EP4473327A1 - Improvements in mas nmr - Google Patents
Improvements in mas nmrInfo
- Publication number
- EP4473327A1 EP4473327A1 EP23702349.4A EP23702349A EP4473327A1 EP 4473327 A1 EP4473327 A1 EP 4473327A1 EP 23702349 A EP23702349 A EP 23702349A EP 4473327 A1 EP4473327 A1 EP 4473327A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- coil
- rotor
- fluid
- probe head
- axis
- Prior art date
- Legal status (The legal status 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 status listed.)
- Withdrawn
Links
Classifications
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- 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
- G01R33/32—Excitation or detection systems, e.g. using radio frequency signals
- G01R33/34—Constructional details, e.g. resonators, specially adapted to MR
- G01R33/34046—Volume type coils, e.g. bird-cage coils; Quadrature bird-cage coils; Circularly polarised coils
- G01R33/34053—Solenoid coils; Toroidal coils
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- 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
- G01R33/32—Excitation or detection systems, e.g. using radio frequency signals
- G01R33/34—Constructional details, e.g. resonators, specially adapted to MR
- G01R33/34092—RF coils specially adapted for NMR spectrometers
Definitions
- the present invention relates to a coil for a probe head of a magnetic resonance spectrometer and to probe heads for a probe of a magnetic resonance spectrometer.
- Magic angle spinning [1-3] (MAS) is necessary in solid state nuclear magnetic resonance (NMR) to obtain high-resolution spectra for characterizing the local chemical environment of biomolecular and inorganic solids [4-17],
- Traditional MAS employees a cylindrical sample container rotating about an axis inclined at the magic angle, which is 54.74° with respect to the external magnetic field.
- a solenoid coil is wrapped tightly around the cylindrical rotor for optimal NMR sensitivity.
- the rotor, coil and stator have to be oriented along the magic angle, resulting in only 80% usage of the radio frequency (RF) power.
- the stator assembly consists of ⁇ 12 precisely machined components to house the rotor and supply bearing and drive gas streams, requiring large probe head space. Rotor wobbling during the spinning at high frequencies may cause rotor crash and stator damage.
- a coil for a probe head of a magnetic resonance spectrometer comprising a rotor.
- the coil is configured to transmit at least one radiofrequency signal in order to excite a sample being received in the rotor. Additionally or alternatively, the coil is configured to receive at least one radiofrequency signal being emitted by the sample in response to an excitation of the sample by a radio frequency signal. That is, the coil preferably corresponds to a radio frequency coil such as a transmit-receive coil capable of transmitting and receiving radiofrequency signals.
- the coil comprises a plurality of turns that are arranged along a coil axis extending along the coil. The plurality of turns of the coil define an ellipsoid shape, preferably a spherical shape.
- defining an ellipsoid shape is understood as the turns of the coil being arranged along the coil axis such, that a fictitious surface that envelopes the plurality of turns has the shape of an ellipsoid.
- the turns of the coils can be designed and/or arranged such that different ellipsoid shapes are formed.
- the turns can be designed and/or arranged such that an ellipsoid shape in the form of a sphere or a spheroid such as an oblate spheroid or a prolate spheroid is formed.
- the ellipsoid shape has the shape of a sphere.
- the plurality of turns of the coil define a spherical shape.
- the coil particularly preferably is a spherical coil.
- the shape of the coil does not correspond to a cylindrical shape as it is the case with the straight solenoid coils for cylindrical rotors known in the state of the art.
- the ellipsoidal coil allows the coil axis to be aligned perpendicular to the direction of the external magnetic field in an NMR spectrometer regardless of the axis of rotation of the rotor. Consequently, if one is defining said direction of the external magnetic field as the z- axis, all of the magnetic field B1 being generated by radiofrequency pulses is generated along an x,y-plane being spanned by x- and y-axis running perpendicularly to the z-axis.
- NMR experiments such as dynamic-angle spinning (DAS) and variable-angle spinning can be performed without compromising the B1 field, whereby the sensitivity is greatly improved.
- DAS dynamic-angle spinning
- variable-angle spinning can be performed without compromising the B1 field, whereby the sensitivity is greatly improved.
- spinning and rotating are used interchangeably.
- a spinning rotor corresponds to a rotating rotor and vice versa.
