Solid-State NMR and Density Functional Theory Studies of Ionization States of Thiamin

J. Phys. Chem. B, 2011, 115 (4), pp 730–736

Thiamin diphosphate (ThDP) is a key coenzyme in sugar metabolism. The 4′-aminopyrimidine ring of ThDP cycles through several ionization and tautomeric states during enzyme catalysis, but it is not fully understood which states are adopted during the individual steps of the catalytic cycle. Thiamin has been synthesized with labels selectively inserted into the C2 and C6′ positions, as well as into the amino group, creating [C2, C6′-13C2] thiamin and [N4′-15N] thiamin. Magic-angle spinning (MAS) NMR spectroscopy has been employed to record the 13C and 15N chemical shift anisotropy (CSA) tensors for C2, C6′, and N4′ atoms. Our results indicate that the isotropic chemical shifts as well as the principal components of the 13C and 15N CSA tensors are very sensitive to the protonation states in these compounds and, therefore, permit differentiating between the two ionization states, 4-aminopyrimidine and 4-aminopyrimidinium. Using density functional theory (DFT), we have calculated the magnetic shielding anisotropy tensors of C2, C6′, and N4′ and found excellent agreement between the computed and the experimental tensors. Our findings indicate that MAS NMR spectroscopy in conjunction with DFT calculations is a sensitive probe of ionization states in the thiamin cofactor. The results of this study will serve as a guide for characterization of ionization and tautomeric states of thiamin in complexes with thiamin-dependent enzymes.

Siting and Mobility of Deuterium Absorbed in Cosputtered Mg0.65Ti0.35. A MAS 2H NMR Study

J. Phys. Chem. C, 2011, 115 (1), pp 288–297

Nanostructured magnesium titanium alloys are interesting lightweight materials for chemical hydrogen storage. We have therefore investigated the siting and dynamics of deuterium absorbed in a Mg0.65Ti0.35 alloy generated by magnetron cosputtering, and made a comparison to the corresponding features in bulk samples of deuterium-loaded Mg0.65Ti0.35 and Mg0.65Sc0.35 prepared by ball-milling and melt-casting, respectively. Magic-angle spinning 2H NMR of cosputtered Mg0.65Ti0.35D1.1 shows partly resolved signals of deuterium located in nonconductive domains at tetrahedral Mg4 and mixed MgnTi4−n sites (4 ppm) and deuterium at Ti4 sites in conducting TiD2 nanodomains (−29 and −68 ppm). No bulk TiD2 signal at −150 ppm is observed, in contrast to what we find in ball-milled Mg0.65Ti0.35D0.65, which is largely phase separated. The deuterium species with shift values of 4 and −29 ppm undergo complete exchange at a subsecond time scale in one- and two-dimensional exchange NMR and must therefore be close together in the lattice. In contrast, deuterium resonating at −68 ppm does not show deuterium exchange and thus appears to be located at more stable sites. The observed deuterium exchange and the reduced Knight shift compared to bulk TiD2 are explained using a model with TiD2 nanoslabs.


Towards Portable High-Resolution NMR Spectroscopy†

Angew. Chem. Int. Ed. 2011, 50, 354 – 356

Analysis on the go: Portable high-resolution NMR spectroscopy is of great interest for many applications. Recent advances in magnet design, spectrometer stability, and acquisition schemes have placed the realization of low-field spectrometers based on room-temperature permanent magnets and that can deliver chemical shift resolution within reach.

Probing the local structures and protonic conduction pathways in scandium substituted BaZrO3 by multinuclear solid-state NMR spectroscopy

from RSC - J. Mater. Chem. latest articles by Clare P. Grey

Abstract

A comprehensive multinuclear solid-state NMR study of scandium-substituted BaZrO₃ is reported. Static low field and MQMAS very high field ⁴⁵Sc NMR data revealed the presence of both 5- and 6-coordinated scandium atoms, 5-coordinated scandium arising from Sc nearby an oxygen vacancy. ¹⁷O NMR spectra showed the presence of up to three different chemical oxygen environments assigned to Zr–O–Zr, Zr–O–Sc and Sc–O–Sc. From the ratios of these different oxygen sites, the distribution of the scandium cations was close to random but indicated that the maximum scandium incorporation was lower than expected, consistent with the observation of Sc₂O₃ impurities at substitution levels of 30% Sc for Zr. ¹H and ⁴⁵Sc NMR data on the hydrated materials revealed the presence of scandium next to protonic defects. Finally, variable temperature ¹H NMR showed the presence of at least two different proton environments in between which proton transfer occurs at ambient temperatures (300 K).

