Synergistic Coassembly of Folic Acid-Based Supramolecular Polymer with a Covalent Polymer Toward Fabricating Functional Antibacterial Biomaterials.

Supramolecular biomaterials can recapitulate the structural and functional facets of the native extracellular matrix and react to biochemical cues, leveraging the unique attributes of noncovalent interactions, including reversibility and tunability. However, the low mechanical properties of supramolecular biomaterials can restrict their utilization in specific applications. Combining the advantages of supramolecular polymers with covalent polymers can lead to the fabrication of tailor-made biomaterials with enhanced mechanical properties/degradability. Herein, we demonstrate a synergistic coassembled self-healing gel as a multifunctional supramolecular material. As the supramolecular polymer component, we chose folic acid (vitamin B9), an important biomolecule that forms a gel comprising one-dimensional (1D) supramolecular polymers. Integrating polyvinyl alcohol (PVA) into this supramolecular gel alters its ultrastructure and augments its mechanical properties. A drastic improvement of complex modulus (G*) (∼3674 times) was observed in the folic acid-PVA gel with 15% w/v PVA (33215 Pa) compared with the folic acid gel (9.04 Pa). The coassembled hydrogels possessed self-healing and injectable/thixotropic attributes and could be printed into specific three-dimensional (3D) shapes. Synergistically, the supramolecular polymers of folic acid also improve the toughness, durability, and ductility of the PVA films. A nanocomposite of the gels with silver nanoparticles exhibited excellent catalytic efficiency and antibacterial activity. The folic acid-PVA coassembled gels and films also possessed high cytocompatibility, substantiated by the 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide (MTT) and live-dead assays. Taken together, the antibacterial and cell-adhesive attributes suggest potential applications of these coassembled biomaterials for tissue engineering and wound healing.

Injectable hydrogel based on liposome self-assembly for controlled release of small hydrophilic molecules.

Controlled release of low molecular weight hydrophilic drugs, administered locally, allows maintenance of high concentrations at the target site, reduces systemic side effects, and improves patient compliance. Injectable hydrogels are commonly used as a vehicle. However, slow release of low molecular weight hydrophilic drugs is very difficult to achieve, mainly due to a rapid diffusion of the drug out of the drug delivery system. Here we present an injectable and self-healing hydrogel based entirely on the self-assembly of liposomes. Gelation of liposomes, without damaging their structural integrity, was induced by modifying the cholesterol content and surface charge. The small hydrophilic molecule, sodium fluorescein, was loaded either within the extra-liposomal space or encapsulated into the aqueous cores of the liposomes. This encapsulation strategy enabled the achievement of controlled and adjustable release profiles, dependent on the mechanical strength of the gel. The hydrogel had a high mechanical strength, minimal swelling, and slow degradation. The liposome-based hydrogel had prolonged mechanical stability in vivo with benign tissue reaction. This work presents a new class of injectable hydrogel that holds promise as a versatile drug delivery system. STATEMENT OF SIGNIFICANCE: The porous nature of hydrogels poses a challenge for delivering small hydrophilic drug, often resulting in initial burst release and shorten duration of release. This issue is particularly pronounced with physically crosslinked hydrogels, since their matrix can swell and dissipate rapidly, but even in cases where the polymers in the hydrogel are covalently cross-linked, small molecules can be rapidly released through its porous mesh. Here we present an injectable self-healing hydrogel based entirely on the self-assembly of liposomes. Small hydrophilic molecules were entrapped inside the extra-liposomal space or loaded into the aqueous cores of the liposomes, allowing controlled and tunable release profiles.

A repertoire of nanoengineered short peptide-based hydrogels and their applications in biotechnology.