- a circumference of the individual turns of the coil with respect to a circumferential direction of the turns is preferably elliptic, particularly preferably circular. That is to say, an individual turn preferably has an elliptic shape and particularly preferably a circular shape when the coil is seen in cross-section, i.e. when seen as a plane section at an angle of 90° with respect to the coil axis.
- the circumference of the individual turns with respect to the circumferential direction of the turns preferably varies with respect to the coil axis. That is to say, it is preferred that the turns extend at different distances from the coil axis. Again in other words, turns of different size such as smaller turns and larger turns are preferred.
- the circumference of the turns preferably becomes increasingly larger and then increasingly smaller. That is, the circumference of the turns in the region of the beginning of the coil and the circumference of the turns in the region of the end of the coil is preferably smaller than the circumference of the turns in a middle region of the coil. That is, the circumference of the turn or turns in the middle region is particularly preferred largest.
- a preferred extension of the coil along an axis extending through a center of the coil and along the coil axis preferably is between 1 millimeter to 20 millimeter, more preferably between 5 millimeter to 15 millimeter.
- a preferred extension of the coil along an axis extending through the center of the coil and perpendicularly to the coil axis preferably is between 1 millimeter to 20 millimeter, more preferably between 5 millimeter to 15 millimeter.
- the coil diameter of the coil preferably is between 1 millimeter to 20 millimeter, more preferably between 5 millimeter to 15 millimeter.
- the coil extension (diameter) preferably depends on a size of the rotor. In fact, it is preferred that the coil extension (diameter) is larger than a rotor diameter of the rotor.
- the coil extension (diameter) is particularly preferably between 0.001 millimeter to 15 millimeter, more preferably between 0.001 millimeter to 4 millimeter larger than the rotor diameter.
- a distance between successive turns of the coil can remain constant or can vary with respect to the coil axis. In the latter case, as an example, it is preferred that the distance between successive turns of the coil is smaller in the middle region of the coil. That is, a higher number of turns is preferred in the middle region of the coil, whereas the number of turns is preferably sparser in the outer regions of the coil, i.e. in the region of the beginning and end of the coil.
- a preferred number of turns is between 2 turns to 10 turns.
- the said coil diameter is defined by the largest turn, i.e. it is preferred that the said coil diameter corresponds to the diameter of the largest turn of the coil.
- the coil in particular its turns, is preferably formed by a wire.
- a wire diameter of the wire can remain constant or can vary with respect to the coil axis.
- a wire diameter of the wire is preferably between 0.0001 millimeter to 2 millimeter.
- various distances between successive turns with respect to the coil axis are conceivable. For instance, a preferred distance between successive turns with respect to the coil axis is between 0.0001 millimeter to 5 millimeter.
- the rotor is at least partially and preferably entirely received in the coil.
- the coil is at least partially and preferably entirely wrapped around the rotor.
- a shape of the rotor preferably corresponds to a shape of the coil. That is, it is preferred that the rotor has an ellipsoid shape, particularly preferably a spherical shape.
- the rotor is preferably rotatable with respect to the coil. In other words, the rotor can rotate or spin within the coil.
- a major advantage of the ellipsoidal rotor being received in the ellipsoidal coil is a greatly improved NMR filling factor and thus sensitivity in the NMR experiment.
- a probe head for a probe of a magnetic resonance spectrometer comprises a rotor being configured to rotate about an axis of rotation, at least one rotation device being configured to generate a rotation of the rotor about the axis of rotation, and at least one coil.
- the rotation device comprises at least one fluid supply device that is configured to supply a fluid to the rotor.
- the coil is configured to transmit at least one radiofrequency signal in order to excite a sample being received in the rotor. Additionally or alternatively, the coil is configured to receive at least one radiofrequency signal being emitted by the sample in response to an excitation of the sample by a radio frequency signal.
- the rotation device further comprises at least one fluid directing device that is configured and/or arranged to direct the fluid being supplied by the fluid supply device to the rotor, and wherein the fluid directing device comprises or consists of the coil.
- the coil can correspond to a coil as described previously.
- various types of coils as they are known in the state of the art could likewise be used.
- the coil could be a saddle coil, a Helmholtz coil, etc.
- the probe head comprises a rotation device that comprises the coil.
- the coil is part of a stator, wherein the stator is understood as the mechanics that supply and affect a fluid flow being used to rotate a rotor.
- Current strategies for rotating rotors require a stator being arranged between the coil and the rotor comprising the sample.
