WO2005101949A2 - A high resolution low temperature solid-state nuclear magnetic resonance probe - Google Patents

A high resolution low temperature solid-state nuclear magnetic resonance probe Download PDF

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Publication number
WO2005101949A2
WO2005101949A2 PCT/EE2005/000005 EE2005000005W WO2005101949A2 WO 2005101949 A2 WO2005101949 A2 WO 2005101949A2 EE 2005000005 W EE2005000005 W EE 2005000005W WO 2005101949 A2 WO2005101949 A2 WO 2005101949A2
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WO
WIPO (PCT)
Prior art keywords
nuclear magnetic
magnetic resonance
rotor
probe
high resolution
Prior art date
Application number
PCT/EE2005/000005
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French (fr)
Other versions
WO2005101949A3 (en
Inventor
Ago Samoson
Ivo Heinmaa
Tiit Tuherm
Andres Reinhold
Jaan Past
Raivo Stern
Tiit ANUPÕLD
Original Assignee
Keemilise Ja Bioloogilise Füüsika Instituut (The National Institute Of Chemical Physics And Biophysics)
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
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Application filed by Keemilise Ja Bioloogilise Füüsika Instituut (The National Institute Of Chemical Physics And Biophysics) filed Critical Keemilise Ja Bioloogilise Füüsika Instituut (The National Institute Of Chemical Physics And Biophysics)
Publication of WO2005101949A2 publication Critical patent/WO2005101949A2/en
Publication of WO2005101949A3 publication Critical patent/WO2005101949A3/en

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Classifications

    • 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
    • G01R33/28—Details of apparatus provided for in groups G01R33/44 - G01R33/64
    • G01R33/30—Sample handling arrangements, e.g. sample cells, spinning mechanisms
    • G01R33/307—Sample handling arrangements, e.g. sample cells, spinning mechanisms specially adapted for moving the sample relative to the MR system, e.g. spinning mechanisms, flow cells or means for positioning the sample inside a spectrometer
    • 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
    • G01R33/28—Details of apparatus provided for in groups G01R33/44 - G01R33/64
    • G01R33/30—Sample handling arrangements, e.g. sample cells, spinning mechanisms
    • G01R33/31—Temperature control thereof

Definitions

  • the invention belongs to the field of nuclear magnetic resonance (NMR) and concerns an NMR probe with a rotor rotating at low temperature (lower than 77K) .
  • High resolution NMR spectra of solid bodies enables obtaining detailed information about the atomic structure and dynamics of substances.
  • the most widespread method for obtaining high resolution NMR spectra is spinning a sample about an axis positioned at the magic angle (54.7°) relative to the external magnetic field direction.
  • a design is used where powder sample is placed in a cylinder shaped rotor that rests with both ends on gas bearings and is driven by a gas stream, directed to the blades of a cylindrical cap, constituting the turbine [Patent E. Lippmaa, et al . US4254373] .
  • the majority of magic angle spinning (MAS) probes operate at room temperature or can be cooled down to about 100K.
  • MAS probe designed by Hackman et al [A.
  • a rotating device was used, where the powder sample was placed in a glass container, one end of which was placed in a thermostat with adjustable temperature and the other end was concentrically placed in a rotor, rotated at a higher temperature. Due to the complexity of the rotating device, the magic-angle spinning speeds remained in the range of few kHz that did not enable wider use of the probe.
  • the task of this invention was to design a nuclear magnetic resonance probe that would enable performing NMR measurements at temperatures near the helium liquefaction temperature under the conditions of high spinning speeds and double resonance.
  • the set task has been solved so that the magic-angle rotating device, which comprises a rotor that contains the substance under study, rests on bearings, is equipped with a turbine and around which a measuring coil is wound, is placed in the helium flowthrough cryostat, where temperature is maintained by a temperature regulator.
  • the cryostat together with the rotating device and a heat exchanger is placed in a superconducting magnet (Fig.l). Gas amounts necessary for the rotation of the rotor to generate gas bearing and helium gas flow directed by the turbine blades are conducted into the rotating device through the heat exchanger, in which room temperature helium gas is cooled by liquid nitrogen first to 77K and then in a tubes- in-the-tube type heat exchanger to lower temperatures . Helium gas exits from the cryostat in the opposite direction, cooling the supply helium gas.
  • the rotating device of the probe is designed for the rotation of small- diameter rotors. Decreasing the diameter of the rotors reduces considerably tribologic heating and ensures low temperatures at high rotation speeds and low gas consumption.
  • FIG 1. shows the design of the low temperature magic-angle- spinning NMR probe .
  • FIG 2. shows polarization transfer and proton decoupled 13 C high resolution spectra in 13 C enriched L-alanine; rotation speed v rot corresponds to the conditions of the so-called "rotation resonance".
  • NMR probe for obtaining spectra on low temperatures has been built according to the design shown in FIG 1.
  • a rotating device for the rotation of rotors with the diameter of 1.8 mm is used in the probe, that enables to reach low temperatures depending on the rotation speed to 7K (at rotation speed 5kHz), 15K (10kHz), 20K(20kHz) shown in FIG. 2.
  • This probe polarization transfer and decoupled double resonance experiments have been carried out, an example of which is 13 CMAS polarization transfer spectrum in 5 g 13 C enriched alanine at the temperatures of 8.3K and 293K.
  • the spectrum registered at 8.3K has an order of magnitude better signal/noise ratio as compared to the high temperature spectrum.

