The theory and practice of hyperpolarization in magnetic resonance using parahydrogen

Richard A. Green1, Ralph W. Adams1, Simon B. Duckett1, Ryan E. Mewis1, David C. Williamson1, Gary Green2
1Department of Chemistry, University of York, Heslington, York, YO10 5DD, United Kingdom
2York Neuroimaging Centre, The Biocentre York Science Park, University of York, Heslington, York YO10 5DG, United Kingdom

Tóm tắt

Từ khóa


Tài liệu tham khảo

Atkins, 2006

Bowers, 1986, Transformation of symmetrization order to nuclear spin magnetization by chemical reaction and nuclear magnetic resonance, Phys. Rev. Lett., 57, 2645, 10.1103/PhysRevLett.57.2645

Eisenschmid, 1987, Para hydrogen induced polarization in hydrogenation reactions, J. Am. Chem. Soc., 109, 8089, 10.1021/ja00260a026

Pravica, 1988, Net NMR alignment by adiabatic transport of parahydrogen addition products to high magnetic field, Chem. Phys. Lett., 145, 255, 10.1016/0009-2614(88)80002-2

Bowers, 1987, Para-hydrogen and synthesis allow dramatically enhanced nuclear alignment, J. Am. Chem. Soc., 109, 10.1021/ja00252a049

Abragam, 1978, Principles of dynamic nuclear polarization, Rep. Prog. Phys., 41, 395, 10.1088/0034-4885/41/3/002

Ardenkjaer-Larsen, 2003, Increase in signal-to-noise ratio of >10,000 times in liquid-state NMR, Proc. Natl. Acad. Sci. USA, 100, 10158, 10.1073/pnas.1733835100

Prisner, 2008, Dynamic nuclear polarization: new experimental and methodology approaches and applications in physics, chemistry, biology and medicine, Appl. Magn. Reson., 34, 213, 10.1007/s00723-008-0137-1

Hausser, 1968, Dynamic nuclear polarization in liquids, Adv. Magn. Reson., 3, 79, 10.1016/B978-1-4832-3116-7.50010-2

Borghini, 1974, Nuclear dynamic polarization by resolved solid-state effect and thermal mixing with an electron spin–spin interaction reservoir, Phys. Lett. A, 48, 244, 10.1016/0375-9601(74)90487-3

Colpa, 1980, Radio-frequency (Rf-) saturation spectroscopy as detected via optical nuclear-polarization – mechanisms due to electron-spin-resonance and NMR transitions in excited triplet-states, Chem. Phys., 47, 73, 10.1016/0301-0104(80)80022-X

Bargon, 1967, Kernresonanz-emissionlinien Wahrend Rascher Radikalreaktionen. I. Aufnahmeverfahren und Beispiele, Z. Naturfors. Sect. A – J. Phys. Sci. A, 22, 1551

Lawler, 1967, Chemically induced dynamic nuclear polarization, J. Am. Chem. Soc., 89, 5519, 10.1021/ja00997a079

Bargon, 1967, Kernresonanz-emissionslinien Wahrend Rascher Radikalreaktionen. 2. Chemisch Induzierte Dynamische Kernpolarisation, Z. Naturfors. Sect. A – J. Phys. Sci. A, 22, 1556

Bargon, 2006, The discovery of chemically induced dynamic polarization (CIDNP), Helv. Chim. Acta, 89, 2082, 10.1002/hlca.200690199

Bhaskar, 1982, Efficiency of spin exchange between rubidium spins and 129Xe nuclei in a gas, Phys. Rev. Lett., 49, 25, 10.1103/PhysRevLett.49.25

Albert, 1994, Biological magnetic-resonance-imaging using laser polarized XE-129, Nature, 370, 199, 10.1038/370199a0

Walker, 1997, Spin-exchange optical pumping of noble-gas nuclei, Rev. Mod. Phys., 69, 629, 10.1103/RevModPhys.69.629

Vieth, 1979, Radio frequency induced magnetic resonance transitions in excited molecular triplet states as detected via optical nuclear polarization, Chem. Phys. Lett., 60, 368, 10.1016/0009-2614(79)80590-4

Pelupessy, 2000, Hartmann–Hahn polarization transfer in liquids: an ideal tool for selective experiments, Concepts Magn. Reson., 12, 103, 10.1002/(SICI)1099-0534(2000)12:3<103::AID-CMR1>3.0.CO;2-#

Hartmann, 1962, Nuclear double resonance in the rotating frame, Phys. Rev., 128, 2042, 10.1103/PhysRev.128.2042

Brewer, 1976, Brute-force nuclear orientation, Hyperfine Interact., 2, 299, 10.1007/BF01021151

Klages, 1997, Parahydrogen induced polarization in the Pt(0)-mediated hydrogenation of alkynes and alkenes, J. Organomet. Chem., 545, 201, 10.1016/S0022-328X(97)00265-9

Nagel, 1998, The enantioselective hydrogenation of N-acyldehydroamino acids, Top. Catal., 5, 3, 10.1023/A:1019141717606

Niessen, 2007, Investigations in supercritical fluids, In Situ NMR Methods Catal., 276, 69, 10.1007/b135837

Blazina, 2004, Applications of the parahydrogen phenomenon in inorganic chemistry, Dalton Trans., 2601, 10.1039/b409606a

Roe, 1998, High resolution NMR techniques in catalysis, Top. Catal., 5, 133, 10.1023/A:1019133515789

