title: J-modulation effects in DOSY experiments and their suppression: the Oneshot45 experiment.
abstract: Diffusion-ordered spectroscopy (DOSY) is a powerful NMR method for identifying compounds in mixtures. DOSY experiments are very demanding of spectral quality; even small deviations from expected behaviour in NMR signals can cause significant distortions in the diffusion domain. This is a particular problem when signals overlap, so it is very important to be able to acquire clean data with as little overlap as possible. DOSY experiments all suffer to a greater or lesser extent from multiplet phase distortions caused by J-modulation, requiring a trade-off between such distortions and gradient pulse width. Multiplet distortions increase spectral overlap and may cause unexpected and misleading apparent diffusion coefficients in DOSY spectra. These effects are described here and a simple and effective remedy, the addition of a 45° purging pulse immediately before the onset of acquisition to remove the unwanted anti-phase terms, is demonstrated. As well as affording significantly cleaner results, the new method allows much longer diffusion-encoding pulses to be used without problems from J-modulation, and hence greatly increases the range of molecular sizes that can be studied for coupled spin systems. The sensitivity loss is negligible and the added phase cycling is modest. The new method is illustrated for a widely-used general purpose DOSY pulse sequence, Oneshot.
authors.affiliation: School of Chemistry, University of Manchester, Manchester M13 9PL, UK.
authors.forename: Adolfo
authors.initials: A
authors.lastname: Botana
authors.forename: Juan A
authors.initials: JA
authors.lastname: Aguilar
authors.forename: Mathias
authors.initials: M
authors.lastname: Nilsson
authors.forename: Gareth A
authors.initials: GA
authors.lastname: Morris
mesh_terms: D000433:1-Propanol; D000080462:Acyclic Monoterpenes; D000465:Algorithms; D000081008:Bicyclic Monoterpenes; D004058:Diffusion; D004121:Dimethyl Sulfoxide; D009682:Magnetic Resonance Spectroscopy / Q000379:methods*; D000439:Pentanols; D011803:Quinine / Q000737:chemistry; D013729:Terpenes / Q000737:chemistry; D014297:Trimethylsilyl Compounds / Q000737:chemistry
chemical_list: D000080462:Acyclic Monoterpenes; D000081008:Bicyclic Monoterpenes; D000439:Pentanols; D013729:Terpenes; D014297:Trimethylsilyl Compounds; C073196:tetramethylsilane; D000433:1-Propanol; D011803:Quinine; C019286:camphene; C007836:geraniol; D004121:Dimethyl Sulfoxide