Joel's Journal Updates

Effects of Guanidinium-Phosphate Hydrogen Bonding on the Membrane-Bound Structure and Activity of an Arginine-Rich Membrane Peptide from Solid-State NMR Spectroscopy
Ming Tang, Alan J. Waring, Robert I. Lehrer, Mei Hong
Angwandte (2008)47, 3202.
Summary:
Barreling through: Guanidinium-phosphate hydrogen bonding significantly affects the structure and activity of the antimicrobial peptide PG-1. Solid-state NMR data show that a mutant of PG-1, having dimethylated Arg residues, adopts an in-plane orientation, interfacial location, and fast uniaxial motion around the membrane normal (see scheme). The less active mutant thus disrupts the membrane by in-plane diffusion, in contrast to the more active wild-type PG-1, which forms immobile transmembrane b-barrels to cause toroidal-pore membrane defects.

Application of Ultrahigh-Field 59Co Solid-State NMR Spectroscopy in the Investigation of the 1,2-Polybutadiene Catalyst [Co(C8H13)(C4H6)]
Patrick Crewdson, David L. Bryce, Frank Rominger, Peter Hofmann
Angwandte (2008)47, 3454.
Summary:
Highly suitable: The 1,2-polybutadiene catalyst [Co(3:2-C8H13)(4-C4H6)] (1) was isolated and structurally characterized by ultrahigh-field 59Co solid-state NMR spectroscopy, demonstrating the utility of this technique. It can be applied to study the formation mechanism of syndiotactic 1,2-polybutadiene.

Determination of NMR Lineshape Anisotropy of Guest Molecules within Inclusion Complexes from Molecular Dynamics Simulations
Saman Alavi, Peter Dornan, Tom K. Woo
ChemPhysChem(2008)9(6),911.
Abstract:
Nonspherical cages in inclusion compounds can result in non-uniform motion of guest species in these cages and anisotropic lineshapes in NMR spectra of the guest. Herein, we develop a methodology to calculate lineshape anisotropy of guest species in cages based on molecular dynamics simulations of the inclusion compound. The methodology is valid for guest atoms with spin 1/2 nuclei and does not depend on the temperature and type of inclusion compound or guest species studied. As an example, the nonspherical shape of the structure I (sI) clathrate hydrate large cages leads to preferential alignment of linear CO2 molecules in directions parallel to the two hexagonal faces of the cages. The angular distribution of the CO2 guests in terms of a polar angle and azimuth angle and small amplitude vibrational motions in the large cage are characterized by molecular dynamics simulations at different temperatures in the stability range of the CO2 sI clathrate. The experimental 13C NMR lineshapes of CO2 guests in the large cages show a reversal of the skew between the low temperature (77 K) and the high temperature (238 K) limits of the stability of the clathrate. We determine the angular distributions of the guests in the cages by classical MD simulations of the sI clathrate and calculate the 13C NMR lineshapes over a range of temperatures. Good agreement between experimental lineshapes and calculated lineshapes is obtained. No assumptions regarding the nature of the guest motions in the cages are required.

Proton Spin Diffusion in Polyethylene as a Function of Magic-Angle Spinning Rate. A Phenomenological Approach.
O. Dmitrenko, Shi Bai, Peter A. Beckmann, Scott van Bramer, Alexander J. Vega, and C. Dybowski
JPCA(2008)112,3046.
Abstract:
The analysis of heavy-metal solids with NMR spectroscopy provides a means of investigating the electronic environment through the dependence of the chemical shift on structure. We have investigated the relation of the 207Pb NMR isotropic chemical shift, span, and skew of a series of solid Pb(II) compounds to lattice parameters. Complementary relativistic spin-orbit density functional calculations on clusters such as PbI64- that model the local environment in the dihalides show a dependence of NMR properties on the local structure in good agreement with experimental results.

Low-Temperature NMR Studies of Zn Tautomerism and Hindered Rotations in Solid Zincocene Derivatives
Juan Miguel Lopez del Amo, Gerd Buntkowsky, Hans-Heinrich Limbach,* Irene Resa, Rafael Fernndez, and Ernesto Carmona
JPCA(2008)112,3557.
Abstract:
Using a combination of NMR methods we have detected and studied fluxional motions in the slip-sandwich structure of solid decamethylzincocene (I, [(5-C5Me5)Zn(1-C5Me5)]). For comparison, we have also studied the solid iminoacyl derivative [(5-C5Me5)Zn(1-C(NXyl)C5Me5)] (II). The variable temperature 13C CPMAS NMR spectra of I indicate fast rotations of both Cp* rings in the molecule down to 156 K as well as the presence of an order-disorder phase transition around 210 K. The disorder is shown to be dynamic arising from a fast combined Zn tautomerism and 1/5 reorganization of the Cp* rings between two degenerate states A and B related by a molecular inversion. In the ordered phase, the degeneracy of A and B is lifted; that is, the two rings X and Y are inequivalent, where X exhibits a larger fraction of time in the 5 state than Y. However, the interconversion is still fast and characterized by a reaction enthalpy of H = 2.4 kJ mol-1 and a reaction entropy of S = 4.9 J K-1 mol-1. In order to obtain quantitative kinetic information, variable temperature 2H NMR experiments were performed on static samples of I-d6 and II-d6 between 300 and 100 K, where in each ring one CH3 is replaced by one CD3 group. For II-d6, the 2H NMR line shapes indicate fast CD3 group rotations and a fast "5 rotation", corresponding to 72 rotational jumps of the 5 coordinated Cp* ring. The latter motion becomes slow around 130 K. By line shape analysis, an activation energy of the 5 rotation of about 21 kJ mol-1 was obtained. 2H NMR line shapes analysis of I-d6 indicates fast CD3 group rotations at all temperatures. Moreover, between 100 and 150 K, a transition from the slow to the fast exchange regime is observed for the 5-fold rotational jumps of both Cp* rings, exhibiting an activation energy of 18 kJ mol-1. This value was corroborated by 2H NMR relaxometry from which additionally the activation energies 6.3 kJ mol-1 and 11.2 kJ mol-1 for the CD3 rotation and the molecular inversion process were determined.

