Effect of the frequency of intramolecular motions on the NMR relaxation in liquid state temperature regime

Equations for the spectral densities of complex motion of a spin pair undergoing internal motion and isotropic/anisotropic overall rotation have been considered. The fluctuations of the interproton distances, caused by internal motion, have been taken into account in the theoretical equations. A method allowing a distinction between the isotropic and the anisotropic overall rotation of molecules has been proposed. The effect of the activation parameters of internal motions (known from the solid state study) on the measured T ₁ relaxation of the ¹³C and ¹H–¹H cross-relaxation rates has been analysed for methyl-β-D-galactopyranoside in DMSO-d6 solution. The conformational trans-gauche jumps of the methylene group are not fast enough to affect the T ₁ value of carbon C6 in the liquid state temperatures regime. Only the methyl group rotation is a very fast internal motion. This motion influences the carbon C7 relaxation and methyl protons–anomeric proton cross-relaxation. The values of interatomic distances between anomeric H(C1) and H(C5) as well as the three methyl protons H(C7) have been calculated from the cross-relaxation rates. The distance H(C1)–H(C7) fluctuates due to the rotation of methyl group. The application of the ‘model-free approach’ to study molecular dynamics in solutions is discussed.     

13C and 1H nuclear spin lattice magnetic relaxation in undoped polyacetylene

Pulsed NMR spin lattice relaxation measurements on ¹³C and ¹H nuclei in undoped trans-polyacetylene have been carried out between 6 and 295 K. The results indicate that the spin lattice relaxation is due to equilibrium fluctuations of the orientational order parameter for the protons while the carbon relaxation can be attributed to their coupling to paramagnetic impurities. In this temperature range no contribution of solitons has been detected in the relaxation mechanisms.     

The Observation and Dynamics of 1H NMR Spin Noise in Methanol

The observation of ¹H spin noise in relation to prior established magnetization and radiation damping has revealed a correlated dynamics. The spin noise of methyl satellites in ¹³C-enriched methanol was observed in the presence of an antiphase magnetization, created by the combination of ¹H–¹³C J coupling evolution and radiofrequency (RF) pulses. A gradient pulse was applied to remove residue spin coherence coming from the RF pulses, and as a result spin noise phenomena were uncovered. While magnetization was in an inverted metastable state, the spin–spin relaxation time was shortened to prevent a super radiation burst. The relation between magnetization, radiation damping, and absorption or emission of the spin noise of methyl satellites has been studied. In relation to magnetization and radiation damping, spin noise bump and dip have been observed simultaneously in the same molecule. Both can be created through a proper inversion of magnetization. The revealed spin noise dynamics of spin system coupling to the probe circuit via radiation damping allows performance of a transformation from dip into bump by proper application of pulses combined with ¹H–¹³C J coupling evolution.     

Nonexponential 1H spin–lattice relaxation and methyl group rotation in molecular solids

We report a quantitative measure of the nonexponential ¹H spin–lattice relaxation resulting from methyl group (CH₃) rotation in six polycrystalline van der Waals solids. We briefly review the subject in general to put the report in context. We then summarize several significant issues to consider when reporting ¹H or ¹⁹F spin–lattice relaxation measurements when the relaxation is resulting from the rotation of a CH₃ or CF₃ group in a molecular solid.     

13C solid-state NMR chromatography by magic angle spinning 1H T1 relaxation ordered spectroscopy

An efficient method to separate the ¹³C NMR spectra of solid mixtures is introduced. The ¹H longitudinal (T₁) relaxation time is used to separate the overlapping ¹³C chemical shift spectra of solid mixtures via an inverse Laplace transform (ILT) of the relaxation dimension. The resulting 2D spectrum of the mixture contains separate ¹³C spectra for each component of the mixture that are identical to ¹³C spectra of the isolated materials. The separation is based on the equalization of ¹H T₁ values in a single domain by rapid ¹H spin diffusion and on the ¹H T₁ value differences between different domains. The introduction of a general ILT scheme enables efficient and reduced data acquisition time. The method is demonstrated on a mixture of two disaccharides and on a commercial drug containing several compounds.     

