Parahydrogen hyperpolarization membrane reactor
In one aspect, the disclosure relates to a compact membrane reactor for parahydrogen induced hyperpolarization, the reactor including an inner tube constructed of a semipermeable membrane, an outer tube surrounding the inner tube, and a means for controlling the magnetic field surrounding the outer tube. In some aspects, multiple compact membrane reactors can be arranged in parallel. In other aspects, the compact membrane reactor is equipped with a mechanism for magnetic field control. Also disclosed are fluid handling systems and sample preparation systems comprising the compact membrane reactors disclosed herein. The compact membrane reactor can be operated in a batch mode, a stopped-flow mode, or a continuous flow mode and can be configured to work with existing NMR spectrometers and MRI instruments.
1 . A sample preparation system for parahydrogen-induced hyperpolarization, the system comprising:
at least one compact membrane reactor, the reactor comprising:
(a) an inner tube comprising a semipermeable membrane;
(b) an outer tube surrounding the inner tube; and
(c) a means for controlling a magnetic field surrounding the outer tube; wherein the means for controlling a magnetic field is configured to hyperpolarize parahydrogen in the outer tube and wherein the hyperpolarized parahydrogen permeates the inner tube and induces hyperpolarization in a sample in the inner tube; and
a fluid handling apparatus, wherein the fluid handling apparatus comprises a batch mode fluid handling apparatus and a catalyst removal unit, wherein the catalyst-removal unit is a column comprising a first medium and wherein the first medium comprises thiol-doped silicon microparticles.
2 . The sample preparation system of claim 1 , wherein the semipermeable membrane comprises a gas-liquid interfacial area of greater than 1000 m 2 /m 3 .
3 . The sample preparation system of claim 1 , wherein the semipermeable membrane comprises an amorphous fluoropolymer.
4 . The sample preparation system of claim 1 , wherein the means for controlling a magnetic field comprises a radio frequency coil, a shielding mechanism, a solenoid powered with direct current, a permanent magnet array, a superconducting magnet, or a combination thereof.
5 . A method of using the sample preparation system of claim 1 to generate high spin polarization on a spin ½ nucleus in a sample, the method comprising: (a) introducing a solution comprising the sample through the inner tube; (b) introducing parahydrogen through the outer tube; and (c) applying a current to the means for controlling a magnetic field to generate a magnetic field.
6 . The method of claim 5 , wherein the spin ½ nucleus comprises 1 H, 13 C, 15 N, 19 F, 31 P, or any combination thereof.
7 . The method of claim 5 , wherein the high spin polarization is generated by hydrogenation.
8 . The method of claim 5 , wherein the high spin polarization is generated by signal amplification by reversible exchange.
9 . The method of claim 5 , wherein the solution comprising the sample further comprises a polarization transfer catalyst.
10 . A method for continuous detection of radiowave amplification by stimulated emission of radiation (RASER) effects in a sample using a nuclear magnetic resonance (NMR) spectrometer, the method comprising: (a) subjecting the sample to the method of claim 5 ; and (b) analyzing the sample using the NMR spectrometer.
11 . The method of claim 10 , wherein RASER effects are observable when parahydrogen pressure in the outer tube is about 90 psi (620.5 kPa).
12 . The method of claim 10 , wherein the RASER effects are observable for a period of time longer than a T 2 relaxation time for protons in the sample.
13 . The method of claim 10 , wherein the RASER effects are observable when the NMR spectrometer has a field strength of from about 1 T to about 10 T.
14 . The sample preparation system of claim 1 , wherein the column further comprises a second medium, and wherein the second medium comprises high iridium affinity MoS extraction sheets.
15 . The sample preparation system of claim 1 , wherein the catalyst-removal unit comprises a nanofiltration membrane having a molecular weight cutoff of from about 150 Da to about 1000 Da.
16 . A hyperpolarized sample prepared by the sample preparation system of claim 1 , wherein the hyperpolarized sample is substantially free of polarization transfer catalyst.