Spherulite formation in green nonaqueous media: The impact of urea on gelation in glycerol.

HYPOTHESIS: Large macroscopic assemblies formed by a surfactant, sodium dodecylsulfate (SDS), and glycerol, can be directed to assemble in a hierarchical manner by the addition of a strong hydrogen-bond donor/acceptor, such as urea. CONTEXT: Self-assembly in complex media is important to a range of applications, for instance in biological media, which are multi-component, to industrial formulations, where additives are present for flavour, texture, and preservation. Here, the gelation and self-assembly of sodium dodecylsulfate (SDS) in glycerol is explored in the presence of an additive, urea. Urea was chosen due to its importance both fundamentally and industrially, but also because of its ability to form strong H-bonds and interact with both glycerol and SDS. EXPERIMENTAL: To cover the variety of length scales present in the gel-like phase, a combination of optical microscopy and small-angle X-ray scattering techniques were used to probe the micro- to nanoscale. FINDINGS: On the microscale, the formation of a spectacular spherulite phase, even at low urea contents - 0.1 wt%, upon cooling was observed, a stark difference to the microfibrillar phase observed in the absence of urea. Interestingly, the nanostructure of the two crystalline phases were similar and showed negligible differences. This suggests that urea is not involved in the SDS/glycerol microfibril formation but instead directs the assembly of spherulites by bundling the microfibrils. These ternary systems are also probed as a function of urea content, SDS concentration, and temperature. The observations in this work highlight the importance of small molecules in the self-assembly process, which is relevant both fundamentally but also industrially, where small molecules are often added to formulations.

Diblock bottlebrush polymer in a non-polar medium: Self-assembly, surface forces, and superlubricity.

Whilst bottlebrush polymers have been studied in aqueous media for their conjectured role in biolubrication, surface forces and friction mediated by bottlebrush polymers in non-polar media have not been previously reported. Here, small-angle neutron scattering (SANS) showed that a diblock bottlebrush copolymer (oligoethyleneglycol acrylate/ethylhexyl acrylate; OEGA/EHA) formed spherical core-shell aggregates in n-dodecane (a model oil) in the polymer concentration range 0.1-2.0 wt%, with a radius of gyration Rg âˆ¼ 7 nm, comprising 40-65 polymer molecules per aggregate. The surface force apparatus (SFA) measurements revealed purely repulsive forces between surfaces bearing inhomogeneous polymer layers of thickness L âˆ¼ 13-23 nm, attributed to adsorption of a mixture of polymer chains and surface-deformed micelles. Despite the surface inhomogeneity, the polymer layers could mediate effective lubrication, demonstrating superlubricity with the friction coefficient as low as µ ∼ 0.003. The analysis of velocity-dependence of friction using the Eyring model shed light on the mechanism of the frictional process. That is, the friction mediation was consistent with the presence of nanoscopic surface aggregates, with possible contributions from a gel-like network formed by the polymer chains on the surface. These unprecedented results, correlating self-assembled polymer micelle structure with the surface forces and friction the polymer layers mediate, highlight the potential of polymers with the diblock bottlebrush architecture widespread in biological living systems, in tailoring desired surface interactions in non-polar media.

Recent Advances in Polymerization-Induced Self-Assembly (PISA) Syntheses in Non-Polar Media.

It is well-known that polymerization-induced self-assembly (PISA) is a powerful and highly versatile technique for the rational synthesis of colloidal dispersions of diblock copolymer nanoparticles, including spheres, worms or vesicles. PISA can be conducted in water, polar solvents or non-polar media. In principle, the latter formulations offer a wide range of potential commercial applications. However, there has been just one review focused on PISA syntheses in non-polar media and this prior article was published in 2016. The purpose of the current review article is to summarize the various advances that have been reported since then. In particular, PISA syntheses conducted using reversible addition-fragmentation chain-transfer (RAFT) polymerization in various n-alkanes, poly(α-olefins), mineral oil, low-viscosity silicone oils or supercritical CO2 are discussed in detail. Selected formulations exhibit thermally induced worm-to-sphere or vesicle-to-worm morphological transitions and the rheological properties of various examples of worm gels in non-polar media are summarized. Finally, visible absorption spectroscopy and small-angle X-ray scattering (SAXS) enable in situ monitoring of nanoparticle formation, while small-angle neutron scattering (SANS) can be used to examine micelle fusion/fission and chain exchange mechanisms.

4-Bromo-Butyric Acid-Assisted In Situ Passivation Strategy for Superstable All-Inorganic Halide Perovskite CsPbX3 Quantum Dots in Polar Media.

A crucial challenge is to develop an in situ passivation treatment strategy for CsPbX3 (CPX, X=Cl, Br, and I) quantum dots (QDs) and simultaneously retain their luminous efficiency and wavelength. Here, a facile method to significantly improve the stability of the CPX QDs via in situ crystallization with the synergistic effect of 4-bromo-butyric acid (BBA) and oleylamine (OLA) in polar solvents including aqueous solution and a possible fundamental mechanism are proposed. Monodispersed CsPbBr3 (CPB) QDs obtained in water show high photoluminescence quantum yields (PLQYs) of 86.4 % and their PL features of CPB QDs have no significant change after being dispersed in aqueous solution for 96 h, which implies the structure of CPB QDs is unchanged. The results provide a viable design strategy to synthesize all-inorganic perovskite CPX QDs with strong stability against the attack of polar solvents and shed more light on their surface chemistry.

Enzymatic synthesis of cholecalciferol glycosides using ß-glucosidase from sweet almond.

ß-Glucosidase from sweet almond (Amygdalus communis var. 'Dulcis') entrapped on to calcium alginate beads catalysed the synthesis of water soluble 17-O-(D-glucopyranosyl)cholecalciferol. Optimum conditions for the reaction were: 60% (w/w D-glucose) ß-glucosidase, 0.12 mM pH 6 phosphate buffer and 30 h incubation period. ß-Glucosidase also catalyzed the reaction with D-glucose 2, D-galactose 3, D-mannose 4 and D-fructose 5 with generally low yields in the range of 3-14%. Both α/ß anomers of D-glucose 2, D-galactose 3 and D-mannose 4 reacted, of which the former two formed C6-O derivatives also.