Low Molecular Weight Gelators Research Articles

Fabricating Shaped and Patterned Supramolecular Multigelator Objects via Diffusion-Adhesion Gel Assembly.

We report the use of acid-diffusion to assemble core-shell supramolecular gel beads with different low-molecular-weight gelators (LMWGs) in the core and shell. These gel beads grow a shell of dibenzylidenesorbitol-based DBS-COOH onto a core comprising DBS-CONHNH2 and agarose that has been loaded with acetic acid. Diffusion of the acid from the core triggers shell assembly. The presence of DBS-CONHNH2 enables the gel core to be loaded with metal nanoparticles (NPs) as acyl hydrazide reduces metal salts in situ. The pH-responsiveness of DBS-COOH allows responsive assembly of the shell with both temporal and spatial control. By fixing multiple gel beads in a Petri dish, the cores become linked to one another by the assembled DBS-COOH gel shell─a process we describe as diffusion-adhesion assembly. By controlling the geometry of the beads with respect to one another, it is possible to pattern the structures, and using a layer-by-layer approach, 3D objects can be fabricated. If some of the beads are loaded with basic DBS-carboxylate instead of CH3COOH, they act as a "sink" for diffusing protons, preventing DBS-COOH shell assembly in the close proximity. Those beads do not adhere to the remainder of the growing gel object and can be simply removed once diffusion-assembly is complete, acting as templates, and enabling the fabrication of 3D "imprinted" multigel architectures. Preloading the gel beads with AuNPs or AgNPs suspends these functional units within the cores at precisely defined locations within a wider gel object. In summary, this approach enables the dynamic fabrication of shaped and patterned gels with embedded metal NPs─such objects have potential next-generation applications in areas including soft nanoelectronics and regenerative medicine.

Scratch‐Resistant Hydrophobic Coating with Supramolecular‐Polymer Co‐Assembly

AbstractSupramolecular assembly for superhydrophobic coatings is known for its efficiency and efficacy. However, the mechanical fragility of the coatings limits their use as coating materials. Herein, the combination of (±)‐N,N'‐(trans‐cyclohexane‐1,2‐diyl)‐bis(perfluorooctanamide) CF7, a cyclohexyl diamide‐based low molecular weight gelator, with acrylate polymers for the generation of semi‐transparent omniphobic coatings with significantly enhanced scratch proofness is presented. CF7 has shown the ability to self‐assemble in common solvents into highly entangled fibrous networks with extreme water repellency. The incorporation of covalent polymers, specifically poly(methyl methacrylate) (PMMA) and poly(trifluoroethyl methacrylate) (PTFEMA), helps to fixate the supramolecular CF7 fibers without interfering with the self‐assembled structures. The resulting coatings, namely CF7/PMMA and CF7/PTFEMA, show significantly improved mechanical resistance as well as optical transparency while maintaining excellent water and oil repellency. Furthermore, the homogeneity of the coating in bulk is confirmed by depth profiling of the 3D distribution of the components using time‐of‐flight secondary ion mass spectrometry imaging, which turns out to be an essential technique in order to characterize such materials.

Amine-rich Nickel(II)-Xerogel as a Highly Active Bifunctional Metallo-organo Catalyst for Aqueous Knoevenagel Condensation and Solvent-free CO2 Cycloaddition.

Metallogels formed from supramolecular interactions of low-molecular-weight gelators (LMWGs) combine the qualities of heterogeneous catalysts and offer the advantages of multifunctionality owing to the facile installation of desired task-specific moieties on the surface and along the channels of the gels. We discuss the applications of a triazole-based Ni(II) gel-derived xerogel (NiXero) having a high density of Ni(II)-nodes and appended primary amines as a recyclable heterogeneous catalyst for Knoevenagel condensation of aldehyde and malononitrile in water and the solvent-free cycloaddition of CO2 to form a series of cyclic carbonates with near-quantitative conversion of the respective epoxides, with low catalyst loading (0.59 mol %), high catalyst stability, and recyclability. The structural advantages of NiXero, due to the concurrent presence of bifunctional Lewis acid-base sites on the channels, open Ni(II) nodes, Ntriazole, pendant -NH2 and its chemical stability, are conducive to the cooperative heterogeneous catalytic activity under mild conditions. This work emphasizes the effective amalgamation of metals with purpose-built ligand systems for the construction of metallogels and their utility as heterogeneous catalysts for desired organic transformations.

