<Superscript>15</Superscript>N–<Superscript>13</Superscript>C Dipole Couplings in Smectic Mesophase of a Thermotropic Ionic Liquid

Unique combination of ionic conductivity and anisotropic physical properties in ionic liquid crystals leads to new dynamic properties exploited in modern technological applications. Structural and dynamics information at atomic level for molecules and ions in mesophases can be obtained by nuclear magnetic resonance (NMR) spectroscopy through the measurements of dipole–dipole spin couplings. While ¹³C–¹H and ¹⁵N–¹H dipolar NMR spectra can be routinely acquired in samples with natural isotopic abundance, recording ¹⁵N–¹³C dipolar NMR spectra is challenging because of the unfavourable combination of two rare isotopes. In the present study, an approach to measure ¹⁵N–¹³C dipole-dipole NMR spectra in static liquid crystalline samples with natural abundance is introduced. We demonstrate that well-resolved spectra can be recorded within 10 h of experimental time using a conventional NMR probe and a moderately strong magnetic field. The technique is applied to a thermotropic smectic mesophase formed by an ionic liquid with imidazolium-based organic cation.     

Bulk magnetization and 1H NMR spectra of magnetically heterogeneous model systems

Bulk magnetization and ¹H static and magic angle spinning (MAS) nuclear magnetic resonance (NMR) spectra of two magnetically heterogeneous model systems based on laponite (LAP) layered silicate or polystyrene (PS) with low and high proton concentration, respectively, and ferrimagnetic Fe₂O₃ nano- or micro-particles have been studied. In LAP+Fe₂O₃, a major contribution to the NMR signal broadening is due to the dipolar coupling between the magnetic moments of protons and magnetic particles. In PS+Fe₂O₃, due to the higher proton concentration in polystyrene and stronger proton–proton dipolar coupling, an additional broadening is observed, i.e. ¹H MAS NMR spectra of magnetically heterogeneous systems are sensitive to both proton–magnetic particles and proton–proton dipolar couplings. An increase of the volume magnetization by ～1 emu/cm³ affects the ¹H NMR signal width in a way that is similar to an increase of the proton concentration by ～2×10²²/cm³. ¹H MAS NMR spectra, along with bulk magnetization measurements, allow the accurate determination of the hydrogen concentration in magnetically heterogeneous systems.     

Study of diamond film by dynamic nuclear polarization-enhanced13C nuclear magnetic resonance spectroscopy

Three chemical vapor deposited diamond films were studied by dynamic nuclear polarization (DNP)-enhanced high-resolution solid-state¹³C nuclear magnetic resonance (NMR) spectroscopy. Enhanced¹³C direct-polarization spectra of diamond films were obtained by irradiating the samples with microwaves at or near electron spin resonance Larmor frequency of carbon center free radicals. No NMR signal for sp² hybridized carbons could be observed. From the curve of the DNP enhancement as a function of frequency, it is found that the dominant DNP mechanism is the solid-state effect. The¹³C cross-polarization spectrum, which is an evidence for existence of the proton defect in the lattice of diamond films, is much broader than the¹³C single pulse spectrum. The reason is discussed shortly.     

Electron and nuclear spin dynamics in plastically deformed silicon crystals enriched in isotope 29Si

Paramagnetic defects of a new type with a concentration of about 10¹⁵ cm^?3 are shown to be generated during the plastic deformation of isotope-rich (72%, 76% ²⁹Si) silicon crystals at a temperature of 950°C. The electron paramagnetic resonance (EPR) spectra of these defects are anisotropic and have a significant width (up to 1 kOe). The nonuniform broadening of the EPR lines is caused by the variation of the internal magnetic field in correlated defect clusters. The nuclear magnetic resonance (NMR) spectra of the deformed crystals consist of Pake doublets split by nuclear spin-spin interaction. The broadening of the NMR spectra is caused by nuclear dipole-dipole relaxation.     

Parallel-plate RF resonator imaging of chemical shift resolved capillary flow

Magnetic resonance imaging has been introduced to study flow in microchannels using pure phase spatial encoding with a microfabricated parallel-plate nuclear magnetic resonance (NMR) probe. The NMR probe and pure phase spatial encoding enhance the sensitivity and resolution of the measurement. In this paper, ¹H NMR spectra and images were acquired at 100 MHz. The B₁ magnetic field is homogeneous and the signal-to-noise ratio of 30 μl doped water for a single scan is 8×10⁴. The high sensitivity of the probe enables velocity mapping of the fluids in the micro-channel with a spatial resolution of 13×13 μm. The parallel-plate probe with pure phase encoding permits the acquisition of NMR spectra; therefore, chemical shift resolved velocity mapping was also undertaken. Results are presented which show separate velocity maps for water and methanol flowing through a straight circular micro-channel. Finally, future performance of these techniques for the study of microfluidics is extrapolated and discussed.     

