Hybrid Biosurfactant: Syntheses of Hybrid Corynomycolic Acid and its Monolayer Formation

Tokuzo Kawase; Sho Sumida; Tatsuo Oida

doi:10.3139/113.110369

Article

Hybrid Biosurfactant: Syntheses of Hybrid Corynomycolic Acid and its Monolayer Formation

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Published/Copyright: May 13, 2015

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From the journal Tenside Surfactants Detergents Volume 52 Issue 3

Abstract

Corynomycolic acids have two hydrophilic heads (OH and COOH) and two hydrophobic tails on adjacent carbon atoms. In this work, hybrid type corynomycolic acids (syn- and anti-isomers) were synthesized via the following three steps: 1) crossed Claisen condensation of t-butyl tridecanoate with ethyl per fluorooctanoate, 2) reduction of C = O to OH, and 3) conversion of COO-t-Bu to COOH using CF₃COOH. Both hydrophilic groups (OH and COOH) of hybrid corynomycolic acid would dissociate to –O^– and –COO^– at alkaline condition (pH = 12) while they remain unchanged at acidic condition (pH < 3). The effect of hybrid structure on the surfactant properties was investigated by the surface tension and surface pressure-area (π-A) measurements. Hybrid type corynomycolic acid gave smaller cmc and γ_cmc than dialkyl type one due to fluoroalkyl chain. With respect to the stereochemistry, the anti-isomer attained a smaller γ_cmc value than the syn-isomer. In π-A measurements, the monolayer of the syn-isomer showed a lower collapsing pressure (∼15 mN m^–¹) than that of the anti-isomer.

Kurzfassung

Corynomycolsäuren haben zwei hydrophile Kopfgruppen (OH und COOH) und zwei hydrophobe Gruppen an benachbarten Kohlenstoff atomen. In dieser Arbeit wurden Hybridtypen der Corynomy colsäuren (syn- und anti-Isomer) in drei Schritten synthetisiert: 1) gekreuzte Claisen-Kondensation von t-Butyltridecanoat mit Ethylperflurooctanoat, 2) Reduktion von C = O zu OH und 3) Umwandlung von COO-t-Bu zu COOH mittels CF₃COOH. Die beiden hydrophilen Gruppen (OH and COOH) der hybriden Corynomycolsäure werden unter alkalischen Bedingungen (pH = 12) zu –O^– und –COO^– dissoziieren, während sie unter sauren Bedingungen unverändert bleiben. Der Einfluss der Hybridstruktur auf die Oberflächeneigenschaften wurde mit Messungen der Oberflächenspannungen und der Oberflächendruck-Fläche-Isothermen (π-A) bestimmt. Wegen der Fluoro alkylkette besitzt die hybride Corynomycolsäure eine gerin gere kritische Mizellenbildungskonzentration (cmc) und Oberflächenspannung an der cmc als die Dialkyltype. Hinsichtlich der Stereochemie erreicht das anti-Isomer kleine γ_cmc-Werte als das syn-Isomer. Die π-A-Bestimmungen ergaben, dass die Monoschicht des syn-Isomer bei niedrigeren Drücken (∼15 mN m^–1) zusammenbricht als die des anti-Isomers.

Key words: Hybrid biosurfactant; corynomycolic acid; surface tension; surface pressure-area isotherm; monolayer

Stichwörter: Hybridbiotensid; Corynomycolsäure; Oberflächenspannung; Oberflächendruck-Fläche-Isoterme; Monoschicht

* Correspondence address, Prof. Dr. Tokuzo Kawase, Department of Chemistry and Materials Technology, Kyoto Institute of Technology, Hashigamicho 1, Matsugasaki, Sakyo-ku, Kyoto 606 – 8585, Japan, Tel.: +81-75-7 24-75 15, Fax: +81-75-7 24-75 15, E-Mail: kawase@kit.ac.jp

Tokuzo Kawase was born in 1951. He is a Professor of chemistry at Kyoto Institute of Technology. He received his D. Engineering from Kyoto University in 1979 and another Ph.D. from Osaka City University in 1995. His current scientific interests are focused on the synthesis of novel surfactants including fluorinated surfactants.

Sho Sumida completed his M.Sc. in applied chemistry from Kyoto Institute of Technology. Presently he is working at NOF Corporation.

Tatsuo Oida is an Associate Professor at Kyoto Institute of Technology. His current scientific interests are focused on the synthesis of novel surfactants and their structure-related surfacant properties. His research interests include synthesis and application of gemini surfactants and polyglycerin based surfactants.

