Proton Spin System Research Articles

Residual dipolar line width in magic-angle spinning proton solid-state NMR.

Magic-angle spinning is routinely used to average anisotropic interactions in solid-state nuclear magnetic resonance (NMR). Due to the fact that the homonuclear dipolar Hamiltonian of a strongly coupled spin system does not commute with itself at different time points during the rotation, second-order and higher-order terms lead to a residual dipolar line broadening in the observed resonances. Additional truncation of the residual broadening due to isotropic chemical-shift differences can be observed. We analyze the residual line broadening in coupled proton spin systems based on theoretical calculations of effective Hamiltonians up to third order using Floquet theory and compare these results to numerically obtained effective Hamiltonians in small spin systems. We show that at spinning frequencies beyond 75 kHz, second-order terms dominate the residual line width, leading to a dependence of the second moment which we use to characterize the line width. However, chemical-shift truncation leads to a partial dependence of the line width which looks as if third-order effective Hamiltonian terms are contributing significantly. At slower spinning frequencies, cross terms between the chemical shift and the dipolar coupling can contribute in third-order effective Hamiltonians. We show that second-order contributions not only broaden the line, but also lead to a shift of the center of gravity of the line. Experimental data reveal such spinning-frequency-dependent line shifts in proton spectra in model substances that can be explained by line shifts induced by the second-order dipolar Hamiltonian.

THE HISTIDINE-REVERSIBLE ANTIBIOTIC HERBICOLIN O PRODUCED BY PANTOEA VAGANS C9-1 IS PANTOCIN A

Pantoea vagans C9-1 is one of the most effective and reliable biocontrol agents against fire blight, and has been commercialized as Blight Ban C9-1. Production of multiple antibiotics contributes to its antagonism of Erwinia amylovora. Here we describe the genetics, chemical isolation and structure of herbicolin O, the histidine-reversible antibiotic produced by P. vagans C9-1. Mutational analyses indicated that biosynthesis of herbicolin O depends on paaAB and a sequence encoding the peptide precursor of pantocin A. The paaABC gene cluster encoding biosynthesis and autoresistance was located within a 28-kb chromosomal genomic island of the complete genome sequence of P. vagans C9-1. The cluster was cloned and expressed in E. coli and purified antibiotic was isolated using improved methods for small peptides. The 1 H NMR spectra of the C9-1 antibiotic closely resembled those of pantocin A produced by P. agglomerans Eh318. Detailed analysis of the proton spin systems showed that the chemical shift values and coupling constants of the protons in C9-1 herbicolin O correspond exactly to those of pantocin A. Based on these genetic and chemical analyses, herbicolin O and pantocin A are confirmed to be the same antibiotic.

The physical mechanism of “inhomogeneous” magnetization transfer MRI

Inhomogeneous MT (ihMT) is a new magnetic resonance imaging technique that shows promise for myelin selectivity. Materials with a high proportion of lipids, such as white matter tissue, show a reduced intensity in magnetic resonance images acquired with selective prepulses at positive and negative offsets simultaneously compared to images with a single positive or negative offset prepulse of the same power. This effect was initially explained on the basis of hole-burning in inhomogeneously broadened lines of the lipid proton spin system. Our results contradict this explanation. ihMT in lipids can be understood with a simple spin-1 model of a coupled methylene proton pair. More generally, Provotorov theory can be used to consider the evolution of dipolar order in the non-aqueous spins during the prepulses. We show that the flip-angle dependence of the proton spectrum of a model lipid system (Prolipid-161) following dipolar order generation is in quantitative agreement with the model. In addition, we directly observe dipolar order and ihMT signals in the non-aqueous components of Prolipid-161 and homogeneously-broadened systems (hair, wood, and tendon) following ihMT prepulses. The observation of ihMT signals in tendon suggests that the technique may not be as specific to myelin as previously thought. Our work shows that ihMT occurs because of dipolar couplings alone, not from a specific type of spectral line broadening as its name suggests.

ChemInform Abstract: Probing Structural and Motional Features of Organic and Inorganic Solids Through Extended Family of Cross‐polarization Experiments

AbstractReview: 35 refs.

Solid-State NMR Study of Poly(3-Hydroxybutyrate) and Ecoflex reser Blends

Biodegradable blends of poly(3-hydroxybutyrate) and aromatic-aliphatic co-polyester Ecoflex® were studied by means of basic solid-state NMR techniques. C NMR spectra pointed at existence of individual components in blends, however, existence of regions in which components affect each other was also deduced from changes of shape of some spectral lines. Analysis of proton spin–lattice relaxation process in laboratory frame running in blends with different fractions of components revealed poor miscibility of these polymers. The domain size of components was calculated based on the values of spin–lattice relaxation times in laboratory frame. Spin–lattice relaxation process in the rotating frame of Ecoflex® proton spin system was only slightly influenced by the blending. Incompatibility of these polymers was confirmed by all realized experiments.

