共查询到20条相似文献,搜索用时 15 毫秒
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Pascal Miéville Puneet Ahuja Riddhiman Sarkar Dr. Sami Jannin Dr. Paul R. Vasos Dr. Sandrine Gerber‐Lemaire Dr. Mor Mishkovsky Dr. Arnaud Comment Dr. Rolf Gruetter Prof. Olivier Ouari Dr. Paul Tordo Prof. Geoffrey Bodenhausen Prof. 《Angewandte Chemie (International ed. in English)》2010,49(35):6182-6185
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Pascal Miéville Puneet Ahuja Dr. Riddhiman Sarkar Dr. Sami Jannin Dr. Paul R. Vasos Dr. Sandrine Gerber‐Lemaire Dr. Mor Mishkovsky Dr. Arnaud Comment Prof. Rolf Gruetter Dr. Olivier Ouari Prof. Paul Tordo Prof. Geoffrey Bodenhausen 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2010,122(43):8004-8004
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Implementation and Characterization of Flow Injection in Dissolution Dynamic Nuclear Polarization NMR Spectroscopy 下载免费PDF全文
The use of dissolution dynamic nuclear polarization (D ‐DNP) offers substantially increased signals in liquid‐state NMR spectroscopy. A challenge in realizing this potential lies in the transfer of the hyperpolarized sample to the NMR detector without loss of hyperpolarization. Here, the use of a flow injection method using high‐pressure liquid leads to improved performance compared to the more common gas‐driven injection, by suppressing residual fluid motions during the NMR experiment while still achieving a short injection time. Apparent diffusion coefficients are determined from pulsed field gradient echo measurements, and are shown to fall below 1.5 times the value of a static sample within 0.8 s. Due to the single‐scan nature of D ‐DNP, pulsed field gradients are often the only choice for coherence selection or encoding, but their application requires stationary fluid. Sample delivery driven by a high‐pressure liquid will improve the applicability of these types of D‐DNP advanced experiments. 相似文献
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Dr. Maria Concistré Dr. Subhradip Paul Marina Carravetta Ilya Kuprov Dr. Philip T. F. Williamson 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(68):15852-15854
Combining dynamic nuclear polarization with proton detection significantly enhances the sensitivity of magic-angle spinning NMR spectroscopy. Herein, the feasibility of proton-detected experiments with slow (10 kHz) magic angle spinning was demonstrated. The improvement in sensitivity permits the acquisition of indirectly detected 14N NMR spectra allowing biomolecular structures to be characterized without recourse to isotope labelling. This provides a new tool for the structural characterization of environmental and medical samples, in which isotope labelling is frequently intractable. 相似文献
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Natural Abundance 15N NMR by Dynamic Nuclear Polarization: Fast Analysis of Binding Sites of a Novel Amine‐Carboxyl‐Linked Immobilized Dirhodium Catalyst 下载免费PDF全文
Torsten Gutmann Jiquan Liu Niels Rothermel Yeping Xu Eva Jaumann Mayke Werner Hergen Breitzke Snorri T. Sigurdsson Gerd Buntkowsky 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(9):3798-3805
A novel heterogeneous dirhodium catalyst has been synthesized. This stable catalyst is constructed from dirhodium acetate dimer (Rh2(OAc)4) units, which are covalently linked to amine‐ and carboxyl‐bifunctionalized mesoporous silica (SBA‐15?NH2?COOH). It shows good efficiency in catalyzing the cyclopropanation reaction of styrene and ethyl diazoacetate (EDA) forming cis‐ and trans‐1‐ethoxycarbonyl‐2‐phenylcyclopropane. To characterize the structure of this catalyst and to confirm the successful immobilization, heteronuclear solid‐state NMR experiments have been performed. The high application potential of dynamic nuclear polarization (DNP) NMR for the analysis of binding sites in this novel catalyst is demonstrated. Signal‐enhanced 13C CP MAS and 15N CP MAS techniques have been employed to detect different carboxyl and amine binding sites in natural abundance on a fast time scale. The interpretation of the experimental chemical shift values for different binding sites has been corroborated by quantum chemical calculations on dirhodium model complexes. 相似文献
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Alexandre Zagdoun Dr. Aaron J. Rossini Dr. Matthew P. Conley Wolfram R. Grüning Martin Schwarzwälder Dr. Moreno Lelli Dr. W. Trent Franks Prof. Dr. Hartmut Oschkinat Prof. Dr. Christophe Copéret Prof. Dr. Lyndon Emsley Dr. Anne Lesage 《Angewandte Chemie (International ed. in English)》2013,52(4):1222-1225
