An aromatic amino acid (phenylglycine) based amphiphile with amide and ester groups and a long fatty acyl chain has been found to form organogels selectively in the fuel hydrocarbon solvents including hexane, heptane, cyclohexane, diesel, kerosene and pump-oil at room temperature. Organogels have been well characterized morphologically by field emission scanning electron microscopy (FE-SEM) and atomic force microscopy (AFM). Morphological studies of these xerogels have revealed the presence of fascinating right-handed twisted nanoribbons (in n-heptane and n-octane). Involvement of different non-covalent interactions among the gelator molecules within the gel matrix has been studied using FT-IR and XRD. The organogel in diesel is mechanically stable with high yield stress (177.8 Pa) and storage modulus (>104 Pa) values, as has been evidenced from the rheological studies. Interestingly, this gelator compound exhibits phase selective gelation properties and the phase selective gelation occurs efficiently and quickly (within 90 s), in oil–water mixtures and the gelator molecule can be recovered and reused several times easily, indicating its applicability in oil spill cleaning.
Self-healable, multi-stimuli responsive metallo-hydrogels based on a series of tyrosine containing amphiphiles have been discovered. Formation of these metallo-gels is highly selective to Ni2+ ions. Moreover, the self-healing property can be modulated by varying the chain length of the corresponding gelator amphiphiles.
A single amino acid (phenylalanine) based pyrene conjugated low molecular weight hydrogelator has been discovered. This amino acid derivative has been found to form hydrogels in a wide range of aqueous solutions of pH 7.46–14 and the estimated minimum gelation concentration (MGC) in phosphate buffer solution at physiological pH 7.46 is 0.037% (w/v) i.e. 0.85 mM. A transparent hydrogel has been produced in the pH range (7.46–10.5), while a translucent hydrogel has been formed at higher pH. The hydrogel has been characterized by field emission scanning electron microscopy (FE-SEM), fluorescence microscopy, differential scanning calorimetry (DSC), circular dichroism (CD), X-ray diffraction (XRD) and rheological studies. A distinct morphological change of the gel nanofibers from helical to tape-like morphology has been noticed in the FE-SEM studies with an increase in pH. These observations have been supported by a significant decrease of the CD signals and different XRD patterns found with the increase in pH. Interestingly, this hydrogel shows a pH dependent thixotropic property. The thixotropic property of the hydrogel has been examined using rheological experiments. This thixotropic property of the hydrogel has been utilized for the encapsulation of vitamin B12 and an anticancer drug, doxorubicin, in the hydrogel matrix without any heating–cooling cycle and sustained release of these bioactive molecules has been studied at physiological temperature (37 °C) and pH (7.46) over a period of about 3 days.
In this study, chiral helical nanofibers have been obtained from suitable, co-assembling, two oppositely charged amino acid based two component hydrogels. An equimolar mixture of an N-terminally protected amino acid Fmoc-(L/D)Glu (Fmoc: N-fluorenyl-9-methoxycarbonyl, Glu: glutamic acid) and (L/D)Lys (Lys: lysine) can co-assemble to form hydrogels. These hydrogels have been characterised using circular dichroism (CD), atomic force microscopy (AFM), transmission electron microscopy (TEM), X-ray powder diffraction, fluorescence spectroscopic and rheological studies. CD and AFM studies have been extensively used to examine the chiral/achiral nature of fibers obtained from different hydrogel systems. The equimolar mixture of two L-isomers, {Fmoc-(L)Glu + (L)Lys} in the assembled state, leads to the exclusive formation of left-handed helical nanofibers, whereas an equimolar mixture of two D-isomers, {Fmoc-(D)Glu + (D)Lys}, gives rise to right-handed helical nanofibers. The CD study of the gel obtained from the {Fmoc-(L)Glu + (L)Lys} system is exactly the mirror image of the CD signal obtained from the gel of the {Fmoc-(D)Glu + (D)Lys} system. These results suggest that the molecular chirality is being translated into the supramolecular helicity and the handedness of these fibers depends on the corresponding molecular chirality in the mixture of the two component system. Reversing the handedness of helical fibers is possible by using enantiomeric building blocks. Co-assembly of racemic and equimolar mixtures of all four components, i.e., [{Fmoc-(L)Glu + (L)Lys} + {Fmoc-(D)Glu + (D)Lys}] can also form hydrogels. Interestingly, in this racemic mixture self-sorting has been observed with the presence of almost equal amount of left- and right-handed helical nanofibers. The equimolar mixture of Fmoc-(L)Glu and L-ornithine/ L-arginine also produces hydrogel with left-handed helical fibers. Moreover, the straight fiber has been observed from the two component hydrogel {Fmoc-(L)Glu + (L)Lys} system in the presence of Ca2+ /Mg2+ ions. This indicates the straight nanofibers are obtained under suitable conditions and acid–base interaction is responsible for making the helical fibers at the nanoscale.