Self-assembled Fibrillar Networks Research Articles

Oleogel-Based Nanoemulsions for Beverages: Effect of Self-Assembled Fibrillar Networks on Stability and Release Properties of Emulsions.

Reducing the use of stabilizers is one of the main challenges in food emulsions, especially for beverages. This work aimed to produce oleogel-structured nanoemulsions (NEs) without additional surfactants. Lecithin-stearic acid (LSa) and lecithin-sorbitan tristearate (LSt) oleogels formed stable NEs under optimized sonication conditions. Microscopy and rheometry revealed that the presence of self-assembled fibrous networks (SAFiNs) in both dispersed and continuous phases provided steric stabilization to NEs. Lecithin acted as crystal habit modifier of SAFiNs and facilitated their phase partitioning. Notably, the short fibers of LSt showed better emulsifying efficiency than the long fibers of LSa. Curcumin release studies under simulated gastrointestinal conditions demonstrated that SAFiNs affect the release capabilities of NEs. Polydispersity index, zeta potential and oil syneresis data showed that the emulsions are stable for six months. Moreover, NEs showed thermal stability upon curcumin release at 25 and 50 °C. These results suggest that the developed oleogel-based NEs are suitable for the delivery of bioactive agents for beverages and other food applications.

Low Molecular Weight Hydrogel for Wound Healing.

Octadecylazanediyl dipropionic acid (C18ADPA) is a zwitterionic amphiphile with a dendritic headgroup. C18ADPA self-assembles to lamellar networks, which encompasses water and forms a low-molecular-weight hydrogel (LMWG). In this study, we use the C18ADPA hydrogel as a drug carrier for the in vivo delivery of a copper salt for wound healing in a mouse model. A structural transition was observed based on cryo-scanning electron microscope (cryo-SEM) images after drug loading. The C18ADPA hydrogel, which had a layered structure, transformed into a self-assembled fibrillar network (SAFiN). The mechanical strength of the LMWG has always been an important issue in its applications. However, due to the structural transition, both the storage and loss moduli increased. In vivo tests showed that wound closure was faster after applying the hydrogel formulation compared with the Vaseline formulation. For the first time, we have also provided histological evidence of these effects on skin tissue. The hydrogel formulation exhibited clear advantages in regenerating tissue structure over traditional delivery formulations.

Shear recovery and temperature stability of Ca2+ and Ag+ glycolipid fibrillar metallogels with unusual β-sheet-like domains.

Low-molecular weight gelators (LMWGs) are small molecules (Mw < ∼1 kDa), which form self-assembled fibrillar network (SAFiN) hydrogels in water. A great majority of SAFiN gels are described by an entangled network of self-assembled fibers, in analogy to a polymer in a good solvent. Here, fibrillation of a biobased glycolipid bolaamphiphile is triggered by Ca2+ or Ag+ ions which are added to its diluted micellar phase. The resulting SAFiN, which forms a hydrogel above 0.5 wt%, has a "nano-fishnet" structure, characterized by a fibrous network of both entangled fibers and β-sheet-like rafts, generally observed for silk fibroin, actin hydrogels or mineral imogolite nanotubes, but generally not known for SAFiN. This work focuses on the strength of the SAFIN gels, their fast recovery after applying a mechanical stimulus (strain) and their unusual resistance to temperature, studied by coupling rheology to small angle X-ray scattering (rheo-SAXS) using synchrotron radiation. The Ca2+-based hydrogel maintains its properties up to 55 °C, while the Ag+-based gel shows a constant elastic modulus up to 70 °C, without the appearance of any gel-to-sol transition temperature. Furthermore, the glycolipid is obtained by fermentation from natural resources (glucose and rapeseed oil), thus showing that naturally engineered compounds can have unprecedented properties, when compared to the wide range of chemically derived amphiphiles.

Halogen- and hydrogen-bonded self-assembled fibrillar networks of substituted 1,3:2,4-dibenzylidene-D-sorbitols (DBS).