Peptide nanotechnology has currently bridged the gap between materials and biological worlds. Bioinspired self-assembly of short-peptide building blocks helps take the leap from molecules to materials by taking inspiration from nature. Owing to their intrinsic biocompatibility, high water content, and extracellular matrix mimicking fibrous morphology, hydrogels engineered from the self-assembly of short peptides exemplify the actualization of peptide nanotechnology into biomedical products. However, the weak mechanical property of these hydrogels jeopardizes their practical applications. Moreover, their functional diversity is limited since they comprise only one building block. Nanoengineering the networks of these hydrogels by incorporating small molecules, polymers, and inorganic/carbon nanomaterials can augment the mechanical properties while retaining their dynamic supramolecular nature. These additives interact with the peptide building blocks supramolecularly and may enhance the branching of the networks via coassembly or crystallographic mismatch. This phenomenon expands the functional diversity of these hydrogels by synergistically combining the attributes of the individual building blocks. This review highlights such nanoengineered peptide hydrogels and their applications in biotechnology. We have included exemplary works on supramolecular modification of the peptide hydrogel networks by integrating other small molecules, synthetic/biopolymers, conductive polymers, and inorganic/carbon nanomaterials and shed light on their various utilities focusing on biotechnology. We finally envision some future prospects in this highly active field of research.

Exploiting Minimalistic Backbone Engineered γ-Phenylalanine for the Formation of Supramolecular Co-Polymer.

Ordered supramolecular hydrogels assembled by modified aromatic amino acids often exhibit low mechanical rigidity. Aiming to stabilize the hydrogel and understand the impact of conformational freedom and hydrophobicity on the self-assembly process, two building blocks based on 9-fluorenyl-methoxycarbonyl-phenylalanine (Fmoc-Phe) gelator which contain two extra methylene units in the backbone, generating Fmoc-γPhe and Fmoc-(3-hydroxy)-γPhe are designed. Fmoc-γPhe spontaneously assembled in aqueous media forming a hydrogel with exceptional mechanical and thermal stability. Moreover, Fmoc-(3-hydroxy)-γPhe, with an extra backbone hydroxyl group decreasing its hydrophobicity while maintaining some molecular flexibility, self-assembled into a transient fibrillar hydrogel, that later formed microcrystalline aggregates through a phase transition. Molecular dynamics simulations and single crystal X-ray analyses reveal the mechanism underlying the two residues' distinct self-assembly behaviors. Finally, Fmoc-γPhe and Fmoc-(3-OH)-γPhe co-assembly to form a supramolecular hydrogel with notable mechanical properties are demonstrated. It has been believed that the understanding of the structure-assembly relationship will enable the design of new functional amino acid-based hydrogels.

Molecular Co-Assembly of Two Building Blocks Harnesses Both their Attributes into a Functional Supramolecular Hydrogel.

Engineering ordered nanostructures through molecular self-assembly of simple building blocks constitutes the essence of modern nanotechnology to develop functional supramolecular biomaterials. However, the lack of adequate chemical and functional diversity often hinders the utilization of unimolecular self-assemblies for practical applications. Co-assembly of two different building blocks can essentially harness both of their attributes and produce nanostructured macro-scale objects with improved physical properties and desired functional complexity. Herein, the authors report the co-operative co-assembly of a modified amino acid, fluorenylmethoxycarbonyl-pentafluoro-phenylalanine (Fmoc-F5 -Phe), and a peptide, Fmoc-Lys(Fmoc)-Arg-Gly-Asp [Fmoc-K(Fmoc)-RGD] into a functional supramolecular hydrogel. A change in the morphology and fluorescence emission, as well as improvement of the mechanical properties in the mixed hydrogels compared to the pristine hydrogels, demonstrate the signature of co-operative co-assembly mechanism. Intriguingly, this approach harnesses the advantages of both components in a synergistic way, resulting in a single homogeneous biomaterial possessing the antimicrobial property of Fmoc-F5 -Phe and the biocompatibility and cell adhesive characteristics of Fmoc-K(Fmoc)-RGD. This work exemplifies the importance of the co-assembly process in nanotechnology and lays the foundation for future developments in supramolecular chemistry by harnessing the advantages of diverse functional building blocks into a mechanically stable functional biomaterial.