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Adam N. Smith Dr. Marc A. Caporini Prof. Gail E. Fanucci Prof. Joanna R. Long 《Angewandte Chemie (International ed. in English)》2015,54(5):1542-1546
Dynamic nuclear polarization (DNP) magic‐angle spinning (MAS) solid‐state NMR (ssNMR) spectroscopy has the potential to enhance NMR signals by orders of magnitude and to enable NMR characterization of proteins which are inherently dilute, such as membrane proteins. In this work spin‐labeled lipid molecules (SL‐lipids), when used as polarizing agents, lead to large and relatively homogeneous DNP enhancements throughout the lipid bilayer and to an embedded lung surfactant mimetic peptide, KL4. Specifically, DNP MAS ssNMR experiments at 600 MHz/395 GHz on KL4 reconstituted in liposomes containing SL‐lipids reveal DNP enhancement values over two times larger for KL4 compared to liposome suspensions containing the biradical TOTAPOL. These findings suggest an alternative sample preparation strategy for DNP MAS ssNMR studies of lipid membranes and integral membrane proteins. 相似文献
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In this work, we review the hyperpolarization technique named chemically induced dynamic nuclear polarization (CIDNP), focusing on the time-resolved variant of this method and its biological applications. We introduce the main principles of polarization formation in liquids at high magnetic fields, provided by the so-called spin sorting mechanism. Applications of CIDNP to studying fast reactions of short-lived free radicals of biologically important molecules are discussed, as well as the potential of the method to probe the structure and magnetic parameters of such radicals. We also explain the principles of protein CIDNP and discuss applications of time-resolved CIDNP to studies of protein structure and dynamics. 相似文献
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Yoh Matsuki Dr. Thorsten Maly Dr. Olivier Ouari Dr. Hakim Karoui Dr. François Le Moigne Dr. Egon Rizzato Dr. Sevdalina Lyubenova Dr. Judith Herzfeld Prof. Thomas Prisner Prof. Paul Tordo Prof. Robert G. Griffin Prof. 《Angewandte Chemie (International ed. in English)》2009,48(27):4996-5000
A new polarizing agent with superior performance in dynamic nuclear polarization experiments is introduced, and utilizes two TEMPO (2,2,6,6‐tetramethylpiperidine‐1‐oxyl) moieties connected through a rigid spiro tether (see structure). The observed NMR signal intensities were enhanced by a factor of 1.4 compared to those of TOTAPOL, a previously described TEMPO‐based biradical with a flexible tether.
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Dissolution dynamic nuclear polarization (DNP) enables high‐sensitivity solution‐phase NMR experiments on long‐lived nuclear spin species such as 15N and 13C. This report explores certain features arising in solution‐state 1H NMR upon polarizing low‐γ nuclear species. Following solid‐state hyperpolarization of both 13C and 1H, solution‐phase 1H NMR experiments on dissolved samples revealed transient effects, whereby peaks arising from protons bonded to the naturally occurring 13C nuclei appeared larger than the typically dominant 12C‐bonded 1H resonances. This enhancement of the satellite peaks was examined in detail with respect to a variety of mechanisms that could potentially explain this observation. Both two‐ and three‐spin phenomena active in the solid state could lead to this kind of effect; still, experimental observations revealed that the enhancement originates from 13C→1H polarization‐transfer processes active in the liquid state. Kinetic equations based on modified heteronuclear cross‐relaxation models were examined, and found to well describe the distinct patterns of growth and decay shown by the 13C‐bound 1H NMR satellite resonances. The dynamics of these novel cross‐relaxation phenomena were determined, and their potential usefulness as tools for investigating hyperpolarized ensembles and for obtaining enhanced‐sensitivity 1H NMR traces was explored. 相似文献
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Dynamic Nuclear Polarization Provides New Insights into Chromophore Structure in Phytochrome Photoreceptors 下载免费PDF全文
Daniel Stöppler Dr. Chen Song Dr. Barth‐Jan van Rossum Michel‐Andreas Geiger Christina Lang Prof. Dr. Maria‐Andrea Mroginski Dr. Anil Pandurang Jagtap Prof. Dr. Snorri Th. Sigurdsson Prof. Dr. Jörg Matysik Prof. Dr. Jon Hughes Prof. Dr. Hartmut Oschkinat 《Angewandte Chemie (International ed. in English)》2016,55(52):16017-16020