Phys. Rev. B

57Fe NMR and spin structure of manganese ferriteH. Štěpánková, B. Sedlák, and V. Chlan, P. Novák and Z. Šimša

Abstract
NMR of 57Fe in five MnFe2O4 single crystals with different degrees of inversion was measured in liquid He temperature. At the zero external field, two lines originating from Fe3+ ions on the octahedral sites are observed at 68.7 and 71.1 MHz, while the line at 72.0 MHz, the amplitude of which increases with increasing inversion, is ascribed to Fe3+ ions on the tetrahedral sites. Measurement in the external field shows that the spin structure is in accord with the Goodenough-Kanamori rules. This contradicts to an abnormal spin structure which Shim et al. [Phys. Rev. B 75, 134406 (2007)] proposed recently on the basis of 57Fe NMR measured in polycrystalline manganese ferrite. Reinterpretation of the NMR in polycrystalline compounds is given.


Phys. Rev. B 77, 104301 (2008)

6Li and 7Li NMR line-shape and stimulated-echo studies of lithium ionic hopping in LiPO3 glass
Sandra Faske, Hellmut Eckert, and Michael Vogel

Abstract
6Li and 7Li NMRs are used to investigate the lithium ion dynamics in LiPO3 glass. In particular, 6Li NMR stimulated-echo experiments are used to provide straightforward access to two-time correlation functions characterizing the lithium ionic hopping motion in the millisecond regime in a glassy ion conductor. Temperature-dependent measurements serve to separate the spin diffusion contribution and the dynamic contribution to the stimulated-echo decays. The 6Li NMR correlation functions of LiPO3 glass describing the lithium ionic motion show pronounced nonexponential decays, which can be well described by a stretched exponential function with a temperature-independent small stretching parameter =0.27, indicating the complex nature of the lithium dynamics. The temperature dependence of the mean correlation times resulting from these stimulated-echo experiments is described by an activation energy Ea=0.66 eV. The values of are in good agreement with time constants from previous electrical and mechanical relaxation studies. At appropriate temperatures, the 6Li and 7Li NMR spectra are superpositions of a broad and a narrow spectral component, which result from slow and fast lithium ions, respectively, on the NMR time scale. A detailed analysis of the temperature dependence of these line shapes provides information about the distribution of correlation times.

Phys. Rev. B 77, 115130 (2008)

Electronic properties of Sc5M4Si10 (M=Co,Rh,Ir) probed by NMR and first-principles calculations
C. S. Lue, R. F. Liu, Y. F. Fu, and C. Cheng

We report a systematic study of 45Sc NMR measurements on the Sc5Co4Si10-type silicides Sc5M4Si10 (M=Co,Rh,Ir). From the central transition line shapes, three nonequivalent Sc sites have been identified. We thus measured the Knight shift and spin-lattice relaxation time (T1) for each of the three crystallographic sites. Results of experimental Knight shift and T1 together with theoretical band structure calculations provide evidence that orbital electrons are responsible for the observed shifts as well as the relaxation rates. In addition, we found no correlation between the Fermi-level density of states and the superconducting transition temperature of the studied materials. Further analyses clearly indicate that the effect of electron-phonon coupling plays a significant role for the superconductivity of Sc5M4Si10, and these materials should be classified as moderate-coupling superconductors.

J. Am. Chem. Soc.

J. Am. Chem. Soc., 130 (14), 4584 -4585, 2008.
Bolalipid Membrane Structure Revealed by Solid-State 2H NMR Spectroscopy
David P. Holland, Andrey V. Struts, Michael F. Brown, and David H. Thompson*

Abstract:
Membranes made from three specifically deuterium-labeled ether-linked bolalipids, [1',1',20',20'-2H4]C20BAS-PC, [2',2',19',19'-2H4]C20BAS-PC, or [10',11'-2H2]C20BAS-PC, were analyzed by 2H NMR spectroscopy. Unlike more common monopolar, ester-linked phospholipids, C20BAS-PC exhibits a high degree of orientational order throughout the membrane and the sn-1 chain of the lipid initially penetrates the bilayer at an orientation different from that of the bilayer normal, resulting in inequivalent deuterium atoms at the C1 position. The approximate hydrophobic layer thickness and area per lipid are 18.4 Å and 60.4 Å2, respectively, at 25 C, and their respective thermal expansion coefficients are within 20% of the monopolar phospholipid, DLPC.

