Polarization Transfer Effects Research Articles

Looped-PROjected SpectroscopY (L-PROSY): A simple approach to enhance backbone/sidechain cross-peaks in 1H NMR

Cross-relaxation and isotropic mixing phenomena leading to the Nuclear Overhauser Effect (NOE) and to the TOCSY experiment, lie at the center of structural determinations by NMR. 2D TOCSY and NOESY exploit these polarization transfer effects to determine inter-site connectivities and molecular geometries under physiologically-relevant conditions. Among these sequences’ drawback, particularly for the case of NOEs, are a lack of sensitivity arising from small structurally-relevant cross peaks. The present study explores the application of multiple Zeno-like projective measurements, to enhance the cross-peaks between spectrally distinct groups in proteins –in particular between amide and aliphatic protons. The enhancement is based on repeating the projection done by Ramsey or TOCSY blocks multiple times, in what we refer to as Looped, PROjected Spectroscopy (L-PROSY). This leads to a reset of the amide/aliphatic transfer processes; the initial slopes of the NOE- or J-transfer effects thus define the cross-peak growth, and a faster cross-peak buildup is achieved upon looping these transfers over the allotted time T1. These projections also help to better preserve the magnetization originating in the amides, resulting in an overall improvement in sensitivity. L-PROSY’s usefulness is demonstrated by incorporating it into two widely used protein NMR experiments: 2D 15N-1H HMQC-NOESY and 15N-filtered 2D NOESY. Different parameters dictating the overall SNR improvement, particularly the protein correlation times and the amide-water chemical exchange rates, were examined, and L-PROSY’s enhancements resulted for all tested proteins. The largest cross-peak enhancements were observed for unstructured proteins, where chemical exchanges with the solvent of the kind that tend to average out NOE cross-peaks in conventional NMR, boost L-PROSY’s cross-peaks by replenishing the amide’s magnetizations within each loop. Enhanced cross-peaks were also found in extensions involving TOCSY-based experiments when applied to proteins with unfolded segments.

Polarization transfer in x-ray transitions due to photoionization in highly charged copper-like ions

Using the density matrix theory and the multi-configuration Dirac–Fock method, the subshell photoionization of highly charged ions is studied, together with their subsequent radiative decay. The effects of polarization transfer on the linear polarization and angular distribution of the characteristic line photoemission for selected Cu-like Zn+, Ba27+, , and ions are investigated. Our results show that the polarization transfer, arising from the originally polarized incident light, may lead to a considerable change in the alignment parameters and the polarization properties of the radiation, the character of which is highly sensitive to the initial photon polarization, yet virtually independent of the photon energy. These characteristics are very similar to those of the electron bremsstrahlung process reported by Märtin et al (2012 Phys. Rev. Lett. 108 264801). The present results are compared with available experimental results and show a good quantitative agreement.

Nonlinear self-polarization of Raman amplified light in fibers

We make a theoretical analysis of the energy transfer from an elliptically polarized pump to vectorial Stokes waves in a Raman amplification process. The analysis is done for cw waves using the general vectorial relations for the Raman susceptibility. In the circular-polarization basis, a simple equation is obtained when the phase shift between circularly polarized components is large, so that the phase-dependent components can be ignored as a result of averaging over propagation length. We show that for realistic initial conditions, most of the input energy of the elliptically polarized pump can transfer to a circularly polarized Stokes wave—an effect that was recently observed in experiments with pulse breakup and broadband spectrum formation in twisted fibers. Numerical simulations were carried out for a fixed ratio of 0.3 between the orthogonal and parallel Raman gains; this is the experimentally measured value for small Raman frequency shifts in silica fibers. The simulation shows that the polarization transfer effect is more pronounced when the input Stokes wave ellipticity coincides with the pump ellipticity.

