Abstract
There has been significant interest over recent years in the production and application of sustainable and green materials. Among these, nanocellulose has incurred great interest because of its exceptional properties and wide range of potential applications, including in Pickering emulsions. However, the production cost of these cellulosic materials has limited their application. In this study, the capability of a new type of cheaper cellulosic material, cellulose filaments (CFs), in formulating stable oil in water Pickering emulsions was investigated and compared with three conventional nanocelluloses, namely cellulose nanocrystals (CNCs), cellulose nanofibrils (CNFs) and TEMPO-oxidized CNFs (TEMPO-CNFs). Results showed that CFs can provide stable surfactant-free emulsions over wide ranges of salt concentration (0–500 mM) and pH (2–10), as indicated by the near-constant oil droplet size and dewatering index of the emulsions. This is due to the ability of CFs to strongly adsorb to the oil and water interface, as evidenced by Cryo-SEM and visualized through labelled CFs with engineered carbohydrate-binding module (CBM2a) conjugated with green fluorescent protein (CBM2a-eGFP) under fluorescent microscopy. Compared to the emulsions stabilized by other types of nanocelluloses, the CF-stabilized emulsion demonstrated a larger average droplet size and comparable (with CNFs) or better (than CNCs and TEMPO-CNFs) stability, which is partially attributed to the higher viscosity of continuous phase in the presence of CFs. The results of this study demonstrate the use of CFs as a novel and cheaper cellulosic material for stabilizing emulsions, which opens the door to a range of markets from the food industry to engineering applications.
Graphical abstract

This is a preview of subscription content, access via your institution.







References
Aaen R, Brodin FW, Simon S et al (2019) Oil-in-water emulsions stabilized by cellulose nanofibrils-the effects of ionic strength and pH. Nanomater (basel, Switzerland) 9:259. https://doi.org/10.3390/nano9020259
Ahankari S, Paliwal P, Subhedar A, Kargarzadeh H (2021) Recent developments in nanocellulose-based aerogels in thermal applications: a review. ACS Nano 15:3849–3874. https://doi.org/10.1021/acsnano.0c09678
Ahmad AL, Zaulkiflee ND, Kusumastuti A, Buddin MMHS (2019) Removal of acetaminophen from aqueous solution by emulsion liquid membrane: emulsion stability study. Ind Eng Chem Res 58:713–719. https://doi.org/10.1021/acs.iecr.8b03562
Bai L, Lv S, Xiang W et al (2019) Oil-in-water Pickering emulsions via microfluidization with cellulose nanocrystals: 1. Formation and stability. Food Hydrocoll 96:699–708. https://doi.org/10.1016/j.foodhyd.2019.04.038
Björkegren S, Freixiela Dias MCA, Lundahl K et al (2020) Phase inversions observed in thermoresponsive pickering emulsions stabilized by surface functionalized colloidal silica. Langmuir 36:2357–2367. https://doi.org/10.1021/acs.langmuir.9b03648
D’Acierno F, Hamad WY, Michal CA, MacLachlan MJ (2020) Thermal degradation of cellulose filaments and nanocrystals. Biomacromol 21:3374–3386. https://doi.org/10.1021/acs.biomac.0c00805
Deng Z, Jung J, Simonsen J, Zhao Y (2018) Cellulose nanocrystals Pickering emulsion incorporated chitosan coatings for improving storability of postharvest Bartlett pears (Pyrus communis) during long-term cold storage. Food Hydrocoll 84:229–237
Fessi N, Nsib MF, Chevalier Y et al (2019) Photocatalytic degradation enhancement in pickering emulsions stabilized by solid particles of bare TiO2. Langmuir 35:2129–2136. https://doi.org/10.1021/acs.langmuir.8b03806
Ghosh P (2009) Colloid and interface science. PHI Learning Pvt. Ltd.