References

1. Dieng, S. Y., Szönyi, S., Jouani, M., Watzke, H. J. and Cambon, A.: Synthesis and physicochemical properties of new vesicle-forming fluorosurfactants derived from substituted dithioacetamides. Colloids Surf. A98 (1995) 43–51. 10.1016/0927-7757(95)03103-KSearch in Google Scholar

2. Oda, R., Huc, I., Danino, D. and Talmon, Y.: Aggregation properties and mixing behavior of hydrocarbon, fluorocarbon, and hybrid hydrocarbon–fluorocarbon cationic dimeric surfactants. Langmuir16 (2000) 9759–9769. 10.1021/la0008075Search in Google Scholar

3. Ohno, A., Kushiyama, A., Kondo, Y., Teranaka, T. and Yoshino, N.: Synthesis and properties of gemini-type hydrocarbon–fluorocarbon hybrid surfactants, J. Fluorine Chem.129 (2008) 577–582. 10.1016/j.jfluchem.2008.03.007Search in Google Scholar

4. Yoshimura, T., Ohno, A. and Esumi, K.: Equilibrium and dynamic surface tension properties of partially fluorinated quaternary ammonium salt gemini surfactants. Langmuir22 (2006) 4643–4648. 10.1021/la0534266Search in Google Scholar PubMed

5. Aydogan, N., Aldis, N. and Guvenir, O.: Interfacial and bulk properties of the new fluorocarbon–hydrocarbon hybrid unsymmetrical bolaform surfactant. Langmuir19 (2003) 10726–10731. 10.1021/la0351921Search in Google Scholar

6. Rosen, M. J. and Tracy, D. J. J.: Gemini surfactants, J. Surfactants Deterg.1 (1998) 547–554. 10.1007/s11743-998-0057-8Search in Google Scholar

7. Guo, W., Zhong, L., Fung, B. M., O’Rear, E. A. and Harwell, J. H.: Hybrid surfactants containing separate hydrocarbon and fluorocarbon chains, J. Phys. Chem.96 (1992) 6738–6742. 10.1021/j100195a038Search in Google Scholar

8. Yoshino, N., Hamano, K., Omiya, Y., Kondo, Y., Ito, A. and Abe, M.: syntheses of hybrid anionic surfactants containing fluorocarbon and hydrocarbon chains, Langmuir11 (1995) 466–469. 10.1021/la00002a016Search in Google Scholar

9. Ito, A., Kamogawa, K., Sakai, H., Hamano, K., Kondo, Y., Yoshino, N. and Abe, M.: Micelle aggregating condition of fluorocarbon-hydrocarbon hybrid surfactants in aqueous solution. Langmuir13 (1997) 2935–2942. 10.1021/la9602426Search in Google Scholar

10. Abe, M., Tobita, K., Sakai, H., Kondo, Y., Yoshino, N., Kasahara, Y., Matsuzawa, H., Iwahashi, M., Momozawa, N. and Nishiyama, K.: Anomalous viscoelasticity of concentrated solutions with a fluorinated hybrid surfactant. Langmuir13 (1997) 2932–2934. 10.1021/la961023nSearch in Google Scholar

11. Peresypkin, A., Clavel, C. and Menger, F. M.: Ambidextrous “hybrid” fluorinated zwitterionic geminis: self-assembly in both organic and aqueous media. Mendeleev Communications17 (2007) 82–84. 10.1016/j.mencom.2007.03.009Search in Google Scholar

12. Asakawa, T., Ozawa, T. and Ohta, A.: Generation of fluorocarbon and hydrocarbon hybrid gemini surfactants controlled by micellar miscibility. J. Oleo Sci.62 (2013) 17–20. 10.5650/jos.62.17Search in Google Scholar PubMed

13. Kawase, T., Okazaki, Y., Sugo, T. and Oida, T.: Syntheses of tartaric acid-based hybrid gemini surfactants containing fluorocarbon and hydrocarbon chains. Tenside Surfactants Detergents52 (2015) 20–28. 10.3139/113.110344Search in Google Scholar

14. Mukherjee, S., Das, P. and Sen, R.: Towards commercial production of microbial surfactants. Trends in Biotechnology24 (2006) 509–515. 10.1016/j.tibtech.2006.09.005Search in Google Scholar PubMed

15. Schoerken, U. and Kempers, P.: Lipid biotechnology: Industrial relevant production processes. Eur. J. Lipid Sci. Technol.111 (2009) 627–645. 10.1002/ejlt.200900057Search in Google Scholar

16. Fujii, T., Yuasa, R. and Kawase, T.: Biodetergent. III Synthesis and properties of corynomycolic acids as biomimetic-surfactant. J. Jpn. Oil Chem. Soc.44 (1995) 419–424. 10.5650/jos1956.44.419Search in Google Scholar