N.M.R. relaxation time studies in liquid methyl iodide

The spin-lattice relaxation times of the various nuclei in methyl iodide, methyl iodide-d ₃, and carbon-13 methyl iodide (¹³C, ¹H, ²D) were measured between 210 and 350 K. The separation of the proton-proton intermolecular relaxation was accomplished by a dilution study in methyl iodide-d ₃; the resulting intermolecular contribution agreed well with the existing theories for this mechanism. It was found that the spin-rotation interaction contributed significantly to the intramolecular relaxation of both the protons and the carbon-13. For both nuclei the separation of the spin-rotation interaction from the intramolecular dipole-dipole interaction was accomplished without making any assumptions about the temperature dependence of the spin-rotation relaxation time. The resulting spin-rotation relaxation times for both carbon-13 and protons offer evidence that the large spin-rotation effects are due to the methyl group reorientation.     

1H and 13C n.m.r. Conformational Analysis of Adrenergic Drugs. Part 2. N-Isopropyl-N- {3-[4(4-Methoxybenzoylamino)Phenoxy]-2-Hydroxypropyl} Ammonium Chloride,a New β1-Blocking Agent

Abstract

Dynamic and structural features of N-Isopropyl-N- {3-[4(4-Methoxybenzoylamino)Phenoxy]-2-Hydroxypropyl} Ammonium Chloride in [²H₆]DMSO were investigated by measuring ¹³C and ¹H spin-lattice relaxation rates and ¹³C- {¹H} and ¹H- {¹H} n.O.e. Correlation times for main and internal reorientational motions were interpreted in terms of internal rotation around the two planal axes. Selective and double-selective ¹H spin-lattice relaxation rates were measured, wherefrom relevant proton-proton intramolecular distances were calculated. It was shown that the β₁? blocking agent assumes a preferred conformation where extensive intramolecular H-bonding prevents segmental motion along the quaternary ammonium sidechain.     

Korringa relaxation time of magnetic ion system near a two-dimensional electron gas

Spin relaxation of Mn ions in a (Cd,Mn)Te quantum well with quasi-two-dimensional carriers (Q2DEG) is investigated. The mechanism of energy transfer is spin-flip scattering of Mn spin with electrons making transitions between spin subbands accompanied by a change in the Mn spin. A calculation of the spin-flip scattering rate shows that the Mn spin relaxation rate is proportional to the coupling constant squared, the density of states squared, and the electron temperature, the so called Korringa relaxation rate. It was found that for small Mn ion concentration, the relaxation time ≈10−7-10−6s is in a good agreement with experimental results. Moreover, the relaxation rate scales with L⁻², L being the well width, and it can be enhanced over its value in bulk.     

2D CP/MASC Isotropic Chemical Shift Correlation Established byH Spin Diffusion

A new 2D solid-state CP/MAS¹³C NMR exchange experiment for through-space isotropic chemical shift correlation is proposed and demonstrated. Through-space correlation is established via a second cross polarization from¹³C to¹H and subsequent¹H spin diffusion. A third cross polarization results in the final¹³C–¹³C isotropic chemical shift correlation. The¹H spin diffusion time is a variable parameter allowing different mean square magnetization displacements to be probed. Experimental results on mixtures of differently¹³C-labeled alanine and polyethylene indicate that this site-selective 2D technique can be used to characterize domain sizes and proximities over a wide range of length scales (1–200 nm) in solids such as polymers or biological materials.     

Paramagnetic Impurities in Graphene Oxide

We report on electron paramagnetic resonance and nuclear magnetic resonance study of graphene oxide produced by the Hummers method. We show that this compound reveals isolated Mn²⁺ ions, which originate from potassium permanganate used in the process of the sample preparation. These ions are likely anchored to the graphene oxide planes and contribute to the ¹H and ¹³C spin–lattice relaxation.     

Fast Dissolution Dynamic Nuclear Polarization NMR of 13C-Enriched 89Y-DOTA Complex: Experimental and Theoretical Considerations

The yttrium complex of 1,4,7,10-tetraazacyclododecane-1,4,7,10-tetra(1′-¹³C-acetic acid) [¹³C]DOTA was synthesized. Fast dissolution dynamic nuclear polarization (DNP) nuclear magnetic resonance (NMR) studies revealed that the ⁸⁹Y, ¹³C, and ¹⁵N nuclei present in the complex could be co-polarized at the same optimum microwave irradiation frequency. The liquid-state spin–lattice relaxation time T ₁ of these nuclei were found to be reasonably long to preserve some or most of the DNP-enhanced polarization after dissolution. The hyperpolarized ¹³C and ⁸⁹Y NMR signals were optimized in different glassing mixtures. The overall results are discussed in light of the thermal mixing model of DNP.     