- These apparatuses have disadvantages such as i) requiring precise design and fabrication of the stator cup and the fluid channel for supplying the fluid for stable spinning, ii) limit the use of inductors such as solenoid coils because of the stator geometry, iii) do not function well in cryogenic environments, and iv) are not durable due to damage caused by the rotating rotor to the softer stator cup.
- Imprecise design and fabrication damages and bad behavior in cryogenic environments negatively affect the sensitivity of the NMR experiments. Besides, the high-precision requirement for the fabrication is associated with high costs. These disadvantages are overcome by the present probe head, wherein the capability of the rotor rotating or spinning within the coil releases the high-precision requirement, making it easier for the stator development of smaller rotors, and again greatly improves the NMR filling factor and thus the sensitivity.
- the fluid directing device is particularly preferably configured and/or arranged such that a bearing force and/or a drive force rotating the rotor about the axis of rotation is generated.
- the bearing force and the drive force are preferably generated by the fluid flowing through a gap between the rotor and the coil as will be explained in greater detail below.
- an initial velocity of the rotor is preferably obtained from the fluid supply device.
- the fluid supply device preferably comprises at least one fluid aperture for supplying the fluid to the rotor.
- the fluid supply device comprises two or more, in particular a plurality of fluid apertures for supplying the fluid to the rotor.
- two or more fluid apertures are preferably arranged to provide rotation of the rotor about the axis of rotation.
- two or more fluid apertures are preferably arranged in at least one or one common plane.
- a probe head for a magnetic resonance spectrometer comprising a rotor being configured to rotate about an axis of rotation, at least one rotation device being configured to generate a rotation of the rotor about the axis of rotation, and at least one coil.
- the coil is configured to transmit at least one radiofrequency signal in order to excite a sample being received in the rotor. Additionally or alternatively, the coil is configured to receive at least one radiofrequency signal being emitted by the sample in response to an excitation of the sample by a radio frequency signal.
- the rotation device comprises at least one fluid supply device that is configured to supply a fluid to the rotor.
- the fluid supply device comprises a plurality of fluid apertures for supplying the fluid to the rotor.
- the plurality of fluid apertures are arranged to provide rotation of the rotor about the axis of rotation. Additionally or alternatively, the plurality of fluid apertures are arranged in at least one or one common plane.
- the one or more common planes the fluid apertures are arranged in preferably runs or run perpendicularly to the rotation axis of the rotor.
- a plurality of fluid apertures in at least one or exactly one common plane results in an overall fluid flow that provides an improved, in particular a higher, drive force to a surface of the rotor.
- a higher drive force leads to a higher spinning frequency or rotation frequency of the rotor about the axis of rotation during magic angle spinning, whereby the NMR sensitivity is improved.
- the fluid apertures are preferably arranged and/or configured such, that a flow of the fluid is split into fluid streams, namely one fluid stream per fluid apertures.
- the fluid apertures are arranged and/or configured such, that the individual fluid streams partially cancel out each other while summing up the drive force, leading to a balance control between the bearing force and the drive force.
- the probe head comprises a coil that corresponds to a coil as described previously.
- various types of coils as they are known in the state of the art could likewise be used.
- the probe head comprising, inter alia, a rotation device comprising the fluid directing device that comprises or consists of the coil preferably comprises a fluid supply device comprising the plurality of fluid apertures being arranged in a common plane and vice versa.
- the coil at least partially and particularly preferably entirely surrounds the rotor. That is, and as mentioned earlier, it is preferred that the rotor is at least partially and preferably entirely received in the coil. In other words, it is preferred that the coil is at least partially and preferably entirely wrapped around the rotor. Moreover, the rotor is preferably rotatable received within the coil and/or rotatable with respect to the coil.
- a gap between the coil and the rotor is preferably 4 millimeter or smaller. Additionally or alternatively, a gap between the coil and the rotor is preferably between 50 micrometer and 4 millimeter, more preferably between 100 micrometer and 2 millimeter, and particularly preferably about 500 micrometer. Said gap can be understood as the spacing being formed between an inner surface of the turns of the coil facing towards an outer side of the rotor and the outer side of the rotor with respect to a direction running perpendicularly to the coil axis. Hence, the coil is tightly wrapped around the rotor, wherein a distance between a sample being received in the rotor and the coil is minimized. Thereby, the NMR filling factor and thus the sensitivity of the NMR experiments are further improved.
- a shape of the rotor preferably corresponds to the shape of the coil.