Natterer, 1997, Parahydrogen induced polarization, Prog. Nucl. Magn. Reson. Spectrosc., 31, 293, 10.1016/S0079-6565(97)00007-1

Harel, 2008, Novel detection schemes of nuclear magnetic resonance and magnetic resonance imaging: applications from analytical chemistry to molecular sensors, Annu. Rev. Anal. Chem., 1, 133, 10.1146/annurev.anchem.1.031207.113018

Dennison, 1927, A note on the specific heat of the hydrogen molecule, Proc. R. Soc. A – Math. Phys. Eng. Sci., 115, 483, 10.1098/rspa.1927.0105

Bonhoeffer, 1929, Experiments on para- and orthohydrogen, Naturwissenschaften, 17, 182, 10.1007/BF01506559

Pauli, 1946, Exclusion principle and quantum mechanics

Phoenix, 1991, Comment on “collapse and revival of the state vector in the jaynes-cummings model: an example of state preparation by a quantum apparatus, Phys. Rev. Lett., 66, 2833, 10.1103/PhysRevLett.66.2833

Fano, 1957, Description of states in quantum mechanics by density matrix and operator techniques, Rev. Mod. Phys., 29, 74, 10.1103/RevModPhys.29.74

Ernst, 1987

Munowitz, 1988

Osborn, 1966, Preparation and properties of tris(triphenylphosphine)halogenorhodium(1) and some reactions thereof including catalytic homogeneous hydrogenation of olefins and acetylenes and their derivatives, J. Chem. Soc. A, 1711, 10.1039/j19660001711

Hommeltoft, 1986, A metal-centered radical-pair mechanism for alkyne hydrogenation with a binuclear rhodium hydride complex – CIDNP without organic radicals, J. Am. Chem. Soc., 108, 5345, 10.1021/ja00277a050

Adams, 2009, Reversible Interactions with para-hydrogen enhance NMR sensitivity by polarization transfer, Science, 323, 1708, 10.1126/science.1168877

Aguilar, 2007, Only para-hydrogen spectroscopy (OPSY), a technique for the selective observation of para-hydrogen enhanced NMR signals, Chem. Commun., 1183, 10.1039/B616307F

Adams, 2009, A theoretical basis for spontaneous polarization transfer in non-hydrogenative parahydrogen-induced polarization, J. Chem. Phys., 131, 194505-1, 10.1063/1.3254386

Bargon, 1993, Orthohydrogen and parahydrogen induced nuclear spin polarization, Z. Phys. Chemie – Int. J. Res. Phys. Chem. Chem. Phys., 180, 65

Kuhn, 2007, Transfer of parahydrogen-induced hyperpolarization to heteronuclei, Top. Curr. Chem., 276, 25, 10.1007/128_064

Duckett, 1999, Applications of the parahydrogen phenomenon: a chemical perspective, Prog. Nucl. Magn. Reson. Spectrosc., 34, 71, 10.1016/S0079-6565(98)00027-2

Duckett, 2003, The study of inorganic systems by NMR spectroscopy in conjunction with parahydrogen-induced polarisation, Eur. J. Inorg. Chem., 2901, 10.1002/ejic.200300119

Hubler, 1999, Investigating the kinetics of homogeneous hydrogenation reactions using PHIP NMR spectroscopy, J. Am. Chem. Soc., 121, 5311, 10.1021/ja984353y

Farkas, 1935

McQuarrie, 2000

Jonischkeit, 2004, Hydrogen induced polarization-nuclear-spin hyperpolarization in catalytic hydrogenations without the enrichment of para- or orthohydrogen, Adv. Synth. Catal., 346, 960, 10.1002/adsc.200404058

Canet, 2006, Para-hydrogen enrichment and hyperpolarization, Concepts Magn. Reson. A, 28A, 321, 10.1002/cmr.a.20065

Pauli, 1925, On the connection of the arrangement of electron groups in atoms with the complex structure of spectra, Z. Phys., 31, 765, 10.1007/BF02980631

Heisenberg, 1927, Multi-body problem and resonance in quantum mechanics II, Z. Phys., 41, 239, 10.1007/BF01391241

Hund, 1927, On the explanation of molecular spectra II, Z. Phys., 42, 93, 10.1007/BF01397124

Messiah, 1999

2003

Harkness, 1932, The equilibrium of para and ortho hydrogen, J. Am. Chem. Soc., 54, 2850, 10.1021/ja01346a503

Sorensen, 1983, Product operator formalism for the description of NMR pulse experiments, Prog. Nucl. Magn. Reson. Spectrosc., 16, 163, 10.1016/0079-6565(84)80005-9

Kay, 1988, A product operator description of AB and ABX spin systems, J. Magn. Res., 77, 258

Wolfram Research, Inc., Mathematica: Version 8.0, Wolfram Research, Inc., Champaign, Illinois, 2010.

