Post-acquisition correction of NMR spectra distorted by dynamic and static field inhomogeneity of cryogen-free magnets.

Post-acquisition correction of NMR spectra is an important part of NMR spectroscopy that enables refined NMR spectra to be obtained, clean from undesirable out-phasing, broadening and noising. We describe analytical and numerical mathematical methods for post-acquisition correction of NMR spectra distorted by static and dynamic magnetic field inhomogeneity caused by imperfections of main superconducting coils and the cold head operation, typical for cryogen-free magnets. For the dynamic inhomogeneity, we apply a variant of the general reference deconvolution method, complemented with our mathematical analysis of spectral parameters. For the static inhomogeneity, we apply the method of a delayed Fourier transform, also supported with our analytical calculations. We verify our approach by correction processing of high-field experimental liquid-state 1H NMR spectra of water and ethanol as well as solid-state 13C MAS NMR spectra of adamantane and obtain good results for both static and dynamic field distortions. This work complements our previous work on instrumental suppression of dynamic distortions caused by the cold head operation. The results presented contribute well to the general field of processing NMR spectra and serve towards a more extensive use of cryogen-free magnets in high-resolution NMR spectroscopy.

Cryogen-free 400 MHz (9.4 T) solid state MAS NMR system with liquid state NMR potential.

We show that the temporal magnetic field distortion generated by the Cold Head operation can be removed and high quality Solid-State Magic Angle Spinning NMR results can be obtained with a cryogen-free magnet. The compact design of the cryogen-free magnets allows for the probe to be inserted either from the bottom (as in most NMR systems) or, more conveniently, from the top. The magnetic field settling time can be made as short as an hour after a field ramp. Therefore, a single cryogen-free magnet can be used at different fixed fields. The magnetic field can be changed every day without compromising the measurement resolution.

A new method to measure the temporal magnetic field instabilities in cryogen-free magnets for magnetic resonance.

Despite the obvious advantages of cryogen-free magnets for NMR such as independence of liquid helium supply and the possibility to use the same magnet at different fields, the practical application of those magnets remains limited because of temporal magnetic field distortions associated with cryogen-free cold head operation. A new experimental method for the simple and reliable detection of the temporal field distortions is described in this paper. The accuracy of the magnetic field measurements by this method is two orders of magnitude higher than by conventional MetroLab Tesla meter. This has enabled us to make improvements in the design of cryogen-free magnets by reducing the amplitude of such field distortions down to sub ppb level. This then results in cryogen-free magnets that are suitable for MRI and MAS NMR applications.

A method for fast field settling in cryogen-free superconducting magnets for NMR.

We propose a fast algorithm to energise a cryogen free magnet to a highly persistent state. A decay rate as low as 0.021 â€‹ppm/h can be achieved in less than an hour after reaching the target field. The decay rate drops further to 0.0004 â€‹ppm/h in the following 48 â€‹h. This procedure can be applied at different values of target field, which makes it feasible to use a single magnet for study of various NMR lines at different fields. The mechanism of establishing a highly stable magnetic field can be understood on the basis of the magnetic properties of the superconducting wire, which were studied using a vibrating sample magnetometer. The results confirm the high quality of the superconducting wire and joints.

On the magnetic field stability of cryogen-free magnets for magnetic resonance applications.

The temporal magnetic field variation associated with Cold Head operation in cryogen-free magnets was studied. Three different mechanisms for such variations were tested separately and rated by their importance. It was found that mechanical displacement of the magnet inside the cryostat is the main issue of magnetic field perturbation. In a cryostat with the Gifford- McMahon type of cryocooler, motion of the displacer with magnetic material inside also produces significant field modulation. The temperature variation of the magnet, although noticeable, leads to smaller field distortions compared to the previous two factors. It was shown that the temporal magnetic field variation could be reduced down to below 20 â€‹ppb level that could be acceptable for MRI and MAS NMR applications. It was also shown that a single cryogen-free magnet could be easily used at different fields on a day-to-day basis without compromising the field stability unlike magnets housed in a liquid helium reservoir.

A spectrometer designed for 6.7 and 14.1 T DNP-enhanced solid-state MAS NMR using quasi-optical microwave transmission.

