Nuclear Magnetic Resonance Line Research Articles

On the Morphology of a Discotic Liquid Crystalline Charge Transfer Complex

Discotic liquid crystalline (DLC) charge transfer (CT) complexes, which combine visible light absorption with rapid charge transfer characteristics within the CT complex, can have a great potential for photovoltaic applications when they can be made to self-assemble in a bulk heterojunction arrangement with separate channels for electron and hole conduction. However, the morphology of some liquid crystalline CT complexes has been under debate for many years. In particular, the liquid crystalline CT complex built from the electron acceptor 2,4,7-trinitro-9-fluorenone (TNF) and discotic molecules has been reported to have the TNF "sandwiched" either between the discotic molecules within the same column or between the columns within the aliphatic tails of the discotic molecules. We present a detailed structural study of the prototypic 1:1 mixture of the discotic 2,3,6,7,10,11-hexakis(hexyloxy)triphenylene (HAT6) and TNF. Nuclear magnetic resonance (NMR) line widths and cross-polarization rates are consistent with the picosecond time scale anisotropic thermal motions of the HAT6 and TNF molecules previously observed. By computational integration of Rietveld refinement analyses of neutron diffraction patterns with density experiments and short-range structural constraints from heteronuclear 2D NMR, we determine that the TNF molecules are vertically oriented between HAT6 columns. The data provide the insight that a morphology of separate hole conducting channels of HAT6 molecules can be realized in the liquid crystalline CT complex.

Microscopic characteristics of dynamic nuclear polarization and selective nuclear depolarization at the ν=2/3 spin phase transition

The ability to manipulate the nuclear spin degree of freedom in semiconductor quantum structures is necessary for development of nuclear spintronics based on solid-state systems. Here, we developed a method to selectively depolarize the nuclear spin, the 〈+Iz〉 or the 〈−Iz〉 component, residing in a GaAs quantum well specimen after dynamic nuclear polarization by applying radio frequency pulse to either spin-unpolarized or spin-polarized nuclear magnetic resonance lines obtained at the spin transition of the filling ν=2/3. Our results are evidence that the spin-unpolarized (spin-polarized) domain mediates the 〈+Iz〉 (〈−Iz〉) nuclear spin polarization.

Solid State Nuclear Magnetic Resonance and X-ray Diffraction Line Profile Analysis of heavily deformed fluorite

The effect of high-energy ball milling on calcium fluoride was studied by X-ray Diffraction (XRD) Line Profile Analysis (LPA) and Solid State Nuclear Magnetic Resonance (NMR) spin–lattice relaxation. The latter technique is especially useful not only to detect the nonhomogeneous effects of the early stages of mechanical grinding, but is also sensitive to the defect structure of the ball milled powders. When supported by Solid State NMR, XRD LPA unveils fine details of the milling effects on fluorite, in terms of increasing dislocation density and progressive refinement of the crystalline size down to the nanoscale.

Spin-lattice relaxation of the methyl group protons in solids revisited: Damped quantum rotation approach

Proton spin-lattice relaxation of the methyl group in solids had been one of the most thoroughly addressed theoretical problems in nuclear magnetic resonance (NMR) spectroscopy, considered at different levels of sophistication. For systems with substantial quantum tunneling effects, several quantum mechanical treatments were reported, although in practical applications the quantum models were always augmented with or replaced by the classical jump model. However, the latter has recently proved invalid in the description of NMR line shape effects in variable-temperature spectra of hindered methyl groups, while the competing theory of damped quantum rotation (DQR) was shown to be adequate. In this work, the spin-lattice relaxation issue for the methyl protons is readdressed using the latter theory. The main outcome is that, while the existing formulas for the relaxation rates remain unchanged, the crucial parameter entering them, the correlation time of the relevant random process, need to be reinterpreted. It proves to be the inverse of one of the two quantum-rate constants entering the DQR model, neither of which, when taken separately, can be related to the jump process. It can be identified with one describing the life-time broadening of the tunnel peaks in inelastic neutron scattering (INS) spectra of the methyl groups. Such a relationship between the relaxation and INS effects was reported from another laboratory long ago, but only for the low-temperature limit where thermal population of the excited torsional levels of the methyl group can be neglected. The whole spectrum of cases encountered in practical relaxation studies on protonated methyl groups is addressed for the first time. Preliminary experimental confirmation of this novel approach is reported, based on already published NMR data for a single crystal of methylmalonic acid. The once extensively debated issues of quenching of the coherent tunneling and of the classical limit in the dynamics of the methyl groups are readdressed and presented in a consistent manner.