Study of synthetic diamonds by dynamic nuclear polarization-enhanced13C nuclear magnetic resonance spectroscopy

Four I_b-type synthetic diamond crystals were studied by dynamic nuclear polarization (DNP)-enhanced high resolution solid state¹³C nuclear magnetic resonance (NMR) spectroscopy. The home built DNP magic-angle-spinning (MAS) NMR spectrometer operates at a field strength of 1.9 T and the highest DNP enhancement factor of synthetic diamonds came near to 10³. Comparing with I_b-type natural diamonds, the¹³C NMR linewidths of synthetic diamonds in static spectra are broader. The¹³C spin-lattice relaxation time and DNP polarization time of synthetic diamond are shorter than those of I_b-type natural diamond. From the hyperfine structure of the DNP enhancement curve, four kinds of nitrogen-centred free radicals could be identified in synthetic diamond.     

High-resolution NMR studies of nifedipine

The paper reports results of¹H and¹³C high-resolution nuclear magnetic resonance studies of nifedipine and signal assignment to particular atoms. High-resolution¹H NMR spectra with no signals attributed to protons in weak fields (δ= 10−12 ppm) imply that H7 atom is strongly connected to the ring and is not involved in the formation of hydrogen bonds.     

Anisotropy of hyperfine interactions as a tool for interpretation of NMR spectra in magnetic materials

Approach for interpretation of nuclear magnetic resonance (NMR) spectra in magnetic materials is presented, consisting in employing the anisotropy of hyperfine interaction. The anisotropic parts of hyperfine magnetic fields on ⁵⁷Fe nuclei are calculated ab initio for a model example of lithium ferrite and utilized to assign the experimental NMR spectral lines to iron sites in the crystal structure.     

Incommensurate helical magnetic order in LiCu<Subscript>2</Subscript>O<Subscript>2</Subscript> and NaCu<Subscript>2</Subscript>O<Subscript>2</Subscript> quasi-one-dimensional compounds

The results of the measurements of the ^{6, 7}Li and ²³Na nuclear magnetic resonance (NMR) and ^{63, 65}Cu nuclear quadrupole resonance in LiCu₂O₂ and NaCu₂O₂ quasi-one-dimensional compounds with a spin chains in the paramagnetic and magnetically ordered states are presented. The shape of the NMR line below T _c = 24 and 13 K for LiCu₂O₂ and NaCu₂O₂, respectively, is characteristic of the incommensurate static modulation of the local magnetic field matching with the incommensurate spiral modulation of the magnetic moments. The differences in the shape of the NMR spectra of ²³Na and ⁷Li are discussed in terms of the features of the crystal structure of LiCu₂O₂ and NaCu₂O₂.     

73Ge NMR spectra in germanium single crystals with different isotopic composition

We have studied the influence of isotopic disorder on the local deformations in Ge single crystals from both experimental and calculation points of view. The nuclear magnetic resonance (NMR) spectra of⁷³Ge nuclei (the nuclear spin equals 9/2) in perfect single crystals of germanium with different isotopic content were measured at temperatures 80, 300 and 450 K. Abnormal broadening of the spectrum was found to occur when the magnetic field was aligned along the [111] axis of a crystal. The observed specific angular dependence of the quadrupole broadening was attributed to isotopic disorder among atoms of germanium sited around the⁷³Ge NMR probe. Local lattice deformations in germanium crystal lattice due to isotopic impurity atoms were calculated in the framework of the adiabatic bond charge model. The results obtained were applied to study random noncubic crystal field interactions with the nuclear quadrupole moments and corresponding effects in NMR spectra. Simulated second and fourth moments of resonance frequency distributions caused by the magnetic dipole-dipole and electric quadrupole interactions are used to analyze the lineshapes, theoretical predictions agree qualitatively with the experimental data.     

