Polarization Transfer Methods Research Articles

Polarization transfer methods for quantitative analysis of flowing mixtures with benchtop 13C NMR spectroscopy.

Benchtop NMR spectroscopy is attractive for process monitoring; however, there are still drawbacks that often hamper its use, namely, the comparatively low spectral resolution in 1H NMR, as well as the low signal intensities and problems with the premagnetization of flowing samples in 13C NMR. We show here that all these problems can be overcome by using 1H-13C polarization transfer methods. Two ternary test mixtures (one with overlapping peaks in the 1H NMR spectrum and one with well-separated peaks, which was used as a reference) were studied with a 1T benchtop NMR spectrometer using the polarization transfer sequence PENDANT (polarization enhancement that is nurtured during attached nucleus testing). The mixtures were analyzed quantitatively in stationary as well as in flow experiments by PENDANT enhanced 13C NMR experiments, and the results were compared with those from the gravimetric sample preparation and from standard 1H and 13C NMR spectroscopy. Furthermore, as a proxy for a process monitoring application, continuous dilution experiments were carried out, and the composition of the mixture was monitored in a flow setup by 13C NMR benchtop spectroscopy with PENDANT. The results demonstrate the high potential of polarization transfer methods for applications in quantitative process analysis with benchtop NMR instruments, in particular with flowing samples.

Inside Cover: A Single‐Scan Ultraselective Heteronuclear Polarization Transfer Method for Unambiguous Complex Structure Assignment (Angew. Chem. Int. Ed. 32/2023)

The unambiguous assignment of NMR signals to complex organic molecules or mixtures is a challenge. In their Research Article (e202304196), Jin Wook Cha, Min-Seon Kim, and Jin-Soo Park suggest an ultrahigh-resolution single-scan NMR method that enables to acquire a hertz-level signal selectivity in both 1H, 13C and their correlation spectra. The method was applied to compounds with high NMR signal complexity, such as chromopeptide and diastereomeric mixtures, and resulted in complete 1H and 13C NMR signal assignment of individual subunits and epimers.

Innentitelbild: A Single‐Scan Ultraselective Heteronuclear Polarization Transfer Method for Unambiguous Complex Structure Assignment (Angew. Chem. 32/2023)

The unambiguous assignment of NMR signals to complex organic molecules or mixtures is a challenge. In their Research Article (e202304196), Jin Wook Cha, Min-Seon Kim, and Jin-Soo Park suggest an ultrahigh-resolution single-scan NMR method that enables to acquire a hertz-level signal selectivity in both 1H, 13C and their correlation spectra. The method was applied to compounds with high NMR signal complexity, such as chromopeptide and diastereomeric mixtures, and resulted in complete 1H and 13C NMR signal assignment of individual subunits and epimers.

A Single‐Scan Ultraselective Heteronuclear Polarization Transfer Method for Unambiguous Complex Structure Assignment

AbstractComplex nuclear magnetic resonance (NMR) signals of organic compounds containing multiple analogous substructures or mixtures pose a significant challenge to structural identification, thus resulting in frequent misassignment of structures. The GEMSTONE method, a single‐scan technique that selectively excites a specific proton signal among the crowded NMR signals, was recently proposed as a solution. However, its extension to the polarization transfer method for heteronuclear spin systems was unsuccessful. Herein, we present an extension method that addresses the altered heteronuclear polarization transfer efficiency and enables the acquisition of ultraselective 13C and 1H‐13C correlation NMR subspectra with hertz‐level signal selectivity in both dimensions. We demonstrate the effectiveness of this technique in the structural analysis of a chromopeptide pharmaceutical and a diastereomeric mixture of a fungicide.

A Single-Scan Ultraselective Heteronuclear Polarization Transfer Method for Unambiguous Complex Structure Assignment.