J. Am. Chem. Soc., 130 (14), 4757 -4766, 2008.
Orientation of Fluorinated Cholesterol in Lipid Bilayers Analyzed by 19F Tensor Calculation and Solid-State NMR
Nobuaki Matsumori, Yusuke Kasai, Tohru Oishi, Michio Murata, and Kaoru Nomura


Abstract:
6-F-cholesterol was reported to exhibit biological and interfacial properties similar to unmodified cholesterol. We have also found that 6-F-cholesterol mimicked the cholesterol activity observed in the systems of amphotericin B and lipid rafts. However, to use 6-F-cholesterol as a molecular probe to explore molecular recognition in membranes, it is indispensable to have detailed knowledge of the dynamic and orientation properties of the molecule in membrane environments. In this paper, we present the molecular orientation of 6-F-cholesterol (30 mol %) in dimyristoylphosphatidylcholine (DMPC) bilayers revealed by combined use of 19F chemical shift anisotropy (CSA), 2H NMR, and C-F rotational echo double resonance (REDOR) experiments. The axis of rotation of 6-F-cholesterol was shown to be in a similar direction to that of cholesterol in DMPC bilayers, which is almost parallel to the long axis of the molecular frame. The molecular order parameter of 6-F-cholesterol was determined to be ca. 0.85, which is within the range of reported values of cholesterol. These findings suggest that the dynamic properties of 6-F-cholesterol in DMPC are quite similar to those of unmodified cholesterol; therefore, the introduction of a fluorine atom at C6 has virtually no effect on cholesterol dynamics in membranes. In addition, this study demonstrates the practical utility of theoretical calculations for determining the 19F CSA principal axes, which would be extremely difficult to obtain experimentally. The combined use of quantum calculations and solid-state 19F NMR will make it possible to apply the orientation information of 19F CSA tensors to membrane systems.

Applied Magnetic Resonance Special Issue: Applications of Solid-State NMR to Characterizing Materials

Issue edited by John V. Hanna and Mark E. Smith:

Calcium Phosphates and Hydroxyapatite: Solid-State NMR Experiments and First-Principles Calculations
F. Pourpoint, C. Gervais , L. Bonhomme-Coury, T. Azaïs, C. Coelho, F. Mauri, B. Alonso, F. Babonneau and C. Bonhomme
Various calcium phosphates and hydroxyapatite (HAp) have been fully characterized by one- and two-dimensional solid-state nuclear magnetic resonance (NMR) experiments and first principles calculations of NMR parameters, such as chemical shift anisotropy (CSA) and electric field gradient tensors for all nuclei. Such compounds act as useful biocompatible materials. The projector augmented wave (PAW) and gauge including PAW methods allowed the complete assignment of spectra, including 1H magic-angle spinning (MAS) spectra for which ultimate resolution is not attained experimentally. 1H CSA tensors and orientation of the principal axes systems have been also discussed. 17O parameters have been calculated for a large variety of oxo-bridges and terminal oxygen atoms, including P–O–Si fragments characteristic for silicophosphate phases. The (δiso, C Q) sets of values allowed the clear distinction between the various oxygen atoms in a calculated 17O 3-quantum MAS experiment. Such an approach should be of great help for the description of interfaces in complex materials, in terms of structure and chemical composition.

Solid-State NMR Studies on Ionic closo -Dodecaborates
I. Tiritiris, T. Schleid and K. Müller
Alkali metal dodecahydro-closo-dodecaborates M2[B12H12] (M = K, Rb, Cs, NH4, N(CH3)4) and the perhalogenated cesium salts Cs2[B12X12] (X = Cl, Br, I) are studied by solid-state 11B nuclear magnetic resonance (NMR) spectroscopy as well as X-ray diffraction (XRD) and differential scanning calorimetry. The present work addresses the molecular dynamics of the anionic [B12X12]2− icosahedra which is examined by variable-temperature 11B NMR line shape studies between 120 and 370 K. Characteristic line shape effects are observed which strongly depend on the actual substituent X and the counterion M+. All alkali metal dodecahydro-closo-dodecaborates M2 [B12H12] exhibit at elevated temperatures 11B NMR spectra with a single isotropic line which proves the presence of an efficient molecular process, resulting in dynamic (rotational) disorder along with vanishing dipolar and quadrupolar interactions. The positional order of the boron clusters, however, remains unaffected, as shown by the XRD data. At lower temperatures, the underlying motions are frozen on the NMR timescale resulting in characteristic 11B NMR spectra with a dominant homonuclear 11B–11B dipolar splitting. The per-halogenated cesium salts Cs2[B12X12] behave differently. Hence, from the experimental 11B NMR spectra at room temperature a substantial mobility is only seen for the [B12Cl12]2− anion. Obviously, the degree of anion mobility depends on the size of the substituent X in the [B12X12]2− clusters (X = H, Cl, Br, I). A quantitative analysis of the experimental 11B NMR spectra of the alkali metal dodecahydro-closo-dodecaborates M2 [B12H12] is achieved by line shape simulations, considering [B12H12]2− ions undergoing reorientational jumps between icosahedral sites. From the motional correlation times the activation energies are derived. It is found that a correlation exists between the activation energies, the motional correlation times and the lattice constant. Hence, the activation energies and correlation times strongly increase with decreasing size of the cation M+, which reflects an increasing sterical hindrance due to a decreasing crystallo-graphic lattice constant in the same direction.

