Temperature-responsive interdrop association of condensed attractive nanoemulsions

Jin Yong Lee; Minchul Sung; Hyemin Seo; Ye Jin Park; Jun Bae Lee; Song Seok Shin; Youngbok Lee; Kyounghee Shin; Jin Woong Kim

Journal of Industrial and Engineering Chemistry, Vol.86, 158-166, June, 2020

DOI10.1016/j.jiec.2020.02.023 Export Citation

Temperature-responsive interdrop association of condensed attractive nanoemulsions

Jin Yong Lee¹, Minchul Sung², Hyemin Seo², Ye Jin Park¹, Jun Bae Lee³, Song Seok Shin⁴, Youngbok Lee^{1, 5}, Kyounghee Shin^{2, †}, and Jin Woong Kim^{1, 2, †}

¹Department of Bionano Technology, Hanyang University, Ansan 15588, Republic of Korea
²School of Chemical Engineering, Sungkyunkwan University, Suwon 16419, Republic of Korea
³Department of Innovation Laboratory, Cosmax R&I Center, Seongnam 13486, Republic of Korea
⁴Department of General Management, SK Bioland Co., Cheongju 28162, Republic of Korea
⁵Department of Chemical and Molecular Engineering, Hanyang University, Ansan 15588, Republic of Korea

E-mail:,

This study introduces a temperature-responsive attractive nanoemulsion (ANE) system, which is characterized by the polymer chain conformation-driven dipolar interaction across different oil droplets in an aqueous medium. To achieve this, highly stable ANEs were produced by co-assembly of amphiphilic triblock copolymers (ATCs), poly(ethylene oxide)-b-poly(ε-caprolactone)-b-poly(ethylene oxide) (PEO-b-PCL-b-PEO), with lecithin at the oil-water interface. The dipolar attraction of the methoxy terminated-PEO (mPEO) of ATCs on one drop surface with the lecithin head located on the other drop surface led to the drop-to-drop association. We showed that the efficiency of this interdrop association was dominantly influenced by the chain conformation of mPEO blocks. From dense suspension rheology studies, it was demonstrated that the ANEs formed a gel-like phase below the lower critical solution temperature (LCST) of the mPEO, but transformed to a liquid-like phase above the LCST, which occurred reversibly, thus enabling the development of temperature-responsive emulsion fluids.

Keywords:Nanoemulsions;Dipolar interaction;Interdrop association;Suspension rheology

[References]

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[2] Ren GH, Sun ZC, Wang ZZ, Zheng XY, Xu ZH, Sun DJ, J. Colloid Interface Sci., 540, 177 (2019)

[3] Helgeson ME, Curr. Opin. Colloid Interface Sci., 25, 39 (2016)

[4] Fryd MM, Mason TG, Annu. Rev. Phys. Chem., 63, 493 (2012)

[5] Kim HS, Mason TG, Adv. Colloid Interface Sci., 247, 397 (2017)

[6] Wilking JN, Graves SM, Chang CB, Meleson K, Lin MY, Mason TG, Phys. Rev. Lett., 96, 015501 (2006)

[7] Wilking JN, Chang CB, Fryd MM, Porcar L, Mason TG, Langmuir, 27(9), 5204 (2011)

[8] Erramreddy VV, Tu S, Ghosh S, RSC Adv., 7, 47818 (2017)

[9] Erramreddy VV, Ghosh S, Langmuir, 30(37), 11062 (2014)

[10] Erramreddy VV, Ghosh S, Colloids Surf. A: Physicochem. Eng. Asp., 484, 144 (2015)

[11] Scheffold F, Cardinaux F, Mason TG, J. Phys. Condens. Matter, 25, 502101 (2013)

[12] Datta SS, Gerrard DD, Rhodes TS, Mason TG, Weitz DA, Phys. Rev. E, 84, 041404 (2011)

[13] Mason TG, Graves SM, Wilking JN, Lin MY, J. Phys. Chem. B, 110(44), 22097 (2006)

[14] Scheffold F, Mason TG, J. Phys. Condens. Matter, 21, 332102 (2009)