Landscapes

  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Magnetic Bearings And Hydrostatic Bearings (AREA)
  • Rolling Contact Bearings (AREA)
  • Magnetic Resonance Imaging Apparatus (AREA)

Abstract

This invention relates to an nuclear magnetic resonance (NMR) probe, which enables registering high resolution NMR double resonance spectra in powder samples by high-speed magic angle spinning at low temperatures. The idea of rotating device used in the design is based on using a small-diameter rotor which is placed in a helium gas flowthrough cryostat, ensuring low temperatures. The spinning of the rotor takes place as a result of gas flow directed to the gas bearings supported turbine. New is the use of an effective heat exchanger for cooling down the bearing and turbine gas.

Description

A HIGH RESOLUTION LOW TEMPERATURE SOLID-STATE NUCLEAR MAGNETIC RESONANCE PROBE
TECHNICAL FIELD
The invention belongs to the field of nuclear magnetic resonance (NMR) and concerns an NMR probe with a rotor rotating at low temperature (lower than 77K) .
BACKROUND ART
High resolution NMR spectra of solid bodies enables obtaining detailed information about the atomic structure and dynamics of substances. The most widespread method for obtaining high resolution NMR spectra is spinning a sample about an axis positioned at the magic angle (54.7°) relative to the external magnetic field direction. Therewith a design is used where powder sample is placed in a cylinder shaped rotor that rests with both ends on gas bearings and is driven by a gas stream, directed to the blades of a cylindrical cap, constituting the turbine [Patent E. Lippmaa, et al . US4254373] . The majority of magic angle spinning (MAS) probes operate at room temperature or can be cooled down to about 100K. The exception is MAS probe, designed by Hackman et al [A. Hackman, H. Seidel, R. D. Kendrick, P. C. Myhre, C. S. Yannoni, J. Magn. Resonance, 1988, vol.79, pl48] that enabled getting high resolution NMR spectra at near liquid He temperatures. In the said probe a rotating device was used, where the powder sample was placed in a glass container, one end of which was placed in a thermostat with adjustable temperature and the other end was concentrically placed in a rotor, rotated at a higher temperature. Due to the complexity of the rotating device, the magic-angle spinning speeds remained in the range of few kHz that did not enable wider use of the probe.
DISCLOSURE OF THE INVENTION
The task of this invention was to design a nuclear magnetic resonance probe that would enable performing NMR measurements at temperatures near the helium liquefaction temperature under the conditions of high spinning speeds and double resonance.
The set task has been solved so that the magic-angle rotating device, which comprises a rotor that contains the substance under study, rests on bearings, is equipped with a turbine and around which a measuring coil is wound, is placed in the helium flowthrough cryostat, where temperature is maintained by a temperature regulator.
The cryostat together with the rotating device and a heat exchanger is placed in a superconducting magnet (Fig.l). Gas amounts necessary for the rotation of the rotor to generate gas bearing and helium gas flow directed by the turbine blades are conducted into the rotating device through the heat exchanger, in which room temperature helium gas is cooled by liquid nitrogen first to 77K and then in a tubes- in-the-tube type heat exchanger to lower temperatures . Helium gas exits from the cryostat in the opposite direction, cooling the supply helium gas. The rotating device of the probe is designed for the rotation of small- diameter rotors. Decreasing the diameter of the rotors reduces considerably tribologic heating and ensures low temperatures at high rotation speeds and low gas consumption. In the design of the rotating device materials with a small thermal expansion coefficient are used. That ensures stable rotation in a wide temperature range. Moderate excessive pressure of helium, generated in the cryostat, prevents electric breakdown on the ends of the measuring coil, allowing to carry out double resonance NMR experiments. Rotation speed is regulated by helium pressure regulators at room temperature.
DESCRIPTION OF THE DRAWINGS
FIG 1. shows the design of the low temperature magic-angle- spinning NMR probe .
FIG 2. shows polarization transfer and proton decoupled 13C high resolution spectra in 13C enriched L-alanine; rotation speed vrot corresponds to the conditions of the so-called "rotation resonance".
DESCRIPTION OF EMBODIMENT An NMR probe for obtaining spectra on low temperatures has been built according to the design shown in FIG 1. A rotating device for the rotation of rotors with the diameter of 1.8 mm is used in the probe, that enables to reach low temperatures depending on the rotation speed to 7K (at rotation speed 5kHz), 15K (10kHz), 20K(20kHz) shown in FIG. 2. With this probe polarization transfer and decoupled double resonance experiments have been carried out, an example of which is 13CMAS polarization transfer spectrum in 5 g 13C enriched alanine at the temperatures of 8.3K and 293K. The spectrum registered at 8.3K has an order of magnitude better signal/noise ratio as compared to the high temperature spectrum.
An important practical application of this probe is studying the structure of biological acromolecules, which due to significant improvement in signal to noise ratio at low temperatures makes such research possible.

