Subscriber access provided by ECOLE NORMALE SUPERIEURE LYON Article Dynamic Nuclear Polarization of Amyloidogenic Peptide Nanocrystals: GNNQQNY, a Core Segment of the Yeast Prion Protein Sup35p iMR Advanced Training Workshop I Patrick C. A. van der Wel, Kan-Nian Hu, Jzef Lewandowski, and Robert G. Griffin J. Am. Chem. Soc., 2006, 128 (33), 10840-10846• DOI: 10.1021/ja0626685 • Publication Date (Web): 02 August 2006 ApplicationsDownloaded of fromDynamic http://pubs.acs.org Nuclear on April 27, 2009 Polarisation DNP no DNP More About This Article Józef Lewandowski Additional resources and features associated with this article are available within the HTML version: April 10 2013 • Supporting Information • Links to the 13 articles that cite this article, as of the time of this article download • Wednesday,Access 10 April to 13 high resolution figures • Links to articles and content related to this article • Copyright permission to reproduce figures and/or text from this article Journal of the American Chemical Society is published by the American Chemical Society. 1155 Sixteenth Street N.W., Washington, DC 20036 2/2/2011 2/2/2011 Why to do DNP? Why bother? MR3 Advanced Topics in MR Lectures 5 and 6: Dynamic Nuclear Polarisation 13C image DNP 13C-lactate .. Walter Kockenberger,Dissolution DNP [email protected] pressure cooker solvent (H O) 100 – 140°C 2 2 – 10 bar chase gas (Helium) (injected) (newly synthesised) 2 – 5 bar • more signal Klaes Golman et al • polarizer faster acquisition • new, previously not possible applications,sample cup now within the reach Wednesday, 10 April 13 Why bother? What’s on the plate? • Sensitivity and spin polarisation • Relevant spin interactions • The spin Hamiltonian for liquid state • Energy levels and populations I • The Solomon equations T. Maly/ R. Griffin, MIT • The Overhauser effect • The spin Hamiltonian for solid state • A small perturbation Things can be more12.6s complicated... • Mixing of states 7.2s • The probability for ‘forbidden’ transitions cross effect thermal mixing Enhancement ε+: ~10000 • Energy levels and populationsHardware II requirements e δ à ωn H 14.2sH en • Dynamics of the solid effect e en gly e n DNP e • Hee n Things can be more complicated... Hee n e n • Experimental strategies |ωe1-ωe2| = ωn e Waldemar Senczenko, UoNn 3 spin model liquids solids Multi-spin model SSSSII SSSSI I I++I++-›-› electron electron nuclear Zeeman dipolar Zeeman II reservoir reservoir reservoir dissolution experiment ++++++›› ωωωe1 sample shuttling I+-I+--›-› Lattice low field high field low field high field I+-I+-++›› I-+I-+-›-› Thermodynamical description I-+I-+++›› temperature jump I--I---›-› I--I--++›› positive enhancement ∆ω∆ω∆ωe = ωωωn 48 1 12 What do you need for DNP? 1. source of large polarisation 2. way to transfer it to the species you care about (relaxation or coherent process) ? 3. detect the high signal for your hyperpolarised species (they have to live long enough) Wednesday, 10 April 13 Hyperpolarisation techniques • laser polarised noble gases (3He and 129Xe) • chemical induced dynamic nuclear polarization (CIDNP) • parahydrogen induced polarization (PHIP) • microwave driven dynamic nuclear polarization (DNP) Wednesday, 10 April 13 Laser polarised noble gases (3He and 129Xe) 3He and 129Xe hyperpolarised using spin-exchange optical pumping (SEOP). SEOP: Circularly polarised infrared laser light excites e- in Cs or Rb ↓ The angular momentum is transferred from metal e- to noble gas nuclei through collisions. Wednesday, 10 April 13 Chemical induced dynamic nuclear polarization (CIDNP) • Using a thermal or photochemical reaction to create hyperpolarisation • Powerful but not general example: photo-CIDNP effect in entire cells of cyanobacteria Janssen, G. J.; Daviso, E.; van Son, M.; de Groot, H. J. M.; Alia, a; Matysik, J. Photosynthesis research 2010, 104, 275–82. Wednesday, 10 April 13 Parahydrogen induced polarization (PHIP) • Using parahydrogen in hydrogenation reactions to create hyperpolarisation • Also known as PASADENA (Parahydrogen and Synthesis Allow Dramatically Enhanced Nuclear Alignment) Wednesday, 10 April 13 Subscriber access provided by ECOLE NORMALE SUPERIEURE LYON Article Mine is bigger than yours. DynamicEnhancements Nuclear Polarization of Amyloidogenic Peptide Nanocrystals: GNNQQNY, a Core Segment of the Yeast Prion Protein Sup35p Patrick C. A. van der Wel, Kan-Nian Hu, Jzef Lewandowski, and Robert G. Griffin J. Am. Chem. Soc., 2006, 128 (33), 10840-10846• DOI: 10.1021/ja0626685 • Publication Date (Web): 02 August 2006 Downloadedenhancement from http://pubs.acs.org on April 27, 2009(ε)? More About This Article van der Wel, P. C. a, Hu, K.-N., Lewandowski, J. R. & Griffin, R. G. J. Am. Chem. Soc. 128, 10840–6 (2006). AdditionalWednesday, resources 10 April and13 features associated with this article are available within the HTML version: • Supporting Information • Links to the 13 articles that cite this article, as of the time of this article download • Access to high resolution figures • Links to articles and content related to this article • Copyright permission to reproduce figures and/or text from this article Journal of the American Chemical Society is published by the American Chemical Society. 