WO2023234979A2 - Magnétométrie à champ élevé avec spins nucléaires hyperpolarisés - Google Patents

Magnétométrie à champ élevé avec spins nucléaires hyperpolarisés Download PDF

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Publication number
WO2023234979A2
WO2023234979A2 PCT/US2022/082002 US2022082002W WO2023234979A2 WO 2023234979 A2 WO2023234979 A2 WO 2023234979A2 US 2022082002 W US2022082002 W US 2022082002W WO 2023234979 A2 WO2023234979 A2 WO 2023234979A2
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Prior art keywords
nuclei
hyperpolarized
analyte
detector
field
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PCT/US2022/082002
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English (en)
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WO2023234979A3 (fr
Inventor
Ashok Ajoy
Ozgur Sahin
Emanuel DRUGA
Paul RESHETIKHIN
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The Regents Of The University Of California
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Publication of WO2023234979A2 publication Critical patent/WO2023234979A2/fr
Publication of WO2023234979A3 publication Critical patent/WO2023234979A3/fr

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    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N24/00—Investigating or analyzing materials by the use of nuclear magnetic resonance, electron paramagnetic resonance or other spin effects
    • G01N24/08—Investigating or analyzing materials by the use of nuclear magnetic resonance, electron paramagnetic resonance or other spin effects by using nuclear magnetic resonance
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01R—MEASURING ELECTRIC VARIABLES; MEASURING MAGNETIC VARIABLES
    • G01R33/00—Arrangements or instruments for measuring magnetic variables
    • G01R33/20—Arrangements or instruments for measuring magnetic variables involving magnetic resonance
    • G01R33/24—Arrangements or instruments for measuring magnetic variables involving magnetic resonance for measuring direction or magnitude of magnetic fields or magnetic flux
    • G01R33/26—Arrangements or instruments for measuring magnetic variables involving magnetic resonance for measuring direction or magnitude of magnetic fields or magnetic flux using optical pumping
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01R—MEASURING ELECTRIC VARIABLES; MEASURING MAGNETIC VARIABLES
    • G01R33/00—Arrangements or instruments for measuring magnetic variables
    • G01R33/20—Arrangements or instruments for measuring magnetic variables involving magnetic resonance
    • G01R33/44—Arrangements or instruments for measuring magnetic variables involving magnetic resonance using nuclear magnetic resonance [NMR]
    • G01R33/46—NMR spectroscopy