Inhibitor-Mediated Structural Transition in a Minimal Amyloid Model.

Despite the fundamental clinical importance of amyloid fibril formation, its mechanism is still enigmatic. Crystallography of minimal amyloid models was a milestone in the understanding of the architecture and biological activities of amyloid fibers. However, the crystal structure of ultimate dipeptide-based amyloids is not yet reported. Herein, we present the crystal structure of a typical amyloid-forming minimal dipeptide, Ac-Phe-Phe-NH2 (Ac-FF-NH2 ), showing a canonical ß-sheet structure at the atomic level. The simplicity of the structure helped in investigating amyloid-inhibition using crystallography, never previously reported for larger peptide models. Interestingly, in the presence of an inhibitor, the supramolecular packing of Ac-FF-NH2 molecules rearranged into a supramolecular 2-fold helix (21 helix). This study promotes our understanding of the mechanism of amyloid formation and of the structural transitions that occur during the inhibition process in a most fundamental model.

Nanoengineered Peptide-Based Antimicrobial Conductive Supramolecular Biomaterial for Cardiac Tissue Engineering.

Owing to their dynamic nature and ordered architecture, supramolecular materials strikingly resemble organic components of living systems. Although short-peptide self-assembled nanostructured hydrogels are regarded as intriguing supramolecular materials for biotechnology, their application is often limited due to their low stability and considerable challenge of combining other desirable properties. Herein, a di-Fmoc-based hydrogelator containing the cell-adhesive Arg-Gly-Asp (RGD) fragment that forms a mechanically stable, self-healing hydrogel is designed. Molecular dynamics simulation reveals the presence of RGD segments on the surface of the hydrogel fibers, highlighting their cell adherence capacity. Aiming to impart conductivity, the 3D network of the hydrogel is further nanoengineered by incorporating polyaniline (PAni). The composite hydrogels demonstrate semiconductivity, excellent antibacterial activity, and DNA binding capacity. Cardiac cells grown on the surface of the composite hydrogels form functional synchronized monolayers. Taken together, the combination of these attributes in a single hydrogel suggests it as an exceptional candidate for functional supramolecular biomaterial designed for electrogenic tissue engineering.

Co-Assembly between Fmoc Diphenylalanine and Diphenylalanine within a 3D Fibrous Viscous Network Confers Atypical Curvature and Branching.

Supramolecular polymer co-assembly is a useful approach to modulate peptide nanostructures. However, the co-assembly scenario where one of the peptide building blocks simultaneously forms a hydrogel is yet to be studied. Herein, we investigate the co-assembly formation of diphenylalanine (FF), and Fmoc-diphenylalanine (FmocFF) within the 3D network of FmocFF hydrogel. The overlapping peptide sequence between the two building blocks leads to their co-assembly within the gel state modulating the nature of the FF crystals. We observe the formation of branched microcrystalline aggregates with an atypical curvature, in contrast to the FF assemblies obtained from aqueous solution. Optical microscopy reveal the sigmoidal kinetic growth profile of these aggregates. Microfluidics and ToF-SIMS experiments exhibit the presence of co-assembled structures of FF and FmocFF in the crystalline aggregates. Molecular dynamics simulation was used to decipher the mechanism of co-assembly formation.

Coassembly-Induced Transformation of Dipeptide Amyloid-Like Structures into Stimuli-Responsive Supramolecular Materials.

