Hartmann-Hahn 2D-map to optimize the RAMP-CPMAS NMR experiment for pharmaceutical materials.

Cross polarization-magic angle spinning (CPMAS) is the most used experiment for solid-state NMR measurements in the pharmaceutical industry, with the well-known variant RAMP-CPMAS its dominant implementation. The experimental work presented in this contribution focuses on the entangled effects of the main parameters of such an experiment. The shape of the RAMP-CP pulse has been considered as well as the contact time duration, and a particular attention also has been devoted to the radio-frequency (RF) field inhomogeneity.

Direct quantification of M/G ratio from (13)C CP-MAS NMR spectra of alginate powders by multivariate curve resolution.

Multivariate curve resolution (MCR) was applied to (13)C cross-polarisation (CP) magic angle spinning (MAS) nuclear magnetic resonance (NMR) spectra of non-depolymerised alginate powders obtained from brown seaweed plus a pure mannuronate sample isolated from Pseudomonas fluorescens for estimation of the mannuronic acid/guluronic acid ratio (M/G ratio). An excellent MCR model with a correlation coefficient of r(2)=0.99 was established between the estimated M/G ratios and the M/G ratios obtained from the traditional (1)H solution state NMR method.

High anion conductivity in a ternary non-equilibrium phase of BaF(2) and CaF(2) with mixed cations.

A highly conductive ternary fluoride with mixed cations is prepared by joint high-energy ball milling of cubic BaF(2) and CaF(2) in the ratio 0.4 : 0.6.

Fast acquisition of multi-dimensional spectra in solid-state NMR enabled by ultra-fast MAS.

The advantages offered by ultra-fast (>60 kHz) magic angle spinning (MAS) rotation for the study of biological samples, notably containing paramagnetic centers are explored. It is shown that optimal conditions for performing solid-state (13)C NMR under 60 kHz MAS are obtained with low-power CW (1)H decoupling, as well as after a low-power (1)H,(13)C cross-polarization step at a double-quantum matching condition. Acquisition with low-power decoupling highlights the existence of rotational decoupling sidebands.

Non-covalent interactions of a drug molecule encapsulated in a hybrid silica gel.

The drug molecule Propranolol has been encapsulated by a sol-gel process in an organic-inorganic hybrid matrix by in-situ self-assembly; the 2D HETCOR solid state NMR spectroscopy provides direct proof of the intimate spatial relationship between the host matrix and guest drug molecules.

93Nb and 17O NMR chemical shifts of niobiophosphate compounds.

Niobiophosphate compounds with a large range of niobium and oxygen environments were studied with (93)Nb and (17)O solid-state NMR. (93)Nb isotropic chemical shift of pure niobate Nb(ONb)(6), pure phosphate Nb(OP)(6) and mixed phosphate-niobate Nb(OP)(x)(ONb)((6-x)) (1 View Article and Find Full Text PDF

Formation of solvent cages around organometallic complexes in thin films of supported ionic liquid.

The first experimental evidence for the formation of ordered three-dimensional structures in solutions of organometallic complexes in a thin film of supported ionic liquid was obtained. The ordering effect leads to drastically reduced mobility of ionic liquid and complex molecules.

Two-dimensional one pulse MAS of half-integer quadrupolar nuclei.

We show that the two-dimensional one pulse (TOP) representation of magic-angle spinning nuclear magnetic resonance data of half-integer quadrupolar nuclei has significant advantages over the conventional one-dimensional spectrum. The TOP spectrum, which correlates NMR frequency to spinning sideband order, provides a rapid determination of the number of sites as well as the size of the their quadrupolar coupling. Additionally, synchronous acquisition spectra of the central and satellite transition resonances can be separated by different projections of the TOP spectrum, with higher resolution spectra often found in the satellite transitions projection.

Proton to carbon-13 INEPT in solid-state NMR spectroscopy.

A refocused INEPT through-bond coherence transfer technique is demonstrated for NMR of rigid organic solids and is shown to provide a valuable building block for the development of NMR correlation experiments in biological solids. The use of efficient proton homonuclear dipolar decoupling in combination with a direct spectral optimization procedure provides minimization of the transverse dephasing of coherences and leads to very efficient through-bond (1)H-(13)C INEPT transfer for crystalline organic compounds. Application of this technique to 2D heteronuclear correlation spectroscopy leads to up to a factor of 3 increase in sensitivity for a carbon-13 enriched sample in comparison to standard through-bond experiments and provides excellent selectivity for one-bond transfer.

Increasing the sensitivity of 2D high-resolution NMR methods applied to quadrupolar nuclei.

Gan and Kwak recently proposed a soft-pulse added mixing (SPAM) idea in the classical two-pulse multiple-quantum magic-angle spinning scheme. In the SPAM method, a soft pi/2 pulse is added after the second hard-pulse (conversion pulse) and all coherence orders in between them are constructively used to obtain the signal. We, here, further extend this idea to distributed samples where the signal mainly results from echo pathways and that from anti-echo pathways dies out after a few t1 increments.

High-resolution 17O NMR spectroscopy of wadsleyite (beta-Mg2SiO4).

The sensitivity of high-resolution 17O (I = 5/2) NMR spectroscopy of solids has advanced significantly in recent years. Here, we show that excellent results are now obtainable from milligram quantities of 17O-enriched materials, thereby allowing the technique to be applied to silicate phases synthesized under very high pressures in a multiple-anvil apparatus. We report the first 17O NMR study of beta-Mg2SiO4 (9.

