基于生物质颗粒的油包水（W/O）型Pickering乳液

doi:10.3969/j.issn.2097-2806.2025.02.002

摘要/Abstract

摘要：

鉴于油包水（W/O）型Pickering乳液广阔的应用前景，其在近年来引起了研究者们的持续关注。目前的研究成果多聚焦于非生物来源的颗粒，此类颗粒在生物相容性、生物降解性以及可持续性等方面存在明显不足，难以满足当前对“绿色”产品的需求。因此，采用生物衍生颗粒作为乳化剂以制备W/O Pickering乳液已成为当前的热点方向。文章旨在对W/O Pickering乳液领域的最新研究进展进行梳理和更新。首先探讨了W/O Pickering乳液的稳定机制以及颗粒特性对其的影响，如润湿性、浓度、大小和形状等。接着重点介绍了不同来源的生物质颗粒乳化剂的研究进展，涵盖了纤维素、淀粉、木质素、玉米醇溶蛋白、多酚晶体和三萜类化合物等。这些颗粒是构建“绿色”W/O Pickering乳液的理想乳化剂。最后进一步分析了基于生物质颗粒的W/O Pickering乳液在食品工业、多孔材料、界面生物催化和微生物培养等领域的具体应用，并强调了它们在可持续发展和环保理念中的重要性。

关键词: 油包水（W/O）型Pickering乳液, 生物衍生颗粒, 乳化剂, 可持续发展

Abstract:

Given its broad range of applications, water-in-oil （W/O） Pickering emulsions have garnered huge interest in recent years. Current research often focuses on non-bio-derived particles, which lack in biocompatibility, biodegradability, and sustainability, failing to meet the growing demand for “green” products. Consequently, using bio-derived particles as emulsifiers to prepare W/O Pickering emulsions has become a hotspot. This article aims to review and update the latest advancements in the field of bio-derived particles-based W/O Pickering emulsions. It first discusses the mechanisms of W/O Pickering emulsions and the influence of particle characteristics on emulsion, such as wettability, concentration, size, and shape. Subsequently, it highlights the progress of emulsifiers from various bio-derived sources, including cellulose, starch, lignin, Zein, polyphenolic crystals, and triterpenoids. These particles are ideal emulsifier for constructing “green” W/O Pickering emulsions. Finally, it further analyzes the applications of bio-derived particles-based W/O Pickering emulsions in the food industry, porous materials, interfacial biocatalysis, and microbial cultivation, emphasizing their importance in sustainable development and environmental protection concepts.

Key words: water-in-oil （W/O） Pickering emulsion, bio-derived particle, emulsifier, sustainable development

中图分类号:

O648.23

蒋伟杰,蒋航. 基于生物质颗粒的油包水（W/O）型Pickering乳液[J]. 日用化学工业（中英文）, 2025, 55(2): 142-153.

Weijie Jiang,Hang Jiang. Water-in-oil (W/O) Pickering emulsions stabilized by bio-based particles[J]. China Surfactant Detergent & Cosmetics, 2025, 55(2): 142-153.

