pH-Responsive Pickering Emulsions Stabilized by Silica Nanoparticles in Combination with N-Dodecyl-β-aminopropionate†

doi:10.7503/cjcu20160477

Abstract

Abstract:

pH-responsive Pickering oil-in-water emulsion with n-decane as oil phase was prepared using negatively charged silica nanoparticles in combination with trace amount of amphoteric surfactant, N-dodecyl-β-aminopropionate(DAP), as stabilizer. The emulsion is stable at pH≤4.0 but unstable at pH≥6.0 at am-bient temperature, and therefore can be cycled between stable and unstable for many times. In acidic aqueous media the amphoteric surfactant molecules of amino acid type are turned to cationic form and can then adsorb at negatively charged silica nanoparticle surface with head-on configuration via electrostatic interaction, ren-dering particles surface activity by in situ hydrophobization. However in neutral and alkali aqueous media the amphoteric surfactant molecules are turned back to amphoteric or anionic forms which mostly desorb from particles surface, triggering de-hydrophobization of the particles and coalescence of the oil droplets in emulsion. The relative mechanisms are revealed by measurements of adsorption, Zeta potential, as well as contact angles.

Key words: pH-Responsive surface active particles, pH-Responsive Pickering emulsions, In situ hydrophobization, Adsorption, Electrostatic interaction

CLC Number:

O647

TrendMD:

LIU Kaihong, LIN Qi, CUI Zhenggang, PEI Xiaomei, JIANG Jianzhong. pH-Responsive Pickering Emulsions Stabilized by Silica Nanoparticles in Combination with N-Dodecyl-β-aminopropionate^†[J]. Chem. J. Chinese Universities, 2017, 38(1): 85.

Figures/Tables 9

Fig.1 Photographs of n-decane-in-water(volume ratio 1:1) emulsions stabilized by 0.5%(mass fraction) silica nanoparticles solely(A), DPA solely at different concentrations(B) and their mixtures(C, D)DPA concentration(from left to right)/(mmol·L-1): (B) 0.03, 0.06, 0.1, 0.3, 0.6, 1, 3; (C), (D) 0.003, 0.006, 0.01, 0.03, 0.06, 0.1, 0.3, 0.6, 1. Taken 24 h after preparation; (D) 1 week after preparation.

Fig.2 Optical micrographs of n-decane-in-water emulsions stabilized by a mixture of 0.5%(mass fraction) silica nanoparticles and DAP at different concentrations(A—C) and by DAP solely(D) taken 24 h after preparationSurfactant concentration/(mmol·L-1): (A) 0.006; (B) 0.3; (C) 0.6; (D) 1.

Fig.3 Photographs of n-decane-in-water emulsions stabilized by a mixture of 0.5%(mass fraction) silica nanoparticles and 0.06 mmol/L DAP with different aqueous pH value, taken 24 h(A), 1 week(B) and 2 months(C) after preparationAqueous pH value(from left to right): 6.77, 6.03, 5.65, 5.32, 5.14, 4.99, 4.58, 4.18, 3.63, 3.30.

Fig.4 Optical micrographs of n-decane-in-water emulsions stabilized by a mixture of 0.5%(mass fraction) silica nanoparticles and 0.06 mmol/L DAP with different pH values taken 24 h(A—C) and 2 months(D) after preparationpH value: (A) 4.58; (B) 3.63; (C) 3.30; (D) 3.63.

Fig.5 Photographs and micrographs(at low pH) of the n-decane-in-water emulsions stabilized by a mixture of 0.5%(mass fraction) silica nanoparticles in combination with 0.06 mmol/L DAP following pH alternation cycling, taken 24 h[cycle 1(A), cycle 2(B), cycle 4(C), cycle 6(D)] and 2 months(cycle 6 only, E) after homogenization(for stable emulsions) and 20 min after dropping NaOH solution with agitation(for unstable emulsions)

Fig.6 Surface tension of aqueous solutions of DAP without(a) and with 0.5% silica nanoparticles(b) as a function of initial concentration(25 ℃)

Fig.7 Adsorption isotherms of DAP at silica nanoparticle/water interface from aqueous media with different pH values at 25 ℃

Fig.8 Zeta potential of silica nanoparticles(0.1%) dispersed in DAP aqueous solution with different pH values as a function of initial DAP concentration(25 ℃)

Fig.9 Contact angle of DAP aqueous solution(0.06 mmol/L) on negatively charged quartz slide as a function of pH measured by captured oil(n-decane) drop method(25 ℃)