NMR Insights into Wasteforms for the Vitrification of High-Level Nuclear Waste
D. Holland , B. G. Parkinson, M. M. Islam, A. Duddridge, J. M. Roderick, A. P. Howes and C. R. Scales
Magic-angle spinning nuclear magnetic resonance of 11B, 29Si and 27Al has been used to study the distribution of nonbridging oxygen atoms (NBO) in an alkali borosilicate glass to which surrogate oxides for high-level radioactive waste have been added. The properties of such glasses are shown to depend on the fraction N 4 of four-coordinated boron atoms (B4) and on the fraction of silicate tetrahedra possessing one NBO, Q3. The aqueous corrosion rate increases with Q3 content, as does weight loss due to evaporation from the melt. The activation energy for direct current conduction scales with N 4. Values of N 4 obtained for these glasses deviate from those predicted by the currently accepted model and are strongly affected by the modifier or intermediate nature of the surrogate oxide and also by its effect on the distribution of NBO between the silicate and borate polyhedra.

MAS NMR Strategies for the Characterization of Supported Molybdenum Catalysts
J.-B. d'Espinose de Lacaillerie and Z. Gan
After recalling a few advances made by 1H, 29Si, and 27Al on the understanding of hydro-desulfuration (HDS) molybdenum-based catalysts supported on amorphous oxides, we critically evaluate the potential of 95Mo magic-angle spinning nuclear magnetic resonance (MAS NMR) for gaining further insight into the structure of uncalcined precursors and sulfided HDS catalysts. It is shown that when performed at a very high field (19.6 T), it is indeed sensitive to the nature of the molybdenum–support interaction. In particular, a wide distribution of the molybdenum environment present on the surface was evidenced. However, the possibility to characterize sulfided catalysts by 95Mo MAS NMR appeared still an unmet challenge.

Solid-State MAS NMR Studies of Sulfonic Acid-Functionalized SBA-15
R. Kanthasamy, I. K. Mbaraka, B. H. Shanks and S. C. Larsen
Solid-state magic-angle spinning (MAS) nuclear magnetic resonance (NMR) was used to characterize propylsulfonic acid-functionalized SBA-15 materials prepared by the cocondensation method. The propylsulfonic acid-group concentration and distribution was systematically varied from 2.5 to 10%. As a way of coupling two acid sites and controlling the acid site spatial distribution, tethered propylsulfonic acid groups were incorporated into SBA-15. 13C, 29Si and 1H MAS NMR were used to determine the extent of functionalization. Probe molecules, such as triethylphosphine oxide and diphenyldiphosphines were used to evaluate acid site strength and acid site distributions, respectively.

Multinuclear MAS NMR Investigation of Sol-Gel and Ball-Milled Nanocrystalline Ga2O3
L. A. O'Dell, S. L. P. Savin, A. V. Chadwick and M. E. Smith
71Ga magic-angle spinning (MAS) nuclear magnetic resonance (NMR) has been used to characterize the structural evolution of nanocrystalline Ga2O3 samples prepared by sol-gel and ball-milling techniques. 29Si and 27Al MAS NMR have also been used to characterize silica and alumina Zener pinning phases. 71Ga NMR parameters are reported for the α- and β-Ga2O3 phases, and more tentatively for the δ-Ga2O3 phase. By simulating the octahedrally coordinated gallium NMR line of β-Ga2O3 using Gaussian distributions in χQ, the extent of disorder in the Ga2O3 crystallites has been quantified. The ball-milled samples contain much more inherent disorder than the sol-gel samples in the nano-phase, which was observed from simulations of the 71Ga MAS NMR spectra. The silica pinning phase produced highly crystalline and densely aggregated nanocrystalline Ga2O3, as well as the smallest nanocrystal sizes.

Covalency Measurements via NMR in Lithium Metal Phosphates
S. L. Wilcke, Y.-J. Lee, E. J. Cairns and J. A. Reimer
31P nuclear magnetic resonance (NMR) shifts on the order of thousands of parts per million are observed for olivine LiMPO4 (M = Mn, Fe, Co, Ni) samples, a promising class of Li ion rechargeable battery electrode materials. Variable-temperature 31P NMR measurements of shift are used to determine that the supertransferred hyperfine interaction is the dominant mechanism giving rise to these unusually large observed 31P shifts. Various models for predicting 31P and 7Li shifts in LiMPO4 (M = Mn, Fe, Co, Ni) were investigated. Alloys of LiFe1−x Mn x PO4, where x varies from 0 to 1, were also investigated by 7Li NMR. Covalency constants, calculated from variable-temperature NMR shifts and magnetic susceptibility data, are determined for the P–O–M bonds in LiMPO4 (M = Mn, Fe, Co, Ni) and compared to the covalency constants of the Li–O–M bond. The sign and relative magnitude of the covalency constants are discussed in terms of positive and negative spin densities at the nuclei of interest. The covalency constants for the Li–O–M and P–O–M bonds were measured for Li1.8Na0.2FeMn2(PO4)3 and compared to the covalency constants measured in the olivine LiMPO4 (M = Mn, Fe, Co, Ni) samples. The Li1.8Na0.2FeMn2(PO4)3 structure has a volume per transition metal atom and Li–O–M bond distances that are similar to those of the olivine LiMPO4 (M = Mn, Fe, Co, Ni) samples.

