Search Results (16)

This work reports on a novel family of silver metallogels based on discrete coordination complexes. Structurally, they consist of dendrimers containing a trinuclear silver metallacycle at the core, with the general formula [M(μ-pz)]₃, and poly(benzyl)ether branched structures with different numbers or terminal alkoxy chains at the periphery. These silver metallodendrimers are able to gel low-polarity solvents such as dodecane or cyclohexane, giving rise to luminescent organogels at room temperature with the property of aggregation-induced emission (AIE). This property means that in solution or the sol state, they are weak emitters, but in the gel state, luminescence is considerably increased. In this particular case, they exhibit blue luminescence. Two different dendritic scaffolds have been studied, finding significant differences in solubility, gel formation and dependence of luminescence on temperature. The results show that properly tailored silver gelators can show luminescence in the gel state. Full article

The incorporation of the metal phase into cellulose hydrogels, resulting in the formation of metallogels, greatly expands their application potential by introducing new functionalities and improving their performance in various fields. The unique antiviral, antibacterial, antifungal, and anticancer properties of metal and metal oxide nanoparticles (Ag, Au, Cu, Cu_xO_y, ZnO, Al₂O₃, TiO₂, etc.), coupled with the biocompatibility of cellulose, allow the development of composite hydrogels with multifunctional therapeutic potential. These materials can serve as efficient carriers for controlled drug delivery, targeting specific cells or pathogens, as well as for the design of artificial tissues or wound and burn dressings. Cellulose-based metallogels can be used in the food packaging industry to provide biodegradable and biocidal materials to extend the shelf life of the goods. Metal and bimetallic nanoparticles (Au, Cu, Ni, AuAg, and AuPt) can catalyze chemical reactions, enabling composite cellulose hydrogels to be used as efficient catalysts in organic synthesis. In addition, metal-loaded hydrogels (with ZnO, TiO₂, Ag, and Fe₃O₄ nanoparticles) can exhibit enhanced adsorption capacities for pollutants, such as dyes, heavy metal ions, and pharmaceuticals, making them valuable materials for water purification and environmental remediation. Magnetic properties imparted to metallogels by iron oxides (Fe₂O₃ and Fe₃O₄) simplify the wastewater treatment process, making it more cost-effective and environmentally friendly. The conductivity of metallogels due to Ag, TiO₂, ZnO, and Al₂O₃ is useful for the design of various sensors. The integration of metal nanoparticles also allows the development of responsive materials, where changes in metal properties can be exploited for stimuli-responsive applications, such as controlled release systems. Overall, the introduction of metal phases augments the functionality of cellulose hydrogels, expanding their versatility for diverse applications across a broad spectrum of industries not envisaged during the initial research stages. Full article

A visible-light-responsive arylazopyrazole-functionalized phenylalanine (4-MeS-AAP-NF) derived ligand was designed and synthesized, and it was found to form metallogels with reversible photo-responsive properties in mixed methanol/water (MeOH/H₂O) solvents. The gelation behavior of the 4-MeS-AAP-NF ligand in the presence of different divalent metal ions in mixed methanol/water (MeOH/H₂O) solvents at pH~11.60 was studied. It was found that the 4-MeS-AAP-NF ligand alone could not self-assemble to form any gels. However, in the presence of divalent metal ions, it readily formed the assembled metallogels in an alkaline aqueous/methanol solution with various morphologies. The results suggest that the gelation process was triggered by divalent metal ions. The presence of the AAP moiety in the gel matrix rendered the metallogel assemblies photo-responsive, and the reversible gel-to-sol phase transition was studied by UV-vis spectroscopy. The gels showed a slow, reversible visible-light-induced gel-to-sol phase transition under blue (λ = 405 nm) and then sol-to-gel transition by green light (λ = 530 nm) irradiation, resulting in the re-formation of the original gel state. The morphology and viscoelastic properties of the yellow–orange opaque metallogels were characterized by scanning electron microscopy (SEM) and rheological measurement, respectively. Full article

The design and development of new luminescent metallogels formed by cyclometalated palladium(II) complexes in protic solvents were investigated by a combination of differential scanning calorimetry (DSC), polarized optical microscopy (POM), and rheology. Cyclometalated palladium(II) complexes based on imine ligand and ancillary benzoylthiourea (BTU) ligand showed red emission in solid and gel states. The formation of a lyotropic liquid crystal phase was observed for the complex bearing shorter alkyl groups on the BTU ligand. This complex also behaved as a thermotropic liquid crystal that displays a monotropic smectic A phase (SmA). Dynamic rheology measurements (frequency sweep in the 5–90 °C range) of the 1-decanol solution of palladium(II) complexes highlighted their supramolecular self-association ability to generate 3D networks and form gels as a final result. Full article