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参考文献 72

[1]	Zembyla M, Murray B S, Sarkar A. Water-in-oil emulsions stabilized by surfactants, biopolymers and/or particles: A review[J]. Trends in Food Science & Technology, 2020, 104: 49-59.
[2]	Chevalier Y, Bolzinger M A. Emulsions stabilized with solid nanoparticles: Pickering emulsions[J]. Colloids and Surfaces A: Physicochemical and Engineering Aspects, 2013, 439: 23-34.
[3]	Yan N, Gray M R, Masliyah J H. On water-in-oil emulsions stabilized by fine solids[J]. Colloids and Surfaces A: Physicochemical and Engineering Aspects, 2001, 193: 97-107.
[4]	Binks B P, Lumsdon S O. Pickering emulsions stabilized by monodisperse latex particles: Effects of particle size[J]. Langmuir, 2001, 17: 4540-4547.
[5]	Jiang H, Zhang S, Sun G, et al. Engineering hybrid microgels as particulate emulsifiers for reversible Pickering emulsions[J]. Chemical Science, 2022, 13: 39-43.
[6]	Dupont H, Maingret V, Schmitt V, et al. New insights into the formulation and polymerization of Pickering emulsions stabilized by natural organic particles[J]. Macromolecules, 2021, 54: 4945-4970.
[7]	Ettelaie R, Lishchuk S V. Detachment force of particles from fluid droplets[J]. Soft Matter, 2015, 11: 4251-4265. doi: 10.1039/c5sm00540j pmid: 25895918
[8]	Binks B P, Lumsdon S O. Influence of particle wettability on the type and stability of surfactant-free emulsions[J]. Langmuir, 2000, 16: 8622-8631.
[9]	Ni L, Yu C, Wei Q B, et al. Pickering emulsion catalysis: Interfacial chemistry, catalyst design, challenges, and perspectives[J]. Angewandte Chemie International Edition, 2022, 61: e202115885.
[10]	Arditty S, Whitby C P, Binks B P, et al. Some general features of limited coalescence in solid-stabilized emulsions[J]. European Physical Journal E, 2003, 11: 273-281. doi: 10.1140/epje/i2003-10018-6 pmid: 15011047
[11]	Zembyla M, Lazidis A, Murray B S, et al. Water-in-oil Pickering emulsions stabilized by synergistic particle-particle interactions[J]. Langmuir, 2019, 35: 13078-13089. doi: 10.1021/acs.langmuir.9b02026 pmid: 31525933
[12]	Einstein A. On the motion of small particles suspended in liquids at rest required by the molecular-kinetic theory of heat[J]. Annalen der Physik, 1905, 17: 549-560.
[13]	Lin Y, Skaff H, Emrick T, et al. Nanoparticle assembly and transport at liquid-liquid interfaces[J]. Science, 2003, 299: 226-229. pmid: 12522244
[14]	Kralchevsky P A, Ivanov I B, Ananthapadmanabhan K P, et al. On the thermodynamics of particle-stabilized emulsions: Curvature effects and catastrophic phase inversion[J]. Langmuir, 2005, 21: 50-63. pmid: 15620284
[15]	Wu D, Binks B P, Honciuc A. Modeling the interfacial energy of surfactant-free amphiphilic Janus nanoparticles from phase inversion in Pickering emulsions[J]. Langmuir, 2018, 34: 1225-1233. doi: 10.1021/acs.langmuir.7b02331 pmid: 28946742
[16]	Briggs N, Raman A K Y, Barrett L, et al. Stable Pickering emulsions using multi-walled carbon nanotubes of varying wettability[J]. Colloids and Surfaces A: Physicochemical and Engineering Aspects, 2018, 537: 227-235.
[17]	Lin K Y A, Yang H, Petit C, et al. Magnetically controllable Pickering emulsion prepared by a reduced graphene oxide-iron oxide composite[J]. Journal of Colloid and Interface Science, 2015, 438: 296-305.
[18]	Yan H, Zhao B, Long Y, et al. New Pickering emulsions stabilized by silica nanowires[J]. Colloids and Surfaces A: Physicochemical and Engineering Aspects, 2015, 482: 639-646.
