Long-range shielding effects in the (1)H NMR spectra of Mosher-like ester derivatives.

The relative magnitudes of the chemical shift differences (Deltadeltas) in the two diastereomers of menthyl esters of known chiral derivatizing agents (CDAs) were compared to those of the alpha-methoxy-alpha-trifluoromethyl-1-naphthylacetyl (MTN((1))A) analogues I. Discrimination of the terminal diastereotopic methyl resonances in esters of the homologous, symmetrical carbinols II was evaluated. Remarkably, the methyls differed in the MTN((1))A esters III even when n = 15; an unexpected crossover in the sign of the Deltadelta values was also observed.

Computational and experimental analysis of pinch-off and scaling.

Pinch-off and scaling during drop formation are studied using high-accuracy computation and ultrafast, high-resolution imaging. The interface of a water drop (viscosity mu is approximately 1 cP) is shown to overturn prior to breakup for the first time in experiments, well before the dynamics transitions from the potential flow (PF) to the inertial-viscous (IV) regime. A drop of 83% glycerol-water solution (mu is approximately 85 cP) is shown to exhibit a transition from the PF to the IV regime both computationally and experimentally. The computed value of the minimum neck radius in the latter case follows Eggers's universal solution until it becomes unstable.