Probing structural and motional features of organic and inorganic solids through extended family of cross-polarization experiments

Combined use of cross-polarization and magic-angle spinning in the middle of the seventies has opened a new era of high-resolution solid-state NMR spectroscopy. Cross-polarization procedure is commonly used to obtain a shorter measuring time and to investigate or exploit one nucleous by means of the other nucleous involved in the polarization transfer. An extended family of cross-polarization experiments including constant time cross-polarization approach, cross-polarization inversion and indirect observation of proton spin system is reviewed and illustrated with applications to a large range of solids.

Elimination of Zero-Quantum artifacts and sensitivity enhancement in perfect echo based 2D NOESY.

Zero-Quantum artifacts seriously degrade the performance of 2D NOESY. Homonuclear J-evolution during t(1) period generates Zero-Quantum and other higher quantum coherences which represent the magnetization loss and the artifacts created. We demonstrate that creation of such artifacts itself can be prevented for shorter t1 period by a perfect echo based decoupling technique during t1 period in a single scan. This is in contrast to existing methods that create unwanted coherence, and subsequently suppress that to produce a clean spectrum with a sensitivity penalty. Although decoupling performance of the present scheme remains robust for echo time 2τ short compared to 1/2J, we show that even a partial decoupling effect for extended t(1) (=2τ) period up to 100 ms along with a Zero-Quantum filter generates NOE spectrum from Cyclosporine A, in which majority of the cross peaks displayed partial sensitivity enhancement with few exceptions. However, in crowded proton spin systems like menthol, the enhancements were not observed and perfect echo NOESY displays similar performance as Zero-Quantum filtered NOESY.

Singlet lifetime measurements in an all-proton chemically equivalent spin system by hyperpolarization and weak spin lock transfers.

Hyperpolarized singlet states provide the opportunity for polarization storage over periods significantly longer than T1. Here, we show how the singlet state in a chemically equivalent proton spin system can be revealed by a weak power spin-lock. This procedure allowed the measurement of the lifetimes of the singlet state in protic solvents. The contributions of different intra- and intermolecular relaxation mechanisms to singlet lifetimes are investigated with this procedure.

A critical evaluation of heteronuclear TOCSY (HEHAHA) experiments for 1H,6Li spin pairs.

Heteronuclear TOCSY (HEHAHA) experiments for (1) H,(6) Li spin pairs in organolithium compounds with adjacent strongly coupled (1) H,(1) H spin systems showed unexpected cross peak behaviour: for n-butyllithium (1) H,(6) Li cross peaks were completely missing, whereas for the dimer of (Z)-2-lithio-1-(o-lithiophenyl)ethane, a cross peak for remote protons was observed even at very short mixing times. It was assumed that strong magnetization transfer within the proton spin systems was responsible for these results, which prevented unambiguous chemical shift assignments. Selective experiments with the (6) Li,(1) H-HET-PLUSH-TACSY sequence then showed the expected (6) Li,(1) H cross peaks for the transfer via the directly coupled (1) H and (6) Li nuclei. For n-butyllithium transfer to H(Cα) via an unresolved heteronuclear coupling constant below 0.1 Hz is unambiguously observed. Cross peaks in the 2D (6) Li,(1) H-HET-PLUSH-TACSY spectra for the dimer of (Z)-2-lithio-1-(o-lithiophenyl)ethane are readily explained by the measured coupling network and the corresponding active mixing conditions.

Selective inversion of 1H resonances in solid-state nuclear magnetic resonance: Use of double-DANTE pulse sequence

We here present a method based on DANTE pulses and homonuclear dipolar decoupling scheme to invert selectively any desired resonance in a proton spin system under magic-angle spinning. Experimental results are reported on a sample of L-histidine·HCl·H2O at magic-angle spinning frequencies of 15 and 60kHz. The results are also substantiated numerically.