Two-Dimensional Dynamic-Director C NMR of Liquid Crystals

A novel nuclear magnetic resonance (NMR) experiment for facilitating the resolution and assignment of liquid crystalline ¹³C NMR spectra is described. The method involves the motor-driven reorientation of the liquid crystalline director, in synchrony with the acquisition of a 2D chemical shift correlation spectrum. By monitoring in this fashion the ¹³C NMR evolution of spins in the liquid crystal at two different director orientations with respect to the magnetic field, the method distinguishes anisotropic from isotropic displacements and can be utilized for assigning the resonances and estimating local degrees of order. Of various potential pairs of angles suitable for such a correlation, the (0°, 90°) choice was found to be most convenient, as it avoids line broadening complications that may otherwise originate from heterogeneities of the oriented phase. The technique thus derived was employed in the analysis of a series of monomeric and polymeric liquid crystal systems.     

13C CPMAS NMR spectroscopic analysis applied to wood characterization

Solid-state nuclear magnetic resonance (NMR) spectroscopic analysis were carried out on recent and archaeological wood. Cross-polarization-magic-angle spinning¹³C NMR spectra obtained from samples of poplar (Populus sp.), oak (Quercus sp.), and silver fir (Abies alba) were examined in this study. The most relevant peaks were assigned according to the extensive literature in the area, and the differences observed discussed in terms of lignin and cellulose composition: by fixing a lignin reference signal intensity, the cellulose and hemicellulose moieties showed a strong depletion compared to the lignin signals in archaeological wood.     

Basics of NMR line shape in quasicrystals

The measurement and analysis of broad nuclear magnetic resonance (NMR) spectra of quasicrystals require experimental methods and theoretical interpretations different from NMR investigations of regular periodic crystals. Frequency- and field-sweep methods for recording quasicrystalline NMR spectra are described and compared with the measurement of²⁷Al NMR spectra of icosahedral AlPdMn and decagonal AlNiCo quasicrystals. The nuclear spin interactions that determine the NMR line shape are the same for both types of the above Al-based quasicrystals, where the electric quadrupolar interaction with the broad distribution of its electric field gradient parameters predominantly determines the shape of the broad satellite “background” intensity. The essential observations are an almost isotropic²⁷Al NMR spectrum of the icosahedral quasicrystals and a strong angular dependence of the spectrum of decagonal quasicrystals.     

Parallelizing acquisitions of solid-state NMR spectra with multi-channel probe and multi-receivers: Applications to nanoporous solids

A five-channel (¹H, ¹⁹F, ³¹P, ²⁷Al, ¹³C) 2.5 mm magic-angle-spinning (MAS) nuclear magnetic resonance (NMR) probe is used in combination with three separate receivers for the parallel acquisitions of one (1D) and two-dimensional (2D) NMR spectra in model fluorinated aluminophosphate and porous Al-based metal-organic framework (MOF). Possible combinations to record simultaneously spectra using this set-up are presented, including (i) parallel acquisitions of quantitative 1D NMR spectra of solids containing nuclei with contrasted T₁ relaxation rates and (ii) parallel acquisitions of 2D heteronuclear NMR spectra. In solids containing numerous different NMR-accessible nuclei, the number of NMR experiments that have to be acquired to get accurate structural information is high. The strategy we present here, i.e. the multiplication of both the number of irradiation channels in the probe and the number of parallel receivers, offers one possibility to optimize this measurement time.     

The stabilization of unusual conformers in guest-host systems: Solid-state NMR investigations of 2-methylhexadecane in urea and thiourea

Solid-state nuclear magnetic resonance (NMR) spectroscopy is employed for the first time on urea and thiourea inclusion compounds (UICs and TICs) containing branched alkyl chains. In the present work,²H and¹³C NMR as well as X-ray diffraction studies of two selectively deuterated 2-methylhexadecanes in UIC and TIC are presented. An analysis of the derivedT ₁ data reveals significant differences between UICs and TICs, which can be attributed to differences in the motional features of the guest species. It is found that four different motional contributions have to be considered, namely, chain rotation, chain wobbling,trans-gauche isomerization and methyl group rotation. 2-Methylhexadecane in UIC exists in an almost all-trans conformation (gauche amount not more than 5%) and undergoes fast chain rotation (6-site jump process, activation energyE _A=16.7 kJ/mol). The analysis of the²H NMR spectra of 2-methylhexadecane-1,1′,2-d₇ in urea proves that the branched chain end exists in an eclipsed conformation. TheT ₁ data of 2-methylhexadecane-3-d₂ in thiourea can be reproduced by an overall rotation (E _A=9.8 kJ/mol) and atrans-gauche isomerization with torsional jumps around the C-3-C-4 bond (E _A=11.0 kJ/mol,gauche population=15%). As for the corresponding UIC, the²H NMR spectra of 2-methylhexadecane-1,1′,2-d₇ in TIC can be only explained by the existence of an eclipsed conformation at the branched chain end.     

