Skip to content
Licensed Unlicensed Requires Authentication Published by De Gruyter September 25, 2021

Synthesis and Aggregation of Novel Sugar-based Gemini Surfactants in Aqueous Solution

Synthese und Aggregation von neuartigen zuckerbasierten Gemini-Tensiden in wässriger Lösung
Ruijuan Wang

Ruijuan Wang is a lecturer at Zhengzhou University of Light Industry. She received her B. Sc (2008) in applied chemistry from Henan University of Technology and M. Sc (2011) in physical chemistry from Yangzhou University in China, and her Ph. D. (2014) in physical chemistry from the Institute of Chemistry, Chinese Academy of Sciences. Her research focuses on developing novel gemini surfactants, studying phase behaviors of surfactants, mixed surfactants and surfactant-polymer mixtures.

EMAIL logo
, Yu Lei

Yu Lei is an undergraduate at Zhengzhou University of Light Industry. He was mainly responsible for surface tension and dynamic light scattering (DLS) measurements.

, Zikun Mei

Zikun Mei is an undergraduate at Zhengzhou University of Light Industry. He was mainly responsible for work on synthesis.

, Dong Wang

Dong Wang is a lecturer at China University of Petroleum (East China). He received his B. Sc (2008) from Shandong University and Ph.D. (2013) from Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences. He was mainly responsible for Cryo-TEM measurement. His research focuses on controllable self-assembly and application of amphiphilic peptides and application of bio-surfactants in oilfield chemistry.

and Zhigang Yin

Zhigang Yin is a professor at Zhengzhou University of Light Industry. He received his B. Sc (1985) in organic chemistry from Zhengzhou University and M. Sc (1989) in fine chemical engineering from Dalian University of Technology, and his Ph. D. (2014) in fine chemical engineering from Dalian University of Technology. His research focuses on synthesis and functionalization of organic intermediates.

EMAIL logo

Abstract

Novel sugar-based gemini surfactants with a 1,3-propan-2-ol spacer (1, 3-(N- alkyl-2-D-glucosaminyl acetyl) propan-2-ol, Glu(n)-3(OH)-Glu(n), n = 12, 14) were synthesized with D-(+)-glucono-1,5-lactone as starting material in two steps, whose structures were confirmed using proton nuclear magnetic resonance spectroscopy (1H NMR) and carbon nuclear magnetic resonance carbon spectroscopy (13C NMR). The micellization of Glu(n)-3(OH)-Glu(n) (n = 12, 14) in aqueous solution at 25.0°C was investigated by using surface tension measurement. The results show that the critical micelle concentration (CMC) of Glu(12)-3(OH)-Glu(12) is around 10–5 mol × L–1, and is one order of magnitude smaller than that of Glu(14)-3(OH)-Glu(14), indicating that the surface activity of Glu(12)-3(OH)-Glu(12) is superior to that of Glu(14)-3(OH)-Glu(14). Moreover, the aggregation behavior of Glu(12)-3(OH)-Glu(12) in aqueous solution at different pH values was investigated by surface tension, dynamic light scattering (DLS), and cryogenic transmission electron microscopic (Cryo-TEM) measurements. The results indicate that the CMC slightly increases with the decrease of the solution pH. The microstructure of Glu(12)-3(OH)-Glu(12) aggregates transitions from micelle to vesicle with the solution pH from acidic to neutral and alkaline. The microstructural transformation of Glu(12)-3(OH)-Glu(12) with the solution pH is mainly determined by the protonation of the two tertiary amine nitrogen atoms in its hydrophilic headgroups.