Solid state NMR study on the thermal decomposition pathway of sodium amidoborane NaNH2BH3

from RSC - J. Mater. Chem. latest articles by Yoshitsugu Kojima
Abstract

The thermal decomposition pathway of sodium amidoborane (NaAB; NaNH₂BH₃) has been investigated in detail by using solid state NMR spectroscopy. ²³Na MAS/3QMAS NMR spectra suggested that NaH and an amorphous Na–N–B–H phase started to be formed as decomposition products even at 79 °C, although NaAB was prepared from NaH and NH₃BH₃ by ball milling at room temperature. Based on the quantitative analyses of the ²³Na MAS spectra, we proposed a decomposition reaction to 200 °C to be NaNH₂BH₃ → Na_0.5NBH_0.5 + 0.5NaH + 2.0H₂. The hypothetical phase Na_0.5NBH_0.5 is amorphous, where the basic molecular unit of the original NaAB is polymerized into a [–BN–]_n network structure. It was also found that the diammoniate of diborane (DADB) and polyaminoborane (PAB) were not formed during the decomposition of NaAB, which are both key compounds on the pyrolysis of ammonia borane (AB).

17O Central Transition NMR

A nice write-up of Gang Wu's solution 17O central transition NMR studies of biomolecules can be found in C&E News

http://pubs.acs.org/cen/news/89/i01/8901notw4.html

The corresponding articles are:

Quadrupole Central Transition 17O NMR Spectroscopy of Biological Macromolecules in Aqueous Solution

Jianfeng Zhu and Gang Wu*

J. Am. Chem. Soc., Article ASAP
DOI: 10.1021/ja1079207

Abstract: We demonstrate a general nuclear magnetic resonance (NMR) spectroscopic approach in obtaining high-resolution 17O (spin-5/2) NMR spectra for biological macromolecules in aqueous solution. This approach, termed quadrupole central transition (QCT) NMR, is based on the multiexponential relaxation properties of half-integer quadrupolar nuclei in molecules undergoing slow isotropic tumbling motion. Under such a circumstance, Redfield’s relaxation theory predicts that the central transition, mI = +1/2 ↔ −1/2, can exhibit relatively long transverse relaxation time constants, thus giving rise to relatively narrow spectral lines. Using three robust protein−ligand complexes of size ranging from 65 to 240 kDa, we have obtained 17O QCT NMR spectra with unprecedented resolution, allowing the chemical environment around the targeted oxygen atoms to be directly probed for the first time. The new QCT approach increases the size limit of molecular systems previously attainable by solution 17O NMR by nearly 3 orders of magnitude (1000-fold). We have also shown that, when both quadrupole and shielding anisotropy interactions are operative, 17O QCT NMR spectra display an analogous transverse relaxation optimized spectroscopy type behavior in that the condition for optimal resolution depends on the applied magnetic field. We conclude that, with the currently available moderate and ultrahigh magnetic fields (14 T and higher), this 17O QCT NMR approach is applicable to a wide variety of biological macromolecules. The new 17O NMR parameters so obtained for biological molecules are complementary to those obtained from 1H, 13C, and 15N NMR studies.


Solid-State 17O NMR Spectroscopy of Large Protein–Ligand Complexes†
Dr. Jianfeng Zhu1, Dr. Eric Ye2, Dr. Victor Terskikh3, Prof. Dr. Gang Wu1
Article first published online: 29 OCT 2010

DOI: 10.1002/anie.201002041

Angewandte Chemie International Edition
Volume 49, Issue 45, pages 8399–8402, November 2, 2010

Keywords:
oxygen-17;protein–ligand interactions;proteins;solid-state NMR spectroscopy;structure refinement

Oxygen, oxygen, everywhere! Poor sensitivity has hindered the development of solid-state 17O NMR spectroscopy as a practical technique for the structural elucidation of protein complexes. However, this has now changed and it has been demonstrated that multinuclear 17O, 27Al, 13C NMR parameters can be used to aid structural refinement for a protein-bound ligand molecule (see picture).