Goi Y, Fujisawa S, Saito T et al (2019) Dual functions of tempo-oxidized cellulose nanofibers in oil-in-water emulsions: a pickering emulsifier and a unique dispersion stabilizer. Langmuir 35:10920–10926. https://doi.org/10.1021/acs.langmuir.9b01977
Gonzalez Ortiz D, Pochat-Bohatier C, Cambedouzou J et al (2020) Current trends in pickering emulsions: particle morphology and applications. Engineering 6:468–482. https://doi.org/10.1016/j.eng.2019.08.017
Gourlay K, Hu J, Arantes V et al (2015) The use of carbohydrate binding modules (CBMs) to monitor changes in fragmentation and cellulose fiber surface morphology during cellulase-and swollenin-induced deconstruction of lignocellulosic substrates. J Biol Chem 290:2938–2945
Hamad WY, Miao C, Beck S (2019) Growing the bioeconomy: advances in the development of applications for cellulose filaments and nanocrystals. Ind Biotechnol 15:133–137
He Y, Wu F, Sun X et al (2013) Factors that affect pickering emulsions stabilized by graphene oxide. ACS Appl Mater Interfaces 5:4843–4855. https://doi.org/10.1021/am400582n
Hébert-Ouellet Y, Meddeb-Mouelhi F, Khatri V et al (2017) Tracking and predicting wood fibers processing with fluorescent carbohydrate binding modules. Green Chem 19:2603–2611
Hu J, Arantes V, Pribowo A et al (2014) Substrate factors that influence the synergistic interaction of AA9 and cellulases during the enzymatic hydrolysis of biomass. Energy Environ Sci 7:2308–2315
Huan S, Ajdary R, Bai L et al (2019) Low solids emulsion gels based on nanocellulose for 3D-printing. Biomacromol 20:635–644. https://doi.org/10.1021/acs.biomac.8b01224
Jiang H, Sheng Y, Ngai T (2020) Pickering emulsions: Versatility of colloidal particles and recent applications. Curr Opin Colloid Interface Sci 49:1–15. https://doi.org/10.1016/j.cocis.2020.04.010
Jiang Y, Zhang Y, Ding L et al (2019) Regenerated cellulose-dispersed polystyrene composites enabled via Pickering emulsion polymerization. Carbohydr Polym 223:115079. https://doi.org/10.1016/j.carbpol.2019.115079
Jiménez-Saelices C, Seantier B, Grohens Y, Capron I (2018) Thermal superinsulating materials made from nanofibrillated cellulose-stabilized pickering emulsions. ACS Appl Mater Interfaces 10:16193–16202. https://doi.org/10.1021/acsami.8b02418
Jiménez-Saelices C, Trongsatitkul T, Lourdin D, Capron I (2020) Chitin pickering emulsion for oil inclusion in composite films. Carbohydr Polym 242:116366. https://doi.org/10.1016/j.carbpol.2020.116366
Kalia S (2016) Biodegradable green composites. John Wiley & Sons
Khan A, Wen Y, Huq T, Ni Y (2018) Cellulosic nanomaterials in food and nutraceutical applications: a review. J Agric Food Chem 66:8–19. https://doi.org/10.1021/acs.jafc.7b04204
Kiss N, Brenn G, Pucher H et al (2011) Formation of O/W emulsions by static mixers for pharmaceutical applications. Chem Eng Sci 66:5084–5094. https://doi.org/10.1016/j.ces.2011.06.065
Lee MC, Dadmohammadi Y, Tan C, Abbaspourrad A (2020) Mitigating the astringency of acidified whey protein in proteinaceous high internal phase emulsions. ACS Appl Bio Mater 3:8438–8445. https://doi.org/10.1021/acsabm.0c00767
Li W, Suzuki T, Minami H (2019) The interface adsorption behavior in a Pickering emulsion stabilized by cylindrical polystyrene particles. J Colloid Interface Sci 552:230–235. https://doi.org/10.1016/j.jcis.2019.05.058
Li Z, Wu H, Yang M et al (2018) Stability mechanism of O/W Pickering emulsions stabilized with regenerated cellulose. Carbohydr Polym 181:224–233. https://doi.org/10.1016/j.carbpol.2017.10.080
Long L, Hu J, Li X et al (2019) The potential of using thermostable xylan-binding domain as a molecular probe to better understand the xylan distribution of cellulosic fibers. ACS Sustain Chem Eng 7:12520–12526
Low LE, Siva SP, Ho YK et al (2020) Recent advances of characterization techniques for the formation, physical properties and stability of Pickering emulsion. Adv Colloid Interface Sci 277:102117. https://doi.org/10.1016/j.cis.2020.102117
