After a brief theoretical description, new gradient-selected, proton-detected heteronuclear correlation sequences are introduced. The gs-HMBC and gs-Relayed-HMQC are closely related to the original gs-HMQC proposed by Hurd and John. A new approach to obtain pure absorption line shapes in gradient selected spectroscopy is used to measure phase-sensitive gs-HMQC spectra, to carry out multiplicity editing in HSQC spectra and to distinguish direct and long-range correlations in HMQC/HSQC-TOCSY spectra.

While the characterization of materials by NMR is hugely important in the physical and biological sciences, it also plays a vital role in medical imaging. This success is all the more impressive because of the inherently low sensitivity of the method. We establish here that [Ir(H)2(IMes)(py)3]Cl undergoes both pyridine (py) loss as well as the reductive elimination of H2. These reversible processes bring para-H2 and py into contact in a magnetically coupled environment, delivering an 8100-fold increase in 1H NMR signal strength relative to non-hyperpolarized py at 3 T. An apparatus that facilitates signal averaging has been built to demonstrate that the efficiency of this process is controlled by the strength of the magnetic field experienced by the complex during the magnetization transfer step. Thermodynamic and kinetic data combined with DFT calculations reveal the involvement of [Ir(H)2(η2-H2)(IMes)(py)2]+, an unlikely yet key intermediate in the reaction. Deuterium labeling yields an additional 60% improvement in signal, an observation that offers insight into strategies for optimizing this approach.

Here we show, for the first time, evidence of the primary molecular structures in humic substances (HS), the most abundant naturally occurring organic molecules on Earth, and their associations as mixtures in terrestrial systems. Multi-dimensional nuclear magnetic resonance (NMR) experiments show us that the major molecular structural components in the mixtures operationally defined as HS are aliphatic acids, ethers, esters and alcohols; aromatic lignin derived fragments; polysaccharides and polypeptides. By means of diffusion ordered spectroscopy, distinct diffusion coefficients consistent with relatively low molecular weight molecules were observed for all the components in the mixtures, and saccharides were the largest single class of component present. Liquid chromatography NMR confirmed that HS components can be easily separated and nuclear Overhauser effect (NOE) enhancements support the finding that the components are of relatively low molecular weight

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Recently, we have introduced the ADEQUATE pulse sequence as a sensitive method to observe 13 C, 13 C correlations in natural products. This kind of experiment suffers from offset-dependent effects of the 180• ( 13 C) pulses. Here we describe an application of smoothed chirp pulses in the ADEQUATE pulse sequence which allows 13 C, 13 C correlations to be run without any offset dependences. This experiment is called chirp ADEQUATE and was applied to d-valerolactone and cholesteryl acetate. This modification will allow a general application of the ADEQUATE pulse sequence.

Diffusion ordered spectroscopy (DOSY) was applied to two extracts of organic matter from the surface horizon of an oak forest soil. It was possible to identify and confirm the presence of numerous aliphatic, aromatic, sugar, and amino acid components that could be separated on the basis of diffusion in DMSO-d6 and D2O. On average, sugar components were identified as the largest molecules in solution, with molecular masses up to approximately 1500 Da followed by the aliphatic and aromatic components. Amino acids with a range of molecular weights were also identified in the mixture. The summation of the individual slices from the DOSY experiment closely resembles the conventional 1H spectra of the material, indicating that the components identified with DOSY represent all the components present in the mixture. The separation of components in the mixture in organic solvent supports new findings that fulvic and humic acids are not cross-linked, high molecular weight macromolecules but are instead aggregates composed of relatively simple molecules that take on colloidal properties in the presence of metal ions in aqueous solution. Using the knowledge that these organic mixtures are combinations of relatively simple entities with well-documented reactivities and behavior will improve our ability to predict and model their interactions and fate under natural conditions.

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