Proton-Detected Solid-State NMR Spectroscopy at Aliphatic Sites: Application to Crystalline Systems

When applied to biomolecules, solid-state NMR suffers from low sensitivity and resolution. The major obstacle to applying proton detection in the solid state is the proton dipolar network, and deuteration can help avoid this problem. In the past, researchers had primarily focused on the investigation of exchangeable protons in these systems. In this Account, we review NMR spectroscopic strategies that allow researchers to observe aliphatic non-exchangeable proton resonances in proteins with high sensitivity and resolution. Our labeling scheme is based on u-[(2)H,(13)C]-glucose and 5-25% H2O (95-75% D2O) in the M9 bacterial growth medium, known as RAP (reduced adjoining protonation). We highlight spectroscopic approaches for obtaining resonance assignments, a prerequisite for any study of structure and dynamics of a protein by NMR spectroscopy. Because of the dilution of the proton spin system in the solid state, solution-state NMR (1)HCC(1)H type strategies cannot easily be transferred to these experiments. Instead, we needed to pursue ((1)H)CC(1)H, CC(1)H, (1)HCC or ((2)H)CC(1)H type experiments. In protonated samples, we obtained distance restraints for structure calculations from samples grown in bacteria in media containing [1,3]-(13)C-glycerol, [2]-(13)C-glycerol, or selectively enriched glucose to dilute the (13)C spin system. In RAP-labeled samples, we obtained a similar dilution effect by randomly introducing protons into an otherwise deuterated matrix. This isotopic labeling scheme allows us to measure the long-range contacts among aliphatic protons, which can then serve as restraints for the three-dimensional structure calculation of a protein. Due to the high gyromagnetic ratio of protons, longer range contacts are more easily accessible for these nuclei than for carbon nuclei in homologous experiments. Finally, the RAP labeling scheme allows access to dynamic parameters, such as longitudinal relaxation times T1, and order parameters S(2) for backbone and side chain carbon resonances. We expect that these measurements will open up new opportunities to obtain a more detailed description of protein backbone and side chain dynamics.

Quantum decoherence and quasi-equilibrium in open quantum systems with few degrees of freedom: Application to 1H NMR of nematic liquid crystals

Explanation of decoherence and quasi-equilibrium in systems with few degrees of freedom demands a deep theoretical analysis that considers the observed system as an open quantum system. In this work, we study the problem of decoherence of an observed system of quantum interacting particles, coupled to a quantum lattice. Our strategy is based on treating the environment and the system-environment Hamiltonians fully quantum mechanically, which yields a representation of the time evolution operator useful for disentangling the different time scales underlying in the observed system dynamics. To describe the possible different stages of the dynamics of the observed system, we introduce quantum mechanical definitions of essentially isolated, essentially adiabatic, and thermal-contact system-environment interactions. This general approach is then applied to the study of decoherence and quasi-equilibrium in proton nuclear magnetic resonance ((1)H NMR) of nematic liquid crystals. A summary of the original results of this work is as follows. We calculate the decoherence function and apply it to describe the evolution of a coherent spin state, induced by the coupling with the molecular environment, in absence of spin-lattice relaxation. By assuming quantum energy conserving or non-demolition interactions, we identify an intermediate time scale, between those controlled by self-interactions and thermalization, where coherence decays irreversibly. This treatment is also adequate for explaining the buildup of quasi-equilibrium of the proton spin system, via the process we called eigen-selectivity. By analyzing a hypothetical time reversal experiment, we identify two sources of coherence loss which are of a very different nature and give rise to distinct time scales of the spin dynamics: (a) reversible or adiabatic quantum decoherence and (b) irreversible or essentially adiabatic quantum decoherence. Local irreversibility arises as a consequence of the uncertainty introduced by the coupling with an infinite quantum environment. The reversible part can be represented by a semiclassical model, similar to standard line-shape adiabatic models. By exploiting the separation existing between the time scales of the spin coherences and the irreversible decoherence, we present a novel technique to obtain the orientational molecular distribution function for a nematic liquid crystal. The procedure is based on the comparison of the observed coherence time evolution and numerical calculation under the adiabatic quantum decoherence approach. As an example, it is used the experimental free induction decay from a nematic PAA(d6) sample to extract such an orientational distribution. This is the first theoretical description of the experimental liquid crystal NMR signal in the time domain. On the contrary, the irreversible decoherence is intrinsically full-quantum mechanical, as it is governed by the commutation properties of the environment and the spin-lattice Hamiltonians. Consistently, it depends on the molecular correlation in a decisive way, since it vanishes under a mean-field model for the molecular dynamics. The results of this work can contribute to the understanding of the open question of the applicability of the spin-temperature concept in spin systems with few degrees of freedom.