Marto J, Pinto P, Fitas M et al (2018) Safety assessment of starch-based personal care products: nanocapsules and pickering emulsions. Toxicol Appl Pharmacol 342:14–21. https://doi.org/10.1016/j.taap.2018.01.018
Mcclements DJ (2007) Critical review of techniques and methodologies for characterization of emulsion Stability. Crit Rev Food Sci Nutr 47:611–649. https://doi.org/10.1080/10408390701289292
Mikulcová V, Bordes R, Minařík A, Kašpárková V (2018) Pickering oil-in-water emulsions stabilized by carboxylated cellulose nanocrystals—Effect of the pH. Food Hydrocoll 80:60–67. https://doi.org/10.1016/j.foodhyd.2018.01.034
Moon RJ, Martini A, Nairn J et al (2011) Cellulose nanomaterials review: structure, properties and nanocomposites. Chem Soc Rev 40:3941–3994. https://doi.org/10.1039/C0CS00108B
Pal R (1996) Effect of droplet size on the rheology of emulsions. AIChE J 42:3181–3190. https://doi.org/10.1002/aic.690421119
Pandey A, Derakhshandeh M, Kedzior SA et al (2018a) Role of interparticle interactions on microstructural and rheological properties of cellulose nanocrystal stabilized emulsions. J Colloid Interface Sci 532:808–818. https://doi.org/10.1016/j.jcis.2018.08.044
Pandey A, Telmadarreie A, Trifkovic M, Bryant S (2018b) Cellulose Nanocrystal Stabilized Emulsions for Conformance Control and Fluid Diversion in Porous Media. In: SPE Annu. Tech. Conf. Exhib. 18
Pickering SU (1907) Cxcvi.—emulsions. J Chem Soc Trans 91:2001–2021
Pöhler T, Ketoja JA, Lappalainen T et al (2020) On the strength improvement of lightweight fibre networks by polymers, fibrils and fines. Cellulose 27:6961–6976. https://doi.org/10.1007/s10570-020-03263-x
Prathapan R, Thapa R, Garnier G, Tabor RF (2016) Modulating the zeta potential of cellulose nanocrystals using salts and surfactants. Colloids Surfaces A Physicochem Eng Asp 509:11–18. https://doi.org/10.1016/j.colsurfa.2016.08.075
Ragesh P, Ganesh VA, Nair SV, Nair AS (2014) A review on ‘self-cleaning and multifunctional materials.’ J Mater Chem A 2:14773–14797
Ramsden W (1904) Separation of solids in the surface-layers of solutions and ‘suspensions’(observations on surface-membranes, bubbles, emulsions, and mechanical coagulation).—Preliminary account. Proc R Soc London 72:156–164
Sauter J (1926) Die Grössenbestimmung der im Gemischnebel von Verbrennungskraftmaschinen vorhandenen Brennstoffteilchen:(Mitteilung aus d. Labor. f. techn. Physik d. Techn. Hochsch. München); mit 26 Abb. u. 8 Zahlentaf. VDI-Verlag
Schramm LL (2014) Emulsions, foams, suspensions, and aerosols: microscience and applications. John Wiley & Sons
Shao P, Feng J, Sun P et al (2020) Recent advances in improving stability of food emulsion by plant polysaccharides. Food Res Int 137:109376. https://doi.org/10.1016/j.foodres.2020.109376
Shi A, Feng X, Wang Q, Adhikari B (2020) Pickering and high internal phase Pickering emulsions stabilized by protein-based particles: a review of synthesis, application and prospective. Food Hydrocoll 109:106117. https://doi.org/10.1016/j.foodhyd.2020.106117
Tan C, McClements DJ (2021) Application of advanced emulsion technology in the food industry: a review and critical evaluation. Foods 10:812
Thomas B, Raj MC, Joy J et al (2018) Nanocellulose, a versatile green platform: from biosources to materials and their applications. Chem Rev 118:11575–11625
Varanasi S, Henzel L, Mendoza L et al (2018) Pickering emulsions electrostatically stabilized by cellulose nanocrystals. Front Chem 6:409
Venkataramani D, Tsulaia A, Amin S (2020) Fundamentals and applications of particle stabilized emulsions in cosmetic formulations. Adv Colloid Interface Sci 283:102234. https://doi.org/10.1016/j.cis.2020.102234