Aime, 2003, Hyperpolarization transfer from parahydrogen to deuterium via carbon-13, J. Chem. Phys., 119, 8890, 10.1063/1.1615522

Aime, 2006, Polarization transfer from para-hydrogen to heteronuclei: effect of H/D substitution. The Case of AA′X and A(2)A′X-2 spin systems, J. Magn. Res., 178, 184, 10.1016/j.jmr.2005.09.008

Korchak, 2009, Para-hydrogen induced polarization in multi-spin systems studied at variable magnetic field, Phys. Chem. Chem. Phys., 11, 11146, 10.1039/b914188j

Canet, 2007, About long-lived nuclear spin states involved in para-hydrogenated molecules, J. Am. Chem. Soc., 129, 1445, 10.1021/ja066313x

Bouguet-Bonnet, 2009, Effect of the static magnetic field strength on parahydrogen induced polarization NMR spectra, J. Chem. Phys., 130, 234507-1, 10.1063/1.3152843

Maple 15, Maplesoft, Waterloo, Ontario, 2011.

The MathsWorks, Inc., MATLAB Version 7.13 Release 2011b, The MathsWorks, Inc., Natick, Massachusetts, 2011.

Smith, 1994, Computer Simulations in magnetic resonance. an object-oriented programming approach, J. Magn. Res. A, 160, 75, 10.1006/jmra.1994.1008

Schiff, 1968

Sengstschmid, 1996, A new excitation sequence to observe the PASADENA effect, J. Magn. Res. A, 120, 249, 10.1006/jmra.1996.0121

Born, 1928, Beweis des Adiabatensatzes (Proof of the adiabatic theorem), Z. Phys., 51, 165, 10.1007/BF01343193

Schaublin, 1974, Fourier spectroscopy of nonequilibrium states, application to CIDNP, overhauser experiments and relaxation time measurements, J. Magn. Res., 13, 196

Natterer, 1998, Investigating catalytic processes with parahydrogen: evolution of zero-quantum coherence in AA′X spin systems, J. Magn. Res., 133, 92, 10.1006/jmre.1998.1421

Haake, 1995, Symmetry breakdown during parahydrogen labeling of symmetrical substrates – proton spin polarization and singlet/triplet mixing due to 13C isotopes in natural abundance, J. Phys. Chem., 99, 17539, 10.1021/j100049a012

Hore, 2000

Bernstein, 1957, The analysis of nuclear magnetic resonance spectra, Can. J. Chem., 35, 65, 10.1139/v57-011

Bargon, 1993, Nuclear magnetic resonance studies of homogeneous catalysis using parahydrogen – analysis of nuclear singlet triplet mixing as a diagnostic tool to characterize intermediates, J. Chem. Phys., 98, 6150, 10.1063/1.464853

Kating, 1993, J. Phys. Chem., 97, 13313, 10.1021/j100152a040

Barkemeyer, 1995, Hetero-NMR enhancement via parahydrogen labeling, J. Am. Chem. Soc., 117, 2927, 10.1021/ja00115a028

Eisenschmid, 1989, INEPT in a chemical way. Polarization transfer from parahydrogen to 31P by oxidative addition and dipolar relaxation, J. Am. Chem. Soc., 111, 7267, 10.1021/ja00200a061

Duckett, 1993, More than INEPT: parahydrogen and INEPT+ give unprecented resonance enhancement to 13C by direct 1H polarization transfer, J. Am. Chem. Soc., 115, 1156, 10.1021/ja00056a054

Johannesson, 2004, Transfer of para-hydrogen spin order into polarization by diabatic field cycling, C. R. Phys., 5, 315, 10.1016/j.crhy.2004.02.001

Kubas, 1988, Molecular hydrogen complexes: coordination of a σ bond to transition metals, Acc. Chem. Res., 21, 120, 10.1021/ar00147a005

Hamiltonian, 1988, An NMR method for distinguishing classical from nonclassical structures in transition-metal polyhydrides, J. Am. Chem. Soc., 110, 4126, 10.1021/ja00221a005

Hubler, 1998, Indirect characterisation of hydrogenation intermediates using PASADENA NMR spectroscopy – evolution of zero-quantum coherence in AB spin systems, Ber. Bunsen-Ges. Phys. Chem, 102, 364, 10.1002/bbpc.19981020313

Guntert, 1993, POMA, a complete mathematica implementation of the NMR product operator formalism, J. Magn. Res. A, 101, 103, 10.1006/jmra.1993.1016

Morris, 1979, Enhancement of nuclear magnetic resonance signals by polarization transfer, J. Am. Chem. Soc., 101, 760, 10.1021/ja00497a058

Sørensen, 1983, Elimination of spectral distortion in polarization transfer experiments. Improvements and comparison of techniques, J. Magn. Res., 51, 477

Haake, 1996, Efficient NMR pulse sequences to transfer the parahydrogen-induced polarization to hetero nuclei, J. Am. Chem. Soc., 118, 8688, 10.1021/ja960067f

Natterer, 1996, Determination of J(CC) coupling constants using parahydrogen-induced polarization, J. Magn. Res. A, 123, 253, 10.1006/jmra.1996.0247

Barkemeyer, 1996, Heteronuclear polarization transfer using selective pulses during hydrogenation with parahydrogen, J. Magn. Res. A, 120, 129, 10.1006/jmra.1996.0109

Ivanov, 2006, Transfer of CIDNP among coupled spins at low magnetic field, Appl. Magn. Reson., 30, 513, 10.1007/BF03166215

Miesel, 2006, Coherence transfer during field-cycling NMR experiments, Chem. Phys. Lett., 425, 71, 10.1016/j.cplett.2006.05.025

Miesel, 2008, Field-cycling effects on dynamic nuclear polarization, Appl. Magn. Reson., 34, 423, 10.1007/s00723-008-0126-4

