NMR Frequency Research Articles

What do we learn from impurities and disorder in high-Tc cuprates?

A series of experimental studies established that the differing morphologies of the phase diagrams versus hole doping nh of the various cuprate families are mostly controlled by defects and disorder. In the minimally disordered cuprate Yttrium Baryum Copper Oxide (YBCO) we introduced controlled detfects that allowed us to probe the metallic and superconducting states. We demonstrate that the extent of the spin glass phase and the superconducting dome can be controlled by the concentration of spinless (Zn, Li) impurities substituted on the planar Cu sites. NMR frequency shift measurements establish that these defects induce, in their vicinity, a cloud with a Kondo-like paramagnetic behavior. Its “Kondo” temperature and spatial extent differ markedly between the pseudogap and strange metal regimes. We have performed transport measurements on single crystals with a controlled content of in-plane vacancies introduced by electron irradiation. At high T, the inelastic scattering of the carriers has been found independent of disorder and completely governed by the excitations of the correlated electronic state. The low T upturns in the resistivity associated with single-site Kondo-like scattering are qualitatively in agreement with local magnetism induced by spinless impurities. The apparent metal insulator crossover is only detected for a very large defect content, and part of the large resistivity upturn remains connected with Kondo-like paramagnetism. In the superconducting state, the defect-induced reduction of Tc scales linearly with the increase in residual resistivity induced by disorder. High-field magnetoresistance experiments permit us to determine the paraconductivity due to superconducting fluctuations. The latter vanishes beyond a temperature T’c and a field H’c that both decrease with increasing in-plane defect content. In the pseudogap regime, the weaker decrease of T’c with respect to that of Tc reveals a large loss of superconducting phase coherence in the presence of disorder. In light of our experimental results, we initiate a discussion of its interplay with pair breaking. Our data also permit us to confirm that the differing phase diagrams are due to competing orders or disorders that are family-specific. In the ideal phase diagram of a disorder-free cuprate, 2D superconductivity should persist at low doping. This ensemble of experimental results provides serious challenges for the theoretical understanding of superconductivity in these correlated electron systems.

Solid-State NMR 13C sensitivity at high magnetic field

Sensitivity is the foundation of every NMR experiment, and the signal-to-noise ratio (SNR) should increase with static (B0) magnetic field, by a proportionality that primarily depends on the design of the NMR probe and receiver. In the low B0 field limit, where the coil geometry is much smaller than the wavelength of the NMR frequency, SNR can increase in proportion to B0 to the power 7/4. For modern magic-angle spinning (MAS) probes, this approximation holds for rotor sizes up to 3.2 mm at 14.1 Tesla (T), corresponding to 600 MHz 1H and 151 MHz 13C Larmor frequencies. To obtain the anticipated benefit of larger coils and/or higher B0 fields requires a quantitative understanding of the contributions to SNR, utilizing standard samples and protocols that reproduce SNR measurements with high accuracy and precision. Here, we present such a systematic and comprehensive study of 13C SNR under MAS over the range of 14.1 to 21.1 T. We evaluate a range of probe designs utilizing 1.6, 2.5 and 3.2 mm rotors, including 24 different sets of measurements on 17 probe configurations using five spectrometers. We utilize N-acetyl valine as the primary standard and compare and contrast with other commonly used standard samples (adamantane, glycine, hexamethylbenzene, and 3-methylglutaric acid). These robust approaches and standard operating procedures provide an improved understanding of the contributions from probe efficiency, receiver noise figure, and B0 dependence in a range of custom-designed and commercially available probes. We find that the optimal raw SNR is obtained with balanced 3.2 mm design at 17.6 T, that the best mass-limited SNR is achieved with a balanced 1.6 mm design at 21.1 T, and that the raw SNR at 21.1 T reaches diminishing returns with rotors larger than 2.5 mm.

Measurements of Nuclear Magnetic Shielding in Molecules.