Winuprasith T, Khomein P, Mitbumrung W et al (2018) Encapsulation of vitamin D3 in pickering emulsions stabilized by nanofibrillated mangosteen cellulose: impact on in vitro digestion and bioaccessibility. Food Hydrocoll 83:153–164
Wu F, Deng J, Hu L et al (2020) Investigation of the stability in Pickering emulsions preparation with commercial cosmetic ingredients. Colloids Surfaces A Physicochem Eng Asp 602:125082 https://doi.org/10.1016/j.colsurfa.2020.125082
Xie C-Y, Meng S-X, Xue L-H et al (2017) Light and magnetic dual-responsive pickering emulsion micro-reactors. Langmuir 33:14139–14148. https://doi.org/10.1021/acs.langmuir.7b03642
Xue F, Zhang Y, Zhang F et al (2017) Tuning the interfacial activity of mesoporous silicas for biphasic interface catalysis reactions. ACS Appl Mater Interfaces 9:8403–8412. https://doi.org/10.1021/acsami.6b16605
Yan H, Chen X, Feng M et al (2019) Entrapment of bacterial cellulose nanocrystals stabilized Pickering emulsions droplets in alginate beads for hydrophobic drug delivery. Colloids Surfaces B Biointerfaces 177:112–120. https://doi.org/10.1016/j.colsurfb.2019.01.057
Yan X, Ma C, Cui F et al (2020) Protein-stabilized Pickering emulsions: Formation, stability, properties, and applications in foods. Trends Food Sci Technol 103:293–303. https://doi.org/10.1016/j.tifs.2020.07.005
Zhang R, Belwal T, Li L et al (2020) Recent advances in polysaccharides stabilized emulsions for encapsulation and delivery of bioactive food ingredients: a review. Carbohydr Polym 242:116388. https://doi.org/10.1016/j.carbpol.2020.116388
Zhang X, Wang Y, Luo X et al (2019) O/W pickering emulsion templated organo-hydrogels with enhanced mechanical strength and energy storage capacity. ACS Appl Bio Mater 2:480–487. https://doi.org/10.1021/acsabm.8b00674
Zhao D, Yu D, Kim M et al (2019) Effects of temperature, light, and pH on the stability of fucoxanthin in an oil-in-water emulsion. Food Chem 291:87–93. https://doi.org/10.1016/j.foodchem.2019.04.002
Zhou Y, Sun S, Bei W et al (2018) Preparation and antimicrobial activity of oregano essential oil Pickering emulsion stabilized by cellulose nanocrystals. Int J Biol Macromol 112:7–13
Zhou Y, Yin D, Chen W et al (2019) A comprehensive review of emulsion and its field application for enhanced oil recovery. Energy Sci Eng 7:1046–1058. https://doi.org/10.1002/ese3.354
Zhu F (2019) Starch based Pickering emulsions: Fabrication, properties, and applications. Trends Food Sci Technol 85:129–137. https://doi.org/10.1016/j.tifs.2019.01.012
Zhu M, Huan S, Liu S et al (2021) Recent development in food emulsion stabilized by plant-based cellulose nanoparticles. Curr Opin Colloid Interface Sci 56:101512. https://doi.org/10.1016/j.cocis.2021.101512
Zhu Y, Lu L-H, Gao J et al (2013) Effect of trace impurities in triglyceride oils on phase inversion of Pickering emulsions stabilized by CaCO3 nanoparticles. Colloids Surf A Physicochem Eng Asp 417:126–132. https://doi.org/10.1016/j.colsurfa.2012.10.043
Acknowledgments
This work is financially supported by the Canada First Research Excellence Fund (CFREF).
Author information
Authors and Affiliations
Corresponding authors
Ethics declarations
Conflict of interest
The authors declare that they have no conflict of interest.
Additional information
Publisher's Note
Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.
Supplementary Information
Below is the link to the electronic supplementary material.
Rights and permissions
About this article
Cite this article
Varamesh, A., Prathapan, R., Telmadarreie, A. et al. Surfactant-free cellulose filaments stabilized oil in water emulsions. Cellulose 29, 985–1001 (2022). https://doi.org/10.1007/s10570-021-04320-9
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s10570-021-04320-9
Keywords
- Pickering emulsions
- Cellulose filaments
- Carbohydrate binding module
- Green materials
- Oil in water emulsions
- Nano/microfibrillated cellulose