Change language
English Deutsch
Change currency
€ EUR £ GBP $ USD
Licensed Unlicensed Requires Authentication Published online by De Gruyter February 21, 2024

Formulating additives in thermoresponsive surfactant-based nematic liquid crystals

  • Patrick Denk

    Patrick Denk MSc, studied chemistry at the University of Regensburg (2015–2020) and received his master’s degree in 2020. Since November 2020 he has been working on his doctorate in Physical Chemistry at the University of Regensburg, Germany.

         , Lauren Matthews

    Lauren Matthews MChem PhD studied Chemistry with Industrial Training (MChem) at the University of Bath (2011–2015), then carried out her doctoral studies in Functional Nanomaterials at the University of Bristol (2016–2020). Since 2020, she has been working as a postdoctoral researcher and then beamline scientist at the ID02 beamline, the European Synchrotron Radiation Facility.

         , Thomas Zemb

    Thomas Zemb holds a master’s degree in nuclear engineering, a PhD in Biophysics (1978), and a Habilitation in Solid-state Physics (1985). As staff scientist at CEA since 1979 and full Professor at INSTN since 1992, he is in charge of research aimed to innovations in separation chemistry, with focus on “ienaics”, the science developed at the Institute for Separation chemistry in Marcoule (ICSM), the academic research Institute he founded in 2004 via an association between CEA/CNRS, ENSCM and the University of Montpellier.

         and Werner Kunz

    Werner Kunz holds a diploma in chemistry, a PhD in Physical Chemistry (1988) and a Habilitation in Physical Chemistry (1992). Since 1997 he is full professor of chemistry at the University of Regensburg and is there head of the Institute of Physical and Theoretical Chemistry. He runs a chair on solution chemistry and a European master programme on colloidal and formulation chemistry (COSOM) and is also in charge of the faculty’s Carl-von-Carlowitz Centre of sustainable chemistry.

     EMAIL logo
From the journal Tenside Surfactants Detergents
https://doi.org/10.1515/tsd-2023-2579

Abstract

Bicelles can be formed by mixing in given mole fractions two ethoxylated alkyl ether carboxylic acid surfactants of very different HLB in water. We determine the effect of adding three of the most used additives in formulation in health- and home care: propylene glycol, glycerol, and ethanol. The effects of additives are determined and compared in a concentrated isotropic phase above the LCST, a pseudo-lamellar phase, and a discotic nematic phase. The two latter are birefringent, and the nematic phase is viscoelastic. Propylene glycol acts as a co-solvent, improving the temperature stability of the nematic phase up to 20 wt% propylene glycol. Further addition of propylene glycol reduces the phase transition temperatures, inducing microstructural changes due to headgroup dehydration and preferential solubilization of the hydrophilic short chain surfactant. Glycerol acts as an anti-solvent, progressively decreasing phase transition temperatures by dehydration of headgroups. Ethanol is a good co-solvent for the surfactant-mixture. Adding up to 5 wt% ethanol increases the temperature stability of the nematic phase. Higher concentrations of ethanol lead to a single isotropic phase with increasingly molecular dissolution of the surfactants. The effect of the considered additives on molecular packing is followed by high resolution X-ray scattering.

Keywords: alkyl ether carboxylic acid; bicelle; lyotropic nematic phase; nematic gel; small-angle scattering
Corresponding author: Werner Kunz, Institute of Physical and Theoretical Chemistry, University of Regensburg, D-93053 Regensburg, Germany, E-mail:

About the authors

Patrick Denk

Patrick Denk MSc, studied chemistry at the University of Regensburg (2015–2020) and received his master’s degree in 2020. Since November 2020 he has been working on his doctorate in Physical Chemistry at the University of Regensburg, Germany.

Lauren Matthews

Lauren Matthews MChem PhD studied Chemistry with Industrial Training (MChem) at the University of Bath (2011–2015), then carried out her doctoral studies in Functional Nanomaterials at the University of Bristol (2016–2020). Since 2020, she has been working as a postdoctoral researcher and then beamline scientist at the ID02 beamline, the European Synchrotron Radiation Facility.

Thomas Zemb

Thomas Zemb holds a master’s degree in nuclear engineering, a PhD in Biophysics (1978), and a Habilitation in Solid-state Physics (1985). As staff scientist at CEA since 1979 and full Professor at INSTN since 1992, he is in charge of research aimed to innovations in separation chemistry, with focus on “ienaics”, the science developed at the Institute for Separation chemistry in Marcoule (ICSM), the academic research Institute he founded in 2004 via an association between CEA/CNRS, ENSCM and the University of Montpellier.