- the rotor preferably comprises a sample chamber that is configured to receive a sample, and wherein a shape of the coil preferably corresponds to a shape of the sample chamber.
- the rotor preferably has an ellipsoidal shape, particularly preferably a spherical shape.
- the sample chamber preferably has a an ellipsoidal shape, particularly preferably a spherical shape. The provision of an ellipsoidal sample chamber increases the sample volume, whereby the NMR filling factor is again greatly improved.
- the fluid supply device preferably comprises a receptacle, and wherein the coil is at least partially and preferably entirely arranged within said receptacle.
- the fluid supply device is preferably arranged external to the coil. Additionally or alternatively, the coil is preferably at least partially and particularly preferably entirely arranged within the fluid supply device.
- the receptacle particularly preferably corresponds to a through-hole extending through the fluid supply device.
- the coil is preferably not received in a stator cup or the like.
- the coil is positioned in a center region of the fluid supply device to ensure stable spinning of the rotor.
- Said center region of the fluid supply device preferably corresponds to a geometrical center of the fluid flows or a geometrical center of the fluid apertures, respectively.
- the geometrical center of the fluid flows or of the fluid apertures is preferably arranged within the common plane the fluid apertures are arranged in, see above. In this way, a balanced fluid pressure can be applied onto the rotor.
- the coil preferably at least partially surrounds the rotor, it is furthermore preferred that the rotor is at least partially and preferably entirely received in the fluid supply device, in particular in the receptacle of the fluid supply device, as well.
- the rotor is preferably arranged within the coil, which in turn is preferably arranged within the fluid supply device.
- the one or more fluid apertures is preferably arranged in a region of the receptacle.
- the fluid aperture(s) are arranged such that they are facing towards and particularly preferably into the receptacle and as such towards the coil and the rotor being arranged within the receptacle.
- the fluid apertures can be arranged flush with a surface of the fluid supply device that delimits the receptacle.
- they can be protruding from the surface of the fluid supply device that delimits the receptacle.
- an aperture direction of the fluid apertures is tangential to an outer surface of the rotor.
- the plurality of the fluid apertures is preferably arranged at least partially and particularly preferably entirely along a circumferential direction of the receptacle. Additionally or alternatively, the plurality of fluid apertures is preferably arranged at least partially and particularly preferably entirely along a circumferential direction of the coil. For instance, in the event of a spherical coil, it is preferred that the plurality of fluid apertures are arranged equatorially about the coil.
- the arrangement of the fluid apertures preferably matches the shape of the rotor and/or the shape of the coil when seen in cross-section.
- the cross-section of the receptacle of the fluid supply device preferably has a circular shape and the arrangement of the fluid apertures is preferably circular as well.
- the circumferential direction of the receptacle and/or the circumferential direction of the coil preferably run about an axis that extends perpendicularly to the coil axis.
- the coil axis can be at any direction on a plane being perpendicular to a direction of a static magnetic field of a magnetic resonance spectrometer when the probe head is received in the magnetic resonance spectrometer, i.e. on a plane being the x,y- plane running perpendicularly to the z-axis if one is defining the z-axis as the direction of the external magnetic field as the z-axis as it is common in the field of NMR.
- the fluid supply device is preferably configured to adjust the axis of rotation of the rotor relative to an adjustment axis of the probe head. Additionally or alternatively, the fluid supply device is preferably configured to adjust the axis of rotation of the rotor relative to a direction of a static magnetic field of a magnetic resonance spectrometer when the probe head is received in the magnetic resonance spectrometer.
- the fluid supply device can be seen as an adjustment device that is configured to adjust the axis of rotation of the rotor relative to the adjustment axis of the probe head or relative to the direction of the static magnetic field.
- the adjustment axis of the probe head preferably runs parallel to a direction of the static magnetic field of the magnetic resonance spectrometer when the probe head is received in the magnetic resonance spectrometer.
- the fluid supply device can be used to find the so-called magic angle.
- the coil is preferably configured stationary during an adjustment by the fluid supply device with respect to the probe head. Additionally or alternatively, the fluid supply device is preferably configured movable during an adjustment with respect to the probe head.
- the fluid supply device preferably adjusts the axis of rotation of the rotor in a nonmechanical manner.
- the fluid supply device is preferably arranged movable, in particular pivotable, in the probe head.
- an orientation of the fluid supply device with respect to the probe head is adjusted as well, for instance by rotating the fluid supply device, whereby the axis of rotation of the rotor is adjusted as well.