Experimental aspects of proton NMR spectroscopy in solids using phase-modulated homonuclear dipolar decoupling.

In this paper we demonstrate experimentally that the continuously phase-modulated homonuclear decoupling sequence DUMBO-1 is suitable for high-resolution proton NMR spectroscopy of rigid solids. Over a wide range of experimental conditions, we show on the model sample L-alanine as well as on small peptides that proton linewidths of less than 0.5 ppm can be obtained under DUMBO-1 decoupling.

1H detection in MAS solid-state NMR spectroscopy of biomacromolecules employing pulsed field gradients for residual solvent suppression.

In this communication, we demonstrate the feasibility of 1H detection in MAS solid-state NMR for a microcrystalline, uniformly 2H,15N-labeled sample of a SH3 domain of chicken alpha-spectrin, using pulsed field gradients for suppression of water magnetization. Today, B0 gradients are employed routinely in solution-state NMR for coherence order selection and solvent suppression. We suggest to use gradients to purge water magnetization which cannot be suppressed using conventional water suppression schemes.

Continuous decomposition of sporopollenin from pollen of Typha angustifolia L. by acidic methanolysis.

Sporopollenin from the pollen of Typha angustifolia L. was exposed to a series of 36 subsequent acidic methanolysis procedures. The remaining decomposition products were investigated using several spectroscopic methods including Fourier transform infrared spectroscopy (FT-IR), solid state 13C nuclear magnetic resonance spectroscopy (13C-CPMAS-NMR) and X-ray photoelectron spectrometry (XPS).

Residual 31P, 35,37Cl dipolar coupling in 31P MAS spectra of chlorocyclophosphazenes.

In 31P MAS NMR spectra of chlorocyclophosphazenes, characteristic splittings have been observed for PCI or PCl2 groups. At different applied magnetic fields, the fine structure and total width of the patterns change in a characteristic way, demonstrating that the splittings are due to indirect spin-spin and residual dipolar interactions with the chlorine nuclei directly bonded to phosphorus. For trans-nongeminal N3P3Cl3(NMe2)3 and N3P3Cl6 as examples, the spectra have been analyzed to obtain information on chlorine nuclear quadrupole coupling constants and 35,37Cl, 3P indirect spin-spin coupling constants.

Sample restriction using magnetic field gradients in high-resolution solid-state NMR.

Many solid-state NMR experiments are sensitive to inhomogeneity in the radiofrequency field. We propose a method to restrict the sample volume, in magic angle spinning experiments, using a static magnetic field gradient and a selective pulse. The position of the gradient is calculated for our experimental configuration and we have simulated the effects of selective pulses to determine the excited volume.

The nature of oxygen in sporopollenin from the pollen of Typha angustifolia L.

Native and peracetylated sporopollenin from the pollen of Typha angustifolia L. was investigated using several spectroscopic methods, inducing Fourier transform infrared spectroscopy (FTIR), solid-state 13C-nuclear magnetic resonance spectroscopy (13C-NMR) and X-ray photoelectron spectrometry (XPS). Interpretation of the experimental data shows that the greater part of oxygen found in sporopollenin originates from hydroxyl groups and must be derived from aliphatics and not from aromatics.

Very fast MAS and MQMAS NMR studies of the spectroscopically challenging minerals kyanite and andalusite on 400, 500, and 800 MHz spectrometers.

The well-characterized minerals kyanite and andalusite have long presented great challenges in using solid state 27Al NMR to determine the isotropic chemical shift deltaCS, quadrupole coupling constant e2qQ/h, and asymmetry parameter eta for each of the inequivalent aluminum sites in these minerals. Indeed, these minerals have frequently been used to test advances in instrumentation. Recent advances in magnet technology (up to 18.

A new sequence for the MQMAS/HETCOR experiment.

Two-dimensional (2D) multiple quantum MAS (magic angle spinning) spectroscopy has been combined with cross-polarisation to obtain a heteronuclear correlation spectrum between a quadrupolar spin-3/2 and a spin-1/2 nucleus. The advantage over the conventional correlation experiment is the increased resolution obtained in the multiple quantum dimension. Pure absorption 2D spectra can be obtained by implementing a zero quantum filter between the evolution of multiple quanta and the subsequent cross-polarisation step.

17O magic-angle spinning nuclear magnetic resonance of CaCO3.

The first 17O magic-angle spinning nuclear magnetic resonance (MAS-NMR) from a carbonate ion in an inorganic compound is reported. The 17O MAS centreband of CaCO3 can be simulated with parameters CQ = 6.97 MHz, eta approximately 1 and an isotropic chemical shift of 204 ppm.

Quantitative structural analysis of mullite by 27Al nuclear magnetic resonance satellite transition spectroscopy.

27Al Nuclear magnetic resonance (NMR) satellite transition spectroscopy has been used for the quantitative investigation of the microstructure of polycrystalline 2/1-type mullite (approximately 76 wt.-% Al2O3 and 24 wt.-% SiO2).

27Al satellite transition spectroscopy (SATRAS) of polycrystalline aluminum borate 9Al2O3.2B2O3.

27Al NMR spectra of polycrystalline aluminum borate 9Al2O3.2B2O3 have been measured at 104, 130 and 156 MHz. The parameters of the quadrupole interaction and the isotropic chemical shifts have been obtained by fitting the CT/MAS pattern and consideration of the inner satellite transitions m = 3/2<-->1/2 and m = - 1/2<-->- 3/2.