Sunday, June 18, 2006

Hiyam's Journal Update

The Journal of Chemical Physics -- 28 May 2006

J. Chem. Phys. 124, 204717 (2006) (10 pages)

Nuclear magnetic resonance structural investigations of ammonia-doped fullerides

T. Shiroka, G. Fumera, O. Ligabue, and M. Riccò G. C. Antonioli

Abstract: The dynamic and structural properties of the ammonia-doped superconducting fulleride (NH3)xNaK2C60 (0.5<1),> NMR techniques. The independence of 23Na quadrupole splitting from the ammonia content x, which, at the same time, substantially affects Tc, suggests a marginal role of the cation position in the superconducting mechanism. On the other hand, a strong reduction of the deuterium quadrupole coupling with respect to the free ammonia value denotes the presence of weak hydrogen bonds between the deuterium atoms and fullerene orbitals. Despite the bond weakness, as evinced by the lively ammonia rotational dynamics even at very low temperatures, the resulting electron localization could explain the observed Tc anomaly. The motion of the ND3–Na group (located in the compound's octahedral voids), as well as the evolution of the ammonia dynamics as a function of temperature, were determined from deuterium NMR line shape analysis and from detailed numerical simulations. While at the lowest measured temperatures only the ammonia rotation around its own C3 axis takes place, above ~25 and 70 K, respectively, also the wobbling of the C3 axis and the ND3 relocation become active, successfully modeled by a strongly correlated motion involving two different time scales. ©2006 American Institute of Physics

The Journal of Chemical Physics -- 14 June 2006

J. Chem. Phys. 124, 224106 (2006) (7 pages)

Relativistic calculation of nuclear magnetic shielding using normalized elimination of the small component K. Kudo, H. Maeda, T. Kawakubo, Y. Ootani, M. Funaki, and H. Fukui

Abstract: The normalized elimination of the small component (NESC) theory, recently proposed by Filatov and Cremer [J. Chem. Phys. 122, 064104 (2005)], is extended to include magnetic interactions and applied to the calculation of the nuclear magnetic shielding in HX (X=F,Cl,Br,I) systems. The NESC calculations are performed at the levels of the zeroth-order regular approximation (ZORA) and the second-order regular approximation (SORA). The calculations show that the NESC-ZORA results are very close to the NESC-SORA results, except for the shielding of the I nucleus. Both the NESC-ZORA and NESC-SORA calculations yield very similar results to the previously reported values obtained using the relativistic infinite-order two-component coupled Hartree-Fock method. The difference between NESC-ZORA and NESC-SORA results is significant for the shieldings of iodine. ©2006
American Institute of Physics

Physical Chemistry Chemical Physics, 2006, 8, 1394 - 1403
DOI: 10.1039/b516765e

Molecular dynamics and ordering of pyridine in its cyclophosphazene inclusion compound as evaluated by solid state 2H NMR spectroscopy

Jorge A. Villanueva-Garibay and Klaus Müller

Variable temperature 2H NMR experiments (line shape analysis, relaxation studies) were carried out on the pyridine-d5–tris-(1,2-dioxyphenyl)-cyclotriphosphazene inclusion compound in the temperature range between 110–300 K. It is found that the pyridine guests are highly mobile throughout the whole temperature range covered here. The observation of three superimposed 2H NMR signals can be understood in terms of a particular (motionally averaged) orientation of the pyridine molecules, which is a consequence of the molecular symmetry of the pyridine guests and the imposed channel restrictions. The experimental data are consistent with a combined rotation on cone–small angle fluctuation model, which assumes a fast molecular reorientation between two superimposed cones with an opening angle for the inner cone between 59–73° (angle of fluctuation between 1–3°). On the basis of this model assumption it is possible to reproduce both the experimental 2H NMR line shapes and the spin–lattice relaxation data in a quantitative way. The analysis of the partially relaxed spectra (inversion recovery experiments) yields the correlation times for this overall motional process. They follow an Arrhenius behavior from which an activation energy of 8.7 ± 0.4 kJ mol–1 is derived. The results are discussed in the framework of the published data for related systems.

Thursday, June 15, 2006

Joel: Journal Updates

Hiyam and Andy
89Y Magic Angle Spinning NMR of Y2Ti2-xSnxO7 Pyrochlores
S.E. Ashbrook, K.R. Whittle, G.R.Lumpkin and I. Farnan
J.Phys.Chem.B (2006)110, 9324.