The origin of nuclear magnetic shielding in diamagnetic molecules is discussed, pointing out various contributions to the shielding from electrons and the effects of intra- and intermolecular interactions. In NMR practice, chemical shifts are determined first as the measure of shielding in observed samples. The descriptions of shielding and chemical shifts are not fully consistent. Gas phase studies permit the withdrawal of intermolecular contributions from shielding and obtaining the magnetic shielding data in isolated molecules. The shielding determination in molecules is possible using at least three methods delivering the reference shielding standards for selected nuclei. The known shielding of one magnetic nucleus can be transferred to other nuclei if the appropriate nuclear magnetic moments are available with satisfactory accuracy. It is possible to determine the nuclear magnetic dipole moments using the most advanced ab initio shielding calculations jointly with the NMR frequencies measurements for small-sized isolated molecules. Helium-3 gas is postulated as all the molecules' primary and universal reference standard of shielding. It can be easily applied using common deuterium lock solvents as the secondary reference standards. The measurements of absolute shielding are available for everyone with the use of standard NMR spectrometers.

Experimental nuclear quadrupole resonance and computational study of the structurally refined topological semimetal TaSb2

The local electric field gradients and magnetic dynamics of TaSb2 have been studied using Sb121, Sb123, and Ta181 nuclear quadrupole resonance (NQR) with density functional theory (DFT) calculations using XRD-determined crystal structures. By measuring all structurally expected 13 NQR lines, the nuclear quadrupole coupling constant (νQ) and asymmetric parameter (η) for Ta, Sb(1), and Sb(2) sites were obtained. These values are all in good agreement with the presented DFT calculations. Principal axes of the electric field gradients was determined for a single-crystal sample by measuring the angular dependencies of NMR frequency under a weak magnetic field. The unusual temperature dependence of η(T) of Sb(2) hints at the suppressed thermal expansion along the a axis. Spin-lattice relaxation rate (1/T1T) measurements reveal an activated-type behavior and an upturn below 30 K. Neither the low-temperature upturn nor the high-temperature activation-type behaviors are reproduced by the calculated 1/T1T based on the calculated density of states (DOS). On the other hand, the agreement between the calculated DOS and specific heat measurements indicates that the band renormalization is small. This fact indicates that TaSb2 deviates from the simple semimetal scenario, and magnetic excitations are not captured by Fermi liquid theory. Published by the American Physical Society 2024

Nuclear Magnetic Resonance for Targeted Metabolomics and Biochemical Sensor

NMR spectroscopy is quantitative, highly reproducible, non-selective and non-destructive. However, NMR costs and complexity hinder a use as point-of-care and biochemical sensor instrumentation. Low field NMR (LF-NMR) is an inexpensive and low footprint technique to obtain physical, chemical, electronic and structural information on small molecules, but suffers from poor spectral dispersion, especially when applied to the analysis of mixtures. Subspectral editing employing optimal control pulses is a suitable approach to cope with the severe signal superpositions in complex mixture spectra at low field.
 We have calculated the optimal control pulse shapes at 0.5 T NMR frequency using the Krotov algorithm. Downsizing the complexity of the algorithm from exponential to polynomial is shown to be possible by using a system approach with each system corresponding to a (small) molecule. In this way compound selective excitation pulses can be calculated. The signals of substructures of the cyclopentenone molecule were excited using optimal control pulses calculated by the Krotov algorithm demonstrating the feasibility of subspectral editing. Likewise, for a mixture of benzoic acid and alanine, editing of the signals of either benzoic acid or alanine employing optimal control pulses was shown to be possible.
 The obtained results are promising and can be extended to the targeted analysis of complex mixtures such as biofluids or metabolic samples at low field strengths opening access for benchtop NMR to point of care settings. Moreover, the LF-NMR was improved to allow a unique detection and reliable quantification of metabolites in biofluids like blood, urine, cerebrospinal fluid, or even tissue. In contrast to standard large scale NMR equipment the portable LF-NMR allows for an analysis of the chemical composition of biofluid samples directly at the patient (point-of-care).
 LF-NMR can be freely programmable for detecting and detecting and sensing sets of small molecules which deliver information on the health status of a person. Such an analytical tool would be useful for the prediction, diagnosis, monitoring and prognosis of diseases, and for supervision of therapeutic interventions.