Ivanov, 2008, Coherent transfer of hyperpolarization in coupled spin systems at variable magnetic field, J. Chem. Phys., 128, 154701-1, 10.1063/1.2901019

Zener, 1932, Non-adiabatic crossing of energy levels, Proc. R. Soc. Lond. Ser. A, 137, 696, 10.1098/rspa.1932.0165

Hasnip, 1998, Parahydrogen enhanced NMR studies on thermally and photochemically generated products from IrH3(CO)(PPh3)2, Chem. Commun., 923, 10.1039/a801224e

Schott, 2004, The reaction of M(CO)3(Ph2PCH2CH2PPh2) (M=Fe, Ru) with parahydrogen: probing the electronic structure of reaction intermediates and the internal rearrangement mechanism for the dihydride products, Dalton Trans., 3218, 10.1039/B407457B

Levitt, 2001

Aime, 1998, Longitudinal nuclear relaxation in an A(2) spin system initially polarized through para-hydrogen, J. Am. Chem. Soc., 120, 6770, 10.1021/ja973240w

S. Bouguet-Bonnet, D. Canet to S.B. Duckett, January 2012.

Wolfram Research, Inc., Mathematica: Version 5.2, Wolfram Research, Inc., Champaign, Illinois, 2005.

Slichter, 1978

Kishore, 1963, The Rayleigh function, Proc. Am. Math. Soc., 14, 527, 10.1090/S0002-9939-1963-0151649-2

Carravetta, 2004, Beyond the T-1 limit: singlet nuclear spin states in low magnetic fields, Phys. Rev. Lett., 92, 153003-1, 10.1103/PhysRevLett.92.153003

Carravetta, 2004, Long-lived nuclear spin states in high-field solution NMR, J. Am. Chem. Soc., 126, 6228, 10.1021/ja0490931

Carravetta, 2005, Theory of long-lived nuclear spin states in solution nuclear magnetic resonance. I. Singlet states in low magnetic field, J. Chem. Phys., 122, 214505-1, 10.1063/1.1893983

M.H. Levitt, Singlet and other states with extended lifetimes Encyclopedia of Magnetic Resonance, 2010. <http://onlinelibrary.wiley.com/doi/10.1002/9780470034590.emrstm1036/abstract>.

Grant, 2008, Long-lived states in solution NMR: theoretical examples in three- and four-spin systems, J. Magn. Res., 193, 177, 10.1016/j.jmr.2008.04.030

Vinogradov, 2008, Hyperpolarized long-lived states in solution NMR: three-spin case study in low field, J. Magn. Res., 194, 46, 10.1016/j.jmr.2008.05.027

Smith, 1994, The Hamiltonians of NMR part IV: NMR relaxation, Concepts Magn. Reson., 6, 137, 10.1002/cmr.1820060205

Kumar, 2000, Cross-correlations in NMR, Prog. Nucl. Magn. Reson. Spectrosc., 37, 191, 10.1016/S0079-6565(00)00023-6

Redfield, 1965, The theory of relaxation processes, Adv. Magn. Reson., 1, 1, 10.1016/B978-1-4832-3114-3.50007-6

Turro, 2008, Demonstration of a chemical transformation inside a fullerene. The reversible conversion of the allotropes of H2@C60, J. Am. Chem. Soc., 130, 10506, 10.1021/ja804311c

Vinogradov, 2007, Long-lived states in solution NMR: selection rules for intramolecular dipolar relaxation in low magnetic fields, J. Magn. Res., 188, 176, 10.1016/j.jmr.2007.05.015

Rose, 1957

R.W. Adams, Ph.D Thesis, University of York, 2009.

Kuhn, 2006, Transfer of parahydrogen-induced hyperpolarization to 19F, J. Phys. Chem. A, 110, 3521, 10.1021/jp056219n

Roth, 2010, Continuous (1)H and (13)C signal enhancement in NMR spectroscopy and MRI using parahydrogen and hollow-fiber membranes, Angew. Chem.-Int. Edit., 49, 8358, 10.1002/anie.201002725

Hovener, 2009, PASADENA hyperpolarization of 13C biomolecules: equipment design and installation, Magn. Reson. Mat. Phys. Biol. Med., 22, 111, 10.1007/s10334-008-0155-x

Roth, 2008, Parahydrogen induced polarization of barbituric acid derivatives: 1H hyperpolarization studies, Magn. Reson. Chem., 46, 713, 10.1002/mrc.2234

Stephan, 2002, 13C PHIP NMR spectra and polarization transfer during the homogeneous hydrogenation of alkynes with parahydrogen, Magn. Reson. Chem., 40, 157, 10.1002/mrc.973

Duckett, 2008, Parahydrogen-based NMR methods as a mechanistic probe in inorganic chemistry, Coord. Chem. Rev., 252, 2278, 10.1016/j.ccr.2008.01.028

Hasnip, 1999, Kinetic and mechanistic examination of NBu4 IrH2(CO)2I2 and NBu4RhH2(CO)2I2 via para-hydrogen enhanced NMR spectroscopy, Chem. Commun., 889, 10.1039/a900961b

Kirss, 1989, Para-hydrogen-induced polarization in rhodium complex-catalyzed hydrogenation reactions, J. Organomet. Chem., 359, C22, 10.1016/0022-328X(89)85265-9

Messerle, 1999, Structure and dynamics in metal phosphine complexes using advanced NMR studies with para-hydrogen induced polarisation, Dalton Trans., 1429, 10.1039/a809948k