The yttrium local environment in the series of pyrochlores Y2Ti2-xSnxO7 was studied using 89Y NMR. Oxides with the pyrochlore structure exhibit a range of interesting physical and chemical properties, resulting in many technological applications, including the encapsulation of lanthanide- and actinide-bearing radioactive waste. The use of the nonradioactive Y3+ cation provides a sensitive probe for any changes in the local structure and ordering with solid solution composition, through 89Y (I ) 1/2) NMR. We confirm that a single pyrochlore phase is formed over the entire compositional range, with Y found only on the eight-coordinated A site. A significant (15 ppm) chemical shift is observed for each Sn substituted into the Y second neighbor coordination environment. The spectral signal intensities of the possible combinations of Sn/Ti neighbors match those predicted statistically assuming a random distribution of Sn4+/Ti4+ on the six-coordinated pyrochlore B site.

Acidity of Mesoporous MoOx/ZrO2 and WOx/ZrO2 Materials: A Combined Solid-State NMR and Theoretical Calculation Study
J. Xu et al.
J.Phys.Chem.B (2006)110, 10662.

The acidity of mesoporous MoOx/ZrO2 and WOx/ZrO2 materials was studied in detail by multinuclear solidstate NMR techniques as well as DFT quantum chemical calculations. The 1H MAS NMR experiments clearly revealed the presence of two different types of strong Brønsted acid sites on both MoOx/ZrO2 and WOx/ZrO2 mesoporous materials, which were able to prontonate adsorbed pyrine-d5 (resulting in 1H NMR signals at chemical shifts in the range 16-19 ppm) as well as adsorbed trimethylphosphine (giving rise to 31P NMR signal at ca. 0 ppm). The 13C NMR of adsorbed 2-13C-acetone indicated that the average Brønsted acid strength of the two mesoporous materials was stronger than that of zeolite HZSM-5 but still weaker than that of 100% H2SO4, which was in good agreement with theoretical predictions. The quantum chemical calculations revealed the detailed structures of the two distinct types of Brønsted acid sites formed on the mesoporous MoOx/ZrO2 and WOx/ZrO2. The existence of both monomer and oligomer Mo (or W) species containing a Mo-OH-Zr (or W-OH-Zr) bridging OH group was confirmed with the former having an acid strength close to zeolite HZSM-5, with the latter having an acid strength similar to sulfated zirconia. On the basis of our NMR experimental and theoretical calculation results, a possible mechanism was proposed for the formation of acid sites on these mesoporous materials.

Determinations of 15N Chemical Shift Anisotropy Magnitudes in a Uniformly 15N,13C-Labeled Microcrystalline Protein by Three-Dimensional Magic-Angle Spinning Nuclear Magnetic Resonance Spectroscopy
B.J. Wylie, W.T. Franks, and C.M. Rienstra
J.Phys.Chem.B (2006)110, 10936.

Amide 15N chemical shift anisotropy (CSA) tensors provide quantitative insight into protein structure and dynamics. Experimental determinations of 15N CSA tensors in biologically relevant molecules have typically been performed by NMR relaxation studies in solution, goniometric analysis of single-crystal spectra, or slow magic-angle spinning (MAS) NMR experiments of microcrystalline samples. Here we present measurements of 15N CSA tensor magnitudes in a protein of known structure by three-dimensional MAS solid-state NMR. Isotropic 15N, 13CR, and 13C¢ chemical shifts in two dimensions resolve site-specific backbone amide recoupled CSA line shapes in the third dimension. Application of the experiments to the 56-residue ‚1 immunoglobulin binding domain of protein G (GB1) enabled 91 independent determinations of 15N tensors at 51 of the 55 backbone amide sites, for which 15N-13CR and/or 15N-13C¢ cross-peaks were resolved in the two-dimensional experiment. For 37 15N signals, both intra- and interresidue correlations were resolved, enabling direct comparison of two experimental data sets to enhance measurement precision. Systematic variations between ‚-sheet and R-helix residues are observed; the average value for the anisotropy parameter, ‰ (‰ ) ‰zz - ‰iso), for R-helical residues is 6 ppm greater than that for the ‚-sheet residues. The results show a variation in ‰ of 15N amide backbone sites between -77 and -115 ppm, with an average value of -103.5 ppm. Some sites (e.g., G41) display smaller anisotropy due to backbone dynamics. In contrast, we observe an unusually large 15N tensor for K50, a residue that has an atypical, positive value for the backbone torsion angle. To our knowledge, this is the most complete experimental analysis of 15N CSA magnitude to date in a solid protein. The availability of previous high-resolution crystal and solution NMR structures, as well as detailed solid-state NMR studies, will enhance the value of these measurements as a benchmark for the development of ab initio calculations of amide 15N shielding tensor magnitudes.