Claims

CLAIM
High resolution low temperature solid state nuclear magnetic resonance probe which comprises a rotor that contains the substance under study, rests on bearings and is equipped with a turbine, c h a r a c t e r i z e d in that the diameter of the rotor is decreased to achieve sufficient cooling with available and limited cooling power and desired rotation speed, and equipped with caps to compensate for cooling-induced contraction, and the rotating device is built of materials, selected according to the relative thermal expansion and according to changes in the properties of gaseous helium at low temperatures, whereas the gas that drives the rotor is pre-cooled by liquid nitrogen and additionally pre-cooled by sub-cooled liquid nitrogen and regulated by valves at room temperature, and the said probe is placed in the cryostat, that comprises a heat exchanger for measuring nuclear magnetic resonance spectra at a temperature lower than 77K and that enables additional cooling of the rotating device by the gaseous or vapors of liquid helium.
PCT/EE2005/000005 2004-04-20 2005-04-18 A high resolution low temperature solid-state nuclear magnetic resonance probe WO2005101949A2 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EEU200400029U EE00582U1 (en) 2004-04-20 2004-04-20 High resolution low temperature solid state nuclear magnetic resonance probe
EEU200400029 2004-04-20

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WO2005101949A2 true WO2005101949A2 (en) 2005-11-03
WO2005101949A3 WO2005101949A3 (en) 2006-08-03

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20130091870A1 (en) * 2011-10-17 2013-04-18 Bruker Biospin Cold gas supply device and NMR installation comprising such a device
CN109187612A (en) * 2018-08-21 2019-01-11 中国科学院广州能源研究所 A kind of method that the solid state nmr of gas hydrate characterizes preceding sample preparation dress sample

Citations (15)

* Cited by examiner, † Cited by third party
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US4254373A (en) * 1977-06-03 1981-03-03 Lippmaa Endel T Sensor for generating nuclear magnetic resonance signals
US4511841A (en) * 1982-06-17 1985-04-16 Chemagnetics, Inc. Method and apparatus for high speed magic angle spinning
US4899111A (en) * 1988-08-03 1990-02-06 The Regents Of The University Of California Probe for high resolution NMR with sample reorientation
US5122745A (en) * 1989-07-28 1992-06-16 The Dow Chemical Company Method and apparatus for determining molecular dynamics of materials
US5202633A (en) * 1990-11-01 1993-04-13 Doty Scientific, Inc. High temperature nmr sample spinner
US5298864A (en) * 1990-03-15 1994-03-29 Bruker Analytische Messtechnik Gmbh Nuclear magnetic resonance spectrometer and method for measuring the nuclear magnetic resonance
US5325059A (en) * 1992-03-26 1994-06-28 Doty Scientific Inc. DOR NMR sample spinner
US5754048A (en) * 1996-07-17 1998-05-19 Bruker Instruments, Inc. Method and apparatus for precisely controlling the periodic motion of an object
US6130537A (en) * 1997-03-20 2000-10-10 Doty Scientific Inc. HR MAS NMR coils with magic angle capacitors
US6320384B1 (en) * 1996-12-23 2001-11-20 David F. Doty Thermal buffering of cross-coils in high-power NMR decoupling
US20030052678A1 (en) * 2001-07-27 2003-03-20 The University Of Chicago Rotational exchange gradient imager for in situ magnetic resonance analyses in ultracentrifuge sedimentation of biological materials and rheology investigations
US20030102867A1 (en) * 2001-10-03 2003-06-05 Jeol Ltd. High-speed sample spinner for solid NMR spectroscopy
US20030199751A1 (en) * 2000-10-13 2003-10-23 Benjamin Gonzalez Method and device for analysing the intracellular chemical state of living cells by nuclear magnetic resonance
US20040070398A1 (en) * 2002-10-15 2004-04-15 Wong Wai Ha RF coil for magic angle spinning probe
US20040222796A1 (en) * 2003-02-04 2004-11-11 Munson Eric Jon Solid-state nuclear magnetic resonance probe