Definitions

  • This disclosure relates to nuclear magnetic resonance (NMR) spectroscopy, more particularly to NMR spectroscopy in high fields.
  • NMR Nuclear Magnetic Resonance
  • NV sensors constructed from the Nitrogen Vacancy (NV) defect center in diamond - electrons that can be optically initialized and interrogated, and made to report on nuclear spins in their environment.
  • NV sensors are still primarily restricted to bulk crystals and operation at low magnetic fields Bo ⁇ 0.05 T). Instead, for applications in NMR, high fields are naturally advantageous because the chemical shift dispersion is larger, and analyte nuclei carry higher polarization.
  • FIGs. 1 A-B shows graphical representations of diamond lattice with hyperpolarized nuclei.
  • FIGs. 2A-C show graphs related to a hyperpolarized sensing sequences.
  • FIGs. 3A-D show graphs related to signals in a NMR spectroscopy system.
  • FIGs. 4A-G show graphs related to enhanced signal delay with an applied AC field.
  • FIGs. 5A-H show graphs related to high-field sensor magnetometry
  • FIGs. 6A-C show graphs related to the frequency response of a 13 C magnetometer.
  • FIGs. 7A-D show graphs related to tracking magnetometer signals in the time domain.
  • FIGs. 8A-C show views of an embodiment of an NMR system and probe.
  • FIG. 1 A shows a diamond lattice with dipolar (dashed lines) coupled 13 C nuclei, hyperpolarized by optically pumped nitrogen vacancy (NV) center defects, shown as blue arrows.
  • FIG. IB Hyperpolarized 13 C nuclei are driven into the x axis (red arrow) via spin-locking. When the AC field (blue) is applied, the spins undergo secondary precessions shown by the arrows. 13 C nuclei in the diamond serve as the primary magnetic field sensors, while NV centers instead play a supporting role in optically initializing them.
  • the senor contains hyperpolarized nuclei. While the cunent discussion focuses on 13 C nuclei, any hyperpolarized nuclei can be used.
  • the sensor is exposed to the analyte nuclei by being brought into proximity to analyte. The detection occurs via time-varying fields produced by the analyte on the probe nuclei.
  • the detector may be optical or radio frequency and detects the changes in the precession of the hyperpolarized nuclei caused by the analyte. These changes allow for identification of the analyte.
  • 13 C nuclei as sensors stem from their attractive properties. Their low y n ⁇ y e /3000, enables control and interrogation at fields in the range of (Bo> 0.05 T).
  • the field may comprise a magnetic field of at least 0.05 T, but may have a range of at least 0.1 T, at least 0.3 T, or a range of 0.5 T.
  • Spin-1/2 13 C sensors can be housed in randomly oriented particles, as they are agnostic to crystallite orientation. They have long rotating frame lifetimes T 2 ⁇ orders of magnitude greater than their NV center counterparts. Similarly, their longitudinal lifetimes Ti > 10 min are long even at modest fields. This can allow a physical separation betw een field regions corresponding to 13 C initialization and sensing, and for the 13 C sensors to be transported between them. 13 C nuclei can be non-destructively readout via
  • the embodiments here demonstrate that these shortcomings can be mitigated. They exploit optical hyperpolarization of 13 C nuclei, as shown in FIG. 1A and spin-lock readout scheme that suppresses evolution under dipolar interactions. The resulting greater than 10,000-fold extension in 13 C lifetimes, from T 2 T 2 “, provides the basis for expanding sensor readout to minute long periods. These long 13 C rotating-frame lifetimes can at least partially offset sensitivity 7 losses arising from the low yn.
  • the sensing strategy' is described in FIG. IB. Hyperpolarized 13 C nuclei are placed along the transverse axis x (red arrow) on the
  • Bloch sphere at high field where they are preserved for multiple-second long T2 periods. Any subsequent deviation of the spin state from x-y plane can be continuously monitored and constitutes the magnetometer signal.
  • Bac(t) BAC COS(2TI/AC 1 )Z at a frequency /AC, the nuclei undergo a secondary precession in the y-z plane that carries an imprint of / C. Long T 2 yields high spectral resolution.
  • FIG. 2 shows the subsequently applied 13 C magnetometry protocol at 7 T. It entails a train of 0 pulses, spinlocking the nuclear spins along x, as shown in FIG. 2A. 13 C nuclei remain in quasi- equilibrium along x for several seconds. Flip angle 0 can be arbitrarily chosen, except for
  • T2 31 s shown by the red line in FIG. 3A.
  • the AC field however causes a comparatively rapid 13 C decay shown by the blue line in FIG. 3A along with magnetization oscillations, shown in FIG. 3C.
  • Sd is obtained via a 73 ms moving average filter applied to S in FIG. 2, and the oscillatory component isolated as So - S - Sd.
  • FIG. 4 shows that the process varies / C, and study the change in integrated value of Sd over a 5 s period, shown in FIG. 3B.
  • the phase of the applied AC field is random.
  • FIG. 4A reveals that the 13 C decay is unaffected for a wide range of frequencies, except for a sharp decay response, referred to here as the dip, centered at resonance fies shown by the dashed vertical line. With a Gaussian fit, the line width is estimated ⁇ 223 Hz.
  • the dip matches intuition developed from average Hamiltonian theory (AHT), shown in FIG. 4B-C, and discussed below. It can be considered to be an extension of dynamical decoupling (DD) sensing for arbitrary 9.
  • FIGs. 4E-F display individual decays in FIG. 4A on a linear scale and logarithmic scale against Points far from resonance (e g. (i) DC and (iv) 5 kHz) exhibit a stretched exponential decay oc exp(-t 1/2 ) characteristic of interactions with the Pl center spin bath. These manifest as the straight lines in FIG. 4F.
  • Points far from resonance e g. (i) DC and (iv) 5 kHz
  • FIG. 4F exhibit a stretched exponential decay oc exp(-t 1/2 ) characteristic of interactions with the Pl center spin bath.
  • FIG. 4G describes the linewidth dependence of the obtained resonance dip as a function of the number of pulses employed. Contrary to DD sensing, the linewidth does not fall with increasing number of pulses, suggesting it is dominated by 13 C dipolar couplings. [0024] Despite this relatively broad linewidth, high-resolution magnetometry can be extracted from the oscillatory component, So, shown in FIG. 3C.
  • FIG. 5B zooms into a representative 22 ms window. Strong 13 C oscillations are evident here. Taking a Fourier transform, one observes four sharp peaks, shown in FIG. 5C. The process identifies the two strongest peaks as being exactly at JAC and 2 fxc, as show n in FIG. 5C with the labels 1 and 2. This discussion refers to them as primary and secondary harmonics respectively. They are zoomed for clarity in FIGs. 5D-E, along with the noise level in FIG. 5F, from where the process extracts the AC magnetometry linewidths as 92 mHz and 96 mHz respectively. Two other smaller peaks in FIG.