Physics of radio emission in gamma-ray pulsars

Propagation of radio emission in a pulsar magnetosphere is reviewed. The effects of polarization transfer, induced scattering and reprocessing to high energies are analysed with a special emphasis on the implications for the gamma-ray pulsars. The possibilities of the pulsar plasma diagnostics based on the observed radio pulse characteristics are also outlined. As an example, the plasma number density profiles obtained from the polarization data for the Vela and the gamma-ray millisecond pulsars J1446-4701, J1939+2134 and J1744-1134 are presented. The number densities derived tend to be the highest/lowest when the radio pulse leads/lags the gamma-ray peak. In the PSR J1939+2134, the plasma density profiles for the main pulse and interpulse appear to fit exactly the same curve, testifying to the origin of both radio components above the same magnetic pole and their propagation through the same plasma flow in opposite directions. The millisecond radio pulse components exhibiting flat position angle curves are suggested to result from the induced scattering of the main pulse by the same particles that generate gamma rays. This is believed to underlie the wide-sense radio/gamma-ray correlation in the millisecond pulsars. The radio quietness of young gamma-ray pulsars is attributed to resonant absorption, whereas the radio loudness to the radio beam escape through the periphery of the open field line tube.

Importance of polarization transfer in reaction products for interpreting and analyzing CIDNP at low magnetic fields

The magnetic field dependence of Chemically Induced Dynamic Nuclear Polarization (CIDNP) was studied for the amino acids N-acetyl histidine, N-acetyl tryptophan and N-acetyl tyrosine. It is demonstrated that at low field CIDNP is strongly affected by polarization redistribution in the diamagnetic molecules. Such a polarization transfer is of coherent nature and is due to spin coherences formed together with non-equilibrium population of the spin states. These coherences clearly manifest themselves in an oscillatory time dependence of polarization. Polarization transfer effects are most pronounced at nuclear spin Level Anti-Crossings (LACs), which also result in sharp features in the CIDNP field dependence. Thus, polarization transfer is an important factor, which has to be taken into account in order to interpret low-field CIDNP data on both qualitative and quantitative level. Possible applications of polarization transfer phenomena are also discussed in the paper. In particular, the role of LACs in spin order transfer is highlighted: LACs provide a new tool for precise manipulation of spin hyperpolarization and NMR enhancement of selected target spins.

Coherent Polarization Transfer Effects Are Crucial for Interpreting Low-Field CIDNP Data

In this work we demonstrate that low-field chemically induced dynamic nuclear polarization (CIDNP) is strongly affected by re-distribution of polarization, which is formed in the course of spin evolution in transient radical pairs, in diamagnetic reaction products. This phenomenon is of importance when the spins of the reaction product are coupled strongly meaning that spin–spin interactions between them are comparable to the differences in their Zeeman interactions with the external magnetic field. In this case, polarization transfer relies on a coherent mechanism; as a consequence, spins can acquire significant polarization even when they have no hyperfine coupling to the electron spins in the radical pairs, i.e., cannot be polarized directly by CIDNP. This is demonstrated by taking CIDNP of n-butylamine as an example: in this case only the α-CH2 protons are polarized directly, which is confirmed by high-field CIDNP, whereas the β-CH2, γ-CH2 and δ-CH3 protons get polarized only indirectly due to the transfer of polarization from the α-CH2 protons. These results show that low-field CIDNP data should be interpreted with care to discriminate between the effects of spin evolution in transient radical pairs and in diamagnetic reaction products.

Coherent transfer of nuclear spin polarization in field-cycling NMR experiments

Coherent polarization transfer effects in a coupled spin network have been studied over a wide field range. The transfer mechanism is based on exciting zero-quantum coherences between the nuclear spin states by means of non-adiabatic field jump from high to low magnetic field. Subsequent evolution of these coherences enables conversion of spin order in the system, which is monitored after field jump back to high field. Such processes are most efficient when the spin system passes through an avoided level crossing during the field variation. The polarization transfer effects have been demonstrated for N-acetyl histidine, which has five scalar coupled protons; the initial spin order has been prepared by applying RF-pulses at high magnetic field. The observed oscillatory transfer kinetics is taken as a clear indication of a coherent mechanism; level crossing effects have also been demonstrated. The experimental data are in very good agreement with the theoretical model of coherent polarization transfer. The method suggested is also valid for other types of initial polarization in the spin system, most notably, for spin hyperpolarization.

Dynamic Nuclear Polarization with Polychlorotriphenylmethyl Radicals: Supramolecular Polarization-Transfer Effects

Ups and downs of DNP: Polychlorinated trityl radicals (see structure: C black, Cl green, Na gray, O red) used for dynamic nuclear polarization (DNP) showed a new transfer mechanism involving quadrupolar chlorine nuclei. The observation of positive or negative enhancements, depending on the substrate, highlights the supramolecular character of the initial polarization-transfer process.