Mn local moments prevent superconductivity in iron pnictides Ba(Fe1−xMnx)2As2

75As nuclear magnetic resonance (NMR) experiments were performed on Ba(Fe1−xMnx)2As2 (xMn = 2.5%, 5% and 12%) single crystals. The Fe layer magnetic susceptibility far from Mn atoms is probed by the 75As NMR line shift and is found similar to that of BaFe2As2, implying that Mn does not induce charge doping. A satellite line associated with the Mn nearest neighbours (n.n.) of 75As displays a Curie-Weiss shift which demonstrates that Mn carries a local magnetic moment. This is confirmed by the main line broadening typical of a RKKY-like Mn-induced staggered spin polarization. The Mn moment is due to the localization of the additional Mn hole. These findings explain why Mn does not induce superconductivity in the pnictides contrary to other dopants such as Co, Ni, Ru or K.

NMR Study in the Iron-SelenideRb0.74Fe1.6Se2: Determination of the Superconducting Phase as Iron Vacancy-FreeRb0.3Fe2Se2

77Se and 87Rb nuclear magnetic resonance (NMR) experiments on Rb0.74Fe1.6Se2 reveal clearly distinct spectra originating from a majority antiferromagnetic (AF) and a minority metallic-superconducting (SC) phase. The very narrow NMR line of the SC phase evidences the absence of Fe vacancies and any trace of AF order. The Rb content of the SC phase is deduced from intensity measurements identifying Rb(0.3(1))Fe2Se2 as the actual composition of the SC fraction. The resulting estimate of 0.15 electrons/Fe brings this class of superconductors 245 family closer to the other Fe-based superconductor families.

Bound water freezing in AntarcticUmbilicaria aprinafrom Schirmacher Oasis

AbstractThe effect of low temperature onUmbilicaria aprinacollected from Schirmacher Oasis, East Antarctica, was determined over a wide range of hydration using proton free induction decays, proton nuclear magnetic resonance (NMR) spectra and differential scanning calorimetry methods. The proton NMR line is a superposition of the broad component from the solid matrix of the thallus and a narrower component from the averaged bound water pool. Proton free induction decays may be resolved into three components: a solid component well described by the Abragam function and two exponentially decaying components from water loosely bound and water tightly bound in the thallus. With decreased temperature the loosely bound water pool (freezing water) is transferred to the tightly bound water pool (non-freezing water), and vanishes below -40°C. Bound water freezing and melting temperatures decrease with the decrease of hydration level, suggesting that heterogeneous ice nucleation is responsible for water freezing. The onset of bound water freezing temperature isc.10°C lower than the melting temperature. TheU. aprinathalli do not reveal the ability to stimulated ice nucleation at higher temperature. Freeze-thaw cycles showed that forn> 5 cycles no substantial change occurs in the difference between melting and freezing temperatures.

Observation of the Partial Fermi Surface Quenching in the Noncentrosymmetric Superconductor Mo3Al2C

We study the normal state properties of a noncentrosymmetric superconductor Mo 3 Al 2 C by means of the nuclear magnetic resonance (NMR) experiment. The change of NMR line shape and the peak of the nuclear spin-echo decay rate at ≃130 K indicate that the Mo 3 Al 2 C exhibits the phase transition prior to the emergence of superconductivity. The reduction in the conduction electron density is inferred from the decrease in the nuclear spin–lattice relaxation rate. By considering the result of the energy band calculation, we discussed the nature of the newly found phase transition.