The implementation of an easy-to-apply NMR cryoporometric instrument for porous materials

Time-domain NMR has been extensively utilised to study various characteristics of fluid-saturated porous,materials for instance their mobility, dynamics, stiffness, viscosity and rigidity features, particularly for solid hydrocarbons, rubbers and other polymers. As a unique time-domain technique available for over 30 years, NMR cryoporometry (NMRC) may be used to obtain pore-size distributions of the measured samples. To accurately control the sample temperature, a Peltier thermo-electrically cooled variable temperature probe has been developed and integrated with a highly compact precision NMR time-domain relaxation spectrometer, therefore providing the community with a high-performance instrument for NMR Cryoporometry. To extend the application of aforementioned high-performance NMRC instrument into more senarios, we designed a series of light-weight, compact and integral models with optional NMR frequencies from 12 MHz up to 23 MHz. The measured sample temperature can be precisely controlled from about −60 °C to +80 °C, with an excellent temperature resolution of 10 mK or better near the probe liquid bulk melting point. Therefore, it offers a fairly wide NMRC pore-size distribution ranging from about 1 nm to 2 μm by using water as the probe liquid in the pores, significantly wider than is possible when applying generic NMR Spectrometers for NMRC. A preliminary example of NMR Cryoporometric measurements on two special cement samples is shown in the paper in which the measured pore scales as well as their repeatability are demonstrated. Furthermore, various nano-materials, such as MOF, zeolite and shale kerogen would be potential materials to study by using these new available NMRC instrument models. We aim to offer this technique as a quantitative and easy-to-apply unitary benck-top tool for an even wider range of porous material.

Optical, electrical and chemical properties of PEO:I2 complex composite films

Synthesized PEO:I2 complex composite films with different I2 concentrations were deposited onto fused silica substrates using a dip-coating method. Incorporation of PEO films with I2 increases the electrical conductivity of the composite, reaching a maximum of 46 mS/cm for 7 wt% I2. The optical and optoelectronic properties of the complex composite films were studied using the transmittance and reflectance spectra in the UV-Vis region. The transmittance of PEO decreases with increasing I2 content. From this study, the optical bandgap energy decreases from 4.42 to 3.28 eV as I2 content increases from 0 to 7 wt%. In addition, the refractive index for PEO films are in the range of 1.66 and 2.00.1H NMR spectra of pure PEO film shows two major peaks at 3.224 ppm and 1.038 ppm, with different widths assigned to the mobile polymer chains in the amorphous phase, whereas the broad component is assigned to the more rigid molecules in the crystalline phase, respectively. By adding I2 to the PEO, both peaks (amorphous and crystal) are shifted to lower NMR frequencies indicating that I2 is acting as a Lewis acid, and PEO is acting as Lewis base. Hence, molecular iodine reacts favorably with PEO molecules through a charge transfer mechanism, and the formation of triiodide ({mathrm{I}}_{3}^{-}), the iodite ({mathrm{IO}}_{2}^{-}) anion, {mathrm{I}}_{2} cdot cdot cdot mathrm{ PEO} and {mathrm{I}}_{2}^{+} cdot cdot cdot mathrm{ PEO} complexes. PEO:I2 complex composite films are expected to be suitable for optical, electrical, and optoelectronic applications.

Spectroscopic Characterization and Antioxidant Properties of Mandelic Acid and Its Derivatives in a Theoretical and Experimental Approach.

The following article discusses the antioxidant properties of mandelic acid and its hydroxy and methoxy derivatives. The antioxidant capacity of these compounds is determined by DPPH, FRAP, CUPRAC and ABTS. The mechanisms underlying the antioxidant properties are described by BDE, IP, PDE, ETE and PA calculation method values and referenced to experimental data. Thermochemistry, HOMO/LUMO energies, dipole moments, charge distribution, IR, RAMAN, NMR frequencies, binding lengths and angles were calculated using the B3LYP method and the 6-311++G(d,p) basis set. The structure of mandelic acid and its derivatives was determined experimentally using IR and RAMAN spectroscopy.