Duckett, 1993, Observation of H-2 oxidative addition to chlorocarbonylbis(triphenylphosphine)rhodium(I) using parahydrogen-induced polarization, J. Am. Chem. Soc., 115, 5292, 10.1021/ja00065a049

Duckett, 1993, Activation of H2 by chlorocarbonylbis(trimethylphosphine)rhodium(I) labilizes CO and produces the new binuclear complex H(Cl)Rh(PMe3)2(MuH)(MuCl)Rh(PMe3)(CO), Chem. Commun., 1185, 10.1039/C39930001185

Duckett, 1995, Rapid characterization of rhodium dihydrides by nuclear-magnetic-resonance spectroscopy using indirect 2-dimensional methods and para-hydrogen, Dalton Trans., 3427, 10.1039/dt9950003427

Dunne, 2004, A combined parahydrogen and theoretical study of H-2 activation by 16-electron d(8) ruthenium(0) complexes and their subsequent catalytic behaviour, Dalton Trans., 3616, 10.1039/b410912k

Hasnip, 2002, Activation of H2 by halocarbonyl bis-phosphine and bis-arsine iridium(I) complexes. The use of parahydrogen induced polarisation to detect species present at low concentration and investigate their reactivity, Dalton Trans., 743, 10.1039/b107444j

Hasnip, 1999, New products in an old reaction: isomeric products from H2 addition to Vaska’s complex and its analogues, Chem. Commun., 1717, 10.1039/a905590h

Wood, 2007, Detection of picomole amounts of biological substrates by para-hydrogen-enhanced NMR methods in conjunction with a suitable receptor complex, J. Am. Chem. Soc., 129, 11012, 10.1021/ja074286k

R. Kandiah, Ph.D Thesis, University of York, 2007.

Aguilar, 2011, Selective detection of hyperpolarized NMR signals derived from para-hydrogen using the only para-hydrogen spectroscopy (OPSY) approach, J. Magn. Res., 208, 49, 10.1016/j.jmr.2010.10.002

Duckett, 1996, Equilibria between isomers of ruthenium dihydride complexes: detection of minor isomers by parahydrogen induced polarisation, Chem. Commun., 383, 10.1039/cc9960000383

Prestwich, 2004, A parahydrogen study of catalytic hydrogenation by diphosphane substituted triruthenium clusters, Eur. J. Inorg. Chem., 4381, 10.1002/ejic.200400455

Schott, 2002, Ruthenium dihydride complexes: NMR studies of intramolecular isomerization and fluxionality including the detection of minor isomers by parahydrogen-induced polarization, Inorg. Chem., 41, 2960, 10.1021/ic011255w

Sleigh, 1999, NMR detection of thermal and photochemical dihydrogen addition products of mono- and tri-nuclear ruthenium complexes containing carbonyl and triphenylphosphine ligands through para-hydrogen induced polarisation, Chem. Commun., 1223, 10.1039/a903321a

Lopez-Serrano, 2007, A para-hydrogen investigation of palladium-catalyzed alkyne hydrogenation, J. Am. Chem. Soc., 129, 6513, 10.1021/ja070331c

Lopez-Serrano, 2006, Palladium-catalyzed hydrogenation: detection of palladium hydrides. A joint study using para-hydrogen-enhanced NMR spectroscopy and density functional theory, J. Am. Chem. Soc., 128, 9596, 10.1021/ja0630137

Lopez-Serrano, 2008, Palladium catalysed alkyne hydrogenation and oligomerisation: a parahydrogen based NMR investigation, Dalton Trans., 4270, 10.1039/b804162h

Godard, 2008, Detection of platinum dihydride bisphosphine complexes and studies of their reactivity through para-hydrogen-enhanced NMR methods, Magn. Reson. Chem., 46, S107, 10.1002/mrc.2342

Bregel, 2002, Mechanistic studies on the addition of dihydrogen to tantalocene complexes, J. Am. Chem. Soc., 124, 13827, 10.1021/ja027005b

Bregel, 2002, A new tantalum dinitrogen complex and a parahydrogen-induced polarization study of its reaction with hydrogen, Inorg. Chem., 41, 4371, 10.1021/ic025578j

Geftakis, 1998, Direct observation of a transition metal alkane complex, CpRe(CO)2(cyclopentane), using NMR spectroscopy, J. Am. Chem. Soc., 120, 9953, 10.1021/ja981702f

Godard, 2002, NMR characterisation of unstable solvent and dihydride complexes generated at low temperature by in-situ UV irradiation, Chem. Commun., 2836, 10.1039/B208007A

Thomas, 1994, In situ NMR investigations of photocatalyzed hydrogenations with parahydrogen in the presence of metal carbonyl compounds of group 6, Angew. Chem.-Int. Edit., 33, 755, 10.1002/anie.199407551

Anwar, 2004, Implementation of NMR quantum computation with parahydrogen-derived high-purity quantum states, Phys. Rev. A, 70, 032324-1, 10.1103/PhysRevA.70.032324

Blazina, 2005, Generation and interrogation of a pure nuclear spin state by parahydrogen-enhanced NMR spectroscopy: a defined initial state for quantum computation, Magn. Reson. Chem., 43, 200, 10.1002/mrc.1540

Blazina, 2006, Contrasting photochemical and thermal reactivity of Ru(CO)(2)(PPh3)(dppe) towards hydrogen rationalised by parahydrogen NMR and DFT studies, Dalton Trans., 2072, 10.1039/b510616h