A combined 77Se NMR and Raman spectroscopic study of the structure of GexSe1-x glasses: Towards a self consistent structural model

The short-range structures of stoichiometric and Se-deficient binary GexSe100−x glasses with 42≥x≥33.33 have been investigated using a combination of Raman and 77Se Car–Purcell–Meiboom–Gill (CPMG) spikelet nuclear magnetic resonance (NMR) spectroscopy. When taken together, these spectroscopic results allow for self-consistent assignment of average 77Se NMR isotropic chemical shifts to Se atoms in various coordination environments in GexSe100−x glasses. Analysis of the compositional variation of the relative concentrations of these Se environments indicates considerable violation of chemical order in the nearest-neighbor coordination environments of the constituent atoms in the stoichiometric Ge33.33Se66.67 glass. On the other hand, the presence of a random distribution of Ge―Ge bonds can be inferred in the Se-deficient glasses. Simulations of the previously published 77Se NMR line shapes of Se-excess glasses on the basis of the revised structural assignments of 77Se NMR chemical shifts obtained in this study conclusively indicate that the structure of these glasses is intermediate between a randomly connected and a fully clustered network of GeSe4 tetrahedra and Se chains.

Quantitative calibration of radiofrequency NMR Stark effects

Nuclear magnetic resonance (NMR) Stark responses can occur in quadrupolar nuclei for an electric field oscillating at twice the usual NMR frequency (2ω(0)). Calibration of responses to an applied E field is needed to establish nuclear spins as probes of native E fields within material and molecular systems. We present an improved approach and apparatus for accurate measurement of quadrupolar Stark effects. Updated values of C(14) (the response parameter in cubic crystals) were obtained for both (69)Ga and (75)As in GaAs. Keys to improvement include a modified implementation of voltage dividers to assess the 2ω(0) amplitude, |E|, and the stabilization of divider response by reduction of stray couplings in 2ω(0) circuitry. Finally, accuracy was enhanced by filtering sets of |E| through a linear response function that we established for the radiofrequency amplifier. Our approach is verified by two types of spectral results. Steady-state 2ω(0) excitation to presaturate NMR spectra yielded C(14) = (2.59 ± 0.06) × 10(12) m(-1) for (69)Ga at room-temperature and 14.1 T. For (75)As, we obtained (3.1 ± 0.1) × 10(12) m(-1). Both values reconcile with earlier results from 77 K and below 1 T, whereas current experiments are at room temperature and 14.1 T. Finally, we present results where few-microsecond pulses of the 2ω(0) field induced small (tens of Hz) changes in high-resolution NMR line shapes. There too, spectra collected vs |E| agree with the model for response, further establishing the validity of our protocols to specify |E|.

High-temperature in situ11B NMR study of network dynamics in boron-containing glass-forming liquids

In situ high-temperature nuclear magnetic resonance (NMR) spectroscopy can be very useful for probing changes in structure and dynamics in glass-forming liquids, and is a unique method for observing chemical exchange among structural species ( e.g. BO 3–BO 4, Q n–Q n+1, and NBO–BO) at the seconds to microseconds time scales. High-temperature 11B MAS NMR line shape measurements were made at about 100 K above the glass transitions on (Na 2O) 0.3(B 2O 3) 0.7 and (Na 2O) 0.2(B 2O 3) 0.21(Al 2O 3) 0.08(SiO 2) 0.51 glass-forming liquids. BO 3 and BO 4 groups are well resolved in 11B MAS NMR spectra at 14.1 T with sample spinning at 5000 Hz. At higher temperatures, partial peak coalescence occurred due to exchange of BO 3 and BO 4. Temperature effects on borate speciation were also determined by varying the fictive temperature ( T f ) of glasses, where T f estimated from differential scanning calorimetry measurements. We combined these complementary data sets to model structural exchange in the liquid state. The time scale of BO 3–BO 4 exchange from NMR data, τ NMR, appears to be “decoupled” from that of the macroscopic shear relaxation process τ s derived from the viscosity, however, at higher temperatures, τ s approaches τ NMR. The “decoupling” at lower temperature may be related to intermediate-range compositional heterogeneities, and/or fast modifier cation diffusivities which trigger “unsuccessful” network exchange events.