Unusual Hindered Rotation of an Unsubstituted Phenyl Group. Variable Temperature 1H NMR Studies and Preliminary 13C Assignments in Ketazolam

An unusual hindered rotation of an unsubstituted phenyl group in the drug, ketazolam, has been found at ambient temperature. Variable temperature lH NMR has been employed to examine the two- fold rotation about the C(sp²)-C(sp³) bond. Chemical shift as- signments of the IH NMR spectra and partial assignments of the ¹³C spectra are supported by off-resonance decoupling, gated decou- pling, and low temperature 2D ^l3C-¹H heteronuclear chemical shift correlation experiments at 200.1 MHz for IH and 50.3 MHz for ¹³C.     

Structural Phase Transition of Perovskite-Type N(CH<Subscript>3</Subscript>)<Subscript>4</Subscript>CdBr<Subscript>3</Subscript> Studied by MAS NMR and Static NMR

The structural geometry change in the perovskite-type N(CH₃)₄CdBr₃ single crystal near the phase transition temperature of T _C = 390 K was investigated using magic angle spinning nuclear magnetic resonance techniques. For ¹H and ¹³C nuclei, the temperature dependences of their chemical shift, spectral intensity, and spin–lattice relaxation time (T _1ρ) in the rotating frame were obtained and analyzed. While the chemical shift and T _1ρ of ¹H showed change near T _C, those of ¹³C did not. In addition, the ¹¹³Cd spin–lattice relaxation time T ₁ in the laboratory frame near T _C show no evidence of anomalous change near the phase transition temperature, which coincides with the measured changes in the ¹H T _1ρ. The driving force for this phase transition was connected to the ¹H in the CH₃ groups.     

Frequency shift and relaxation of muon-spin-precession in Cd1−xMnxTe

Transverse-field muon spin roation (μSR) is studied in Cd_1−xMn_xTe, x=0.4 and 0.6 mixed crystals. A large temperature dependent frequency shift and a strong relaxation of the μSR-signal are observed. In the vicinity of the spinglass transition, the relaxation rate becomes so large that the signal disappears. The rate of Mn spin fluctuations causing the μ⁺-line narrowing at high temperatures is estimated to be of the order of 10⁹ S⁻¹.     

Relaxation-induced dipolar exchange with recoupling-An MAS NMR method for determining heteronuclear distances without irradiating the second spin

A new magic-angle spinning NMR method for distance determination between unlike spins, where one of the two spins in question is not irradiated at all, is introduced. Relaxation-induced dipolar exchange with recoupling (RIDER) experiments can be performed with conventional double-resonance equipment and utilize the familiar π-pulse trains to recouple the heteronuclear dipolar interaction under magic-angle spinning conditions. Longitudinal relaxation of the passive spin during a delay between two recoupling periods results in a dephasing of the heteronuclear coherence and consequently a dephasing of the magnetization detected after the second recoupling period. The information about the dipolar coupling is obtained by recording normalized dephasing curves in a fashion similar to the REDOR experiment. At intermediate mixing times, the dephasing curves also depend on the relaxation properties of the passive spin, i.e., on single- and double-quantum longitudinal relaxation times for the case of I = 1 nuclei, and these relaxation times can be estimated with this new method. To a good approximation, the experiment does not depend on possible quadrupolar interactions of the passive spin, which makes RIDER an attractive method when distances to quadrupolar nuclei are to be determined. The new method is demonstrated experimentally with ¹⁴N and ²H as heteronuclei and observation of ¹³C in natural abundance.     

