Peeling back the layers: Investigating the effects of polyelectrolyte layering on surface structure and stability of oil-in-water nanoemulsions

Tran, Emma; Mapile, Ashley N.; Richmond, Geraldine L.

doi:10.1016/j.jcis.2021.04.115

Peeling back the layers: Investigating the effects of polyelectrolyte layering on surface structure and stability of oil-in-water nanoemulsions

Journal Article · Sat Apr 24 00:00:00 EDT 2021 · Journal of Colloid and Interface Science

DOI:https://doi.org/10.1016/j.jcis.2021.04.115· OSTI ID:1977261

Tran, Emma ^[1]; Mapile, Ashley N. ^[2]; Richmond, Geraldine L. ^[2]

University of Oregon, Eugene, OR (United States); OSTI
University of Oregon, Eugene, OR (United States)

Layer-by-layer deposition of polyelectrolytes is a useful technique for modifying surface functionalities. For drug delivery systems, alternating layers of biopolymers coat nanoemulsions, which house and protect the cargo until the time and destination of delivery. In this report we investigate molecular factors contributing to the stability and interfacial properties of nanoemulsions prepared by a co-adsorption of polymers poly(styrene sulfonate) and polyethylenimine (PEI), and surfactant dodecyltrimethylammonium bromide. We hypothesize the interplay between electrosteric and hydrophobic effects upon multi-polymer co-adsorption contributes to both macroscopic and molecular-level interfacial properties of nanoemulsions. To probe interfacial layering properties, we use vibrational sum frequency scattering spectroscopy with ζ -potential measurements to determine the adsorptive behavior and molecular conformational arrangement of the polymer layers. Complementing these interfacial studies are dynamic light scattering experiments measuring the nanoemulsion size distribution and polydispersity index over a 30-day period. Our light scattering, ζ -potential, and spectroscopic results of the nanoemulsion surface show that the duration of droplet stability and the degree of molecular orientation of adsorbed polymers can be tuned by surfactant concentration, PEI concentration, and pH. These results illustrate how molecular surface properties of multi-polymer coated nanoemulsions contribute to synergistic effects and droplet stability, enabling advancements in applications surrounding biopharmaceuticals, cosmetics, and food sciences.

View Accepted Manuscript (DOE)

Research Organization:: University of Oregon, Eugene, OR (United States)

Sponsoring Organization:: USDOE Office of Science (SC)

Grant/Contract Number:: SC0014278

OSTI ID:: 1977261

Alternate ID(s):: OSTI ID: 1785130

Journal Information:: Journal of Colloid and Interface Science, Journal Name: Journal of Colloid and Interface Science Journal Issue: C Vol. 599; ISSN 0021-9797

Publisher:: ElsevierCopyright Statement

Country of Publication:: United States

Language:: English

References (55)