Complex nuclear magnetic resonance (NMR) signals of organic compounds containing multiple analogous substructures or mixtures pose a significant challenge to structural identification, thus resulting in frequent misassignment of structures. The GEMSTONE method, a single-scan technique that selectively excites a specific proton signal among the crowded NMR signals, was recently proposed as a solution. However, its extension to the polarization transfer method for heteronuclear spin systems was unsuccessful. Here, we present an extension method that addresses the altered heteronuclear polarization transfer efficiency and enables the acquisition of ultraselective 13C and 1H-13C correlation NMR subspectra with hertz-level signal selectivity in both dimensions. We demonstrate the effectiveness of this technique in the structural analysis of a chromopeptide pharmaceutical and a diastereomeric mixture fungicide.

Proton and neutron form factors with quark orbital excitations

Nucleon form factors play an especially important role in studying the dynamics of nucleons and explicit structure of the wave functions at arbitrary nucleon velocity. The purpose of the paper is to explain theoretically all four nucleon form factors measured experimentally in the cross section measurements (by the Rosenbluth method), yielding almost equal normalized form factors $G^p_E,G^p_M,G^n_M$, as well as in the polarization transfer experiments, where a strongly decreasing proton electric form factor has been discovered. It is shown, using relativistic hyperspherical formalism, that the nucleon wave functions in the lowest approximation provide almost equal normalized form factors as seen in the Rosenbluth cross sections, but in the higher components they contain a large admixture of the quark orbital momenta, which strongly decreases $G^p_E$ and this effect is possibly detected in the polarization transfer method (not seen in the classical cross section experiments). Moreover, the same admixture of the higher components explains the small positive form factor $G^n_E$. The resulting form factors, $G^p_M(Q),G^p_E(Q),G^n_M(Q)$ are calculated up to $Q^2\approx 10$ GeV$^2$, using the standard and the Lorentz contracted wave functions and shown to be in reasonable agreement with experimental data.

New prediction of elastic scattering cross sections ratio Re+ e− based on phenomenological two-photon exchange corrections

The proton’s electric and magnetic form factors (FFs) and their ratio Rp = are fundamental and essential ingredients needed to parametrize the internal structure of the proton as well as many composite particles. However, the inconsistency in the results reported on these FFs and their ratio as measured by the Rosenbluth method and the polarization transfer method has led the community to believe that such a discrepancy is due to a systematic difference between the two methods. It was proposed that missing higher order radiative correction to the electron-proton elastic scattering cross section σR (ϵ, Q 2) and in particular two-photon exchange correction (TPE) should be applied in order to reconcile these measurements. The effect of TPE on electron-proton scattering observables was studied extensively in the last few years. However, the most direct method for measuring TPE contributions is the comparison of positron-proton and electron-proton elastic scattering cross sections ratio Re+ e− (ϵ, Q 2). In this proceedings, I present a new prediction of the ratio Re+ e− as determined using a new parametrization of TPE corrections to σR . I then compare my results to several previous phenomenological extractions, TPE hadronic calculations, and previous and recent direct measurements of Re+ e− .

Proton form factor ratio μpGEp/GMp from double spin asymmetry

The ratio of the electric and magnetic form factor of the proton, $\mu_p G_E^p/G_M^p$, has been measured for elastic electron-proton scattering with polarized beam and target up to four-momentum transfer squared, $Q^2=5.66$ (GeV/c)$^2$ using the double spin asymmetry for target spin orientation aligned nearly perpendicular to the beam momentum direction. This measurement of $\mu_p G_E^p/G_M^p$ agrees with the $Q^2$ dependence of previous recoil polarization data and reconfirms the discrepancy at high $Q^2$ between the Rosenbluth and the polarization-transfer method with a different measurement technique and systematic uncertainties uncorrelated to those of the recoil-polarization measurements. The form factor ratio at $Q^2$=2.06 (GeV/c)$^2$ has been measured as $\mu_p G_E^p/G_M^p = 0.720 \pm 0.176_{stat} \pm 0.039_{sys}$, which is in agreement with an earlier measurement with the polarized target technique at similar kinematics. The form factor ratio at $Q^2$=5.66 (GeV/c)$^2$ has been determined as $\mu_p G_E^p/G_M^p=0.244\pm0.353_{stat}\pm0.013_{sys}$, which represents the highest $Q^2$ reach with the double spin asymmetry with polarized target to date.