1155 Sixteenth Street N.W., Washington, DC 20036 Mine is bigger than yours. Enhancements DNP enhancement; same sample at the same temperature ε → SNR microwave on/SNR microwave off DNP enhancement; same sample at the room temperature ε†→ ε×Boltzmann factor sensitivity enhancement; compared to a non-DNP sample at the same temperature Σ → ε×θ×√(κ) ratio of T1 for dry material and impregnated with radical solution paramagnetic quenching sensitivity enhancement; compared to a non-DNP sample at the room temperature Σ†→ ε×θ×√(κ)×Boltzmann factor Wednesday, 10 April 13 What do you need for microwave driven DNP? polarizing agent/ microwave source unpaired electrons - e + NMR/MRI set up oh, and a sample, off course... Wednesday, 10 April 13 Implementations of microwave driven dynamic nuclear polarization (DNP) improve the resolution of images of cells HF-liquid DNP Shuttleand other DNP biological systems; Pomplun and Glaser (DOI: 10.1039/c003751f) high frequency liquid DNP: in situ liquiddiscuss sample theoretical is rapidly methods moved for optimizing microwave excitation at the NMR fromtime the domainlow field, DNP where experiments, the an area that has thus far received little attention. detection field polarization is performed, to a All of these approaches are potentially highapplicable field region to a wide for NMR range of important NMRdetection experiments in biology, chemistry, physics and medicine, and their success- ful development will have an enormous impact on the field. Accordingly, a number of academic and industrial Dissolutionresearch groups have DNP recently initiated High Field efforts to overcome the current limita- tions of the techniques. Technical MAS DNP advances in the area of high-frequency the samplemicrowave is polarized sources in andthe components, solid and gyrotron as a microwave state atof very various low DNP temperatures approaches (Fig. 1), will source, solid sample (typicallybe 1–4 of vital K) and importance magnetic for the further irradiated with fields of development3–7 T, rapidly of dissolved, the DNP method, microwaves at the NMR and finallyespecially transferred at the to highest either magnetic a fields available for NMR ( 20 T). In addition, detection field high resolution NMR spectrometero implementationor a MR imager of microwave time domain experiments should open many Fig. 1 Typical experimental approaches for dynamic nuclear polarization spectrometers. new areas of application, just as rf time domain experiments did for high resolu- process, and resolution in low tempera- Applications of this method range from tion solid state and solution NMR. ture MAS experiments, is addressed here MR imaging of metabolites to studies of Other avenues, such as the optimization Downloaded on 07/04/2013 07:54:53. by Barnes et al. (DOI: 10.1039/c003763j). chemical reaction mechanisms (Bowen of polarizing agents, the development Wednesday, 10 April 13 Recently a commercial MAS DNP spec- and Hilty, DOI: 10.1039/c002316g; of new types of polarization transfer Published on 19 May 2010 http://pubs.rsc.org | doi:10.1039/C0CP90019B trometer became available that is Ludwig et al., DOI: 10.1039/c002700f; methods, and the design of new experi- described in this issue together with some Panek et al., DOI: 10.1039/c002710n; ments focusing on selectivity, contrast recent results obtained with the instru- Cudalbu et al., DOI: 10.1039/c002309b). and additional structural restraints, are ment (Rosay et al., DOI: 10.1039/ An essential ingredient of every DNP ripe for investigation. Thus, collaborative c003685b; Debelouchina et al., DOI: experiment is a stable polarizing agent, efforts among researchers from chemistry, 10.1039/c003661g). Also in this issue, and for the first 50 years of DNP these physics, biology, medicine, and the direct transfers to low-g nuclei (2H, 13C, consisted of readily available monomeric engineering disciplines will be required etc.) are discussed, and the enhance- paramagnetic centers such as a metal, or to optimize DNP for applications in ments, field profiles, and preferred organic radicals like BDPA or TEMPO. high-field NMR and MRI. We foresee polarizing agents are shown to be system More recently, several new polarizing a very bright and expansive future for dependent (Maly et al., DOI: 10.1039/ agents have been introduced that are this field, well into the 21st century. c003705b).40 In Dissolution DNP (lower more efficient in that they produce larger right) the sample is polarized in the solid enhancements at lower concentrations.41–44 state at very low temperatures (typically Four articles describe these new agents: References 1–4 K) and magnetic fields of 3–7 T, narrow line trityl radicals, biradicals and 1 R. R. Ernst and W. A. Anderson, Rev. Sci. rapidly dissolved, and finally transferred spin labeled polymers that separate Instrum., 1966, 37, 93–102. to either a high resolution NMR spectro- at higher temperatures and therefore 2 P. Styles, N. Soffe, C. Scott, D.