Substituting the sole primary hydroxyl group of the low molecular weight organogelator (LMOG), 1,3:2,4-dibenzylidene-D-sorbitol (DBS), with a halogen atom (Cl, Br, or I; i.e., 6-Cl-DBS, 6-Br-DBS, or 6-I-DBS) drastically alters the supramolecular self-assembled fibrillar network (SAFiN) that forms when the molecules aggregate. The SAFiN varies depending on the solvent properties, impacting the role of non-covalent hydrogen- and halogen-bonding interactions along and between fibers. The halogenated DBS derivatives have more coherent crystalline fibers than DBS, with larger length-to-width aspect ratios. High-resolution synchrotron powder X-ray diffraction of each wet-state gel in toluene and DFT optimization obtained complete structures for the three halogenated DBS derivatives in their SAFiNs. The presence of a halogen atom reduces the reliance on hydrogen bonding by enabling new halogen bonding interactions that impact the self-assembly behavior, especially in solvents of higher polarity. For 6-I-DBS and 6-Br-DBS, the primary forces driving molecular self-assembly are C-H⋯π and intermolecular halogen-to-halogen interactions, and there is one unique molecule in each unit cell. However, the Cl atoms of 6-Cl-DBS are not close, and its SAFiN structures rely more on hydrogen bonding. As a result, the enhanced hydrogen bonding, electronic differences among the halogens, and spatial factors allow its unit cell to include two independent molecules of 6-Cl-DBS.

Robust and Multifunctional Kirigami Electronics with a Tough and Permeable Aramid Nanofiber Framework.

Kirigami designs are advantageous for the construction of wearable electronics due to their high stretchability and conformability on the 3D dynamic surfaces of the skin. However, suitable materials technologies that enable robust kirigami devices with desired functionality for skin-interfaces remain limited. Here, a versatile materials platform based on a composite nanofiber framework (CNFF) is exploited for the engineering of wearable kirigami electronics. The self-assembled fibrillar network involving aramid nanofibers and poly(vinyl alcohol) combines high toughness, permeability, and manufacturability, which are desirable for the fabrication of hybrid devices. Multiscale simulations are conducted to explain the high fracture resistance of theCNFF-based kirigami structures and provide essential guidance for the design, which can be further generalized to other kirigami devices. Various microelectronic sensors and electroactive polymers are integrated onto a CNFF-based materials platform to achieve electrocardiogram(ECG), electromyogram (EMG), skin-temperature measurements, and measurement of other physiological parameters. These mechanically robust, multifunctional, lightweight, and biocompatible kirigami devices can shed new insights for the development of advanced wearable systems and human-machine interfaces.

Energy Landscape of the Sugar Conformation Controls the Sol-to-Gel Transition in Self-Assembled Bola Glycolipid Hydrogels

Self-assembled fibrillar network hydrogels and organogels are commonly obtained through a crystallization process as fibers upon being induced by external stimuli such as temperature or pH. The gel-to-sol-to-gel transition is generally readily reversible, and the rate of change of the stimulus determines the fiber homogeneity and eventual elastic properties of the gels. However, recent work shows that in some specific cases, fibrillation occurs for a given molecular conformation and the sol-to-gel transition depends on the relative energetic stability of one conformation over the other and not on the rate of change of the stimuli. We observe such a phenomenon on a class of bolaform glycolipids, sophorosides, similar to the well-known sophorolipid biosurfactants but composed of two symmetric sophorose units. A combination of oscillatory rheology, small-angle X-ray scattering (SAXS), cryogenic transmission electron microscopy, and in situ rheology coupled with SAXS using synchrotron radiation shows that below 14 °C, twisted nanofibers are the thermodynamic phase. Between 14 and about 33 °C, nanofibers coexist with micelles and a strong hydrogel forms, the sol-to-gel transition being readily reversible in this temperature range. However, above the annealing temperature of about 40 °C, the micelle morphology becomes kinetically trapped for hours, even upon cooling, whichever the rate, to 4 °C. A combination of solution and solid-state nuclear magnetic resonance spectroscopy studies suggests two different conformations of the 1″, 1′, and 2′ carbon stereocenters of sophorose, precisely at the β(1,2) glycosidic bond, for which several combinations of the dihedral angles are known to provide at least three energetic minima of comparable magnitude, with each corresponding to a given sophorose conformation.

