Barskiy Danila A, Salnikov Oleg G, Shchepin Roman V, Feldman Matthew A, Coffey Aaron M, Kovtunov Kirill V, Koptyug Igor V, Chekmenev Eduard Y
Vanderbilt University Institute of Imaging Sciences , Nashville, Tennessee 37232, United States.
International Tomography Center SB RAS, Novosibirsk 630090, Russia; Novosibirsk State University, Novosibirsk 630090, Russia.
J Phys Chem C Nanomater Interfaces. 2016 Dec 29;120(51):29098-29106. doi: 10.1021/acs.jpcc.6b07555. Epub 2016 Oct 26.
Parahydrogen-induced polarization (PHIP) is an NMR hyperpolarization technique that increases nuclear spin polarization by orders of magnitude, and it is particularly well-suited to study hydrogenation reactions. However, the use of high-field NMR spectroscopy is not always possible, especially in the context of potential industrial-scale reactor applications. On the other hand, the direct low-field NMR detection of reaction products with enhanced nuclear spin polarization is challenging due to near complete signal cancellation from nascent parahydrogen protons. We show that hydrogenation products prepared by PHIP can be irradiated with weak (on the order of spin-spin couplings of a few hertz) alternating magnetic field (called Spin-Lock Induced Crossing or SLIC) and consequently efficiently detected at low magnetic field (e.g., 0.05 T used here) using examples of several types of organic molecules containing a vinyl moiety. The detected hyperpolarized signals from several reaction products at tens of millimolar concentrations were enhanced by 10000-fold, producing NMR signals an order of magnitude greater than the background signal from protonated solvents.
仲氢诱导极化(PHIP)是一种核磁共振超极化技术,它能将核自旋极化提高几个数量级,特别适合用于研究氢化反应。然而,高场核磁共振光谱并不总是可行的,尤其是在潜在的工业规模反应器应用的背景下。另一方面,由于新生仲氢质子几乎完全抵消信号,直接在低场核磁共振中检测具有增强核自旋极化的反应产物具有挑战性。我们表明,通过PHIP制备的氢化产物可以用弱(几赫兹的自旋 - 自旋耦合量级)交变磁场(称为自旋锁定诱导交叉或SLIC)进行辐照,因此使用几种含有乙烯基部分的有机分子实例,能够在低磁场(例如这里使用的0.05 T)下有效地检测到。在数十毫摩尔浓度下,几种反应产物检测到的超极化信号增强了10000倍,产生的核磁共振信号比质子化溶剂的背景信号大一个数量级。