Zusammenfassung

Es wurden die folgenden neuartigen Geminitenside auf Zuckerbasis mit einem 1,3-Propan-2-ol-Spacer mit D-(+)-Glucono-1,5-Lacton als Ausgangsmaterial in zwei Schritten synthetisiert: (1,3-(N-alkyl-2-D-glucosaminylacetyl)-propan-2-ol, Glu(n)-3(OH)-Glu(n), n = 12, 14). Ihre Strukturen wurden mittels Protonen-Kernspinresonanzspektroskopie (1H-NMR) und Kohlenstoff-13-Kernspinresonanz-Kohlenstoffspektroskropie (13C-NMR) bestätigt. Die Mizellenbildung von Glu(n)-3(OH)-Glu(n) (n = 12, 14) in wässriger Lösung wurde bei 25 °C mit Hilfe der Oberflächenspannungsmessung untersucht. Die Ergebnisse zeigen, dass die kritische Mizellenkonzentration (CMC) von Glu(12)-3(OH)-Glu(12) etwa 10–5 mol L–1 beträgt und eine Größenordnung kleiner ist als die von Glu(14)-3(OH)-Glu(14), was darauf hinweist, dass die Oberflächenaktivität von Glu(12)-3(OH)-Glu(12) der von Glu(14)-3(OH)-Glu(14) überlegen ist. Darüber hinaus wurde das Aggregationsverhalten von Glu(12)-3(OH)-Glu(12) in wässriger Lösung bei verschiedenen pH-Werten durch Messungen der Oberflächenspannung, der dynamischen Lichtstreuung (DLS) und der kryogenen Transmissionselektronenmikroskopie (Cryo-TEM) bestimmt. Die Ergebnisse zeigen, dass die CMC mit der Abnahme des pH-Wertes der Lösung leicht ansteigt. Die Mikrostruktur der Glu(12)-3(OH)-Glu(12)-Aggregate geht mit dem Lösungs-pH von sauer zu neutral und alkalisch von Mizelle zu Vesikel über. Die mikrostrukturelle Transformation von Glu(12)-3(OH)-Glu(12) mit dem Lösungs-pH wird hauptsächlich durch die Protonierung der beiden tertiären Amin-Stickstoffatome in seinen hydrophilen Kopfgruppen bestimmt.


Dr. Ruijuan Wang School of Material and Chemical Engineering
Dr. Zhigang Yin Henan Engineering Research Center of Catalysis and Seperation of Cyclohexanol Zhengzhou University of Light Industry Zhengzhou, Henan 450002 P.R.China

About the authors

Dr. Ruijuan Wang

Ruijuan Wang is a lecturer at Zhengzhou University of Light Industry. She received her B. Sc (2008) in applied chemistry from Henan University of Technology and M. Sc (2011) in physical chemistry from Yangzhou University in China, and her Ph. D. (2014) in physical chemistry from the Institute of Chemistry, Chinese Academy of Sciences. Her research focuses on developing novel gemini surfactants, studying phase behaviors of surfactants, mixed surfactants and surfactant-polymer mixtures.

Yu Lei

Yu Lei is an undergraduate at Zhengzhou University of Light Industry. He was mainly responsible for surface tension and dynamic light scattering (DLS) measurements.

Zikun Mei

Zikun Mei is an undergraduate at Zhengzhou University of Light Industry. He was mainly responsible for work on synthesis.

Dong Wang

Dong Wang is a lecturer at China University of Petroleum (East China). He received his B. Sc (2008) from Shandong University and Ph.D. (2013) from Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences. He was mainly responsible for Cryo-TEM measurement. His research focuses on controllable self-assembly and application of amphiphilic peptides and application of bio-surfactants in oilfield chemistry.

Dr. Zhigang Yin

Zhigang Yin is a professor at Zhengzhou University of Light Industry. He received his B. Sc (1985) in organic chemistry from Zhengzhou University and M. Sc (1989) in fine chemical engineering from Dalian University of Technology, and his Ph. D. (2014) in fine chemical engineering from Dalian University of Technology. His research focuses on synthesis and functionalization of organic intermediates.

Acknowledgements

This work was supported by the Foundation of Henan Educational Committee (19B150019), Foundation of Henan Department of Science and Technology (CLY20170165) and the Doctoral Research Fund of Zhengzhou University of Light Industry (2014BSJJ063).

References

1 Menger, F. M. and Littau, C. A.: Gemini-surfactants: synthesis and properties, Journal of the American Chemical Society 113 (1991) 1451–1452. DOI:10.1021/ja00004a07710.1021/ja00004a077Search in Google Scholar

2 Wang, R., Wang, D., Yin, Z., Yang, X. and Liu, Q.: Micellization of carboxylic acid gemini surfactant and its interaction with amino acid surfactant in aqueous solution, Journal of Surfactants & Detergents 22 (2019) 411–419. DOI:10.1002/jsde.1223910.1002/jsde.12239Search in Google Scholar

3 Wang, R., Yan, H., Hu, W., Li, Y. and Mei, Z.: Micellization of anionic sulfonate gemini surfactants and their interactions with anionic polyacrylamide, Journal of Surfactants and Detergents 21 (2018) 81–90. DOI:10.1002/jsde.1200310.1002/jsde.12003Search in Google Scholar

4 Wang, R., Yan, H., Ma, W. and Li, Y.: Complex formation between cationic gemini surfactant and sodium carboxymethylcellulose in the absence and presence of organic salt, Colloids and Surfaces A: Physicochemical and Engineering Aspects 509 (2016) 293–300. DOI:10.1016/j.colsurfa.2016.09.02310.1016/j.colsurfa.2016.09.023Search in Google Scholar

