共查询到20条相似文献,搜索用时 15 毫秒
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The experimental studies of the dynamic nuclear polarization In the chemical reactions(CINDP)[1-11] discover some characteristic peculiarities — the unusual behaviour of the spin multiplets, the appearance of nuclear polarization in the products of cage radical recombination, and finally, the dependence of the sign of polarization upon the type of reaction in which the radical participates. These pecularities are specific for CINDP and differentiate CINDP from the ordinary two-frequency dynamic nuclear polarization. 相似文献
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Dynamic nuclear polarization (DNP) transfers electron spin-polarization to nuclear spins in close proximity, increasing sensitivity by two-to-three orders of magnitude. This enables nuclear magnetic resonance (NMR) experiments on samples with low concentrations of analyte. The requirement of using cryogenic temperatures in DNP-enhanced solid-state NMR (ssNMR) experiments may impair the resolution and hence limit its broad application to biological systems. In this work, we introduce a “High-Temperature DNP” approach, which aims at increasing spectral resolution by performing experiments at temperatures of around 180?K instead of?~100?K. By utilizing the extraordinary enhancements obtained on deuterated proteins, still sufficiently large DNP enhancements of 11–18 are obtained for proton and carbon, respectively. We recorded high sensitivity 2D 13C–13C spectra in?~9?min with higher resolution than at 100?K, which has similar resolution to the one obtained at room temperature for some favorable residues. 相似文献
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Dr. David J. Lurie I. Nicholson J. S. McLay J. R. Mallard 《Applied magnetic resonance》1992,3(5):917-925
The technique of Field-Cycled Dynamic Nuclear Polarization (FC-DNP) involves the EPR irradiation of a free radical solution and the subsequent observation of the NMR signal, the experiment being carried out at a range of magnetic field strengths in order to measure the free radical’s EPR spectrum. In this work FC-DNP has been used to study the EPR spectrum of DMPO spin-trapped hydroxyl free radicals at magnetic field strengths between 0.5 mT and 13.0 mT (5–130 Gauss). The low-field EPR spectrum contains six separate EPR lines, in contrast to the well-known X-band spectrum where only four are seen. Knowledge of the spin-adduct’s EPR spectrum will be of use to workers involved in low-field EPR, especially those conducting biological or in-vivo spin-trapping experiments. 相似文献
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LIAO JiZhi 《理论物理通讯》1999,31(4):619-624
The solid-effect rate equations for the dynamic nuclear polarization of spin-1/2 (tritium or hydrogen) or spin-1 (deuterium) nuclei are derived in the limiting case of the electronspin-resonance line width being much smaller than the nuclear-magnetic-resonance frequency. The exact analytical solutions of the rate equations for spin-1/2 nuclei are given, while the rate equations for spin-1 nuclei, which are nonlinear, are solved in decoupling approximation. The nuclear polarization and the electronic polarization as well as the times to polarization are calculated in low temperature limit. It is found that there is an optimal radio frequency pumping rate for the nuclear polarizations, which is not considered until now. 相似文献
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We describe a low-temperature thermodynamic model for dynamic nuclear polarization (DNP) via continuous-wave partial saturation of electron spin resonance (ESR) lines that are both homogeneously and inhomogeneously broadened. It is a variant of a reasoning proposed by Borghini, which in turn used Redfield’s thermodynamic treatment of saturation. Our variant is furthermore based on Provotorov’s insight that under partial saturation of a coupled-spin system two distinct spin temperatures should appear in a thermodynamical theory. We apply our model to DNP results obtained at a temperature of 1.2?K and in magnetic fields of 3.35 and 5?T on 1-13C labeled sodium acetate dissolved in a frozen D2O/ethanol-d6 solution doped with the free radical TEMPO. 相似文献
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G. Annino J. A. Villanueva-Garibay P. J. M. van Bentum A. A. K. Klaassen A. P. M. Kentgens 《Applied magnetic resonance》2010,37(1-4):851-864
