NMR Transitions Research Articles

Weighted AnX multiplets

That the NMR transition of a spin-1/2 nucleus is split into n evenly spaced lines by indirect dipole–dipole (J) coupling to n magnetically equivalent nuclei, whose successive amplitudes follow the nth row of Pascal’s triangle, is an elementary result in NMR. Described here are a family of less well known multiplet structures with different amplitudes for the evenly spaced lines. The amplitudes can be derived from the nth row of Pascal’s triangle by weighting the corresponding value of the row by z or z2, where z is related to the summed magnetic quantum number of the magnetically equivalent spins. z1-multiplets have been described in INEPT experiments. A z2-multiplet can be indirectly observed in HSQC experiments when the decoupling pulse during t1 is removed, i.e., an F1-coupled HSQC. While not difficult to generate and despite some reported usefulness, to the best of our knowledge, z2-multiplets have not been rigorously described in previous literature.

Solvent promoted tautomerism in thione-containing tetraazatricyclics: evidence from 1H NMR spectroscopy and transition state studies.

Tautomerism in the nitro substituted thione-containing traazatricyclics has been investigated. Evidence from 1H NMR indicating the existence of the tautomers has been augmented with computational studies providing evidence of the stability or otherwise of these tautomers. The role of water and DMSO in the formation of the tautomers has been explained. The role of the nitro group in assisting in the formation of the tautomers has been discussed.

Mixture designs to investigate the role of alkali and alkaline earth cations on composition-structure-property relationships in ternary borate glass networks

Sixteen borate glass compositions, modified with K2O and SrO, were established using a design of mixtures approach and were subjected to chemical and physical characterization (11B MAS NMR, density, and glass transition temperature (Tg)). The analysis intended to establish the influence of K2O and SrO on the composition-structure-property relationships for borate glass networks. The effects of γ-radiation on the glass networks were also examined to determine the impact that sterilization may have on the glass properties. Structural analysis showed that both K2O and SrO influenced the fraction of three- and four-fold coordinated boron groups independent of the cation. Thermal analysis of the glasses revealed that SrO significantly increases the glass transition temperature while both SrO and K2O have comparable impacts on glass stability. These data suggest that Sr2+ cations cross-link the networks. Contrastingly, K+ appears to stabilize B4 structures. All sixteen compositions retained their chemical and physical characteristics following sterilization.

NMR of quadrupole noble gases in liquid crystals

ABSTRACT NMR spectroscopy of quadrupolar noble gases, 21Ne (spin 3/2), 83Kr (9/2), 131Xe (3/2), dissolved in thermotropic liquid crystals enables the derivation of versatile information about the physical properties of the materials. The spectra display fine structures, triplets and nonets, which reveal quadrupole couplings. These, in turn, can be used in the determination of electric field gradients (EFG), orientational order parameters, and tilt angles. Comparison of 129Xe and 131Xe chemical shifts reveals second-order quadrupole shifts (SOQS) in circumstances where the ratio of quadrupole coupling and magnetic flux density is suitable. The 131Xe SOQS is shown to distinguish between uniaxial and biaxial nematic phases. Both 83Kr and 131Xe NMR spectra may display asymmetry around the central transition because of the SOQS, which can be used to identify biaxiality in nematic phases. As a curiosity, the effect of possible hexadecapole coupling on the 83Kr NMR transitions of krypton in liquid crystals is discussed.

Scalar relaxation of NMR transitions at ultralow magnetic field.

Nuclear magnetic resonance signals for 1H in simple chlorinated, brominated and deuterated liquids were detected at field strengths between 1 nT and a few μT to investigate the influence of scalar relaxation of the second kind (SR2K). SR2K describes the acceleration in magnetization decay rate for a spin-1/2 nucleus that is scalar coupled to a fast-relaxing quadrupolar nucleus. In agreement with simple theoretical models, the experimental data show that couplings to nuclei with small, nonzero quadrupole moments (2H) give rise to higher transverse relaxation rates at ultralow field than rapidly relaxing quadrupolar nuclei (Cl and Br). This behavior is opposite to the case normally encountered in high-field NMR, and demonstrates that certain nuclei in the spin system may be "weakly coupled" or even decoupled when the applied magnetic field is zero. The results show that the capability for precision determination of NMR frequencies and molecular structural information depends strongly on the composition and topology of the nuclear spin system.

