NMR Hyperpolarization Techniques for Biomedicine

Nikolaou, Panayiotis; Goodson, Boyd M.; Chekmenev, Eduard Y.

doi:10.1002/chem.201405253

Cited by 262 publications

(388 citation statements)

References 142 publications

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“…One of the more active areas of research is the development of hyperpolarized (HP) agents that include both gases and liquid state metabolites that are tailored for applications in the study of lung disease and in vivo metabolism. It is somewhat uncommon to have a single review encompass HP gases and HP 13 C and 15 N liquid state agents, although a limited number of such reviews do exist [1, 2]. This segregation of literature is partly because these fields have been historically divided into different research communities.…”

Section: Introductionmentioning

confidence: 99%

Magnetic resonance imaging with hyperpolarized agents: methods and applications

et al. 2017

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In the past decade, hyperpolarized (HP) contrast agents have been under active development for MRI applications to address the twin challenges of functional and quantitative imaging. Both HP helium (3He) and xenon (129Xe) gases have reached the stage where they are under study in clinical research. HP 129Xe, in particular, is poised for larger scale clinical research to investigate asthma, chronic obstructive pulmonary disease, and fibrotic lung diseases. With advances in polarizer technology and unique capabilities for imaging of 129Xe gas exchange into lung tissue and blood, HP 129Xe MRI is attracting new attention. In parallel, HP 13C and 15N MRI methods have steadily advanced in a wide range of pre-clinical research applications for imaging metabolism in various cancers and cardiac disease. The HP [1-13C] pyruvate MRI technique, in particular, has undergone phase I trials in prostate cancer and is poised for investigational new drug trials at multiple institutions in cancer and cardiac applications. This review treats the methodology behind both HP gases and HP 13C and 15N liquid state agents. Gas and liquid phase HP agents share similar technologies for achieving non-equilibrium polarization outside the field of the MRI scanner, strategies for image data acquisition, and translational challenges in moving from pre-clinical to clinical research. To cover the wide array of methods and applications, this review is organized by numerical section into 1) a brief introduction, 2) the physical and biological properties of the most common polarized agents with a brief summary of applications and methods of polarization, 3) methods for image acquisition and reconstruction specific to improving data acquisition efficiency for HP MRI, 4) the main physical properties that enable unique measures of physiology or metabolic pathways, followed by a more detailed review of the literature describing the use of HP agents to study 5) metabolic pathways in cancer and cardiac disease and 6) lung function in both pre-clinical and clinical research studies, 7) some future directions and challenges, and 8) an overall summary.

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Section: Introductionmentioning

confidence: 99%

Magnetic resonance imaging with hyperpolarized agents: methods and applications

et al. 2017

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“…22 PHIP offers a number of advantages compared to d-DNP and SEOP, that is, (i) very fast (<1 min) hyperpolarization production speed, (ii) low cost, and (iii) straightforward scalability. 8 In addition, PHIP naturally employs hydrogenation reactions and therefore can find promising applications beyond biomedicine. For example, it could be a useful modality for in situ detection and imaging of industrial-scale hydrogenation and hydrogen-involving reactions, 23,24 which represent a significant fraction of all industrial chemical processes.…”

Section: Introductionmentioning

confidence: 99%

NMR SLIC Sensing of Hydrogenation Reactions Using Parahydrogen in Low Magnetic Fields

et al. 2016

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Parahydrogen-induced polarization (PHIP) is an NMR hyperpolarization technique that increases nuclear spin polarization by orders of magnitude, and it is particularly well-suited to study hydrogenation reactions. However, the use of high-field NMR spectroscopy is not always possible, especially in the context of potential industrial-scale reactor applications. On the other hand, the direct low-field NMR detection of reaction products with enhanced nuclear spin polarization is challenging due to near complete signal cancellation from nascent parahydrogen protons. We show that hydrogenation products prepared by PHIP can be irradiated with weak (on the order of spin–spin couplings of a few hertz) alternating magnetic field (called Spin-Lock Induced Crossing or SLIC) and consequently efficiently detected at low magnetic field (e.g., 0.05 T used here) using examples of several types of organic molecules containing a vinyl moiety. The detected hyperpolarized signals from several reaction products at tens of millimolar concentrations were enhanced by 10000-fold, producing NMR signals an order of magnitude greater than the background signal from protonated solvents.