The Challenge of Paramagnetism in Two-Dimensional 6,7Li Exchange NMR
L. S. Cahill, R. P. Chapman, C. W. Kirby and G. R. Goward
6,7Li fast magic-angle spinning solid-state nuclear magnetic resonance (NMR) spectroscopy is used to study LiMn2O4 and Li3V2(PO4)3. The presence of paramagnetic transition metal centers in these materials has a profound effect on the resulting NMR spectra. Lithium ion mobility has been studied by two-dimensional (2-D) exchange spectroscopy (EXSY) in Li3V2(PO4)3 but an absence of lithium ion exchange was observed for LiMn2O4. Several differences between the two materials are explored to explain these results. LiMn2O4 experiences a greater donation of electron spin density to the Li nucleus via the Fermi-contact interaction when compared with Li3V2(PO4)3. This contributes to a greater hyperfine chemical shift and a larger dependence of chemical shift on temperature. The delocalized electrons in LiMn2O4 cause temperature-independent T 1 relaxation rates and shorter relative T 2 values. The relative rates of ionic conductivity and spin–lattice or spin–spin relaxation in LiMn2O4 and Li3V2(PO4)3 are contrasted to illustrate the constraints on the use of 2-D EXSY to characterize ion dynamics in paramagnetic materials.

Shift Anisotropy Tensors in Amorphous Natural-Abundance Solids: High-Resolution 29Si Chemical Shift Anisotropy Distributions under Very Slow Sample Rotation
D. Sakellariou and T. Charpentier
The magic-angle turning technique is applied to amorphous natural-abundance silicate materials and high-resolution silicon-29 correlations between the isotropic and anisotropic chemical shifts are obtained. Very narrow tilted spinning sideband patterns are resolved in the two-dimensional spectra whose line width corresponds to the natural line width of the silicon nuclei. Various numerical approaches are implemented to extract the distribution of the chemical shift anisotropy tensors in these materials and their results are compared.

NMR Studies of Heat-Induced Transitions in Structure and Cation Binding Environments of a Strontium-Saturated Swelling Mica
G. M. Bowers, M. C. Davis, R. Ravella, S. Komarneni and K. T. Mueller
In this work, we combine 27Al, 29Si, 19F, and 23Na magic-angle spinning (MAS) nuclear magnetic resonance (NMR) to characterize the structure and interlayer cation environments in a strontium-saturated member of the swelling mica family before and after a heat-induced collapse of the interlayer space. The 27Al and 29Si MAS NMR demonstrate that the sample consists mainly of swelling mica, though the composition does not match the ideal structural formula. Aluminum NMR also shows that a portion of the aluminum shifts from a tetrahedral to an octahedral coordination environment upon heating. Changes in the 29Si and 19F NMR after heating are consistent with a structural rearrangement of the tetrahedral sheet to permit the binding of larger cations in the ditrigonal cavity. The 23Na MAS NMR results indicate the presence of three unique sodium environments before and after heating. The heat-invariant resonance is consistent with the presence of sodium carbonate. The other two resonances are associated with interlayer sodium and reflect a migration of sodium to a dominantly anhydrous ditrigonal binding structure with heating. Quantitative elemental analysis and NMR data presented here suggest strontium is bound deep within the ditrigonal cavity of the collapsed micas.

NMR Study of a Rare-Earth Aluminoborosilicate Glass with Varying CaO-to-Na2O Ratio
A. Quintas, T. Charpentier, O. Majérus, D. Caurant, J.-L. Dussossoy and P. Vermaut
The effect of substituting two Na+ by one Ca2+ in a rare-earth aluminoborosilicate glass is investigated by multinuclear magic-angle spinning (MAS) and multiple-quantum (MQ)MAS nuclear magnetic resonance (NMR) spectroscopy. Quantitative analysis of the 23Na and 27Al MAS/MQMAS data along with the 11B MAS NMR data provides complementary information enabling to cast light on different structural key points. A strong decrease of the N 4 = BO4/(BO3 + BO4) ratio is observed consecutively to this substitution, indicating that sodium is more favorable than calcium to the formation of BO4 units. The experimental N 4 ratio is compared to the Dell and Bray model prediction and it is shown that several adjustments, due to the presence in our glass of Nd and Zr, are necessary to obtain acceptable agreement with experimental data. 29Si MAS NMR data also put in evidence an effect of the substitution on the polymerization degree. Glass in glass phase separation is clearly detected when the ratio of CaO to Na2O is greater than 1 and a different evolution of NMR parameters is observed for the ratio of CaO to Na2O being less than or equal to 1. Concerning aluminum charge compensation, it is demonstrated that, as long as no phase separation is detected, the negative charge of AlO4 − entities is almost exclusively balanced by sodium cations. Finally, changes of the sodium ions organization within the glass network are also evidenced by spin–lattice relaxation and spin echo decay measurements.