Hyperfine-enhanced gyromagnetic ratio of a nuclear spin in diamond

The nuclear spin gyromagnetic ratio can be enhanced by hyperfine coupling to the electronic spin. Here we show wide tunability of this enhancement on a 15N nuclear spin intrinsic to a single nitrogen-vacancy center in diamond. We perform control of the nuclear spin near the ground state level anti-crossing (GSLAC), where the enhancement of the gyromagnetic ratio from the ground state hyperfine coupling is maximized. We demonstrate a two order of magnitude enhancement of the effective nuclear gyromagnetic ratio compared to the value obtained at 500 G, a typical operating field that is suitable for nuclear spin polarization. Finally, we show that with strong enhancements, the nuclear spin ultimately suffers dephasing from the inhomogeneous broadening of the NMR transition frequency at the GSLAC.

Optically enabled magnetic resonance study ofAs75andSb121inSi28

The electron and nuclear spins of donor impurities in enriched $^{28}\mathrm{Si}$ have great potential as long-lived qubits for a silicon-based quantum information technology. The ability to resolve the hyperfine-split neutral donor ground-state levels in the near-infrared donor bound exciton transitions of the ubiquitous phosphorus impurity in highly isotopically enriched $^{28}\mathrm{Si}$ has led to new methods of hyperpolarizing and measuring the donor electron and nuclear spins. This has resulted in optically assisted magnetic resonance methods that have permitted the measurement of remarkably long nuclear coherence times for both the neutral and ionized phosphorus donor in very lightly doped and highly enriched $^{28}\mathrm{Si}$. Other shallow donors such as arsenic, antimony, and bismuth offer the potential of larger hyperfine couplings and nuclear spins as compared to phosphorus. Here, we investigate whether donor bound exciton transitions can be used to initialize and read out the nuclear spins of arsenic and antimony in $^{28}\mathrm{Si}$. The projective readout of the electron and nuclear spins is demonstrated for both $^{75}\mathrm{As}$ and $^{121}\mathrm{Sb}$, and these optical transitions can strongly hyperpolarize the nuclear spin of $^{75}\mathrm{As}$. Only a small nuclear hyperpolarization is achieved for $^{121}\mathrm{Sb}$, likely due to the relative weakness of the no-phonon transition of the Sb donor bound exciton. Optically assisted EPR and NMR is demonstrated for $^{75}\mathrm{As}$, including Hahn echo coherence time measurements of the six NMR transitions.

Synthesis, spectroscopic characterization and DFT calculations of N-Methyl-2-(2ʹ-hydroxyphenyl)benzimidazole derivatives

1-Methyl-2-(2ʹ-hydroxyphenyl)benzimidazole (1) and 1-Methyl-2-(2ʹ-hydroxy-4ʹ-methylphenyl)benzimidazole (2) compounds have been synthesized and characterized by XRD, IE-MS, FT-IR, UV–Vis and 1H, 13C NMR techniques. The crystal structure of both compounds is stabilized with very strong O–H … N hydrogen-bond and π–π interactions. In the compound 1, an infinite chain structure with a trans-zigzag type was formed along the crystallographic [101] direction. Quantum mechanical calculations of energies, geometries, vibrational wavenumbers, NMR and electronic transitions were carried out by DFT using B3LYP functional combined with 6.31G(d,p) basis set. Calculated bond lengths, bond angles and dihedral angles were only slightly different from the experimental ones. The vibrational study was interpreted by means of potential energy distribution (PED). The electronic absorption spectra of the both compounds were predicted by using the time-dependent DFT methods and good agreement was found between the computational and the experimental values. The chemical shifts (1H and 13C NMR) and isotropic shielding values were calculated by using the gauge-invariant atomic orbital (GIAO) method. The analyses of HOMO and LUMO have been used to explain the charge transfer within the molecule.

