Investigating the Emulsifying Mechanism of Stereoisomeric Sugar Fatty Acyl Molecular Gelators.

The emulsifying mechanism of supramolecular stereoisomeric sugar fatty acyl molecular gelators was evaluated. In-house-synthesized mannitol dioctanoate (M8) and sorbitol dioctanoate (S8) were tested. The stereoisomeric difference between the sugar groups significantly affected the gelation and emulsifying properties of the gelators. M8 and S8 formed oleogels at 2 and 3.5% (w/v) and emulsified water up to 30 and 60% (v/v), respectively. Microscopy showed that the gelator fibers are at the W/O interfaces, demonstrating a solid particle or network mode of stabilization. The long fibers of M8 were unable to completely encompass the water droplets, resulting in poor emulsification. Small, hair-like fibers of S8 showed better emulsification. When sunflower wax (SFW, 1% w/v) was added as a coemulsifier, synergetic action between the wax and S8 improved the stability of emulsions. Such synergy was not seen between SFW and M8, henceforth emulsion stability was not improved. This study proved that a subtle stereoisomeric difference at the molecular level can greatly alter the supramolecular and emulsifying properties of sugar-fatty acyl compounds.

A Heat Transfer Model and Supporting Experiments to Guide the Uniform Gelation of Molecular Oleogels During Scale-up.

The quest for novel vegetable oil structuring strategies has been progressing since the discovery of the deleterious impacts of trans fats. Although oleogelation using bioderived molecular gelators has been proven to be successful as an alternative to traditional hydrogenation methods, efforts are needed to meet the industrial requirements. A major constraint during the fabrication of oleogels is to achieve consistency in physical properties during scale-up. Experiments showed that gelation fails to occur when larger volumes were prepared based on the minimum gelation concentration (MGC) of gelators, determined using the smallest oil volume (1 mL), a general laboratory practice. This observation was consistent with all the molecular gelators used in this study; sorbitol dioctanoate, mannitol dioctanoate, and 12-hydroxystearic acid. To understand this behavior, a mathematical model was developed since gelator network propagation is governed by the cooling rate. The model indicates that maintenance of a minimal thermal gradient via uniform heat dissipation and gelation time is necessary to achieve homogeneous gel propagation across the vial. With these predictions, we hypothesized and confirmed that oleogels with constant surface area-to-volume ratio could result in identical gelation times and consistent physical properties (MGC, melting temperature, melting enthalpy, yield stress, solid phase content, and oil binding capacity) during scale-up.

Self-assembled Trehalose Amphiphiles as Molecular Gels: A Unique Formulation to Wax-free Cosmetics.

Trehalose has been used as an emollient and antioxidant in cosmetics. However, we aimed to explore trehalose amphiphiles as oil structuring agents for the preparation of gel-based lip balms as part of wax-free cosmetics. This article describes the synthesis of trehalose fatty acyl amphiphiles and their corresponding oleogel-based lip balms. Trehalose dialkanoates were synthesized by esterifying the two primary hydroxyls of trehalose with fatty acids (C4-C12) using a facile, regioselective lipase catalysis. The gelation potential of as-synthesized amphiphiles was evaluated in organic solvents and vegetable oils. Stable oleogels were subjected to X-ray diffraction (XRD), thermal (DSC), and rheological studies and further used for the preparation of lip balms. Trehalose dioctanoate (Tr8), trehalose didecanoate (Tr10) were found to be super gelators as their minimum gelation concentration is ≤ 0.2 wt%. XRD studies revealed their hexagonal columnar molecular packing while forming the fibrillar networks. Rheometry proved that the fatty acyl chain length of amphiphiles can influence the strength and flow properties of oleogels. Further rheometry (at 25 °C, 37 °C, and 50 °C) and DSC studies have validated that Tr8- and Tr10-based oleogels are stable for commercial applications. Tr8- and Tr10-based olive oil oleogels were used for the preparation of lip balms. The preliminary results suggested that the cumulative effect of trehalose's emolliency and vegetable oil gelling nature can be achieved with trehalose amphiphiles, specifically, Tr8 and Tr10. This study has also demonstrated that Tr8- and Tr10-based lip balms can be used as an alternative to beeswax and plant wax lip balms, indicating their huge potential to succeed as a new paradigm to formulate wax-free cosmetics.

Freestanding organogels by molecular velcro of unsaturated amphiphiles.