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“…[9,14] Therefore, examination of the nature of the active sites for titania-supported nanoparticles in the contexto ft he pairwise addition of hydrogen may open up new possibilities for the rational preparation of catalysts that are able to maximize the observed PHIP effects and for the production of hyperpolarizedm olecular contrast agents potentially suitable for in vivo magnetic resonance imaging investigations. [14][15][16] In catalysis, it is well known that metals supported on titania exhibit the strong metal-support interaction (SMSI) effect. [17,18] This phenomenoni sk nown to modifyt he selectivity and activity of ac atalyst.…”

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confidence: 99%

Strong Metal–Support Interactions for Palladium Supported on TiO₂ Catalysts in the Heterogeneous Hydrogenation with Parahydrogen

et al. 2015

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Parahydrogen-induced polarization (PHIP) was successfully utilized to demonstrate the strong metal-support interaction (SMSI) effect for palladium supported on titania catalysts. Heterogeneous hydrogenation of 1,3-butadiene over Pd/TiO 2 catalysts led to the formation of 1-and 2-butenes and butane, and hyperpolarized products were obtained if parahydrogen was used in the reaction. However,i fthe catalysts were reduced in H 2 flow at 500 8Cb efore the hydrogenation reaction, the observed polarization levels were significantly lower or even zero, which was indicative of the suppression of the pairwise addition of hydrogen route. This observation indicated the possibility to detect the SMSI effect by the PHIP technique. Moreover, by using X-ray photoelectron spectroscopy it wass hown that Pd is partially presentasPd d + after reduction under ahydrogen atmosphere at 500 8C. These results were confirmed by transmissione lectron microscopy,w hich revealed the formation of Pd d + and the dissolution of Pd in the titania lattice.The hydrogenation of unsaturated compounds with parahydrogen leads to the observation of the parahydrogen-induced polarization (PHIP) phenomenon. [1,2] This resultsi nas ignificant enhancement in the NMR signals of the corresponding reaction products or intermediates. In the case of homogeneous catalytic hydrogenation, as ingle metal center often plays the role of the active site for hydrogen activation, and therefore, the pairwise hydrogen addition route is the major mechanism for such processes. [3,4] In contrast, heterogeneous pairwise addition of hydrogen is uncommon. Nevertheless, it can be successfully observed by the PHIP technique, [5][6][7] contrary to the implications of the Horiuti-Polanyi mechanism [8] widely accepted for ab road range of supported metal nanoparticles. Therefore, understanding the nature of active sites that can add two hydrogen atoms from the same hydrogen molecule as ap air to asubstrate molecule is ah ighly important task. [9][10][11] Recently,i tw as shown that the nature of the catalyst support can have as ignificant impact on the rate of the pairwise addition of hydrogen. [12,13] Remarkably,t itania-supported metal catalysts were shown to exhibit much higher levels of the pairwise addition of hydrogen (and larger PHIP effects) relative to that exhibited by metals on other supports. [9,14] Therefore, examination of the nature of the active sites for titania-supported nanoparticles in the contexto ft he pairwise addition of hydrogen may open up new possibilities for the rational preparation of catalysts that are able to maximize the observed PHIP effects and for the production of hyperpolarizedm olecular contrast agents potentially suitable for in vivo magnetic resonance imaging investigations. [14][15][16] In catalysis, it is well known that metals supported on titania exhibit the strong metal-support interaction (SMSI) effect. [17,18] This phenomenoni sk nown to modifyt he selectivity and activity of ac atalyst. [19,20] Therefore, significant alteration in the s...

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NMR Hyperpolarization Techniques for Biomedicine

Cited by 262 publications

References 142 publications

Magnetic resonance imaging with hyperpolarized agents: methods and applications

Magnetic resonance imaging with hyperpolarized agents: methods and applications

NMR SLIC Sensing of Hydrogenation Reactions Using Parahydrogen in Low Magnetic Fields

Strong Metal–Support Interactions for Palladium Supported on TiO₂ Catalysts in the Heterogeneous Hydrogenation with Parahydrogen

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NMR Hyperpolarization Techniques for Biomedicine

Cited by 262 publications

References 142 publications

Magnetic resonance imaging with hyperpolarized agents: methods and applications

Magnetic resonance imaging with hyperpolarized agents: methods and applications

NMR SLIC Sensing of Hydrogenation Reactions Using Parahydrogen in Low Magnetic Fields

Strong Metal–Support Interactions for Palladium Supported on TiO2 Catalysts in the Heterogeneous Hydrogenation with Parahydrogen

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Strong Metal–Support Interactions for Palladium Supported on TiO₂ Catalysts in the Heterogeneous Hydrogenation with Parahydrogen