Solid-State NMR

A practical guide for the setup of a 1H-31P-13C double cross-polarization (DCP) experiment

Publication year: 2010
Source: Solid State Nuclear Magnetic Resonance, In Press, Accepted Manuscript, Available online 13 December 2010
Wlodzimierz, Ciesielski , Hassan, Kassasir , Marek J., Potrzebowski

O-phospho-L-threonine is a convenient sample to setup a ¹H-³¹P-¹³C double cross-polarization (DCP) Hartmann-Hahn match. The ¹H-³¹P-¹³C technique is extremely sensitive to the rate of sample spinning. Both zero-quantum (ZQ) and double-quantum (DQ) cross-polarization operate at an average spinning rate (6–7 kHz). At higher spinning rates (10 kHz), the DQCP mechanism dominates and leads to a reduction of signal intensity, in particular for lower ³¹P rf field strength. The application of two shape pulses during the second cross-polarization greatly improves the signal to noise ratio allowing the recording of better quality spectra. ³¹P-¹³C SPECIFIC-CP (spectrally induced filtering in combination with cross-polarization) experiments can be carried out under ZQCP and DQCP condition if careful attention is paid to the choice of RF field amplitudes and carriers Ω. Application of 1D and 2D ¹H-³¹P-¹³C experiments is demonstrated on model samples; disodium ATP hydrate and O-phospho-L-tyrosine.

Multinuclear NMR study of silica fiberglass modified with zirconia

Publication year: 2010
Source: Solid State Nuclear Magnetic Resonance, In Press, Accepted Manuscript, Available online 29 December 2010
O.B., Lapina , D.F, Khabibulin , V.V., Terskikh

Silica fiberglass textiles are emerging as uniquely suited supports in catalysis which offer unprecedented flexibility in designing advanced catalytic systems for chemical and auto industries. During manufacturing fiberglass materials are often modified with additives of various nature to improve glass properties. Glass network formers, such as zirconia and alumina, are known to provide the glass fibers with higher strength and to slow down undesirable devitrification processes. In this work multinuclear ¹H, ²³Na, ²⁹Si, and ⁹¹Zr NMR spectroscopy was used to characterize the effect of zirconia on the molecular-level fiberglass structure. ²⁹Si NMR results help in understanding why zirconia-modified fiberglass is more stable towards devitrification comparing with pure silica glass. Internal void spaces formed in zirconia-silica glass fibers after acidic leaching correlate with sodium and water distributions in the starting bulk glass as probed by ²³Na and ¹H NMR. These voids spaces are important for stabilization of catalytically active species in the supported catalysts. Potentials of high-field ⁹¹Zr NMR spectroscopy to study zirconia-containing glasses and similarly disordered systems are illustrated.

Kinetics of 1H→13C NMR cross-polarization in polymorphs and solvates of the antipsychotic drug olanzapine

Publication year: 2011
Source: Solid State Nuclear Magnetic Resonance, In Press, Accepted Manuscript, Available online 4 January 2011
Waclaw, Kolodziejski , Joanna, Herold , Marzena, Kuras , Irena, Wawrzycka-Gorczyca , Anna E., Koziol

The ¹H→¹³C NMR cross-polarization (CP) was studied under magic-angle spinning at 7.5 kHz in various crystal forms of the antipsychotic drug olanzapine: two polymorphs (metastable I and stable II) and eight solvates containing organic solvent and water molecules. The CP kinetics followed the non-classical I-I^*-S model, in which CP begins in a spin cluster of proximate abundant spins I^* and rare spins S, then is controlled by spin diffusion of the abundant spins I from bulk to the I^* spins of the spin cluster and finally is governed by spin-lattice relaxation of the abundant spins in the rotating frame. The corresponding CP kinetics parameters were determined and analyzed. It was demonstrated that the, λ and T_df values (the CP time constant, the cluster composition parameter and the ¹H spin-diffusion constant, respectively) were very useful to discriminate the functional groups, especially in the 3D parameter space. In order to conveniently analyze the large amount (1 7 5) of the collected CP parameters, the number of the observed variables was reduced using the principal component (PC) analysis. The 2D plot of PC2 vs. PC1 showed adequate separation of the CH₃, CH₂, CH and C cases (C stands for carbons without adjacent hydrogens). It was demonstrated that those cases were located along the PC1 axis in the order of increasing ¹H-¹³C dipolar couplings: C32. Our study showed the I-I^*-S model at work and established ranges of its parameters for various functional groups.

