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1

Wörner, Jakob, Jing Chen, Adelbert Bacher et Stefan Weber. « Non-classical disproportionation revealed by photo-chemically induced dynamic nuclear polarization NMR ». Magnetic Resonance 2, no 1 (7 mai 2021) : 281–90. http://dx.doi.org/10.5194/mr-2-281-2021.

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Abstract. Photo-chemically induced dynamic nuclear polarization (photo-CIDNP) was used to observe the light-induced disproportionation reaction of 6,7,8-trimethyllumazine starting out from its triplet state to generate a pair of radicals comprising a one-electron reduced and a one-electron oxidized species. Our evidence is based on the measurement of two marker proton hyperfine couplings, Aiso(H(6α)) and Aiso(H(8α)), which we correlated to predictions from density functional theory. The ratio of these two hyperfine couplings is reversed in the oxidized and the reduced radical species. Observation of the dismutation reaction is facilitated by the exceptional C–H acidity of the methyl group at position 7 of 6,7,8-trimethyllumazine and the slow proton exchange associated with it, which leads to NMR-distinguishable anionic (TML−) and neutral (TMLH) protonation forms.
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2

Abramova, Tatyana V., Olga B. Morozova, Vladimir N. Silnikov et Alexandra V. Yurkovskaya. « Synthesis of nucleotide–amino acid conjugates designed for photo-CIDNP experiments by a phosphotriester approach ». Beilstein Journal of Organic Chemistry 9 (18 décembre 2013) : 2898–909. http://dx.doi.org/10.3762/bjoc.9.326.

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Conjugates of 2’-deoxyguanosine, L-tryptophan and benzophenone designed to study pathways of fast radical reactions by the photo Chemically Induced Dynamic Nuclear Polarization (photo-CIDNP) method were obtained by the phosphotriester block liquid phase synthesis. The phosphotriester approach to the oligonucleotide synthesis was shown to be a versatile and economic strategy for preparing the required amount of high quality samples of nucleotide–amino acid conjugates.
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3

Zhukov, Ivan V., Alexey S. Kiryutin, Mikhail S. Panov, Natalya N. Fishman, Olga B. Morozova, Nikita N. Lukzen, Konstantin L. Ivanov, Hans-Martin Vieth, Renad Z. Sagdeev et Alexandra V. Yurkovskaya. « Exchange interaction in short-lived flavine adenine dinucleotide biradical in aqueous solution revisited by CIDNP (chemically induced dynamic nuclear polarization) and nuclear magnetic relaxation dispersion ». Magnetic Resonance 2, no 1 (13 avril 2021) : 139–48. http://dx.doi.org/10.5194/mr-2-139-2021.

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Abstract. Flavin adenine dinucleotide (FAD) is an important cofactor in many light-sensitive enzymes. The role of the adenine moiety of FAD in light-induced electron transfer was obscured, because it involves an adenine radical, which is short-lived with a weak chromophore. However, an intramolecular electron transfer from adenine to flavin was revealed several years ago by Robert Kaptein by using chemically induced dynamic nuclear polarization (CIDNP). The question of whether one or two types of biradicals of FAD in aqueous solution are formed stays unresolved so far. In the present work, we revisited the CIDNP study of FAD using a robust mechanical sample shuttling setup covering a wide magnetic field range with sample illumination by a light-emitting diode. Also, a cost efficient fast field cycling apparatus with high spectral resolution detection up to 16.4 T for nuclear magnetic relaxation dispersion studies was built based on a 700 MHz NMR spectrometer. Site-specific proton relaxation dispersion data for FAD show a strong restriction of the relative motion of its isoalloxazine and adenine rings with coincident correlation times for adenine, flavin, and their ribityl phosphate linker. This finding is consistent with the assumption that the molecular structure of FAD is rigid and compact. The structure with close proximity of the isoalloxazine and purine moieties is favorable for reversible light-induced intramolecular electron transfer from adenine to triplet excited flavin with formation of a transient spin-correlated triplet biradical F⚫−-A⚫+. Spin-selective recombination of the biradical leads to the formation of CIDNP with a common emissive maximum at 4.0 mT detected for adenine and flavin protons. Careful correction of the CIDNP data for relaxation losses during sample shuttling shows that only a single maximum of CIDNP is formed in the magnetic field range from 0.1 mT to 9 T; thus, only one type of FAD biradical is detectable. Modeling of the CIDNP field dependence provides good agreement with the experimental data for a normal distance distribution between the two radical centers around 0.89 nm and an effective electron exchange interaction of −2.0 mT.
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4

Goez, Martin, et Gerd Eckert. « Photoinduced electron transfer sensitization investigated by chemically induced dynamic nuclear polarizatioin (CIDNP) ». Physical Chemistry Chemical Physics 8, no 45 (2006) : 5294. http://dx.doi.org/10.1039/b609026e.