Interpretation of 1H and 2H spin–lattice relaxation dispersions: Insights from molecular dynamics simulations of polymer melts

We demonstrate that molecular dynamics simulations are a versatile tool to ascertain the interpretation of spin–lattice relaxation data. For ¹H, our simulation approach allows us to separate and to compare intra- and inter-molecular contributions to spin–lattice relaxation dispersions. Dealing with the important example of polymer melts, we show that the intramolecular parts of ¹H spectral densities and correlation functions are governed by rotational motion, while their inter-molecular counterparts provide access to translational motion, in particular, to mean-squared displacements and self-diffusion coefficients. Exploiting that the full microscopic information is available from molecular dynamics simulations, we determine the range of validity of experimental approaches, which often assume Gaussian dynamics, and we provide guidelines for the determination of free parameters required in experimental analyses. For ²H, we examine the traditional methodology to extract correlation times of complex dynamics from relaxation data. Furthermore, based on knowledge from our computational study, it is shown that measurement of ²H spin–lattice relaxation dispersions allows one to disentangle the intra- and inter-molecular contributions to the corresponding ¹H data in experimental work. Altogether, our simulation results yield a solid basis for future ¹H and ²H spin–lattice relaxation analysis.     

Relaxation Effects in a System of a Spin-1/2 Nucleus Coupled to a Quadrupolar Spin Subjected to RF Irradiation: Evaluation of Broadband Decoupling Schemes

We have investigated the suitability and performance of various decoupling methods on systems in which an observed spin-1/2 nucleusI(¹³C or¹⁵N) is scalar-coupled to a quadrupolar spinS(²H). Simulations and experiments have been conducted by varying the strength of the irradiating radiofrequency (RF) field, RF offset, relaxation times, and decoupling schemes applied in the vicinity of theS-spin resonance. TheT₁relaxation of the quadrupolar spin has previously been shown to influence the efficiency of continuous wave (CW) decoupling applied on resonance in such spin systems. Similarly, the performance of broadband decoupling sequences should also be affected by relaxation. However, virtually all of the more commonly used broadband decoupling schemes have been developed without consideration of relaxation effects. As a consequence, it is not obvious how one selects a suitable sequence for decoupling quadrupolar nuclei with exotic relaxation behavior. Herein we demonstrate that, despite its simplicity, WALTZ-16 decoupling is relatively robust under a wide range of conditions. In these systems it performs as well as the more recently developed decoupling schemes for wide bandwidth applications such as GARP-1 and CHIRP-95. It is suggested that in macromolecular motional regimes, broadband deuterium decoupling can be achieved with relatively low RF amplitudes (500–700 Hz) using WALTZ-16 multiple pulse decoupling.     

A New Two-Dimensional Pulse Sequence for T2* Measurements of Protons in C Isotopomers

A new two-dimensional pulse sequence for T₂* measurement of protons directly coupled to ¹³C spins is proposed. The sequence measures the tranverse relaxation time of heteronuclear proton single-quantum coherence under conditions of free precession and is therefore well suited to evaluate relaxation losses of proton magnetization during preparation delays of heteronuclear pulse experiments in analytical NMR. The relevant part of the pulse sequence can be inserted as a “building block” into any direct or inverse detecting H,C correlation pulse sequence if proton spin–spin relaxation is to be investigated. In this contribution, the building block is inserted into a HETCOR as well as into a HMQC pulse sequence. Experimental results for the HETCOR-based sequence are given.     

Proton magnetic relaxation in solutions of E. coli ribosomal RNA containing Mn2+ ions

A study has been made over a range of temperatures and magnetic field strengths of the spin relaxation of water protons in aqueous solutions of E. coli ribosomal RNA containing Mn²⁺ ions. The effects of the paramagnetic ions are enhanced in the presence of the RNA. As the temperature falls T ₁ passes through a minimum value, the magnitude of which is field dependent, and this is attributed to a change in dipolar relaxation mechanism from rotation of the aquocomplex to electron spin relaxation. The relevance of this work is assessed in relation to other work on proton relaxation enhancement in Mn²⁺-containing solutions of biopolymers.     

13C- and 1H-NMR Relaxation Investigation of a Polyciclic Nitrogen Compound: 3,3-Dimethyl-1,5-diphenyl-9-hydroxy-bispidinium Iodide

The rigid polycyclic nitrogen compound was considered as a test for the reliability of internuclear distances calculated by ¹H-NMR spin-lattice relaxation rates. The ‘isotropic’ motional correlation time was calculated from ¹³C relaxation rates (τ_C = 0.11 ns at 298 K). Dipolar cross-relaxation rates were calculated by measuring non-, mono- and double-selective proton spin-lattice relaxation rates. All the experimental relaxation rates were thoroughly accounted for by dipolar pairwise interactions. Only at high temperatures a certain contribution from the spin rotational mechanism was apparent.