Skip to main content
Log in

Self-assembly of aromatic biscarbamate gelators: effect of spacer length on the gelation and rheology

  • Original Paper: Supramolecular materials
  • Published:
Journal of Sol-Gel Science and Technology Aims and scope Submit manuscript

Abstract

Low molecular weight biscarbamate organogelators (LMWBGs) with simple molecular structures that could gel different types of organic solvents were synthesized. The LMWBGs were composed of a long hydrophobic tail of linear fatty alcohol (C8–C18) and an aromatic core and could gel organic solvents such as xylene, toluene, NMP, cyclohexanol and chlorobenzene at a concentration of 10–15 mg/mL. Gelation studies indicated that the alkyl chain length residues did not affect the gelation time which was generally around 10–15 min leading to opaque gels in all the solvents. The gels in p-xylene were studied by FTIR spectroscopy and differential scanning calorimetry (DSC) for the nature of the interactions between the gelators and the solvent. FTIR spectroscopic studies revealed that hydrogen bonding and van der Waals interactions were the driving forces for the formation of the gels, while solid-state UV–visible studies revealed the existence of π–π interaction in the xerogel. The gel melting temperatures were found to decrease and then increase with increasing alkyl chain length as observed in DSC. The microscopic observations (FE-SEM) suggested that the gelator molecules self-assembled leading to nano- and microfibres in the turbid gel, and as the alkyl chain length increased, the width of the fibres increased. Rheological studies evinced the viscoelastic nature of the soft gels viscoelasticity increased with increasing gelator concentration, while fluidity increased with increasing chain length. The X-ray diffraction analysis revealed that in the xerogels from p-xylene the molecules aggregated into a layered structure. This study on the influence of alkyl side chains shows that hydrogen bonding and van der Waals interactions play a significant role in the morphology of such self-assembled structures.

Graphical Abstract

This is a preview of subscription content, log in via an institution to check access.

Access this article

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Scheme 1
Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5
Fig. 6
Fig. 7
Fig. 8
Fig. 9
Fig. 10

Similar content being viewed by others

References

  1. Philp D, Stoddart JF (1996) Self-assembly in natural and unnatural systems. Angew Chem Int Ed Engl 35:1154–1196

    Article  Google Scholar 

  2. Fuhrhop JH, Köning J (1994) Membranes and molecular assemblies: the synkinetic approach, royal society of chemistry, Cambridge. Royal Society of Chemistry, Cambridge

    Google Scholar 

  3. Lehn JM (1995) Supramolecular chemistry. VCH, Weinheim

    Book  Google Scholar 

  4. Ye E, Pei LC, Ankshita P, Xiaotian F, Cally O, Valerie JJY, Xian JL (2014) Supramolecular soft biomaterials for biomedical applications. Mater Today 17:194–202

    Article  Google Scholar 

  5. Terech P, Weiss RG (1997) Low molecular mass gelators of organic liquids and the properties of their gels. Chem Rev 97:3133–3159

    Article  Google Scholar 

  6. Jung JH, Lee JH, Silverman JR, John G (2013) Coordination polymer gels with important environmental and biological applications. Chem Soc Rev 42:924–936

    Article  Google Scholar 

  7. Segarra-Maset MD, Nebot VJ, Miravet JF, Escuder B (2013) Control of molecular gelation by chemical stimuli. Chem Soc Rev 42:7086–7098

    Article  Google Scholar 

  8. Moniruzzaman M, Sahin A, Winey KI (2009) Improved mechanical strength and electrical conductivity of organogels containing carbon nanotubes. Carbon 47:645–650

    Article  Google Scholar 

  9. Tew GN, Scott RW, Klein ML, Degrado WF (2010) De novo design of antimicrobial polymers, foldamers, and small molecules: from discovery to practical applications. Acc Chem Res 43:30

    Article  Google Scholar 

  10. Horne WS, Gellman SH (2008) Foldamers with heterogeneous backbones. Acc Chem Res 41:1399

    Article  Google Scholar 

  11. Gellman SH (1998) Foldamers: a manifesto. Acc Chem Res 31:173

    Article  Google Scholar 

  12. Hill DJ, Mio MJ, Prince RB, Hughes TS, Moore JS (2001) A field guide to foldamers. Chem Rev 101:3893

    Article  Google Scholar 

  13. Sanford AR, Yamato K, Yang X, Yuan L, Han Y, Gong B (2004) Well-defined secondary structures. Eur J Biochem 271:1416

    Article  Google Scholar 

  14. Yang X, Martinovic S, Smith RD, Gong B (2003) Duplex foldamers from assembly induced folding. J Am Chem Soc 125:9932

    Article  Google Scholar 

  15. Archer EA, Gong H, Krische MJ (2001) Hydrogen bonding in noncovalent synthesis: selectivity and the directed organization of molecular strands. Tetrahedron 57:1139–1159