Laser-Heated High-Temperature NMR: A Time-Resolution Study
R. Winter, A. Jones, R. Shaw-West, M. Wolff, P. Florian and D. Massiot
The time resolution achievable in in situ high-temperature nuclear magnetic resonance experiments is investigated using laser heating of refractory materials. Three case studies using 27Al in alumina nanoparticles, 29Si in silicon carbide and 23Na in a glass-forming mixture of sodium carbonate and quartz have been conducted to distinguish the cases of (a) a fast-relaxing, high natural abundance nucleus, (b) a probe nucleus with low abundance and low spin–lattice relaxation rate, and (c) a complex and changing system of industrial relevance. The most suitable nucleus for in situ high-temperature studies is one with high abundance but slow relaxation because the differential relaxation time between hot and cold parts of the sample effectively removes the signal from the cold material. There is no "in situ penalty" from the diminishing Boltzmann polarization at high temperature since this effect is balanced by a corresponding increase of the spin–lattice relaxation rate.

Crystalline Aluminium Borates with the Mullite Structure: A 11B and 27Al Solid-State NMR Study
K. J. D. MacKenzie, M. E. Smith, T. F. Kemp and D. Voll
27Al magic-angle spinning (MAS) nuclear magnetic resonance (NMR) spectra were acquired at 8.45, 14.1 and 16.45 T for a series of aluminium borates with the mullite structure (Al6−x B x O9, where x has nominal values of 1 to 4) augmented with 27Al multiple-quantum MAS NMR spectra at 8.45 T. Even though the 27Al NMR spectra are complex, simulation of the combined set of data produced a relatively well-defined set of parameters (e.g., quadrupolar interaction, isotropic chemical shift, etc.) for each site. The 11B MAS NMR spectra of the same compounds were also acquired at 14.1 T. Linear changes in the X-ray a-, b- and c-cell parameters with composition suggest that these compounds constitute a continuous series. Based on a Rietveld structural refinement of the compound synthesized as Al4B2O9, the resulting site occupancies and relative site distortions allow the identification of particular sites with specific NM resonances. Changes in the 27Al and 11B MAS NMR spectra of the related compounds with x = 1–4 show at the lowest Al contents a greater degree of asymmetry in the Al sites of the octahedral chains. A fairly distorted cross-linking tetrahedral site, which persists throughout the composition range, is accompanied in the lower Al compositions by two 5-fold coordinated Al–O units which are replaced by two more-regular tetrahedral Al–O sites as the Al content increases. In the compounds of lowest Al composition (i.e., highest B content) both the tetrahedral and trigonal cross-linking sites are distinguishable, but as the Al content increases, the BO4 units progressively disappear.

29Si, 27Al, 1H and 23Na MAS NMR Study of the Bonding Character in Aluminosilicate Inorganic Polymers
M. R. Rowles, J. V. Hanna , K. J. Pike, M. E. Smith and B. H. O'Connor
29Si, 27Al, 1H and 23Na solid-state magic-angle spinning (MAS) nuclear magnetic resonance (NMR) has been used to relate nominal composition, bonding character and compressive strength properties in aluminosilicate inorganic polymers (AIPs). The 29Si chemical shift varies systematically with Si-to-Al ratio, indicating that the immediate structural environment of Si is altering with nominal composition. Fast 1H MAS and 29Si T SiH/T 1ρ relaxation measurements demonstrated that occluded pore H2O mobility within the disordered cavities is slow in comparison with H2O mobility characteristics observed within the ordered channel structures of zeolites. The 27Al MAS NMR data show that the Al coordination remains predominantly 4-coordinate. In comparison with the 29Si MAS data, the corresponding 27Al MAS line shapes are relatively narrow, suggesting that the AlO4 tetrahedral geometry is largely unperturbed and the dominant source of structural disorder is propagated by large distributions of Si–O bond angles and bond lengths. Corresponding 23Na MAS and multiple-quantum MAS NMR data indicate that Na speciation is dominated by distributions of hydration states; however, more highly resolved 23Na resonances observed in some preparations supported the existence of short-range order. New structural elements are proposed to account for the existence of these Na resonances and an improved model for the structure of AIPs has also been proposed.

A Theoretical Study of 51V Electric Field Gradient Tensors in Pyrovanadates and Metavanadates
A. Y. H. Lo, J. V. Hanna and R. W. Schurko
A computational study of the 51V electric field gradient (EFG) tensors in pyrovanadates, α-Zn2V2O7, Cd2V2O7, β-Mg2V2O7 and BaCaV2O7, and the metavanadates, LiVO3, α-NaVO3, KVO3, ZnV2O6 and MgV2O6, is presented. Restricted Hartree–Fock and hybrid density functional theory calculations have been used to investigate the effects of the size of vanadium-oxygen clusters, basis set size, proton-termination and embedded cluster techniques on the accuracy of the calculated EFG tensors. Good agreement between theory and experiment is obtained for most of the vanadates. A sound methodology is suggested for calculating the EFG tensor in pyrovanadates which contain isolated V2O7 4− clusters. For metavanadates, the charges of the bridging oxygen atoms can be differentiated from those of terminal oxygen atoms by terminating the former with hydrogen atoms, and embedded cluster molecular orbital calculations are useful in accounting for the long-range electrostatic interactions which influence the EFG tensor components. EFG tensor orientations vary for different pyrovanadate structural types, and individual components are confined by symmetry elements in the metavanadates. A preliminary comparison is made between 51V EFG tensors calculated with ab initio and plane wave methods. Theoretical EFG tensor components and orientations, in combination with experimental 51V solid-state nuclear magnetic resonance data, are demonstrated to be useful tools for prediction of molecular structure.