Carbohydrate-derived molecular gelators have found many practical applications as soft materials. To better understand the structure and molecular gelation relationship and further explore the applications of sugar-based gelators, we designed and synthesized eight trimeric branched sugar triazole derivatives and studied their self-assembling properties. These included glucose, glucosamine, galactose, and maltose derivatives. Interestingly, the gelation properties of these compounds exhibited correlations with the peripheral sugar structures. The maltose derivative did not form gels in the tested solvents, but all other compounds exhibited gelation properties in at least one of the solvents. Glucose derivatives showed superior performance, followed by glucosamine derivatives. They typically formed gels in toluene and alcohols; some formed gels in ethanol-water mixtures or DMSO water mixtures. The glycoclusters 9 and 10 demonstrated rate acceleration for the copper-catalyzed azide-alkyne cycloaddition (CuAAC) reactions. These were further studied for their metallogels formation properties, and the copper metallogels from compound 9 were successfully utilized to catalyze click reactions. These metallogels were able to form a gel column, which was effective in converting the reactants into the triazole products in multiple cycles. Moreover, the same gel column was used to transform a second click reaction using different reactants. The synthesis and characterization of these compounds and their applications for catalytic reactions were discussed. Full article

Metallogels represent a class of composite materials in which a metal can be a part of the gel network as a coordinated ion, act as a cross-linker, or be incorporated as metal nanoparticles in the gel matrix. Cellulose is a natural polymer that has a set of beneficial ecological, economic, and other properties that make it sustainable: wide availability, renewability of raw materials, low-cost, biocompatibility, and biodegradability. That is why metallogels based on cellulose hydrogels and additionally enriched with new properties delivered by metals offer exciting opportunities for advanced biomaterials. Cellulosic metallogels can be either transparent or opaque, which is determined by the nature of the raw materials for the hydrogel and the metal content in the metallogel. They also exhibit a variety of colors depending on the type of metal or its compounds. Due to the introduction of metals, the mechanical strength, thermal stability, and swelling ability of cellulosic materials are improved; however, in certain conditions, metal nanoparticles can deteriorate these characteristics. The embedding of metal into the hydrogel generally does not alter the supramolecular structure of the cellulose matrix, but the crystallinity index changes after decoration with metal particles. Metallogels containing silver (0), gold (0), and Zn(II) reveal antimicrobial and antiviral properties; in some cases, promotion of cell activity and proliferation are reported. The pore system of cellulose-based metallogels allows for a prolonged biocidal effect. Thus, the incorporation of metals into cellulose-based gels introduces unique properties and functionalities of this material. Full article

Metallogels are a class of materials produced by the complexation of polymer gels with metal ions that can form coordination bonds with the functional groups of the gel. Hydrogels with metal phases attract special attention due to the numerous possibilities for functionalization. Cellulose is preferable for the production of hydrogels from economic, ecological, physical, chemical, and biological points of view since it is inexpensive, renewable, versatile, non-toxic, reveals high mechanical and thermal stability, has a porous structure, an imposing number of reactive OH groups, and good biocompatibility. Due to the poor solubility of natural cellulose, the hydrogels are commonly produced from cellulose derivatives that require multiple chemical manipulations. However, there is a number of techniques of hydrogel preparation via dissolution and regeneration of non-derivatized cellulose of various origins. Thus, hydrogels can be produced from plant-derived cellulose, lignocellulose and cellulose wastes, including agricultural, food and paper wastes. The advantages and limitations of using solvents are discussed in this review with regard to the possibility of industrial scaling up. Metallogels are often formed on the basis of ready-made hydrogels, which is why the choice of an adequate solvent is important for obtaining desirable results. The methods of the preparation of cellulose metallogels with d-transition metals in the present state of the art are reviewed. Full article