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5

Goez, Martin, et Gerd Eckert. « Olefin Isomerizationvia Radical-Ion Pairs in Triplet States Studied by Chemically Induced Dynamic Nuclear Polarization (CIDNP) ». Helvetica Chimica Acta 89, no 10 (octobre 2006) : 2183–99. http://dx.doi.org/10.1002/hlca.200690205.

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6

Goez, Martin, et Martin Vogtherr. « Electron self-exchange activation parameters of diethyl sulfide and tetrahydrothiophene ». Beilstein Journal of Organic Chemistry 9 (19 juillet 2013) : 1448–54. http://dx.doi.org/10.3762/bjoc.9.164.

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Electron transfer between the title compounds and their radical cations, which were generated by photoinduced electron transfer from the sulfides to excited 2,4,6-triphenylpyrylium cations, was investigated by time-resolved measurements of chemically induced dynamic nuclear polarization (CIDNP) in acetonitrile. The strongly negative activation entropies provide evidence for an associative–dissociative electron exchange involving dimeric radical cations. Despite this mechanistic complication, the free energies of activation were found to be well reproduced by the Marcus theory of electron transfer, with the activation barrier still dominated by solvent reorganization.
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7

Goez, Martin, et Rainer Heun. « Monte Carlo Simulations of Diffusion in a Coulomb Potential. Applications to Chemically Induced Dynamic Nuclear Polarization (CIDNP) ». Journal of Physical Chemistry A 105, no 45 (novembre 2001) : 10446–53. http://dx.doi.org/10.1021/jp012537k.

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8

Ivanov, K. L., K. Miesel, Hans-Martin Vieth, A. V. Yurkovskaya et R. Z. Sagdeev. « 2D NMR Nutation Analysis of Non-Thermal Polarization of Coupled Multi-Spin Systems ». Zeitschrift für Physikalische Chemie 217, no 12 (1 décembre 2003) : 1641–59. http://dx.doi.org/10.1524/zpch.217.12.1641.20479.

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AbstractA new, convenient method of analyzing the spin polarization of a non-equilibrium system of N coupled nuclei is described and applied to photo-reactions exhibiting chemically induced dynamic nuclear polarization (CIDNP). It is based on the Fourier analysis of the variation of NMR line intensities as a function of the radio frequency excitation pulse length. A relationship between the spectral components at various harmonic order and the alignment in the spin multiplet is established. In application to the Norrish type I photolysis of cyclodecanone we demonstrate that at low magnetic field the rate determining step in the reaction kinetics depends on the mutual orientation of at least four pairs of non-equivalent spins.
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9

Lehnig, Manfred, et Michael Kirsch. « 15N Chemically Induced Dynamic Nuclear Polarization (15N-CIDNP) Investigations of the Peroxynitrite Decay and Nitration ofN-Acetyl-L-tyrosine ». Helvetica Chimica Acta 89, no 10 (octobre 2006) : 2144–66. http://dx.doi.org/10.1002/hlca.200690203.

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10

Shkrob, Ilya A., Valery F. Tarasov et Elena G. Bagryanskaya. « Electron spin exchange in micellized radical pairs. I. 13C low field chemically induced dynamic nuclear polarization (CIDNP) and 13C radio frequency stimulated nuclear polarization (SNP) ». Chemical Physics 153, no 3 (juin 1991) : 427–41. http://dx.doi.org/10.1016/0301-0104(91)80056-n.

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11

Grosse, Stefan, Alexandra V. Yurkovskaya, Jakob Lopez et Hans-Martin Vieth. « Field Dependence of Chemically Induced Dynamic Nuclear Polarization (CIDNP) in the Photoreaction ofN-Acetyl Histidine with 2,2‘-Dipyridyl in Aqueous Solution ». Journal of Physical Chemistry A 105, no 26 (juillet 2001) : 6311–19. http://dx.doi.org/10.1021/jp004582i.