Conformational transition of proteins and peptides into highly stable, ß-sheet-rich structures is observed in many amyloid-associated neurodegenerative disorders, yet the precise mechanism of amyloid formation at the molecular level remains poorly understood due to the complex molecular structures. Short peptides provide simplified models for studying the molecular basis of the assembly mechanism that governs ß-sheet fibrillation processes underlying the formation and inhibition of amyloid-like structures. Herein, we report a supramolecular coassembly strategy for the inhibition and transformation of stable ß-sheet-rich amyloid-derived dipeptide self-assemblies into adaptable secondary structural fibrillar assemblies by mixing with bipyridine derivatives. The interplay between the type and mixing ratio of bipyridine derivatives allowed the variable coassembly process with stimuli-responsive functional properties, studied by various experimental characterizations and computational methods. Furthermore, the resulting coassemblies showed functional redox- and photoresponsive properties, making them promising candidates for controllable drug release and fluorescent imprint. This work presents a coassembly strategy not only to explore the mechanism of amyloid-like structure formation and inhibition at the molecular level but also to manipulate amyloid-like structures into responsive supramolecular coassemblies for material science and biotechnology applications.

Nanomechanical Properties and Phase Behavior of Phenylalanine Amyloid Ribbon Assemblies and Amorphous Self-Healing Hydrogels.

Phenylalanine was the minimalistic and first of numerous nonproteinaceous building blocks to be demonstrated to form amyloid-like fibrils. This unexpected organization of such a simple building block into canonical architecture, which was previously observed only with proteins and peptides, has numerous implications for medicine and supramolecular chemistry. However, the morphology of phenylalanine fibrils and their mechanical properties was never characterized in solutions. Here, using electron and atomic force microscopy, we analyze the morphological and mechanical properties of phenylalanine fibrils in both air and fluids. The fibrils demonstrate an exceptionally high Young's modulus (up to 30 GPa) and are found to be composed of intertwined protofilaments in a helical or twisted ribbon morphology. In addition, X-ray scattering experiments provide convincing evidence of an amyloidal cross-ß-like secondary structure within the nanoassemblies. Furthermore, increasing the phenylalanine concentration results in the formation of highly homogenous, noncrystalline, self-healing hydrogels that display storage and loss moduli significantly higher than similar noncovalently cross-linked biomolecular nanofibrillar scaffolds. These remarkably stiff nanofibrillar hydrogels can be harnessed for various technological and biomedical applications, such as self-healing, printable, structural, load-bearing 3D scaffolds. The properties of this simple but quite remarkable hydrogel open a possibility to utilize it in the biomaterial industry.

Unusual Two-Step Assembly of a Minimalistic Dipeptide-Based Functional Hypergelator.

Self-assembled peptide hydrogels represent the realization of peptide nanotechnology into biomedical products. There is a continuous quest to identify the simplest building blocks and optimize their critical gelation concentration (CGC). Herein, a minimalistic, de novo dipeptide, Fmoc-Lys(Fmoc)-Asp, as an hydrogelator with the lowest CGC ever reported, almost fourfold lower as compared to that of a large hexadecapeptide previously described, is reported. The dipeptide self-assembles through an unusual and unprecedented two-step process as elucidated by solid-state NMR and molecular dynamics simulation. The hydrogel is cytocompatible and supports 2D/3D cell growth. Conductive composite gels composed of Fmoc-Lys(Fmoc)-Asp and a conductive polymer exhibit excellent DNA binding. Fmoc-Lys(Fmoc)-Asp exhibits the lowest CGC and highest mechanical properties when compared to a library of dipeptide analogues, thus validating the uniqueness of the molecular design which confers useful properties for various potential applications.

Expanding the Functional Scope of the Fmoc-Diphenylalanine Hydrogelator by Introducing a Rigidifying and Chemically Active Urea Backbone Modification.