    Article  Google Scholar 

  16. Zimmerman SC, Corbin PS (2000) Heteroaromatic modules for self-assembly using multiple hydrogen bonds. Struct Bonding (Berlin) 96:63–94

    Article  Google Scholar 

  17. Schmuck C, Wienand W (2001) Self-complementary quadruple hydrogen-bonding motifs as a functional principle: from dimeric supramolecules to supramolecular polymers. Angew Chem Int Ed 40:4363–4369

    Article  Google Scholar 

  18. Khanna S, Moniruzzaman M, Sundararajan PR (2006) Influence of Single versus Double Hydrogen-Bonding Motif on the Crystallization and Morphology of Self-Assembling Carbamates with Alkyl Side Chains: model System for Polyurethanes. J Phys Chem B 110:15251–15260

    Article  Google Scholar 

  19. Sangeetha NM, Maitra Uday (2005) supramolecular gels: functions and uses. Chem Soc Rev 34:821–836

    Article  Google Scholar 

  20. Branco MC, Schneider JP (2009) Self-assembling materials for therapeutic delivery. Acta Biomater 5:817–831

    Article  Google Scholar 

  21. Babu SS, Praveen VK, Ajayaghosh A (2014) Functional π-gelators and their applications. Chem Rev 114:1973–2129

    Article  Google Scholar 

  22. Srivastava SP, Saxena AK, Tendon RS, Shekhar V (1997) Measurement and prediction of solubility of petroleum waxes in organic solvents. Fuel 76:625–630

    Article  Google Scholar 

  23. Kanakaiah V, Latha M, Sravan B, Palanisamy Aruna, Vatsala Rani J (2014) Rechargeable magnesium carbon-fluoride battery with electrolyte gel of ionic liquid and low molecular weight gelator. J Electrochem Soc 161:A1586–A1592

    Article  Google Scholar 

  24. Fernanda PM, Marangoni AG (2009) AOCS official method Cj 2-95 X-ray diffraction analysis of fats. In: Official methods and recommended practices of the AOCS, 6th edn. 2011–2012 Methods and Additions and Revisions

  25. DeMan JM, deMan L (2001) Texture of fats. In: Marangoni A, Narine S, Marcel Dekker (eds) Physical properties of lipids, p 191–217. Analytical Methods, Procedures and Theory for the Physical Characterization of Fats Section 1: X-Ray Powder Diffractometry (XRD)

  26. Li Yuangang, Liu Kaiqiang, Liu Jing, Peng Junxia, Feng Xuli, Fang Yu (2006) Amino acid derivatives of cholesterol as “latent” organogelators with hydrogen chloride as a protonation reagent. Langmuir 22:7016–7020

    Article  Google Scholar 

  27. Xue Min, Gao Di, Chen Xiangli, Liu Kaiqiang, Fang Yu (2011) New dimeric cholesteryl-based A (LS) < sub > 2 </sub > gelators with remarkable gelling abilities: organogel formation at room temperature. J Colloid Interface Sci 361:556–564

    Article  Google Scholar 

  28. Peng Junxia, Liu Kaiqiang, Liu Jing, Zhang Qiuhong, Feng Xuli, Fang Yu (2008) New dicholesteryl-based gelators: chirality and spacer length effect. Langmuir 24:2992–3000

    Article  Google Scholar 

  29. Dastidar Parthasarathi (2008) Supramolecular gelling agents: can they be designed. Chem Soc Rev 37:2699–2715

    Article  Google Scholar 

  30. Rogers MA, Weiss RG (2015) Systematic modifications of alkane-based molecular gelators and the consequences to the structures and properties of their gels. New J, Chem

    Google Scholar 

  31. Willemen HM, Vermonden T, Marcelis AT, Sudhölter EJ (2002) Alkyl derivatives of cholic acid as organogelators: one-component and two-component gels. Langmuir 18:7102–7106

    Article  Google Scholar 

  32. Willemen HM, Vermonden Tina, Marcelis Antonius, Sudhölter Ernst JR (2001) N-Cholyl amino acid alkyl Esters-A novel class of organogelators. EJOC 12:2329–2335

    Article  Google Scholar 

  33. Sravan B, Kamalakar K, Karuna MSL, Palanisamy Aruna (2014) Studies on organogelation of self-assembling bis urea type low molecular weight molecules. J Sol-Gel Sci Technol 71:372–379

