共查询到20条相似文献,搜索用时 15 毫秒
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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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Ryunosuke Hata Dr. Hiroshi Nonaka Dr. Yoichi Takakusagi Prof. Dr. Kazuhiro Ichikawa Prof. Dr. Shinsuke Sando 《Angewandte Chemie (International ed. in English)》2016,55(5):1765-1768
Aminopeptidase N (APN) is an important enzyme that is involved in tumor angiogenesis. Detection of APN activity can thus lead to early diagnosis and elucidation of tumor development. Although some molecular probes for APN have been developed, the detection of APN activity in opaque biological samples remains a challenge. To this end, we designed a hyperpolarized NMR probe [1‐13C]Ala‐NH2 which satisfies the prerequisites for APN detection, namely, sufficient retention of the hyperpolarized state, a high reactivity to APN, and an APN‐induced chemical shift change. The [1‐13C]Ala‐NH2 probe allowed sensitive detection of APN activity using 13C NMR spectroscopy. 相似文献
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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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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 (International ed. in English)》2010,49(43):7834-7834
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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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《化学:亚洲杂志》2017,12(9):949-953
Hyperpolarization is an emerging method that dramatically enhances NMR signal intensity. As a result of their increased sensitivity, hyperpolarized (HP) NMR molecular probes can be used to perform time‐resolved spectroscopy and imaging in vitro and in vivo. It is, however, challenging to design such probes de novo. Herein, the [1‐13C]α‐amino acid is reported as a scaffold structure to design HP 13C NMR molecular probes. The [1‐13C]α‐amino acid can be converted to various HP 13C chemical probes that show sufficient chemical shift change by altering the chemical state of the α nitrogen upon interaction with the target. Several previously reported HP probes could be explained by this design principle. To demonstrate the versatility of this approach, two α‐amino‐acid‐based HP 13C chemical probes, sensitive to pH and Ca2+ ion, were developed and used to detect targets. 相似文献
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Dr. Kirill V. Kovtunov Ekaterina V. Pokochueva Oleg G. Salnikov Dr. Samuel F. Cousin Dr. Dennis Kurzbach Dr. Basile Vuichoud Prof. Sami Jannin Prof. Eduard Y. Chekmenev Prof. Boyd M. Goodson Dr. Danila A. Barskiy Prof. Igor V. Koptyug 《化学:亚洲杂志》2018,13(15):1857-1871
The intensity of NMR signals can be enhanced by several orders of magnitude by using various techniques for the hyperpolarization of different molecules. Such approaches can overcome the main sensitivity challenges facing modern NMR/magnetic resonance imaging (MRI) techniques, whilst hyperpolarized fluids can also be used in a variety of applications in material science and biomedicine. This Focus Review considers the fundamentals of the preparation of hyperpolarized liquids and gases by using dissolution dynamic nuclear polarization (d‐DNP) and parahydrogen‐based techniques, such as signal amplification by reversible exchange (SABRE) and parahydrogen‐induced polarization (PHIP), in both heterogeneous and homogeneous processes. The various new aspects in the formation and utilization of hyperpolarized fluids, along with the possibility of observing NMR signal enhancement, are described. 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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Prof. Dr. Jan‐Henrik Ardenkjaer‐Larsen Prof. Dr. Gregory S. Boebinger Prof. Dr. Arnaud Comment Prof. Dr. Simon Duckett Prof. Dr. Arthur S. Edison Dr. Frank Engelke Prof. Dr. Christian Griesinger Prof. Dr. Robert G. Griffin Prof. Dr. Christian Hilty Prof. Dr. Hidaeki Maeda Prof. Dr. Giacomo Parigi Prof. Dr. Thomas Prisner Dr. Enrico Ravera Prof. Dr. Jan van Bentum Prof. Dr. Shimon Vega Prof. Dr. Andrew Webb Prof. Dr. Claudio Luchinat Prof. Dr. Harald Schwalbe Prof. Dr. Lucio Frydman 《Angewandte Chemie (International ed. in English)》2015,54(32):9162-9185
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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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Understanding J‐Modulation during Spatial Encoding for Sensitivity‐Optimized Ultrafast NMR Spectroscopy 下载免费PDF全文
Boris Gouilleux Laetitia Rouger Benoît Charrier Dr. Ilya Kuprov Prof. Serge Akoka Dr. Jean‐Nicolas Dumez Dr. Patrick Giraudeau 《Chemphyschem》2015,16(14):3093-3100
Ultrafast (UF) NMR spectroscopy is an approach that yields 2D spectra in a single scan. This methodology has become a powerful analytical tool that is used in a large array of applications. However, UF NMR spectroscopy still suffers from an intrinsic low sensitivity, and from the need to compromise between sensitivity, spectral width, and resolution. In particular, the modulation of signal intensities by the spin–spin J‐coupling interaction (J‐modulation) impacts significantly on the intensities of the spectral peaks. This effect can lead to large sensitivity losses and even to missing spectral peaks, depending on the nature of the spin system. Herein, a general simulation package (Spinach) is used to describe J‐modulation effects in UF experiments. The results from simulations match with experimental data and the results of product operator calculations. Several methods are proposed to optimize the sensitivity in UF COSY spectra. The potential and drawbacks of the different strategies are also discussed. These approaches provide a way to adjust the sensitivity of UF experiments for a large range of applications. 相似文献
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Dr. Carlos Fernández‐de‐Alba Dr. Hiroki Takahashi Alexandre Richard Yves Chenavier Dr. Lionel Dubois Vincent Maurel Dr. Daniel Lee Dr. Sabine Hediger Dr. Gaël De Paëpe 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(12):4512-4517
Magic‐angle spinning dynamic nuclear polarization (MAS‐DNP) has been proven to be a powerful technique to enhance the sensitivity of solid‐state NMR (SSNMR) in a wide range of systems. Here, we show that DNP can be used to polarize lipids using a lipid‐anchored polarizing agent. More specifically, we introduce a C16‐functionalized biradical, which allows localization of the polarizing agents in the lipid bilayer and DNP experiments to be performed in the absence of excess cryo‐protectant molecules (glycerol, dimethyl sulfoxide, etc.). This constitutes another original example of the matrix‐free DNP approach that we recently introduced. 相似文献