Peptidomimetic low-molecular-weight hydrogelators, a class of peptide-like molecules with various backbone amide modifications, typically give rise to hydrogels of diverse properties and increased stability compared to peptide hydrogelators. Here, a new peptidomimetic low-molecular-weight hydrogelator is designed based on the well-studied N-fluorenylmethoxycarbonyl diphenylalanine (Fmoc-FF) peptide by replacing the amide bond with a frequently employed amide bond surrogate, the urea moiety, aiming to increase hydrogen bonding capabilities. This designed ureidopeptide, termed Fmoc-Phe-NHCONH-Phe-OH (Fmoc-FuF), forms hydrogels with improved mechanical properties, as compared to those formed by the unmodified Fmoc-FF. A combination of experimental and computational structural methods shows that hydrogen bonding and aromatic interactions facilitate Fmoc-FuF gel formation. The Fmoc-FuF hydrogel possesses properties favorable for biomedical applications, including shear thinning, self-healing, and in vitro cellular biocompatibility. Additionally, the Fmoc-FuF, but not Fmoc-FF, hydrogel presents a range of functionalities useful for other applications, including antifouling, slow release of urea encapsulated in the gel at a high concentration, selective mechanical response to fluoride anions, and reduction of metal ions into catalytic nanoparticles. This study demonstrates how a simple backbone modification can enhance the mechanical properties and functional scope of a peptide hydrogel.

Composite of Peptide-Supramolecular Polymer and Covalent Polymer Comprises a New Multifunctional, Bio-Inspired Soft Material.

Peptide-based supramolecular hydrogels are utilized as functional materials in tissue engineering, axonal regeneration, and controlled drug delivery. The Arg-Gly-Asp (RGD) ligand based supramolecular gels have immense potential in this respect, as this tripeptide is known to promote cell adhesion. Although several RGD-based supramolecular hydrogels have been reported, most of them are devoid of adequate resilience and long-range stability for in vitro cell culture. In a quest to improve the mechanical properties of these tripeptide-based gels and their durability in cell culture media, the Fmoc-RGD hydrogelator is non-covalently functionalized with a biocompatible and biodegradable polymer, chitosan, resulting in a composite hydrogel with enhanced gelation rate, mechanical properties and cell media durability. Interestingly, both Fmoc-RGD and Fmoc-RGD/chitosan composite hydrogels exhibit thixotropic properties. The utilization of the Fmoc-RGD/chitosan composite hydrogel as a scaffold for 2D and 3D cell cultures is demonstrated. The composite hydrogel is found to have notable antibacterial activity, which stems from the inherent antibacterial properties of chitosan. Furthermore, the composite hydrogels are able to produce ultra-small, mono-dispersed, silver nanoparticles (AgNPs) arranged on the fiber axis. Therefore, the authors' approach harnesses the attributes of both the supramolecular-polymer (Fmoc-RGD) and the covalent-polymer (chitosan) component, resulting in a composite hydrogel with excellent potential.

Metal-Ion Modulated Structural Transformation of Amyloid-Like Dipeptide Supramolecular Self-Assembly.

The misfolding of proteins and peptides potentially leads to a conformation transition from an α-helix or random coil to ß-sheet-rich fibril structures, which are associated with various amyloid degenerative disorders. Inhibition of the ß-sheet aggregate formation and control of the structural transition could therefore attenuate the development of amyloid-associated diseases. However, the structural transitions of proteins and peptides are extraordinarily complex processes that are still not fully understood and thus challenging to manipulate. To simplify this complexity, herein, the effect of metal ions on the inhibition of amyloid-like ß-sheet dipeptide self-assembly is investigated. By changing the type and ratio of the metal ion/dipeptide mixture, structural transformation is achieved from a ß-sheet to a superhelix or random coil, as confirmed by experimental results and computational studies. Furthermore, the obtained supramolecular metallogel exhibits excellent in vitro DNA binding and diffusion capability due to the positive charge of the metal/dipeptide complex. This work may facilitate the understanding of the role of metal ions in inhibiting amyloid formation and broaden the future applications of supramolecular metallogels in three-dimensional (3D) DNA biochip, cell culture, and drug delivery.

A Self-Healing, All-Organic, Conducting, Composite Peptide Hydrogel as Pressure Sensor and Electrogenic Cell Soft Substrate.