Another Rod paper
Grand Canonical Monte Carlo Simulations of the 129Xe NMR Line Shapes of Xenon Adsorbed in ((+/-)-[Co(en)3]Cl3
D.N. Sears, R.E. Wasylishen, and T. Ueda
J.Phys.Chem.B (2006)110, 11120.

The 129Xe NMR line shapes of xenon adsorbed in the nanochannels of the (()-[Co(en)3]Cl3 ionic crystal have been calculated by grand canonical Monte Carlo (GCMC) simulations. The results of our GCMC simulations illustrate their utility in predicting 129Xe NMR chemical shifts in systems containing a transition metal. In particular, the nanochannels of (()-[Co(en)3]Cl3 provide a simple, yet interesting, model system that serves as a building block toward understanding xenon chemical shifts in more complex porous materials containing transition metals. Using only the Xe-C and Xe-H potentials and shielding response functions derived from the Xe@CH4 van der Waals complex to model the interior of the channel, the GCMC simulations correctly predict the 129Xe NMR line shapes observed experimentally (Ueda, T.; Eguchi, T.; Nakamura, N.; Wasylishen, R. E. J. Phys. Chem. B 2003, 107, 180-185). At low xenon loading, the simulated 129Xe NMR line shape is axially symmetric with chemical-shift tensor components ‰| ) 379 ppm and ‰^ ) 274 ppm. Although the simulated isotropic chemical shift, ‰iso ) 309 ppm, is overestimated, the anisotropy of the chemical-shift tensor is correctly predicted. The simulations provide an explanation for the observed trend in the 129Xe NMR line shapes as a function of the overhead xenon pressure: ‰^ increased from 274 to 292 ppm, while ‰| changed by only 3 ppm over the entire xenon loading range. The overestimation of the isotropic chemical shifts is explained based upon the results of quantum mechanical 129Xe shielding calculations of xenon interacting with an isolated (()-[Co(en)3]Cl3 molecule. The xenon chemical shift is shown to be reduced by about 12% going from the Xe@[Co(en)3]Cl3 van der Waals complex to the Xe@C2H6 fragment.

Wednesday, June 14, 2006

JACS: Ashbrook and Wimperis; 27Al MQMAS and STMAS as probes of dynamics in microporous solids

J. Am. Chem. Soc., 128 (24), 8054 -8062, 2006. 10.1021/ja057682g S0002-7863(05)07682-1

Dynamics on the Microsecond Timescale in Microporous Aluminophosphate AlPO-14 as Evidenced by 27Al MQMAS and STMAS NMR Spectroscopy

Sasa Antonijevic, Sharon E. Ashbrook, Silke Biedasek, Richard I. Walton,* Stephen Wimperis,*# and Huaixin Yang

Contribution from the Institut des Sciences et Ingénierie Chimiques, Ecole Polytechnique Fédérale de Lausanne, 1015 Lausanne, Switzerland, School of Chemistry and EaStCHEM, University of St Andrews, St Andrews KY16 9ST, United Kingdom, Institut für Technische und Makromolekulare Chemie, Universität Hamburg, 20146 Hamburg, Germany, Department of Chemistry, The Open University, Milton Keynes MK7 6AA, United Kingdom, Department of Chemistry and WestCHEM, University of Glasgow, Glasgow G12 8QQ, United Kingdom, and Beijing National Laboratory for Condensed Matter Physics, Institute of Physics, Chinese Academy of Sciences, Beijing 100080, China;
Received November 11, 2005