Werner Kunz

Werner Kunz holds a diploma in chemistry, a PhD in Physical Chemistry (1988) and a Habilitation in Physical Chemistry (1992). Since 1997 he is full professor of chemistry at the University of Regensburg and is there head of the Institute of Physical and Theoretical Chemistry. He runs a chair on solution chemistry and a European master programme on colloidal and formulation chemistry (COSOM) and is also in charge of the faculty’s Carl-von-Carlowitz Centre of sustainable chemistry.

Acknowledgments

The authors thank the ESRF for granting beam time. The authors also thank Kao Chemicals GmbH, in particular Dr. Thomas Myrdek, for providing the surfactants free of charge and for sharing information about the surfactants. Dr. Wagner Menezes da Silva is gratefully acknowledged for performing the quantitative 13C-NMR spectroscopy.

  1. Research ethics: Not applicable.

  2. Author contributions: The authors have accepted responsibility for the entire content of this manuscript and approved its submission. Patrick Denk: methodology, validation, formal analysis, investigation, visualization, writing – original draft. Lauren Matthews: methodology, validation, formal analysis, investigation. Thomas Zemb: conceptualization, supervision, writing – review and editing. Werner Kunz: conceptualization, supervision, writing – review and editing.

  3. Competing interests: The authors state no conflict of interest.

  4. Research funding: None declared.

  5. Data availability: The raw data are available from the authors on request.

References

1. Raffard, G., Steinbruckner, S., Arnold, A., Davis, J. H., Dufourc, E. J. Temperature – composition diagram of dimyristoylphosphatidylcholine–dicaproylphosphatidylcholine “bicelles” self-orienting in the magnetic field. A solid state 2H and 31P NMR study. Langmuir 2000, 16, 7655–7662; https://doi.org/10.1021/la000564g.Search in Google Scholar

2. Nieh, M.-P., Glinka, C. J., Krueger, S., Prosser, R. S., Katsaras, J. SANS study of the structural phases of magnetically alignable lanthanide-doped phospholipid mixtures. Langmuir 2001, 17, 2629–2638; https://doi.org/10.1021/la001567w.Search in Google Scholar

3. Katsaras, J., Harroun, T. A., Pencer, J., Nieh, M.-P. “Bicellar” lipid mixtures as used in biochemical and biophysical studies. Naturwissenschaften 2005, 92, 355–366; https://doi.org/10.1007/s00114-005-0641-1.Search in Google Scholar PubMed

4. Barbosa-Barros, L., Rodríguez, G., Barba, C., Cócera, M., Rubio, L., Estelrich, J., López-Iglesias, C., de la Maza, A., López, O. Bicelles: lipid nanostructured platforms with potential dermal applications. Small 2012, 8, 807–818; https://doi.org/10.1002/smll.201101545.Search in Google Scholar PubMed

5. Sanders, C. R., Schwonek, J. P. Characterization of magnetically orientable bilayers in mixtures of dihexanoylphosphatidylcholine and dimyristoylphosphatidylcholine by solid-state NMR. Biochemistry 1992, 31, 8898–8905; https://doi.org/10.1021/bi00152a029.Search in Google Scholar PubMed

6. Israelachvili, J. N., Mitchell, D. J., Ninham, B. W. Theory of self-assembly of hydrocarbon amphiphiles into micelles and bilayers. J. Chem. Soc., Faraday Trans. 2 1976, 72, 1525–1568; https://doi.org/10.1039/F29767201525.Search in Google Scholar

7. van Dam, L., Karlsson, G., Edwards, K. Direct observation and characterization of DMPC/DHPC aggregates under conditions relevant for biological solution NMR. Biochim. Biophys. Acta Biomembr. 2004, 1664, 241–256; https://doi.org/10.1016/j.bbamem.2004.06.005.Search in Google Scholar PubMed

8. Meister, A., Dubois, M., Belloni, L., Zemb, T. Equation of state of self-assembled disklike and icosahedral crystallites in the dilute range. Langmuir 2003, 19, 7259–7263; https://doi.org/10.1021/la0346806.Search in Google Scholar