Conducting polymer hydrogels (CPHs) emerge as excellent functional materials, as they harness the advantages of conducting polymers with the mechanical properties and continuous 3D nanostructures of hydrogels. This bicomponent organization results in soft, all-organic, conducting micro-/nanostructures with multifarious material applications. However, the application of CPHs as functional materials for biomedical applications is currently limited due to the necessity to combine the features of biocompatibility, self-healing, and fine-tuning of the mechanical properties. To overcome this issue, we choose to combine a protected dipeptide as the supramolecular gelator, owing to its intrinsic biocompatibility and excellent gelation ability, with the conductive polymer polyaniline (PAni), which was polymerized in situ. Thus, a two-component, all-organic, conducting hydrogel was formed. Spectroscopic evidence reveals the formation of the emeraldine salt form of PAni by intrinsic doping. The composite hydrogel is mechanically rigid with a very high storage modulus ( G') value of ∼2 MPa, and the rigidity was tuned by changing the peptide concentration. The hydrogel exhibits ohmic conductivity, pressure sensitivity, and, importantly, self-healing features. By virtue of its self-healing property, the polymeric nonmetallic hydrogel can reinstate its intrinsic conductivity when two of its macroscopically separated blocks are rejoined. High cell viability of cardiomyocytes grown on the composite hydrogel demonstrates its noncytotoxicity. These combined attributes of the hydrogel allowed its utilization for dynamic range pressure sensing and as a conductive interface for electrogenic cardiac cells. The composite hydrogel supports cardiomyocyte organization into a spontaneously contracting system. The composite hydrogel thus has considerable potential for various applications.

Injectable Hydrogel of Vitamin B9 for the Controlled Release of Both Hydrophilic and Hydrophobic Anticancer Drugs.

Folic acid (FA), vitamin B9 , is a good receptor of drugs triggering cellular uptake via endocytosis. FA is sparingly soluble in water. Herein, a new approach for the formation of FA hydrogel by the hydrolysis of glucono-δ-lactone in PBS buffer under physiological conditions has been reported. The gel has a fibrillar network morphology attributable to intermolecular H-bonding and π-stacking interactions. The thixotropic property of the gel is used for the encapsulation of both hydrophilic [doxorubicin (DOX)] and hydrophobic [camptothecin (CPT)] drugs. The loading of DOX and CPT into the gel is attributed to the H-bonding interaction between FA and drugs. The release of DOX is sustainable at pH 4 and 7, and the Peppas model indicates that at pH 7 the diffusion of the drug is Fickian but it is non-Fickian at pH 4. The release of CPT is monitored by fluorescence spectroscopy, which also corroborates the combined release of both drugs. The metylthiazolyldiphenyltetrazolium bromide assay of FA hydrogel demonstrates nontoxic behavior and that the cytotoxicity of the DOX-loaded FA hydrogel is higher than that of pure DOX, with a minimal effect on normal cells.

Amino Acid Based Self-assembled Nanostructures: Complex Structures from Remarkably Simple Building Blocks.

Amino acids are the simplest biological building blocks capable of forming discreet nanostructures by supramolecular self-assembly. The understanding of the process of organization of amino acid nanostructures is of fundamental importance for the study of metabolic diseases as well as for materials science applications. Although peptide self-assembled structures have been the topic of many review articles, much less attention has been devoted to the ability of amino acid building blocks, both natural and synthetic, to form ordered assemblies with defined architectures and notable physical properties, by the process of self-association. Herein, we try to shed light on amino acid based nanostructures, their fabrication and implications. We discuss self-assembled nanostructures, including hydrogels with nanoscale order, obtained from both modified and unmodified single amino acids. We also envision some future prospects in this emerging field.

Influence of Chain Length on the Self-Assembly of Poly(ε-caprolactone)-Grafted Graphene Quantum Dots.