[15] Scheffold F, Wilking JN, Haberko J, Cardinaux F, Mason TG, Soft Matter, 10, 5040 (2014)

[16] Lozsan A, Colloid Polym. Sci., 290, 1561 (2012)

[17] Montesi A, Pena AA, Pasquali M, Phys. Rev. Lett., 92, 058303 (2004)

[18] Kim J, Gao Y, Hebebrand C, Peirtsegaele E, Helgeson ME, Soft Matter, 9, 6897 (2013)

[19] Philip J, Jaykumar T, Kalyanasundaram P, Raj B, Mondain-Monval O, Phys. Rev. E Stat. Nonlin. Soft Matter Phys., 66, 011406 (2002)

[20] Philip J, Prakash GG, Jaykumar T, Kalyanasundaram P, Mondain-Monval O, Raj B, Langmuir, 18(12), 4625 (2002)

[21] Helgeson ME, Gao Y, Moran SE, Lee J, Godfrin M, Tripathi A, Bose A, Doyle PS, Soft Matter, 10, 3122 (2014)

[22] Yukuyama MN, Ghisleni DD, Pinto TJ, Bou-Chacra NA, Int. J. Cosmet. Sci., 38, 13 (2016)

[23] Huang Q, Yu H, Ru Q, J. Food Sci., 75, R50 (2010)

[24] Wulff-Perez M, Torcello-Gomez A, Galvez-Ruiz MJ, Martin-Rodriguez A, Food Hydrocolloids, 23, 1096 (2009)

[25] Padmavathy N, Das Ghosh L, Meka SRK, Chatterjee K, ACS Appl. Mater. Interfaces, 10, 21816 (2018)

[26] Gotchev G, Kolarov T, Khristov K, Exerowa D, Colloids Surf. A: Physicochem. Eng. Asp., 354, 56 (2010)

[27] Tadros T, Adv. Colloid Interface Sci., 147-148, 281 (2009)

[28] Shin K, Gong G, Cuadrado J, Jeon S, Seo M, Choi HS, Hwang JS, Lee Y, Fernandez-Nieves A, Kim JW, Chem. Eur. J., 23, 4292 (2017)

[29] Odenwald M, Eicke HF, Meier W, Macromolecules, 28(14), 5069 (1995)

[30] Han S, An H, Tao H, Li L, Qi Y, Ma Y, Li X, Wang R, Zhang J, Chem. Commun., 54, 3174 (2018)

[31] Duan G, Kumar A, Li SG, Cheng CM, Lee D, J. Colloid Interface Sci., 537, 579 (2019)

[32] Ramirez P, Stocco A, Munoz J, Miller R, J. Colloid Interface Sci., 378, 135 (2012)

[33] Wulff-Perez M, Martin-Rodriguez A, Galvez-Ruiz MJ, de Vicente J, Colloid Polym. Sci., 291, 709 (2012)

[34] Cheng LC, Godfrin PD, Swan JW, Doyle PS, Soft Matter, 14, 5604 (2018)

[35] Nam YS, Kim JW, Shim J, Han SH, Kim HK, Langmuir, 26(16), 13038 (2010)

[36] Zaibudeen AW, Philip J, Colloids Surf. A: Physicochem. Eng. Asp., 518, 98 (2017)

[37] Feng H, Lu X, Wang W, Kang NG, Mays JW, Polymers, 9, 494 (2017)

[38] Bodratti AM, Sarkar B, Alexandridis P, Adv. Colloid Interface Sci., 244, 132 (2017)

[39] Monteux C, Comptes Rendus Physique, 15, 775 (2014)

[40] Charoongchit P, Suksiriworapong J, Mao S, Sapin-Minet A, Maincent P, Junyaprasert VB, Acta Biomater., 61, 180 (2017)

[41] Torcello-Gomez A, Wulff-Perez M, Galvez-Ruiz MJ, Martin-Rodriguez A, Cabrerizo-Vilchez M, Maldonado-Valderrama J, Adv. Colloid Interface Sci., 206, 414 (2014)

[42] Grinberg VY, Burova TV, Grinberg NV, Dubovik AS, Papkov VS, Khokhlov AR, Polymer, 73, 86 (2015)