The structure of interfaces probed by sum-frequency spectroscopy Bain, Coil D.; Davies, Paul B.; Ong, T. Hui Surface and Interface Analysis, Vol. 17, Issue 7 https://doi.org/10.1002/sia.740170721	journal	June 1991
The physical stability and digestibility of β-carotene in oil-in-water sodium caseinate nanoemulsion Zhang, Yixin; He, Shenghua; Li, Yueming Journal of Food Measurement and Characterization, Vol. 11, Issue 2 https://doi.org/10.1007/s11694-016-9457-2	journal	December 2016
Dynamic light scattering: a practical guide and applications in biomedical sciences Stetefeld, Jörg; McKenna, Sean A.; Patel, Trushar R. Biophysical Reviews, Vol. 8, Issue 4 https://doi.org/10.1007/s12551-016-0218-6	journal	October 2016
Buildup of ultrathin multilayer films by a self-assembly process: III. Consecutively alternating adsorption of anionic and cationic polyelectrolytes on charged surfaces Decher, G.; Hong, J. D.; Schmitt, J. Thin Solid Films, Vol. 210-211 https://doi.org/10.1016/0040-6090(92)90417-A	journal	April 1992
The role of the surfactant head group in the emulsification process: Single surfactant systems Goloub, Tanya; Pugh, Robert J. Journal of Colloid and Interface Science, Vol. 257, Issue 2 https://doi.org/10.1016/S0021-9797(02)00047-4	journal	January 2003
Layer-by-layer assembled protein/polymer hybrid films: nanoconstruction via specific recognition Cassier, T.; Lowack, K.; Decher, G. Supramolecular Science, Vol. 5, Issue 3-4 https://doi.org/10.1016/S0968-5677(98)00024-8	journal	July 1998
Layer-by-layer self-assembled shells for drug delivery Ariga, Katsuhiko; Lvov, Yuri M.; Kawakami, Kohsaku Advanced Drug Delivery Reviews, Vol. 63, Issue 9 https://doi.org/10.1016/j.addr.2011.03.016	journal	August 2011
Tissue integration of growth factor-eluting layer-by-layer polyelectrolyte multilayer coated implants Macdonald, Mara L.; Samuel, Raymond E.; Shah, Nisarg J. Biomaterials, Vol. 32, Issue 5 https://doi.org/10.1016/j.biomaterials.2010.10.052	journal	February 2011
Nanoemulsions: a new vehicle for skincare products Sonneville-Aubrun, O.; Simonnet, J. -T.; L'Alloret, F. Advances in Colloid and Interface Science, Vol. 108-109 https://doi.org/10.1016/j.cis.2003.10.026	journal	May 2004
Biocompatible long-sustained release oil-core polyelectrolyte nanocarriers: From controlling physical state and stability to biological impact Szczepanowicz, Krzysztof; Bazylińska, Urszula; Pietkiewicz, Jadwiga Advances in Colloid and Interface Science, Vol. 222 https://doi.org/10.1016/j.cis.2014.10.005	journal	August 2015
AFM study of adhesion and interactions between polyelectrolyte bilayers assembly Czerwieniec, Bartosz; Strawski, Marcin; Granicka, Ludomira H. Colloids and Surfaces A: Physicochemical and Engineering Aspects, Vol. 555 https://doi.org/10.1016/j.colsurfa.2018.07.006	journal	October 2018
Oil drop deposition on solid surfaces in mixed polymer-surfactant solutions in relation to hair- and skin-care applications Stanimirova, Rumyana D.; Kralchevsky, Peter A.; Danov, Krassimir D. Colloids and Surfaces A: Physicochemical and Engineering Aspects, Vol. 577 https://doi.org/10.1016/j.colsurfa.2019.05.044	journal	September 2019
Breakdown mechanisms of oil-in-water emulsions stabilised with Pluronic F127 and co-surfactants Kabong, Mwamb A.; Focke, Walter W.; Du Toit, Elizabeth L. Colloids and Surfaces A: Physicochemical and Engineering Aspects, Vol. 585 https://doi.org/10.1016/j.colsurfa.2019.124101	journal	January 2020
Nanoemulsions: An emerging platform for increasing the efficacy of nutraceuticals in foods Zhang, Ruojie; Zhang, Zipei; McClements, David Julian Colloids and Surfaces B: Biointerfaces, Vol. 194 https://doi.org/10.1016/j.colsurfb.2020.111202	journal	October 2020
