Ocean temperature response to idealized Gleissberg and de Vries solar cycles in a comprehensive climate model

The ~90-year Gleissberg and ~200-year de Vries cycles have been identified as two distinctive quasi-periodic components of Holocene solar activity. Evidence exists for the impact of such multi-decadal to centennial-scale variability in total solar irradiance (TSI) on climate, but concerning the ocean, this evidence is mainly restricted to the surface response. Here we use a comprehensive global climate model to study the impact of idealized solar forcing, representing the Gleissberg and de Vries cycles, on global ocean potential temperature at different depth levels, after a recent proxy record indicates a signal of TSI anomalies in the northeastern Atlantic at mid-depth. Potential impacts of TSI anomalies on deeper oceanic levels are climatically relevant due to their possible effect on ocean circulation by altering water mass characteristics. Simulated solar anomalies are shown to penetrate the ocean down to at least deep-water levels. Despite the fact that the two forcing periods differ only by a factor of ~2, the spatial pattern of response is significantly distinctive between the experiments, suggesting different mechanisms for solar signal propagation. These are related to advection by North Atlantic Deep Water flow (200-year forcing), and barotropic adjustment in the South Atlantic in response to a latitudinal shift of the westerly wind belt (90-year forcing).

Highly stereoselective decarboxylation of (+)-1-Bromo-1-chloro-2,2,2-trifluoropropanoic acid gives (+)-1-Bromo-1-chloro-2,2,2-trifluoroethane ((+)-Halothane) with retention of configuration

The absolute configuration of the title acid (2) has been determined to be S by X-ray crystallography. Thus, decarboxylation of 2 produces (S)-(+)-halothane with 99% retention of configuration. This behavior is compared to other stereoselective decarboxylation reactions of ?-haloacids from the literature that also give high degrees of retention of configuration when in the form of their quaternary ammonium salts, which contain one proton. The proton of the ammonium salt is necessary to protonate the anionic intermediate formed from decarboxylation. In the absence of this relatively acidic proton, we had previously found that using triethylene glycol (TEG) as both solvent and proton source for the decarboxylation reaction of acid 2 caused poor stereoselectivity. This was in contrast to 1,2,2,2-tetrafluoro-1-methoxypropionic acid (6), which showed a high degree of retention of configuration in TEG. To rationalize this differing behavior we report DFT studies at PCM-B3LYP/6-31++G** level of theory (the results were additionally confirmed with 6-311++G** and aug-cc-pVDZ basis sets). The energy barrier to inversion of configuration of the anionic reaction intermediate of acid 2 (11) is 10.23 kcal/mol. However, we find that the anionic intermediate from acid 6 (10) would rather undergo ?-elimination instead of inversion of configuration. Thus the planar transition state required for inversion of configuration is never reached, regardless of the rate of proton transfer to the anion.