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A set of four structurally related glycolipids are described: two of them have one glucose unit connected to either stearic or oleic acid, and two other ones have a diglucose headgroup (sophorose) similarly connected to either stearic or oleic acid. The self-assembly properties of these compounds, poorly known, are important to know due to their use in various fields of application from cleaning to cosmetics to medical. At basic pH, they all form mainly small micellar aggregates. At acidic pH, the oleic and stearic derivatives of the monoglucose form, respectively, vesicles and bilayer, while the same derivatives of the sophorose headgroup form micelles and twisted ribbons. We use pH-resolved in situ small angle X-ray scattering (SAXS) under synchrotron radiation to characterize the pH-dependent mechanism of evolution from micelles to the more complex aggregates at acidic pH. By pointing out the importance of the COO - /COOH ratio, the melting temperature, T m , of the lipid moieties, hydration of the glycosidic headgroup, the packing parameter, membrane rigidity, and edge stabilization, we are now able to draw a precise picture of the full self-assembly mechanism. This work is a didactical illustration of the complexity of the self-assembly process of a stimuli-responsive amphiphile during which many concomitant parameters play a key role at different stages of the process.

Classical antibacterial surfaces usually involve antiadhesive and/or biocidal strategies. Glycosylated surfaces are usually used to prevent biofilm formation via antiadhesive mechanisms. We report here the first example of a glycosylated surface with biocidal properties created by the covalent grafting of sophorolipids (a sophorose unit linked by a glycosidic bond to an oleic acid) through a self-assembled monolayer (SAM) of short aminothiols on gold (111) surfaces. The biocidal effect of such surfaces on Gram+ bacteria was assessed by a wide combination of techniques including microscopy observations, fluorescent staining, and bacterial growth tests. About 50% of the bacteria are killed via alteration of the cell envelope. In addition, the roles of the sophorose unit and aliphatic chain configuration are highlighted by the lack of activity of substrates modified, respectively, with sophorose-free oleic acid and sophorolipid-derivative having a saturated aliphatic chain. This system demonstrates thus the direct implication of a carbohydrate in the destabilization and disruption of the bacterial cell envelope.

Short-chain carboxylates such as acetate are easily produced through mixed culture fermentation of many biological waste streams, although routinely digested to biogas and combusted rather than harvested. We developed a pipeline to extract and upgrade short-chain carboxylates to esters via membrane electrolysis and biphasic esterification. Carboxylate-rich broths are electrolyzed in a cathodic chamber from which anions flux across an anion exchange membrane into an anodic chamber, resulting in a clean acid concentrate with neither solids nor biomass. Next, the aqueous carboxylic acid concentrate reacts with added alcohol in a water-excluding phase to generate volatile esters. In a batch extraction, 96 ± 1.6% of the total acetate was extracted in 48 h from biorefinery thin stillage (5 g L(-1) acetate) at 379 g m(-2) d(-1) (36% Coulombic efficiency). With continuously regenerated thin stillage, the anolyte was concentrated to 14 g/L acetic acid, and converted at 2.64 g (acetate) L(-1) h(-1) in the first hour to ethyl acetate by the addition of excess ethanol and heating to 70 °C, with a final total conversion of 58 ± 3%. This processing pipeline enables direct production of fine chemicals following undefined mixed culture fermentation, embedding carbon in industrial chemicals rather than returning them to the atmosphere as carbon dioxide.