Formation and stabilization of nanoemulsion-based vitamin E delivery systems using natural biopolymers: Whey protein isolate and gum arabic Ozturk, Bengu; Argin, Sanem; Ozilgen, Mustafa Food Chemistry, Vol. 188 https://doi.org/10.1016/j.foodchem.2015.05.005	journal	December 2015
Characteristics of polyelectrolyte multilayers: Effect of PEI anchoring layer and posttreatment after deposition Kolasińska, Marta; Krastev, Rumen; Warszyński, Piotr Journal of Colloid and Interface Science, Vol. 305, Issue 1 https://doi.org/10.1016/j.jcis.2006.09.035	journal	January 2007
Characterization of pH-induced changes in the morphology of polyelectrolyte multilayers assembled from poly(allylamine) and low molecular weight poly(acrylic acid) Sun, Bin; Flessner, Ryan M.; Saurer, Eric M. Journal of Colloid and Interface Science, Vol. 355, Issue 2 https://doi.org/10.1016/j.jcis.2010.12.019	journal	March 2011
On the growth mechanisms of nanoemulsions Nazarzadeh, Elijah; Anthonypillai, Tania; Sajjadi, Shahriar Journal of Colloid and Interface Science, Vol. 397 https://doi.org/10.1016/j.jcis.2012.12.018	journal	May 2013
Polymer mediated layer-by-layer assembly of different shaped gold nanoparticles Budy, Stephen M.; Hamilton, Desmond J.; Cai, Yuheng Journal of Colloid and Interface Science, Vol. 487 https://doi.org/10.1016/j.jcis.2016.10.022	journal	February 2017
CO2-responsive surfactants with tunable switching pH Lu, Yi; Sun, Dejun; Ralston, John Journal of Colloid and Interface Science, Vol. 557 https://doi.org/10.1016/j.jcis.2019.08.110	journal	December 2019
Nanoemulsion: Concepts, development and applications in drug delivery Singh, Yuvraj; Meher, Jaya Gopal; Raval, Kavit Journal of Controlled Release, Vol. 252 https://doi.org/10.1016/j.jconrel.2017.03.008	journal	April 2017
A formula for correlating p K a values determined in D 2 O and H 2 O Krȩżel, Artur; Bal, Wojciech Journal of Inorganic Biochemistry, Vol. 98, Issue 1 https://doi.org/10.1016/j.jinorgbio.2003.10.001	journal	January 2004
Pore-Level Observations of an Alkali-Induced Mild O/W Emulsion Flooding for Economic Enhanced Oil Recovery Ning, Jian; Wei, Bing; Mao, Runxue Energy & Fuels, Vol. 32, Issue 10 https://doi.org/10.1021/acs.energyfuels.8b02493	journal	September 2018
Comparison of Emulsion and Nanoemulsion Delivery Systems: The Chemical Stability of Curcumin Decreases as Oil Droplet Size Decreases Kharat, Mahesh; Aberg, Joy; Dai, Taotao Journal of Agricultural and Food Chemistry, Vol. 68, Issue 34 https://doi.org/10.1021/acs.jafc.0c01877	journal	July 2020
Probing the Molecular Structure of Coadsorbed Polyethylenimine and Charged Surfactants at the Nanoemulsion Droplet Surface Tran, Emma; Carpenter, Andrew P.; Richmond, Geraldine L. Langmuir, Vol. 36, Issue 31 https://doi.org/10.1021/acs.langmuir.0c01095	journal	July 2020
Effects of Aggregate Charge and Subphase Ionic Strength on the Properties of Spread Polyelectrolyte/Surfactant Films at the Air/Water Interface under Static and Dynamic Conditions Tummino, Andrea; Toscano, Jutta; Sebastiani, Federica Langmuir, Vol. 34, Issue 6 https://doi.org/10.1021/acs.langmuir.7b03960	journal	January 2018
Molecular Interactions Leading to the Coadsorption of Surfactant Dodecyltrimethylammonium Bromide and Poly(styrenesulfonate) at the Oil/Water Interface Schabes, Brandon K.; Hopkins, Emma J.; Richmond, Geraldine L. Langmuir, Vol. 35, Issue 22 https://doi.org/10.1021/acs.langmuir.9b00873	journal	May 2019