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12

Yang, Li, Mao-Xi Zhang, You-Cheng Liu, Zhong-Li Liu et Yuan L. Chow. « Triplex promoted intersystem crossing of ion–radical pairs in the photosensitized valence isomerization of quadricyclane : chemically induced dynamic nuclear polarization (CIDNP) evidence ». J. Chem. Soc., Chem. Commun., no 10 (1995) : 1055–56. http://dx.doi.org/10.1039/c39950001055.

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13

Sieber, Hans-Christian, Rivka Adar, Rafael Arango, Maria Burchert, Herbert Kaltner, Gian Kayser, Emadeddin Tajkhorshid et al. « Involvement of Laser Photo-CIDNP(Chemically Induced Dynamic Nuclear Polarization)-Reactive Amino Acid Side Chains in Ligand Binding by Galactoside-Specific Lectins in Solution ». European Journal of Biochemistry 249, no 1 (octobre 1997) : 27–38. http://dx.doi.org/10.1111/j.1432-1033.1997.00027.x.

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14

Polyakov, N. E., M. B. Taraban, A. I. Kruppa, N. I. Avdievich, V. V. Mokrushin, P. V. Schastnev, T. V. Leshina, V. Lüsis, D. Muceniece et G. Duburs. « The mechanisms of oxidation of NADH analogues 3. Stimulated nuclear polarization (SNP) and chemically induced dynamic nuclear polarization (CIDNP) in low magnetic fields in photo-oxidation reactions of 1,4-dihydropyridines with quinones ». Journal of Photochemistry and Photobiology A : Chemistry 74, no 1 (août 1993) : 75–79. http://dx.doi.org/10.1016/1010-6030(93)80153-z.

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15

Morozova, Olga B., Yuri P. Tsentalovich, Alexandra V. Yurkovskaya et Renad Z. Sagdeev. « Consecutive Biradicals during the Photolysis of 2,12-Dihydroxy-2,12-dimethylcyclododecanone : Low- and High-Field Chemically Induced Dynamic Nuclear Polarizations (CIDNP) Study ». Journal of Physical Chemistry A 102, no 20 (mai 1998) : 3492–97. http://dx.doi.org/10.1021/jp980271k.

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16

Janssen, Geertje J., Patrick Eschenbach, Patrick Kurle, Bela E. Bode, Johannes Neugebauer, Huub J. M. de Groot, Jörg Matysik et Alia Alia. « Analysis of the electronic structure of the primary electron donor of photosystem I of <i>Spirodela</i> ; <i>oligorrhiza</i> ; by photochemically induced dynamic nuclear polarization (photo-CIDNP) solid-state nuclear magnetic resonance (NMR) ». Magnetic Resonance 1, no 2 (13 novembre 2020) : 261–74. http://dx.doi.org/10.5194/mr-1-261-2020.

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Abstract. The electron donor in photosystem I (PSI), the chlorophyll dimer P700, is studied by photochemically induced dynamic nuclear polarization (photo-CIDNP) magic angle spinning (MAS) nuclear magnetic resonance (NMR) on selectively 13C and uniformly 15N labeled PSI core preparations (PSI-100) obtained from the aquatic plant duckweed (Spirodela oligorrhiza). Light-induced signals originate from the isotope-labeled nuclei of the cofactors involved in the spin-correlated radical pair forming upon light excitation. Signals are assigned to the two donor cofactors (Chl a and Chl a') and the two acceptor cofactors (both Chl a). Light-induced signals originating from both donor and acceptor cofactors demonstrate that electron transfer occurs through both branches of cofactors in the pseudo-C2 symmetric reaction center (RC). The experimental results supported by quantum chemical calculations indicate that this functional symmetry occurs in PSI despite similarly sized chemical shift differences between the cofactors of PSI and the functionally asymmetric special pair donor of the bacterial RC of Rhodobacter sphaeroides. This contributes to converging evidence that local differences in time-averaged electronic ground-state properties, over the donor are of little importance for the functional symmetry breaking across photosynthetic RC species.
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17

Siebert, Hans-Christian, Sabine André, Gerd Reuter, Hans-Joachim Gabius, Robert Kaptein et Johannes F. G. Vliegenthart. « Effect of enzymatic desialylation of human serum amyloid P component on surface exposure of laser photo CIDNP (chemically induced dynamic nuclear polarization) - reactive histidine, tryptophan and tyrosine residues ». FEBS Letters 371, no 1 (28 août 1995) : 13–16. http://dx.doi.org/10.1016/0014-5793(95)00845-z.

