Self-Assembling Nanoarchitectonics of Twisted Nanofibers of Fluorescent Amphiphiles as Chemo-Resistive Sensor for Methanol Detection.

The inhalation, ingestion, and body absorption of noxious gases lead to severe tissue damage, ophthalmological issues, and neurodegenerative disorders; death may even occur when recognized too late. In particular, methanol gas present in traces can cause blindness, non-reversible organ failure, and even death. Even though ample materials are available for the detection of methanol in other alcoholic analogs at ppm level, their scope is very limited because of the use of either toxic or expensive raw materials or tedious fabrication procedures. In this paper, we report on a simple synthesis of fluorescent amphiphiles achieved using a starting material derived from renewable resources, this material being methyl ricinoleate in good yields. The newly synthesized bio-based amphiphiles were prone to form a gel in a broad range of solvents. The morphology of the gel and the molecular-level interaction involved in the self-assembly process were thoroughly investigated. Rheological studies were carried out to probe the stability, thermal processability, and thixotropic behavior. In order to evaluate the potential application of the self-assembled gel in the field of sensors, we performed sensor measurements. Interestingly, the twisted fibers derived from the molecular assembly could be able to display a stable and selective response towards methanol. We believe that the bottom-up assembled system holds great promise in the environmental, healthcare, medicine, and biological fields.

Glycolipid-Based Oleogels and Organogels: Promising Nanostructured Structuring Agents.

Over the past few decades, the scientific community is actively involved in the development of edible structuring agents suitable for food, cosmetics, agricultural, pharmaceutical, and biotechnology applications. In particular, edible oil structuring using simple amphiphiles would be the best alternative for the currently used trans and saturated fatty acids, which cause deleterious health effects and cardiovascular problems. In this report, we have made an attempt to address the aforementioned consequences, by synthesizing a new class of structuring agents by a judicious combination of δ-gluconolactone and ricinoleic acid, compounds classified as GRAS, using simple steps in good yield. To our delight, the synthesized glycolipids self-assemble in a wide variety of vegetable oils and commercially viable glycerol, ethylene glycol, and polyethylene glycol via various intermolecular interactions to form a gel. The morphology of molecular gels was investigated by optical microscopy and FESEM analysis, which reveal the existence of a tubular architecture with a diameter ranging from 75 to 150 nm. Rheological studies disclosed the viscoelastic nature, thermal processability, and thixotropic behavior of both oleogels and organogels. Altogether, self-assembled oleogel and organogel reported in this paper would potentially be used in food, agricultural, cosmetics, pharmaceutical, and biotechnological applications.

Fabrication of Biobased Hydrophobic Hybrid Cotton Fabrics Using Molecular Self-Assembly: Applications in the Development of Gas Sensor Fabrics.

Inadvertent inhalation of various volatile organic compounds during industrial processes, such as coal and metal mining, metal manufacturing, paper and pulp industry, food processing, petroleum refining, and concrete and chemical industries, has caused an adverse effect on human health. In particular, exposure to trimethylamine (TMA), a fishy odor poisonous gas, resulted in numerous health hazards such as neurotoxicity, irritation in eyes, nose, skin, and throat, blurred vision, and many more. According to the environmental protection agency, TMA in the level of 0.10 ppm is generally considered as safe, and excess dose results in "trimethylaminuria" or "fish odor syndrome." In order to avoid the health hazards associated with the inhalation of TMA, there is an urge to design a sensor for TMA detection even at low levels for use in food-processing industries, medical diagnosis, and environment. In this report, for the first time, we have developed a TMA sensor fabric using a sequential self-assembly process from silver-incorporated glycolipids. Formation of self-assembled supramolecular architecture, interaction of the assembled structure with the cotton fabric, and sensing mechanism were completely investigated with the help of various instrumental methods. To our surprise, the developed fabric displayed a transient response for 1-500 ppm of TMA and a stable response toward 100 ppm of TMA for 15 days. We believe that the reported flexible TMA sensor fabrics developed via the sequential self-assembly process hold great promise for various innovative applications in environment, healthcare, medicine, and biology.

Smart supramolecular gels of enolizable amphiphilic glycosylfuran.

The implementation of a novel approach in the development of stimuli responsive supramolecular gels is an important objective that challenges material chemists and biologists in order to access an exclusively new category of smart materials. In this report, non-toxic, bio-based amphiphilic glycosylfurans were designed and synthesized using a biocatalyst, Novozyme 435, an immobilized lipase B from Candida antarctica. The self-assembly of these compounds generated oleogels and hydrogels. To our delight, these bio-based amphiphilic glycosylfurans furnished an in situ stimuli responsive hydrogel with simultaneous encapsulation of various biologically relevant molecules and ions. For the first time we are reporting hydrogelation via in situ molecular tuning followed by a self-sorting mechanism. The sol-to-gel transition in the reported smart hydrogel was observed by the addition of acidic buffer of pH 4.0, which could be potentially used for the stimuli responsive delivery of a signalling molecule, H2S and other biomolecules that regulate many physiological and pathological processes.

Lipase-Catalyzed Synthesis of Furan-Based Oligoesters and their Self-Assembly-Assisted Polymerization.

We investigate the synthesis of bio-based hydrophilic and hydrophobic oligoesters, which in turn are derived from easily accessible monomers from natural resources. In addition to the selection of renewable monomers, Novozyme 435, an immobilized lipase B from Candida antarctica was used for the oligomerization of monomers. The reaction conditions for oligomerization using Novozyme 435 were established to obtain a moderate-to-good yield. The average number of repeating units and the molecular weight distribution of hydrophilic and hydrophobic oligoester were identified by using NMR spectroscopy, gel-permeation chromatography, and MS. The oligoester derived from a hydrophilic monomer self-assembled to form a viscous solution, which upon further heating resulted in the formation of a polymer by the intermolecular Diels-Alder reaction. The viscosity of the solution and the assembly of oligoester to form a fibrous structure were investigated by using rheological studies, XRD, and SEM. The molecular weight of the cross-linked polymer was identified by using matrix-assisted laser desorption/ionization-MS. The thermal properties of the bio-based polymers were investigated by using thermogravimetric analysis and differential scanning calorimetry. For the first time, the self-assembly-assisted polymerization of an oligoester is reported using the intermolecular Diels-Alder reaction, which opens a new avenue in the field of polymer science.