Performance and reproducibility of 13C and 15N hyperpolarization using a cryogen-free DNP polarizer

The setup, operational procedures and performance of a cryogen-free device for producing hyperpolarized contrast agents using dissolution dynamic nuclear polarization (dDNP) in a preclinical imaging center is described. The polarization was optimized using the solid-state, DNP-enhanced NMR signal to calibrate the sample position, microwave and NMR frequency and power and flip angle. The polarization of a standard formulation to yield ~ 4 mL, 60 mM 1-13C-pyruvic acid in an aqueous solution was quantified in five experiments to P(13C) = (38 ± 6) % (19 ± 1) s after dissolution. The mono-exponential time constant of the build-up of the solid-state polarization was quantified to (1032 ± 22) s. We achieved a duty cycle of 1.5 h that includes sample loading, monitoring the polarization build-up, dissolution and preparation for the next run. After injection of the contrast agent in vivo, pyruvate, pyruvate hydrate, lactate, and alanine were observed, by measuring metabolite maps. Based on this work sequence, hyperpolarized 15N urea was obtained (P(15N) = (5.6 ± 0.8) % (30 ± 3) s after dissolution).

Probing Nuclear Dipole Moments and Magnetic Shielding Constants through 3-Helium NMR Spectroscopy

Multinuclear NMR studies of the gaseous mixtures that involve volatile compounds and 3He atoms are featured in this review. The precise analyses of 3He and other nuclei resonance frequencies show linear dependencies on gas density. Extrapolation of the gas phase results to the zero-pressure limit gives the ν0(3He) and ν0(nX) resonance frequencies of nuclei in a single 3-helium atom and nuclei in molecules at a given temperature. The NMR frequency comparison method provides an approach for determining different nuclear magnetic moments. The application of quantum chemical shielding calculations, which include a more complete and careful theoretical treatment, allows the shielding of isolated molecules to be achieved with great accuracy and precision. They are used for the evaluation of nuclear moments, without shielding impacts on the bare nuclei, for: 10/11B, 13C, 14N, 17O, 19F, 21Ne, 29Si, 31P, 33S, 35/37Cl, 33S, 83Kr, 129/131Xe, and 183W. On the other hand, new results of nuclear moments were used for the reevaluation of absolute nuclear magnetic shielding in the molecules under study. Additionally, 3He gas in water solutions of lithium and sodium salts was used for measuring 6/7Li and 23Na magnetic moments and reevaluating the shielding parameters of Li+ and Na+ water-solvated cations. In this paper, guest 3He atoms that play a role in probing the electron density in many host macromolecules are also presented.

Magnetism and the Trimeron Bond.

A review of progress in understanding the Verwey transition in magnetite (Fe3O4) over the past decade is presented. This electronic and structural transition at TV ≈ 125 K was reported in 1939 and has since been a contentious issue in magnetism. Long range Fe2+/Fe3+ charge ordering has been confirmed below the transition from crystal structure refinement, and Fe2+ orbital ordering and formation of trimerons through weak bonding of Fe2+ states to two Fe neighbors has been discovered. This model has accounted for many spectroscopic observations such as the 57Fe NMR frequencies. The trimeron lifetime has been measured, and trimeron soft modes have been observed. The origin of the first to second order crossover of Verwey transitions in doped magnetites has been revealed by a nanoparticle study. Electronic and structural fluctuations are found to persist to temperatures far above TV and local structural distortions track the bulk magnetization, disappearing at the 850 K Curie transition. New binary mixed-valent iron oxides discovered at high pressure are found to have electronic transitions and orbital molecule ground states similar to those of magnetite.