Recent Developments in Layer-by-Layer Technique for Drug Delivery Applications Kurapati, Rajendra; Groth, Thomas W.; Raichur, Ashok M. ACS Applied Bio Materials, Vol. 2, Issue 12 https://doi.org/10.1021/acsabm.9b00703	journal	September 2019
Thin and Flexible Ion Sensors Based on Polyelectrolyte Multilayers Assembled onto the Carbon Adhesive Tape Stekolshchikova, Anna A.; Radaev, Anton V.; Orlova, Olga Yu. ACS Omega, Vol. 4, Issue 13 https://doi.org/10.1021/acsomega.9b01464	journal	September 2019
Layer-by-Layer Polyelectrolyte/Inhibitor Nanostructures for Metal Corrosion Protection Andreeva, Daria V.; Skorb, Ekaterina V.; Shchukin, Dmitry G. ACS Applied Materials & Interfaces, Vol. 2, Issue 7 https://doi.org/10.1021/am1002712	journal	June 2010
Sum-Frequency Spectroscopy of Surfactant Monolayers at the Oil−Water Interface Knock, Mona Marie; Bell, Graham R.; Hill, Elisabeth K. The Journal of Physical Chemistry B, Vol. 107, Issue 39 https://doi.org/10.1021/jp027047m	journal	October 2003
Surface Structure of Sodium Dodecyl Sulfate Surfactant and Oil at the Oil-in-Water Droplet Liquid/Liquid Interface: A Manifestation of a Nonequilibrium Surface State de Aguiar, Hilton B.; Strader, Matthew L.; de Beer, Alex G. F. The Journal of Physical Chemistry B, Vol. 115, Issue 12 https://doi.org/10.1021/jp200536k	journal	March 2011
Stability of Foam Films of Oppositely Charged Polyelectrolyte/Surfactant Mixtures: Effect of Isoelectric Point Kristen-Hochrein, Nora; Laschewsky, André; Miller, Reinhard The Journal of Physical Chemistry B, Vol. 115, Issue 49 https://doi.org/10.1021/jp206964k	journal	December 2011
Structural Changes in a Polyelectrolyte Multilayer Assembly Investigated by Reflection Absorption Infrared Spectroscopy and Sum Frequency Generation Spectroscopy Kett, Peter J. N.; Casford, Michael T. L.; Yang, Amanda Y. The Journal of Physical Chemistry B, Vol. 113, Issue 6 https://doi.org/10.1021/jp807453w	journal	January 2009
Molecular Ordering of Layer-by-Layer Polyelectrolyte Films Studied by Sum-Frequency Vibrational Spectroscopy Silva, Heurison S.; Miranda, Paulo B. The Journal of Physical Chemistry B, Vol. 113, Issue 30 https://doi.org/10.1021/jp904196h	journal	July 2009
Layer-by-Layer Assemblies of Semiconductor Quantum Dots for Nanostructured Photovoltaic Devices Jin, Ho; Choi, Sukyung; Lee, Hyo Joong The Journal of Physical Chemistry Letters, Vol. 4, Issue 15 https://doi.org/10.1021/jz400910x	journal	July 2013
Quantitative analysis of monolayer composition by sum-frequency vibrational spectroscopy Bain, Colin D.; Davies, Paul B.; Ong, T. Hui. Langmuir, Vol. 7, Issue 8 https://doi.org/10.1021/la00056a003	journal	August 1991
Adsorption of Sodium Dodecyl Sulfate in the Presence of Poly(ethylenimine) and Sodium Chloride Studied Using Sum Frequency Vibrational Spectroscopy Windsor, Rosemary; Neivandt, David J.; Davies, Paul B. Langmuir, Vol. 17, Issue 23 https://doi.org/10.1021/la010505i	journal	October 2001
The Structure of Layer-by-Layer Self-Assembled Glucose Oxidase and Os(Bpy) ₂ ClPyCH ₂ NH−Poly(allylamine) Multilayers: Ellipsometric and Quartz Crystal Microbalance Studies Forzani, Erica S.; Otero, Marcelo; Pérez, Manuel A. Langmuir, Vol. 18, Issue 10 https://doi.org/10.1021/la025507x	journal	May 2002
Binding of Sodium Dodecyl Sulfate with Linear and Branched Polyethyleneimines in Aqueous Solution at Different pH Values Wang, Hao; Wang, Yilin; Yan, Haike Langmuir, Vol. 22, Issue 4 https://doi.org/10.1021/la051988j	journal	February 2006
Effects of Ionic Strength on the Surface Tension and Nonequilibrium Interfacial Characteristics of Poly(sodium styrenesulfonate)/Dodecyltrimethylammonium Bromide Mixtures Ábrahám, Ágnes; Kardos, Attila; Mezei, Amália Langmuir, Vol. 30, Issue 17 https://doi.org/10.1021/la500637v	journal	April 2014