The multifarious applications of graphene quantum dots (GQDs) necessitate surface modifications to enhance their solution processability. Herein, we report the synthesis and self-assembly of GQDs grafted with poly(ε-caprolactone) (PCL) of different degrees of polymerization (3, 7, 15, and 21) produced from ring-opening polymerization. Optical and morphological studies unveil the transformation of the assemblies from J-aggregates to H-aggregates, accompanied by an alteration in morphology from toroid to spheroid to rodlike structures with increasing chain length of PCL. Functionalized GQDs with lower chain lengths of PCL at higher concentration also assemble into liquid-crystalline phases as observed from birefringent textures, which are later correlated to the formation of columnar hexagonal (Colh) mesophases. However, no such behavior is observed at higher chain lengths of PCL under identical conditions. Therefore, it is evident that the variation in the PCL chain length plays a crucial role in the self-assembly, which is primarily triggered by the van der Waals force between the polymer chains dictating the π stacking of GQDs, resulting in different self- aggregated behavior.

Enhancement of Energy Storage and Photoresponse Properties of Folic Acid-Polyaniline Hybrid Hydrogel by in Situ Growth of Ag Nanoparticles.

Electrically conductive hydrogels are a fascinating class of materials that exhibit multifarious applications such as photoresponse, energy storage, etc., and the three-dimensional micro- and nanofibrillar structures of the gels are the key to those applications. Herein, we have synthesized a hybrid hydrogel based on folic acid (F) and polyaniline (PANI) in which F acts as a supramolecular cross-linker of PANI chains. The gels are mechanically robust and are characterized by field-emission scanning electron microscopy, transmission electron microscopy, and spectroscopic, rheological, and universal testing measurements. The hybrid xerogel exhibit a BET surface area 238 m2 g-1, conductivity of 0.04 S/cm, specific capacitance of 295 F/g at a current density of 1A/g, and photocurrent of ∼2 mA under white-light illumination. Silver nanoparticles (AgNPs) are in situ grown to elegantly improve the conductivity, energy storage, and photoresponse capability of the gels. The formation of AgNPs drastically improves the specific capacitances up to 646 F/g (at current density 1A/g), excellent rate capability (403 F/g at 20 A/g), and stable cycling performance with a retention ratio of 74% after 5000 cycles. The AgNPs embedded gel exhibits dramatic enhancement of photocurrent to 56 mA, and its time-dependent photoillumination corroborates faster rise and decay of current compared to those of folic acid-polyaniline hydrogel.

A Comparative Account of the Kinetics of Light-Induced E-Z Isomerization of an Anthracene-Based Organogelator in Sol, Gel, Xerogel, and Powder States: Fiber to Crystal Transformation.

The organogel of (E)-N'-(anthracene-10-ylmethylene)-3,4,5-tris(dodecyloxy)benzohydrazide (I) in methyl cyclohexane having a fibrillar network structure exhibits excellent fluorescence, which decreases sharply with time upon photoirradiation at λ = 365 nm. It has been attributed to the transformation of the E isomer of I to the Z isomer, and the kinetics of E-Z isomerization are compared for the sol, gel, xerogel, and powder states. The rate constants at different temperatures are measured from Avrami plots and its increase with an increase in temperature, indicating temperature acts as a promoter for photoirradiated E-Z isomeization along the imine (C═N) bond. In the powder form, the rate constant values are the lowest compared to those of other states for all temperatures and the xerogels exhibit the highest rate of E-Z isomerization. The rate constants of sol and gel states mostly lie between the two. The wide-angle X-ray scattering pattern changes after ultraviolet (UV) irradiation with the generation of new sharp peaks whose intensities increase with an increase in irradiation time. A polarized optical microscopic study indicates formation of small crystalline dots on the fibers in the gels, dendritic morphology on the xerogel fibers, and large needlelike morphology at the surface boundary of the solid. The dried I gel exhibits a melting peak at 96.7 °C, but upon irradiation, two peaks are observed at 98.5 and 152.7 °C; the latter has been attributed to the melting of crystals of Z isomers. Similar higher melting peaks are observed both for the xerogel and for powders after UV irradiation; the powders exhibit the highest meting peak at 159.4 °C. Possible reasons for the variation of rate constant values in the four different states and the difference in morphology and melting points of crystals of Z isomers of I are discussed.