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Publication number Priority date Publication date Assignee Title
US4254373A (en) * 1977-06-03 1981-03-03 Lippmaa Endel T Sensor for generating nuclear magnetic resonance signals
US4511841A (en) * 1982-06-17 1985-04-16 Chemagnetics, Inc. Method and apparatus for high speed magic angle spinning
US4899111A (en) * 1988-08-03 1990-02-06 The Regents Of The University Of California Probe for high resolution NMR with sample reorientation
US5122745A (en) * 1989-07-28 1992-06-16 The Dow Chemical Company Method and apparatus for determining molecular dynamics of materials
US5298864A (en) * 1990-03-15 1994-03-29 Bruker Analytische Messtechnik Gmbh Nuclear magnetic resonance spectrometer and method for measuring the nuclear magnetic resonance
US5202633A (en) * 1990-11-01 1993-04-13 Doty Scientific, Inc. High temperature nmr sample spinner
US5325059A (en) * 1992-03-26 1994-06-28 Doty Scientific Inc. DOR NMR sample spinner
US5754048A (en) * 1996-07-17 1998-05-19 Bruker Instruments, Inc. Method and apparatus for precisely controlling the periodic motion of an object
US6320384B1 (en) * 1996-12-23 2001-11-20 David F. Doty Thermal buffering of cross-coils in high-power NMR decoupling
US6130537A (en) * 1997-03-20 2000-10-10 Doty Scientific Inc. HR MAS NMR coils with magic angle capacitors
US20030199751A1 (en) * 2000-10-13 2003-10-23 Benjamin Gonzalez Method and device for analysing the intracellular chemical state of living cells by nuclear magnetic resonance
US20030052678A1 (en) * 2001-07-27 2003-03-20 The University Of Chicago Rotational exchange gradient imager for in situ magnetic resonance analyses in ultracentrifuge sedimentation of biological materials and rheology investigations
US20030102867A1 (en) * 2001-10-03 2003-06-05 Jeol Ltd. High-speed sample spinner for solid NMR spectroscopy
US20040070398A1 (en) * 2002-10-15 2004-04-15 Wong Wai Ha RF coil for magic angle spinning probe
US20040222796A1 (en) * 2003-02-04 2004-11-11 Munson Eric Jon Solid-state nuclear magnetic resonance probe

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HACKMANN A ET AL: "Magic-Angle Spinning NMR at Near-Liquid-Helium Temperatures" JOURNAL OF MAGNETIC RESONANCE, ACADEMIC PRESS, ORLANDO, FL, USA, vol. 79, no. 1, August 1988 (1988-08), pages 148-153, XP002377650 cited in the application *
MARTIN R W ET AL: "Variable temperature system using vortex tube cooling and fiber optic temperature measurement for low temperature magic angle spinning NMR" JOURNAL OF MAGNETIC RESONANCE, ACADEMIC PRESS, ORLANDO, FL, US, vol. 168, no. 2, 27 March 2004 (2004-03-27), pages 202-209, XP004508572 ISSN: 1090-7807 *
MARTIN RACHEL W ET AL: "Design of a triple resonance magic angle sample spinning probe for high field solid state nuclear magnetic resonance" REVIEW OF SCIENTIFIC INSTRUMENTS, AMERICAN INSTITUTE OF PHYSICS, US, vol. 74, no. 6, June 2003 (2003-06), pages 3045-3061, XP012040877 ISSN: 0034-6748 *
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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20130091870A1 (en) * 2011-10-17 2013-04-18 Bruker Biospin Cold gas supply device and NMR installation comprising such a device
US10041629B2 (en) * 2011-10-17 2018-08-07 Bruker Biospin Cold gas supply device and NMR installation comprising such a device
CN109187612A (en) * 2018-08-21 2019-01-11 中国科学院广州能源研究所 A kind of method that the solid state nmr of gas hydrate characterizes preceding sample preparation dress sample

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EE00582U1 (en) 2006-01-16
WO2005101949A3 (en) 2006-08-03

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