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Björn C. Dollmann Dr. Andrei L. Kleschyov Dr. Vasily Sen Dr. Valery Golubev Prof. Dr. Laura M. Schreiber Prof. Dr. Hans W. Spiess Dr. Kerstin Münnemann Dr. Dariush Hinderberger 《Chemphyschem》2010,11(17):3656-3663
A potentially biocompatible class of spin‐labeled macromolecules, spin‐labeled (SL) heparins, and their use as nuclear magnetic resonance (NMR) signal enhancers are introduced. The signal enhancement is achieved through Overhauser‐type dynamic nuclear polarization (DNP). All presented SL‐heparins show high 1H DNP enhancement factors up to E=?110, which validates that effectively more than one hyperfine line can be saturated even for spin‐labeled polarizing agents. The parameters for the Overhauser‐type DNP are determined and discussed. A striking result is that for spin‐labeled heparins, the off‐resonant electron paramagnetic resonance (EPR) hyperfine lines contribute a non‐negligible part to the total saturation, even in the absence of Heisenberg spin exchange (HSE) and electron spin‐nuclear spin relaxation (T1ne). As a result, we conclude that one can optimize the use of, for example, biomacromolecules for DNP, for which only small sample amounts are available, by using heterogeneously distributed radicals attached to the molecule. 相似文献
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Dao Le Fabio Ziarelli Trang N. T. Phan Giulia Mollica Pierre Thureau Fabien Aussenac Olivier Ouari Didier Gigmes Paul Tordo Stphane Viel 《Macromolecular rapid communications》2015,36(15):1416-1421
High‐field dynamic nuclear polarization (DNP) has emerged as a powerful technique for improving the sensitivity of solid‐state NMR (SSNMR), yielding significant sensitivity enhancements for a variety of samples, including polymers. Overall, depending upon the type of polymer, the molecular weight, and the DNP sample preparation method, sensitivity enhancements between 5 and 40 have been reported. These promising enhancements remain, however, far from the theoretical maximum (>1000). Crucial to the success of DNP SSNMR is the DNP signal enhancement (εDNP), which is the ratio of the NMR signal intensities with and without DNP. It is shown here that, for polymers exhibiting high affinity toward molecular oxygen (e.g., polystyrene), removing part of the absorbed (paramagnetic) oxygen from the solid‐state samples available as powders (instead of dissolved or dispersed in a solvent) increases proton nuclear relaxation times and εDNP, hereby providing up to a two‐fold sensitivity increase (i.e., a four‐fold reduction in experimental time).
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An important development in the field of NMR spectroscopy has been the advent of hyperpolarization approaches, capable of yielding nuclear spin states whose value exceeds by orders‐of‐magnitude what even the highest‐field spectrometers can afford under Boltzmann equilibrium. Included among these methods is an ex situ dynamic nuclear polarization (DNP) approach, which yields liquid‐phase samples possessing spin polarizations of up to 50 %. Although capable of providing an NMR sensitivity equivalent to the averaging of about 1 000 000 scans, this methodology is constrained to extract its “superspectrum” within a single—or at most a few—transients. This makes it a poor starting point for conventional 2D NMR acquisition experiments, which require a large number of scans that are identical to one another except for the increment of a certain t1 delay. It has been recently suggested that by merging this ex situ DNP approach with spatially encoded “ultrafast” methods, a suitable starting point could arise for the acquisition of 2D spectra on hyperpolarized liquids. Herein, we describe the experimental principles, potential features, and current limitations of such integration between the two methodologies. For a variety of small molecules, these new hyperpolarized ultrafast experiments can, for equivalent overall durations, provide heteronuclear correlation spectra at significantly lower concentrations than those currently achievable by conventional 2D NMR acquisitions. A variety of challenges still remain to be solved before bringing the full potential of this new integrated 2D NMR approach to fruition; these outstanding issues are discussed. 相似文献