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18

Ageeva, Aleksandra A., Simon V. Babenko, Ilya M. Magin, Victor F. Plyusnin, Polina S. Kuznetsova, Alexander A. Stepanov, Sergey F. Vasilevsky, Nikolay E. Polyakov, Alexander B. Doktorov et Tatyana V. Leshina. « Stereoselectivity of Electron and Energy Transfer in the Quenching of (S/R)-Ketoprofen-(S)-Tryptophan Dyad Excited State ». International Journal of Molecular Sciences 21, no 15 (28 juillet 2020) : 5370. http://dx.doi.org/10.3390/ijms21155370.

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Photoinduced elementary processes in chiral linked systems, consisting of drugs and tryptophan (Trp) residues, attract considerable attention due to several aspects. First of all, these are models that allow one to trace the full and partial charge transfer underlying the binding of drugs to enzymes and receptors. On the other hand, Trp fluorescence is widely used to establish the structure and conformational mobility of proteins due to its high sensitivity to the microenvironment. Therefore, the study of mechanisms of Trp fluorescence quenching in various systems has both fundamental and practical interest. An analysis of the photo-chemically induced dynamic nuclear polarization (CIDNP) and Trp fluorescence quenching in (R/S)-ketoprofen-(S)-tryptophan ((S/R)-KP-(S)-Trp) dyad carried out in this work allowed us to trace the intramolecular reversible electron transfer (ET) and obtain evidence in favor of the resonance energy transfer (RET). The fraction of dyad’s singlet excited state, quenched via ET, was shown to be 7.5 times greater for the (S,S)-diastereomer than for the (R,S) analog. At the same time, the ratio of the fluorescence quantum yields shows that quenching effectiveness of (S,S)-diastereomer to be 5.4 times lower than for the (R,S) analog. It means that the main mechanism of Trp fluorescence quenching in (S/R)-KP-(S)-Trp dyad is RET.
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19

Fedin, M. V., E. G. Bagryanskaya et P. A. Purtov. « Theoretical and experimental studies of chemically induced dynamic nuclear polarization kinetics in recombination of radical pairs by the method of switched external magnetic field. II. 13C CIDNP of micellized radical pairs ». Journal of Chemical Physics 111, no 12 (22 septembre 1999) : 5491–502. http://dx.doi.org/10.1063/1.479862.

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von der Lieth, Claus-Wilhelm, Hans-Christian Siebert, Emadeddin Tajkhorshid, Susanne Kruse, Roland Schauer, Robert Kaptein, Hans-Joachim Gabius, Reinhard G. Kleineidam et Johannes F. G. Vliegenthart. « Knowledge-based Homology Modeling and Experimental Determination of Amino Acid Side Chain Accessibility by the Laser Photo CIDNP (Chemically Induced Dynamic Nuclear Polarization) Approach in Solution : Lessons from the Small Sialidase of Clostridium perfringens ». Journal of Molecular Modeling 2, no 11 (1 novembre 1996) : 446–55. http://dx.doi.org/10.1007/s0089460020446.

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21

Bargon, Joachim. « The Discovery of Chemically Induced Dynamic Polarization (CIDNP) ». Helvetica Chimica Acta 89, no 10 (octobre 2006) : 2082–102. http://dx.doi.org/10.1002/hlca.200690199.

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22

Goez, Martin. « An introduction to chemically induced dynamic nuclear polarization ». Concepts in Magnetic Resonance 7, no 1 (1995) : 69–86. http://dx.doi.org/10.1002/cmr.1820070105.

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Torres, Felix, Alexander Sobol, Jason Greenwald, Alois Renn, Olga Morozova, Alexandra Yurkovskaya et Roland Riek. « Molecular features toward high photo-CIDNP hyperpolariztion explored through the oxidocyclization of tryptophan ». Physical Chemistry Chemical Physics 23, no 11 (2021) : 6641–50. http://dx.doi.org/10.1039/d0cp06068b.