Fushitani, 2002, Nuclear spin selection rule in the photochemical reaction of CH3 in solid parahydrogen, J. Chem. Phys., 116, 10739, 10.1063/1.1480003

Aime, 2001, Investigating pathways of molecular H-2 exchange in (mu-H)(2)Os-3(CO)(10), Organometallics, 20, 2924, 10.1021/om0100378

Aime, 1999, A novel application of para H-2: the reversible addition/elimination of H-2 at a Ru-3 cluster revealed by the enhanced NMR emission resonance from molecular hydrogen, J. Phys. Chem. A, 103, 9702, 10.1021/jp992668+

Blazina, 2001, NMR studies of Ru-3(CO)(10)(PMe2Ph)(2) and Ru-3(CO)(10)(PPh3)(2) and their H-2 addition products: detection of new isomers with complex dynamic behavior, J. Am. Chem. Soc., 123, 9760, 10.1021/ja004245n

Blazina, 2001, Direct comparison of hydrogenation catalysis by intact versus fragmented triruthenium clusters, Angew. Chem.-Int. Edit., 40, 3874, 10.1002/1521-3773(20011015)40:20<3874::AID-ANIE3874>3.0.CO;2-9

Blazina, 2004, New insights into catalytic hydrogenation by phosphido-substituted triruthenium clusters: confirmation of intact cluster catalysis by parahydrogen NMR, Dalton Trans., 2108, 10.1039/B405030D

Webb, 2005, Microcoil nuclear magnetic resonance spectroscopy, J. Pharm. Biomed. Anal., 38, 892, 10.1016/j.jpba.2005.01.048

Niessen, 2002, The toroid cavity autoclave for high-pressure and variable-temperature in situ nuclear magnetic resonance studies, Rev. Sci. Instrum., 73, 1259, 10.1063/1.1447306

Woelk, 1992, High-pressure NMR probes for the in situ investigation of gas/liquid reactions, Rev. Sci. Instrum., 63, 3307, 10.1063/1.1142543

Chekmenev, 2008, PASADENA hyperpolarization of succinic acid for MRI and NMR spectroscopy, J. Am. Chem. Soc., 130, 4212, 10.1021/ja7101218

Duckett, 1994, Observation of new intermediates in hydrogenation catalyzed by Wilkinsons catalyst, RhCl(PPh3)(3), using parahydrogen-induced polarization, J. Am. Chem. Soc., 116, 10548, 10.1021/ja00102a023

Duckett, 1997, Observation of new intermediates in hydrogenation catalyzed by Wilkinson’s catalyst, RhCl(PPh(3))(3), using parahydrogen-induced polarization (vol. 116, pg. 10548, 1994), J. Am. Chem. Soc., 119, 2068, 10.1021/ja975400+

Colebrooke, 2004, Hydrogenation studies involving halobis(phosphine)-rhodium(I) dimers: use of parahydrogen induced polarisation to detect species present at low concentration, Chem.-Eur. J., 10, 2459, 10.1002/chem.200305466

Bargon, 1990, NMR study of nuclear spin polarization during chemical reactions with ortho hydrogen, Angew. Chem.-Int. Edit., 29, 58, 10.1002/anie.199000581

Colebrooke, 2000, Characterisation and kinetic behaviour of H2Rh(PPh3)(2)(mu-Cl)(2)Rh(PPh3)(alkene) and related binuclear complexes detected during hydrogenation studies involving parahydrogen induced polarisation, Chem. Commun., 685, 10.1039/b000607f

Atesin, 2007, Diastereoselective oxidative addition of dihydrogen to Irl(CO)((R)-BINAP) and Ir(CO)(2)((R)-BINAP) SbF6, Inorg. Chem., 46, 1196, 10.1021/ic061471a

Giernoth, 1998, Intermediate product-catalyst complexes in the homogeneous hydrogenation of styrene derivatives with parahydrogen and cationic Rh-I catalysts, Angew. Chem.-Int. Edit., 37, 2473, 10.1002/(SICI)1521-3773(19981002)37:18<2473::AID-ANIE2473>3.0.CO;2-J

Kirss, 1988, Para hydrogen induced polarization in hydrogenation reactions catalyzed by ruthenium–phosphine complexes, J. Am. Chem. Soc., 110, 8564, 10.1021/ja00233a053

Kluwer, 2005, Kinetic and spectroscopic studies of the palladium(Ar-bian)-catalyzed semi-hydrogenation of 4-octyne, J. Am. Chem. Soc., 127, 15470, 10.1021/ja052729j

Niessen, 2000, In situ PHIP-NMR studies during the stereoselective hydrogenation of sorbic acid with a Cp*Ru(+) catalyst, Magn. Reson. Chem., 38, 747, 10.1002/1097-458X(200009)38:9<747::AID-MRC715>3.0.CO;2-2

Kirss, 1989, Di(phosphine)-bridged complexes of palladium. Parahydrogen-induced polarization in hydrogenation reactions and structure determination of tris(μ-bis(diphenylphosphino) methane)dipalladium, Pd2(dppm)3, Inorg. Chem., 28, 3372, 10.1021/ic00316a027

Sulman, 1999, Study of homogeneous hydrogenation of acetylene compounds with para-hydrogen and Pd(0) and Pt(0) complexes by in situ NMR spectroscopy, React. Kinet. Catal. Lett., 67, 117, 10.1007/BF02475836