  • the bandwidth ® 1/(2T) here is determined by the interpulse interval in FIG. 2A.
  • FIG. 5G show s the data in FIG. 5C in a logarithmic scale, with the harmonics marked.
  • FIG. 5H shows the scaling of the harmonic intensities with
  • the inventors performed experiments to determine the frequency response of the sensor, unraveling the sensitivity' profile at different frequencies, shown in FIG. 6.
  • the experiments seek to determine how it relates to the /res dip in FIG. 4.
  • the AC field mimics the effect of the analyte on the nuclei.
  • I refers to spin-1/2 Pauli matrices
  • WL is the nuclear Larmor frequency
  • (po is the initial (arbitrary) phase of the AC field
  • J ⁇ bki> ⁇ 663 Hz.
  • the spins are prepared initially along x in a state p(0) ⁇ sA. where e ⁇ 0.2% is the hyperpolarization level.
  • AHT average Hamiltonian theory
  • FIG. 2C shows the toggling frame Hamiltonians , which consists only of single body terms and hence can be plotted in a phasor representation.
  • the average Hamiltonian evident from the symmetrically distributed phasors in FIG. 4(i).
  • the DC field is decoupled.
  • the resonant AC case (/AC fns). The analysis here is simplest to carry out assuming a square-wave, as opposed to sinusoidal, field.
  • the phasor diagram is asymmetrical and the average Hamiltonian after four pulses, H AC oc — ly.
  • H AC oc average Hamiltonian after four pulses
  • the spins are undergoing a “secondary” precession in the rotating frame around x at frequency Q c ff. For each point on this motion, they are also precessing in the lab frame at ML.
  • Eq. (3) illustrates that the oscillations observed in FIG. 5 are equivalent to w atching the Larmor precession of the spins in the rotating frame. Since the sequence suppresses static I-field inhomogeneity, the lifetime of the oscillations can extend up to T ⁇ , as evidenced in FIG. 5A.
  • the growing oscillation strength in FIG. 5A indicates the spins tipping further away from the x axis. However, projections of the spin vector away from x do undergo dipolar decay, and the true amplitude of the oscillations observed depend on an interplay betwee and Ac.
  • FIG. 7 is analogous to the AC field driving a rapid adiabatic passage in the rotating frame.
  • 13 C sensor resolution is 5 ⁇ 1/NT.
  • FIG. 5 demonstrates a resolution better than 100 mHz.
  • finite memory limitations restricted capturing the 13 C Larmor precession here to t ⁇ 30s as shown in FIG. 5A. Overcoming these memory limits can allow acquisition of the entire spin-lock decay, lasting over 573 s. Under these conditions, an estimate a resolution of 2.2 mHz is feasible. This would correspond to a field precision of 3 ppt at a 7 T bias field, more than sufficient precision to discriminate chemical shifts.
  • RF interrogated sensing presents advantages in scattering environments. All data here were carried out with the diamond immersed in ⁇ 4mL water, over 2000-fold the volume of the sample. Traditional NV sensors are ineffective in this regime due to scattering losses and concomitant fluorescence fluctuations. Similarly, optically hyperpolarized sensors present advantages because majority of the sensor volume can be illuminated by the impinging lasers, with no geometrical constraints from requirements of collection optics. The experiments employed an array of low-cost laser diode sources for hyperpolarization, allowing recruiting a large volume of spins for sensing with a low overhead. Extension to powder samples could be advantageous for optimally packing a sensor volume.
  • the embodiments here have proposed and demonstrated a high-field magnetometry approach with hyperpolarized 13 C nuclear spins in diamond. Sensing leveraged long transverse spin 13 C lifetimes and their ability to be continuously interrogated, while mitigating effects due to interspin interaction.
  • the embodiments demonstrated magnetometry 7 with high- resolution (. lOOmHz) and at high-field (7T), yielding advantages over counterpart NV sensors in this regime. This work opens avenues for NMR sensors at high fields, and suggests interesting possibilities for employing dynamic nuclear polarization for quantum sensing.
  • FIG. 8 shows a probe set up used in the above experiments that gives on overview of the basic components of a system.
  • FIG. 8A shows an embodiment of internal probe, or sensor or detector, components showing a RF coil used for 13 C NMR and a z-coil by which the test AC is applied.
  • the probe 10 has the RF coil 12 and the z-coil 14 into the centers of which the sensor is shuttled.
  • the probe may include capacitors 16 to manage the electrical signals in the detector.
  • FIG. 8B shows a zoomed out view of the sensor.
  • the probe comprises oxygen-free high (thermal) conductivity (OFHC) coil, and an OFHC shield 18.
  • the OFHC shield is 54 nm in diameter.
  • the funnel 20 provides a port through which the hyperpolarized nuclei can be inserted into the probe after exposure to the analyte.
  • Both coils connect to independent rigid coaxial cables 36 and 58, but share a common ground.
  • the diamond sensor may be held under water in a test tube and then shuttled into the center of the RF coil.
  • FIG. 8C displays an embodiment of a circuit.
  • the upper block 30 shows an embodiment of a circuit used for the AC field application.
  • the upper block 30 is only used as an estimation of an analyte. Analytes generate a time-varying field, referred here as an AC field, that affects the hyperpolarized nuclei, so the block 30 generates a low-level AC field to mimic the effect of exposure to an analyte.
  • an AC field time-varying field
  • the NMR block 40 shows an embodiment of an NMR excitation and detection circuit.
  • the NMR block 40 includes a signal generator 44 to generate the signals at RF frequencies.
  • a quarter wave plate or line 46 and the filter 48 one embodiment a bandpass filter, ensure a high signal-to-noise ratio of the RF signal.
  • a transmit and receive switch 56 allows switching between the two modes of the circuit.
  • the RF field coil 12 comprises an RF saddle coil.
  • On the detection side of the switch 52 is an amplifier 54 and a NMR spectrometer that can detect the changes in the spins for analysis and identification of the analyte.
  • the process of using this detector involves exposing hyperpolarized nuclei to an analyte.
  • the hyperpolarization of the nuclei may occur in one of many ways, as mentioned above.
  • the hyperpolarized nuclei after exposure to the analyte, is interrogated by application of a radio frequency signal, typically in the form of a pulse sequence.
  • the nuclei is inserted into a probe structure that resides inside a magnet that generates a high-field magnetic field.
  • the resulting responses of the material generate a series of points that can be processed and analyzed to allow identification of analyte.