This contribution presents a novel design of a double-resonance structure for high-field dynamic nuclear polarization operating at 95 GHz and 144 MHz, in which a miniaturized radiofrequency coil is integrated within a single-mode nonradiative dielectric resonator. After a detailed discussion of the design principles, the conversion factors of this system are determined by means of microwave and radiofrequency measurements. The obtained results, 1.68 mT/W1/2 for the microwave conversion factor and 0.8 mT/W1/2 for the radiofrequency conversion factor, represent the state-of-the-art among the double-resonance structures. Simultaneous electron paramagnetic resonance and liquid-state 1H nuclear magnetic resonance experiments are performed on samples of nitroxide radical 2,2,6,6-tetramethylpiperidine-1-oxyl dissolved in a mixture of water and dioxane. A maximum dynamic nuclear polarization enhancement of about ?16 is obtained at a microwave power of 70 mW with a radical concentration of 10 mM in nanoliter-sized sample volumes. These results are discussed in view of further improvements and applications of the proposed double-resonance structure. 相似文献
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Marcello Alecci David J. Lurie 《Journal of magnetic resonance (San Diego, Calif. : 1997)》1999,138(2):313-319
EPR irradiation by a train of inverting pulses has potential advantages over continuous-wave EPR irradiation in DNP applications; however, it has previously been used only at high field (5 T). This paper presents the design and testing of an apparatus for performing pulsed DNP experiments at 10 mT with large samples (17 ml). Experimental results using pulsed DNP with an aqueous solution of a narrow-linewidth paramagnetic probe are presented. A maximum DNP enhancement of about -36 with a train of inverting pulses (width 500 ns, repetition time 4 micros) was measured. A preliminary comparison showed that, when the same enhancement value is considered, the pulsed DNP technique requires an average power that is about three times higher than that required with the CW irradiation. However, for in vivo DNP applications it is very important to minimize the average power deposited in the sample. From the experimental results reported in this work, when considering the maximum enhancement, the pulsed technique requires only 2% of the average power necessary with the CW DNP technique. We believe that this reduction in the average power can be important for future DNP studies with large biological samples. 相似文献
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Kelvin L. Billingsley Jae Mo Park Sonal Josan Ralph Hurd Dirk Mayer Eleanor Spielman-Sun Dwight G. Nishimura James D. Brooks Daniel Spielman 《Magnetic resonance imaging》2014
Recent advancements in the field of hyperpolarized 13C magnetic resonance spectroscopy (MRS) have yielded powerful techniques capable of real-time analysis of metabolic pathways. These non-invasive methods have increasingly shown application in impacting disease diagnosis and have further been employed in mechanistic studies of disease onset and progression. Our goals were to investigate branched-chain aminotransferase (BCAT) activity in prostate cancer with a novel molecular probe, hyperpolarized [1-13C]-2-ketoisocaproate ([1-13C]-KIC), and explore the potential of branched-chain amino acid (BCAA) metabolism to serve as a biomarker. Using traditional spectrophotometric assays, BCAT enzymatic activities were determined in vitro for various sources of prostate cancer (human, transgenic adenocarcinoma of the mouse prostate (TRAMP) mouse and human cell lines). These preliminary studies indicated that low levels of BCAT activity were present in all models of prostate cancer but enzymatic levels are altered significantly in prostate cancer relative to healthy tissue. The MR spectroscopic studies were conducted with two cellular models (PC-3 and DU-145) that exhibited levels of BCAA metabolism comparable to the human disease state. Hyperpolarized [1-13C]-KIC was administered to prostate cancer cell lines, and the conversion of [1-13C]-KIC to the metabolic product, [1-13C]-leucine ([1-13C]-Leu), could be monitored via hyperpolarized 13C MRS. 相似文献
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该文介绍了一种自行设计和构建的可扩展脉冲动态核极化谱仪,可以实现核磁共振波谱与磁共振成像的功能.该仪器的新颖设计主要有:1) 采用基于PCIe 的分布式总线结构,能够极大地提高数据传输效率和通信可靠性,实现精确控制脉冲序列;2) 采用外部高速的DDR 芯片存储脉冲序列元素和FID 数据,可以极大的提高脉冲序列的执行速度,减少快速成像序列的TR 时间间隔;3) 采用时钟移相技术,可以精确产生分辨率为纳秒级别的数字脉冲.最后对该仪器的动态核极化-磁共振波谱与核磁共振成像功能进行了实验验证. 相似文献