Vazquez-Serrano, 2002, Catalytic olefin hydrogenation using N-heterocyclic carbene-phosphine complexes of iridium, Chem. Commun., 2518, 10.1039/B208403A

Harthun, 1995, The use of in situ NMR spectroscopy and parahydrogen as tools for chiral synthesis, Tetrahedron Lett., 36, 7423, 10.1016/0040-4039(95)01540-X

Ulrich, 2000, Parahydrogen-induced polarization in the presence of NMR shift reagents, Magn. Reson. Chem., 38, 33, 10.1002/(SICI)1097-458X(200001)38:1<33::AID-MRC591>3.0.CO;2-4

Viale, 2008, The detection of PHIP effects allows new insights into the mechanism of olefin isomerisation during catalytic hydrogenation, Eur. J. Inorg. Chem., 4348, 10.1002/ejic.200800356

Jang, 1996, Definitive evidence for a pairwise addition of hydrogen to a platinum bis(phosphine) complex using parahydrogen-induced polarization, Organometallics, 15, 2863, 10.1021/om960295i

Zhou, 2005, Parahydrogen derived illumination of pyridine based coordination products obtained from reactions involving rhodium phosphine complexes, Dalton Trans., 3773, 10.1039/b508149a

Chinn, 1992, Rates of catalytic-hydrogenation estimated spectroscopically through enhanced resonances, J. Am. Chem. Soc., 114, 1908, 10.1021/ja00031a070

Koch, 2000, Examination of subsequent reaction products enhanced through parahydrogen-induced nuclear polarization (PHIP), Magn. Reson. Chem., 38, 216, 10.1002/(SICI)1097-458X(200003)38:3<216::AID-MRC635>3.0.CO;2-B

Godard, 2005, Detection of intermediates in cobalt-catalyzed hydroformylation using para-hydrogen-induced polarization, J. Am. Chem. Soc., 127, 4994, 10.1021/ja0434533

Godard, 2004, New perspectives in hydroformylation: a para-hydrogen study, Chem. Commun., 1826, 10.1039/B404547E

Dunne, 2004, Detection and reactivity of Pd((C8H14)PCH2CH2P(C8H14))(CHPhCH2Ph)(H) as determined by parahydrogen-enhanced NMR spectroscopy, J. Am. Chem. Soc., 126, 16708, 10.1021/ja044875f

Permin, 2002, One-hydrogen polarization in hydroformylation promoted by platinum-tin and iridium carbonyl complexes: a new type of parahydrogen-induced effect, J. Am. Chem. Soc., 124, 12406, 10.1021/ja026698t

Fox, 2006, A model iridium hydroformylation system with the large bite angle ligand xantphos: reactivity with parahydrogen and implications for hydroformylation catalysis, Inorg. Chem., 45, 7197, 10.1021/ic060731l

Gutmann, 2009, Para-hydrogen induced polarization in homogeneous phase-an example of how ionic liquids affect homogenization and thus activation of catalysts, Phys. Chem. Chem. Phys., 11, 9170, 10.1039/b908198d

Kovtunov, 2008, Observation of parahydrogen-induced polarization in heterogeneous hydrogenation on supported metal catalysts, Angew. Chem.-Int. Edit., 47, 1492, 10.1002/anie.200704881

Balu, 2009, Para-hydrogen induced polarisation effects in liquid phase hydrogenations catalysed by supported metal nanoparticles, Dalton Trans., 5074, 10.1039/b906449d

Kovtunov, 2010, Parahydrogen-induced polarization in heterogeneous hydrogenations catalyzed by an immobilized Au(III) complex, J. Phys. Chem. Lett., 1, 1705, 10.1021/jz100391j

Koptyug, 2007, para-hydrogen-induced polarization in heterogeneous hydrogenation reactions, J. Am. Chem. Soc., 129, 5580, 10.1021/ja068653o

Bouchard, 2007, Para-hydrogen-enhanced hyperpolarized gas-phase magnetic resonance imaging, Angew. Chem.-Int. Edit., 46, 4064, 10.1002/anie.200700830

Bouchard, 2008, NMR imaging of catalytic hydrogenation in microreactors with the use of para-hydrogen, Science, 319, 442, 10.1126/science.1151787

Carson, 2001, The PASADENA effect at a solid surface: High-sensitivity nuclear magnetic resonance of hydrogen chemisorption, J. Am. Chem. Soc., 123, 11821, 10.1021/ja010572z

Atkinson, 2009, Spontaneous transfer of parahydrogen derived spin order to pyridine at low magnetic field, J. Am. Chem. Soc., 131, 13362, 10.1021/ja903601p

Cowley, 2011, Iridium N-heterocyclic carbene complexes as efficient catalysts for magnetization transfer from para-hydrogen, J. Am. Chem. Soc., 133, 6134, 10.1021/ja200299u

Hubler, 2000, In situ transfer of parahydrogen-induced nuclear spin polarization – structural characterization of hydrogenation intermediates, Angew. Chem.-Int. Edit., 39, 3701, 10.1002/1521-3773(20001016)39:20<3701::AID-ANIE3701>3.0.CO;2-L

Hovener, 2009, Quality assurance of PASADENA hyperpolarization for 13C biomolecules, Magn. Reson. Mat. Phys. Biol. Med., 22, 123, 10.1007/s10334-008-0154-y