5 Fan, Y. X., Han, Y. C. and Wang, Y. L.: Effects of molecular structures on aggregation behavior of gemini surfactants in aqueous solutions, Acta Physico-Chimica Sinica 32 (2016) 214–226. DOI:10.3866/PKU.WHXB20151102210.3866/PKU.WHXB201511022Search in Google Scholar

6 Pérez, L., Pinazo, A., Pons, R. and Infante, M.: Gemini surfactants from natural amino acids, Advances in Colloid & Interface Science 205 (2014) 134–155. PMid:24238395; DOI:10.1016/j.cis.2013.10.02010.1016/j.cis.2013.10.020Search in Google Scholar PubMed

7 Wang, R., WanYan, R., Yang, S., Wang, D. and Yin, Z.: Synthesis and aggregation of novel sugar-based gemini surfactant with a N, N’-acetylethylenediamine spacer in aqueous solution, Journal of Surfactants and Detergents 23 (2020) 697–703. DOI:10.1002/jsde.1242410.1002/jsde.12424Search in Google Scholar

8 Singh, N. and Sharma, L.: Synthesis, characteristics and application of novel non-ionic gemini surfactants as reverse micellar systems for encapsulation of some aromatic a-amino acids in n-hexane, Tenside Surfactants Detergents 57 (2020) 247–251. DOI:10.3139/113.11068210.3139/113.110682Search in Google Scholar

9 Sharma, L., Saroj and Singh, N.: Micellar encapsulation of some polycyclic aromatic hydrocarbons by glucose derived non-?ionic gemini surfactants in aqueous medium. Tenside Surfactants Detergents 51 (2014) 441–444. DOI:10.3139/113.11032710.3139/113.110327Search in Google Scholar

10 Shi, J., Li, Q. D. and Xia, X. C.: Synthesis and properties of sugar-based gemini surfactants. Tenside Surfactants Detergents 43 (2006) 204–209. DOI:10.3139/113.10030910.3139/113.100309Search in Google Scholar

11 Castro, M. J. L., Kovensky, J. and Cirelli, A. F.: Gemini surfactants from alkyl glucosides, Tetrahedron Letters 38 (1997) 3995–3998. DOI:10.1016/S0040-4039(97)00817-410.1016/S0040-4039(97)00817-4Search in Google Scholar

12 Castro, M. J. L., Kovensky, J. and Cirelli, A. F.: New dimeric surfactants from alkyl glucosides, Tetrahedron 55 (1999) 12711–12722. DOI: 10.1016/S0040-4020(99)00786-310.1016/S0040-4020(99)00786-3Search in Google Scholar

13 Mariano, C., José, K. and Alicia, C.: Structure-properties relationship of dimeric surfactants from butyl glucosides, Molecules 5 (2000) 608–609. DOI:10.3390/5030060810.3390/50300608Search in Google Scholar

14 Castro, M. J. L., Cirelli, A. F. and Kovensky, J.: Synthesis and interfacial properties of sugar-based surfactants composed of homo-and heterodimers, Journal of Surfactants & Detergents 9 (2006) 279–286. DOI: 10.1007/s11743-006-5008-x10.1007/s11743-006-5008-xSearch in Google Scholar

15 Gan, C., Hong, L. and Kunliang, C.: Novel sugar-based gemini surfactants and their surface properties, Journal of Surfactants & Detergents 21 (2018) 859–866. DOI:10.1002/jsde.1218710.1002/jsde.12187Search in Google Scholar

16 Gan, C., Cai, K., Qu, X., Li, H., Wei, L. and Cheng, R.: Glucose-based novel gemini surfactants: Surface activities, aggregation properties and a preliminary study as nanocarrier for resveratrol, Journal of Molecular Liquids 283 (2019) 781–787. DOI:10.1016/j.molliq.2019.03.15310.1016/j.molliq.2019.03.153Search in Google Scholar

17 Sakai, K., Umezawa, S., Tamura, M., Takamatsu, Y., Tsuchiya, K., Torigoe, K., Ohkubo, T., Yoshimura, T., Esumi, K. and Sakai, H.: Adsorption and micellization behavior of novel gluconamide-type gemini surfactants, Journal of Colloid and Interface Science 318 (2008) 440–448. PMid:18031755; DOI:10.1016/j.jcis.2007.10.03910.1016/j.jcis.2007.10.039Search in Google Scholar PubMed

18 Tomokazu, Y., Shin, U., Akihiko, F., Kanjiro, T., Kenichi, S., Hideki, S., Masahiko, A. and Kunio, E.: Equilibrium surface tension, dynamic surface tension, and micellization properties of lactobionamide-type sugar-based Gemini surfactants, Journal of Oleo Science 62 (2013) 353–362. PMid:23728326; DOI:10.5650/jos.62.35310.5650/jos.62.353Search in Google Scholar PubMed