Near-Zero-Field Nuclear Magnetic Resonance

We investigate nuclear magnetic resonance (NMR) in near zero field, where the Zeeman interaction can be treated as a perturbation to the electron mediated scalar interaction (Jcoupling). This is in stark contrast to the high-field case, where heteronuclear Jcouplings are normally treated as a small perturbation. We show that the presence of very small magnetic fields results in splitting of the zero-field NMR lines, imparting considerable additional information to the pure zero-field spectra. Experimental results are in good agreement with first-order perturbation theory and with full numerical simulation when perturbation theory breaks down. We present simple rules for understanding the splitting patterns in near-zero-field NMR, which can be applied to molecules with nontrivial spectra.

Magnetic properties of the magnetoelectric compound Cu2OSeO3: Magnetization and 77Se NMR study

We present magnetization and 77Se Nuclear Magnetic Resonance (NMR) measurements in single crystals of the magneteoelectric compound Cu2OSeO3. The temperature and field dependence of the magnetization suggest a ferrimagnetic ordering at Tc ≃ 60 K in a 3up-1down configuration. The easy axis of the magnetization is along the [100] crystallographic direction. The 77Se NMR line shape data collected at 14.09 T are consistent with the symmetries imposed by the cubic P213 space group in the temperature range 20–290 K and confirm that the magnetic transition is not accompanied by any lowering of the crystal symmetry as has recently been proposed by Bos et al. [Phys. Rev. B 78 094416 (2008)].

Fractional Spin Textures in the Frustrated MagnetSrCr9pGa12−9pO19

We consider the archetypal frustrated antiferromagnet SrCr(9p)Ga(12-9p)O₁₉ in its well-known spin-liquid state, and demonstrate that a Cr(3+) spin S=3/2 ion in direct proximity to a pair of vacancies (in disordered p<1 samples) is cloaked by a spatially extended spin texture that encodes the correlations of the parent spin liquid. In this spin-liquid regime, our analytic theory predicts that the combined object has a magnetic response identical to a classical spin of length S/2=3/4, which dominates over the small intrinsic susceptibility of the pure system. This fractional-spin texture leaves an unmistakable imprint on the measured ⁷¹Ga nuclear magnetic resonance line shapes, which we compute using Monte Carlo simulations and compare with experimental data.

Radiation Induced Redox Reactions and Fragmentation of Constituent Ions in Ionic Liquids. 2. Imidazolium Cations

In part 1 of this study, radiolytic degradation of constituent anions in ionic liquids (ILs) was examined. The present study continues the themes addressed in part 1 and examines the radiation chemistry of 1,3-dialkyl substituted imidazolium cations, which currently comprise the most practically important and versatile class of ionic liquid cations. For comparison, we also examined 1,3-dimethoxy- and 2-methyl-substituted imidazolium and 1-butyl-4-methylpyridinium cations. In addition to identification of radicals using electron paramagnetic resonance spectroscopy (EPR) and selective deuterium substitution, we analyzed stable radiolytic products using (1)H and (13)C nuclear magnetic resonance (NMR) and tandem electrospray ionization mass spectrometry (ESMS). Our EPR studies reveal rich chemistry initiated through "ionization of the ions": oxidation and the formation of radical dications in the aliphatic arms of the parent cations (leading to deprotonation and the formation of alkyl radicals in these arms) and reduction of the parent cation, yielding 2-imidazolyl radicals. The subsequent reactions of these radicals depend on the nature of the IL. If the cation is 2-substituted, the resulting 2-imidazolyl radical is relatively stable. If there is no substitution at C(2), the radical then either is protonated or reacts with the parent cation forming a C(2)-C(2) σσ*-bound dimer radical cation. In addition to these reactions, when methoxy or C(α)-substituted alkyl groups occupy the N(1,3) positions, their elimination is observed. The elimination of methyl groups from N(1,3) was not observed. Product analyses of imidazolium liquids irradiated in the very-high-dose regime (6.7 MGy) reveal several detrimental processes, including volatilization, acidification, and oligomerization. The latter yields a polymer with m/z of 650 ± 300 whose radiolytic yield increases with dose (~0.23 monomer units per 100 eV for 1-methyl-3-butylimidazolium trifluorosulfonate). Gradual generation of this polymer accounts for the steady increase in the viscosity of the ILs upon irradiation. Previous studies at lower dose have missed this species due to its wide mass distribution (stretching out to m/z 1600) and broad NMR lines, which make it harder to detect at lower concentrations. Among other observed changes is the formation of water immiscible fractions in hydrophilic ILs and water miscible fractions in hydrophobic ILs. The latter is due to anion fragmentation. The import of these observations for use of ILs as extraction solvents in nuclear cycle separations is discussed.