Probing the Secondary Structure of Membrane Proteins with the Pulsed EPR Technique: Electron Spin Ehco Envelope Modulation (ESEEM)

Despite the importance and large number of membrane proteins, relatively limited structural information is known about them. New biophysical techniques are needed to probe their structural properties. Their hydrophobic nature and low expression yields cause difficulties for traditional structural techniques such as x-ray crystallography and solution NMR. ESEEM spectroscopy indirectly observes NMR transitions through an electron spin coupled to a nearby NMR active nucleus. ESEEM can detect weak dipolar interactions between a NMR active nucleus and a spin label out to a distance of approximately 8 Å. The modulation depth for weakly coupled nuclei is scaled by 1/r6. A novel approach is being developed to probe the secondary structure of membrane proteins and peptides qualitatively utilizing the three-pulse Electron Spin Echo Envelope Modulation (ESEEM) pulse sequence. In order to demonstrate the practicality of this biophysical technique, the M2delta subunit of AChR (α-helical) and KIGAKI(β-sheet) peptides were incorporated into phospholipids bicelle to probe their secondary structure with ESSEM spectroscopy. Utilizing site-directed spin-labeling (SDSL) coupled with deuterated amino acid labeling of the peptides, the corresponding ESEEM spectra reveal characteristic patterns for α-helix and β-sheet structures. This ESSEM secondary structural approach can be used with different deuterated amino acids and provide pertinent qualitative structural information on membrane proteins in a short period of time (10 minutes) with small amounts of sample (30 µg).

(14)N overtone transition in double rotation solid-state NMR.

Solid-state NMR transitions involving outer energy levels of the spin-1 (14)N nucleus are immune, to first order in perturbation theory, to the broadening caused by the nuclear quadrupole interaction. The corresponding overtone spectra, when acquired in conjunction with magic-angle sample spinning, result in lines, which are just a few kHz wide, permitting the direct detection of nitrogen compounds without the need for labeling. Despite the success of this technique, "overtone" resonances are still broadened due to indirect, second order effects arising from the large quadrupolar interaction. Here we demonstrate that another order of magnitude in spectral resolution may be gained by using double rotation. This brings the width of the (14)N solid-state NMR lines much closer to the region commonly associated with high-resolution solid-state NMR spectroscopy of (15)N and demonstrates the improvements in resolution that may be possible through the development of pulsed methodologies to suppress these second order effects.

Identification of Fe3+–Li+ complexes in ZnO by means of high-frequency EPR/ENDOR spectroscopy

Theoretical prediction of a high Curie temperature in ZnO doped with Mn, Fe, and other transition metals has stimulated the investigation of these materials by many research groups. Although charge-compensated Fe3+ centers in ZnO:Fe have been observed by means of EPR and have been known for decades, conclusions on the chemical nature of these defects are still contradictory. Originally, these centers were treated as Fe3+–Li+ complexes with both ions occupying adjacent cationic sites. Recently, however, the centers were interpreted as a substitutional Fe3+ ion with a vacancy at an adjacent zinc or oxygen site (Fe-VZn or Fe-VO). In order to determine the chemical nature of the impurity associated with Fe3+, electron-nuclear double resonance (ENDOR) spectroscopy was used. ENDOR measurements reveal NMR transitions corresponding to nuclei with g-factor gN=2.171 and spin I=3/2. This unambiguously shows presence of Li as a charge compensator and also resolves contradictions with the theoretical prediction of the Fe-VO formation energy. The electric field gradients at the 7Li nuclei (within the Fe3+–Li+ complexes) were estimated to be significantly lower than the gradient at undistorted Zn sites.

Ultra-Wideline Solid-State NMR Spectroscopy

Although solid-state NMR (SSNMR) provides rich information about molecular structure and dynamics, the small spin population differences between pairs of spin states that give rise to NMR transitions make it an inherently insensitive spectroscopic technique in terms of signal acquisition. Scientists have continuously addressed this issue via improvements in NMR hardware and probes, increases in the strength of the magnetic field, and the development of innovative pulse sequences and acquisition methodologies. As a result, researchers can now study NMR-active nuclides previously thought to be unobservable or too unreceptive for routine examination via SSNMR. Several factors can make it extremely challenging to detect signal or acquire spectra using SSNMR: (i) low gyromagnetic ratios (i.e., low Larmor frequencies), (ii) low natural abundances or dilution of the nuclide of interest (e.g., metal nuclides in proteins or in organometallic catalysts supported on silica), (iii) inconvenient relaxation characteristics (e.g., very long longitudinal or very short transverse relaxation times), and/or (iv) extremely broad powder patterns arising from large anisotropic NMR interactions. Our research group has been particularly interested in efficient acquisition of broad NMR powder patterns for a variety of spin-1/2 and quadrupolar (spin > 1/2) nuclides. Traditionally, researchers have used the term "wideline" NMR to refer to experiments yielding broad (1)H and (2)H SSNMR spectra ranging from tens of kHz to ∼250 kHz in breadth. With modern FT NMR hardware, uniform excitation in these spectral ranges is relatively easy, allowing for the acquisition of high quality spectra. However, spectra that range in breadth from ca. 250 kHz to tens of MHz cannot be uniformly excited with conventional, high-power rectangular pulses. Rather, researchers must apply special methodologies to acquire such spectra, which have inherently low S/N because the signal intensity is spread across such large spectral breadths. We have suggested the term ultra-wideline NMR (UWNMR) spectroscopy to describe this set of methodologies. This Account describes recent developments in pulse sequences and strategies for the efficient acquisition of UWNMR spectra. After an introduction to anisotropically broadened NMR patterns, we give a brief history of methods used to acquire UWNMR spectra. We then discuss new acquisition methodologies, including the acquisition of CPMG echo trains and the application of pulses capable of broadband excitation and refocusing. Finally, we present several applications of UWNMR methods that use these broadband pulses.