19 Warwel, S., Brüse, F. and Schier, H.: Glucamine-based gemini surfactants I: Gemini surfactants from long-chainN-alkyl glucamines and a,x-diepoxides, Journal of Surfactants & Detergents 7 (2004) 181–186. DOI: 10.1007/s11743-004-0302-110.1007/s11743-004-0302-1Search in Google Scholar

20 Warwel, S. and Brüse, F.: Glucamine-based gemini surfactants II: Gemini surfactants from long-chain N-alkyl glucamines and epoxy resins, Journal of Surfactants & Detergents 7 (2004) 187–193. DOI:10.1007/s11743-004-0303-010.1007/s11743-004-0303-0Search in Google Scholar

21 Johnsson, M., Wagenaar, A., Stuart, M. C. A. and Engberts, J. B. F. N.: Sugar-based gemini surfactants with pH-dependent aggregation behavior: vesicle-to-micelle transition, critical micelle concentration, and vesicle surface charge reversal, Langmuir 19 (2003) 4609–4618. DOI:10.1021/la034327010.1021/la0343270Search in Google Scholar

22 Johnsson, M., Wagenaar, A. and Engberts, J. B. F. N.: Sugar-based gemini surfactant with a vesicle-to-micelle transition at acidic pH and a reversible vesicle flocculation near neutral pH, Journal of the American Chemical Society 125 (2003) 757–760. PMid:12526675; DOI:10.1021/ja028195t10.1021/ja028195tSearch in Google Scholar PubMed

23 Johnsson, M. and Engberts, J. B. F. N.: Novel sugar-based gemini surfactants: aggregation properties in aqueous solution, Journal of Physical Organic Chemistry 17 (2004) 934–944. DOI:10.1002/poc.81710.1002/poc.817Search in Google Scholar

24 Laska, U., Wilk, A., Maliszewska, I. and Syper, L.: Novel glucose-derived gemini surfactants with a 1,1-ethylenebisurea spacer: Preparation, thermotropic behavior, and biological properties, Journal of Surfactants & Detergents 9 (2006) 115–124. DOI:10.1007/s11743-006-0380-010.1007/s11743-006-0380-0Search in Google Scholar

25 Wagenaar, A. and Engberts, J. B. F. N.: Synthesis of nonionic reduced-sugar based bola amphiphiles and gemini surfactants with an a, x-diamino-(oxa)alkyl spacer, Tetrahedron 63 (2007) 10622–10629. DOI:10.1016/j.tet.2007.08.02310.1016/j.tet.2007.08.023Search in Google Scholar

26 Menger, F. M. and Mbadugha, B. N. A.: Gemini surfactants with a disaccharide spacer, Journal of the American Chemical Society 123 (2001) 875–885. PMid:11456621; DOI:10.1021/ja003317810.1021/ja0033178Search in Google Scholar PubMed

27 Fielden, M. L., Perrin, C., Kremer, A., Bergsma, M., Stuart, M. C., Camilleri, P. and Engberts, J. B. F. N.: Sugar-based tertiary amino gemini surfactants with a vesicle-to-micelle transition in the endosomal pH range mediate efficient transfection in vitro, European Journal of Biochemistry 268 (2001) 1269–1279. PMid:11231278; DOI:10.1046/j.1432-1327.2001.01995.x10.1046/j.1432-1327.2001.01995.xSearch in Google Scholar PubMed

28 Wang, R., Ma, L., Yang, X., Yang, Z. and Mei, Z.: Nonionic glycosyl Gemini surfactant containing hydroxyl linking group and preparation method thereof. (2018) CN108940117A. Zhengzhou: Zhengzhou University of Light Industry.Search in Google Scholar

29 Burczyk, B., Wilk, K. A., Sokołowski, A. and Syper, L.: Synthesis and surface properties of N-alkyl-N-methylgluconamides and N-alkyl-N-methyllactobionamides, Journal of Colloid and Interface Science 240 (2001) 552–558. PMid:11482965; DOI:10.1006/jcis.2001.770410.1006/jcis.2001.7704Search in Google Scholar PubMed

Received: 2020-06-12
Accepted: 2021-01-21
Published Online: 2021-09-25
Published in Print: 2021-09-30

© 2021 Walter de Gruyter GmbH, Berlin/Boston, Germany

Downloaded on 8.12.2022 from https://www.degruyter.com/document/doi/10.1515/tsd-2020-2292/html
Scroll Up Arrow