Kurt W. Zilm

Chemical shift referencing in MAS solid state NMR.

Solid state 13C magic angle spinning (MAS) NMR spectra are typically referenced externally using a probe which does not incorporate a field frequency lock. Solution NMR shifts on the other hand are more often determined with respect to an internal reference and using a deuterium based field frequency lock. Further differences arise in solution NMR of proteins and nucleic acids where both 13C and 1H shifts are referenced by recording the frequency of the 1H resonance of DSS (sodium salt of 2,2-dimethyl-2-silapentane-5-sulphonic acid) instead of TMS (tetramethylsilane). In this note we investigate the difficulties in relating shifts measured relative to TMS and DSS by these various approaches in solution and solids NMR, and calibrate adamantane as an external 13C standard for solids NMR. We find that external chemical shift referencing of magic angle spinning spectra is typically quite reproducible and accurate, with better than +/-0.03 ppm accuracy being straight forward to achieve. Solid state and liquid phase NMR shifts obtained by magic angle spinning with external referencing agree with those measured using typical solution NMR hardware with the sample tube aligned with the applied field as long as magnetic susceptibility corrections and solvent shifts are taken into account. The DSS and TMS reference scales for 13C and 1H are related accurately using MAS NMR. Large solvent shifts for the 13C resonance in TMS in either deuterochloroform or methanol are observed, being +0.71 ppm and -0.74 ppm from external TMS, respectively. The ratio of the 13C resonance frequencies for the two carbons in solid adamantane to the 1H resonance of TMS is reported.

Further conventions for NMR shielding and chemical shifts (IUPAC Recommendations 2008)

IUPAC has published a number of recommendations regarding the reporting of nuclear magnetic resonance (NMR) data, especially chemical shifts. The most recent publication [Pure Appl. Chem.73, 1795 (2001)] recommended that tetramethylsilane (TMS) serve as a universal reference for reporting the shifts of all nuclides, but it deferred recommendations for several aspects of this subject. This document first examines the extent to which the 1H shielding in TMS itself is subject to change by variation in temperature, concentration, and solvent. On the basis of recently published results, it has been established that the shielding of TMS in solution [along with that of sodium-3-(trimethylsilyl)propanesulfonate, DSS, often used as a reference for aqueous solutions] varies only slightly with temperature but is subject to solvent perturbations of a few tenths of a parts per million (ppm). Recommendations are given for reporting chemical shifts under most routine experimental conditions and for quantifying effects of temperature and solvent variation, including the use of magnetic susceptibility corrections and of magic-angle spinning (MAS). This document provides the first IUPAC recommendations for referencing and reporting chemical shifts in solids, based on high-resolution MAS studies. Procedures are given for relating 13C NMR chemical shifts in solids to the scales used for high-resolution studies in the liquid phase. The notation and terminology used for describing chemical shift and shielding tensors in solids is reviewed in some detail, and recommendations are given for best practice.

Preparation of protein nanocrystals and their characterization by solid state NMR.

Preparation of proteins in their crystalline state has been found to be important in producing stable therapeutic protein formulations, cross-linked enzyme crystals for application in industrial processes, generating novel porous media for separations, and of course in structure elucidation. Of these applications only X-ray crystallography requires large crystals, defined here as being crystals 100s of microns or greater in size. Smaller crystals have attractive attributes in many instances, and are just as useful in structure determination by solid state NMR (ssNMR) as are large crystals. In this paper we outline a simple set of procedures for preparing nanocrystalline protein samples for ssNMR or other applications and describe the characterization of their crystallinity by ssNMR and X-ray powder diffraction. The approach is demonstrated in application to five different proteins: ubiquitin, lysozyme, ribonuclease A, streptavidin, and cytochrome c. In all instances the nanocrystals produced are found to be highly crystalline as judged by natural abundance 13C ssNMR and optical and electron microscopy. We show for ubiquitin that nanocrystals prepared by rapid batch crystallization yield equivalent 13C ssNMR spectra to those of larger X-ray diffraction quality crystals. Single crystal and powder X-ray diffraction measurements are made to compare the degree of order present in polycrystalline, nanocrystalline, and lyophilized ubiquitin. Solid state 13C NMR is also used to show that ubiquitin nanocrystals are thermally robust, giving no indication of loss of local order after repeated temperature cycling between liquid nitrogen and room temperature. The methods developed are rapid and should scale well from the tenths of milligram to multi-gram scales, and as such should find wide utility in the preparation of protein nanocrystals for applications in catalysis, separations, and especially in sample preparation for structural studies using ssNMR.

Carbon-13 CP/MAS spectroscopy of coal macerals

Abstract 13 C n.m.r. spectra of kerogen concentrates isolated from several different subbituminous to high-volatile bituminous coal macerals have been obtained by a combined cross polarization/magic-angle spinning technique. The samples comprise three vitrinites, two sporinites, two alginites and one fusinite, all of Upper Paleozoic age. It is shown that this technique can be used to differentiate the maceral types by providing characteristic spectral fingerprints. Aromaticities decrease in the order fusinite vitrinite sporinite alginite, as expected with the rank range studied. Furthermore, fine spectral details provide general information on the nature and distribution of discrete structural moieties and their variations with both type and rank.