A simple amphiphile, N-cardanyltaurine amide (NCT) with different degrees of cis-unsaturation in its tail resulted in the formation of strong organogels. Interestingly, this is in contrast to the commonly accepted notion that introducing unsaturation in alkyl chains enhances fluidity in lipid assemblies. The physico-chemical and first-principles DFT calculations confirmed the pegging of 'kinked' unsaturated side chains, where the hydrophobic interlocking as in Velcro fasteners leads to a network of cylindrical micelles, resulting in self-standing organogels. Textural profile analysis and spectroscopic details substantiated the dynamic assembly to resemble a 3D network of gelators rather than being a cross-linked or polymerized matrix of monomers.

Sucralose hydrogels: Peering into the reactivity of sucralose versus sucrose under lipase catalyzed trans-esterification.

Sucralose differs from sucrose only by virtue of having three Cl groups instead of OH groups. Its intriguing features include being noncaloric, noncariogenic, ∼600 times sweeter than sucrose, stable at high temperatures/acidic pH's, and void of disagreeable aftertastes. These properties are attractive as food additive, one of which is as hydrogel obtainable via the technique of molecular gelation using a sucralose-derived low-molecular weight gelator (LMWG). Such hydrogels are highly responsive to external stimuli like temperature, because the LMWGs self-assemble via non-covalent interactions and could thus be utilized in applications like control-release. We found that sucralose to be unreactive under lipase biocatalysis, unlike sucrose. Hence, the aim of this work was (i) to use computational simulations to further understand sucralose's lack of enzymatic reactivity and (ii) to synthesize the sucralose-based amphiphiles using conventional chemical synthesis and systematically study their tendency towards hydrogelation. Sucrose and sucralose were docked with a high-resolution atomic structure of lipase B from Candida antarctica, modeling the esterification transition state with an active site serine. In extended molecular dynamics simulations, sucrose remained in the active site due to multiple sugar-protein hydrogen bonds. The oxygen-to-chlorine substitutions in sucralose disrupted this hydrogen bonding network. Consistent with observed lack of enzymatic conversion, in multiple simulations, sucralose would rapidly dissociate from the active site. The sucralose-based LMWGs were subsequently synthesized using base-catalyzed conventional chemical synthesis. Three of the sucralose-based amphiphiles (SL-5, SL-6 and SL-7) proved to be successful hydrogelators. The gelators also showed the ability to gel selected beverages. The LMWGs gelled quantities of water and beverage up to 71 and 55 times their weight, respectively, and remain thermally stable up to 144 °C.

Tuning Aesthetic and Mechanical Properties of Oleogels via Formulation of Enzyme-Enabled Stereoisomeric Molecular Gelators.

The mechanistic resemblance of oil-based molecular gels (oleogels) to solid fats (trans and saturated) makes molecular gelation an ideal alternative in developing fat-based food and cosmetic products. The recent upsurge in the preference for oleogels (structured oils) is due to them being healthier than conventional solid fats. The present study reveals a simple means of modulating the mechanical and aesthetic properties of oleogels by physically mixing two isomeric low-molecular-weight gelators, mannitol dioctanoate (M8) and sorbitol dioctanoate (S8), which have contrasting oil-structuring behaviors; while M8 formed oleogels with a higher gel strength, the S8 gels were more aesthetic, translucent, and appealing. The gelators were synthesized by enzyme catalysis (a generally regarded as safe protocol). The M8/S8 gels were systematically and thoroughly characterized using a suite of analytical techniques, including minimum gelation concentration, gel melting point, rheological storage modulus, oil binding capacity, light transmittance, and optical microscopy. The results showed that the percentage of light transmittance, which is associated with aesthetics, increased from about 40 to 95% with an increasing fraction of S8 from 0 to 1. Parameters associated with mechanical strength, such as rheology, were also quite responsive to varying proportions of the gelators. The storage modulus (G', a rheological property) increased from about 3300 to about 12 500 Pa with an increasing fraction of M8. As the fraction of M8 increased, the solid fat content (SFC) changed from about 3.51 to 2.08%, while the oil binding capacity changed from about 70.2 to 100.0. This work enables the modulation of the aesthetic and organoleptic properties of a gel via a simple formulation of stereoisomeric molecular gelators.

Unravelling the secret of seed-based gels in water: the nanoscale 3D network formation.