Simultaneous effects of relaxation and polarization transfer in LaF 3-type crystals as sources of dynamic information

Fluorine nuclear magnetic resonance (NMR) spin-lattice relaxation dispersion has been measured for pure LaF 3 and La 1− x Sr x F 3− x for admixture concentrations x ranging from 0.01% up to 16%. The relaxation dispersion experiments have been carried out in a wide frequency range (20 kHz–40 MHz) at temperatures between 300 and 1400 K. The data have been analyzed using the recently published [J. Magn. Res. 179 (2006) 250] relaxation model for multispin systems of mutually interacting quadrupolar and dipolar nuclei. Rate constants of the fluorine ionic jumps within and among distinct fluorine sublattices have been extracted. Characteristic effects of the polarization transfer between fluorine and lanthanum spins have been observed and attributed to slow dynamics within one of the fluorine sublattices.

Evolution of solid state systems containing mutually coupled dipolar and quadrupole spins: Perturbation treatment

Perturbation approach to time evolution of multi-spin systems containing quadrupole and dipolar spins has been presented and discussed. The treatment comprises polarization transfer effects, field-dependent relaxation processes of dipolar as well as quadrupole spins and combined results of both of them. Complete theories dealing with various aspects of the spin dynamic processes have been proposed. Because of an educational character of this paper, relevant assumptions, limitations and even particular steps of the proposed treatments have been discussed in detail. Special emphasis is put on understanding of validity regimes of the perturbation treatment, depending on relative strengths of spin interactions and timescales of relevant motional processes affecting them. Motional regimes required for spins to be involved in essentially different evolution pathways like polarization transfers or relaxation have been illustrated by experimental examples.

Radiative corrections to polarized inelastic scattering in the coincidence setup

The coplete analysis of the model-independent leading radiative corrections to cross-section and polarization observables in semi-inclusive deep-inelastic electron-nucleus scattering with detection of a proton and scattered electron in coincidence has been performed. The basis of the calculations consists of the Drell-Yan like representation in electrodynamics for both spin-independent and spin-dependent parts of the cross-section in terms of the electron structure functions. The applications to the polarization transfer effect from longitudinally polarized electron beam to detected proton as well as to scattering by the polarized target are considered.

A systematic study of the lactate lineshape in PRESS‐localized proton spectroscopy

J-coupled resonances such as lactate exhibit complex behavior in PRESS-localized spectroscopy. Polarization transfer effects due to nonideal slice profiles can lead to substantial errors in quantification unless recognized. In this work, it is shown how these effects can be predicted in a systematic way given the sequence timing and the RF pulse envelopes. Experimental results are presented to highlight the problems of working at the popular echo time of 2/J.

Adiabatic transfer of net electron polarization to nuclear polarization

A new type of spin chemical experiment is suggested which utilizes adiabatic reversion of a low magnetic B 0 field for an efficient transfer of net electron spin polarization, as arising from some CIDEP mechanism, to the nuclear polarization of radicals. After trapping the radicals in diamagnetic products and transferring the sample to a NMR probe, the adiabatic polarization transfer effect can be measured as induced CIDNP, as in the recently established SNP method. The optimum conditions concerning delay time and duration of the B 0 field switching, as well as the trapping rate constant are analysed quantitatively for a radical with one nuclear spin I = 1/2. Owing to their efficiency and some parameters that can be controlled in the experiment, adiabatic polarization transfer effects should have clear advantages over experiments relying on DNP effects due to the Overhauser mechanism.

Polarization-Transfer Effects in Localized Double-Spin-Echo Spectroscopy of Weakly Coupled Homonuclear Spin Systems

In point-resolved spectroscopy (PRESS), fast echo-time-dependent signal modulations of the multiplets of weakly coupled homonuclear spin systems occur. They are caused by polarization-transfer effects that are explained by calculations with the product-operator formalism. The impact of slice profiles and transmitter adjustment and the difference of the polarization-transfer effects between AX and AX 3 systems are explained. Experiments with echo-time variation were performed with slice-selective pulses of different quality of profile. Experiments were carried out with a solution of calcium lactate in a 1.5 T Siemens whole-body imager. The experimental results confirm the theoretical calculations. It is stated that in localized double-spin-echo spectroscopy, especially at echo times of TE = 2/ J, the polarization-transfer effects must be considered. This knowledge is important in lactate spectroscopy in vivo, where the assumptions for 2/ J range between 270 and 290 ms, leading to different signal intensities of lactate in PRESS spectra.