Binding of Sodium Dodecyl Sulfate to Some Polyethyleneimines and Their Ethoxylated Derivatives at Different pH Values. Electromotive Force and Microcalorimetry Studies Li, Y.; Ghoreishi, S. M.; Warr, J. Langmuir, Vol. 16, Issue 7 https://doi.org/10.1021/la9910172	journal	April 2000
Internal structure of layer-by-layer adsorbed polyelectrolyte films: a neutron and x-ray reflectivity study Schmitt, Johannes; Gruenewald, Torsten; Decher, Gero Macromolecules, Vol. 26, Issue 25 https://doi.org/10.1021/ma00077a052	journal	December 1993
Layer-by-Layer Assembly of Polyelectrolytes in Nanofluidic Devices DeRocher, Jonathan P.; Mao, Pan; Han, Jongyoon Macromolecules, Vol. 43, Issue 5 https://doi.org/10.1021/ma902451s	journal	March 2010
Nanoemulsions: formation, properties and applications Gupta, Ankur; Eral, H. Burak; Hatton, T. Alan Soft Matter, Vol. 12, Issue 11 https://doi.org/10.1039/C5SM02958A	journal	January 2016
Influence of the polymer backbone rigidity on polyelectrolyte–surfactant complexes at the air/water interface Ritacco, Hernan; Albouy, Pierre-Antoine; Bhattacharyya, Amitabha Physical Chemistry Chemical Physics, Vol. 2, Issue 22 https://doi.org/10.1039/b004657o	journal	January 2000
Formation and stability of nanoemulsions with mixed ionic–nonionic surfactants Wang, Lijuan; Tabor, Rico; Eastoe, Julian Physical Chemistry Chemical Physics, Vol. 11, Issue 42 https://doi.org/10.1039/b912460h	journal	January 2009
Novel approach to long sustained multilayer nanocapsules: influence of surfactant head groups and polyelectrolyte layer number on the release of hydrophobic compounds Bazylińska, Urszula; Skrzela, Renata; Szczepanowicz, Krzysztof Soft Matter, Vol. 7, Issue 13 https://doi.org/10.1039/c1sm05395g	journal	January 2011
Molecular characterization of water and surfactant AOT at nanoemulsion surfaces Hensel, Jennifer K.; Carpenter, Andrew P.; Ciszewski, Regina K. Proceedings of the National Academy of Sciences, Vol. 114, Issue 51 https://doi.org/10.1073/pnas.1700099114	journal	July 2017
Nonlinear optical scattering: The concept of effective susceptibility Roke, Sylvie; Bonn, Mischa; Petukhov, Andrei V. Physical Review B, Vol. 70, Issue 11 https://doi.org/10.1103/PhysRevB.70.115106	journal	September 2004
Sum frequency generation scattering from the interface of an isotropic particle: Geometrical and chiral effects de Beer, Alex G. F.; Roke, Sylvie Physical Review B, Vol. 75, Issue 24 https://doi.org/10.1103/PhysRevB.75.245438	journal	June 2007
Vibrational Sum Frequency Scattering from a Submicron Suspension Roke, Sylvie; Roeterdink, Wim G.; Wijnhoven, Judith E. G. J. Physical Review Letters, Vol. 91, Issue 25 https://doi.org/10.1103/PhysRevLett.91.258302	journal	December 2003
Dynamic light scattering Goldburg, W. I. American Journal of Physics, Vol. 67, Issue 12 https://doi.org/10.1119/1.19101	journal	December 1999
Natural oil nanoemulsions as cores for layer-by-layer encapsulation Adamczak, M.; Para, G.; Simon, C. Journal of Microencapsulation, Vol. 30, Issue 5 https://doi.org/10.3109/02652048.2012.752536	journal	December 2012
Drug Release Properties of Diflunisal from Layer-By-Layer Self-Assembled κ-Carrageenan/Chitosan Nanocapsules: Effect of Deposited Layers Rochín-Wong, Sarai; Rosas-Durazo, Aarón; Zavala-Rivera, Paul Polymers, Vol. 10, Issue 7 https://doi.org/10.3390/polym10070760	journal	July 2018

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Peeling back the layers: Investigating the effects of polyelectrolyte layering on surface structure and stability of oil-in-water nanoemulsions

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