Controllable fabrication of metal-confined carbon nanotubes from the self-templated conversion of supramolecular gel nanofibers

Nanostructured supramolecular gels with self-assembled fibrillar networks are promising candidates for fabricating advanced functional materials for energy-related applications. Several fundamental challenges, including poor structural stability and monotonous fibrous morphology, greatly hinder their practical applications. To the best of our knowledge, supramolecular gel-derived carbon nanotubes (CNTs) have not been reported in the literature. Herein, we present a unique strategy for controllable fabrication of metal-confined carbon nanotubes (M/CNT) from the self-templated conversion of guanosine-based supramolecular gel (GSMG) nanofibers. Benefitting from the high tunability of GSMGs, it was demonstrated that the introduction of metal source (Ni and Fe) to improve the stability of the material and simply changing the KOH concentrations in the precursor materials, the structure of GSMG nanofibers derived active materials was controllably tuned from metal-constrained solid carbon nanofiber to hollow M/CNT. The optimized NiFe/B, N-CNT showed a superior oxygen evolution reaction catalytic activity with a low overpotential of 355 mV at a current density of 10 mA cm−2. By taking advantage of the unique structural features of supramolecular gels, this strategy provides a simple and effective synthetic route for functional CNT.

Hydrogel Formation by Glutamic-acid-based Organogelator Using Surfactant-mediated Gelation.

Hydrogels formed by low-molecular-weight gelators have reversible sol-gel transition and responsiveness to various stimuli, and are used in cosmetics and drug applications. It is challenging to obtain hydrogels using novel gelators because subtle differences in their molecular architecture affect gelation. Organogelators (which form organogels) are insoluble in water, and their use as hydrogelators has not previously been considered. However, a surfactant-mediated gelation method was reported in which organogelators were solubilized in water by surfactants to form hydrogels using 12-hydroxyoctadecanoic acid. To investigate whether this method can be applied with other organogelators, the formation of hydrogel using a glutamic-acid-based organogelator was studied here. Hydrogels were formed by solubilizing 1:1 mixtures of glutamate-based organogelators, N-lauroyl-L-glutamic acid dibuthylamide, and N-2-ethylhexanoyl-L-glutamic acid dibutylamide in aqueous micellar solutions of anionic surfactant (sodium lauroyl glutamate) and cationic surfactant (cetyltrimethylammonium chloride). The minimum gelation concentration of the hydrogel was ~0.2-0.6 wt%. By changing the molar fraction of cetyltrimethylammonium chloride in the mixed surfactant, either spherical or wormlike micelles were formed. The hydrogel with wormlike micelles had a higher sol-gel transition temperature than that with spherical micelles and formed fine self-assembled fibrillar networks. Additionally, the hydrogel with the spherical micelles was elastic, whereas that with wormlike micelles was viscoelastic, suggesting that networks of the organogelators and wormlike micelles coexisted in the hydrogel from the wormlike micellar solution. Moreover, the hydrogel suppressed the reduction in the storage modulus at higher temperatures compared with the micellar aqueous solution, indicating that the elastic properties of the organogelator networks were maintained at high temperatures. The gel fibers of the hydrogel partially formed a loosely aggregated structure as the temperature increased, the fibers bundled via hydrophobic interactions, and new cross-linking points formed spontaneously. This phenomenon corresponded with an inflection point in the temperature-dependent storage modulus of the hydrogel.

Palmitic acid sophorolipid biosurfactant: from self-assembled fibrillar network (SAFiN) to hydrogels with fast recovery.