Antiferromagnetic spin pumping via hyperfine interaction

Spin pumping is an interfacial spin current generation from the ferromagnetic layer to the non-magnetic metal at its interface. The polarization of the pumped spin current $$\mathbf {J}_s \propto \mathbf {m}\times \dot{\mathbf {m}}$$ depends on the dynamics of the magnetic moment $$\mathbf {m}$$ . When the materials are based on light transition metals, mechanism behind the spin current transfer is dominated by the exchange interaction between spin of localized d-electrons and itinerant conduction electrons. In heavier transition metals, however, the interaction is not limited to the exchange interaction. The spin of the conduction electron can interact to its nuclear spin by means of hyperfine interaction, as observed in the shift of NMR frequency. By studying the spin polarization of conduction electron of the non-magnetic metallic layer due to a nuclear magnetic moment $$\mathbf{I}$$ of the ferromagnetic layer, we show that the hyperfine interaction can mediate the spin pumping. The polarization of the spin current generation is shown to have a similar form $${J}_s\propto \mathbf {I}\times \dot{\mathbf {I}}$$ .

Development of 20 cm sample bore size dynamic nuclear polarization (DNP)-MRI at 16 mT and redox metabolic imaging of acute hepatitis rat model

Tissue redox metabolism is involved in various diseases, and an understanding of the spatio-temporal dynamics of tissue redox metabolism could be useful for diagnosis of progression and treatment. In in vivo dynamic nuclear polarization (DNP)-MRI, electron paramagnetic resonance (EPR) irradiation at the resonance frequency of nitroxyl radicals administered as a redox probe for induction of DNP, increases the intensity of MRI signals. For electron spin, it is necessary to apply a resonant frequency 658 times higher than that required for nuclear spin because of the higher magnetic moment of unpaired electrons. Previous studies using a disease model of small animals and in vivo DNP-MRI have revealed that an abnormal redox status is involved in many diseases, and that it could be used to visualize the dynamics of alterations in redox metabolism. To use the current methods in clinical practice, the development of a prototype DNP-MRI system for preclinical examinations of large animals is indispensable for clarifying the problems peculiar to the increase in size of the DNP-MRI device. Therefore, we developed a in vivo DNP-MRI system with a sample bore size of 20 cm and a 16-mT magnetic field using a U-shaped permanent magnet. Because the NMR frequency is very low, we adopted a digital radiofrequency transmission/reception system with excellent filter and dynamic range characteristics and equipped with a digital eddy current compensation system to suppress large eddy currents. The pulse sequence was based on the fast spin-echo sequence, which was improved for low frequency and large-eddy current equipment. The in vivo DNP-MRI system developed was used to non-invasively image the redox reaction of a carbamoyl-PROXYL probe in the livers of large rats weighing 800 g. Furthermore, DNP-MRI analysis was able to capture significant changes in redox metabolism in hepatitis-model rats.

23Na MRI on 0,5T clinical scanner

Object. The purpose of this work is to reveal the possibilities of low-field 23Na MRI. It was supposed to obtain images of various human organs using the 3D-scanning method, and to do this with minimal hardware modifications of a typical clinical 0,5T scanner. Materials and methods. The proprietary receiving coils, originally intended for registering proton signals (21,1 MHz), were transformed to transceiver ones and tuned to the sodium Larmor frequency of 5,6 MHz. The scanning was carried out by the 3D-gradient echo method with the parameters: TR/TE=44,7/12 ms, FA=45° and isotropic resolution of 6 mm. To increase SNR, apodization in k-space was applied during data processing. Results. 23Na MRI (including volumetric reconstructions) of several human organs – head, breast, heart, joints were obtained with SNR up to 15. Discussion. When developing low-field 23Na MRI, it is advisable to focus on recording only the T2long component (>15 ms). In this case, it is possible to narrow the receiver bandwidth as much as possible and thereby minimize noise. In addition, the requirements for the transmission path are reduced. As a result, for debugging MRI methods, the equipment of a typical clinical scanner, which is supplemented by coils tuned to the sodium NMR frequency only, can be used.