High-Temperature Dynamic Nuclear Polarization Enhanced Magic-Angle-Spinning NMR

Dynamic nuclear polarization (DNP) transfers electron spin-polarization to nuclear spins in close proximity, increasing sensitivity by two-to-three orders of magnitude. This enables nuclear magnetic resonance (NMR) experiments on samples with low concentrations of analyte. The requirement of using cryogenic temperatures in DNP-enhanced solid-state NMR (ssNMR) experiments may impair the resolution and hence limit its broad application to biological systems. In this work, we introduce a “High-Temperature DNP” approach, which aims at increasing spectral resolution by performing experiments at temperatures of around 180?K instead of?~100?K. By utilizing the extraordinary enhancements obtained on deuterated proteins, still sufficiently large DNP enhancements of 11–18 are obtained for proton and carbon, respectively. We recorded high sensitivity 2D ¹³C–¹³C spectra in?~9?min with higher resolution than at 100?K, which has similar resolution to the one obtained at room temperature for some favorable residues.     

A localization method for the measurement of fast relaxing13C NMR signals in humans at high magnetic fields

Nuclear magnetic resonance (NMR) signals with shortT ₁ andT ₂, such as the¹³C signal of glycogen, are difficult to localize in three dimensions without major signal loss. A pulse sequence that accomplishes the spatial localization of¹H-decoupled¹³C NMR signals on a whole-body scanner within the Food and Drug Administration guidelines for specific absorption rates was designed. The method uses an optimized three-dimensional outer volume suppression scheme combined with one-dimensional image-selected in vivo spectroscopy and surface coil detection. The localization performance of the sequence was validated at 4 T with double chambered phantoms and¹³C magnetic resonance imaging. Localized¹³C spectra were acquired from human brain and muscle.     

Structural investigation of non-stoichiometric CuInS<Subscript>2</Subscript> by <Superscript>63</Superscript>Cu and <Superscript>115</Superscript>In nuclear magnetic resonance

Results of studies of non-stoichiometric CuInS₂ semiconductor by ⁶³Cu and ¹¹⁵In nuclear magnetic resonance are presented. It was established that deviation of the composition from stoichiometry causes a quadrupolebroadened region of the NMR spectrum to change most. In this case a central peak whose shape is governed by the chemical shift anisotropy remains unaffected. NMR spectra reveal two types of structural distortions in the nearest surroundings of the In atoms.     

X-Band ESR and51V NMR study of the Haldane system PbNi2−xMgxV2O8

The temperature and angular dependence of the X-band electron spin resonance (ESR) and⁵¹V nuclear magnetic resonance (NMR) spectra have been measured in a recently discovered Haldenegap system, PbNi_2-xMg_xV₂O₈ (0≤x≤0.24). The angular dependence of the ESR signal suggests that both the spin diffusion as well as the magnetic anisotropy determine the electronic spin correlation functions. However, in doped samples the magnetic anisotropy increasingly dominates the spin dynamics on cooling. The huge broadening of the⁵¹V NMR spectra in doped samples at low temperatures provides evidence for localized magnetic moments in the vicinity of the Mg impurities. Locally distorted structure around each Mg impurity may slightly modify the magnetic interactions and be potentially responsible for the antiferromagnetic ordering (belowT _N≈ 3.5K) in doped compositions.     

Nuclear magnetic resonance study of ultrananocrystalline diamonds

We report on a nuclear magnetic resonance (NMR) study of ultrananocrystalline diamond (UNCD) materials produced by detonation technique. Analysis of the ¹³C and ¹H NMR spectra, spin-spin and spin-lattice relaxation times in purified UNCD samples is presented. Our measurements show that UNCD particles consist of a diamond core that is partially covered by a sp ²-carbon fullerene-like shell. The uncovered part of outer diamond surface comprises a number of hydrocarbon groups that saturate the dangling bonds. Our findings are discussed along with recent calculations of the UNCD structure. Significant increase in the spin-lattice relaxation rate (in comparison with that of natural diamond), as well as stretched exponential character of the magnetization recovery, are attributed to the interaction of nuclear spins with paramagnetic centers which are likely fabrication-driven dangling bonds with unpaired electrons. We show that these centers are located mainly at the interface between the diamond core and shell.