Nanofibres are an interesting phase into which amphiphilic molecules can self-assemble. Described for a large number of synthetic lipids, they were seldom reported for natural lipids like microbial amphiphiles, known as biosurfactants. In this work, we show that the palmitic acid congener of sophorolipids (SLC16:0), one of the most studied families of biosurfactants, spontaneously forms a self-assembled fibre network (SAFiN) at pH below 6 through a pH jump process. pH-resolved in situ small-angle X-ray scattering (SAXS) shows a continuous micelle-to-fibre transition, characterized by an enhanced core-shell contrast between pH 9 and pH 7 and micellar fusion into a flat membrane between pH 7 and pH 6, approximately. Below pH 6, homogeneous, infinitely long nanofibres form by peeling off the membranes. Eventually, the nanofibre network spontaneously forms a thixotropic hydrogel with fast recovery rates after applying an oscillatory strain amplitude out of the linear viscoelastic regime: after being submitted to strain amplitudes during 5 min, the hydrogel recovers about 80% and 100% of its initial elastic modulus after, respectively, 20 s and 10 min. Finally, the strength of the hydrogel depends on the medium's final pH, with an elastic modulus fivefold higher at pH 3 than at pH 6. This article is part of the theme issue 'Bio-derived and bioinspired sustainable advanced materials for emerging technologies (part 1)'.

Supramolecular Fractal Growth of Self-Assembled Fibrillar Networks.

Complex morphologies, as is the case in self-assembled fibrillar networks (SAFiNs) of 1,3:2,4-Dibenzylidene sorbitol (DBS), are often characterized by their Fractal dimension and not Euclidean. Self-similarity presents for DBS-polyethylene glycol (PEG) SAFiNs in the Cayley Tree branching pattern, similar box-counting fractal dimensions across length scales, and fractals derived from the Avrami model. Irrespective of the crystallization temperature, fractal values corresponded to limited diffusion aggregation and not ballistic particle–cluster aggregation. Additionally, the fractal dimension of the SAFiN was affected more by changes in solvent viscosity (e.g., PEG200 compared to PEG600) than crystallization temperature. Most surprising was the evidence of Cayley branching not only for the radial fibers within the spherulitic but also on the fiber surfaces.

Multiphase Assembly of Small Molecule Microcrystalline Peptide Hydrogel Allows Immunomodulatory Combination Therapy for Long-Term Heart Transplant Survival.

Combination therapies that target multiple pathways involved in immune rejection of transplants hold promise for patients in need of restorative surgery. Herein, a noninteracting multiphase molecular assembly approach is developed to crystallize tofacitinib, a potent JAK1/3 inhibitor, within a shear-thinning self-assembled fibrillar peptide hydrogel network. The resulting microcrystalline tofacitinib hydrogel (MTH) can be syringe-injected directly to the grafting site during surgery to locally deliver the small molecule. The rate of drug delivered from MTH is largely controlled by the dissolution of the encapsulated microcrystals. A single application of MTH, in combination with systemically delivered CTLA4-Ig, a co-stimulation inhibitor, affords significant graft survival in mice receiving heterotopic heart transplants. Locoregional studies indicate that the local delivery of tofacitinib at the graft site enabled by MTH is required for the observed enhanced graft survival.

Amino Acid-Containing Phase-Selective Organogelators: A Water-Based Delivery System for Oil Spill Treatment.

The simple structural modification of replacing a terminal carboxylic acid with a primary amide group was found to lower the minimum gelation concentration (MGC), by at least an order of magnitude, for a series of N-lauroyl-l-amino acid phase-selective organogelators in decane. The amide-functionalized analogue N-lauroyl-l-alanine-CONH2 was demonstrated to gel a broad range of solvents from diesel to THF at MGCs of 2.5% w/v or less, as well as to produce gels with a higher thermal stability (ca. 30 °C) and enhanced mechanical properties (5 times increase in complex modulus), compared to the carboxylic acid analogue, N-lauroyl-l-alanine-COOH. These improved properties may be due to the additional hydrogen bonding in the primary amide analogue as revealed by SCXRD. Most significantly for this study, the introduction of the primary amide functionality enabled N-lauroyl-l-alanine-CONH2 to form a self-assembled fibrillar network in water. The aqueous network could then actively uptake and rapidly gel decane, diesel, and diluted bitumen (“dilbit”) with MGCs of 2.5% w/v or less. This aqueous delivery method is advantageous for oil-remediation applications as no harmful carrier solvents are required and the gel can be easily separated from the water, allowing the oil to be recovered and the gelator recycled.