Chem. Mater

Chem. Mater., 20 (6), 2205–2217, 2008.
A Solid-State NMR, X-ray Diffraction, and Ab Initio Investigation into the Structures of Novel Tantalum Oxyfluoride Clusters
Todd M. Alam,*† Jacalyn S. Clawson,†‡ François Bonhomme,† Steven G. Thoma,† Mark A. Rodriguez,† Shaohui Zheng,§ and Jochen Autschbach§

Abstract
A series of tantalum oxyfluoride materials containing the [Ta4F16O4]4− and [Ta8F24O12]8− anion clusters have been synthesized and characterized using X-ray diffraction (XRD) and solid-state nuclear magnetic resonance (SSNMR) spectroscopy. The structure of both tantalum oxyfluoride materials display octahedrally bonded tantalum atoms with bridging oxygen and terminal fluoride atoms. The [Ta4F16O4]4− cluster is an eight-membered ring, whereas the [Ta8F24O12]8- cluster forms a cagelike structure. Solid-state dynamics of these clusters were explored by monitoring the impact of temperature on the one-dimensional (1D) 19F magic angle spinning (MAS) NMR, 13C cross-polarization (CP) MAS NMR, and two-dimensional (2D) double quantum (DQ) 19F MAS NMR spectra. The DQ 19F NMR correlation experiments allowed the through space connectivity between the different resolved fluorine environments to be determined, thus aiding in the spectral assignment and structural refinement of these materials. Ab initio 19F NMR chemical shift calculations were used to assist in the interpretation of the 19F NMR spectra. The influence of scalar relativistic and Ta−F spin–orbit coupling on the 19F NMR shielding calculation arising from bonding to tantalum atoms is also addressed.

Chem. Mater

Chem. Mater., 20 (6), 2412–2422, 2008.
Direct Synthesis and Solid-State NMR Characterization of Cubic Mesoporous Silica SBA-1 Functionalized with Phenyl Groups
Hsien-Ming Kao,*† Chia-Hsiu Liao,† Tzu-Ti Hung,† Yu-Chi Pan,† and Anthony S. T. Chiang‡

Abstract:
Well-ordered mesoporous silicas SBA-1 (cubic Pm3n symmetry) functionalized with phenyl groups have been synthesized via co-condensation of tetraethoxysilane (TEOS) and phenyltriethoxysilane (PhTES) under acidic conditions. The synthesis parameters such as temperature, type of surfactant, and synthesis composition have been systematically investigated as a function of PhTES contents. The phenyl-containing units are incorporated quantitatively and reach a maximum PhTES loading up to 33 mol % (based on silicon) without a significant degradation of the structural ordering of the Pm3n mesophase. A combination of multinuclear (1H, 13C, 29Si) solid-state NMR and two-dimensional (2D) solid-state NMR correlation techniques such as 13C{1H} and 29Si{1H} HETCOR (heteronuclear correlation) and 1H-1H exchange NMR has been used to establish framework locations of phenyl functional groups that are incorporated in the mesoporous structure and their interactions with the surfactant molecules. 2D 13C{1H} HETCOR NMR experiments reveal that the phenyl moieties are in close spatial proximity to the trimethylammonium headgroups of the cationic surfactant species in the as-synthesized materials, suggesting that there are some specific interactions between them to maintain the surfactant packing parameter (g) smaller than 1/3 necessary for the formation of the cubic mesophase. The detection of couplings between the protons associated with various 29Si species via 29Si{1H} HETCOR NMR established that the T silicon species due to the phenyl groups incorporated are in closer proximity to the Q4 silicon species than to the Q3 silicon species. This observation also provides direct molecular-level evidence for the co-condensation of PhTES and TEOS in the synthesis of mesoporous organosilicas.

J. Am. Chem. Soc.

J. Am. Chem. Soc., 130 (12), 3722 -3723, 2008.

Direct Observation of the Active Center for Methane Dehydroaromatization Using an Ultrahigh Field 95Mo NMR Spectroscopy
Heng Zheng, Ding Ma, Xinhe Bao,* Jian Zhi Hu, Ja Hun Kwak, Yong Wang, and Charles H. F. Peden

Abstract:
The use of an ultrahigh magnetic field spectrometer and 95Mo isotope enrichment facilitate the direct observation of the local structure of Mo species on Mo/zeolite catalysts by 95Mo NMR. Top trace: The experimental 95Mo NMR spectrum of 6Mo/HZSM-5. Bottom traces: The simulated overall spectrum (orange), the spectral component corresponding to MoO3 (purple), and the component corresponding to the exchanged Mo species (green). The exchanged Mo species proved to be the active center for the methane dehydroaromatization (MDA) reaction.

