Dihydroxyacetone: A User Guide for a Challenging Bio-Based Synthon.

1,3-dihydroxyacetone (DHA) is an underrated bio-based synthon, with a broad range of reactivities. It is produced for the revalorization of glycerol, a major side-product of the growing biodiesel industry. The overwhelming majority of DHA produced worldwide is intended for application as a self-tanning agent in cosmetic formulations. This review provides an overview of the discovery, physical and chemical properties of DHA, and of its industrial production routes from glycerol. Microbial fermentation is the only industrial-scaled route but advances in electrooxidation and aerobic oxidation are also reported. This review focuses on the plurality of reactivities of DHA to help chemists interested in bio-based building blocks see the potential of DHA for this application. The handling of DHA is delicate as it can undergo dimerization as well as isomerization reactions in aqueous solutions at room temperature. DHA can also be involved in further side-reactions, yielding original side-products, as well as compounds of interest. If this peculiar reactivity was harnessed, DHA could help address current sustainability challenges encountered in the synthesis of speciality polymers, ranging from biocompatible polymers to innovative polymers with cutting-edge properties and improved biodegradability.

Template-Directed Synthesis of Titania Nanocages with Four Tetrahedrally Arranged Open Windows.

Original titania nanocages are fabricated from sacrificial silica/polystyrene tetrapod-like templates. Here the template synthesis, titania deposition and nanocage development through polystyrene dissolution and subsequent silica etching are described. Discussion about the competitive deposition of titania on the biphasic templates is particularly emphasized. The morphology of the nanocages is investigated by TEM, STEM, EDX mapping and electron tomography.

Microstructure-driven self-assembly and rheological properties of multi-responsive soft microgel suspensions.

HYPOTHESES: The deformation and swelling ability of microgels is influenced by the crosslinking distribution. Varying microgels microstructure is expected to obtain suspensions with different flow behavior and thereby, different rheological properties. EXPERIMENTS: Different multi-responsive microgels were synthesized using two different crosslinkers and varying their amounts: N,N-methylene bis-acrylamide (MBA) and oligo(ethylene glycol) diacrylate (OEGDA). The rheological results were obtained by zero-shear viscosity and long-time creep measurements on concentrated microgel suspensions Microgel microstructure was analyzed by 1H nuclear magnetic resonance transverse relaxation measurements. FINDINGS: At a constant crosslinking rate, we show that the viscosity of OEGDA-crosslinked microgels diverges at a higher concentration than MBA ones, suggesting a looser shell and less restricted dangling chains at the periphery for the later. By scaling with the effective volume fraction, the viscosity curves of the different microgel suspensions reduce into a single curve and closely follow hard sphere models up to ϕeff < 0.45. The results from creep tests revealed a much higher yield stress for MBA-crosslinked microgels, strengthening the hypothesis of a looser shell for the later. Finally, transverse relaxation (T2) NMR measurements demonstrated that, although all microgels exhibit a core-shell microstructure, MBA samples present a less crosslinked shell corroborating with the rheological results.

Versatile oligo(ethylene glycol)-based biocompatible microgels for loading/release of active bio(macro)molecules.

The present study aims in the understanding of the effect of oligo(ethylene glycol)-based biocompatible microgels inner structure on the encapsulation/release mechanisms of different types of cosmetic active molecules. For that, multi-responsive microgels were synthesized using three types of cross-linkers: ethylene glycol dimethacrylate (EGDMA), oligo(ethylene glycol) diacrylate (OEGDA) and N,N-methylenebisacrylamide (MBA). The inner morphology of the microgels synthesized was studied by 1H-nuclear magnetic resonance (1H NMR) and small-angle neutron scattering (SANS) techniques and no effect of cross-linker type on microgel microstructure was observed in the case of analysing purified microgel dispersions. Moreover, all the microgels synthesized presented conventional swelling/de-swelling behavior as a function of temperature and pH. Two hydrophobic, one hydrophilic, and one macromolecule as cosmetic active molecules were effectively loaded into different microgel particles via hydrophobic interactions and hydrogen-bonding interactions between -OH groups of active molecules and ether oxygens of different microgel particles. Their release profiles as a function of cross-linker type used and encapsulated amounts were studied by Peppas-Sahlin model. No effect of the cross-linker type was observed due to the similar inner structure of all the microgels synthesized.