Probing Early-Stage Aggregation of Low Molecular Weight Gelator in an Organic Solvent.

Molecular gels are formed by the supramolecular assembly of low molecular weight gelators (LMWGs) in organic solvents or water. Despite significant advances in the field, our understanding of how gelator molecules lead to complex self-assembled fibrillar network (SAFIN) is rather poor. Here, we present molecular dynamics simulations to gain insights into the early-stage aggregation of self-assembled fibrillar network (SAFIN) of 12-hydroxyoctadecanamide (12-HSAm) in octane. Our simulations reveal that the hydroxyl group located at the 12th carbon position plays an important role in the fiber formation. If the hydroxyl group is removed from the backbone, then we find that the aggregates adopt a bilayer morphology rather than cylindrical fibers. Analysis of fibers reveals different morphologies such as cylindrical, tape, and junction zones. A typical cylindrical fiber diameter is 2.4-3.4 nm, while the tape-like fibers are 4.4-8.6 nm in width and 2.4-4.2 nm in depth. In the fibers, we observe that the majority of the gelator molecules interact with neighboring molecules with only one interaction site, leading to growth of the fiber in one dimension. Our simulations help explain the role of functional groups in the self-assembly of small molecules leading to gel formation.

Applications of fat mimetics for the replacement of saturated and hydrogenated fat in food products

Driven by the need for trans and saturated fat replacement strategies, the field of fat mimetics has made tremendous advances over the past decade. Fat mimetics include polymeric networks of ethylcellulose, emulsion-templated networks of proteins and polysaccharides, colloidal and self-assembled fibrillar networks of polar lipid crystals, as well as solid o/w emulsions of oil trapped within crystallized lamellar mesophases. Extensive research has gone into formulating various food products with fat mimetics. These include, bakery products (cakes and laminated pastries), chocolate, dairy products (cream cheese), margarines and spreads, and meat products. The clean-label nature of the ingredients used to produce fat mimetics and their demonstrated functionality makes them a promising alternative to solid fats in food products.

Adsorption of Rose Bengal on a self-assembled fibrillar network affords a thermally switchable oxygenation photocatalyst and a thermochromic soft material

Rose Bengal (RB) can be homogeneously dispersed in dichloromethane by its adsorption on the fibrillar network of a molecular gel formed in this solvent. The RB loaded gel was visualized by confocal scanning laser microscopy, revealing homogenous distribution all over the self-assembled fibers. Thermal gel disassembly provokes discoloration of the system because of protonation of RB by the acidic molecular gelator. Thermochromism was evaluated by UV–vis spectroscopy, showing that color change is fully reversible and associated with gel assembly/disassembly, as corroborated by 1H NMR determination of the amount of free gelator. Singlet oxygen photogeneration from the RB-loaded gel was assayed using 9,10-dimethylanthracene as a 1O2 trap. It was found that the photosensitizing activity of the system is on /off thermally switched, controlled by reversibly gel formation, resulting in a smart thermoresponsive photocatalytic material.

