Porous ultrathin-shell microcapsules designed by microfluidics for selective permeation and stimuli-triggered release

doi:10.1007/s11705-022-2201-z

Front. Chem. Sci. Eng.

2022, Vol. 16

Issue (11) : 1643-1650 https://doi.org/10.1007/s11705-022-2201-z

RESEARCH ARTICLE

Porous ultrathin-shell microcapsules designed by microfluidics for selective permeation and stimuli-triggered release

Li Chen^1,^2,³, Yao Xiao², Zhiming Zhang², Chun-Xia Zhao⁴, Baoling Guo¹(

), Fangfu Ye^3,⁵(

), Dong Chen^2,⁶(

)

¹. Department of Oncology, Longyan First Affiliated Hospital of Fujian Medical University, Longyan 364000, China
². Zhejiang Key Laboratory of Smart Biomaterials, College of Chemical and Biological Engineering, Zhejiang University, Hangzhou 310027, China
³. Wenzhou Institute, University of Chinese Academy of Sciences, Wenzhou 325001, China
⁴. Faculty of Engineering, Computer, and Mathematical Sciences, The University of Adelaide, Adelaide, SA 5005, Australia
⁵. Beijing National Laboratory for Condensed Matter Physics, Institute of Physics, Chinese Academy of Sciences, Beijing 100190, China
⁶. College of Energy Engineering and State Key Laboratory of Fluid Power and Mechatronic Systems, Zhejiang University, Hangzhou 310027, China

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Abstract

Microcapsules are versatile delivery vehicles and widely used in various areas. Generally, microcapsules with solid shells lack selective permeation and only exhibit a simple release mode. Here, we use ultrathin-shell water-in-oil-in-water double emulsions as templates and design porous ultrathin-shell microcapsules for selective permeation and multiple stimuli-triggered release. After preparation of double emulsions by microfluidic devices, negatively charged shellac nanoparticles dispersed in the inner water core electrostatically complex with positively charged telechelic α,ω-diamino functionalized polydimethylsiloxane polymers dissolved in the middle oil shell at the water/oil interface, thus forming a porous shell of shellac nanoparticles cross-linked by telechelic polymers. Subsequently, the double emulsions become porous microcapsules upon evaporation of the middle oil phase. The porous ultrathin-shell microcapsules exhibit excellent properties, including tunable size, selective permeation and stimuli-triggered release. Small molecules or particles can diffuse across the shell, while large molecules or particles are encapsulated in the core, and release of the encapsulated cargos can be triggered by osmotic shock or a pH change. Due to their unique performance, porous ultrathin-shell microcapsules present promising platforms for various applications, such as drug delivery.

Keywords microcapsule emulsion microfluidics selective permeation stimuli-triggered release

Corresponding Author(s): Baoling Guo,Fangfu Ye,Dong Chen

Online First Date: 03 November 2022 Issue Date: 13 December 2022

Cite this article:

Li Chen,Yao Xiao,Zhiming Zhang, et al. Porous ultrathin-shell microcapsules designed by microfluidics for selective permeation and stimuli-triggered release[J]. Front. Chem. Sci. Eng., 2022, 16(11): 1643-1650.

URL:

https://academic.hep.com.cn/fcse/EN/10.1007/s11705-022-2201-z
https://academic.hep.com.cn/fcse/EN/Y2022/V16/I11/1643

Fig.1 Design and preparation of porous ultrathin-shell microcapsules. (a) Schematic illustration of the preparation of ultrathin-shell W/O/W double emulsions using a glass capillary microfluidic device. Shellac NPs were dispersed in the inner water phase, and telechelic NH₂-PDMS-NH₂ molecules were dissolved in the middle oil phase. (b) Negatively charged shellac NPs electrostatically complexed with positively charged telechelic polymers at the water/oil interface, and porous ultrathin-shell microcapsules were formed upon evaporation of the n-hexane. Since telechelic NH₂-PDMS-NH₂ molecules possess two amino end groups, telechelic molecules were able to bridge neighboring shellac NPs, thus forming a cross-linked network. Optical microscope images of (c) ultrathin-shell double emulsions and (d) porous ultrathin-shell microcapsules. (e) Fluorescent confocal microscope image of a porous ultrathin-shell microcapsule with Nile red loaded in the shellac NPs. (f) SEM image of a collapsed porous ultrathin-shell microcapsule.