Development of Gelled-Oil Nanoparticles for the Encapsulation and Release of Berberine.

In this study, a new drug carrier based on gelled-oil nanoparticles (GNPs) was designed and synthesized for the encapsulation and release of the model hydrophobic drug, berberine chloride (BCl). Two compositions with different oil phases were examined, sesame oil (SO) and cinnamaldehyde (Cin), which were emulsified with water, stabilized with Tween 80 (Tw80), and gelled using an N-alkylated primary oxalamide low-molecular-weight gelator (LMWG) to give stable dispersions of GNPs between 100 and 200 nm in size. The GNP formulation with Cin was significantly favored over SO due to (1) lower gel melting temperatures, (2) higher gel mechanical strength, and (3) significantly higher solubility, encapsulation efficiency, and loading of BCl. Also, the solubility and loading of BCl in Cin were significantly increased (at least 7-fold) with the addition of cinnamic acid. In vitro release studies showed that the release of BCl from the GNPs was independent of gelator concentration and lower than that for BCl solution and the corresponding nanoemulsion (no LWMG). Also, cell internalization studies suggested that the N-alkylated primary oxalamide LMWG did not interfere with the internalization efficiency of BCl into mouse mast cells. Altogether, this work demonstrates the potential use of these new GNP formulations for biomedical studies involving the encapsulation of drugs and nutraceuticals and their controlled release.

A semiconducting supramolecular novel Co(II)-metallogel based on 5-aminoisophthalic acid gelator: Toward efficient microelectronic device application

A novel ultrasonication method was successfully employed to prepare a metallogel using 5-aminoisophthalic acid as a low molecular weight gelator and cobalt(II)-acetate in N,N-dimethyl formamide at room temperature. Mechanical properties were analyzed through rheological analysis, microstructure through scanning electron microscopy and EDX mapping, and formation strategy via FT-IR and Raman spectroscopy. Crystalline nature was confirmed by PXRD analysis. The gel exhibited a strong semiconducting nature, supported by optical band gap estimation, electronic device characterization, and charge carrier mobility assessment. Remarkably high electron mobility, potentially surpassing reported metallogels, was observed.

Effect of Imposing Spatial Constraints on Low Molecular Weight Gels.

We outline the effect of imposing spatial constraints during gelation on hydrogels formed by dipeptide-based low molecular weight gelators. The gels were formed via either a solvent switch or a change in pH and formed in different sized vessels to produce gels of different thickness while maintaining the same volume. The different methods of gelation led to gels with different underlying microstructure. Confocal microscopy was used to visualize the resulting microstructures, while the corresponding mechanical properties were probed via cavitation rheology. We show that solvent-switch-triggered gels are sensitive to imposed spatial constraints, in both altered microstructure and mechanical properties, while their pH-triggered equivalents are not. These results are significant because it is often necessary to form gels of different thicknesses for different analytical techniques. Also, gels of different thicknesses are utilized between various applications of these materials. Our data show that it is important to consider the spatial constraints imposed in these situations.

Hydrogel Nanocomposite Towards Optical Sensing of Spermine in Biomedical and Real-Life Food Samples and Remediation of Toxic Dyes from Wastewater.

