Sensitive, quantitative carbon-13 NMR spectra by mechanical sample translation.
Collecting a truly quantitative carbon-13 spectrum is a time-consuming chore. Very long relaxation delays, required between transients to allow the z-magnetization, M(z), of the spin with the longest T(1) to return to the equilibrium value, M(0), must precede each transient. These long delays also reduce sensitivity, as fewer transients per unit time can be acquired. In addition, sometimes T(1) is not known to within even a factor of two: a conservative guess for the relaxation delay then leads to very low sensitivity. We demonstrate a fresh method to bypass these problems and collect quantitative carbon-13 spectra by swapping the sample volume after each acquisition with a different portion where the magnetization is already equilibrated to M(0). Loading larger sample volumes of 10-20 mL into an unusually long (1520 mm) 5 mm OD. NMR tube and vertically sliding the tube between acquisitions accomplishes the swap. The relaxation delay can then be skipped altogether. The spectra are thus both quantitative, and far more sensitive. We demonstrate the moving tube technique on two small molecules (thymol and butylhydroxytoluene) and show good carbon-13 quantification. The gain in sensitivity can be as much as 10-fold for slowly-relaxing (13)C resonances. These experiments show that quantitative, sensitive carbon-13 spectra are possible whenever sufficient sample volumes are available. The method is applicable to any slow-relaxing nuclear spin species, such as (29)Si, (15)N and other low-gamma nuclei.
Donovan
Kevin J
KJ
Chemistry Department, University of California, Irvine, CA 92697-2025, USA.
Allen
Mary
M
Martin
Rachel W
RW
Shaka
A J
AJ
D002084:Butylated Hydroxytoluene / Q000737:chemistry; D002247:Carbon Isotopes; D002725:Chloroform / Q000737:chemistry; D009682:Magnetic Resonance Spectroscopy / Q000295:instrumentation / Q000379:methods*; D013943:Thymol / Q000737:chemistry
D002247:Carbon Isotopes; D002084:Butylated Hydroxytoluene; D013943:Thymol; D002725:Chloroform