Multifunctional biocomposites based on collagen and keratin with properties for agriculture and industry applications

In this work, we optimize the performance of a previously proposed method for transferring parahydrogen induced polarization to “insensitive” spin-1/2 NMR (Nuclear Magnetic Resonance) nuclei, which have low gyromagnetic ratio and low natural abundance. By optimizing the reaction conditions and pressure of the parahydrogen gas and using adiabatically switched radiofrequency fields we achieve high polarization transfer efficiency and report carbon spin polarization of dimethyl acetylene dicarboxylate reaching 35%, which corresponds to 13C NMR signal enhancements of about 43,000 at 9.4 Tesla. Such polarization levels allow one to work with mM concentrations at natural carbon abundance and to detect 13C NMR signal in single scan. In combination with a pseudo phase cycle, the polarization transfer method used here also enables efficient suppression of unwanted background signals.

Polarization of low-γ nuclei by transferring spin order of parahydrogen at high magnetic fields.

In this work, we optimize the performance of a previously proposed method for transferring parahydrogen induced polarization to "insensitive" spin-1/2 NMR (Nuclear Magnetic Resonance) nuclei, which have low gyromagnetic ratio and low natural abundance. By optimizing the reaction conditions and pressure of the parahydrogen gas and using adiabatically switched radiofrequency fields we achieve high polarization transfer efficiency and report carbon spin polarization of dimethyl acetylene dicarboxylate reaching 35%, which corresponds to 13C NMR signal enhancements of about 43,000 at 9.4 Tesla. Such polarization levels allow one to work with mM concentrations at natural carbon abundance and to detect 13C NMR signal in single scan. In combination with a pseudo phase cycle, the polarization transfer method used here also enables efficient suppression of unwanted background signals.

14N overtone NMR under MAS: Signal enhancement using cross-polarization methods.

Polarization transfer methods are widely adopted for the purpose of correlating different nuclear species as well as to achieve signal enhancement. Polarization transfer from 1H to the 14N overtone transition (Δm = 2) can be achieved using cross polarization methods under magic-angle spinning conditions, where spin locks of the order of several milliseconds can be obtained on common bio-solids (α-glycine and N-acetylvaline). Signal enhancement factors up to 4.4 per scan, can be achieved under favorable conditions, despite MHz-sized quadrupolar interaction. Moreover, we present a detailed theoretical treatment and accurate numerical simulations which are in excellent agreement the unusual experimental matching conditions observed for cross-polarization to 14N overtone.

Low-Field Nuclear Polarization Using Nitrogen Vacancy Centers in Diamonds.

It was recently demonstrated that bulk nuclear polarization can be obtained using nitrogen vacancy (NV) color centers in diamonds, even at ambient conditions. This is based on the optical polarization of the NV electron spin, and using several polarization transfer methods. One such method is the nuclear orientation via electron spin locking (NOVEL) sequence, where a spin-locked sequence is applied on the NV spin, with a microwave power equal to the nuclear precession frequency. This was performed at relatively high fields, to allow for both polarization transfer and noise decoupling. As a result, this scheme requires accurate magnetic field alignment in order preserve the NV properties. Such a requirement may be undesired or impractical in many practical scenarios. Here we present a new sequence, termed the refocused NOVEL, which can be used for polarization transfer (and detection) even at low fields. Numerical simulations are performed, taking into account both the spin Hamiltonian and spin decoherence, and we show that, under realistic parameters, it can outperform the NOVEL sequence.

Comparison of direct 13C and indirect 1H-[13C] MR detection methods for the study of dynamic metabolic turnover in the human brain

