Electrophilic Bromination in Flow: A Safe and Sustainable Alternative to the Use of Molecular Bromine in Batch.

Bromination reactions are crucial in today's chemical industry since the versatility of the formed organobromides makes them suitable building blocks for numerous syntheses. However, the use of the toxic and highly reactive molecular bromine (Br2) makes these brominations very challenging and hazardous. We describe here a safe and straightforward protocol for bromination in continuous flow. The hazardous Br2 or KOBr is generated in situ by reacting an oxidant (NaOCl) with HBr or KBr, respectively, which is directly coupled to the bromination reaction and a quench of residual bromine. This protocol was demonstrated by polybrominating both alkenes and aromatic substrates in a wide variety of solvents, with yields ranging from 78% to 99%. The protocol can easily be adapted for the bromination of other substrates in an academic and industrial environment.

Fruity flavors from waste: A novel process to upgrade crude glycerol to ethyl valerate.

Valeric acid and its ester derivatives are chemical compounds with a high industrial interest. Here we report a new approach to produce them from crude glycerol, by combining propionic acid fermentation with chain elongation. Propionic acid was produced by Propionibacterium acidipropionici (8.49 ±â€¯1.40 g·L-1). In the subsequent mixed population chain elongation, valeric acid was the dominant product (5.3 ±â€¯0.69 g·L-1) of the chain elongation process. Residual glycerol negatively impacted the selectivity of mixed culture chain elongation towards valeric acid, whereas this was unaffected when Clostridium kluyveri was used as bio-catalyst. Valeric acid could be selectively isolated and upgraded to ethyl valerate by using dodecane as extractant and medium for esterification, whereas shorter-chain carboxylic acids could be recovered by using a 10 wt% solution of trioctylphosphine oxide (TOPO) in dodecane. Overall, our work shows that the combined fermentation, electrochemistry and homogeneous catalysis enables fine chemical production from side streams.

Extraction and Esterification of Low-Titer Short-Chain Volatile Fatty Acids from Anaerobic Fermentation with Ionic Liquids.

Ionic liquids can both act as a solvent and mediate esterification to valorize low-titer volatile fatty acids and generate organic solvents from renewable carbon sources including biowaste and CO2 . In this study, four phosphonium ionic liquids were tested for single-stage extraction of acetic acid from a dilute stream and esterification to ethyl acetate with added ethanol and heat. The esterification proceeded with a maximum conversion of 85.9±1.3 % after 30 min at 75 °C at a 1:1 stoichiometric ratio of reactants. Extraction and esterification can be tailored using mixed-anion ionic liquids; this is demonstrated herein using a common trihexyl(tetradecyl)phosphonium cation and a mixed chloride and bis(trifluoromethylsulfonyl)imide anion ionic liquid. As a further proof-of-concept, ethyl acetate was generated from an ionic liquid-driven esterification of an acetic acid extractant generated using CO2 as the only carbon source by microbial electrosynthesis.

Could autonomous motivation hold the key to successfully implementing lifestyle changes in affective disorders? A multicentre cross sectional study.

There is a need for theoretically-based research on the motivational processes linked to the adoption and maintenance of an active lifestyle in people with affective disorders. Within the Self-Determination Theory (SDT) framework, we investigated the SDT tenets in people with major depressive disorder or bipolar disorder by examining the factor structure of the Behavioural Regulation in Exercise Questionnaire-2 (BREQ-2) and by investigating associations between motivation, the Positive and Negative Affect Scale (PANAS) and International Physical Activity Questionnaire (IPAQ) scores. A total of 165 patients (105 ♀) (45.6 ± 14.2 years) agreed to participate. An exploratory factor analysis demonstrated sufficient convergence with the original factor for amotivation, and external and introjected regulation. The items of identified and intrinsic regulation loaded on the same factor, which was labelled autonomous regulation. Significant correlations were found between the total IPAQ score and the subscales amotivation, external regulation, introjected regulation and autonomous regulation. The relative autonomy index (RAI) was associated with the PANAS scores. Differences in RAI were found between physically inactive and active participants. Our results suggest that in people with affective disorders the level of autonomous motivation may play an important role in the adoption and maintenance of health promoting behaviours.