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      Propane- d 6 Heterogeneously Hyperpolarized by Parahydrogen

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          Abstract

          Long-lived spin states of hyperpolarized propane- d 6 gas were demonstrated following pairwise addition of parahydrogen gas to propene- d 6 using heterogeneous parahydrogen-induced polarization (HET-PHIP). Hyperpolarized molecules were synthesized using Rh/TiO 2 solid catalyst with 1.6 nm Rh nanoparticles. Hyperpolarized ( P H ∼ 1%) propane- d 6 was detected at high magnetic field (9.4 T) spectroscopically and by high-resolution 3D gradient-echo MRI (4.7 T) as the gas flowed through the radiofrequency coil with a spatial and temporal resolution of 0.5 × 0.5 × 0.5 mm 3 and 17.7 s, respectively. Stopped-flow hyperpolarized propane- d 6 gas was also detected at 0.0475 T with an observed nuclear spin polarization of P H ∼ 0.1% and a relatively long lifetime with T 1,eff = 6.0 ± 0.3 s. Importantly, it was shown that the hyperpolarized protons of the deuterated product obtained via pairwise parahydrogen addition could be detected directly at low magnetic field. Importantly, the relatively long low-field T 1,eff of HP propane- d 6 gas is not susceptible to paramagnetic impurities as tested by exposure to ∼0.2 atm oxygen. This long lifetime and nontoxic nature of propane gas could be useful for bioimaging applications including potentially pulmonary low-field MRI. The feasibility of high-resolution low-field 2D gradient-echo MRI was demonstrated with 0.88 × 0.88 mm 2 spatial and ∼0.7 s temporal resolution, respectively, at 0.0475 T.

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          Increase in signal-to-noise ratio of > 10,000 times in liquid-state NMR.

          A method for obtaining strongly polarized nuclear spins in solution has been developed. The method uses low temperature, high magnetic field, and dynamic nuclear polarization (DNP) to strongly polarize nuclear spins in the solid state. The solid sample is subsequently dissolved rapidly in a suitable solvent to create a solution of molecules with hyperpolarized nuclear spins. The polarization is performed in a DNP polarizer, consisting of a super-conducting magnet (3.35 T) and a liquid-helium cooled sample space. The sample is irradiated with microwaves at approximately 94 GHz. Subsequent to polarization, the sample is dissolved by an injection system inside the DNP magnet. The dissolution process effectively preserves the nuclear polarization. The resulting hyperpolarized liquid sample can be transferred to a high-resolution NMR spectrometer, where an enhanced NMR signal can be acquired, or it may be used as an agent for in vivo imaging or spectroscopy. In this article we describe the use of the method on aqueous solutions of [13C]urea. Polarizations of 37% for 13C and 7.8% for 15N, respectively, were obtained after the dissolution. These polarizations correspond to an enhancement of 44,400 for 13C and 23,500 for 15N, respectively, compared with thermal equilibrium at 9.4 T and room temperature. The method can be used generally for signal enhancement and reduction of measurement time in liquid-state NMR and opens up for a variety of in vitro and in vivo applications of DNP-enhanced NMR.
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            Analysis of cancer metabolism by imaging hyperpolarized nuclei: prospects for translation to clinical research.

            A major challenge in cancer biology is to monitor and understand cancer metabolism in vivo with the goal of improved diagnosis and perhaps therapy. Because of the complexity of biochemical pathways, tracer methods are required for detecting specific enzyme-catalyzed reactions. Stable isotopes such as (13)C or (15)N with detection by nuclear magnetic resonance provide the necessary information about tissue biochemistry, but the crucial metabolites are present in low concentration and therefore are beyond the detection threshold of traditional magnetic resonance methods. A solution is to improve sensitivity by a factor of 10,000 or more by temporarily redistributing the populations of nuclear spins in a magnetic field, a process termed hyperpolarization. Although this effect is short-lived, hyperpolarized molecules can be generated in an aqueous solution and infused in vivo where metabolism generates products that can be imaged. This discovery lifts the primary constraint on magnetic resonance imaging for monitoring metabolism-poor sensitivity-while preserving the advantage of biochemical information. The purpose of this report was to briefly summarize the known abnormalities in cancer metabolism, the value and limitations of current imaging methods for metabolism, and the principles of hyperpolarization. Recent preclinical applications are described. Hyperpolarization technology is still in its infancy, and current polarizer equipment and methods are suboptimal. Nevertheless, there are no fundamental barriers to rapid translation of this exciting technology to clinical research and perhaps clinical care.
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              Hyperpolarized 129Xe MRI of the human lung.

              By permitting direct visualization of the airspaces of the lung, magnetic resonance imaging (MRI) using hyperpolarized gases provides unique strategies for evaluating pulmonary structure and function. Although the vast majority of research in humans has been performed using hyperpolarized (3)He, recent contraction in the supply of (3)He and consequent increases in price have turned attention to the alternative agent, hyperpolarized (129) Xe. Compared to (3)He, (129)Xe yields reduced signal due to its smaller magnetic moment. Nonetheless, taking advantage of advances in gas-polarization technology, recent studies in humans using techniques for measuring ventilation, diffusion, and partial pressure of oxygen have demonstrated results for hyperpolarized (129)Xe comparable to those previously demonstrated using hyperpolarized (3)He. In addition, xenon has the advantage of readily dissolving in lung tissue and blood following inhalation, which makes hyperpolarized (129)Xe particularly attractive for exploring certain characteristics of lung function, such as gas exchange and uptake, which cannot be accessed using (3)He. Preliminary results from methods for imaging (129) Xe dissolved in the human lung suggest that these approaches will provide new opportunities for quantifying relationships among gas delivery, exchange, and transport, and thus show substantial potential to broaden our understanding of lung disease. Finally, recent changes in the commercial landscape of the hyperpolarized-gas field now make it possible for this innovative technology to move beyond the research laboratory.
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                Author and article information

                Journal
                J Phys Chem C Nanomater Interfaces
                J Phys Chem C Nanomater Interfaces
                jy
                jpccck
                The Journal of Physical Chemistry. C, Nanomaterials and Interfaces
                American Chemical Society
                1932-7447
                1932-7455
                06 November 2015
                06 November 2014
                04 December 2014
                : 118
                : 48
                : 28234-28243
                Affiliations
                []International Tomography Center , 3A Institutskaya St., Novosibirsk 630090, Russia
                []Novosibirsk State University , 2 Pirogova St., Novosibirsk, 630090, Russia
                [3] §Institute of Imaging Science, Department of Radiology, Department of Biomedical Engineering, Department of Physics and Astronomy, #Department of Biochemistry, #Vanderbilt-Ingram Cancer Center, Vanderbilt University , Nashville, Tennessee 37232-2310, United States
                []Boreskov Institute of Catalysis , SB RAS, 5 Acad. Lavrentiev Pr., Novosibirsk 630090, Russia
                Author notes
                Article
                10.1021/jp508719n
                4259496
                25506406
                01b81641-4d00-4d38-bc89-f29fda0cfbf8
                Copyright © 2014 American Chemical Society

                This is an open access article published under an ACS AuthorChoice License, which permits copying and redistribution of the article or any adaptations for non-commercial purposes.

                History
                : 28 August 2014
                : 06 November 2014
                Funding
                National Institutes of Health, United States
                Categories
                Article
                Custom metadata
                jp508719n
                jp-2014-08719n

                Thin films & surfaces
                Thin films & surfaces

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