No abstract

A series of N,N'-dialkyl-4,13-diaza-18-crown-6 lariat ethers possessing two C8H17 (2), (CH2)3C8F17 (3), (CH2)3C10F21 (4), and (CH2)2C8F17 (5) side arms were synthesized in good yields by N-alkylation of 4,13-diaza-18-crown-6. Potassium picrate could be extracted from an aqueous solution into an organic phase by all of the perfluoroalkylated macrocycles demonstrating their potential to be used as phase-transfer catalysts, and preliminary studies on a classical nucleophilic substitution established that they each gave higher catalytic activities under solid-liquid than under liquid-liquid phase-transfer conditions. The light fluorous macrocycles gave similar, if not better, catalytic activity compared to the parent, non-fluorinated phase-transfer catalyst 2 under solid-liquid conditions in conventional organic solvents in both an aliphatic and an aromatic nucleophilic substitution. N,N'-Bis(1H,1H,2H,2H,3H,3H-perfluoroundecyl)-4,13-diaza-18-crown-6 (3) was recycled six times in the iodide displacement reaction of 1-bromooctane and four times in the fluoride displacement reaction of 2,4-dinitrochlorobenzene using fluorous solid-phase extraction without any loss in activity.

Abstract:The fluorous tertiary phosphine [R f6 -

Abstract Background Brain imaging studies have shown altered amygdala activity during emotion processing in children and adolescents with oppositional defiant disorder (ODD) and conduct disorder (CD) compared to typically developing children and adolescents (TD). Here we aimed to assess whether aggression-related subtypes (reactive and proactive aggression) and callous-unemotional (CU) traits predicted variation in amygdala activity and skin conductance (SC) response during emotion processing. Methods We included 177 participants (n = 108 cases with disruptive behaviour and/or ODD/CD and n = 69 TD), aged 8–18 years, across nine sites in Europe, as part of the EU Aggressotype and MATRICS projects. All participants performed an emotional face-matching functional magnetic resonance imaging task. Results Differences between cases and TD in affective processing, as well as specificity of activation patterns for aggression subtypes and CU traits, were assessed. Simultaneous SC recordings were acquired in a subsample (n = 63). Cases compared to TDs showed higher amygdala activity in response to negative faces (fearful and angry) v. shapes. Subtyping cases according to aggression-related subtypes did not significantly influence on amygdala activity; while stratification based on CU traits was more sensitive and revealed decreased amygdala activity in the high CU group. SC responses were significantly lower in cases and negatively correlated with CU traits, reactive and proactive aggression. Conclusions Our results showed differences in amygdala activity and SC responses to emotional faces between cases with ODD/CD and TD, while CU traits moderate both central (amygdala) and peripheral (SC) responses. Our insights regarding subtypes and trait-specific aggression could be used for improved diagnostics and personalized treatment.