A Dynamic Nuclear Polarisation (DNP) enhanced solid-state Magic Angle Spinning (MAS) NMR spectrometer operating at 6.7 T is described and demonstrated. The 187 GHz TE(13) fundamental mode of the FU CW VII gyrotron is used as the microwave source for this magnetic field strength and 284 MHz (1)H DNP-NMR. The spectrometer is designed for use with microwave frequencies up to 395 GHz (the TE(16) second-harmonic mode of the gyrotron) for DNP at 14.1T (600 MHz (1)H NMR). The pulsed microwave output from the gyrotron is converted to a quasi-optical Gaussian beam using a Vlasov antenna and transmitted to the NMR probe via an optical bench, with beam splitters for monitoring and adjusting the microwave power, a ferrite rotator to isolate the gyrotron from the reflected power and a Martin-Puplett interferometer for adjusting the polarisation. The Gaussian beam is reflected by curved mirrors inside the DNP-MAS-NMR probe to be incident at the sample along the MAS rotation axis. The beam is focussed to a ~1 mm waist at the top of the rotor and then gradually diverges to give much more efficient coupling throughout the sample than designs using direct waveguide irradiation. The probe can be used in triple channel HXY mode for 600 MHz (1)H and double channel HX mode for 284 MHz (1)H, with MAS sample temperatures ≥85 K. Initial data at 6.7 T and ~1 W pulsed microwave power are presented with (13)C enhancements of 60 for a frozen urea solution ((1)H-(13)C CP), 16 for bacteriorhodopsin in purple membrane ((1)H-(13)C CP) and 22 for (15)N in a frozen glycine solution ((1)H-(15)N CP) being obtained. In comparison with designs which irradiate perpendicular to the rotation axis the approach used here provides a highly efficient use of the incident microwave beam and an NMR-optimised coil design.

Determination of the temperature dependence of the dynamic nuclear polarisation enhancement of water protons at 3.4 Tesla.

It is shown that the temperature dependence of the DNP enhancement of the NMR signal from water protons at 3.4 T using TEMPOL as a polarising agent can be obtained provided that the nuclear relaxation, T(1I), is sufficiently fast and the resolution sufficient to measure the (1)H NMR shift. For high radical concentrations (∼100 mM) the leakage factor is approximately 1 and, provided sufficient microwave power is available, the saturation factor is also approximately 1. In this situation the DNP enhancement is solely a product of the ratio of the electron and nuclear gyromagnetic ratios and the coupling factor enabling the latter to be directly determined. Although the use of high microwave power levels needed to ensure saturation causes rapid heating of the sample, this does not prevent maximum DNP enhancements, ε(0), being obtained since T(1I) is very much less than the characteristic heating time at these concentrations. It is necessary, however, to know the temperature variation of T(1I) to allow accurate modelling of the behaviour. The DNP enhancement is found to vary linearly with temperature with ε(0)(T) = -2 ± 2 - (1.35 ± 0.02)T for 6 °C ≤ T ≤ 100 °C. The value determined for the coupling factor, 0.055 ± 0.003 at 25 °C, agrees very well with the molecular dynamics simulations of Sezer et al. (Phys. Chem. Chem. Phys., 2009, 11, 6626) who calculated 0.0534, however the experimental values increase much more rapidly with increasing temperature than predicted by these simulations. Large DNP enhancements (|ε(0)| > 100) are reported at high temperatures but it is also shown that significant enhancements (e.g.∼40) can be achieved whilst maintaining the sample temperature at 40 °C by adjusting the microwave power and irradiation time. In addition, short polarisation times enable rapid data acquisition which permits further enhancement of the signal, such that useful liquid state DNP-NMR experiments could be carried out on very small samples.

DNP enhanced NMR using a high-power 94 GHz microwave source: a study of the TEMPOL radical in toluene.

DNP enhanced (1)H NMR at 143 MHz in toluene is investigated using an NMR spectrometer coupled with a modified EPR spectrometer operating at 94 GHz and TEMPOL as the polarisation agent. A 100 W microwave amplifier was incorporated into the output stage of the EPR instrument so that high microwave powers could be delivered to the probe in either CW or pulsed mode. The maximum enhancement for the ring protons increases from approximately -16 for a 5 mM TEMPOL solution to approximately -50 for a 20 mM solution at a microwave power of approximately 480 mW. The temperature dependence of the enhancement, the NMR relaxation rates and the ESR spectrum of TEMPOL were also studied in an effort to obtain information on the dynamics of the system.