Multiple-quantum magic angle spinning (MQMAS) and satellite-transition magic angle spinning (STMAS) are two well-known techniques for obtaining high-resolution, or "isotropic", NMR spectra of quadrupolar nuclei. It has recently been shown that dynamics-driven modulation of the quadrupolar interaction on the microsecond timescale results in linewidths in isotropic STMAS spectra that are strongly broadened, while, in contrast, the isotropic MQMAS linewidths remain narrow. Here, we use this novel methodology in an 27Al (I = 5/2) NMR study of the calcined-dehydrated aluminophosphate AlPO-14 and two forms of as-synthesized AlPO-14, one prepared with isopropylamine (C3H7NH2) as the template molecule and one with piperidine (C5H10NH). For completeness, the 31P and 13C (both I = 1/2) MAS NMR spectra are also presented. A comparison of the 27Al MQMAS and STMAS NMR results show that, although calcined AlPO-14 appears to have a rigid framework structure, the extent of motion in the two as-synthesized forms is significant, with clear evidence for dynamics on the microsecond timescale in the immediate environments of all four Al sites in each material. Variable-temperature 27Al STMAS NMR studies of the two as-synthesized AlPO forms reveal the dynamics to be complex, with the motions of both the guest water molecules and organic template molecules shown to be contributing. The sensitivity of the STMAS NMR experiment to the presence of microsecond timescale dynamics is such that it seems likely that this methodology will prove useful in NMR studies of host-guest interactions in a wide variety of framework materials.

Tuesday, June 13, 2006

JACS, Berger; 31P NMR, ab initio and IR; phosphorus CS tensors

J. Am. Chem. Soc., ASAP Article 10.1021/ja057085u S0002-7863(05)07085-X
Web Release Date: June 10, 2006

Copyright © 2006 American Chemical Society
Electronic Properties of Furyl Substituents at Phosphorus and Their Influence on 31P NMR Chemical Shifts

Marco Ackermann, Aurelia Pascariu, Thomas Höcher, Hans-Ullrich Siehl, and Stefan Berger*

Contribution from the Institut für Analytische Chemie, Fakultät für Chemie und Mineralogie, Universität Leipzig, Linnéstr. 3, D-04103 Leipzig, Germany and Abteilung für Organische Chemie I, Fakultät für Naturwissenschaften, Universität Ulm, D-89069 Ulm, Germany


The electronic properties of 2-furyl and 3-furyl substituents attached to phosphanes and phosphonium salts were studied by means of IR spectroscopy and experimental and computational 31P NMR spectroscopy. The heteroaromatic systems proved to be electron withdrawing with respect to phenyl substituents. However, phosphorus atoms with attached furyl substituents are strongly shielded in NMR. The reason for this phenomenon was studied by solid state 31P MAS NMR experiments. The chemical shift tensor was extracted, and the orientation within the molecules was determined. The tensor component 33, which is effected the most by furyl systems, is oriented perpendicular to the P-C bonds of the substituents. P-furyl bonds are shorter than P-phenyl bonds. We assume therefore a lower ground-state energy of the molecules, because of the electron withdrawing properties of the 2-furyl systems. The para component of the 31P NMR magnetic shielding is therefore smaller, which results in an overall increase of the magnetic shielding.

CPL, Blaha et al: 27Al and plane wave (WIEN) calculations

Chemical Physics Letters
Volume 424, Issues 4-6 , 24 June 2006, Pages 321-326

27Al NMR experiments and quadrupolar parameter ab initio calculations: Crystallographic structure refinement of ß-Ba3AlF9

M. Body, G. Silly, C. Legein, J.-Y. Buzaré, F. Calvayrac and P. Blaha

aLaboratoire de Physique de l’Etat Condensé, CNRS UMR 6087, Institut de Recherche en Ingénierie Moléculaire et Matériaux Fonctionnels, CNRS FR 2575, Université du Maine, Avenue Olivier Messiaen, 72085 Le Mans Cedex 9, France
bLaboratoire des Oxydes et Fluorures, CNRS UMR 6010, Institut de Recherche en Ingénierie Moléculaire et Matériaux Fonctionnels, CNRS FR 2575, Université du Maine, Avenue Olivier Messiaen, 72085 Le Mans Cedex 9, France
cLaboratoire de Physicochimie de la Matière Condensée, CNRS UMR 5617, Institut Charles Gerhardt, CNRS FR 1878, Université de Montpellier II, Place Eugène Bataillon, C.C. 03, 34095 Montpellier Cedex 5, France
dInstitute of Materials Chemistry, Vienna University of Technology A-1060 Vienna, Getreidemarkt 9/165-TC, Austria


27Al quadrupolar parameters are determined for the three aluminium sites in ß-Ba3AlF9 from the reconstruction of experimental SATRAS and MQ-MAS NMR spectra. These quadrupolar parameters are then computed using the DFT linearized augmented plane wave method implemented in the WIEN2k code.