Band-selective spin echoes for in vivo localized 1H NMR spectroscopy.

This study describes a new single spin-echo spatial localization sequence, BASSALE or BAnd-Selective Spin echo Acquisition for Localized Editing, that overcomes a number of the limitations of the STEAM and PRESS volume selection pulse sequences. It achieves conformal volume localization in a single shot by spatially tailored suppression of all magnetization outside a 2D region of interest followed by selection of a single orthogonal slice. This separation of spatial localization from the echo formation process has permitted use of a spectrally selective cosine-modulated sinc refocusing pulse to acquire localized 1H spectra with the water suppression efficiency of STEAM and the sensitivity of PRESS. Echoes formed by such spectrally selective pulses have been termed band-selective spin echoes. The BASSALE sequence attains shorter echo times than PRESS, inhibits scalar spin-spin interactions to permit localized editing and T2 relaxometry of metabolites with J-coupled spins (e.g., lactate), is insensitive to homonuclear multiple-quantum and polarization transfer effects, and can be made sensitive or insensitive to spin displacement effects. Applications are shown both with phantoms and in situ in the rat brain.

NMR Study of the Solution-State Dynamics and Solid-State Structure of Tri-n-butyltin Fluoride

Dynamics and structure of tri-n-butyltin fluoride in n-hexane solutions were probed using (tin-119) nuclear magnetic resonance spin relaxation methodologies. Significant relaxation-induced polarization transfer effects were observed and exploited. The experimental observations indicate that the tri-n-butyl fluoride exists in a polymeric form in solution. For a 0.10% (w/w) solution at 25 [degree]C, NMR reveals significant orientational/exchange relaxation on both the microsecond and nanosecond time scales. Solution-state and solid-state parameters are compared and contrasted. 26 refs., 3 figs., 1 tab.

Photochemically induced nuclear polarization study of the accessibility of tyrosines in insulin

The accessible tyrosines of bovine insulin were studied by the photochemically induced dynamic nuclear polarization (photo-CIDNP) method. Tyrosine 1H nuclear polarization is observed in acidic, neutral, and basic solutions at all concentrations studied, in the absence of added salts as well as in the presence of 0.05-0.1 M chloride or phosphate. At pH 2.1 in the presence of chloride, at concentrations of 640 microM and above, most of the nuclear polarization at delta 6.82 originates from one group of tyrosines. On the basis of the crystallographic model, these are assumed to be the A14 tyrosines. We explored the possibility of a genuine concentration dependence of the photo-CIDNP intensity of insulin due to aggregation. In order to discern between such effects and trivial kinetic effects traceable to the optical irradiation method, the effects of concentration changes on polarization were examined in three apparently nonassociating trypsin inhibitor proteins. In insulin, the intensity of Tyr-A 14 polarization changes slowly at concentrations above 1 mM, suggesting that these residues are similarly accessible in all association states. At insulin concentrations below 320 microM, additional tyrosine emission signals were observed. These signals are probably due to B16 and B26 tyrosines of monomers. Polarization transfer effects from Tyr-A14 are evident in the tetramer and hexamer. Enhanced absorption effects in the two histidines (B5 and B10) of the insulin monomer were observed at pH 10 in the presence of 0.1 M phosphate.

Polarization transfer effects in ( [formula omitted] reactions on light nuclei at θ = 0°

Transverse polarization transfer coefficients K y y′ have been measured at a reaction angle of 0° for the reactions 9 Be( p , n ) 9 B, 11 C and 13 C( p , n ) 13 N . In the energy range covered by these measurements, i.e., from about 7 to 15 MeV, the K y y′ (0) values are generally positive. The polarization transfer excitation functions all show considerable structure which we largely attribute to compound nucleus effects.