[19]	Elias Machado J P, de Freitas R A, Wypych F. Layered clay minerals, synthetic layered double hydroxides and hydroxide salts applied as Pickering emulsifiers[J]. Applied Clay Science, 2019, 169: 10-20. doi: 10.1016/j.clay.2018.12.007
[20]	Sarkar A, Dickinson E. Sustainable food-grade Pickering emulsions stabilized by plant-based particles[J]. Current Opinion in Colloid &Interface Science, 2020, 49: 69-81.
[21]	Laitinen O, Ojala J, Sirviö J A, et al. Sustainable stabilization of oil in water emulsions by cellulose nanocrystals synthesized from deep eutectic solvents[J]. Cellulose, 2017, 24: 1679-1689.
[22]	Kalashnikova I, Bizot H, Bertoncini P, et al. Cellulosic nanorods of various aspect ratios for oil in water Pickering emulsions[J]. Soft Matter, 2013, 9: 952-959.
[23]	Pang B, Liu H, Liu P, et al. Water-in-oil Pickering emulsions stabilized by stearoylated microcrystalline cellulose[J]. Journal of Colloid and Interface Science, 2018, 513: 629-637. doi: S0021-9797(17)31384-X pmid: 29207345
[24]	Guo J, Du W, Gao Y, et al. Cellulose nanocrystals as water-in-oil Pickering emulsifiers via intercalative modification[J]. Colloids and Surfaces A: Physicochemical and Engineering Aspects, 2017, 529: 634-642.
[25]	刘灿灿, 孙潇鹏, 宋洪波. 淀粉在Pickering乳液中的应用研究[J]. 食品工业, 2018, 39: 272-276.
[26]	Li C, Li Y, Sun P, et al. Pickering emulsions stabilized by native starch granules[J]. Colloids and Surfaces A: Physicochemical and Engineering Aspects, 2013, 431: 142-149.
[27]	Zhai K, Pei X, Wang C, et al. Water-in-oil Pickering emulsion polymerization of N-isopropyl acrylamide using starch-based nanoparticles as emulsifier[J]. International Journal of Biological Macromolecules, 2019, 131: 1032-1037. doi: S0141-8130(18)35349-2 pmid: 30898598
[28]	Patel A R, Velikov K P. Zein as a source of functional colloidal nano-and microstructures[J]. Current Opinion in Colloid & Interface Science, 2014, 19: 450-458.
[29]	Rutkevičius M, Allred S, Velev O D, et al. Stabilization of oil continuous emulsions with colloidal particles from water-insoluble plant proteins[J]. Food Hydrocolloids, 2018, 82: 89-95.
[30]	Bollhorst T, Rezwan K, Maas M. Colloidal capsules: Nano-and microcapsules with colloidal particle shells[J]. Chemical Society Reviews, 2017, 46: 2091-2126. doi: 10.1039/c6cs00632a pmid: 28230870
[31]	Jiang W, Jiang H, Liu W, et al. Pickering emulsion templated proteinaceous microsphere with bio-stimuli responsiveness[J]. Acta Physico-Chimica Sinica, 2023, 39: 132-139.
[32]	Jiang W, Guan X, Liu W, et al. Pickering emulsion templated proteinaceous microparticles as glutathione-responsive carriers for endocytosis in tumor cells[J]. Nanoscale Horizons, 2024, 9: 536-543. doi: 10.1039/d3nh00551h pmid: 38390971
[33]	Jiang H, Hu X, Jiang W, et al. Water-in-oil Pickering emulsions stabilized by hydrophobized protein microspheres[J]. Langmuir, 2022, 38: 12273-12280.
[34]	Thakur V K, Thakur M K. Recent advances in green hydrogels from lignin: A review[J]. International Journal of Biological Macromolecules, 2015, 72: 834-847. pmid: 25304747
[35]	Gould J, Garcia-Garcia G, Wolf B. Pickering particles prepared from food waste[J]. Materials, 2016, 9: 791.
[36]	Zembyla M, Murray B S, Sarkar A. Water-in-oil Pickering emulsions stabilized by water-insoluble polyphenol crystals[J]. Langmuir, 2018, 34: 10001-10011. doi: 10.1021/acs.langmuir.8b01438 pmid: 30074808
[37]	Zembyla M, Murray B S, Radford S J, et al. Water-in-oil Pickering emulsions stabilized by an interfacial complex of water-insoluble polyphenol crystals and protein[J]. Journal of Colloid and Interface Science, 2019, 548: 88-99. doi: S0021-9797(19)30420-5 pmid: 30981966