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Abstract

Un système de spectroscopie magnétique nucléaire comprend un capteur contenant des noyaux hyperpolarisés, et un détecteur pour détecter des changements de précession des noyaux de capteur lorsqu'ils sont exposés à un analyte. Un procédé de spectroscopie magnétique nucléaire comprend l'exposition d'un capteur contenant des noyaux hyperpolarisés à un analyte, à l'aide d'un détecteur pour détecter des changements de précession des noyaux de diamant hyperpolarisés provoqués par l'analyte, et l'identification de l'analyte par l'intermédiaire des changements.
PCT/US2022/082002 2021-12-20 2022-12-20 Magnétométrie à champ élevé avec spins nucléaires hyperpolarisés WO2023234979A2 (fr)

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WO2023234979A3 (fr) * 2021-12-20 2024-04-04 The Regents Of The University Of California Magnétométrie à champ élevé avec spins nucléaires hyperpolarisés

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US5468467A (en) * 1993-04-23 1995-11-21 Bracco International B.V. Methods for the in vivo measurement of the concentration of non-imaging nmr-detectable xenobiotic compounds
US5642625A (en) * 1996-03-29 1997-07-01 The Trustees Of Princeton University High volume hyperpolarizer for spin-polarized noble gas
GB0308586D0 (en) * 2003-04-14 2003-05-21 Amersham Health R & D Ab Method and arrangements in NMR spectroscopy
WO2020208103A1 (fr) * 2019-04-08 2020-10-15 Nvision Imaging Technologies Gmbh Système d'évaluation de molécules hyperpolarisées dans un échantillon biologique
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WO2023234979A3 (fr) * 2021-12-20 2024-04-04 The Regents Of The University Of California Magnétométrie à champ élevé avec spins nucléaires hyperpolarisés

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