Inorg. Chem.

Solvent Effects and Dynamic Averaging of ¹⁹⁵Pt NMR Shielding in Cisplatin Derivatives

Lionel A. Truflandier, Kiplangat Sutter, and Jochen Autschbach*

jochena@buffalo.edu

Inorg. Chem., Article ASAP

DOI: 10.1021/ic102174b

Publication Date (Web): January 4, 2011

The influences of solvent effects and dynamic averaging on the ¹⁹⁵Pt NMR shielding and chemical shifts of cisplatin and three cisplatin derivatives in aqueous solution were computed using explicit and implicit solvation models. Within the density functional theory framework, these simulations were carried out by combining ab initio molecular dynamics (aiMD) simulations for the phase space sampling with all-electron relativistic NMR shielding tensor calculations using the zeroth-order regular approximation. Structural analyses support the presence of a solvent-assisted “inverse” or “anionic” hydration previously observed in similar square-planar transition-metal complexes. Comparisons with computationally less demanding implicit solvent models show that error cancellation is ubiquitous when dealing with liquid-state NMR simulations. After aiMD averaging, the calculated chemical shifts for the four complexes are in good agreement with experiment, with relative deviations between theory and experiment of about 5% on average (1% of the Pt^II chemical shift range).

J. Phys. Chem. A

Crystal Structure Based Design of Signal Enhancement Schemes for Solid-State NMR of Insensitive Half-Integer Quadrupolar Nuclei

Luke A. O’Dell* and Christopher I. Ratcliffe
luke.odell@nrc-cnrc.gc.ca

J. Phys. Chem. A, Article ASAP

DOI: 10.1021/jp111531e

Publication Date (Web): December 21, 2010

A combination of density functional and optimal control theory has been used to generate amplitude- and phase-modulated excitation pulses tailored specifically for the ³³S nuclei in taurine, based on one of several reported crystal structures. The pulses resulted in significant signal enhancement (stemming from population transfer from the satellite transitions) without the need for any experimental optimization. This allowed an accurate determination of the ³³S NMR interaction parameters at natural abundance and at a moderate magnetic field strength (11.7 T). The ³³S NMR parameters, along with those measured from ¹⁴N using frequency-swept pulses, were then used to assess the accuracy of various proposed crystal structures.

___________________________________________________

Interactions of Volatile Organic Compounds with Syndiotactic Polystyrene Crystalline Nanocavities
Alexandra R. Albunia*, Patrizia Oliva, and Alfonso Grassi
aalbunia@unisa.it

J. Phys. Chem. A, Article ASAP

DOI: 10.1021/jp1090608

Publication Date (Web): December 17, 2010

The interaction of some volatile organic compounds, namely, 1,2-dichloroethane, 1,2-dibromoethane, and 1,1,2,2-tetrachloroethane, included in the δ crystalline phase of syndiotactic polystyrene (sPS) has been studied in terms of conformation, orientation, and dynamical behavior. By combination of X-ray diffraction (XRD), Fourier-transform infrared (FTIR), and solid-state ²H NMR analyses, it has been shown that despite the differences in guest molecular properties (mass, boiling temperature, and volume), stable sPS/guest δ-clathrate cocrystals are formed since the nanoporous δ crystalline form has a flexible structure able to adapt itself to the guest molecule. As a consequence of inclusion, it has been shown that the guest diffusivity is strongly reduced and the dynamical processes are constrained, particularly when these guests are in trans
conformation. This suggests the nanoporous sPS δ form to be an efficient tool for water and air purification through volatile organic compound absorption.