9. Dubois, M., Belloni, L., Zemb, Th., Demé, B., Gulik-Krzywicki, Th. Formation of rigid nanodiscs: edge formation and molecular separation. In Trends in Colloid and Interface Science XIV. Progress in Colloid and Polymer Science; Springer: Berlin, Heidelberg, Vol. 115, 2000; pp. 238–242.10.1007/3-540-46545-6_47Search in Google Scholar

10. Dubois, M., Lizunov, V., Meister, A., Gulik-Krzywicki, T., Verbavatz, J. M., Perez, E., Zimmerberg, J., Zemb, T. Shape control through molecular segregation in giant surfactant aggregates. Proc. Natl. Acad. Sci. U. S. A. 2004, 101, 15082–15087; https://doi.org/10.1073/pnas.0400837101.Search in Google Scholar PubMed PubMed Central

11. Park, S. H., Opella, S. J. Triton X-100 as the “Short-chain lipid” improves the magnetic alignment and stability of membrane proteins in phosphatidylcholine bilayers for oriented-sample solid-state NMR spectroscopy. J. Am. Chem. Soc. 2010, 132, 12552–12553; https://doi.org/10.1021/ja1055565.Search in Google Scholar PubMed PubMed Central

12. Taguchi, S., Kimura, Y., Akiyama, Y., Tachibana, Y., Yamamoto, T. Fluorescent anisotropy evaluation of bicelle formation employing carboxyl BODIPY and pyrromethene. J. Oleo Sci. 2022, 71, ess21295; https://doi.org/10.5650/jos.ess21295.Search in Google Scholar PubMed

13. Dubois, M., Gulik-Krzywicki, T., Demé, B., Zemb, T. Rigid organic nanodisks of controlled size: a catanionic formulation. C. R. Acad. Sci. 1998, 1, 567–575; https://doi.org/10.1016/S1387-1609(98)80012-1.Search in Google Scholar

14. Lawson, K. D., Flautt, T. J. Magnetically oriented lyotropic liquid crystalline phases. J. Am. Chem. Soc. 1967, 89, 5489–5491; https://doi.org/10.1021/ja00997a054.Search in Google Scholar

15. Amaral, L. Q., Pimentel, C. A., Tavares, M. R., Vanin, J. A. Study of a magnetically oriented lyotropic mesophase. J. Chem. Phys. 1979, 71, 2940–2945; https://doi.org/10.1063/1.438696.Search in Google Scholar

16. Forrest, B. J., Fujiwara, F. Y., Reeves, L. W. Order profiles of host decyl sulfate and decylammonium chains and guest carboxylic acids and carboxylates in aligned type II DM lyomesophases. J. Phys. Chem. 1980, 84, 662–670; https://doi.org/10.1021/j100443a019.Search in Google Scholar

17. Dörfler, H.-D., Görgens, C. Mizellpolymorphie lyotroper mesophasen. Tenside Surfactants Deterg. 1999, 36, 314–321; https://doi.org/10.1515/tsd-1999-360509.Search in Google Scholar

18. Dietrich, C. F., Rudquist, P., Lorenz, K., Giesselmann, F. Chiral structures from achiral micellar lyotropic liquid crystals under capillary confinement. Langmuir 2017, 33, 5852–5862; https://doi.org/10.1021/acs.langmuir.7b01074.Search in Google Scholar PubMed

19. Colafemmina, G., Recchia, R., Ferrante, A. S., Amin, S., Palazzo, G. Lauric acid-induced formation of a lyotropic nematic phase of disk-Shaped micelles. J. Phys. Chem. B 2010, 114, 7250–7260; https://doi.org/10.1021/jp1020774.Search in Google Scholar PubMed

20. Yu, L. J., Saupe, A. Observation of a biaxial nematic phase in potassium laurate-1-decanol-water mixtures. Phys. Rev. Lett. 1980, 45, 1000–1003; https://doi.org/10.1103/PhysRevLett.45.1000.Search in Google Scholar

21. Anachkov, S. E., Kralchevsky, P. A., Danov, K. D., Georgieva, G. S., Ananthapadmanabhan, K. P. Disclike vs. cylindrical micelles: generalized model of micelle growth and data interpretation. J. Colloid Interface Sci. 2014, 416, 258–273; https://doi.org/10.1016/j.jcis.2013.11.002.Search in Google Scholar PubMed