Utility of coupled-HSQC experiments in the intact structural elucidation of three complex saponins from Blighia sapida

The structures of three complex saponins from the fruit pods of Blighia sapida have been elucidated and their 1H and 13C NMR spectra assigned employing a variety of one- and two-dimensional NMR techniques without degradative chemistry. The saponins have either four or six monosaccharide units linked to a triterpene aglycone. High-resolution, proton-coupled-HSQC spectra were important for determining both the identities of the intact monosaccharide units and coupling constants in strongly coupled proton spin systems. These NMR experiments will prove crucial as the complexity of saponin structures reaches the limit that can be determined solely by NMR.

Spontaneous emission of NMR signals in hyperpolarized proton spin systems

Hyperpolarization of nuclear spins is gaining increasing interest as a tool for improving the signal-to-noise ratio of NMR and MRI. While in principle, hyperpolarized samples are amenable to the same or similar experiments as are used in conventional NMR, the large spin polarization may give rise to unexpected effects. Here, spontaneous emission of signal was observed from proton spin systems, which were hyperpolarized to negative spin temperature by dynamic nuclear polarization (DNP). An unexpected feature of these emissions is that, without any radio-frequency excitation, multiple beats arise that cannot be explained by the Bloch equations with radiation damping. However, we show that a simple modification to these equations, which takes into account an additional supply of hyperpolarized magnetization from a reservoir outside of the active detection region, can phenomenologically describe the observed signal. The observed effect demonstrates that even well-known mechanisms of spin evolution can give rise to unexpected effects when working with hyperpolarized samples, which may need to be addressed through the development of new experimental techniques.

NMR dipolar constants of motion in liquid crystals: Jeener–Broekaert, double quantum coherence experiments and numerical calculation on a 10-spin cluster

Two proton quasi-equilibrium states were previously observed in nematic liquid crystals, namely the S and W quasi-invariants. Even though the experimental evidence suggested that they originate in a partition of the spin dipolar energy into a strong and a weak part, respectively, from a theoretical viewpoint, the existence of an appropriate energy scale which allows such energy separation remains to be confirmed and a representation of the quasi-invariants is still to be given. We compare the dipolar NMR signals yielded both by the Jeener–Broekaert (JB) experiment as a function of the preparation time and the free evolution of the double quantum coherence (DQC) spectra excited from the S state, with numerical calculations carried out from first principles under different models for the dipolar quasi-invariants, in a 10-spin cluster which represents the 5CB ( 4 ′ -pentyl-4-biphenyl-carbonitrile) molecule. The calculated signals qualitatively agree with the experiments and the DQC spectra as a function of the single-quantum detection time are sensible enough to the different models to allow both to probe the physical nature of the initial dipolar-ordered state and to assign a subset of dipolar interactions to each constant of motion, which are compatible with the experiments. As a criterion for selecting a suitable quasi-equilibrium model of the 5CB molecule, we impose on the time evolution operator consistency with the occurrence of two dipolar quasi-invariants, that is, the calculated spectra must be unaffected by truncation of non-secular terms of the weaker dipolar energy. We find that defining the S quasi-invariant as the subset of the dipolar interactions of each proton with its two nearest neighbours yields a realistic characterization of the dipolar constants of motion in 5CB. We conclude that the proton-spin system of the 5CB molecule admits a partition of the dipolar energy into a bilinear strong and a multiple-spin weak contributions therefore providing two orthogonal constants of motion, which can be prepared and observed by means of the JB experiment. This feature, which implies the existence of two timescales of very different nature in the proton-spin dynamics, is ultimately dictated by the topology of the spin distribution in the dipole network and can be expected in other liquid crystals. Knowledge of the nature of the dipolar quasi-invariants will be useful in studies of dipolar-order relaxation, decoherence and multiple quantum NMR experiments where the initial state is a dipolar-ordered one.

Double resonance experiments in low magnetic field: Dynamic polarization of protons by 14N and measurement of low NQR frequencies

The possibilities of dynamically polarizing proton spin system via the quadrupole 14N spin system in low magnetic field are analyzed. The increase of the proton magnetization is calculated. The polarization rate of the proton spin system is related to the transition probabilities per unit time between the 14N quadrupole energy levels and proton energy levels. The experiments performed in 1,3,5-triazine confirm the results of the theoretical analysis. A new double resonance technique is proposed for the measurement of nuclear quadrupole resonance frequencies ν Q of the order of 100 kHz and lower. The technique is based on magnetic field cycling between a high and a low static magnetic field and observation of the proton NMR signal in the high magnetic field. In the low magnetic field the quadrupole nuclei and protons resonantly interact at the proton Larmor frequency ν H = ν Q/2. The quadrupole nuclei are simultaneously excited by a resonant rf magnetic field oriented along the direction of the low static magnetic field. The experimental procedure is described and the sensitivity of the new technique is estimated. Some examples of the measurement of low 14N and 2H nuclear quadrupole resonance frequencies are presented.