A fine agreement between experimental and calculated values is obtained only after optimizing the ß-Ba3AlF9 structure. The optimized structure is more satisfactory than the previously published one from a crystallographic point of view (bond lengths and angles).

This approach which allows to refine crystallographic structures especially when they lack accuracy may be extendable to other compounds containing quadrupolar nuclei.

Monday, June 12, 2006

Hiyam's Journal Updates

Quadrupolar coupling selective cross-polarization in solid state NMR
Physical Chemistry Chemical Physics, 2006, 8, 1994 - 1999

Mattias Edén

A new strategy is presented for achieving selective heteronuclear polarization transfers from half-integer quadrupolar spins in magic-angle spinning (MAS) NMR. By combining cross-polarization with a recently introduced RAPT pulse sequence that selectively excites the signal of a half-integer quadrupolar nucleus based on its quadrupolar coupling constant magnitude, we demonstrate that hetero-nuclei in its close proximity may be selectively excited. Selective 23Na 1H polarization transfers are demonstrated in Na2MoO4·2H2O, Na2HPO4·2H2O and a mixture of NaHCO3 and Na2HPO4·2H2O.
Medium-range order in sodium phosphate glasses: A quantitative rotational echo double resonance solid state NMR study
Physical Chemistry Chemical Physics, 2006, 8, 2276 - 2285

Wenzel Strojek and Hellmut Eckert

Sodium ultraphosphate glasses (Na2O)x(P2O5)1–x show a strongly non-linear dependence of the glass transition temperatures Tg(x) on composition. To explore the structural origins of this behaviour, local and medium range ordering processes have been investigated by state-of-the-art 23Na high-resolution and dipolar NMR spectroscopies. In particular, 31P{23Na} and 23Na{31P} rotational echo double resonance (REDOR) experiments have been analyzed to yield quantitative constraints for the structural description of these glasses. The sodium ions are found to be randomly distributed and, for x <>(2) unit at a distance of 330 pm. In this region, unusual compositional trends observed for the 23Na chemical shifts and nuclear electric quadrupolar coupling constants, measured by triple-quantum magic-angle spinning (TQMAS) NMR, suggest a systematic decrease of Na coordination number with x. At higher sodium contents (x > 0.25), the magnitude of the 31P{23Na} dipolar interaction increases markedly, indicating a significantly increased extent of Q(2)-Na-Q(2) crosslinking. Based on these results, a comprehensive description of medium-range order in sodium ultraphosphate glasses is developed, suggesting that the Tg(x) dependence is closely linked to changes in the relative phosphorus/sodium distance distributions.

Graphical abstract image for this article  (ID: b518080e)

Acid sites and oxidation center in molybdena supported on tin oxide as studied by solid-state NMR spectroscopy and theoretical calculation
Physical Chemistry Chemical Physics, 2006, 8, 2378 - 2384

Jiqing Wang, Yongchao Su, Jun Xu, Chaohui Ye and Feng Deng

Solid-state NMR spectroscopy and density functional theory (DFT) calculations were employed to study the structure and properties, especially the solid acidity, of molybdenum oxide supported on tin oxide. As demonstrated by solid-state NMR experiments, Mo species are mainly dispersed on the surface of SnO2 support rather than significantly dissolved into the SnO2 structure and Brønsted as well as Lewis acid sites are present on the MoO3/SnO2 catalyst. Acid strength of the supported metal oxide is stronger than those of zeolites, e.g., HY and HZSM-5, though the concentration of acid sites is relatively lower. The DFT calculated 13C chemical shift for acetone adsorbed on MoO3/SnO2 is in good agreement with the experimental value, which confirms our proposed structure of –Mo–(OH)–Sn– for the Brønsted acid site. Reducibility of the supported metal oxide is also demonstrated by solid-state NMR experiments and an active oxidation center of this catalyst is proposed as well.