Fig.2 Tuning the size of ultrathin-shell W/O/W double emulsions, which were used as templates for preparation of porous ultrathin-shell microcapsules. (a) Dependence of the emulsion size on the inner phase flow rate. The flow rates of the middle and outer phases were fixed at 800 and 10000 μL?h^–1, respectively. (b) Dependence of the emulsion size on the middle phase flow rate. The flow rates of the inner and outer phases were kept constant at 200 and 10000 μL?h^–1, respectively. (c) Dependence of the emulsion size on the outer phase flow rate. The flow rates of the inner and middle phases were kept constant at 200 and 800 μL?h^–1, respectively. Red ink was dissolved in the inner phase for better visualization.

Fig.3 Selective permeation of porous ultrathin-shell microcapsules. (a) Schematic illustration of selective permeation of small molecules or particles across the porous ultrathin shell. Fluorescence confocal microscope images of (b) rhodamine B molecules with size of ~1 nm and (c) rhodamine B-stained PLLA NPs with size of ~60 nm encapsulated in the porous ultrathin-shell microcapsules. Nile red was loaded in shellac NPs, and its fluorescent color (green) was excited by a 488 nm laser and observed between 500 nm and 520 nm. The fluorescent color (red) of rhodamine B was excited by a 543 nm laser and observed between 650 and 800 nm.

Fig.4 Stimuli-triggered release of porous ultrathin-shell microcapsules. (a) Schematic illustration of osmotic pressure-triggered release. (b) Sequences of snapshots showing swelling and rupture of the porous ultrathin-shell microcapsules triggered by osmotic pressure. The microcapsules contained 50 mg?mL^–1 PEG in the core, and water was added to the continuous phase to impose an osmotic pressure. (c) Schematic illustration of pH-triggered release. (d) Sequences of snapshots showing disintegration of the porous ultrathin-shell microcapsules under alkaline condition. NaOH solution was added to the continuous phase, and shellac NPs were dissolved after the pH change, leading to disintegration of the microcapsules.