Chia (Salvia hispanica) and basil (Ocimum basilicum) seeds have the intrinsic ability to form a hydrogel concomitant with moisture-retention, slow releasing capability and proposed health benefits such as curbing diabetes and obesity by delaying digestion process. However, the underlying mode of gelation at nanoscopic level is not clearly explained or explored. The present study elucidates and corroborates the hypothesis that the gelling behavior of such seeds is due to their nanoscale 3D-network formation. The preliminary study revealed the influence of several conditions like polarity, pH and hydrophilicity/hydrophobicity on fiber extrusion from the seeds which leads to gelation. Optical microscopic analysis clearly demonstrated bundles of fibers emanating from the seed coat while in contact with water, and live growth of fibers to form 3D network. Scanning electron microscope (SEM) and transmission electron microscope (TEM) studies confirmed 3D network formation with fiber diameters ranging from 20 to 50 nm.

Fat for the future: designing multifunctional molecular oleogels.

With the deadline for replacing partially hydrogenated oils less than a year away, there is a compelling need to develop functional, healthy, and nutritious materials that can be used to turn liquid oils into semi-solid fats. Toward that end, our research group has successfully demonstrated the design and synthesis of a new family of naturally derived molecular gelators through a simple GRAS (Generally Recognized as Safe) protocol. These gelators can potentially form stable oleogels with a variety of vegetable oils for food and personal care applications.

Radiation-Responsive Esculin-Derived Molecular Gels as Signal Enhancers for Optical Imaging.

Recent interest in detecting visible photons that emanate from interactions of ionizing radiation (IR) with matter has spurred the development of multifunctional materials that amplify the optical signal from radiotracers. Tailored stimuli-responsive systems may be paired with diagnostic radionuclides to improve surgical guidance and aid in detecting therapeutic radionuclides otherwise difficult to image with conventional nuclear medicine approaches. Because light emanating from these interactions is typically low in intensity and blue-weighted (i.e., greatly scattered and absorbed in vivo), it is imperative to increase or shift the photon flux for improved detection. To address this challenge, a gel that is both scintillating and fluorescent is used to enhance the optical photon output in image mapping for cancer imaging. Tailoring biobased materials to synthesize thixotropic thermoreversible hydrogels (a minimum gelation concentration of 0.12 wt %) offers image-aiding systems which are not only functional but also potentially economical, safe, and environmentally friendly. These robust gels (0.66 wt %, ∼900 Pa) respond predictably to different types of IRs including ß- and γ-emitters, resulting in a doubling of the detectable photon flux from these emitters. The synthesis and formulation of such a gel are explored with a focus on its physicochemical and mechanical properties, before being utilized to enhance the visible photon flux from a panel of radionuclides as detected. The possibility of developing a topical cream of this gel makes this system an attractive potential alternative to current techniques, and the multifunctionality of the gelator may serve to inspire future next-generation materials.

Sugar based amphiphiles: easily accessible and efficient crude oil spill thickening agents.

In this work, we demonstrate the use of biomass for the catalytic production of phase-selective gelators (PSGs) as a cost-effective, environmentally benign and ideal method for crude oil spill remediation, as well as execute the study exclusively in crude oil. The use of PSGs has recently provided great promise relative to that of their traditional counterparts. However, the use of PSGs with crude oil is much more complicated due to its complex composition. All of the current PSG methods are demonstrated with refined oils or do not employ eco-friendly methods like enzymatic synthesis. Our current project entails studying sugar alcohol-derived amphiphiles for their phase-selective gelation in crude oil; the PSGs are derived from renewable, benign materials and synthesized via a simple, single-step, enzymatic catalysis that required no purification. The results showed that, after a rigorous and systematic testing, the mannitol-derived amphiphile using 8-carbon alkyl chain length (M-8) turned out to be the best crude oil PSG among the studied amphiphiles. M-8 demonstrated a versatility towards thickening of different crude oil types, an efficient ability towards selective gelation of the oil (forming crude oil gel that is over sixty-one-times its mass and stable up to 109.7 °C) in a crude oil/water mixture, and an ability to form gel under practical situations such as seawater conditions. These qualities, in addition to the use of a simple and environmentally benign method to synthesize the structuring agents, make this amphiphile very practical in real life application.

Functional self-assembled lipidic systems derived from renewable resources.

Self-assembled lipidic amphiphile systems can create a variety of multi-functional soft materials with value-added properties. When employing natural reagents and following biocatalytic syntheses, self-assembling monomers may be inherently designed for degradation, making them potential alternatives to conventional and persistent polymers. By using non-covalent forces, self-assembled amphiphiles can form nanotubes, fibers, and other stimuli responsive architectures prime for further applied research and incorporation into commercial products. By viewing these lipid derivatives under a lens of green principles, there is the hope that in developing a structure-function relationship and functional smart materials that research may remain safe, economic, and efficient.