Ishii, 2007, Hyperpolarized 13C MRI of the pulmonary vasculature and parenchyma, Magn. Reson. Med., 57, 459, 10.1002/mrm.21168

Johansson, 2004, Perfusion assessment with bolus differentiation: a technique applicable to hyperpolarized tracers, Magn. Reson. Med., 52, 1043, 10.1002/mrm.20247

Magnusson, 2007, Passive catheter tracking during interventional MRI using hyperpolarized C-13, Magn. Reson. Med., 57, 1140, 10.1002/mrm.21239

Reineri, 2008, New hyperpolarized contrast agents for 13C-MRI from para-hydrogenation of oligooxyethylenic alkynes, J. Am. Chem. Soc., 130, 15047, 10.1021/ja8059733

Kadleck, 2010, Optimal transfer of spin-order between a singlet nuclear pair and a heteronucleus, J. Magn. Reson., 205

Chekmenev, 2009, Hyperpolarized H-1 NMR employing low gamma nucleus for spin polarization storage, J. Am. Chem. Soc., 131, 3164, 10.1021/ja809634u

Atkinson, 2009, Para-hydrogen induced polarization without incorporation of para-hydrogen into the analyte, Inorg. Chem., 48, 663, 10.1021/ic8020029

Sleigh, 1996, NMR studies on ligand exchange at IrH2Cl(CO)(PPh3)2 and IrH2Cl(PPh3)3 by para-hydrogen induced polarisation, Chem. Commun., 2395, 10.1039/cc9960002395

Mishkovsky, 2008, Progress in hyperpolarized ultrafast 2D NMR spectroscopy, ChemPhysChem, 9, 2340, 10.1002/cphc.200800461

Jonischkeit, 2006, Generating long-lasting 1H and 13C hyperpolarization in small molecules with parahydrogen-induced polarization, J. Chem. Phys., 124, 201109-1, 10.1063/1.2209235

Warren, 2009, Increasing hyperpolarized spin lifetimes through true singlet eigenstates, Science, 323, 1711, 10.1126/science.1167693

Pichler, 2008, Latest advances in molecular imaging instrumentation, J. Nucl. Med., 49, 5S, 10.2967/jnumed.108.045880

Golman, 2003, Silvanus Thompson memorial lecture molecular imaging using hyperpolarized 13C, Br. J. Radiol., 76, S118, 10.1259/bjr/26631666

Wilson, 2009, Generation of hyperpolarized substrates by secondary labeling with [1,1-C-13] acetic anhydride, Proc. Natl. Acad. Sci. USA, 106, 5503, 10.1073/pnas.0810190106

Gallagher, 2009, Biomedical applications of hyperpolarized 13C magnetic resonance imaging, Prog. Nucl. Magn. Reson. Spectrosc., 55, 285, 10.1016/j.pnmrs.2009.06.001

Geraldes, 2009, Classification and basic properties of contrast agents for magnetic resonance imaging, Contrast Media Mol. Imag., 4, 1, 10.1002/cmmi.265

Goldman, 2005, Conversion of a proton pair para order into C-13 polarization by rf irradiation, for use in MRI, C. R. Phys., 6, 575, 10.1016/j.crhy.2005.03.002

Goldman, 2006, Design and implementation of 13C hyperpolarization from para-hydrogen, for new MRI contrast agents, C. R. Chim., 9, 357, 10.1016/j.crci.2005.05.010

Ivanov, 2009, Separation of integral and multiplet nuclear polarization by means of spin echo magnetization phase analysis, Dokl. Phys. Chem., 427, 121, 10.1134/S0012501609070021

Xu, 2008, Submillimeter-resolution magnetic resonance imaging at the Earth’s magnetic field with an atomic magnetometer, Phys. Rev. A, 78, 013404-1, 10.1103/PhysRevA.78.013404

Ross, 2010, Hyperpolarized MR imaging: neurologic applications of hyperpolarized metabolism, Am. J. Neuroradiol., 31, 24, 10.3174/ajnr.A1790

Golman, 2001, Parahydrogen-induced polarization in imaging: subsecond 13C angiography, Magn. Reson. Med., 46, 1, 10.1002/mrm.1152

Goldman, 2005, Hyperpolarization of 13C through order transfer from parahydrogen: a new contrast agent for MRI, Magn. Reson. Imag., 23, 153, 10.1016/j.mri.2004.11.031

Bhattacharya, 2005, Ultra-fast three dimensional imaging of hyperpolarized 13C in vivo, Magn. Reson. Mat. Phys. Biol. Med., 18, 245, 10.1007/s10334-005-0007-x

Bhattacharya, 2007, Towards hyperpolarized C-13-succinate imaging of brain cancer, J. Magn. Res., 186, 150, 10.1016/j.jmr.2007.01.017

Aime, 2005, Para-hydrogenation of unsaturated moieties on poly(lysine) derived substrates for the development of novel hyperpolarized MRI contrast agents, Org. Biomol. Chem., 3, 3948, 10.1039/b510693a

Reineri, 2010, Para-hydrogenated glucose derivatives as potential (13)C-hyperpolarized probes for magnetic resonance imaging, J. Am. Chem. Soc., 132, 7186, 10.1021/ja101399q

Theis, 2011, Parahydrogen-enhanced zero-field nuclear magnetic resonance, Nat. Phys., 7, 10.1038/nphys1986