ChemInform Abstract: Two‐Dimensional Higher Quantum Correlation and Resolved Techniques for the Analyses of Complex 1H NMR Spectra of Scalar‐Coupled Spins

AbstractReview: 94 refs.

Matrix-dependent modulation of anisotropic effects on NMR spectra from 7Li+ and 23Na+ encapsulated in cryptands

(7)Li and (23)Na NMR spectra of the respective cations in gelatin and ι-carrageenan gels containing cryptand-[2.1.1] (for Li(+)) or cryptand-[2.2.2] (for Na(+)) displayed two transitions: the one at higher frequency corresponded to the cation surrounded by gel, the other to cation inside its appropriately sized cryptand. While binding to cryptands yielded much broader lines and shorter T (1) relaxation times, anisotropic splitting in first order (7)Li or (23)Na NMR spectra was not detected. Stretching the gels resulted in increasing the anisotropic electric field gradient tensor; thus, the NMR transitions of the cation in the gel were split (removal of degeneracy) to display its characteristic 3:4:3 triplet for spin=3/2 nuclei. The transitions of the cryptand-bound cations (Li(+)-cryptand-[2.1.1] and Na(+)-cryptand-[2.2.2]) showed different extents of interaction with the electric field gradient tensor depending on the composition of the gel matrix. The NMR signal for (7)Li(+)-cryptand-[2.1.1] in stretched gelatin gel showed a five-fold increased splitting as compared to the (7)Li(+) signal in the reference gel. In stretched ι-carrageenan gels, no anisotropic splitting from the cryptand-bound Li(+) was recorded. Steady-state irradiation envelopes or z-spectra showed evidence of Li(+) exchange between isotropic (cryptand) and anisotropic (gel) sites only at higher temperatures (55°C). For Na(+) bound to the cryptand-[2.2.2], anisotropic splitting (three-fold smaller compared with the (23)Na signal in the reference gel) was only recorded in stretched ι-carrageenan gels, whereas gelatin gels showed only anisotropic splitting for the (23)Na signal in the reference gel.

2-[(1H-Benzimidazol-2-ylmethyl)-amino]-benzoic acid methyl ester: Crystal structure, DFT calculations and biological activity evaluation

In the present study, structural properties of 2-[(1H-benzimidazol-2-ylmethyl)-amino]-benzoic acid methyl ester have been studied extensively by spectral methods and X-ray crystallography. Quantum mechanical calculations of energies, geometries, vibrational wavenumbers, NMR and electronic transitions were carried out by DFT using B3LYP functional combined with 6-31G(d) basis set. Natural bond orbitals (NBO) analysis and frontier molecular orbitals were performed at the same level of theory. DFT calculations showed good agreement between the theoretical and experimental values of optimized and X-ray structure as well as between the vibrational and NMR spectroscopy. The title compound was screened for its antibacterial activity referring to Tetracycline as standard antibacterial agent.

