Sugar-Based Organogelators for Various Applications.

In this Feature Article, we discuss the design strategy, syntheses, and the self-assembly of various sugar-based gelators to form organogels. We illustrate the use of organogels formed by these sugar-based gelators for various applications such as (a) development of scratch-free, shatter-free, soft-optical devices using oil gels formed by mannitol-based gelators, (b) marine oil-spill recovery using sugar-based phase selective organogelators, (c) preparation of semiconducting cotton cloths using a diyne functionalized sugar gelator, (d) development of sugar arrays on glass slides using a polymerizable diyne functionalized sugar gelator for efficient lectin binding, (e) development of sintering resistant hybrid CaO-silica material for the absorption of CO2, (f) preparation of porous polystyrene-crown ether matrix for the selective alkali metal ions sequestration, and (g) preparation of porous polystyrene, structured silica, and fluorescent gels using a library of sugar-based gelators, and also the mechanism of gelation of some of these gelators have been discussed. We have also given our perspective toward exploring sugar-based gelators for advanced applications.

Organogel-Derived Covalent-Noncovalent Hybrid Polymers as Alkali Metal-Ion Scavengers for Partial Deionization of Water.

We show that crown ethers (CEs) 1-5 congeal both polar and nonpolar solvents via their self-assembly through weak noncovalent interactions (NCIs) such as CH···O and CH···π interactions. Diisopropylidene-mannitol (6) is a known gelator that self-assembles through stronger OH···O H bonding. These two gelators together also congeal nonpolar solvents via their individual self-assembly. Gelator 6 self-assembles swiftly to fibers, which act as templates and attract CE to their surface through H bonding and thereby facilitate their self-assembly through weak NCI. Polymerization of styrene gels made from CE and 6, followed by the washing off of the sacrificial gelator 6, yields robust porous polystyrene-crown ether hybrid matrices (PCH), having pore-exposed CEs. These PCHs not only were efficient in sequestering alkali metal ions from aqueous solutions but also can be recycled. This novel use of organogels for making solid sorbents for metal-ion scavenging might be of great interest.

Organogelator-Cellulose Composite for Practical and Eco-Friendly Marine Oil-Spill Recovery.

Marine oil spills pose serious threats to the ecosystem and economy. There is much interest in developing sorbents that can tackle such spills. We have developed a novel sorbent by impregnating cellulose pulp with a sugar-derived oleogelator, 1,2:5,6-di-O-cyclohexylidene-mannitol. The gelator molecules mask the surface-exposed hydroxyl groups of cellulose fibrils by engaging them in H-bonding and expose their hydrophobic parts making the fibers temporarily hydrophobic (water contact angle 110°). This sorbent absorbs oil effectively, selectively and instantly from oil-water mixtures due to its hydrophobicity. Then the gelator molecules get released uniformly in the oil and later self-assemble to fibers, as evident from SEM analysis, congealing the oil within the matrix. This hierarchical entrapment of the oil by non-covalent polymeric fibers within a covalent polymer matrix makes the gel very strong (230-fold increase in the yield stress) and rigid, making it suitable for practical use.

CaO nanocrystals grown over SiO2 microtubes for efficient CO2 capture: organogel sets the platform.

Materials that can capture and store CO2 are important. Though CaO is a cheap sorbent, it is inefficient for practical purposes due to sintering and poor diffusion of CO2 through the surface-CaCO3 layer. We have developed a high performance, sintering-resistant CaO-based sorbent by uniformly nanofabricating the CaO nanocrystals on SiO2 microtubes made by organogel templated polymerization.

Hopping-mediated anion transport through a mannitol-based rosette ion channel.

Artificial anion selective ion channels with single-file multiple anion-recognition sites are rare. Here, we have designed, by hypothesis, a small molecule that self-organizes to form a barrel rosette ion channel in the lipid membrane environment. Being amphiphilic in nature, this molecule forms nanotubes through intermolecular hydrogen bond formation, while its hydrophobic counterpart is stabilized by hydrophobic interactions in the membrane. The anion selectivity of the channel was investigated by fluorescence-based vesicle assay and planar bilayer conductance measurements. The ion transport by a modified hopping mechanism was demonstrated by molecular dynamics simulation studies.

Vinylogy in orthoester hydrolysis: total syntheses of cyclophellitol, valienamine, gabosine K, valienone, gabosine G, 1-epi-streptol, streptol, and uvamalol A.

C7-cyclitols represent an important category of natural products possessing a broad spectrum of biological activities. As each member of these compounds is structurally unique, the usual practice is to synthesize them individually from appropriate polyhydroxylated chiral pools. We have observed an unusual vinylogy in acid mediated hydrolysis of enol ethers of myo-inositol 1,3,5-orthoesters giving a synthetically versatile polyhydroxylated cyclohexenal intermediate. We have exploited this unprecedented reaction for developing a general strategy for the rapid and efficient syntheses of several structurally diverse natural products of C7-cyclitol family. We have made an appropriately protected advanced intermediate 25 in five steps from the cheap and commercially available myo-inositol, and this common intermediate has been used to synthesize eight natural products in racemic form. We could synthesize (±)-cyclophellitol in seven steps, (±)-valienamine in five steps, (±)-gabosine I in five steps, (±)-gabosine G in six steps, (±)-gabosine K in three steps, (±)-streptol in six steps, (±)-1-epi-streptol in two steps, and (±)-uvamalol A in five steps from this intermediate.

A mannitol based phase selective supergelator offers a simple, viable and greener method to combat marine oil spills.

Though phase selective organogelators (PSOGs) are thought to be useful for oil spill recovery, all known PSOGs require a water-miscible carrier solvent for their introduction. Providing a simple, cheap, green and practical solution to the problem of oil spills, we report a nontoxic super-PSOG that can be sprayed aerially in a carrier solvent destined to get co-congealed with the oil.