Accelerated acquisition of wideline solid-state NMR spectra of spin 3/2 nuclei by frequency-stepped indirect detection experiments.

73% of all NMR-active nuclei are quadrupolar nuclei with a nuclear spin I > 1/2. The broadening of the solid-state NMR signals by the quadrupolar interaction often leads to poor sensitivity and low resolution. In this work we present experimental and theoretical investigations of magic angle spinning (MAS) 1H{X} double-echo resonance-echo saturation-pulse double-resonance (DE-RESPDOR) and Y{X} J-resolved solid-state NMR experiments for the indirect detection of spin 3/2 quadrupolar nuclei (X = spin 3/2 nuclei, Y = spin 1/2 nuclei). In these experiments, the spectrum of the quadrupolar nucleus is reconstructed by plotting the observed dephasing of the detected spin as a function of the transmitter offset of the indirectly detected spin. Numerical simulations were used to investigate the achievable levels of dephasing and to predict the lineshapes of indirectly detected NMR spectra of the quadrupolar nucleus. We demonstrate 1H, 31P and 207Pb detection of 35Cl, 81Br, and 63Cu (I = 3/2) nuclei in trans-Cl2Pt(NH3)2 (transplatin), (CH3NH3)PbCl3 (methylammonium lead chloride, MAPbCl3), (CH3NH3)PbBr3 (methylammonium lead bromide, MAPbBr3) and CH3C(CH2PPh2)3CuI (1,1,1-tris(diphenylphosphinomethyl)ethane copper(I) iodide, triphosCuI), respectively. In all of these experiments, we were able to detect megahertz wide central transition or satellite transition powder patterns. Significant time savings and gains in sensitivity were attained in several test cases. Additionally, the indirect detection experiments provide valuable structural information because they confirm the presence of dipolar or scalar couplings between the detected nucleus and the quadrupolar nucleus of interest. Finally, numerical simulations suggest these methods are also potentially applicable to abundant spin 5/2 and spin 7/2 quadrupolar nuclei.

Formation of Stable Radicals by Mechanochemistry and Their Application for Magic Angle Spinning Dynamic Nuclear Polarization Solid-State NMR Spectroscopy.

High-field magic angle spinning (MAS) dynamic nuclear polarization (DNP) is becoming a common technique for improving the sensitivity of solid-state nuclear magnetic resonance (SSNMR) by the hyperpolarization of nuclear spins. Recently, we have shown that gamma irradiation is capable of creating long-lived free radicals that are amenable to MAS DNP in quartz and a variety of organic solids. Here, we demonstrate that ball milling is able to generate millimolar concentrations of stable radical species in diverse materials such as polystyrene, cellulose, borosilicate glass, and fused quartz. High-field electron paramagnetic resonance (EPR) was used to obtain further insight into the nature of the radicals formed in ball milled quartz and borosilicate glass. We further show that radicals generated in quartz by ball milling can be used for solid-effect DNP. We obtained 29Si DNP enhancements of approximately 114 and 33 at 110 K and room temperature, respectively, from a sample of ball milled quartz.

Ergothioneine, Ovothiol A, and Selenoneine-Histidine-Derived, Biologically Significant, Trace Global Alkaloids.

The history, chemistry, biology, and biosynthesis of the globally occurring histidine-derived alkaloids ergothioneine (10), ovothiol A (11), and selenoneine (12) are reviewed comparatively and their significance to human well-being is discussed.