Nanocomposites such as graphene oxide (GO) have been incorporated into hydrogels to enhance conventional hydrogels' properties and develop new functions. Unique and strong molecular interactions between GO and low molecular weight gelators allow the fabrication of various functional hydrogels suitable for different applications. In the present study, we report a stable and soft nanocomposite hydrogel comprising a pyrene-based chiral amphipath having an amino acid (l-phenylalanine) core with pendant oligo-oxyethylene hydrophilic chains and GO. The mechanical and viscoelastic properties of the nanocomposite hydrogel were thoroughly studied using various spectroscopic, microscopic, and mechanical techniques. Even without GO, native hydrogels could form a self-supported thermoreversible and thixotropic hydrogel composed of the fibrillar network. Unlike native hydrogels, the morphological investigation of nanocomposite gels shows the presence of cross-linked nanosheet-like structures. The combined effect of π-π stacking and H-bonding interactions is the driving force for the formation of such composite hydrogels. Moreover, the nanocomposite hydrogels possess significantly superior mechanical stiffness than the native hydrogels. Interestingly, the thixotropic properties observed with the parent gel were retained even in the presence of carbon nanomaterials (GO). The nanocomposite hydrogel could be employed in the optical sensing of a biogenic polyamine, spermine, resulting in a visible gel-to-sol transition. The superior electrostatic interaction between the GOs and spermine molecules might have led to the release of entrapped fluorogenic dyes from the hydrogel network and a turn-on emission response. The sensory system was employed to analyze spermine content in human urine samples and decomposed food items. A gel-coated paper strip was also developed for onsite detection of the spermine. The nanocomposite hydrogel was further utilized to remove toxic organic dyes such as methylene blue (MB) and rhodamine B (RhB) from the aqueous media. The nanocomposite hydrogel thus showed excellent dye removal capabilities and was also found to be recyclable. Calculations of different mechanical parameters suggest that the dye removal efficiency of the nanocomposite hydrogel was better for MB than for RhB.

Gelation properties of amino-acid-based bis-urea compounds in organic solvents and in the presence of surfactants

ABSTRACT Self-assembled systems based on low-molecular-weight gelators (LMWGs) and micelle-forming surfactants are stabilized by non-covalent and non-interfering interactions. The simultaneous self-assembly of LMWGs and surfactants in a solution could lead to the formation of fibrillar networks with encapsulated surfactant micelles. In this study, the gelation properties of amino-acid-derived low-molecular-weight bis-urea compounds in water, various organic solvents, and surfactant solutions, including anionic surfactants sodium dodecyl sulfate and dodecylbenzene sulfonic acid, cationic surfactant cetrimonium bromide, and nonionic surfactants polysorbate 80 and octyl-β-d-glucopyranoside, were investigated. In the presence of surfactants, the nature of the linker of the bis-urea compounds influences the aggregation between gelator molecules. Compounds with cyclic and aromatic linkers effectively form gels at surfactant concentrations above a critical micelle concentration (CMC). The different fiber morphologies observed for surfactant gels based on imaging analysis suggest that the structure of the bis-urea compounds influences self-assembly. Rheological measurements revealed the solid-like nature of the gels and their high thermal stability. The viscoelastic nature of the surfactant gels offers potential use in various commercial applications, including home care products.

Synthesis and application of chalcone derivative organogels

A series of novel naphthalene-chalcone gelators, Gb1–6, with different alkyl units, were designed and synthesized as potential low molecular weight gelators. The prepared gelators demonstrated gelation behavior in various organic solvents and fuel phases. The results indicated that the alkyl chains played a significant role in the gelation behavior of the gelators. The thermal stability results revealed that, at the same concentration, an increase in the length of the alkyl chains of the gelators led to an increase in the gel-sol transition temperature. The gelators were subjected to FT-IR, SEM, and XRD analysis, which demonstrated the presence of π-π stacking, van der Waals forces, and hydrogen bonding during the self-assembly process of the gel. UV–visible absorption and emission spectroscopy of the gelators were also studied, and it was discovered that gelators Gb2 and Gb5 exhibited a minimum detection limit of 0.28 μM and 0.16 μM, respectively, for hydrazine hydrate. Additionally, the gel was utilized for the recovery of oil from oil-water mixtures and for the identification of fuel adulteration.