Graphical abstract image for this article  (ID: b516833c)

Friday, June 09, 2006

JPCB: Francesconi and Polenova, 31P of paramagnetic Keggin solids

Probing Local Environments in Paramagnetic Europium-Substituted Keggin Solids by 31P Magic Angle Spinning NMR Spectroscopy

Wenlin Huang, Mark Schopfer, Cheng Zhang, Robertha C. Howell, Becky A. Gee, Lynn C. Francesconi,* and Tatyana Polenova*

Department of Chemistry and Biochemistry, University of Delaware, Newark, Delaware 19716, Department of Chemistry, City University of New York-Hunter College, 695 Park Avenue, New York, New York 10021, and Department of Chemistry and Biochemistry, Long Island University-Brooklyn Campus, 1 University Plaza, Brooklyn, New York 11201


Paramagnetic Eu-substituted Keggin oxopolytungstates crystallize in different forms, determined by the nature of the counterions. The crystal packing is in turn responsible for the variations in the geometry of paramagnetic Eu sites with respect to the anion core. We probed the paramagnetic environments in a series of Eu-substituted Keggin solids, by 31P magic angle spinning NMR spectroscopy. 31P spinning sideband envelopes are dominated by the electron-nuclear dipolar interaction. For the compounds under investigation, both the magnitude and the asymmetry parameter of the electron-nuclear dipolar coupling tensor are sensitive to the mutual arrangements of paramagnetic Eu sites in the crystal lattice. and also report on the stoichiometry of the anion. The electron-nuclear dipolar coupling tensors were calculated from the crystallographic coordinates and the experimentally determined effective magnetic moments, assuming a point dipole approximation. The computed tensors are in very good agreement with the experimental spectra. Furthermore, the P-Eu distance estimates, accurate to within 0.06-0.12 Å, can be obtained directly from the magnitude of the electron-nuclear dipolar coupling. This work demonstrates that 31P MAS NMR spectroscopy is a useful probe for investigating local environments in paramagnetic Keggin solids.

PCCP: high pressure 129Xe NMR to probe effects of pressure and density

Phys. Chem. Chem. Phys., 2006, (Advance Article)
DOI: 10.1039/b604633a

Local structure of xenon adsorbed in the nanospaces of zeolites as studied by high-pressure 129Xe NMR

Hironori Omi, Takahiro Ueda, Noriko Kato, Keisuke Miyakubo and Taro Eguchia

aDepartment of Chemistry, Graduate School of Science, Osaka University, Toyonaka, Osaka, 560-0043, Japan

bThe Museum of Osaka University, Toyonaka, Osaka, 560-0043, Japan. E-mail:; Fax: +81-6-6850-5785; Tel: +81-6-6850-5778

Received (in CAMBS) 30th March 2006, Accepted 30th May 2006

Pressure (0–10 MPa) and local density dependence of 129Xe NMR chemical shift of xenon in various microporous materials was investigated using an in situ high-pressure probe. The density dependence of the chemical shift was analyzed using virial expansion of the chemical shift by xenon density. Results indicate that the second virial coefficient depends on the pore size and shape, and that the void space affects xenon–xenon interaction in both microporous and mesoporous materials. Furthermore, to interpret the magnitude of the virial coefficient in terms of the local structure of the adsorbed xenon, we analyzed the local structure of adsorbed xenon in molecular sieve 5A using Xen clusters, thereby allowing description of the density dependence of the chemical shift. We also demonstrated the cluster models validity by applying it to molecular sieves 13X and ZSM-5. The latter showed that the adsorbed xenon exists as a xenon monomer up to the filling of about 0.6 in micropores. Larger xenon clusters up to n= 4 have been grown with increasing filling of xenon. According to analyses using the Xen cluster model, the second virial coefficient is related closely with the xenon cluster size, which contributes greatly to the chemical shift in the low loading region.

