Net NMR alignment by adiabatic transport of parahydrogen addition products to high magnetic field
TL;DR: In this article, a field-cycling method is demonstrated whereby the nuclear spin order of para-enriched H2 is inserted adiabatically into a product molecule formed by molecular addition.
About: This article is published in Chemical Physics Letters.The article was published on 1988-04-08. It has received 366 citations till now. The article focuses on the topics: Nuclear magnetic resonance spectroscopy & Spin polarization.
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TL;DR: Nuclear magnetic resonance (NMR) spectroscopy continues to evolve as a primary technique in the study of solids as discussed by the authors, enabling increasingly complex structural and dynamical behavior to be probed at a molecular level and thus add to our understanding of macroscopic properties of materials.
Abstract: Nuclear magnetic resonance (NMR) spectroscopy continues to evolve as a primary technique in the study of solids. This review briefly describes some developments in modern NMR that demonstrate its exciting potential as an analytical tool in fields as diverse as physics, chemistry, biology, geology, and materials science. Topics covered include motional narrowing by sample reorientation, multiple-quantum and overtone spectroscopy, probing porous solids with guest atoms and molecules, two-dimensional NMR studies of chemical exchange and spin diffusion, experiments at extreme temperatures, NMR imaging of solid materials, and low-frequency and zero-field magnetic resonance. These developments permit increasingly complex structural and dynamical behavior to be probed at a molecular level and thus add to our understanding of macroscopic properties of materials.
365 citations
297 citations
217 citations
University of Kiel1, Southern Illinois University Carbondale2, University of Florida3, Max Planck Society4, Novosibirsk State University5, Otto-von-Guericke University Magdeburg6, Hebrew University of Jerusalem7, New York University8, University of Turin9, Duke University10, Vanderbilt University11, Cedars-Sinai Medical Center12, University of Texas MD Anderson Cancer Center13, Russian Academy of Sciences14, Wayne State University15
TL;DR: Considerable progress has been made in the past decade in the area of pH2 -based hyperpolarization techniques for biomedical applications, covering the areas of spin physics, catalysis, instrumentation, preparation of the contrast agents, and applications.
Abstract: Magnetic resonance (MR) is one of the most versatile and useful physical effects used for human imaging, chemical analysis, and the elucidation of molecular structures. However, its full potential is rarely used, because only a small fraction of the nuclear spin ensemble is polarized, that is, aligned with the applied static magnetic field. Hyperpolarization methods seek other means to increase the polarization and thus the MR signal. A unique source of pure spin order is the entangled singlet spin state of dihydrogen, parahydrogen (pH2 ), which is inherently stable and long-lived. When brought into contact with another molecule, this "spin order on demand" allows the MR signal to be enhanced by several orders of magnitude. Considerable progress has been made in the past decade in the area of pH2 -based hyperpolarization techniques for biomedical applications. It is the goal of this Review to provide a selective overview of these developments, covering the areas of spin physics, catalysis, instrumentation, preparation of the contrast agents, and applications.
217 citations
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TL;DR: The PASADENA effect as mentioned in this paper is a method for transient high-sensitivity proton spin-labelling by molecular addition of dihydrogen, which can be converted to magnetization observable by NMR.
