Fink, A.; Bohn, E. J. Colloid Interface Sci. 1968, 26, 62. doi: 10.1016/0021-9797(68)90272-5 doi: 10.1016/0021-9797(68)90272-5
38. [38]
  Binks, B. P.; Fletcher, P. D. I.; Thompson, M. A.; Elliott, R. P. Langmuir 2013, 29, 5723. doi: 10.1021/la4008697 doi: 10.1021/la4008697
39. [39]
  Sun, G.; Yi, Z.; Ngai, T. Acta Phys. -Chim. Sin. 2020, 36, 1910005. doi: 10.3866/PKU.WHXB201910005
40. [40]
  Zou, H.; Ettelaie, R.; Yan, S.; Xue, N.; Yang, H. Acta Phys. -Chim. Sin. 2020, 36, 1910006. doi: 10.3866/PKU.WHXB201910006
41. [41]
  Jiang, H.; Sheng, Y.; Ngai, T. Curr. Opin. Colloid Interface Sci. 2020, 49, 1. doi: 10.1016/j.cocis.2020.04.010 doi: 10.1016/j.cocis.2020.04.010
42. [42]
  Huang, D.; Sun, M.; Bu, Y.; Luo, F.; Lin, C.; Lin, Z.; Weng, Z.; Yang, F.; Wu, D. J. Mater. Chem. B 2019, 7, 2330. doi: 10.1039/c8tb02928h doi: 10.1039/c8tb02928h
43. [43]
  Vian, A.; Amstad, E. Soft Matter 2019, 15, 1290. doi: 10.1039/c8sm02047g doi: 10.1039/c8sm02047g
44. [44]
  Webber, M. J.; Appel, E. A.; Meijer, E. W.; Langer, R. Nat. Mater. 2016, 15, 13. doi: 10.1038/nmat4474 doi: 10.1038/nmat4474
45. [45]
  Zhou, Y.; Song, J.; Wang, L.; Xue, X.; Liu, X.; Xie, H.; Huang, X. Biomacromolecules 2017, 18, 2446. doi: 10.1021/acs.biomac.7b00598 doi: 10.1021/acs.biomac.7b00598
1. [1]
  Yong-Dan Zhao , Yidan Wang , Rongrong Wang , Lina Chen , Hengtong Zuo , Xi Wang , Jihong Qiang , Geng Wang , Qingxia Li , Canqi Ping , Shuqiu Zhang , Hao Wang . Reversing artemisinin resistance by leveraging thermo-responsive nanoplatform to downregulating GSH. Chinese Chemical Letters, 2024, 35(6): 108929-. doi: 10.1016/j.cclet.2023.108929
2. [2]
  Qin Li , Ziyao Jia , Ye Chen , Mingze Ma , Lin Li , Tao Huang . A Journey into the Enigmatic World of Pickering Emulsion: A Chemical Science Popularization Experiment. University Chemistry, 2024, 39(9): 311-318. doi: 10.3866/PKU.DXHX202306035
3. [3]
  Wenjia Wang , Xingyue He , Xiaojie Wang , Tiantian Zhao , Osamu Muraoka , Genzoh Tanabe , Weijia Xie , Tianjiao Zhou , Lei Xing , Qingri Jin , Hulin Jiang . Glutathione-depleted cyclodextrin pseudo-polyrotaxane nanoparticles for anti-inflammatory oxaliplatin (Ⅳ) prodrug delivery and enhanced colorectal cancer therapy. Chinese Chemical Letters, 2024, 35(4): 108656-. doi: 10.1016/j.cclet.2023.108656
4. [4]
  Linjie Ju , Zhongxi Huang , Qian Shen , Chan Fu , Shuanghe Li , Wenjie Duan , Chenfeng Xu , Weizhen An , Zhiqiang Zhai , Jifu Wei , Changmin Yu , Guoren Zhou . Glutathione depletion based Pt(Ⅳ) hybrid mesoporous organosilica delivery system to conquer cisplatin chemoresistance: A “one stone three birds” strategy. Chinese Chemical Letters, 2024, 35(10): 109450-. doi: 10.1016/j.cclet.2023.109450
5. [5]
  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
6. [6]
  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
7. [7]
  Zeyu XU , Tongzhou LU , Haibo SHAO , Jianming WANG . Preparation and electrochemical lithium storage performance of porous silicon microsphere composite with metal modification and carbon coating. Chinese Journal of Inorganic Chemistry, 2024, 40(10): 1995-2008. doi: 10.11862/CJIC.20240164
8. [8]
  Yanqi Wu , Yuhong Guan , Peilin Huang , Hui Chen , Liping Bai , Zhihong Jiang . Preparation of norovirus GII loop mediated isothermal amplification freeze-drying microsphere reagents and its application in an on-site integrated rapid detection platform. Chinese Chemical Letters, 2024, 35(9): 109308-. doi: 10.1016/j.cclet.2023.109308
9. [9]
  Si-Hua Liu , Jun-Hao Zhou , Jian-Ke Sun . Interconnecting zero-dimensional porous organic cages into sub-8 nm nanofilm for bio-inspired separation. Chinese Journal of Structural Chemistry, 2024, 43(7): 100312-100312. doi: 10.1016/j.cjsc.2024.100312