22. Sheu, E. Y., Lo Nostro, P., Capuzzi, G., Baglioni, P. Micelle and microemulsion properties of cesium di-dodecyl-dimethylsulfosuccinate, Cs-AOT. Langmuir 1999, 15, 6671–6676; https://doi.org/10.1021/la990059n.Search in Google Scholar

23. Boden, N., Corne, S. A., Jolley, K. W. Lyotropic mesomorphism of the cesium pentadecafluorooctanoate/water system: high-resolution phase diagram. J. Phys. Chem. 1987, 91, 4092–4105; https://doi.org/10.1021/j100299a031.Search in Google Scholar

24. Holmes, M. C., Reynolds, D. J., Boden, N. Concentration-temperature dependence of the size and shape of the micelles in the cesium pentadecafluorooctanoate/water system. J. Phys. Chem. 1987, 91, 5257–5262; https://doi.org/10.1021/j100304a025.Search in Google Scholar

25. Forrest, B. J., Reeves, L. W. New lyotropic liquid crystals composed of finite nonspherical micelles. Chem. Rev. 1981, 81, 1–14; https://doi.org/10.1021/cr00041a001.Search in Google Scholar

26. Hendrikx, V., Charvolin, J., Rawiso, M., Liebert, L., Holmes, M. C. Anisotropic aggregates of amphiphilic molecules in lyotropic nematic phases. J. Phys. Chem. 1983, 87, 3991–3999; https://doi.org/10.1021/j100243a039.Search in Google Scholar

27. Dufourc, E. J. Bicelles and nanodiscs for biophysical chemistry. Biochim. Biophys. Acta Biomembr. 2021, 1863, 183478; https://doi.org/10.1016/j.bbamem.2020.183478.Search in Google Scholar PubMed

28. Loudet-Courreges, C., Nallet, F., Dufourc, E. J., Oda, R. Unprecedented observation of days-long remnant orientation of phospholipid bicelles: a small-angle X-ray scattering and theoretical study. Langmuir 2011, 27, 9122–9130; https://doi.org/10.1021/la1050817.Search in Google Scholar PubMed

29. Venkata Sai, D., Mirri, G., Kouwer, P. H. J., Sahoo, R., Musevic, I., Dhara, S. Unusual temperature dependence of elastic constants of an ambient-temperature discotic nematic liquid crystal. Soft Matter 2016, 12, 2960–2964; https://doi.org/10.1039/C6SM00065G.Search in Google Scholar PubMed

30. de Andrade Lima, L. R. P., Rey, A. D. Linear viscoelasticity of discotic mesophases. Chem. Eng. Sci. 2004, 59, 3891–3905; https://doi.org/10.1016/j.ces.2004.06.016.Search in Google Scholar

31. Nikzad, A., Akbari, A., Grecov, D. Rheological properties of discotic nematic liquid crystals: graphene oxide dispersions study. Liq. Cryst. 2021, 48, 1685–1698; https://doi.org/10.1080/02678292.2021.1897890.Search in Google Scholar

32. Risi, C. L. S., Figueiredo Neto, A. M., Fernandes, P. R. G., Sampaio, A. R., Akpinar, E., Santos, M. B. L. Shear viscosity and rheology of ternary and quaternary lyotropic liquid crystals in discotic and calamitic nematic phases. Rheol. Acta 2015, 54, 529–543; https://doi.org/10.1007/s00397-015-0850-2.Search in Google Scholar

33. Denk, P., Matthews, L., Prévost, S., Zemb, T., Kunz, W. A dilute nematic gel produced by intramicellar segregation of two polyoxyethylene alkyl ether carboxylic acids. J. Colloid Interface Sci. 2024, 659, 833–848; https://doi.org/10.1016/j.jcis.2024.01.014.Search in Google Scholar PubMed

34. Shigeta, K., Olsson, U., Kunieda, H. Effect of alcohols (propanol, propylene glycol, and glycerol) on cloud point and micellar structure in long-poly(oxyethylene)n oleyl ethers systems. In Studies in Surface Science and Catalysis; Elsevier Inc.: Amsterdam, Vol. 132, 2001; pp. 93–96.10.1016/S0167-2991(01)82042-5Search in Google Scholar

35. Romero, C. M., Escamilla, A. P., Ribeiro, A. C. F., Esteso, M. A. Effect of 1,2-propanediol on the critical micelle concentration of decyltrimethylammonium bromide at temperatures from 293.15 K to 308.15 K. Int. J. Mol. Sci. 2022, 23, 15884; https://doi.org/10.3390/ijms232415884.Search in Google Scholar PubMed PubMed Central