Pulse FT NMR of non-equilibrium states of half-integer spin quadrupolar nuclei in single crystals

For quadrupolar nuclei with spin quantum numbers equal to 3/2, 5/2 and 7/2, the intensities of the NMR transitions in a single crystal are examined as a function of the rf excitation flip angle. Single-quantum NMR intensities are calculated using density matrix theory beginning under various non-equilibrium conditions and are compared with those determined experimentally. As a representative spin-3/2 system, the flip-angle dependence of the (23)Na NMR intensities of a single crystal of NaNO(3) was investigated beginning with the inversion of the populations associated with one of the satellite transitions. Subsequently, the populations of both satellite transitions were inverted using highly frequency-selective hyperbolic secant pulses. Calculated and experimental intensities are in good agreement. As an example of a spin-5/2 system, the flip-angle dependence of the (27)Al NMR transition intensities was determined using a single crystal of sapphire, Al(2)O(3), starting under different nuclear spin population conditions. The experimental trends mimicked those predicted by the density matrix calculations but the agreement was not as good as for the spin-3/2 case. Some SIMPSON simulations were also carried out to confirm the results generated by our density matrix calculations. The theoretical flip-angle behavior of the NMR transition intensities obtained from a spin-7/2 spin system is also discussed.

High-Field Dynamic Nuclear Polarization in Aqueous Solutions

Unexpected high DNP enhancements of more than 10 have been achieved in liquid water samples at room temperature and magnetic fields of 9.2 T (corresponding to 400 MHz (1)H NMR frequency and 260 GHz EPR frequency). The liquid samples were polarized in situ using a double-resonance structure, which allows simultaneous excitation of NMR and EPR transitions and achieves significant DNP enhancements at very low incident microwave power of only 45 mW. These results demonstrate the first important step toward the application of DNP to high-resolution NMR, increasing the sensitivity on biomolecules with small sample volumes and at physiologically low concentrations.

Melting and freezing of water in cylindrical silica nanopores

Freezing and melting of H(2)O and D(2)O in the cylindrical pores of well-characterized MCM-41 silica materials (pore diameters from 2.5 to 4.4 nm) was studied by differential scanning calorimetry (DSC) and (1)H NMR cryoporometry. Well-resolved DSC melting and freezing peaks were obtained for pore diameters down to 3.0 nm, but not in 2.5 nm pores. The pore size dependence of the melting point depression DeltaT(m) can be represented by the Gibbs-Thomson equation when the existence of a layer of nonfreezing water at the pore walls is taken into account. The DSC measurements also show that the hysteresis connected with the phase transition, and the melting enthalpy of water in the pores, both vanish near a pore diameter D* approximately equal to 2.8 nm. It is concluded that D* represents a lower limit for first-order melting/freezing in the pores. The NMR spin echo measurements show that a transition from low to high mobility of water molecules takes place in all MCM-41 materials, including the one with 2.5 nm pores, but the transition revealed by NMR occurs at a higher temperature than indicated by the DSC melting peaks. The disagreement between the NMR and DSC transition temperatures becomes more pronounced as the pore size decreases. This is attributed to the fact that with decreasing pore size an increasing fraction of the water molecules is situated in the first and second molecular layers next to the pore wall, and these molecules have slower dynamics than the molecules in the core of the pore.

Sensitivity enhancement of solid-state NMR spectra of half-integer spin quadrupolar nuclei: Double- or single-frequency sweeps? Insights from the hyperbolic secant experiment

Improved sensitivity enhancements of the central NMR transition of non-integer spin quadrupolar nuclei in MAS powder samples are realized when only a single satellite transition spinning side band is irradiated using a conventional double-frequency sweep experiment compared to irradiation of the entire spinning side band manifold. For example, for 87Rb in RbClO 4, enhancement factors of 2.2 versus 1.9 are observed when only one satellite transition spinning side band is targeted versus the entire spinning side band manifold. Similarly, for 27Al in Al(acac) 3, the corresponding enhancement was 3.4 compared to 2.6.

Sensitivity enhancement of NMR spectra of half-integer spin quadrupolar nuclei in solids using hyperbolic secant pulses

The experimental factors influencing the enhancements achievable for the central NMR transition, m I = 1/2 → m I = −1/2, of spin-3/2 and spin-5/2 nuclei in the solid state using hyperbolic secant, HS, pulses for population transfer are investigated. In the case of powder samples spinning at the magic angle, it is found that the spinning frequency, the bandwidth and the frequency offset of the HS pulse play a crucial role in determining the maximum enhancements. Specifically, the bandwidth must be set to the spinning frequency for maximum signal enhancements. The 87Rb NMR enhancement obtained for RbClO 4 using HS pulses was relatively insensitive to the magic angle spinning frequency; however, in the case of Al(acac) 3, the 27Al enhancement increased with MAS frequency. In order to obtain an adiabatic HS sweep, one should optimize the rf field for a given pulse duration or optimize the pulse duration for a given rf field.