J. Chem. Phys.

Solid-state NMR covariance of homonuclear correlation spectra
J. Chem. Phys. 128, 134502 (2008)
Bingwen Hu, Jean-Paul Amoureux, Julien Trebosc, Michael Deschamps, and Gregory Tricot

Direct covariance NMR spectroscopy, which does not involve a Fourier transformation along the indirect dimension, is demonstrated to obtain homonuclear correlation two-dimensional (2D) spectra in the solid state. In contrast to the usual 2D Fourier transform (2D-FT) NMR, in a 2D covariance (2D-Cov) spectrum the spectral resolution in the indirect dimension is determined by the resolution along the detection dimension, thereby largely reducing the time-consuming indirect sampling requirement. The covariance method does not need any separate phase correction or apodization along the indirect dimension because it uses those applied in the detection dimension. We compare in detail the specifications obtained with 2D-FT and 2D-Cov, for narrow and broad resonances. The efficiency of the covariance data treatment is demonstrated in organic and inorganic samples that are both well crystallized and amorphous, for spin −1/2 nuclei with 13C, 29Si, and 31P through-space or through-bond homonuclear 2D correlation spectra. In all cases, the experimental time has been reduced by at least a factor of 10, without any loss of resolution and signal to noise ratio, with respect to what is necessary with the 2D-FT NMR. According to this method, we have been able to study the silicate network of glasses by 2D NMR within reasonable experimental time despite the very long relaxation time of the 29Si nucleus. The main limitation of the 2D-Cov data treatment is related to the introduction of autocorrelated peaks onto the diagonal, which does not represent any actual connectivity.

Inorg. Chem. - 2D 45Sc NMR of ScAgSn

Inorg. Chem., 46 (3), 771 -779, 2007. 10.1021/ic061691o S0020-1669(06)01691-0

New Stannide ScAgSn: Determination of the Superstructure via Two-Dimensional 45Sc Solid State NMR

C. Peter Sebastian, Long Zhang, Constanze Fehse, Rolf-Dieter Hoffmann, Hellmut Eckert,* and Rainer Pöttgen*

Institut für Anorganische und Analytische Chemie and NRW Graduate School of Chemistry, Universität Münster, Corrensstrasse 30, D-48149 Münster, Germany, and Institut für Physikalische Chemie and NRW Graduate School of Chemistry, Universität Münster, Corrensstrasse 30, D-48149 Münster, Germany

Received September 7, 2006

Abstract:

The new stannide ScAgSn was synthesized by induction melting of the elements in a sealed tantalum tube and subsequent annealing. ScAgSn crystallizes with a pronounced subcell structure: ZrNiAl type, P 2m, a = 708.2(2) pm, c = 433.9(1) pm, wR2 = 0.1264, 321 F2 values, and 14 variables. The Guinier powder pattern reveals weak superstructure reflections pointing to a TiFeSi-type structural arrangement: I2cm, a = 708.1(1) pm, b = 1225.2(2) pm, c = 869.9(1) pm, wR2 = 0.0787, 5556 F2 values, and 49 variables. So far the growth of high-quality single crystals failed. Determination of the superstructure was partly based on merohedral triplet X-ray data augmented by 119Sn Mössbauer spectroscopy and 119Sn and 45Sc solid-state NMR data. In particular, the observation of three crystallographically inequivalent sites in 45Sc NMR triple quantum magic-angle spinning (TQ-MAS) NMR spectra provided unambiguous proof of the superstructure proposed. The ScAgSn structure consists of a three-dimensional [AgSn] network (with Ag-Sn distances between 273 and 280 pm) in which the scandium atoms are located in distorted hexagonal channels, each having five tin and two silver nearest neighbors. Both crystallographically independent tin sites have a tricapped trigonal prismatic coordination, that is, [Sn1Sc6Ag3] and [Sn2Ag6Sc3] environments, which are well distinguished in the 119Sn NMR and Mössbauer spectra because of their different site symmetries.

JACS - 95Mo NMR of metal sites in zeolites

J. Am. Chem. Soc., 130 (12), 3722 -3723, 2008.

10.1021/ja7110916

Direct Observation of the Active Center for Methane Dehydroaromatization Using an Ultrahigh Field ⁹⁵Mo NMR Spectroscopy

Heng Zheng, Ding Ma, Xinhe Bao,* Jian Zhi Hu, Ja Hun Kwak, Yong Wang, and Charles H. F. Peden

State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, P.R. China, and Pacific Northwest National Laboratory, P. O. Box 999, MS K8-98, Richland, Washington 99352

xhbao@dicp.ac.cn

Received December 14, 2007

Abstract:

The use of an ultrahigh magnetic field spectrometer and ⁹⁵Mo isotope enrichment facilitate the direct observation of the local structure of Mo species on Mo/zeolite catalysts by ⁹⁵Mo NMR. Top trace: The experimental ⁹⁵Mo NMR spectrum of 6Mo/HZSM-5. Bottom traces: The simulated overall spectrum (orange), the spectral component corresponding to MoO₃ (purple), and the component corresponding to the exchanged Mo species (green). The exchanged Mo species proved to be the active center for the methane dehydroaromatization (MDA) reaction.