Instantaneous Gelation of a Self-Healable Wide-Bandgap Semiconducting Supramolecular Mg(II)-Metallohydrogel: An Efficient Nonvolatile Memory Design with Supreme Endurance

An efficient strategy for room-temperature, atmospheric-pressure synthesis of a supramolecular metallohydrogel of the Mg(II) ion, i.e., Mg@3AP, using the metal-coordinating organic ligand 3-amino-1-propanol as a low-molecular-weight gelator (LMWG) in a water medium has been developed. Through a rheological analysis, we looked into the mechanical properties of the supramolecular Mg(II)-metallohydrogel. The self-healing nature of the metallohydrogel is confirmed along with the thixotropic characteristics. Investigation using field emission scanning electron microscopy revealed the hierarchical network of the supramolecular metallohydrogel. The EDX elemental mapping confirms the primary chemical constituents of the metallohydrogel. The possible metallohydrogel formation strategy has been analyzed through FT-IR spectroscopic studies. In this work, Schottky diode structures in a metal–semiconductor–metal geometry structures based on a magnesium(II) metallohydrogel (Mg@3AP) have been constructed, and charge transport behavior has been observed. Furthermore, here, it is demonstrated that the resistive random access memory (RRAM) device based on Mg@3AP exhibits bipolar resistive switching behavior at room temperature and ambient conditions. We have also looked into the switching mechanism through the formation (rupture) of conductive filaments between the metal electrodes to understand the process of resistive switching behavior. With a high on/off ratio (∼100), this RRAM device exhibits remarkable switching endurance over 10,000 switching cycles. These structures are suitable for use in nonvolatile memory design, neuromorphic computing, flexible electronics, and optoelectronics, among other fields, due to their simple fabrication procedures, reliable resistive switching behavior, and stability of the current system.

Grafted polymeric organogel using low molecular weight gelator as an effective medium for expulsion and purification of cationic dyes and organic pollutants from contaminated surface water

An increase in water pollution is a major concern for the safety of living organisms. The present work revolves around synthesizing an organogel capable of absorbing contaminated pollutants like solvents and removing cationic dyes from water surfaces. The organogel prepared using a LMWG (low molecular weight gelator) was characterized using FT-IR, SEM, NMR, TGA, and XRD spectra. Water contact angle determination was also carried out to observe the hydrophobicity. Swelling kinetics, adsorption isotherm, and intra-particle diffusion model are reported after the respective absorption and adsorption study by the gel. The highest swelling was observed in Acetic acid with swelling of 10 times its original weight. Adsorption of dyes exhibited the highest removal efficiency of 99.35% within 60 min. The organogel holds the capability to reuse dye solutions for up to 10 cycles while also holding the capacity to remove from a binary mixture of dyes. The prepared organogel serves as a potential adsorbent for environmental remediation with the potential of maximum swelling and selectivity for cationic dyes.

Para-Methoxybenzylidene Acetal-Protected D-Glucosamine Derivatives as pH-Responsive Gelators and Their Applications for Drug Delivery.

Carbohydrate-based low molecular weight gelators (LMWGs) are compounds with the capability to self-assemble into complex molecular networks within a solvent, leading to solvent immobilization. This process of gel formation depends on noncovalent interactions, including Van der Waals, hydrogen bonding, and π-π stacking. Due to their potential applications in environmental remediation, drug delivery, and tissue engineering, these molecules have emerged as an important area of research. In particular, various 4,6-O-benzylidene acetal-protected D-glucosamine derivatives have shown promising gelation abilities. In this study, a series of C-2-carbamate derivatives containing a para-methoxy benzylidene acetal functional group were synthesized and characterized. These compounds exhibited good gelation properties in several organic solvents and aqueous mixtures. Upon removal of the acetal functional group under acidic conditions, a number of deprotected free sugar derivatives were also synthesized. Analysis of these free sugar derivatives revealed two compounds were hydrogelators while their precursors did not form hydrogels. For those protected carbamates that are hydrogelators, removal of the 4,6-protection will result in a more water-soluble compound that produces a transition from gel to solution. Given the ability of these compounds to form gels from solution or solution from gels in situ in response to acidic environments, these compounds may have practical applications as stimuli-responsive gelators in an aqueous medium. In turn, one hydrogelator was studied for the encapsulation and release of naproxen and chloroquine. The hydrogel exhibited sustained drug release over a period of several days, with the release of chloroquine being faster at lower pH due to the acid lability of the gelator molecule. The synthesis, characterization, gelation properties, and studies on drug diffusion are discussed.