Simultaneous Determination of the Magnetic Moments of 6Li and 7Li Nuclei Using an NMR Spectrometer

The ratio of NMR frequencies of lithium isotopes f(7Li)/f(6Li) = 2.6409061846(13) was determined with an error of 4.9·10–10. The use of a nuclear magnetic resonance spectrometer operating in the mode of simultaneous registration of signals from two nuclei to obtain data allowed the random and systematic errors in the measurement results to be reduced by an order of magnitude. The ratio of the resonant frequencies of water protons and 7Li ions was determined: f(H2O)/f(7Li) = 2.557100473(9) with an error of 3.5·10–9 for solutions with an extremely low concentration of LiOH*H2O salt in water and at a temperature of 25°C. Based on the obtained data, the magnetic moments of lithium nuclei were calculated: μ(6Li) = 0.8220454(25)μN, μ(7Li) = 3.2564171(98)μN. The known data on the magnetic moment of the proton and data on the electronic shielding of these nuclei were used. A comparison of the experimental data for μ(6Li) and μ(7Li) and the corresponding theoretical calculation data was performed.

Synthesis, structure analysis, biological activity and molecular docking studies of some hydrazones derived from 4-aminobenzohydrazide

(E)-4-Amino-N′-(substituted benzylidene) benzohydrazides (1-8) were synthesized by condensing 4-aminobenzohydrazide with an appropriate aldehyde in the molar ratio of 1:1 in methanol as solvent. Single crystal X-ray diffraction has been recorded for compound 1. For all the synthesized compounds, FT-IR,1H and 13C NMR spectra have been recorded. Also antibacterial and docking studies have been done for all compounds 1-8. Since for compound1 only single crystal X-ray analysis has been carried out, its structural characterization have been done in detail, characterisation of remaining compounds 2-8 have been carried out by comparing their FT-IR, 1H and 13C NMR spectral data with that of compound 1. Single crystal X-ray analysis of 1 show that the compound exists in E-configuration about azomethine double bond. The crystal state of the compound was stabilised by the hydrogen bond present in the molecule. DFT calculations using the B3LYP/6-311++G method have been carried out for 1 to get the optimized geometry, IR and NMR frequencies, Mulliken charge distribution, molecular electrostatic potential (MEP) and energies of HOMO – LUMO. A good agreement between the DFT predicted and the experimentally measured IR and NMR spectra of 1 was found. Analysis of MEP and Mulliken atomic charges bar diagram of 1, confirms the chemical reactivity and existence of intermolecular hydrogen bonding of the molecule. The result of antibacterial and antifungal activities shows that the compounds 2, 4, 7 and 8 showed good antibacterial activity against the tested bacteria and the compounds 1, 3, 5 and 6showed good antifungal activities against all the three fungal strains. These results showed that electron donating and electron withdrawing groups play important roles in antibacterial and antifungal activities of the compounds1-8, respectively. Molecular docking studies of compounds 1-8shows that the various ligand of compounds 1-8 shows glide score values lies between -5.923 to -7.298, among these the compounds 6 and 8 showed excellent glide score values.

Precision current regulator for NMR electromagnets

When using electromagnets or non-persistent superconducting magnets, the field stability can be directly proportional to the current stability. We present here a simple design for a current regulator based upon a high-precision, dc-dc fluxgate transformer. The output current and NMR frequency are stabilized by about a factor of 50, over times of order one hour. The method can be applied to essentially any current supply.

Synthesis, crystal structure analysis, biological activity and molecular docking studies of (E)-4-amino-N'-(1-phenylethylidene)benzohydrazide

• ( E )−4-Amino-N'-(1-phenylethylidene) benzohydrazide have been synthesized and characterized by physical, spectral and analytical data. • Intermolecular interactions in the crystal packing have been studied. • IR and NMR spectra, DFT analysis and frontier molecular orbitals have been studied. • Antimicrobial and docking studies have been carried out. ( E )-4-Amino-N'-(1-phenylethylidene) benzohydrazide ( 4-APEBH ) is synthesized by condensing 4-aminobenzohydrazide with acetophenone in the molar ratio of 1:1 using methanol as solvent .Structural elucidation of 4-APEBH have been carried out using single crystal X-ray crystallography, FT-IR, 1 H NMR and 13 C NMR spectra. X-ray analysis of 4 -APEBH shows that the compound exists in E- configuration about azomethine double bond. DFT calculations using B3LYP/6-311 ++ G method have been carried out for 4-APEBH to get the optimized geometry, IR and NMR frequencies and energies of HOMO – LUMO. Antimicrobial activity and docking studies of 4-APEBH revealed that the molecule posses antibacterial activity and the ability of drug resistance, respectively.