J. Chem. Phys.

Electrical and ionic conductivity effects on magic-angle spinning nuclear magnetic resonance parameters of CuI

from Journal of Chemical Physics: All Topics

James P. Yesinowski, Harold D. Ladouceur, Andrew P. Purdy, and Joel B. Miller

We investigate experimentally and theoretically the effects of two different types of conductivity, electrical and ionic, upon magic-angle spinning NMR spectra. The experimental demonstration of these effects involves ⁶³Cu, ⁶⁵Cu, and ¹²⁷I variable temperature MAS-NMR experiments on samples of γ-CuI, a Cu⁺-ion conductor at elevated temperatures as well as a wide bandgap semiconductor. We extend previous observations that the chemical shifts depend very strongly upon the square of the spinning-speed as well as the particular sample studied and the magnetic field strength. By using the ²⁰⁷Pb resonance of lead nitrate mixed with the γ-CuI as an internal chemical shift thermometer we show that frictional heating effects of the rotor do not account for the observations. Instead, we find that spinning bulk CuI, a p-type semiconductor due to Cu⁺vacancies in nonstoichiometric samples, in a magnetic field generates induced AC electric currents from the Lorentz force that can resistively heat the sample by over 200 °C. These induced currents oscillate along the rotor spinning axis at the spinning speed. Their associated heating effects are disrupted in samples containing inert filler material, indicating the existence of macroscopic current pathways between micron-sized crystallites. Accurate measurements of the temperature-dependence of the ⁶³Cu and ¹²⁷I chemical shifts in such diluted samples reveal that they are of similar magnitude (ca. 0.27 ppm/K) but opposite sign (being negative for ⁶³Cu), and appear to depend slightly upon the particular sample. This relationship is identical to the corresponding slopes of the chemical shifts versus square of the spinning speed, again consistent with sample heating as the source of the observed large shift changes. Higher drive-gas pressures are required to spin samples that have higher effective electrical conductivities, indicating the presence of a braking effect arising from the induced currents produced by rotating a conductor in a homogeneous magnetic field. We present a theoretical analysis and finite-element simulations that account for the magnitude and rapid time-scale of the resistive heating effects and the quadratic spinning speed dependence of the chemical shift observed experimentally. Known thermophysical properties are used as inputs to the model, the sole adjustable parameter being a scaling of the bulk thermal conductivity of CuI in order to account for the effective thermal conductivity of the rotating powdered sample. In addition to the dramatic consequences of electrical conductivity in the sample,ionic conductivity also influences the spectra. All three nuclei exhibit quadrupolar satellite transitions extending over several hundred kilohertz that reflect defects perturbing the cubic symmetry of the zincblende lattice. Broadening of these satellite transitions with increasing temperature arises from the onset of Cu⁺ ion jumps to sites with different electric field gradients, a process that interferes with the formation of rotational echoes. This broadening has been quantitatively analyzed for the ⁶³Cu and ⁶⁵Cu nuclei using a simple model in the literature to yield an activation barrier of 0.64 eV (61.7 kJ/mole) for the Cu⁺ ion jumping motion responsible for the ionic conductivity that agrees with earlier results based on ⁶³Cu NMR relaxation times of static samples

Communication: Critical dynamics and nuclear relaxation in lipid bilayers

Harden McConnell

Membrane composition fluctuations affect deuterium nuclear magnetic relaxation in lipid bilayers. The time dependence of the fluctuations depends on lipid diffusion. Near a miscibility critical point this diffusion involves an advective hydrodynamic coupling to the aqueous phase. The corresponding diffusion coefficient depends on both the critical length and the fluctuation wavelength. We calculate the effects of these dynamics on transverse deuterium nuclear relaxation in the 0.1^o–10^o range above the critical temperature.

Phys. Rev. Lett.

Detection of Phase Biaxiality in Liquid Crystals by Use of the Quadrupole Shift in ^{131} Xe NMR Spectra

from Recent Articles in Phys. Rev. Lett. by Jukka P. Jokisaari, Anu M. Kantola, Juhani A. Lounila, and L. Petri Ingman

An experimental method to unambiguously distinguish between uniaxial and biaxial liquid crystal phases is introduced. The method is based on the second order quadrupole shift (SOQS) observable in ¹³¹Xe NMR spectra of xenon dissolved in liquid crystals. It is shown that besides revealing the biaxiality, the ¹³¹Xe SOQS offers a novel method to determine the tilt angle in smectic C phases. As an example, the ¹³¹Xe SOQS in a ferroelectric liquid crystal is reported. It yields up a biaxial phase in between isotropic and smectic C phases.