Quasiequilibrium states in thermotropic liquid crystals studied by multiple-quantum NMR

Previous work showed that by means of the Jeener-Broekaert (JB) experiment, two quasiequilibrium states can be selectively prepared in the proton spin system of thermotropic nematic liquid crystals (LCs) in a strong magnetic field. The similarity of the experimental results obtained in a variety of LC in a broad Larmor frequency range, with crystal hydrates, supports the assumption that also in LC the two spin reservoirs, into which the Zeeman order is transferred, originate in the dipolar energy and that they are associated with a separation in energy scales: A constant of motion related to the stronger dipolar interactions (S), and a second one (W) corresponding to the secular part of the weaker dipolar interactions with regard to the Zeeman and the strong dipolar part. We study the nature of these quasi-invariants in nematic 5CB (4(')-pentyl-4-biphenyl-carbonitrile) and measure their relaxation times by encoding the multiple-quantum coherences of the states following the JB pulse pair on two orthogonal bases, Z and X. The experiments were also performed in powder adamantane at 301 K which is used as a reference compound having only one dipolar quasi-invariant. We show that the evolution of the quantum states during the buildup of the quasiequilibrium state in 5CB prepared under the S condition is similar to the case of powder adamantane and that their quasiequilibrium density operators have the same tensor structure. In contrast, the second constant of motion, whose explicit operator form is not known, involves a richer composition of multiple-quantum coherences of even order on the X basis, in consistency with the truncation inherent in its definition. We exploited the exclusive presence of coherences of +/-4,+/-6,+/-8, besides 0 and +/-2 under the W condition to measure the spin-lattice relaxation time T(W) accurately, so avoiding experimental difficulties that usually impair dipolar order relaxation measurement such as Zeeman contamination at high fields and also superposition of the different quasi-invariants. This procedure opens the possibility of measuring the spin-lattice relaxation of a quasi-invariant independent of the Zeeman and S reservoirs, so incorporating a new relaxation parameter useful for studying the complex molecular dynamics in mesophases. In fact, we report the first measurement of T(W) in a LC at high magnetic fields. Comparison of the obtained value with the one corresponding to a lower field (16 MHz) points out that the relaxation of the W-order strongly depends on the intensity of the external magnetic field, similarly to the case of the S reservoir, indicating that the relaxation of the W-quasi-invariant is also governed by the cooperative molecular motions.

Proton spin system in pentacene and its interaction with photoexcited triplet electron spin

AbstractReading of single spin states is the main experimental problem in quantum computing. Pentacene is one of a few molecules on which the optical read‐out of single spin experiments were performed. The shape of optical single molecule spectroscopy (ODMR) signal depends on an interaction of triplet state of two unpaired electron spins with proton bath. These protons form a Heisenberg chain with N = 14 nodes. We investigate the symmetry of this system in selected inversed spin sectors of 214 nuclear spin configurations. In particular all exact Bethe solutions for two reversed spins have been derived. The interaction of electron and proton spin systems has been addressed. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)

1H NMR spectra and echoes in Pd–H and Pd–Ag–H alloys

The paper presents the experimental results of rigid-lattice proton magnetic resonance spectra and second moments in Pd–H, Pd 0.90Ag 0.10–H, Pd 0.80Ag 0.20–H, Pd 0.75Ag 0.25–H, and Pd 0.65Ag 0.35–H alloys at T = 2.4 K in a wide hydrogen concentration range. Free induction decay (FID), solid and inhomogeneous echoes were detected and interpreted. The interpretation based on dipole–dipole interaction of homogeneously distributed proton spin system is satisfactory at high hydrogen concentration, but an inhomogeneous field of paramagnetic origin (most probably coming from Fe impurities) plays the dominant role at small hydrogen content. An unexpected correlation was found between the macroscopic magnetic susceptibility and the second moment coming from the inhomogeneous internal field.

Long-lived nuclear spin states in the solution NMR of four-spin systems

The existence of long-lived nuclear spin states in four-spin systems is explored by solution-state NMR experiments. Long-lived states are proved to exist in three different natural product molecules, each containing either a AA′ BB′ or a AA′ XX′ proton spin system. The measured state lifetimes are between four and eight times the spin–lattice relaxation time constants.