10. [10]
  Maitri Bhattacharjee , Rekha Boruah Smriti , R. N. Dutta Purkayastha , Waldemar Maniukiewicz , Shubhamoy Chowdhury , Debasish Maiti , Tamanna Akhtar . Synthesis, structural characterization, bio-activity, and density functional theory calculation on Cu(Ⅱ) complexes with hydrazone-based Schiff base ligands. Chinese Journal of Inorganic Chemistry, 2024, 40(7): 1409-1422. doi: 10.11862/CJIC.20240007
11. [11]
  Pei Cao , Yilan Wang , Lejian Yu , Miao Wang , Liming Zhao , Xu Hou . Dynamic asymmetric mechanical responsive carbon nanotube fiber for ionic logic gate. Chinese Chemical Letters, 2024, 35(6): 109421-. doi: 10.1016/j.cclet.2023.109421
12. [12]
  Hailong He , Wenbing Wang , Wenmin Pang , Chen Zou , Dan Peng . Double stimulus-responsive palladium catalysts for ethylene polymerization and copolymerization. Chinese Chemical Letters, 2024, 35(7): 109534-. doi: 10.1016/j.cclet.2024.109534
13. [13]
  Haijing Cui , Weihao Zhu , Chuning Yue , Ming Yang , Wenzhi Ren , Aiguo Wu . Recent progress of ultrasound-responsive titanium dioxide sonosensitizers in cancer treatment. Chinese Chemical Letters, 2024, 35(10): 109727-. doi: 10.1016/j.cclet.2024.109727
14. [14]
  Jianye Kang , Xinyu Yang , Xuhao Yang , Jiahui Sun , Yuhang Liu , Shutao Wang , Wenlong Song . Carbon dots-enhanced pH-responsive lubricating hydrogel based on reversible dynamic covalent bondings. Chinese Chemical Letters, 2024, 35(5): 109297-. doi: 10.1016/j.cclet.2023.109297
15. [15]
  Yiran Tao , Chunlei Dai , Zhaoxiang Xie , Xinru You , Kaiwen Li , Jun Wu , Hai Huang . Redox responsive polymeric nanoparticles enhance the efficacy of cyclin dependent kinase 7 inhibitor for enhanced treatment of prostate cancer. Chinese Chemical Letters, 2024, 35(8): 109170-. doi: 10.1016/j.cclet.2023.109170
16. [16]
  Jingqi Xin , Shupeng Han , Meichen Zheng , Chenfeng Xu , Zhongxi Huang , Bin Wang , Changmin Yu , Feifei An , Yu Ren . A nitroreductase-responsive nanoprobe with homogeneous composition and high loading for preoperative non-invasive tumor imaging and intraoperative guidance. Chinese Chemical Letters, 2024, 35(7): 109165-. doi: 10.1016/j.cclet.2023.109165
17. [17]
  Jingting Wang , Yuanyuan Chen , Linlin Han , Shasha Xia , Xingyao Zhang , Peng Xue , Yuejun Kang , Jian Ming , Zhigang Xu . Microenvironment responsive pod-structured astaxanthin nanocarrier for ameliorating inflammatory bowel disease. Chinese Chemical Letters, 2024, 35(7): 109029-. doi: 10.1016/j.cclet.2023.109029
18. [18]
  Rui Wang , He Qi , Haijiao Zheng , Qiong Jia . Light/pH dual-responsive magnetic metal-organic frameworks composites for phosphorylated peptide enrichment. Chinese Chemical Letters, 2024, 35(7): 109215-. doi: 10.1016/j.cclet.2023.109215
19. [19]
  Ling-Ling Wu , Xiangchuan Meng , Qingyang Zhang , Xiaowan Han , Feiya Yang , Qinghua Wang , Hai-Yu Hu , Nianzeng Xing . Heavy-atom engineered hypoxia-responsive probes for precisive photoacoustic imaging and cancer therapy. Chinese Chemical Letters, 2024, 35(4): 108663-. doi: 10.1016/j.cclet.2023.108663
20. [20]
  Liangji Chen , Zhen Yuan , Fudong Feng , Xin Zhou , Zhile Xiong , Wuji Wei , Hao Zhang , Banglin Chen , Shengchang Xiang , Zhangjing Zhang . A hydrogen-bonded organic framework containing fluorescent carbazole and responsive pyridyl units for sensing organic acids. Chinese Chemical Letters, 2024, 35(9): 109344-. doi: 10.1016/j.cclet.2023.109344

Get Citation

PDF

XML

Metrics

PDF Downloads(6)
Abstract views(982)
HTML views(50)

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