Recently, stimuli-responsive supramolecular gels have received significant attention because their properties can be modulated through external stimuli such as heat, light, electricity, magnetic fields, mechanical stress, pH, ions, chemicals and enzymes. Among these gels, stimuli-responsive supramolecular metallogels have shown promising applications in material science because of their fascinating redox, optical, electronic and magnetic properties. In this review, research progress on stimuli-responsive supramolecular metallogels in recent years is systematically summarized. According to external stimulus sources, stimuli-responsive supramolecular metallogels, including chemical, physical and multiple stimuli-responsive metallogels, are discussed separately. Moreover, challenges, suggestions and opportunities regarding the development of novel stimuli-responsive metallogels are presented. We believe the knowledge and inspiration gained from this review will deepen the current understanding of stimuli-responsive smart metallogels and encourage more scientists to provide valuable contributions to this topic in the coming decades. Full article

The nature of functional groups and their relative position and orientation play an important role in tuning the gelation properties of stimuli-responsive supramolecular gels. In this work, we synthesized and characterized mono-/bis-pyridyl-N-oxide compounds of N-(4-pyridyl)nicotinamide (L₁–L₃). The gelation properties of these N-oxide compounds were compared with the reported isomeric counterpart mono-/bis-pyridyl-N-oxide compounds of N-(4-pyridyl)isonicotinamide. Hydrogels obtained with L₁ and L₃ were thermally and mechanically more stable than the corresponding isomeric counterparts. The surface morphology of the xerogels of di-N-oxides (L₃ and diNO) obtained from the water was studied using scanning electron microscopy (SEM), which revealed that the relative position of N-oxide moieties did not have a prominent effect on the gel morphology. The solid-state structural analysis was performed using single-crystal X-ray diffraction to understand the key mechanism in gel formation. The versatile nature of N-oxide moieties makes these gels highly responsive toward an external stimulus, and the stimuli-responsive behavior of the gels in water and aqueous mixtures was studied in the presence of various salts. We studied the effect of various salts on the gelation behavior of the hydrogels, and the results indicated that the salts could induce gelation in L₁ and L₃ below the minimum gelator concentration of the gelators. The mechanical properties were evaluated by rheological experiments, indicating that the modified compounds displayed enhanced gel strength in most cases. Interestingly, cadmium chloride formed supergelator at a very low concentration (0.7 wt% of L₃), and robust hydrogels were obtained at higher concentrations of L₃. These results show that the relative position of N-oxide moieties is crucial for the effective interaction of the gelator with salts/ions resulting in LMWGs with tunable properties. Full article

The self-assembly of carbohydrate-based low molecular weight gelators has led to useful advanced soft materials. The interactions of the gelators with various cations and anions are important in creating novel molecular architectures and expanding the scope of the small molecular gelators. In this study, a series of thirteen new C-2 carbamates of the 4,6-O-phenylethylidene acetal-protected D-glucosamine derivatives has been synthesized and characterized. These compounds are rationally designed from a common sugar template. All carbamates synthesized were found to be efficient gelators and three compounds are also hydrogelators. The resulting gels were characterized using optical microscopy, atomic force microscopy, and rheology. The gelation mechanisms were further elucidated using ¹H NMR spectroscopy at different temperatures. The isopropyl carbamate hydrogelator 7 formed hydrogels at 0.2 wt% and also formed gels with several tetra alkyl ammonium salts, and showed effectiveness in the creation of gel electrolytes. The formation of metallogels using earth-abundant metal ions such as copper, nickel, iron, zinc, as well as silver and lead salts was evaluated for a few gelators. Using chemiluminescence spectroscopy, the metal–organic xerogels showed enzyme-like properties and enhanced luminescence for luminol. In addition, we also studied the applications of several gels for drug immobilizations and the gels showed sustained release of naproxen from the gel matrices. This robust sugar carbamate-derived gelator system can be used as the scaffold for the design of other functional materials with various types of applications. Full article

Carbohydrate-based low-molecular-weight gelators (LMWGs) are useful classes of compounds due to their numerous applications. Among sugar-based LMWGs, certain peracetylated sugar beta-triazole derivatives were found to be effective organogelators and showed interesting self-assembling properties. To further understand the structural influence towards molecular assemblies and obtain new functional materials with interesting properties, we designed and synthesized a library of tetraacetyl beta-1-triazolyl alkyl-D-glucosides and D-galactosides, in which a two or three carbon spacer is inserted between the anomeric position and the triazole moiety. A series of 16 glucose derivatives and 14 galactose derivatives were synthesized and analyzed. The self-assembling properties of these new triazole containing glycoconjugates in different solvents were analyzed. Several glucose derivatives were found to be effective LMWGs, with compound 7a forming gels in a variety of organic solvents as well as in the presence of metal ions in aqueous solutions. The organogels formed by several compounds were characterized using optical microscopy, atomic force microscopy (AFM) and UV-vis spectroscopy, etc. The co-gels formed by compound 7a with the Fmoc derivative 7i showed interesting fluorescence enhancement upon gelation. Several gelators were also characterized using powder X-ray diffraction and FT-IR spectroscopy. The potential applications of these sugar-based gelators for drug delivery and dye removal were also studied. Full article