Carbon-13 magnetic resonance of coal-derived liquids

Abstract Carbon-13 Nuclear Magnetic Resonance Spectroscopy has been applied to coal-derived liquids in order to obtain additional information regarding molecular structure and composition. The data have demonstrated that, although the chemical structure is extremely complex, a significant amount of material is present in the form of normal paraffinic material both as free paraffins and alkyl substituents on aromatic and hydroaromatic materials. Semiquantitative estimates are made of the alkyl content of the liquids and the atom percentage of this material that must exist in the unprocessed coal.

13C NMR spectroscopy in diamonds using dynamic nuclear polarization

Abstract In diamonds unpaired electrons associated with nitrogen impurities can be used to enhance the 13 C NMR signal via the solid-state effect. 13 C spectra of three natural and two synthetic diamonds are shown that were obtained in this manner in 10–30 min.

Design of a triple resonance magic angle sample spinning probe for high field solid state nuclear magnetic resonance

Standard design and construction practices used in building nuclear magnetic resonance (NMR) probes for the study of solid state samples become difficult if not entirely impractical to implement as the 1H resonance frequency approaches the self resonance frequency of commercial capacitors. We describe an approach that utilizes short variable transmission line segments as tunable reactances. Such an approach effectively controls stray reactances and provides a higher Q alternative to ceramic chip capacitors. The particular probe described is built to accommodate a 2.5 mm magic angle spinning rotor system, and is triply tuned to 13C, 15N, and 1H frequencies for use at 18.8 T (200, 80, and 800 MHz, respectively). Isolation of the three radio frequency (rf) channels is achieved using both a rejection trap and a transmission line notch filter. The compact geometry of this design allows three channels with high power handling capability to fit in a medium bore (63 mm) magnet. Extended time variable temperature ...

Further conventions for NMR shielding and chemical shifts (IUPAC Recommendations 2008).

IUPAC has published a number of recommendations regarding the reporting of nuclear magnetic resonance (NMR) data, especially chemical shifts. The most recent publication [Pure Appl. Chem. 73, 1795 (2001)] recommended that tetramethylsilane (TMS) serve as a universal reference for reporting the shifts of all nuclides, but it deferred recommendations for several aspects of this subject. This document first examines the extent to which the 1H shielding in TMS itself is subject to change by variation in temperature, concentration, and solvent. On the basis of recently published results, it has been established that the shielding of TMS in solution [along with that of sodium‐3‐(trimethylsilyl)propanesulfonate, DSS, often used as a reference for aqueous solutions] varies only slightly with temperature but is subject to solvent perturbations of a few tenths of a part per million (ppm). Recommendations are given for reporting chemical shifts under most routine experimental conditions and for quantifying effects of temperature and solvent variation, including the use of magnetic susceptibility corrections and of magic‐angle spinning (MAS).

A comparison of the carbon-13 n.m.r. spectra of solid coals and their liquids obtained by catalytic hydrogenation

Abstract High-volatile bituminous and lignite coals have been studied by means of carbon-13 n.m.r. employing cross-polarization and magic-angle-spinning techniques. The solids spectra have been compared to those of the coal-derived liquids. By artificially broadening the high-resolution spectra of the liquids, a striking similarity in line shape and position is observed when the liquid spectra are compared with those of the corresponding solid coal. It is noted however that certain bands visible in the solid are no longer present in the liquefied state. The significance of these results is discussed in terms of carbon skeletal structures present in the solids but not in the liquids.

Further conventions for NMR shielding and chemical shifts IUPAC recommendations 2008.

IUPAC has published a number of recommendations regarding the reporting of nuclear magnetic resonance (NMR) data, especially chemical shifts. The most recent publication [Pure Appl. Chem. 73, 1795 (2001)] recommended that tetramethylsilane (TMS) serve as a universal reference for reporting the shifts of all nuclides, but it deferred recommendations for several aspects of this subject. This document first examines the extent to which the (1)H shielding in TMS itself is subject to change by variation in temperature, concentration, and solvent. On the basis of recently published results, it has been established that the shielding of TMS in solution [along with that of sodium-3-(trimethylsilyl)propanesulfonate, DSS, often used as a reference for aqueous solutions] varies only slightly with temperature but is subject to solvent perturbations of a few tenths of a part per million (ppm). Recommendations are given for reporting chemical shifts under most routine experimental conditions and for quantifying effects of temperature and solvent variation, including the use of magnetic susceptibility corrections and of magic-angle spinning (MAS). This document provides the first IUPAC recommendations for referencing and reporting chemical shifts in solids, based on high-resolution MAS studies. Procedures are given for relating (13)C NMR chemical shifts in solids to the scales used for high-resolution studies in the liquid phase. The notation and terminology used for describing chemical shift and shielding tensors in solids are reviewed in some detail, and recommendations are given for best practice.