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Morozova, Olga B., et Konstantin L. Ivanov. « Time-Resolved Chemically Induced Dynamic Nuclear Polarization of Biologically Important Molecules ». ChemPhysChem 20, no 2 (28 novembre 2018) : 197–215. http://dx.doi.org/10.1002/cphc.201800566.

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25

Roth, Heinz D., Richard S. Hutton, Kuo Chu Hwang, Nicholas J. Turro et Kevin M. Welsh. « Chemically induced dynamic nuclear polarization in systems containing large hyperfine coupling constants ». Journal of Physical Chemistry 93, no 15 (juillet 1989) : 5697–701. http://dx.doi.org/10.1021/j100352a013.

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Rykov, Stanislav V., Igor V. Khudyakov, Eugeniy D. Skakovsky, Hugh D. Burrows, Sebastião J. Formosinho et Maria da Graça M. Miguel. « 1H chemically induced dynamic nuclear polarization in the photodecomposition of uranyl carboxylates ». J. Chem. Soc., Perkin Trans. 2, no 6 (1991) : 835–39. http://dx.doi.org/10.1039/p29910000835.

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27

Sadykov, R. A., et N. M. Shishlov. « Chemically induced dynamic nuclear polarization in reactions of trialkylaluminium and benzoyl peroxide ». Journal of Organometallic Chemistry 369, no 1 (juin 1989) : 1–7. http://dx.doi.org/10.1016/0022-328x(81)80001-0.

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28

Jeschke, Gunnar. « A New Mechanism for Chemically Induced Dynamic Nuclear Polarization in the Solid State ». Journal of the American Chemical Society 132, no 29 (28 juillet 2010) : 10205. http://dx.doi.org/10.1021/ja104063g.

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Jeschke, Gunnar. « A New Mechanism for Chemically Induced Dynamic Nuclear Polarization in the Solid State ». Journal of the American Chemical Society 120, no 18 (mai 1998) : 4425–29. http://dx.doi.org/10.1021/ja973744u.

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30

Liu, You-Cheng, Zhong-Li Liu, Mao-Xi Zhang et Li Yang. « Photoinduced electron transfer via benzoquinone as evidenced by chemically induced dynamic nuclear polarization ». Journal of Photochemistry and Photobiology A : Chemistry 67, no 3 (août 1992) : 279–86. http://dx.doi.org/10.1016/1010-6030(92)87002-q.

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31

Morozova, Olga B., P. J. Hore, Renad Z. Sagdeev et Alexandra V. Yurkovskaya. « Intramolecular Electron Transfer in Lysozyme Studied by Time-Resolved Chemically Induced Dynamic Nuclear Polarization ». Journal of Physical Chemistry B 109, no 46 (novembre 2005) : 21971–78. http://dx.doi.org/10.1021/jp053394v.

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Pershin, A. D., V. F. Tarasov, V. K. Potapov et A. Z. Yankelevich. « Chemically induced dynamic nuclear polarization in photolysis of 4-benzoyl-4-phenyl-1,3-dioxolane ». Bulletin of the Academy of Sciences of the USSR Division of Chemical Science 34, no 2 (février 1985) : 247–51. http://dx.doi.org/10.1007/bf00951262.

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MAURER, Till, Christian LUCKE et Heinz RUTERJANS. « Investigation of the membrane-active peptides melittin and glucagon by photochemically induced dynamic-nuclear-polarization (photo-CIDNP) NMR ». European Journal of Biochemistry 196, no 1 (février 1991) : 135–41. http://dx.doi.org/10.1111/j.1432-1033.1991.tb15796.x.

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Hwang, Kuo Chu, Nicholas J. Turro, Heinz D. Roth et Charles Doubleday. « Suppression of chemically induced dynamic nuclear polarization enhancements by nuclei with large hyperfine coupling constants ». Journal of Physical Chemistry 95, no 1 (janvier 1991) : 63–67. http://dx.doi.org/10.1021/j100154a016.

