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]
  Xingqun Pu , Rongrong Liu , Yuting Xie , Chenjing Yang , Jingyi Chen , Baoling Guo , Chun-Xia Zhao , Peng Zhao , Jian Ruan , Fangfu Ye , David A Weitz , Dong Chen . One-step preparation of biocompatible amphiphilic dimer nanoparticles with tunable particle morphology and surface property for interface stabilization and drug delivery. Chinese Chemical Letters, 2025, 36(3): 109820-. doi: 10.1016/j.cclet.2024.109820
3. [3]
  Chanqi Ye , Jia Zhang , Jie Shen , Ruyin Chen , Qiong Li , Peng Zhao , Dong Chen , Jian Ruan . Attractive Pickering emulsion gel loaded with oxaliplatin and lactate dehydrogenase inhibitor increases the anti-tumor effect in hepatocellular carcinoma. Chinese Chemical Letters, 2025, 36(7): 110519-. doi: 10.1016/j.cclet.2024.110519
4. [4]
  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
5. [5]
  Zhihui Zhang , Ru Sun , Chong Bian , Hongbo Wang , Zhen Zhao , Panpan Lv , Jianzhong Lu , Haixin Zhang , Hulie Zeng , Yuanyuan Chen , Zhijuan Cao . A dual-protease-triggered chemiluminescent probe for precise tumor imaging. Chinese Chemical Letters, 2025, 36(2): 109784-. doi: 10.1016/j.cclet.2024.109784
6. [6]
  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
7. [7]
  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
8. [8]
  Hong-Guang Fu , Xuan Wu , Hui-Juan Wang , Fanjun Zhang , Yong Chen , Jing Xu . Color-tunable multi-stimuli-responsive luminescent system based on diarylethene and photoacid. Chinese Chemical Letters, 2025, 36(8): 110741-. doi: 10.1016/j.cclet.2024.110741
9. [9]
  Zhiyao Yang , Kuirong Fu , Wentao Yu , Along Jia , Xinnan Chen , Yimin Cai , Xiaowei Li , Wen Feng , Lihua Yuan . A multi-stimuli responsive [3]rotaxane based on hydrogen-bonded aramide azo-macrocycles. Chinese Chemical Letters, 2025, 36(9): 110842-. doi: 10.1016/j.cclet.2025.110842
10. [10]
  Xiaosheng Zhao , Jie Gao , Kun Shi , Chixiang Zhang , Wenliang Ma , Guo Lyu , Jun Zhang , Jing Lu , Qiangqiang Liu , Xianjin Luo , Kunru Yu , Jianguo Li , Qiang Ge , Jiming Cai , Chang Liu , Zhiyong Qian . A new radioactive microsphere: Y-90 carbon microsphere for selective internal radiation therapy of advanced liver cancer. Chinese Chemical Letters, 2025, 36(8): 110662-. doi: 10.1016/j.cclet.2024.110662
11. [11]
  Mao-Fan Li , Ming‐Yu Guo , De-Xuan Liu , Xiao-Xian Chen , Wei-Jian Xu , Wei-Xiong Zhang . Multi-stimuli responsive behaviors in a new chiral hybrid nitroprusside salt (R-3-hydroxypyrrolidinium)₂[Fe(CN)₅(NO)]. Chinese Chemical Letters, 2024, 35(12): 109507-. doi: 10.1016/j.cclet.2024.109507
12. [12]
  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
13. [13]
  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
14. [14]
  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
15. [15]
  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
16. [16]
  Wenjuan Liu , Shanshan Zhang , Yu Wang , Bin Fang , Weirui Wang , Shujing Song , Tomohiro Hakozaki . Three-channel imaging reveals the comprehensive protein modifications and their impact on skin appearance induced by multiple stimuli. Chinese Chemical Letters, 2025, 36(6): 111182-. doi: 10.1016/j.cclet.2025.111182
17. [17]
  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
18. [18]
  Saadullah Khattak , Hong-Tao Xu , Jianliang Shen . Bio-electronic bandage: Self-powered performances to accelerate intestinal wound healing. Chinese Chemical Letters, 2024, 35(12): 110210-. doi: 10.1016/j.cclet.2024.110210
19. [19]
  Yuanmao Fu , Ziang Wang , Kefan Wu , Feiyang Li , Xian Zhang , Hongyuan Cui , Xiaolin Wang , Hui Guo , Yuezhong Meng . Bio-inspired multifunctional hydrogels with adhesive, anti-bacterial, anti-icing and sensing properties. Chinese Chemical Letters, 2025, 36(7): 110479-. doi: 10.1016/j.cclet.2024.110479
20. [20]
  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

Get Citation

PDF

XML

Metrics

PDF Downloads(9)
Abstract views(2608)
HTML views(132)

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