1	H Lee, C H Choi, A Abbaspourrad, C Wesner, M Caggioni, T Zhu, D A Weitz. Encapsulation and enhanced retention of fragrance in polymer microcapsules. ACS Applied Materials & Interfaces, 2016, 8(6): 4007–4013 https://doi.org/10.1021/acsami.5b11351
2	C Nam, J Yoon, S A Ryu, C H Choi, H Lee. Water and oil insoluble PEGDA-based microcapsule: biocompatible and multicomponent encapsulation. ACS Applied Materials & Interfaces, 2018, 10(47): 40366–40371 https://doi.org/10.1021/acsami.8b16876
3	J O Chu, Y Choi, D W Kim, H S Jeong, J P Park, D A Weitz, S J Lee, H Lee, C H Choi. Cell-inspired hydrogel microcapsules with a thin oil layer for enhanced retention of highly reactive antioxidants. ACS Applied Materials & Interfaces, 2022, 14(2): 2597–2604 https://doi.org/10.1021/acsami.1c20748
4	S D Ling, Y Geng, A Chen, Y Du, J Xu. Enhanced single-cell encapsulation in microfluidic devices: from droplet generation to single-cell analysis. Biomicrofluidics, 2020, 14(6): 61508 https://doi.org/10.1063/5.0018785
5	J Pessi, H A Santos, I Miroshnyk, D A JoukoYliruusi, S Weitz. Microfluidics-assisted engineering of polymeric microcapsules with high encapsulation efficiency for protein drug delivery. International Journal of Pharmaceutics, 2014, 472(1): 82–87 https://doi.org/10.1016/j.ijpharm.2014.06.012
6	C H Choi, H Lee, A Abbaspourrad, J H Kim, J Fan, M Caggioni, C Wesner, T Zhu, D A Weitz. Triple emulsion drops with an ultrathin water layer: high encapsulation efficiency and enhanced cargo retention in microcapsules. Advanced Materials, 2016, 28(17): 3340–3344 https://doi.org/10.1002/adma.201505801
7	P Zhu, T Kong, X Tang, L Wang. Well-defined porous membranes for robust omniphobic surfaces via microfluidic emulsion templating. Nature Communications, 2017, 8(1): 15823 https://doi.org/10.1038/ncomms15823
8	L Chen, Y Xiao, Q Wu, X Yan, P Zhao, J Ruan, J Shan, D Chen, D A Weitz, F Ye. Emulsion designer using microfluidic three-dimensional droplet printing in droplet. Small, 2021, 17(39): 2102579 https://doi.org/10.1002/smll.202102579
9	G Sobczak, T Wojciechowski, V Sashuk. Submicron colloidosomes of tunable size and wall thickness. Langmuir, 2017, 33(7): 1725–1731 https://doi.org/10.1021/acs.langmuir.6b04159
10	S Wu, Z Xin, S Zhao, S Sun. High-throughput droplet microfluidic synthesis of hierarchical metal−organic framework nanosheet microcapsules. Nano Research, 2019, 12(11): 2736–2742 https://doi.org/10.1007/s12274-019-2507-4
11	J P Hitchcock, A L Tasker, E A Baxter, S Biggs, O J Cayre. Long-term retention of small, volatile molecular species within metallic microcapsules. ACS Applied Materials & Interfaces, 2015, 7(27): 14808–14815 https://doi.org/10.1021/acsami.5b03116
12	M J Zhang, P Zhang, L D Qiu, T Chen, W Wang, L Y Chu. Controllable microfluidic fabrication of microstructured functional materials. Biomicrofluidics, 2020, 14(6): 061501 https://doi.org/10.1063/5.0027907
13	F He, W Wang, X H He, X L Yang, M Li, R Xie, X J Ju, Z Liu, L Y Chu. Controllable multicompartmental capsules with distinct cores and shells for synergistic release. ACS Applied Materials & Interfaces, 2016, 8(13): 8743–8754 https://doi.org/10.1021/acsami.6b01278
14	X R You, X J Ju, F He, Y Wang, Z Liu, W Wang, L Y Chu. Polymersomes with rapid K(+)-triggered drug-release behaviors. ACS Applied Materials & Interfaces, 2017, 9(22): 19258–19268 https://doi.org/10.1021/acsami.7b05701
15	R Geryak, E Quigley, S Kim, V F Korolovych, R Calabrese, D L Kaplan, V V Tsukruk. Tunable interfacial properties in silk ionomer microcapsules with tailored multilayer interactions. Macromolecular Bioscience, 2019, 19(3): 1800176 https://doi.org/10.1002/mabi.201800176
16	T Tian, J Ruan, J Zhang, C X Zhao, D Chen, J Shan. Nanocarrier-based tumor-targeting drug delivery systems for hepatocellular carcinoma treatments: enhanced therapeutic efficacy and reduced drug toxicity. Journal of Biomedical Nanotechnology, 2022, 18(3): 660–676 https://doi.org/10.1166/jbn.2022.3297
