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51.
Chekmenev EY Chow SK Tofan D Weitekamp DP Ross BD Bhattacharya P 《The journal of physical chemistry. B》2008,112(20):6285-6287
The binding of amphiphilic molecules to lipid bilayers is followed by 19F NMR using chemical shift and line shape differences between the solution and membrane-tethered states of -CF 3 and -CHF 2 groups. A chemical shift separation of 1.6 ppm combined with a high natural abundance and high sensitivity of 19F nuclei offers an advantage of using 19F NMR spectroscopy as an efficient tool for rapid time-resolved screening of pharmaceuticals for membrane binding. We illustrate the approach with molecules containing both fluorinated tails and an acrylate moiety, resolving the signals of molecules in solution from those bound to synthetic dimyristoylphosphatidylcholine bilayers both with and without magic angle sample spinning. The potential in vitro and in vivo biomedical applications are outlined. The presented method is applicable with the conventional NMR equipment, magnetic fields of several Tesla, stationary samples, and natural abundance isotopes. 相似文献
52.
Chekmenev EY Jones SM Nikolayeva YN Vollmar BS Wagner TJ Gor'kov PL Brey WW Manion MN Daugherty KC Cotten M 《Journal of the American Chemical Society》2006,128(16):5308-5309
High magnetic field solid-state NMR was performed on amphipathic cationic antimicrobial peptides from fish to characterize their secondary structure and orientation in hydrated phospholipid bilayers. High-resolution distance and orientational restraints on 13C- and 15N-labeled amidated piscidins 1 and 3 provided site-specific information establishing alpha-helicity and an orientation parallel to the membrane surface. Few membrane-bound natural peptides with this topology have been structurally studied at high resolution in the presence of hydrated lipid bilayers. This orientation was foreseen since the partitioning of amphipathic cationic antimicrobial peptides at the water-bilayer interface allows for favorable peptide-lipid interactions, and it may be related to the mechanism of action. The enhanced resolution obtained at 900 MHz evidences a determinant advantage of ultra-high-field NMR for the structural determination of multiple-labeled peptides and proteins. 相似文献
53.
Max E. Gemeinhardt Miranda N. Limbach Thomas R. Gebhardt Clark W. Eriksson Shannon L. Eriksson Jacob R. Lindale Elysia A. Goodson Prof. Warren S. Warren Eduard Y. Chekmenev Boyd M. Goodson 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(1):426-431
Herein, we demonstrate “direct” 13C hyperpolarization of 13C-acetate via signal amplification by reversible exchange (SABRE). The standard SABRE homogeneous catalyst [Ir-IMes; [IrCl(COD)(IMes)], (IMes=1,3-bis(2,4,6-trimethylphenyl), imidazole-2-ylidene; COD=cyclooctadiene)] was first activated in the presence of an auxiliary substrate (pyridine) in alcohol. Following addition of sodium 1-13C-acetate, parahydrogen bubbling within a microtesla magnetic field (i.e. under conditions of SABRE in shield enables alignment transfer to heteronuclei, SABRE-SHEATH) resulted in positive enhancements of up to ≈100-fold in the 13C NMR signal compared to thermal equilibrium at 9.4 T. The present results are consistent with a mechanism of “direct” transfer of spin order from parahydrogen to 13C spins of acetate weakly bound to the catalyst, under conditions of fast exchange with respect to the 13C acetate resonance, but we find that relaxation dynamics at microtesla fields alter the optimal matching from the traditional SABRE-SHEATH picture. Further development of this approach could lead to new ways to rapidly, cheaply, and simply hyperpolarize a broad range of substrates (e.g. metabolites with carboxyl groups) for various applications, including biomedical NMR and MRI of cellular and in vivo metabolism. 相似文献
54.
Panayiotis Nikolaou Aaron M. Coffey Laura L. Walkup Brogan M. Gust Nicholas Whiting Hayley Newton Iga Muradyan Mikayel Dabaghyan Kaili Ranta Gregory D. Moroz Matthew S. Rosen Samuel Patz Michael J. Barlow Eduard Y. Chekmenev Boyd M. Goodson 《Magnetic resonance imaging》2014
Here we provide a full report on the construction, components, and capabilities of our consortium’s “open-source” large-scale (~ 1 L/h) 129Xe hyperpolarizer for clinical, pre-clinical, and materials NMR/MRI (Nikolaou et al., Proc. Natl. Acad. Sci. USA, 110, 14150 (2013)). The ‘hyperpolarizer’ is automated and built mostly of off-the-shelf components; moreover, it is designed to be cost-effective and installed in both research laboratories and clinical settings with materials costing less than $125,000. The device runs in the xenon-rich regime (up to 1800 Torr Xe in 0.5 L) in either stopped-flow or single-batch mode—making cryo-collection of the hyperpolarized gas unnecessary for many applications. In-cell 129Xe nuclear spin polarization values of ~ 30%–90% have been measured for Xe loadings of ~ 300–1600 Torr. Typical 129Xe polarization build-up and T1 relaxation time constants were ~ 8.5 min and ~ 1.9 h respectively under our spin-exchange optical pumping conditions; such ratios, combined with near-unity Rb electron spin polarizations enabled by the high resonant laser power (up to ~ 200 W), permit such high PXe values to be achieved despite the high in-cell Xe densities. Importantly, most of the polarization is maintained during efficient HP gas transfer to other containers, and ultra-long 129Xe relaxation times (up to nearly 6 h) were observed in Tedlar bags following transport to a clinical 3 T scanner for MR spectroscopy and imaging as a prelude to in vivo experiments. The device has received FDA IND approval for a clinical study of chronic obstructive pulmonary disease subjects. The primary focus of this paper is on the technical/engineering development of the polarizer, with the explicit goals of facilitating the adaptation of design features and operative modes into other laboratories, and of spurring the further advancement of HP-gas MR applications in biomedicine. 相似文献
55.