[38]	Wan Z, Xia H, Guo S, et al. Water-in-oil Pickering emulsions stabilized solely by a naturally occurring steroidal sapogenin: Diosgenin[J]. Food Research International, 2021, 147: 110573.
[39]	Liu Y, Xia H, Guo S, et al. Development and characterization of a novel naturally occurring pentacyclic triterpene self-stabilized Pickering emulsion[J]. Colloids and Surfaces A: Physicochemical and Engineering Aspects, 2022, 634: 127908.
[40]	Lan M, Song Y, Ou S, et al. Water-in-oil Pickering emulsions stabilized solely by water-dispersible phytosterol particles[J]. Langmuir, 2020, 36: 14991-14998. doi: 10.1021/acs.langmuir.0c02301 pmid: 33256410
[41]	Wang C, Jiang H, Li Y. Water-in-oil Pickering emulsions stabilized by phytosterol/chitosan complex particles[J]. Colloids and Surfaces A: Physicochemical and Engineering Aspects, 2023, 657: 1-9.
[42]	王诚蕾. 植物甾醇/壳聚糖复合颗粒稳定的Pickering乳液的制备与应用研究[D]. 无锡: 江南大学, 2023.
[43]	Mwangi W W, Lim H P, Low L E, et al. Food-grade Pickering emulsions for encapsulation and delivery of bioactives[J]. Trends in Food Science & Technology, 2020, 100: 320-332.
[44]	Frasch-Melnik S, Norton I T, Spyropoulos F. Fat-crystal stabilised W/O emulsions for controlled salt release[J]. Journal of Food Engineering, 2010, 98: 437-442.
[45]	Chivero P, Gohtani S, Yoshii H, et al. Assessment of soy soluble polysaccharide, gum arabic and OSA-starch as emulsifiers for mayonnaise-like emulsions[J]. LWT-Food Science and Technology, 2016, 69: 59-66.
[46]	Gao Z, Yang X, Wu N, et al. Protein-based Pickering emulsion and oil gel prepared by complexes of zein colloidal particles and stearate[J]. Journal of Agricultural and Food Chemistry, 2014, 62: 2672-2678.
[47]	Skelhon T S, Grossiord N, Morgan A R, et al. Quiescent water-in-oil Pickering emulsions as a route toward healthier fruit juice infused chocolate confectionary[J]. Journal of Materials Chemistry, 2012, 22: 19289-19295.
[48]	Yang X, Chen L, Li Y, et al. Hierarchically porous materials: Synthesis strategies and structure design[J]. Chemical Society Reviews, 2017, 46: 481-558.
[49]	Jiao B, Shi A, Wang Q, et al. High-internal-phase Pickering emulsions stabilized solely by peanut-protein-isolate microgel particles with multiple potential applications[J]. Angewandte Chemie International Edition, 2018, 57: 9274-9278.
[50]	Tang X, Wang Z, Yu D, et al. Fabrication of ultrastable water-in-oil high internal phase emulsion as versatile delivery vehicle through synergetic stabilization[J]. Food Hydrocolloids, 2022, 126: 107455.
[51]	Du L, Zhou S, Huang Y, et al. Investigation on the structure characteristics, stability evaluation, and oral tribology of natural oleanolic acid-based water-in-oil high internal phase and multiple Pickering emulsions as realistic fat analogues[J]. Food Chemistry, 2025, 465: 142121.
[52]	Mutti F G, Knaus T, Scrutton N S, et al. Conversion of alcohols to enantiopure amines through dual-enzyme hydrogen-borrowing cascades[J]. Science, 2015, 349: 1525-1529. doi: 10.1126/science.aac9283 pmid: 26404833
[53]	Vazquez-Gonzalez M, Wang C, Willner I, et al. Biocatalytic cascades operating on macromolecular scaffolds and in confined environments[J]. Nature Catalysis, 2020, 3: 256-273.
[54]	Yang D, Zeng Q, Tan K, et al. Lipase-entrapped colloidosomes with light-responsive wettability for efficient and recyclable Pickering interfacial biocatalysis[J]. Green Chemistry, 2024, 26: 10824-10828.