- the coil preferably defines a coil axis.
- said coil axis preferably runs perpendicularly to an adjustment axis A of the probe head. Additionally or alternatively, said coil axis preferably runs perpendicularly to a direction of a static magnetic field B of a magnetic resonance spectrometer when the probe head is received in the magnetic resonance spectrometer. Additionally or alternatively, said coil axis preferably runs within a plane extending perpendicularly to the adjustment axis A of the probe head and/or perpendicularly to the direction of a static magnetic field B of a magnetic resonance spectrometer when the probe head is received in the magnetic resonance spectrometer.
- Said plane can be seen as the x,y-plane being spanned by x- and y-axis running perpendicularly to the z-axis if one is defining the z-axis as the direction of the external magnetic field as the z-axis as it is common in the field of NMR.
- a preferred probe head comprises an ellipsoidal rotor being surrounded by an ellipsoidal coil, wherein said coil in turn is part of or provides the fluid directing device of the rotation device.
- the rotation device preferably furthermore comprises the fluid supply device that comprises a plurality of fluid apertures being arranged in a common plane, and wherein the coil is surrounded by the fluid supply device.
- FIG. 1 shows a perspective view of an NMR probe head comprising a rotation device and a rotor, wherein the rotation device comprises a fluid supply device and a fluid directing device;
- Fig. 2 shows a side view of the NMR probe head according to figure 1 ;
- Fig. 3 shows a front view of the fluid supply device and the rotor of the NMR probe head according to figure 1 ;
- Fig. 4 shows a side view of the fluid supply device and the rotor of the NMR probe head according to figure 1 ;
- Fig. 5a shows a front view of a spherical coil being wound around a spherical rotor
- Fig. 5b shows a high frequency finite element simulation for the spherical coil being wound around the spherical rotor according to figure 5a;
- Fig. 6b shows a high frequency finite element simulation for the cylindrical coil being wound around the cylindrical rotor according to figure 6a;
- Fig. 7a shows a first embodiment of a rotor of an NMR probe head
- Fig. 7b shows a sectional view of the rotor according to figure 7b
- Fig. 8a shows a second embodiment of a rotor of an NMR probe head
- Fig. 9a shows a third embodiment of a rotor of an NMR probe head
- Fig. 9b shows a sectional view of the rotor according to figure 9a
- Fig. 10a shows 79 Br spectra of KBr within the rotors of figures 7a to 9b;
- Fig. 10b shows an expansion view of the center peak in figure 10a.
- the probe head 2 is designed for a 9.5 mm spherical rotor 3 on a customized narrow-bore transmission line probe [21], but with the capability to be retrofit onto any kind of probes.
- the coil 1 in the depicted probe head 2 corresponds to a spherical solenoid coil wrapped tightly around a spherical rotor 3.
- the spherical solenoid coil 1 functions as an RF coil and keeps the rotor 3 position in the center of the fluid supply device 6, see figure 1.
- the depicted probe head 2 comprises a capacitor 11 being used to tune and match an electric circuit of the entire probe. Thereby, an efficient transmission of correct RF signals is ensured.
- the rotation device 9 comprises a fluid supply device 6 that is configured to supply a fluid to the rotor 3.
- the fluid supply device 6 comprises a receptacle 8 in the form of a through-hole extending through the fluid supply device 6, and wherein the coil 1 and the rotor 3 are arranged within said receptacle 8. That is to say, and as readily follows from figures 1 to 4, the fluid supply device 6 is arranged external to the coil 1.
- the fluid supply device 6 has the shape of a ring, within which the coil 1 and the rotor 3 are arranged.
- the fluid supply device 6 can be referred to as a ring stator.
- a gas tube 12 made from rubber is used to deliver the fluid being used to rotate the rotor 3 into the ring stator 6, while maintaining the rotation flexibility of the ring stator 6 for magic angle adjustment, see figures 1 and 2 and additional explanations provided further below.
- Said fluid corresponds to gas, which can be referred to as spinning gas.
- the fluid supply device 6 comprises a plurality of fluid apertures 7, 7a, ... for supplying the fluid to the rotor 3, and wherein the plurality of fluid apertures 7, 7a, ... are arranged in a common plane P.
- the fluid apertures 7, 7a, ... are arranged and configured such, that a flow of the fluid is split into fluid streams, namely one fluid stream per fluid aperture 7, 7a, ... , which corresponds here to six streams flowing out of six fluid apertures 7, 7a, ....