JPCA, de Dios, CS tensoirs in 4-aminoquinolines; heme-drug interactions

J. Phys. Chem. A, ASAP Article 10.1021/jp061320t S1089-5639(06)01320-X
Web Release Date: June 6, 2006

Relationship between NMR Shielding and Heme Binding Strength for a Series of 7-Substituted Quinolines

Leah B. Casabianca and Angel C. de Dios*

Department of Chemistry, Georgetown University, 37th and O Streets NW, Washington, DC 20057


Chemical shielding tensors are calculated for the carbons in a series of 4-aminoquinolines with different substituents at the 7-position. The 11 component is used as a measure of the relative -electron density at each carbon. By comparing the -electron density at each carbon with the log K of binding to heme (Kaschula et al. J. Med. Chem. 2002, 45, 3531), the drug-heme association is found to increase with increasing -electron density at the carbons meta to the substituent and with decreasing -electron density at the carbons ortho and para to the substituent. The greatest change in -electron density is at the ortho carbons, and log K increases with a decrease in -electron density on the ring containing the substituent, which corresponds to an increase in the -dipole between the two rings. An examination of the solution structures of the - complexes formed by amodiaquine and quinine with heme (Leed et al. Biochemistry 2002, 41, 10245. de Dios et al. Inorg. Chem. 2004, 43, 8078) shows that the -dipoles in each drug and in the porphyrin ring of heme may be paired. The chloro-substituted compound has an association constant that is an order of magnitude higher than the other compounds in the series, but the -electron density at the ring containing the substituent is not correspondingly low. This lack of correlation indicates that the Cl-substituted compound may be binding to heme in a manner that differs from the other compounds in the series.

JPCB: Stebbins and Du, 17O, 23Na NMR of Na germanate glasses

J. Phys. Chem., ASAP Article 10.1021/jp0615510 S1520-6106(06)01551-3
Web Release Date: June 3, 2006

Oxygen Sites and Network Coordination in Sodium Germanate Glasses and Crystals: High-Resolution Oxygen-17 and Sodium-23 NMR

Lin-Shu Du and Jonathan F. Stebbins*

Department of Geological and Environmental Sciences, Stanford University, Stanford, California 94305-2115


Sodium germanate glasses are well-studied materials in which, unlike silicates but analogous to borates, the major structural consequence of alkali addition is generally thought to involve a coordination number increase of the network-forming Ge cations. However, the nature of this change, in particular quantifying fractions of nonbridging oxygens and of five- and/or six-coordinated Ge, has remained unresolved. We present here high-resolution 17O results, including triple-quantum MAS NMR (3QMAS), on a series of crystalline model compounds that allow the definition of ranges of chemical shifts corresponding to oxygens bonded to various coordinations of Ge. These include quartz- and rutile-structured GeO2, Na4Ge9O20, Na2Ge4O9, and Na2GeO3 (germanium dioxide, sodium enneagermanate, sodium tetragermanate, and sodium metagermanate). 3QMAS spectra of Na-germanate glasses ranging from 0% to 27% Na2O clearly show the development of partially resolved peaks as alkali is added, corresponding to signals from nonbridging oxygens (in the highest Na glasses) and to oxygen bridging between one four-coordinated and one higher coordinated Ge. As in conventional models of this system, nonbridging oxygen contents are much lower than in corresponding silicates. Although we do not directly distinguish between five- and six-coordinated Ge, modeling of bridging oxygen populations and comparison with measured speciation suggest that substantial proportions of both species are likely to be present. High-field 23Na MAS NMR shows systematic decreases in mean Na-O bond distance and/or coordination number with increasing alkali content that can be compared with published results for high-temperature liquids. These results, as well as comparison of molar volumes of glasses and high-temperature liquids, suggest the possibility of significant temperature effects on liquid structure.

JACS, Bodenhausen, indirect detection of 14N spectra via residual dipolar coupling - similar to Gan's work?

J. Am. Chem. Soc., ASAP Article 10.1021/ja0618898 S0002-7863(06)01889-0
Web Release Date: May 26, 2006

Nitrogen-14 NMR Spectroscopy Using Residual Dipolar Splittings in Solids

Simone Cavadini, Adonis Lupulescu, Sasa Antonijevic,* and Geoffrey Bodenhausen

Laboratoire de Résonance Magnétique Biomoléculaire, Ecole Polytechnique Fédérale de Lausanne, Batochime, CH-1015 Lausanne, Switzerland, and Département de Chimie, associé au CNRS, Ecole Normale Supérieure, 24 rue Lhomond 75231, Paris Cedex 05, France


It is shown that nuclear magnetic resonance (NMR) spectra of nitrogen-14 (spin I = 1) can be obtained by indirect detection in powders spinning at the magic angle (MAS). The method relies on the transfer of coherence from a neighboring nucleus with S = 1/2, such as carbon-13, to single- or double-quantum transitions of nitrogen-14 nuclei. The transfer of coherence occurs through second-order quadrupole-dipole cross terms, also known as residual dipolar splittings. The two-dimensional NMR spectra reveal powder patterns determined by the second-order quadrupolar interactions of nitrogen-14. Analysis of the spectra yields the quadrupolar coupling.

