13C-1H HSQC Experiment of Probe Molecules Aligned in Thermotropic Liquid Crystals: Sensitivity and Resolution Enhancement in the Indirect Dimension

The spectra of molecules oriented in liquid crystalline media are dominated by partially averaged dipolar couplings. In the 13C–1H HSQC, due to the inefficient hetero-nuclear dipolar decoupling in the indirect dimension, normally carried out by using a π pulse, there is a considerable loss of resolution. Furthermore, in such strongly orienting media the 1H–1H and 13C–1H dipolar couplings leads to fast dephasing of transverse magnetization causing inefficient polarization transfer and hence the loss of sensitivity in the indirect dimension. In this study we have carried out 13C–1H HSQC experiment with efficient polarization transfer from 1H to 13C for molecules aligned in liquid crystalline media. The homonuclear dipolar decoupling using FFLG during the INEPT transfer delays and also during evolution period combined with the π pulse heteronuclear decoupling in the t1 period has been applied. The studies showed a significant reduction in partially averaged dipolar couplings and thereby enhancement in the resolution and sensitivity in the indirect dimension. This has been demonstrated on pyridazine and pyrimidine oriented in the liquid crystal. The two closely resonating carbons in pyrimidine are better resolved in the present study compared to the earlier work [H.S. Vinay Deepak, Anu Joy, N. Suryaprakash, Determination of natural abundance 15N–1H and 13C–1H dipolar couplings of molecules in a strongly orienting media using two-dimensional inverse experiments, Magn. Reson. Chem. 44 (2006) 553–565].

Rapid δ18O and δ13C isotopic shifts in late Pleistocene marine varves on the California margin

Upper Pleistocene sediments on the continental slope off Northern California contain alternations of varves and bioturbation produced by fluctuations in intensity of the coastal upwelling system. Stable isotopic analyses of benthic Foraminifera across a particularly well developed varve/bioturbation sequence deposited ~26,000 years ago reveal rapid shifts of ~0.25‰ in δ18O and ~0.4‰ in δ13C. The δ18O shift occurs within a varved section. Based on varve counts, the isotopic change occurred in less than 100 years. Timing and magnitude of the shift coincide with similar shifts observed in almost all other high-resolution δ18O records that have been interpreted as primarily representing global in-volume fluctuations.