Metal-ligand interactions have emerged as an important tool to trigger and modulate self-assembly, and to tune the properties of the final supramolecular materials. Herein, we report the metal-cation induced self-assembly of a pyrene–peptide conjugate to form hydrogels. The peptide has been rationally designed to favor the formation of β-sheet 1D assemblies and metal coordination through the Glu side chains. We studied in detail the self-assembly process in the presence of H⁺, Li⁺, Na⁺, K⁺, Ca²⁺, Ni²⁺, Cu²⁺, Zn²⁺, Cd²⁺, Co²⁺, Fe³⁺, and Cr³⁺ and found that the morphology and mechanical properties of the hydrogels are ion-dependent. Moreover, thanks to the presence of the metal, new applications could be explored. Cu²⁺ metallogels could be used for amine sensing and meat freshness monitoring, while Zn²⁺ metallogels showed good selectivity for cationic dye adsorption and separation. Full article

The development of supramolecular systems showing aurophilic interactions in solution is gaining much attention in the last years. This is due to the intriguing photophysical properties of gold(I) complexes, which usually confer to these supramolecular assemblies interesting luminescent properties, as well as the possibility of morphological modulation, through fine tuning of inter- and intramolecular aurophilic interactions, in synergy with the formation of other supramolecular contacts. In this work, an overview of the advances made in this area since 2015 is presented. A large variety of systems showing different spectroscopical and structural topologies has been reported. Moreover, these supramolecular assemblies have proven to be useful in a wide range of applications. Full article

Carbohydrate based low molecular weight gelators have been an intense subject of study over the past decade. The self-assembling systems built from natural products have high significance as biocompatible materials and renewable resources. The versatile structures available from naturally existing monosaccharides have enriched the molecular libraries that can be used for the construction of gelators. The bottom-up strategy in designing low molecular weight gelators (LMWGs) for a variety of applications has been adopted by many researchers. Rational design, along with some serendipitous discoveries, has resulted in multiple classes of molecular gelators. This review covers the literature from 2017–2020 on monosaccharide based gelators, including common hexoses, pentoses, along with some disaccharides and their derivatives. The structure-based design and structure to gelation property relationships are reviewed first, followed by stimuli-responsive gelators. The last section focuses on the applications of the sugar based gelators, including their utilization in environmental remediation, ion sensing, catalysis, drug delivery and 3D-printing. We will also review the available LMWGs and their structure correlations to the desired properties for different applications. This review aims at elucidating the design principles and structural features that are pertinent to various applications and hope to provide certain guidelines for researchers that are working at the interface of chemistry, biochemistry, and materials science. Full article

In this article, we review a dynamic covalent gel system developed as a high temperature well construction fluid. The key gel/fluid phase changes and related materials properties are addressable via the constitutional and coordination dynamics of the equilibrium and non-equilibrium molecular species comprising the material. The interplay between these species and external stimuli leads to material adaptability. Specifically, the introduction of metal ions into a non-equilibrium hemiaminal gel reverts this phase into a non-equilibrium liquid. When heated, this liquid transforms itself catalytically into the thermodynamically favoured closed-ring polyhexahydrotriazine (PHT) gel product. The temperature stability of different PHT gel formulations is evaluated as a function of the inclusion of various salts. It is possible to revert this thermodynamic PHT gel back into a liquid. This pH dependent transformation depends on the R groups linking the hexahydrotriazines (HTs) to one another. While polyethylene glycol (PEG) based PHT gels revert to liquids with water and mild protonation conditions, in comparison, polypropylene glycol (PPG) based gels require stronger acid conditions with heat, or a different more nucleophilically driven ring-opening mechanism by, for example, phosphines. The covalent dynamic chemistry in this chemical system gives way to many possible applications in addition to the high temperature solution-gelation (sol-gels) for which it has been primarily designed. Full article