Mixed Conductive, Injectable, and Fluorescent Supramolecular Eutectogel Composites.

Eutectogels are an emerging family of soft ionic materials alternative to ionic liquid gels and organogels, offering fresh perspectives for designing functional dynamic platforms in water-free environments. Herein, the first example of mixed ionic and electronic conducting supramolecular eutectogel compositesis reported. A fluorescent glutamic acid-derived low-molecular-weight gelator (LMWG) was found to self-assemble into nanofibrillar networks in deep eutectic solvents (DES)/ poly(3,4-ethylenedioxythiophene) (PEDOT): chondroitin sulfate dispersions. These dynamic materials displayed excellent injectability and self-healing properties, high ionic conductivity (up to 10-2 S cm-1), good biocompatibility, and fluorescence imaging ability. This set of features turns the mixed conducting supramolecular eutectogels into promising adaptive materials for bioimaging and electrostimulation applications.

Mixed Conductive, Injectable, and Fluorescent Supramolecular Eutectogel Composites

AbstractEutectogels are an emerging family of soft ionic materials alternative to ionic liquid gels and organogels, offering fresh perspectives for designing functional dynamic platforms in water‐free environments. Herein, the first example of mixed ionic and electronic conducting supramolecular eutectogel composites is reported. A fluorescent glutamic acid‐derived low‐molecular‐weight gelator (LMWG) was found to self‐assemble into nanofibrillar networks in deep eutectic solvents (DES)/poly(3,4‐ethylenedioxythiophene) (PEDOT): chondroitin sulfate dispersions. These dynamic materials displayed excellent injectability and self‐healing properties, high ionic conductivity (up to 10−2 S cm−1), good biocompatibility, and fluorescence imaging ability. This set of features turns the mixed conducting supramolecular eutectogels into promising adaptive materials for bioimaging and electrostimulation applications.

Dielectric Study on Supramolecular Gels by Fiber Structure Formation from Low-Molecular-Weight Gelator/Water Mixtures.

There are various types of gel materials used in a wide range of fields, and their gelation mechanisms are extremely diverse. Furthermore, in the case of hydrogels, there exist some difficulties in understanding complicated molecular mechanisms especially with water molecules interacting through hydrogen bonding as solvents. In the present work, the molecular mechanism of the structural formation of fibrous super-molecular gel by the low molecular weight gelator, N-oleyl lactobionamide/water mixture was elucidated using the broadband dielectric spectroscopy (BDS) method. The dynamic behaviors observed for the solute and water molecules indicated hierarchical structure formation processes in various time scales. The relaxation curves obtained at various temperatures in the cooling and heating processes showed relaxation processes respectively reflecting the dynamic behaviors of water molecules in the 10 GHz frequency region, solute molecules interacting with water in MHz region, and ion-reflecting structures of the sample and electrode in kHz region. These relaxation processes, characterized by the relaxation parameters, showed remarkable changes around the sol-gel transition temperature, 37.8 °C, determined by the falling ball method and over the temperature range, around 53 °C. The latter change suggested a structure formation of rod micelles appearing as precursors before cross-linking into the three-dimensional network of the supramolecular gels. These results clearly demonstrate how effective relaxation parameter analysis is for understanding the gelation mechanism in detail.

Photothermal Perylene Bisimide Hydrogels.

Gels formed using a perylene bisimide (PBI) as a low molecular weight gelator can show the photothermal effect. Formation of the PBI radical anion results in new absorption bands forming, meaning that subsequent irradiation with a wavelength of light overlapping with the new absorption band leads to heating of the gel. This approach can be used to heat the gel, as well as the surrounding milieu. We show how we can use electrochemical methods as well as multicomponent systems to form the radical anion without the need for UV light, and how we can use the photothermal effect to induce phase transitions in the solutions above the gels by exploiting photothermal behavior.

