Asish Pal

Two‐Component Hydrogels Comprising Fatty Acids and Amines: Structure, Properties, and Application as a Template for the Synthesis of Metal Nanoparticles

Stearic acid or eicosanoic acid mixed with di- or oligomeric amines in specific molar ratios form stable gels in water. The formation of such hydrogels depends on the hydrophobicity of the fatty acid, and also on the type of amine used. The gelation properties of these two-component systems were investigated using electron microscopy, FTIR spectroscopy, 1H NMR spectroscopy, differential scanning calorimetry (DSC), and both single-crystal and cast-film X-ray diffraction. Results of FTIR spectral analysis suggest salt formation during gelation. 1H NMR analysis of the gels indicates that the fatty acid chains are immobilized in the gel state and when the gel melts, these chains regain their mobility. Analysis of DSC data indicates that increase in the spacer length in the di-/oligomeric amine lowers the gel-melting temperature. Two of these gelator salts developed into crystals and structural details of such systems could be secured by single-crystal X-ray diffraction analysis. The structural information of the salts thus obtained was compared with the XRD data of the self-supporting films of those gels. Such analyses provided pertinent structural insight into the supramolecular interactions that prevail within these gelator assemblies. Analysis of the crystal structure confirmed that multilayered lamellar aggregates exist in the gel and it also showed that the three-dimensional ordering observed in the crystalline phase is retained in only one direction in the gel state. Finally, the hydrogel was used as a medium for the synthesis of silver nanoparticles. The nanoparticles were found to position themselves on the fibers and produced a long, ordered assembly of gel-nanoparticle composite.

Structure and properties of two component hydrogels comprising lithocholic acid and organic amines

We demonstrate the aptitude of supramolecular hydrogel formation using simple bile acid such as lithocholic acid in aqueous solution in the presence of various dimeric or oligomeric amines. By variation of the choice of the amines in such mixtures the gelation properties could be modulated. However, the replacement of lithocholic acid (LCA) by cholic acid or deoxycholic acid resulted in no hydrogel formation. FT-IR studies confirm that the carboxylate and ammonium residues of the two components are involved in the salt (ion-pair) formation. This promotes further assembly of the components reinforced by a continuous hydrogen bonded network leading to gelation. Electron microscopy shows the morphology of the internal organization of gels of two component systems which also depends significantly on the amine part. Variation of the amine component from the simple 1,2-ethanediamine (EDA) to oligomeric amines in such gels of lithocholic acid changes the morphology of the assembly from long one-dimensional nanotubes to three-dimensional complex structures. Single crystal X-ray diffraction analysis with one of the amine-LCA complexes suggested the motif of fiber formation where the amines interact with the carboxylate and hydroxyl moieties through electrostatic forces and hydrogen bonding. From small angle neutron scattering study, it becomes clear that the weak gel from LCA-EDA shows scattering oscillation due to the presence of non-interacting nanotubules while for gels of LCA with oligomeric amines the individual fibers come together to form complex three-dimensional organizations of higher length scale. The rheological properties of this class of two component system provide clear evidence that the flow behavior can be modulated varying the acid-amine ratio.

Carbon nanotube reinforced supramolecular gels with electrically conducting, viscoelastic and near-infrared sensitive properties

Pristine and long-chain functionalized single-walled carbon nanotubes (SWNTs) were incorporated successfully in supramolecular organogels formed by an all-trans tri(p-phenylenevinylene) bis-aldoxime to give rise to new nanocomposites with interesting mechanical, thermal and electrical properties. Variable-temperature UV-vis and fluorescence spectra reveal both pristine and functionalized SWNTs promote aggregation of the gelator molecules and result in quenching of the UV-vis and fluorescence intensity. Electron microscopy and confocal microscopy show the existence of a densely packed and directionally aligned fibrous network in the resulting nanocomposites. Differential scanning calorimetry (DSC) of the composites shows that incorporation of SWNTs increases the gel formation temperature. The DSC of the xerogels of 1-SWNT composites indicates formation of different thermotropic mesophases which is also evident from polarized optical microscopy. The reinforced aggregation of the gelators on SWNT doping was reflected in the mechanical properties of the composites. Rheology of the composites demonstrates the formation of a rigid and viscoelastic solid-like assembly on SWNT incorporation. The composites from gel-SWNTs were found to be semiconducting in nature and showed enhanced electrical conductivity compared to that of the native organogel. Upon irradiation with a near IR laser at 1064 nm for 5 min it was possible to selectively induce a gel-to-sol phase transition of the nanocomposites, while irradiation for even 30 min of the native organogel under identical conditions did not cause any gel-to-sol conversion.