17	X Xie, W Zhang, A Abbaspourrad, J Ahn, A Bader, S Bose, A Vegas, J Lin, J Tao, T Hang, H Lee, N Iverson, G Bisker, L Li, M S Strano, D A Weitz, D G Anderson. Microfluidic fabrication of colloidal nanomaterials-encapsulated microcapsules for biomolecular sensing. Nano Letters, 2017, 17(3): 2015–2020 https://doi.org/10.1021/acs.nanolett.7b00026
18	H Sun, H Zheng, Q Tang, Y Dong, F Qu, Y Wang, G Yang, T Meng. Monodisperse alginate microcapsules with spatially confined bioactive molecules via microfluid-generated W/W/O emulsions. ACS Applied Materials & Interfaces, 2019, 11(40): 37313–37321 https://doi.org/10.1021/acsami.9b12479
19	I Polenz, S S Datta, D A Weitz. Controlling the morphology of polyurea microcapsules using microfluidics. Langmuir, 2014, 30(40): 13405–13410 https://doi.org/10.1021/la503234z
20	Z Sun, C Yang, M Eggersdorfer, J Cui, Y Li, M Hai, D Chen, D A Weitz. A general strategy for one-step fabrication of biocompatible microcapsules with controlled active release. Chinese Chemical Letters, 2020, 31(1): 249–252 https://doi.org/10.1016/j.cclet.2019.04.040
21	Z Liu, X J Ju, W Wang, R Xie, L Jiang, Q Chen, Y Q Zhang, J F Wu, L Y Chu. Stimuli-responsive capsule membranes for controlled release in pharmaceutical applications. Current Pharmaceutical Design, 2017, 23(2): 295–301 https://doi.org/10.2174/1381612822666161021141429
22	L Chen, C Yang, Y Xiao, X Yan, L Hu, M Eggersdorfer, D Chen, D A Weitz, F Ye. Millifluidics, microfluidics, and nanofluidics: manipulating fluids at varying length scales. Materials Today Nano, 2021, 16: 100136 https://doi.org/10.1016/j.mtnano.2021.100136
23	Z Sun, X Yan, Y Xiao, L Hu, M Eggersdorfer, D Chen, Z Yang, D A Weitz. Pickering emulsions stabilized by colloidal surfactants: role of solid particles. Particuology, 2022, 64: 153–163 https://doi.org/10.1016/j.partic.2021.06.004
24	Y H Choi, J Hwang, S H Han, C Lee, S Jeon, S Kim. Thermo-responsive microcapsules with tunable molecular permeability for controlled encapsulation and release. Advanced Functional Materials, 2021, 31(24): 2100782 https://doi.org/10.1002/adfm.202100782
25	T Y Lee, M Ku, B Kim, S Lee, J Yang, S H Kim. Microfluidic production of biodegradable microcapsules for sustained release of hydrophilic actives. Small, 2017, 13(29): 1700646 https://doi.org/10.1002/smll.201700646
26	J Perrotton, R Ahijado-Guzmán, L H Moleiro, B Tinao, A Guerrero-Martinez, E Amstad, F Monroy, L R Arriaga. Microfluidic fabrication of vesicles with hybrid lipid/nanoparticle bilayer membranes. Soft Matter, 2019, 15(6): 1388–1395 https://doi.org/10.1039/C8SM02050G
27	B Wu, C Yang, Q Xin, L Kong, M Eggersdorfer, J Ruan, P Zhao, J Shan, K Liu, D Chen, D A Weitz, X Gao. Attractive Pickering emulsion gels. Advanced Materials, 2021, 33(33): 2102362 https://doi.org/10.1002/adma.202102362
28	X Yan, B Wu, Q Wu, L Chen, F Ye, D Chen. Interfacial engineering of attractive Pickering emulsion gel-templated porous materials for enhanced solar vapor generation. Energies, 2021, 14(19): 6077 https://doi.org/10.3390/en14196077
29	G Luo, Y Yu, Y Yuan, X Chen, Z Liu, T Kong. Freeform, reconfigurable embedded printing of all-aqueous 3D architectures. Advanced Materials, 2019, 31(49): 1904631 https://doi.org/10.1002/adma.201904631
30	J G Werner, D A Weitz, H Lee, U Wiesner. Ordered mesoporous microcapsules from double emulsion confined block copolymer self-assembly. ACS Nano, 2021, 15(2): 3490–3499 https://doi.org/10.1021/acsnano.1c00068
31	B Thierry, H J Griesser. Dense PEG layers for efficient immunotargeting of nanoparticles to cancer cells. Journal of Materials Chemistry, 2012, 22(18): 8810 https://doi.org/10.1039/c2jm30210a
32	L R Schiller, M Emmett, C A Santa Ana, J S Fordtran. Osmotic effects of polyethylene glycol. Gastroenterology, 1988, 94(4): 933–941 https://doi.org/10.1016/0016-5085(88)90550-1

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