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HORI, Akira, Fumiaki HAYASHI, Yoshimasa KYOGOKU et Hideo AKUTSU. « A photo-chemically induced dynamic nuclear polarization NMR study on rabbit and bovine cytochrome b5 ». European Journal of Biochemistry 174, no 3 (juin 1988) : 503–8. http://dx.doi.org/10.1111/j.1432-1033.1988.tb14127.x.

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Shkrob, I. A. « A violation of the magnetic equivalence of nuclei in chemically induced dynamic nuclear polarization spectroscopy ». Chemical Physics Letters 210, no 4-6 (juillet 1993) : 432–36. http://dx.doi.org/10.1016/0009-2614(93)87049-9.

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Afanasyeva, M. S., P. A. Purtov, M. B. Taraban, T. V. Leshina et C. B. Grissom. « Photoinitiated oxidation of NADH catalyzed by horseradish peroxidase studied by chemically induced dynamic nuclear polarization ». Russian Chemical Bulletin 55, no 7 (juillet 2006) : 1132–36. http://dx.doi.org/10.1007/s11172-006-0389-6.

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Buchachenko, A. L., I. V. Khudyakov, E. S. Klimtchuk, L. A. Margulis et A. Z. Yankelevitch. « Chemically induced dynamic nuclear polarization in the photo-oxidation of benzylic acid with uranyl nitrate ». Journal of Photochemistry and Photobiology A : Chemistry 46, no 3 (mars 1989) : 281–84. http://dx.doi.org/10.1016/1010-6030(89)87044-3.

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Porkhun, V. I., A. V. Arshinov et A. G. Podoprigora. « Chemically Induced Dynamic Nuclear Polarization in Photoreduction Reactions of 1,4-Benzoquinone in an Acidic Medium ». Russian Journal of General Chemistry 91, no 4 (avril 2021) : 593–95. http://dx.doi.org/10.1134/s1070363221040022.

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Perrier, Sandrine, Epiphanie Mugeniwabagara, Andrée Kirsch-De Mesmaeker, P. J. Hore et Michel Luhmer. « Exploring Photoreactions between Polyazaaromatic Ru(II) Complexes and Biomolecules by Chemically Induced Dynamic Nuclear Polarization Measurements ». Journal of the American Chemical Society 131, no 34 (2 septembre 2009) : 12458–65. http://dx.doi.org/10.1021/ja9024287.

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41

Purtov, P. A., et K. M. Salikhov. « Semiclassical description of hyperfine interaction in calculating chemically induced dynamic nuclear polarization in weak magnetic fields ». Theoretical and Experimental Chemistry 23, no 2 (1987) : 192–95. http://dx.doi.org/10.1007/bf00534581.

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Polyakov, N. E., et T. V. Leshina. « Study of chemically induced dynamic nuclear polarization field dependencies in the photoreduction of quinones by amines ». Journal of Photochemistry and Photobiology A : Chemistry 55, no 1 (décembre 1990) : 43–51. http://dx.doi.org/10.1016/1010-6030(90)80017-r.

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43

Sadykov, R. A., et I. H. Teregulov. « Chemically induced dynamic nuclear polarization and reaction of Et3Al with CCl4 catalyzed by Ni(acac)2 ». Russian Chemical Bulletin 47, no 8 (août 1998) : 1537–40. http://dx.doi.org/10.1007/bf02495605.

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44

Goez, Martin, Jaroslaw Rozwadowski et Bronislaw Marciniak. « Photoinduced Electron Transfer, Decarboxylation, and Radical Fragmentation of Cysteine Derivatives : A Chemically Induced Dynamic Nuclear Polarization Study ». Journal of the American Chemical Society 118, no 12 (janvier 1996) : 2882–91. http://dx.doi.org/10.1021/ja9536678.

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45

Morozova, Olga B., Peter S. Sherin et Alexandra V. Yurkovskaya. « Competition of singlet and triplet recombination of radical pairs in photoreactions of carboxy benzophenones and aromatic amino acids ». Physical Chemistry Chemical Physics 21, no 4 (2019) : 2017–28. http://dx.doi.org/10.1039/c8cp06760k.