Coexisting hydrophobic compartments through self-sorting in rod-like micelles of bisurea bolaamphiphiles.

Multiple, coexisting hydrophobic compartments have been created in water using molecular self-sorting among mixtures of bolaamphiphiles with differently spaced urea groups in their hydrophobic parts. The selective incorporation of bisurea functionalized fluorescent probes showed that different bolaamphiphiles form separate populations of rod-like micelles, which dynamically coexist in solution, each micelle binding to its correspondingly functionalized guests.

Controlling the Structure and Length of Self‐Synthesizing Supramolecular Polymers through Nucleated Growth and Disassembly

Directing self-assembly processes out-of-equilibrium to yield kinetically trapped materials with well-defined dimensions remains a considerable challenge. Kinetically controlled assembly of self-synthesizing peptide-functionalized macrocycles through a nucleation-growth mechanism is reported. Spontaneous fiber formation in this system is effectively shut down as most of the material is diverted into metastable non-assembling trimeric and tetrameric macrocycles. However, upon adding seeds to this mixture, well-defined fibers with controllable lengths and narrow polydispersities are obtained. This seeded growth strategy also allows access to supramolecular triblock copolymers. The resulting noncovalent assemblies can be further stabilized through covalent capture. Taken together, these results show that self-synthesizing materials, through their interplay between dynamic covalent bonds and noncovalent interactions, are uniquely suited for out-of-equilibrium self-assembly.

Synthesis and properties of novel nanocomposites made of single-walled carbon nanotubes and low molecular mass organogels and their thermo-responsive behavior triggered by near IR radiation

For the preparation of novel organogel–carbon nanotube nanocomposites, pristine single-walled carbon nanotubes (SWNT) were incorporated into physical gels formed by an L-alanine based low molecular mass organogelator (LMOG). The gelation process and the properties of the resulting nanocomposites were found to depend on the kind of SWNTs incorporated in the gels. With pristine SWNTs, only a limited amount could be dispersed in the organogels. Attempted incorporation of higher amounts of pristine SWNTs led to precipitation from the gel. To improve their solubility in the gel matrix, a variety of SWNTs functionalized with different aliphatic and aromatic chains were synthesized. Scanning electron microscope images of the nanocomposites showed that the texture and organization of the gel aggregates were altered upon the incorporation of SWNTs. The microstructures of the nanocomposites were found to depend on the kind of SWNTs used. Incorporation of functionalized SWNTs into the organogels depressed the sol to gel transition temperature, with the n-hexadecyl chain functionalized SWNTs being more effective than the n-dodecyl chain functionalized counterpart. Rheological investigations of pristine SWNT containing gels indicated that the flow of nanocomposites became resistant to applied stress at a very low wt% of SWNT incorporation. Again more effective control of flow behavior was achieved with functionalized SWNTs possessing longer hydrocarbon chains. This happens presumably via effective interdigitation of the pendant chains with the fatty acid amides of L-alanine in the gel assembly. Remarkably, using near IR laser irradiation at 1064 nm for a short duration (1 min) at room temperature, it was possible to selectively induce a gel-to-sol phase transition of the nanocomposites, while prolonged irradiation (30 min) of the organogel under identical conditions did not cause gel melting.

Choice of the End Functional Groups in Tri(p-phenylenevinylene) Derivatives Controls Its Physical Gelation Abilities†