JACS, Mark Smith et al, 17O NMR applied to biological molecules; DOR applications

J. Am. Chem. Soc., ASAP Article 10.1021/ja062031l S0002-7863(06)02031-2
Web Release Date: May 26, 2006

New Limits for Solid-State 17O NMR Spectroscopy: Complete Resolution of Multiple Oxygen Sites in a Simple Biomolecule

Alan Wong, Andy P. Howes, Kevin J. Pike, Vincent Lemaître, Anthony Watts, Tiit Anupõld, Jaan Past, Ago Samoson, Ray Dupree,* and Mark E. Smith*

Department of Physics, University of Warwick, Coventry CV4 7AL, United Kingdom, Biochemistry Department, University of Oxford, South Parks Road, Oxford OX1 3QU, United Kingdom, and National Institute for Chemical Physics and Biophysics, Akadeemia Tee 23, Tallinn, Estonia


A solid-state 17O NMR 1H-decoupled double angle rotation (DOR) study of monosodium L-glutamate monohydrate (L-MSG) is reported. It is shown that all eight inequivalent sites can be resolved with DOR line widths (~65 Hz) ~120 times narrower than those in the MAS spectrum. The lines are tentatively assigned on the basis of their behavior under proton decoupling and the isotropic chemical shift and the quadrupole interaction parameter for each extracted by a combination of DOR and 3Q MAS at variable magnetic fields. With a shift range of ~45 ppm for these similar oxygen sites and spectral resolution under DOR comparable to that for spin-1/2 nuclei, solid-state 17O NMR should have tremendous potential in the study of biomolecules.

JACS: Wasylishen & Forgeron, 95MO NMR and DFT calculations

J. Am. Chem. Soc., ASAP Article 10.1021/ja060124x S0002-7863(06)00124-7
Web Release Date: May 25, 2006

A Solid-State 95Mo NMR and Computational Investigation of Dodecahedral and Square Antiprismatic Octacyanomolybdate(IV) Anions: Is the Point-Charge Approximation an Accurate Probe of Local Symmetry?

Michelle A. M. Forgeron and Roderick E. Wasylishen*

Contribution from the Department of Chemistry, Gunning/Lemieux Chemistry Centre, University of Alberta, Edmonton, Alberta, Canada T6G 2G2


Solid-state 95Mo NMR spectroscopy is shown to be an efficient and effective tool for analyzing the diamagnetic octacyanomolybdate(IV) anions, Mo(CN)84-, of approximate dodecahedral, D2d, and square antiprismatic, D4d, symmetry. The sensitivity of the Mo magnetic shielding () and electric field gradient (EFG) tensors to small changes in the local structure of these anions allows the approximate D2d and D4d Mo(CN)84- anions to be readily distinguished. The use of high applied magnetic fields, 11.75, 17.63 and 21.1 T, amplifies the overall sensitivity of the NMR experiment and enables more accurate characterization of the Mo and EFG tensors. Although the magnitudes of the Mo and EFG interactions are comparable for the D2d and D4d Mo(CN)84- anions, the relative values and orientations of the principal components of the Mo and EFG tensors give rise to 95Mo NMR line shapes that are significantly different at the fields utilized here. Quantum chemical calculations of the Mo and EFG tensors, using zeroth-order regular approximation density functional theory (ZORA DFT) and restricted Hartree-Fock (RHF) methods, have also been carried out and are in good agreement with experiment. The most significant and surprising result from the DFT and RHF calculations is a significant EFG at Mo for an isolated Mo(CN)84- anion possessing an ideal square antiprismatic structure; this is contrary to the point-charge approximation, PCA, which predicts a zero EFG at Mo for this structure.

Friday, June 02, 2006

Cory's Journals - May 2006

May 2006 articles from the journals that I am responsible for will be placed in their usual folder by the end of today.