Gelling Lyotropic Liquid Crystals with the Organogelator 1,3:2,4-Dibenzylidene-d-sorbitol Part I: Phase Studies and Sol–Gel Transitions

Gelled lyotropic liquid crystals (gelled LLCs) are the combination of an LLC and a gel network. One method for obtaining gelled LLCs is the addition of a low molecular weight gelator, which forms gels via self-assembled fibrillar networks, to an aqueous surfactant solution. A potent gelator for LLCs is the LMW organogelator 1,3:2,4-dibenzylidene-d-sorbitol (DBS). This gelator gels the lamellar Lα phase, the bicontinuous cubic V1 phase, and the hexagonal H1 phase of the system H2O-C12E7 (heptaethylene glycol monododecyl ether) without influencing the phase boundaries as visual phase studies and rheometry show. Varying the DBS mass fraction η, one can adjust the sol-gel transition temperature Tsol-gel of the gelled LLCs. At η = 0.0075, all Tsol-gel values are below the LLC-to-isotropic phase transition temperatures TLLC-iso, that is, the LLCs are formed first while cooling down, followed by gel formation. At η = 0.015, however, Tsol-gel > TLLC-iso, that is, the gel is formed in an isotropic solvent, which becomes an LLC while cooling down. The system H2O-C12E7 is the first where an adjustment of the gelator concentration allowed us to decouple gel and LLC formation for all three LLCs, that is, gel and LLC formation happen one after the other and not simultaneously. This allows us to study whether the structure and thus the properties of gelled LLCs can be manipulated by the order of gel and LLC formation. We discuss our findings in light of the following question: are our gelled LLCs truly orthogonal self-assembled systems, that is, do the LLCs and the gel network form and coexist independently?

In between molecules and self-assembled fibrillar networks: highly stable nanogel particles from a low molecular weight hydrogelator.

The preparation of molecular, non-polymeric nanogels from a low molecular weight hydrogelator is reported. The molecular nanogels are expected to overcome issues associated with the use of polymeric nanogels in biomedicine such as biodegradability, stimuli responsiveness, polydispersity, and batch-to-batch reproducibility. Nanogels formed by compound 1 were reproducibly prepared by sonication of a xerogel in PBS, with a total concentration of ca. 2 mM. The intensity averaged diameter of ca. 200 nm was determined by DLS. Electron microscopy (TEM and cryo-TEM) showed spherical particles. Light scattering (SALS) indicates that water is the main component of the nanoparticles, and the concentration of 1 in the nanogels is ca. 3 mg mL-1. These particles can be considered to constitute an intermediate state between free molecules and self-assembled fibrillar networks. The nanogels present excellent temporal and thermal stability and accessible hydrophobic domains, as demonstrated by the incorporation of the fluorescent dye Nile Red.

A dual pH-responsive supramolecular gelator with aggregation-induced emission properties.

Functionalising AIE-active aromatic thioethers with self-complementary zwitterionic binding sites leads to a dual pH-responsive supramolecular organogelator with aggregation-induced emission (AIE) properties. The self-assembled fibrillar gel network is highly fluorescent (λem = 490 nm), whereas the addition of both acid and base leads to the sol state with a loss of emission. More over, the gel was found to be thermo- and mechanoresponsive.

Self-assembled fibrillar networks induced by two methods: a new unmodified natural product gel

The discovery of new NPGs and the study of their self-assembing properties.

Sizing Down a Supramolecular Gel into Micro- and Nanoparticles.

A low molecular weight gelator with a fluorescent 1,8-naphthalimide unit forms micro- and nanoparticles in aqueous media. Slow addition of a DMSO solution of the gelator into water affords either a self-assembled fibrillar network, sheaf-like microparticles, or nanoparticles depending to the concentration used in the experiment. The micro- and nanoparticles were characterized by dynamic light scattering (DLS), electron microscopy, and fluorescence measurements. In an initial assay of particle loading, Rose Bengal and Rhodamine 123 were shown to be incorporated in the particles. Light-promoted singlet oxygen generation capabilities of Rose Bengal were modulated by its incorporation in the particles. Additionally, the particles were found to promote the transport of Rhodamine 123 into human lung carcinoma live cells. These results indicate that nanoparticles arising from low molecular weight gelators may represent a new type of nanocarriers, being a potential alternative to polymeric nanogels used in nanomedicine.