New supramolecular organogels based on all-trans-tri(p-phenylenevinylene) (TPV) systems possessing different terminal groups, e.g., oxime, hydrazone, phenylhydrazone, and semicarbazone have been synthesized. The self-assembly properties of the compounds that gelate in specific organic solvents and the aggregation motifs of these molecules in the organogels were investigated using UV-vis, fluorescence, FT-IR, and 1H NMR spectroscopy, electron microscopy, differential scanning calorimetry (DSC), and rheology. The temperature variable UV-vis and fluorescence spectroscopy in different solvents clearly show the aggregation pattern of the self-assemblies promoted by hydrogen bonding, aromatic pi-stacking, and van der Waals interactions among the individual TPV units. Gelation could be controlled by variation in the number of hydrogen-bonding donors and acceptors in the terminal functional groups of this class of gelators. Also wherever gelation is observed, the individual fibers in gels change to other types of networks in their aggregates depending on the number of hydrogen-bonding sites in the terminal functions. Comparison of the thermal stability of the gels obtained from DSC data of different gelators demonstrates higher phase transition temperature and enthalpy for the hydrazone-based gelator. Rheological studies indicate that the presence of more hydrogen-bonding donors in the periphery of the gelator molecules makes the gel more viscoelastic solidlike. However, in the presence of more numbers of hydrogen-bonding donor/acceptors at the periphery of TPVs such as with semicarbazone a precipitation as opposed to gelation was observed. Clearly, the choice of the end functional groups and the number of hydrogen-bonding groups in the TPV backbone holds the key and modulates the effective length of the chromophore, resulting in interesting optical properties.

Role of Capping Ligands on the Nanoparticles in the Modulation of Properties of a Hybrid Matrix of Nanoparticles in a 2D Film and in a Supramolecular Organogel

We incorporate various gold nanoparticles (AuNPs) capped with different ligands in two-dimensional films and three-dimensional aggregates derived from N-stearoyl-L-alanine and N-lauroyl-L-alanine, respectively. The assemblies of N-stearoyl-L-alanine afforded stable films at the air-water interface. More compact assemblies were formed upon incorporation of AuNPs in the air-water interface of N-stearoyl-L-alanine. We then examined the effects of incorporation of various AuNPs functionalized with different capping ligands in three-dimensional assemblies of N-lauroyl-L-alanine, a compound that formed a gel in hydrocarbons. The profound influence of nanoparticle incorporation into physical gels was evident from evaluation of various microscopic and bulk properties. The interaction of AuNPs with the gelator assembly was found to depend critically on the capping ligands protecting the Au surface of the gold nanoparticles. Transmission electron microscopy (TEM) showed a long-range directional assembly of certain AuNPs along the gel fibers. Scanning electron microscopy (SEM) images of the freeze-dried gels and nanocomposites indicate that the morphological transformation in the composite microstructures depends significantly on the capping agent of the nanoparticles. Differential scanning calorimetry (DSC) showed that gel formation from sol occurred at a lower temperature upon incorporation of AuNPs having capping ligands that were able to align and noncovalently interact with the gel fibers. Rheological studies indicate that the gel-nanoparticle composites exhibit significantly greater viscoelasticity compared to the native gel alone when the capping ligands are able to interact through interdigitation into the gelator assembly. Thus, it was possible to define a clear relationship between the materials and the molecular-level properties by means of manipulation of the information inscribed on the NP surface.

Physical gelation of binary mixtures of hydrocarbons mediated by n-lauroyl-L-alanine and characterization of their thermal and mechanical properties.

Fatty acid amides, such as n-lauroyl-L-alanine, gelate both aliphatic and aromatic hydrocarbon solvents efficiently. In addition this compound is found to gelate the binary solvent mixtures comprised of aromatic hydrocarbon, e.g., toluene and aliphatic hydrocarbons, e.g., n-heptane. Scanning electron microscopy and atomic force microscopy show that the fiber thickness of the gel assembly increases progressively in the binary mixture of n-heptane and toluene with increasing percentage of toluene. The self-assembly patterns of the gels in individual solvents, n-heptane and toluene, are however different. The toluene gel consists of predominantly one type of morphological species, while n-heptane gel has more than one species leading to the polymorphic nature of the gel. The n-heptane gel is thermally more stable than the toluene gel as evident from the measurement using differential scanning calorimetry. The thermal stability of the gels prepared in the binary mixture of n-heptane and toluene is dependent on the composition of solvent mixture. Rheology of the gels shows that they are shear-thinning material and show characteristic behavior of soft viscoelastic solid. For the gels prepared from binary solvent mixture of toluene and n-heptane, with incorporation of more toluene in the binary mixture, the gel becomes a more viscoelastic solid. The time sweep rheology experiment demonstrates that the gel made in n-heptane has faster gel formation kinetics than that prepared in toluene.

Self-sorting in rodlike micelles of chiral bisurea bolaamphiphiles.

We have demonstrated the formation of segregated enantiomeric dynamic rods in water, from the self-sorting of chiral trans-1,2-bisureido cyclohexane-based bolaamphiphiles. Fluorescence probes have been used to investigate the self-sorting through forming exciplex and FRET.