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Time-resolved chemically induced dynamic nuclear polarization and transient absorption were applied to reveal the branching ratio of the singlet and triplet recombination channels in the reaction of short-lived radicals of carboxy benzophenones and the aromatic amino acids.
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46

Goez, Martin, Isabell Frisch et Ingo Sartorius. « Electron and hydrogen self-exchange of free radicals of sterically hindered tertiary aliphatic amines investigated by photo-CIDNP ». Beilstein Journal of Organic Chemistry 9 (26 février 2013) : 437–46. http://dx.doi.org/10.3762/bjoc.9.46.

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The photoreactions of diazabicyclo[2,2,2]octane (DABCO) and triisopropylamine (TIPA) with the sensitizers anthraquinone (AQ) and xanthone (XA) or benzophenone (BP) were investigated by time-resolved photo-CIDNP (photochemically induced dynamic nuclear polarization) experiments. By varying the radical-pair concentration, it was ensured that these measurements respond only to self-exchange reactions of the free amine-derived radicals (radical cations DH • + or α-amino alkyl radicals D • ) with the parent amine DH; the acid–base equilibrium between DH • + and D • also plays no role. Although the sensitizer does not at all participate in the observed processes, it has a pronounced influence on the CIDNP kinetics because the reaction occurs through successive radical pairs. With AQ, the polarizations stem from the initially formed radical-ion pairs, and escaping DH • + then undergoes electron self-exchange with DH. In the reaction sensitized with XA (or BP), the polarizations arise in a secondary pair of neutral radicals that is rapidly produced by in-cage proton transfer, and the CIDNP kinetics are due to hydrogen self-exchange between escaping D • and DH. For TIPA, the activation parameters of both self-exchange reactions were determined. Outer-sphere reorganization energies obtained with the Marcus theory gave very good agreement between experimental and calculated values of ∆G ‡ 298.
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47

Kolesnikov, S. P., V. Ya Li, V. I. Valyaev et T. V. Leshina. « Study of the reaction of the superacid HGeCl3 with olefins by the chemically induced dynamic nuclear polarization method ». Bulletin of the Academy of Sciences of the USSR Division of Chemical Science 36, no 7 (juillet 1987) : 1495–98. http://dx.doi.org/10.1007/bf01557532.

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Maryasova, V. I., A. S. Zanina, A. I. Kruppa et T. V. Leshina. « 1H chemically induced dynamic nuclear polarization study of photoinitiated interaction between acetylenic ketones and electron and hydrogen donors ». Journal of Photochemistry and Photobiology A : Chemistry 61, no 2 (octobre 1991) : 201–8. http://dx.doi.org/10.1016/1010-6030(91)85088-x.

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49

Boelens, Rolf, Konstantin Ivanov et Jörg Matysik. « Introduction to a special issue of <i>Magnetic Resonance</i> ; in honour of Robert Kaptein at the occasion of his 80th birthday ». Magnetic Resonance 2, no 1 (17 juin 2021) : 465–74. http://dx.doi.org/10.5194/mr-2-465-2021.

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Abstract. This publication, in honour of Robert Kaptein's 80th birthday, contains contributions from colleagues, many of whom have worked with him, and others who admire his work and have been stimulated by his research. The contributions show current research in biomolecular NMR, spin hyperpolarisation and spin chemistry, including CIDNP (chemically induced dynamic nuclear polarisation), topics to which he has contributed enormously. His proposal of the radical pair mechanism was the birth of the field of spin chemistry, and the laser CIDNP NMR experiment on a protein was a major breakthrough in hyperpolarisation research. He set milestones for biomolecular NMR by developing computational methods for protein structure determination, including restrained molecular dynamics and 3D NMR methodology. With a lac repressor headpiece, he determined one of the first protein structures determined by NMR. His studies of the lac repressor provided the first examples of detailed studies of protein nucleic acid complexes by NMR. This deepened our understanding of protein DNA recognition and led to a molecular model for protein sliding along the DNA. Furthermore, he played a leading role in establishing the cluster of NMR large-scale facilities in Europe. This editorial gives an introduction to the publication and is followed by a biography describing his contributions to magnetic resonance.
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Porkhun, V. I., Yu V. Aristova et N. N. Litinskaya. « Investigation of the models of the primary charge transfer in photosynthesis using the chemically induced dynamic nuclear polarization effects ». Russian Journal of General Chemistry 86, no 9 (septembre 2016) : 2143–44. http://dx.doi.org/10.1134/s1070363216090310.

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