Structures of β-hairpin antimicrobial protegrin peptides in lipopolysaccharide membranes: mechanism of gram selectivity obtained from solid-state nuclear magnetic resonance.

The structural basis for the gram selectivity of two disulfide-bonded β-hairpin antimicrobial peptides (AMPs) is investigated using solid-state nuclear magnetic resonance (NMR) spectroscopy. The hexa-arginine PG-1 exhibits potent activities against both gram-positive and gram-negative bacteria, while a mutant of PG-1 with only three cationic residues maintains gram-positive activity but is 30-fold less active against gram-negative bacteria. We determined the topological structure and lipid interactions of these two peptides in a lipopolysaccharide (LPS)-rich membrane that mimics the outer membrane of gram-negative bacteria and in the POPE/POPG membrane, which mimics the membrane of gram-positive bacteria. (31)P NMR line shapes indicate that both peptides cause less orientational disorder in the LPS-rich membrane than in the POPE/POPG membrane. (13)C chemical shifts and (13)C-(1)H dipolar couplings show that both peptides maintain their β-hairpin conformation in these membranes and are largely immobilized, but the mutant exhibits noticeable intermediate-time scale motion in the LPS membrane at physiological temperature, suggesting shallow insertion. Indeed, (1)H spin diffusion from lipid chains to the peptides shows that PG-1 fully inserts into the LPS-rich membrane whereas the mutant does not. The (13)C-(31)P distances between the most hydrophobically embedded Arg of PG-1 and the lipid (31)P are significantly longer in the LPS membrane than in the POPE/POPG membrane, indicating that PG-1 does not cause toroidal pore defects in the LPS membrane, in contrast to its behavior in the POPE/POPG membrane. Taken together, these data indicate that PG-1 causes transmembrane pores of the barrel-stave type in the LPS membrane, thus allowing further translocation of the peptide into the inner membrane of gram-negative bacteria to kill the cells. In comparison, the less cationic mutant cannot fully cross the LPS membrane because of weaker electrostatic attractions, thus causing weaker antimicrobial activities. Therefore, strong electrostatic attraction between the peptide and the membrane surface, ensured by having a sufficient number of Arg residues, is essential for potent antimicrobial activities against gram-negative bacteria. The data provide a rational basis for controlling gram selectivity of AMPs by adjusting the charge densities.

Alteration of Hydrogen Bonding in the Vicinity of Histidine 48 Disrupts Millisecond Motions in RNase A