[55]	Jiang H, Liu L, Li Y, et al. Inverse Pickering emulsion stabilized by binary particles with contrasting characteristics and functionality for interfacial biocatalysis[J]. ACS Applied Materials & Interfaces, 2020, 12: 4989-4997.
[56]	Li K, Zou H, Ettelaie R, et al. Spatial localization of two enzymes at Pickering emulsion droplet interfaces for cascade reactions[J]. Angewandte Chemie International Edition, 2023, 62: e202300794.
[57]	Zhang M, Ettelaie R, Li T, et al. Pickering emulsion droplets and solid microspheres acting synergistically for continuous-flow cascade reactions[J]. Nature Catalysis, 2024, 7: 295-306.
[58]	Sun Z, Hübner R, Li J, et al. Artificially sporulated Escherichia coli cells as a robust cell factory for interfacial biocatalysis[J]. Nature Communications, 2022, 13: 3142.
[59]	Sun Z, Wu C. Pickering emulsions biocatalysis: Recent developments and emerging trends[J]. Small, 2024, 20: 2402208.
[60]	Qi L, Luo Z, Lu X. Modulation of starch nanoparticle surface characteristics for the facile construction of recyclable Pickering interfacial enzymatic catalysis[J]. Green Chemistry, 2019, 21: 2412-2427.
[61]	Yang X, Wang Y, Bai R, et al. Pickering emulsion-enhanced interfacial biocatalysis: Tailored alginate microparticles act as particulate emulsifier and enzyme carrier[J]. Green Chemistry, 2019, 21: 2229-2231. doi: 10.1039/c8gc03573c
[62]	Jiang H, Hu X, Li Y, et al. Engineering proteinaceous colloidosomes as enzyme carriers for efficient and recyclable Pickering interfacial biocatalysis[J]. Chemical Science, 2021, 12: 12463-12467. doi: 10.1039/d1sc03693a pmid: 34603677
[63]	Jakiela S, Kaminski T S, Cybulski O, et al. Bacterial growth and adaptation in microdroplet chemostats[J]. Angewandte Chemie International Edition, 2013, 52: 8908-8911.
[64]	Pan M, Rosenfeld L, Kin M, et al. Fluorinated Pickering emulsions impede interfacial transport and form rigid interface for the growth of anchorage-dependent cells[J]. ACS Applied Materials & Interfaces, 2014, 6: 21446-21453.
[65]	Haji F, Cheon J, Baek J, et al. Application of Pickering emulsions in probiotic encapsulation: A review[J]. Current Research in Food Science, 2022 (5): 1603-1615.
[66]	Zhou X, Chen C, Cao C, et al. Enhancing reaction rate in a Pickering emulsion system with natural magnetotactic bacteria as nanoscale magnetic stirring bars[J]. Chemical Science, 2018, 9: 2575-2580. doi: 10.1039/c7sc05164f pmid: 29719712
[67]	Chen Z, Zhou L, Bing W, et al. Light controlled reversible inversion of nanophosphor-stabilized Pickering emulsions for biphasic enantioselective biocatalysis[J]. Journal of the American Chemical Society, 2014, 136: 7498-7504. doi: 10.1021/ja503123m pmid: 24784766
[68]	Jiang H, Qi L, Li Y, et al. Localizing anaerobic microbial cultivation and recovery through intelligent Pickering emulsion phase inversion[J]. CCS Chemistry, 2024.
[69]	Miao X, Wu Q. Biodiesel production from heterotrophic microalgal oil[J]. Bioresource Technology, 2006, 97: 841-846. doi: 10.1016/j.biortech.2005.04.008 pmid: 15936938
[70]	Tambat V S, Patel A K, Singhania R R, et al. Sustainable mixotrophic microalgae refinery of astaxanthin and lipid from Chlorella zofingiensis[J]. Bioresource Technology, 2023, 387: 129635.
[71]	Di Caprio F. Methods to quantify biological contaminants in microalgae cultures[J]. Algal Research, 2020, 49: 101943.
[72]	Qi L, Hang T, Jiang W, et al. Proteinaceous microsphere-based water-in-oil Pickering emulsions for preservation of Chlorella Cells[J]. Polymers, 2024, 16: 647.