    Article  Google Scholar 

  34. Delbecq F, Masuda Y, Ogue Y, Kawai T (2012) Salt complexes of two-component N-acylamino acid diastereoisomers: self-assembly studies and modulation of gelation abilities. Tetrahedron Lett 53:6588–6593

    Article  Google Scholar 

  35. Ducouret G, Chassenieux C, Martins S, Lequeux F, Bouteiller L (2007) Rheological characterisation of bis-urea based viscoelastic solutions in an apolar solvent. J Colloid Interface Sci 310:624–629

    Article  Google Scholar 

  36. Isare B, Bouteiller L, Ducouret G, Lequeux F (2009) Tuning reversible supramolecular polymer properties through co-monomer addition. Supramol Chem 21:416–421

    Article  Google Scholar 

  37. Ajish JK, Kumar KA, Subramanian M, Kumar M (2014) D-Glucose based bisacrylamide crosslinker: synthesis and study of homogeneous biocompatible glycopolymeric hydrogels. RSC Adv 4:59370–59378

    Article  Google Scholar 

  38. Pal A, Mahapatra RD, Dey J (2014) Understanding the role Of H-bonding in self-aggregation in organic liquids by fatty acid amphiphiles with a hydrocarbon tail containing different H-bonding linker groups. Langmuir 30:13791–13798

    Article  Google Scholar 

  39. Wuerthner F, Bauer C, Stepanenko V, Yagai SA (2008) Black perylene bisimide super gelator with an unexpected J-type absorption band. Adv Mater 20:1695–1698

    Article  Google Scholar 

  40. Chung JW, An BK, Park SYA (2008) Thermoreversible and proton-induced gel – sol phase transition with remarkable fluorescence variation. Chem Mater 20:6750–6755

    Article  Google Scholar 

  41. Würthner F, Thalacker C, Diele S, Tschierske C (2001) Fluorescent J-type aggregates and thermotropic columnar mesophases of perylene bisimide dyes. Chem Eur J 7:2245–2253

    Article  Google Scholar 

  42. Shirakawa M, Kawano SI, Fujita N, Sada K, Shinkai S (2003) Hydrogen-bond-assisted control of H versus J aggregation mode of porphyrins stacks in an organogel system. J Org Chem 68:5037–5044

    Article  Google Scholar 

  43. Bai B, Mao X, Wei J, Wei Z, Wang H, Li M (2015) Selective anion-responsive organogel based on a gelator containing hydrazide and azobenzene units. Sens Actuator B-Chem 211:268–274

    Article  Google Scholar 

  44. Ajayaghosh A, Praveen VK (2007) π-Organogels of self-assembled p-phenylenevinylenes: soft materials with distinct size, shape, and functions. Acc Chem Res 40:644–656

    Article  Google Scholar 

  45. Dhinakaran MK, Soundarajan K, Das TM (2014) Synthesis of novel benzimidazole-carbazole-N-glycosylamines and their self-assembly into nanofibers, New. J Chem 38:4371–4379

    Google Scholar 

  46. Huang YD, Tu W, Yuan YQ, Fan DL (2014) Novel organogelators based on pyrazine-2, 5-dicarboxylic acid derivatives and their mesomorphic behaviors. Tetrahedron 70:1274–1282

    Article  Google Scholar 

  47. Alimova LL, Atovmyan EG, Filipenko OS (1987) The crystal and molecular-structure of hexamethylene-1, 6-(0, 0’-didecyl)-diuretane. Kristallografiya 32:97–101

    Google Scholar 

  48. López-Martínez A, Morales-Rueda JA, Dibildox-Alvarado E, Charó-Alonso MA, Marangoni AG, Toro-Vazquez JF (2014) Comparing the crystallization and rheological behavior of organogels developed by pure and commercial monoglycerides in vegetable oil. Food Res Int 64:946–957

    Article  Google Scholar 

Download references

Acknowledgments

Sravan Baddi is indebted to Council of Scientific and Industrial Research (CSIR), India, for Senior Research Fellowship (SRF).

Author information

Authors and Affiliations

Authors

Corresponding author

Correspondence to Aruna Palanisamy.

Electronic supplementary material

Below is the link to the electronic supplementary material.

Supplementary material 1 (DOCX 1928 kb)

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

baddi, S., Sarma, D.S. & Palanisamy, A. Self-assembly of aromatic biscarbamate gelators: effect of spacer length on the gelation and rheology. J Sol-Gel Sci Technol 79, 637–649 (2016). https://doi.org/10.1007/s10971-016-4036-x

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s10971-016-4036-x

Keywords

Navigation