A wide range of direct 13C and indirect 1H-[13C] MR detection methods exist to probe dynamic metabolic pathways in the human brain. Choosing an optimal detection method is difficult as sequence-specific features regarding spatial localization, broadband decoupling, spectral resolution, power requirements and sensitivity complicate a straightforward comparison. Here we combine density matrix simulations with experimentally determined values for intrinsic 1H and 13C sensitivity, T1 and T2 relaxation and transmit efficiency to allow selection of an optimal 13C MR detection method for a given application and magnetic field. The indirect proton-observed, carbon-edited (POCE) detection method provides the highest accuracy at reasonable RF power deposition both at 4T and 7T. The various polarization transfer methods all have comparable performances, but may become infeasible at 7T due to the high RF power deposition. 2D MR methods have limited value for the metabolites considered (primarily glutamate, glutamine and γ-amino butyric acid (GABA)), but may prove valuable when additional information can be extracted, such as isotopomers or lipid composition. While providing the lowest accuracy, the detection of non-protonated carbons is the simplest to implement with the lowest RF power deposition. The magnetic field homogeneity is one of the most important parameters affecting the detection accuracy for all metabolites and all acquisition methods.

71Ga-77Se connectivities and proximities in gallium selenide crystal and glass probed by solid-state NMR

We introduce two-dimensional (2D) 71Ga-77Se through-bond and through-space correlation experiments. Such correlations are achieved using (i) the J-mediated Refocused Insensitive Nuclei Enhanced by Polarization Transfer (J-RINEPT) method with 71Ga excitation and 77Se Carr-Purcell-Meiboon-Gill (CPMG) detection, as well as (ii) the J- or dipolar-mediated Hetero-nuclear Multiple-Quantum Correlation (J- or D-HMQC) schemes with 71Ga excitation and quadrupolar CPMG (QCPMG) detection. These methods are applied to the crystalline β-Ga2Se3 and the 0.2Ga2Se3-0.8GeSe2 glass. Such glass leads to a homogeneous and reproducible glass–ceramic, which is a good alternative to single-crystalline Ge and polycrystalline ZnSe materials for making lenses transparent in the IR range for thermal imaging applications. We show that 2D 71Ga-77Se correlation experiments allow resolving the 77Se signals of molecular units, which are not resolved in the 1D 77Se CPMG spectrum. Additionally, the build-up curves of the J-RINEPT and the J-HMQC experiments allow the estimate of the 71Ga-77Se J-couplings via one and three-bonds in the three-dimensional network of β-Ga2Se3. Furthermore, these build-up curves show that the one-bond 1J71Ga-77Se couplings in the 0.2Ga2Se3-0.8GeSe2 glass are similar to those measured for β-Ga2Se3. We also report 2D 71Ga Satellite Transition Magic-Angle Spinning (STMAS) spectrum of β-Ga2Se3 using QCPMG detection at high magnetic field and high Magic-Angle Spinning frequency using large radio frequency field. Such spectrum allows separating the signal of β-Ga2Se3 and that of an impurity.

$\Delta (1232)$ resonance contribution to two-photon exchange in electron-proton scattering revisited

We revisit the question of the contributions of two-photon exchange with $\Delta(1232)$ excitation to the electron-proton scattering in a hadronic model. Three improvements over the previous calculations are made, namely, correct vertex function for $\gamma N\rightarrow\Delta$, realistic $\gamma N\Delta$ form factors, and coupling constants. The discrepancy between the values of $R\equiv \mu_p G_E/G_M$ extracted from Rosenbluth technique and polarization transfer method can be reasonably accounted for if the data of Andivahis {\it et al.} \cite{Andivahis94} are analyzed. However, substantial discrepancy remains if the data of Qattan {\it et al.} \cite{Qattan05} are used. For the ratio $R^\pm$ between $e^\pm p$ scatterings, our predictions appear to be in satisfactory agreement with the preliminary data from VEPP-3. The agreement between our model predictions and the recent measurements on single spin asymmetry, transverse and longitudinal recoil proton polarizations ranges from good to poor.

Proton form factors and two-photon exchange in elastic electron-proton scattering

Proton electromagnetic form factors are among the most important sources of information about the internal structure of the proton. Two different methods for measuring these form factors, the method proposed by Rosenbluth and the polarization-transfer method, yield contradictory results. It is assumed that this contradiction can be removed upon taking into account the hard part of the contribution of two-photon exchange to the cross section for elastic electron-proton scattering. This contribution can measured experimentally via a precision comparison of the cross sections for the elastic scattering of positrons and electrons on protons. Such a measurement, performed at the VEPP-3 storage ring in Novosibirsk at the beam energies of 1.6 and 1.0 GeV for positron (electron) scattering angles in the ranges of θe = 15°–25° and 55°–75° in the first case and in the range of θe = 65°–105° in the second case is described in the present article. Preliminary results of this experiment and their comparison with theoretical predictions are described.