36. Marszall, L., Van Valkenburg, J. W. The effect of glycols on the hydrophile–lipophile balance and the micelle formation of nonionic surfactants. J. Am. Oil Chem. Soc. 1982, 59, 84–87; https://doi.org/10.1007/BF02678718.Search in Google Scholar

37. Dreiss, C. A. Wormlike micelles: where do we stand? Recent developments, linear rheology and scattering techniques. Soft Matter 2007, 3, 956; https://doi.org/10.1039/b705775j.Search in Google Scholar PubMed

38. Danov, K. D., Kralchevsky, P. A., Stoyanov, S. D., Cook, J. L., Stott, I. P., Pelan, E. G. Growth of wormlike micelles in nonionic surfactant solutions: quantitative theory vs. experiment. Adv. Colloid Interface Sci. 2018, 256, 1–22; https://doi.org/10.1016/j.cis.2018.05.006.Search in Google Scholar PubMed

39. D’Errico, G., Ciccarelli, D., Ortona, O. Effect of glycerol on micelle formation by ionic and nonionic surfactants at 25 °C. J. Colloid Interface Sci. 2005, 286, 747–754; https://doi.org/10.1016/j.jcis.2005.01.030.Search in Google Scholar PubMed

40. Cantù, L., Corti, M., Degiorgio, V., Hoffmann, H., Ulbricht, W. Nonionic micelles in mixed water-glycerol solvent. J. Colloid Interface Sci. 1987, 116, 384–389; https://doi.org/10.1016/0021-9797(87)90134-2.Search in Google Scholar

41. Volk, A., Kähler, C. J. Density model for aqueous glycerol solutions. Exp. Fluids 2018, 59, 75; https://doi.org/10.1007/s00348-018-2527-y.Search in Google Scholar

42. Alauddin, M., Parvin, T., Begum, T. Effect of organic additives on the cloud point of triton X-100 micelles. J. Appl. Sci. 2009, 9, 2301–2306; https://doi.org/10.3923/jas.2009.2301.2306.Search in Google Scholar

43. Cattelaens, F., Jäger, M., Myrdek, T. Purification of carboxymethylated fatty alcohol derivates using ion exchange resins. J. Surfactants Deterg. 2023, 26, 111–117; https://doi.org/10.1002/jsde.12641.Search in Google Scholar

44. Zana, R. Aqueous surfactant-alcohol systems: a review. Adv. Colloid Interface Sci. 1995, 57, 1–64; https://doi.org/10.1016/0001-8686(95)00235-I.Search in Google Scholar

45. Denk, P., Prévost, S., Matthews, L., Prasser, Q., Zemb, T., Kunz, W. The effect of ethanol on fibrillar hydrogels formed by glycyrrhizic acid monoammonium salt. J. Colloid Interface Sci. 2023, 630, 762–775; https://doi.org/10.1016/j.jcis.2022.10.138.Search in Google Scholar PubMed

46. Suzuki, H. Studies of the effect of ethanol and sodium chloride on the micellization of sodium dodecyl sulfate by gel filtration. Bull. Chem. Soc. Jpn. 1976, 1470–1474; https://doi.org/10.1246/bcsj.49.1470.Search in Google Scholar

47. Becher, P. Nonionic surface-active compounds. X. Effect of solvent on micellar properties. J. Colloid Sci. 1965, 20, 728–731; https://doi.org/10.1016/0095-8522(65)90046-2.Search in Google Scholar

48. Denk, P., El Maangar, A., Prévost, S., Silva, W., Gschwind, R., Zemb, T., Kunz, W. Cloud point, auto-coacervation, and nematic ordering of micelles formed by ethylene oxide containing carboxylate surfactants. J. Colloid Interface Sci. 2022, 621, 470–488; https://doi.org/10.1016/j.jcis.2022.04.046.Search in Google Scholar PubMed

Supplementary Material

This article contains supplementary material (https://doi.org/10.1515/tsd-2023-2579).

Received: 2023-12-28
Accepted: 2024-02-06
Published Online: 2024-02-21

© 2024 Walter de Gruyter GmbH, Berlin/Boston

From the journal
Tenside Surfactants Detergents
Tenside Surfactants Detergents

Journal

Downloaded on 27.4.2024 from https://www.degruyter.com/document/doi/10.1515/tsd-2023-2579/html
Scroll to top button