Light-induced defect creation processes and light-induced defects in hydrogenated amorphous silicon

We have proposed a model of light-induced defect creation processes and light-induced defects. Recently, important results using pulsed electron-nuclear double resonance (ENDOR) by Fehr et al. [M. Fehr, A. Schnegg, C. Teutloff, R. Bittl, O. Astakhov, F. Finger, B. Rech, K. Lips, Phys. Status Solidi A 207, 552 (2010)] have been reported, so that these results are interpreted on the basis of our model. Fehr et al. have observed ENDOR signals due to hydrogen nuclei distributed around a dangling bond. The ENDOR spectra due to hydrogen nuclei being located with distance of r from the dangling bond have been calculated, taking into accounts the dipolar interaction, and also the Fermi-type contact hyperfine interaction for the H-related dangling bond (HDB) that is a dangling bond having hydrogen at a nearby site. The typical features of the observed ENDOR spectra are that the spectrum has a shoulder at the low frequency side from the natural NMR frequency of hydrogen and it has a dip in the central part. The calculated ENDOR spectrum of HDB exhibits such a shoulder. This is consistent with our model of light-induced defects such as HDB. The ENDOR spectra with various values of r are calculated. In this paper, we also deal with the distant ENDOR precisely, using the theory of distant ENDOR by Lambe et al. [J. Lambe, N. Laurance, K.C. McIrvine, R.W. Terhune, Phys. Rev. 122, 1161 (1961)]. The calculated distant ENDOR spectrum shows a dip in the central part. Concerning the dip, Fehr et al. attribute the dip to be due to the suppression of the matrix ENDOR line (this is called the artifact). Thus, it is not obvious whether the dip is due to such an artifact or the central part of the distant ENDOR spectrum.

Critical Role of Confinement in the NMR Surface Relaxation and Diffusion of n-Heptane in a Polymer Matrix Revealed by MD Simulations.

The mechanism behind the NMR surface-relaxation times (T1S,2S) and the large T1S/T2S ratio of light hydrocarbons confined in the nanopores of kerogen remains poorly understood and consequently has engendered much debate. Toward bringing a molecular-scale resolution to this problem, we present molecular dynamics (MD) simulations of 1H NMR relaxation and diffusion of n-heptane in a polymer matrix. The high-viscosity polymer is a model for kerogen and bitumen that provides an organic "surface" for heptane. Diffusion of n-heptane shows a power-law dependence on the concentration of n-heptane (ϕC7) in the polymer matrix, consistent with Archie's model of tortuosity. We calculate the autocorrelation function G(t) for 1H-1H dipole-dipole interactions of n-heptane in the polymer matrix and use this to generate the NMR frequency (f0) dependence of T1S,2S as a function of ϕC7. We find that increasing molecular confinement increases the correlation time, which decreases the surface-relaxation times for n-heptane in the polymer matrix. For weak confinement (ϕC7 > 50 vol %), we find that T1S/T2S ≃ 1. Under strong confinement (ϕC7 ≲ 50 vol %), we find that T1S/T2S ≳ 4 increases with decreasing ϕC7 and that the dispersion relation T1S ∝ f0 is consistent with previously reported measurements of polydisperse polymers and bitumen. Such frequency dependence in bitumen has been previously attributed to paramagnetism; instead, our studies suggests that 1H-1H dipole-dipole interactions enhanced by organic nanopore confinement dominate the NMR response in saturated organic-rich shales.