Christopher Nelson Dr. Andreas B. Schmidt Isaiah Adelabu Shiraz Nantogma Prof. Dr. Valerij G. Kiselev Abubakar Abdurraheem Henri de Maissin Dr. Sören Lehmkuhl Prof. Dr. Stephan Appelt Prof. Thomas Theis Prof. Eduard Y. Chekmenev 《Angewandte Chemie (International ed. in English)》2023,62(5):e202218484
The feasibility of Carbon-13 Radiofrequency (RF) Amplification by Stimulated Emission of Radiation (C-13 RASER) is demonstrated on a bolus of liquid hyperpolarized ethyl [1-13C]acetate. Hyperpolarized ethyl [1-13C]acetate was prepared via pairwise addition of parahydrogen to vinyl [1-13C]acetate and polarization transfer from nascent parahydrogen-derived protons to the carbon-13 nucleus via magnetic field cycling yielding C-13 nuclear spin polarization of approximately 6 %. RASER signals were detected from samples with concentration ranging from 0.12 to 1 M concentration using a non-cryogenic 1.4T NMR spectrometer equipped with a radio-frequency detection coil with a quality factor (Q) of 32 without any modifications. C-13 RASER signals were observed for several minutes on a single bolus of hyperpolarized substrate to achieve 21 mHz NMR linewidths. The feasibility of creating long-lasting C-13 RASER on biomolecular carriers opens a wide range of new opportunities for the rapidly expanding field of C-13 magnetic resonance hyperpolarization. 相似文献
56.
Dr. David O. Guarin Sameer M. Joshi Anna Samoilenko Mohammad S. H. Kabir Erin E. Hardy Dr. Atsush M. Takahashi Prof. Jan H. Ardenkjaer-Larsen Prof. Eduard Y. Chekmenev Dr. Yi-Fen Yen 《Angewandte Chemie (International ed. in English)》2023,62(31):e202219181
We report dissolution Dynamic Nuclear Polarization (d-DNP) of [15N3]metronidazole ([15N3]MNZ) for the first time. Metronidazole is a clinically approved antibiotic, which can be potentially employed as a hypoxia-sensing molecular probe using 15N hyperpolarized (HP) nucleus. The DNP process is very efficient for [15N3]MNZ with an exponential build-up constant of 13.8 min using trityl radical. After dissolution and sample transfer to a nearby 4.7 T Magnetic Resonance Imaging scanner, HP [15N3]MNZ lasted remarkably long with T1 values up to 343 s and 15N polarizations up to 6.4 %. A time series of HP [15N3]MNZ images was acquired in vitro using a steady state free precession sequence on the 15NO2 peak. The signal lasted over 13 min with notably long T2 of 20.5 s. HP [15N3]MNZ was injected in the tail vein of a healthy rat, and dynamic spectroscopy was performed over the rat brain. The in vivo HP 15N signals persisted over 70 s, demonstrating an unprecedented opportunity for in vivo studies. 相似文献
57.
Md Shahabuddin Alam Xinlin Li Drew O. Brittin Saiful Islam Prof. Dr. Pravas Deria Prof. Dr. Eduard Y. Chekmenev Prof. Dr. Boyd M. Goodson 《Angewandte Chemie (International ed. in English)》2023,62(8):e202213581
Hyperpolarized orthohydrogen (o-H2) is a frequent product of parahydrogen-based hyperpolarization approaches like signal amplification by reversible exchange (SABRE), where the hyperpolarized o-H2 signal is usually absorptive. We describe a novel manifestation of this effect wherein large antiphase o-H2 signals are observed, with 1H enhancements up to ≈500-fold (effective polarization PH≈1.6 %). This anomalous effect is attained only when using an intact heterogeneous catalyst constructed using a metal–organic framework (MOF) and is qualitatively independent of substrate nature. This seemingly paradoxical observation is analogous to the “partial negative line” (PNL) effect recently explained in the context of Parahydrogen Induced Polarization (PHIP) by Ivanov and co-workers. The two-spin order of the o-H2 resonance is manifested by a two-fold higher Rabi frequency, and the lifetime of the antiphase HP o-H2 resonance is extended by several-fold. 相似文献