Using Solution History to Control Hydrogel Properties of a Perylene Bisimide.

pH dependence on water soluble aggregates is well-known in the field of low molecular weight gelators (LMWGs), with different aggregates sometimes having very different properties depending on their final pH. This aggregation determines their applications and performance. Here, we investigate the pH dependence of perylene bisimide gels; initially solutions are formed at a high pH and gels form as the pH is decreased. We find it is not only the final pH but also the starting pH that can impact the resulting gel. We use small angle neutron scattering (SANS), rheology, 1 H NMR spectroscopy and absorption spectroscopy to examine the effect of starting pH on gelation kinetics and final gel properties. Adjusting the solution from pH 9 (where there are few or no aggregates) to pH 6 results in the formation of different worm-like micelles than the ones directly formed at pH 6, leading to again gels with different mechanical properties. This work highlights the importance of controlling the pH of solutions before gelation, but also opens up more possible morphologies and therefore more properties from the same molecule.

Gelled lyotropic nematic liquid crystals

ABSTRACT Lyotropic liquid crystal gels (LLC gels) are versatile materials which combine the anisotropy of a liquid crystal with the mechanical stability of a gel. We succeeded in gelling the rare calamitic nematic NC phase of two different micellar LLC systems with the low molecular weight gelator (LMWG) 3,5-bis-(5-hexylcarbamoyl-pentoxy)-benzoic acid hexyl ester (BHPB-6). The systems of choice are: (1) a binary LLC system with the surfactant N,N-dimethyl-N-ethyl-1-hexadecylammonium bromide (CDEAB) and water; (2) a ternary LLC system with the surfactant N,N,N-trimethyl-N-tetradecylammonium bromide (C14TAB), n-decanol, and water. The obtained gels show optical birefringence and no macroscopic flow. Freeze fracture electron microscopy (FFEM) images show ribbon-like gel fibres that form the gel network and can stack into thicker bundles, while small-angle X-ray scattering (SAXS) confirms the coexistence of the nematic NC phase and the gel network. The growth of the gel network was monitored with time-resolved SAXS measurements. Additionally, significant gel ageing effects were observed in rheology measurements, showing that the gel strengthens with time. With this study, we considerably broaden the pool of available surfactant-based LLC gels and pave a way to macroscopically aligned LLC gels with the goal to apply them as stimuli-responsive actuators and sensors.

Molecular dynamics study of low molecular weight gel forming salt-triggered dipeptide

Molecular dynamics simulation method was used to study the aggregation of Na and Ca salts in different concentrations of Naphthalene-dipeptide (2NapFF) solutions. The results show that high-valence Ca2+ triggers the formation of a gel at a certain dipeptide concentration, and the low-valence Na+ system follows the aggregation law of general surfactants. The results also show that hydrophobic and electrostatic forces are the main driving forces for the formation of dipeptide aggregates, and that hydrogen bonds do not play a major role in the formation of dipeptide solution aggregates. Hydrophobic and electrostatic effects are the main driving forces for the formation of gels in dipeptide solutions triggered by Ca2+. Electrostatic attraction drives Ca2+ to form a weak coordination with four oxygen atoms on two carboxyl groups, which causes the dipeptide molecules to form a gel with a branched network structure.

Correlation between Physical Properties of 12-Hydroxystearic Acid Organogels and Hansen Solubility Parameters.

The Hansen solubility parameter (HSP) is a useful index for reasoning the gelation behavior of low-molecular-weight gelators (LMWGs). However, the conventional HSP-based methods only "classify" solvents that can and cannot form gels and require many trials to achieve this. For engineering purposes, quantitative estimation of gel properties using the HSP is highly desired. In this study, we measured critical gelation concentrations based on three distinct definitions, mechanical strength, and light transmittance of organogels prepared with 12-hydroxystearic acid (12HSA) and correlated them with the HSP of solvents. The results demonstrated that the mechanical strength, in particular, strongly correlated with the distance of 12HSA and solvent in the HSP space. Additionally, the results indicated that the constant volume-based concentration should be used when comparing the properties of organogels to a different solvent. These findings are helpful in efficiently determining the gelation sphere of new LMWGs in HSP space and contribute to designing organogels with tunable physical properties.