The motion of amino acid residues on the millisecond (ms) time scale is involved in the tight regulation of catalytic function in numerous enzyme systems. Using a combination of mutational, enzymological, and relaxation-compensated (15)N Carr-Purcell-Meiboom-Gill (CPMG) methods, we have previously established the conformational significance of the distant His48 residue and the neighboring loop 1 in RNase A function. These studies suggested that RNase A relies on an intricate network of hydrogen bonding interactions involved in propagating functionally relevant, long-range ms motions to the catalytic site of the enzyme. To further investigate the dynamic importance of this H-bonding network, this study focuses on the individual replacement of Thr17 and Thr82 with alanine, effectively altering the key H-bonding interactions that connect loop 1 and His48 to the rest of the protein. (15)N CPMG dispersion studies, nuclear magnetic resonance (NMR) chemical shift analysis, and NMR line shape analysis of point mutants T17A and T82A demonstrate that the evolutionarily conserved single H-bond linking His48 to Thr82 is essential for propagating ms motions from His48 to the active site of RNase A on the time scale of catalytic turnover, whereas the T17A mutation increases the off rate and conformational exchange motions in loop 1. Accumulating evidence from our mutational studies indicates that residues experiencing conformational exchange in RNase A can be grouped into two separate clusters displaying distinct dynamical features, which appear to be independently affected by mutation. Overall, this study illuminates how tightly controlled and finely tuned ms motions are in RNase A, suggesting that designed modulation of protein motions may be possible.

Efficient design of multituned transmission line NMR probes: The electrical engineering approach

Transmission line-based multi-channel solid state NMR probes have many advantages regarding the cost of construction, number of RF-channels, and achievable RF-power levels. Nevertheless, these probes are only rarely employed in solid state-NMR-labs, mainly owing to the difficult experimental determination of the necessary RF-parameters. Here, the efficient design of multi-channel solid state MAS-NMR probes employing transmission line theory and modern techniques of electrical engineering is presented. As technical realization a five-channel ( 1H, 31P, 13C, 2H and 15N) probe for operation at 7 Tesla is described. This very cost efficient design goal is a multi port single coil transmission line probe based on the design developed by Schaefer and McKay. The electrical performance of the probe is determined by measuring of Scattering matrix parameters (S-parameters) in particular input/output ports. These parameters are compared to the calculated parameters of the design employing the S-matrix formalism. It is shown that the S-matrix formalism provides an excellent tool for examination of transmission line probes and thus the tool for a rational design of these probes. On the other hand, the resulting design provides excellent electrical performance. From a point of view of Nuclear Magnetic Resonance (NMR), calibration spectra of particular ports (channels) are of great importance. The estimation of the π / 2 pulses length for all five NMR channels is presented.

1H NMR study of rehydration/dehydration and water mobility in β-cyclodextrin

The processes of dehydration and rehydration of β-cyclodextrin were studied by analysis of the 1H NMR (nuclear magnetic resonance) line shape. Dehydration was carried in an open ampoule as a function of temperature and above 400 K total dehydration of β-cyclodextrin was observed. This result was confirmed by the thermogravimetry (TG) measurements. Rehydration was studied as a function of time at room temperature. After 40 days, β-cyclodextrin was found to absorb eight water molecules. The analysis of temperature changes in the shape of the 1H NMR line of β-cyclodextrin kept in a closed ampoule and its dielectric measurements provided information on the mobility of water molecules. The water molecules were found to perform complex molecular motions, that is, reorientational jumps below 200 K and additionally, translational motion (diffusion) above 200 K.

Dynamics in the isotropic and nematic phases of bent-core liquid crystals: NMR perspectives

The dynamic properties of low-molecular-weight bent-core liquid crystals were revealed to be unusual with respect to the analogous rod-like mesogens. First pioneering investigations based on dynamic light scattering measurements were followed by intense and deep studies based on nuclear magnetic resonance (NMR) spectroscopy, mainly 2H NMR relaxation and line width analyses, 1H NMR relaxometry and diffusometry. These studies were of help in identifying the molecular motions responsible of the observed slow relaxation and the large 2H NMR spectral width. Viscosity and rheology measurements provided further elements confirming the slow dynamics of bent-core liquid crystals at a macroscopic level. All these experimental techniques indicate the presence of restricted dynamic motions as a distinctive feature of bent-core liquid crystals both in the isotropic and nematic phases. In this review, the case of several bent-core mesogens studied by different NMR methods is reported and the main results are discussed in view of the recent achievements concerning the tendency of bent-core molecules to form aggregates or temporary clusters both in the isotropic and nematic phases.