References 55

[1]	Aveyard R., Binks B. P., Clint J. H., Adv. Colloid Interface Sci., 2003, 100, 503—546
[2]	Jiang J. Z., Zhu Y., Cui Z. G., Binks B. P., Angew. Chem. Int. Ed., 2013, 52(47), 12373—12376
[3]	Li T., Zhang L., Chen Y., Guo Y. J., Du X. Y., Chem. J. Chinese Universities,2015, 36(4), 772—780
	(李涛, 张龙, 陈颖, 郭亚军, 杜雪岩. 高等学校化学学报, 2015, 36(4), 772—780)
[4]	Gao Y. J., Zhang L., Hou J. J., Ma Y. B., Qiu H., Zhang W. J., Du X. Y., Chem. J. Chinese Universities,2016, 37(6), 1202—1207
	(郭亚军, 张龙, 后洁琼, 马泳波, 秋虎, 张文娟, 杜雪岩. 高等学校化学学报, 2016, 37(6), 1202—1207)
[5]	Tang J. T., Quinlan P. J., Tam K. C., Soft Matter,2015, 11(18), 3512—3529
[6]	Binks B. P., Murakami R., Armes S. P., Fujii S., Angew. Chem. Int. Ed., 2005, 44(30), 4795—4798
[7]	Zoppe J. O., Venditti R. A., Rojas O. J., J. Colloid Interface Sci., 2012, 369, 202—209
[8]	Saigal T., Dong H. C., Matyjaszewski K., Tilton R. D., Langmuir,2010, 26(19), 15200—15209
[9]	Tan T. T. Y., Ahsan A., Reithofer M. R., Tay S. W., Tan S. Y., Hor T. S. A., Chin J. M., Chew B. K. J., Wang X. B., Langmuir,2014, 30(12), 3448—3454
[10]	Anwar N., Williams T., Grimme B., Kuehne A. J. C., ACS Macro Lett., 2013, 2(9), 766—769
[11]	Liu P. W., Lu W. Q., Wang W. J., Li B. G., Zhu S. P., Langmuir,2014, 30(34), 10248—10255
[12]	Liang C., Liu Q. X., Xu Z. H., ACS Appl. Mater. Interfaces,2014, 6(9), 6898—6904
[13]	Zhang Q., Yu G. Q., Wang W. J., Yuan H. M., Li B. G., Zhu S. P., Langmuir,2012, 28(14), 5940—5946
[14]	Su X., Jessop P. G., Cunningham M. F., Macromol., 2012, 45(2), 666—670
[15]	Pinaud J., Kowal E., Cunningham M. F., Jessop P. G., ACS Macro Lett., 2012, 1(9), 1103—1107
[16]	Zhang Q., Wang W. J., Lu Y. Y., Li B. G., Zhu S. P., Macromol., 2011, 44(16), 6539—6545
[17]	Lin S. J., Theato P., Macromol. Rapid Commun., 2013, 34(14), 1118—1133
[18]	Zhang Q., Yu G. Q., Wang W. J., Yuan H. M., Li B. G., Zhu S. P., Macromol., 2013, 46(4), 1261—1267
[19]	Quesada M., Muniesa C., Botella P., Quesada M., Muniesa C., Botella P., Chem. Mater., 2013, 25(13), 2597—2602
[20]	Lam S., Blanco E., Smoukov S. K., Velikov K. P., Velev O. D., J. Am. Chem. Soc., 2011, 133(35), 13856—13859
[21]	Blanco E., Lam S., Smoukov S. K., Velikov K. P., Khan S. A., Velev O. D., Langmuir,2013, 29(32), 10019—10027
[22]	Morse A. J., Armes S. P., Thompson K. L., Dupin D., Fielding L. A., Mills P., Swart R., Langmuir,2013, 29(18), 5466—5475
[23]	Liu H., Wang C. Y., Zou S. W., Wei Z. J., Tong Z., Langmuir,2012, 28(30), 11017—11024
[24]	Fujii S., Suzaki M., Armes S. P., Dupin D., Hamasaki S., Aono K., Nakamura Y., Langmuir,2011, 27(13), 8067—8074
[25]	Binks B. P., Murakami R., Armes S. P., Fujii S., Schmid A., Langmuir,2007, 23(17), 8691—8694
[26]	Yi C. L., Yang Y. Q., Zhu Y., Liu N., Liu X. Y., Luo J., Jiang M., Langmuir,2012, 28(25), 9211—9222
[27]	Fujii S., Okada M., Furuzone T., J. Colloid Interface Sci., 2007, 315(1), 287—292
[28]	Yu D., Lin Z., Li Y., Colloid Surface A,2013, 422, 100—109