Abstract: The PASADENA effect is a method for transient high-sensitivity proton spin-labelling by molecular addition of dihydrogen. When the parahydrogen mole fraction differs from the high-temperature limit of 1/4, this population difference constitutes a form of spin order which can be converted to magnetization observable by NMR. Large NMR signals are observed, if subsequent to the hydrogen addition, the two protons experience magnetic inequivalence and spin-spin coupling and if observation is made before spin-lattice relaxation restores the equilibrium spin order. The analogous effect for D2 is also possible. The kinetic mechanisms of the homogeneous hydrogenation catalysts which permit the realization of the PASADENA effect have been the target of the experimental applications. The enhancement of the NMR transitions has facilitated the determination of true molecular rate constants. Ordinarily, the activity of a catalyst is assessed by dividing the observed rate by the total catalyst concentration. However, the question as to whether most of the catalytic rate is due to a tiny fraction of active species or a large fraction with a relatively low molecular rate is not clearly addressed by such an analysis. This ambiguity is entirely avoided in the PASADENA studies, since only active catalyst molecules can contribute to the enhanced signals from which all kinetic inferences are made. The sensitivity enhancement has also led to the identification of a novel intermediate in the mechanism for the Rh(DIPHOS)+ catalyzed hydrogenation of styrene. The rate of conversion of this species into product and starting material has been studied using two-dimensional NMR. The dramatically improved sensitivity should make it possible to observe key catalytic intermediates which do not build up in sufficient quantity to allow detection by conventional NMR arising from Curie-Law magnetization. The study of surface sites which bind pairwise with H2 is also a potentially fruitful area for future experimental work. The ambient temperature NMR spectroscopy of surfaces is not often feasible due to sensitivity limitations. Simulations have been performed using typical shift and coupling parameters in an effort to characterize the enhanced lineshapes which can be expected. The inverse of the PASADENA effect has also been proposed, whereby the spin order of a molecule containing hydrogen is probed by measuring the branching ratio to ortho and para dihydrogen. This RAYMOND phenomenon (radiowave application yields modulated ortho number desorbed) has the potential for measuring precursor NMR with extraordinary sensitivity, since it finesses the need for detection of radiowaves.
775 citations
TL;DR: A method of obtaining very large nuclear-spin polarizations and a means of extending the resultant sensitivity enhancement to other spins is proposed in which the transfer of order occurs through population differences not associated with magnetization.
Abstract: A method of obtaining very large nuclear-spin polarizations is proposed and illustrated by density-operator calculations. The prediction is that chemical reaction and rf irradiation can convert the scalar parahydrogen state into polarization of order unity on the nuclear spins of the products of molecular-hydrogen addition reactions. A means of extending the resultant sensitivity enhancement to other spins is proposed in which the transfer of order occurs through population differences not associated with magnetization.
697 citations
01 Jan 1991
TL;DR: The PASADENA effect as mentioned in this paper is a method for transient high-sensitivity proton spin-labelling by molecular addition of dihydrogen, which can be converted to magnetization observable by NMR.
Abstract: The PASADENA effect is a method for transient high-sensitivity proton spin-labelling by molecular addition of dihydrogen. When the parahydrogen mole fraction differs from the high-temperature limit of 1/4, this population difference constitutes a form of spin order which can be converted to magnetization observable by NMR. Large NMR signals are observed, if subsequent to the hydrogen addition, the two protons experience magnetic inequivalence and spin-spin coupling and if observation is made before spin-lattice relaxation restores the equilibrium spin order. The analogous effect for D2 is also possible. The kinetic mechanisms of the homogeneous hydrogenation catalysts which permit the realization of the PASADENA effect have been the target of the experimental applications. The enhancement of the NMR transitions has facilitated the determination of true molecular rate constants. Ordinarily, the activity of a catalyst is assessed by dividing the observed rate by the total catalyst concentration. However, the question as to whether most of the catalytic rate is due to a tiny fraction of active species or a large fraction with a relatively low molecular rate is not clearly addressed by such an analysis. This ambiguity is entirely avoided in the PASADENA studies, since only active catalyst molecules can contribute to the enhanced signals from which all kinetic inferences are made. The sensitivity enhancement has also led to the identification of a novel intermediate in the mechanism for the Rh(DIPHOS)+ catalyzed hydrogenation of styrene. The rate of conversion of this species into product and starting material has been studied using two-dimensional NMR. The dramatically improved sensitivity should make it possible to observe key catalytic intermediates which do not build up in sufficient quantity to allow detection by conventional NMR arising from Curie-Law magnetization. The study of surface sites which bind pairwise with H2 is also a potentially fruitful area for future experimental work. The ambient temperature NMR spectroscopy of surfaces is not often feasible due to sensitivity limitations. Simulations have been performed using typical shift and coupling parameters in an effort to characterize the enhanced lineshapes which can be expected. The inverse of the PASADENA effect has also been proposed, whereby the spin order of a molecule containing hydrogen is probed by measuring the branching ratio to ortho and para dihydrogen. This RAYMOND phenomenon (radiowave application yields modulated ortho number desorbed) has the potential for measuring precursor NMR with extraordinary sensitivity, since it finesses the need for detection of radiowaves.
596 citations
95 citations