Measurement of the Two-Photon Exchange Contribution to the Elastice±pScattering Cross Sections at the VEPP-3 Storage Ring

The ratio of the elastic e(+)p to e(-)p scattering cross sections has been measured precisely, allowing the determination of the two-photon exchange contribution to these processes. This neglected contribution is believed to be the cause of the discrepancy between the Rosenbluth and polarization transfer methods of measuring the proton electromagnetic form factors. The experiment was performed at the VEPP-3 storage ring at beam energies of 1.6 and 1.0 GeV and at lepton scattering angles between 15° and 105°. The data obtained show evidence of a significant two-photon exchange effect. The results are compared with several theoretical predictions.

The Proton Form Factor Ratio Measurements at Jefferson Lab

The ratio of the proton form factors, GEp/GMp, has been measured from Q2 of 0.5 GeV2 to 8.5 GeV2, at the Jefferson Laboratory, using the polarization transfer method. This ratio is extracted directly from the measured ratio of the transverse and longitudinal polarization components of the recoiling proton in elastic electron-proton scattering. The discovery that the proton form factor ratio measured in these experiments decreases approximately linearly with four-momentum transfer, Q2, for values above ? 1 GeV2, is one of the most significant results to come out of JLab. These results have had a large impact on progress in hadronic physics; and have required a significant rethinking of nucleon structure. The increasingly common use of the double-polarization technique to measure the nucleon form factors, in the last 15 years, has resulted in a dramatic improvement of the quality of all four nucleon electromagnetic form factors, GEp, GMp, GEn and GMn. There is an approved experiment at JLab, GEP(V), to continue the ratio measurements to 12 GeV2. A dedicated experimental setup, the Super Bigbite Spectrometer (SBS), will be built for this purpose. It will be equipped with a focal plane polarimeter to measure the polarization of the recoil protons. The scattered electrons will be detected in an electromagnetic calorimeter. In this presentation, I will review the status of the proton elastic electromagnetic form factors and discuss a number of theoretical approaches to describe nucleon form factors.

EM Form Factors and OLYMPUS

The elastic form factors of the nucleon characterize the distributions of charge and magnetization in momentum space and are important input for calculations of strong interaction phenomena and nuclear structure. The dramatic discrepancy in the observed ratio of elastic proton form factors between the Rosenbluth separation and polarization transfer methods has invoked numerous theoretical and experimental investigations. The previously neglected effect from two-photon exchange has become the favored explana- tion for the discrepancy. While the effect can not be calculated from first principles, it can be verified experimentally in several ways, most stringently by comparing the positron- proton and electron-proton elastic cross sections. The OLYMPUS experiment at DESY has been carried out to quantify the effect of two-photon exchange using intense stored positron and electron beams along with an internal unpolarized hydrogen target and a large acceptance detector to measure the ratio of the positron-proton and electron-proton elastic scattering cross sections. The status of proton form factor measurements and of the experimental efforts to verify the effect of two-photon exchange is presented, with some emphasis on the OLYMPUS experiment.

Probing two-photon exchange with OLYMPUS

Two-photon exchange is believed to be responsible for the discrepancies in the proton electric to magnetic form factor ratio found with the Rosenbluth and polarization transfer methods. If this explanation is correct, one expects significant di erences in the lepton-proton cross sections between positrons and electrons. The OLYMPUS experi- ment at DESY in Hamburg, Germany was designed to measure the ratio of unpolarized positron-proton and electron-proton elastic scattering cross sections over a wide kine- matic range with high precision, in order to quantify the e ect of two-photon exchange. The experiment used intense beams of electrons and positrons stored in the DORIS ring at 2.0 GeV interacting with an internal windowless hydrogen gas target. The current status of OLYMPUS will be discussed.