[29]	Yang H., Zhou T., Zhang W., Angew Chem. Int. Ed., 2013, 52(29), 7455—7459
[30]	Motornov M., Sheparovych R., Lupitskyy R., MacWillianms E., Hoy O., Luzinov I., Minko S., Adv. Func. Mater., 2007, 17(14), 2307—2314
[31]	Yang F., Niu Q., Lan Q., Sun D., J. Colloid Interface Sci., 2007, 306(2), 285—295
[32]	Amalvy J. I., Unali G. F., Li Y., Granger-Bevan S., Armes S. P., Binks B. P., Rodrigues J. A., Whiteby C. P., Langmuir,2004, 20(11), 4345—4354
[33]	Morse A. J., Madsen J., Growney D. J., Armes S. P., Mills P., Swart R., Langmuir,2014, 30(42), 12509—12519
[34]	Wang Z. P., Floris P. J. T. R., van Hest J. C. M., Chem. Commun., 2014, 50(93), 14550—14553
[35]	Nguyen B. T., Wang W. K., Saunders B. R., Benyahia L., Nicolai T., Langmuir,2015, 31(12), 3605—3611
[36]	Lu J., Zhou W., Chen J., Jin Y. L., Walters K. B., Ding S. J., RSC Adv., 2015, 5(13), 9416—9424
[37]	Richtering W., Langmuir, 2012, 28(50), 17218—17229
[38]	Yamagami T., Kitayama Y., Okubo M., Langmuir,2014, 30(26), 7823—7832
[39]	Tang J., Lee M. F. X., Zhang W., Zhao B. X., Berry R. M., Tam K. C., Biomacromolecules,2014, 15(8), 3052—3062
[40]	Fujii S., Akiyama K., Nakayama S., Hamasaki S., Yusa S., Nakamura Y., Soft Matter,2015, 11(3), 572—579
[41]	Rahman M. M., Chehimi M. M., Fessi H., Elaissari A., J. Colloid Interface Sci., 2011, 360(2), 556—564
[42]	Brugger B., Richtering W., Adv. Mater., 2007, 19(19), 2973—2978
[43]	Fameau A. L., Lam S., Velev O. D., Chem. Sci., 2013, 4(10), 3874—3881
[44]	Zhou P., Liu B., Yang F. X., Wang Q., Qu X. Z., Yang Z. Z., Chem. J. Chinese Universities,2015, 36(7), 1431—1436
	(周鹏, 刘宝, 杨福鑫, 王倩, 屈小中, 杨振忠. 高等学校化学学报, 2015, 36(7), 1431—1436)
[45]	Yan H. Q., Chen X. Q., Li J. C., Feng Y. H., Wu J. B., Ling Q., Shi Z. F., Wang X. H., Chem. J. Chinese Universities,2016, 37(5), 1018—1024
	(颜慧琼, 陈秀琼, 李嘉诚, 冯玉红, 伍剑博, 林强, 史载峰, 王向辉. 高等学校化学学报, 2016, 37(5), 1018—1024)
[46]	Cui Z. G., Yang L. L., Cui Y. Z., Binks B. P., Langmuir,2010, 26(7), 4717—4724
[47]	Binks B. P., Rodrigues J. A., Angew. Chem. Int. Ed., 2007, 46(28), 5389—5392
[48]	Cui Z. G., Cui C. F., Zhu Y., Binks B. P., Langmuir,2012, 28(1), 314—320
[49]	Chen Z., Cui C. F., Cui Z. G., Chem. J. Chinese Universities,2010, 31(11), 2246—2253
	(陈钊, 崔晨芳, 崔正刚. 高等学校化学学报, 2010, 31(11), 2246—2253)
[50]	Zhu Y., Jiang J. Z., Cui Z. G., Binks B. P., Soft Matter,2014, 10(48), 9739—9745
[51]	Zhu Y., Jiang J. Z., Liu K. H., Cui Z. G., Binks B. P., Langmuir,2015, 31(11), 3301—3307
[52]	Zhu Y., Pei X. M., Jiang J. Z., Cui Z. G., Binks B. P., Langmuir,2015, 31(47), 12937—12943
[53]	Bettayeb B., Descoteaux C., Benoit F., Chapados C., Bérubé G., J. Surfact. Deterg., 2009, 12(3), 237—247
[54]	Xu H.J., Liu X. M., Cao H. X., Ma D. G., 1999, (Suppl.), 47—49
	(许虎君, 刘学民, 曹红霞, 马德广. 日用化学品科学, 1999, (增刊), 47—49
[55]	Worthen A. J., Foster L. M., Dong J., Bollinger J. A., Peterman A. H., Pastora L. E., Bryant S. L.,Truskett T. M., Bielawski C. W., Johnston K. P., Langmuir,2014, 30(4), 984—994