17. Fujii, T., Yuasa, R. and Kawase, T.: Biodetergent. IV Monolayers of corynomycolic acids at air-water interface. Colloid Polymer Sci.277 (1999) 334–339. 10.1007/s003960050389Search in Google Scholar

18. Viscontini, M. and Merckling, N.: Über eine neue Methode von β-Ketosäure ester-Synthese. Helv. Chim. Acta35 (1952) 2280–2282. 10.1002/hlca.19520350714Search in Google Scholar

19. Andrés, J. M., Pedrosa, R., Pérez, A. and Pérez-Encabo, A.: Diastereoselective synthesis of enantiopure γ-amino-β-hydroxy acids by Reformatsky reaction of chiral α-dibenzylamino aldehydes. Tetrahedron57 (2001) 8521–8530. 10.1016/S0040-4020(01)00804-3Search in Google Scholar

20. Chen, Y. L., Sano, M., Kawaguchi, M., Yu, H. and Zografi, G.: Static and dynamic properties of pentadecanoic acid monolayers at the air-water interface. Langmuir2 (1986) 349–354. 10.1021/la00069a018Search in Google Scholar

21. Kajiyama, T., Morimoto, N., Uchida, M. and Oishi, Y.: Static viscoelastic characteristics-aggregation structure relationships of monolayers at air–water interface. Chem. Lett.18 (1989) 1047–1050. 10.1246/cl.1989.1047Search in Google Scholar

22. Kajiyama, T., Oishi, Y., Uchida, M., Morimoto, N., Ishikawa, J. and Tanimoto, Y.: Evaluation of melting and crystalline relaxation temperatures of fatty acids monolayers on the water surface and their importances for molecular aggregation states in monolayers. Bull. Chem. Soc. Jpn.65 (1992) 864–870. 10.1246/bcsj.65.864Search in Google Scholar

23. Cooper, D. G., Zajic, J. E. and Denis, C.: Surface active properties of a biosurfactant from Corynebacterium lepus. J. Am. Oil Chem. Soc.58 (1981) 77–80. 10.1007/BF02666059Search in Google Scholar

24. Seimiya, T.: Enthalpy of hydrophobic hydration separately estimated for each -CH₂-, -CF₂-, and -OCH₂CH₂- unit component of amphiphiles and of related compounds. J. Colloid Interface Sci.266 (2003) 422–429. 10.1016/S0021-9797(03)00715-XSearch in Google Scholar PubMed

25. Aisaka, T., Oida, T. and Kawase, T.: A novel synthesis of succinic acid type Gemini surfactant by the functional group interconversion of Corynomicolic acid. J. Oleo Sci.56 (2007) 633–644;. 10.5650/jos.56.633Search in Google Scholar PubMed

26. Anh, N. T., Eisenstein, O., Lefour, J.-M. and Dau, M.-E.: Orbital factors and asymmetric induction, J. Am. Chem. Soc.95 (1973) 6146–6147. 10.1021/ja00799a068Search in Google Scholar

27. Cram, D. J. and Elhafez, F. A. A.: Studies in Stereochemistry. X. The rule of “steric control of asymmetric induction” in the syntheses of acyclic systems. J. Am. Chem. Soc.74 (1952) 5828–5835. 10.1021/ja01143a007Search in Google Scholar

28. Rosen, M. J. and Kunjappu, J. T.: Surfactants and Interfacial Phenomena. 4th Edition, John Wiley and Sons New York (2012). 10.1002/9781118228920Search in Google Scholar

29. Kaganer, V. M., Möhwald, H. and Dutta, P.: Structure and phase transitions in Langmuir monolayers. Rev. Mod. Phys.71 (1999) 779–819. 10.1103/RevModPhys.71.779Search in Google Scholar

30. Agrawal, M. L. and Neuman, R. D.: Surface diffusion in monomolecular films. I. Lateral profile shift in radiotracer method. J. Colloid Interface Sci.121 (1988) 355–365. 10.1016/0021-9797(88)90439-0Search in Google Scholar

31. Kawase, T., Saito, I. and Oida, T.: Effects of hydrophobic chain length on temperature dependency of monolayer behavior of ester type tartaric gemini. J. Oleo. Sci.60 (2011) 61–69. 10.5650/jos.60.61Search in Google Scholar PubMed

Published Online: 2015-05-13

Published in Print: 2015-05-15

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https://doi.org/10.3139/113.110369

Keywords for this article

Hybrid biosurfactant; corynomycolic acid; surface tension; surface pressure-area isotherm; monolayer