- the fluid apertures 7, 7a, ... are arranged in a region of the receptacle 8.
- the fluid apertures 7, 7a, ... are protruding from a surface 13 of the fluid supply device 6 that delimits the receptacle 8. Furthermore, the fluid apertures 7, 7a, ... are arranged at an angle p with respect to the surface 13 of the fluid supply device 6 delimiting the receptacle 8 and also at an angle y with respect to an outer surface 14 of the rotor 3. Here, the fluid apertures 7, 7a, ... are arranged at an angle Y of 22° with respect to the outer surface 14 of the rotor 3.
- a flow direction F of the spinning gas is indicated with the arrows.
- the splitting of the spinning gas into different gas streams by the ring stator 6 is different from the stator with the semispherical stator cup to supply a single gas stream known from the state of the art [18-21],
- Both kinds of stators known from the prior art lack individual control of the bearing and drive forces, but the six gas streams from the ring stator 6 according to the invention and flowing toward the rotor 3 can partially cancel out each other and sum up the drive force, leading to a balance control between the bearing and drive forces.
- spinning of spherical rotors 3 within the coil 1 according to the invention releases the requirement for high-precision 3D printing, which was essential for the previous stator designs with a semispherical cup.
- the spherical rotor 3 spins around a center axis Z that is perpendicular to the ring stator 6.
- a spinning frequency of the spherical rotor 3 can be measured using fiber optics.
- the fluid supply device 6 is arranged movable, in particular pivotable, in the probe head 2. To this end, the fluid supply device 6 is pivotally mounted on two rods 16 that allow the fluid supply device 6 to pivot within the probe head 2. Moreover, the fluid supply device 6 is configured to adjust the axis of rotation R of the rotor 3 relative to an adjustment axis A of the probe head 2 as well as relative to a direction of a static magnetic field B of a magnetic resonance spectrometer when the probe head 2 is received in the magnetic resonance spectrometer. As indicated in figure 4, the adjustment axis A of the probe head 2 runs parallel to the direction of the static magnetic field B of the magnetic resonance spectrometer when the probe head 2 is received in the magnetic resonance spectrometer.
- the fluid supply device 6 can be used to adjust the axis of rotation R of the rotor 3 to the so-called magic angle a of 54.7°, see figure 4.
- the magic angle a can be adjusted by a mechanical movement such as a pivoting or rotation of the ring stator 6 through the rods 16 being connected to the ring stator 6.
- the coil 1 stays static while the axis of rotation R of the rotor 3 tunes with the movement of the ring stator 6.
- the coil 1 comprises a plurality of turns 4, 4a, ... that are arranged along a coil axis C extending along the coil 1.
- said coil axis C runs perpendicularly to the adjustment axis A of the probe head 2 as well as to the direction of the static magnetic field B of a magnetic resonance spectrometer when the probe head 2 is received in the magnetic resonance spectrometer.
- said coil axis C runs within a plane extending perpendicularly to the adjustment axis A of the probe head 2 and the direction of a static magnetic field B.
- the rotor 3 is entirely received in the coil 1.
- the coil 1 is entirely wrapped around the rotor 3, and wherein the shape of the rotor 3 corresponds to the shape of the coil 1 , i.e. both the rotor 3 as well as the coil 1 are spherical.
- the coil 1 is tightly wrapped around the rotor 3, wherein gap G between the coil 1 and the rotor is 4 millimeter or smaller. Said gap G corresponds to a spacing being formed between an inner surface 17 of the turns 4, 4a, ... of the coil 1 facing towards the outer surface 14 of the rotor 3 and said outer surface 14 of the rotor 3 with respect to a direction running perpendicularly to the coil axis C.
- the coil 1 not only serves the purpose of transmitting and receiving radiofrequency signals, but also constitutes a fluid directing device 10 that is configured and arranged to direct the fluid being supplied by the fluid supply device 6 to the rotor 3.
- the coil is configured and arranged such, that is generates a bearing force and a drive force that rotates the rotor 3 about its axis of rotation R. Said bearing and drive forces are generated by the fluid being supplied by the fluid supply device 6 and that flows through the gap G being formed between the rotor 3 and the coil 1.
- the plurality of turns 4, 4a, .... of the coil 1 define an ellipsoid shape, in the depicted example a spherical shape.
- the circumference of the individual turns 4, 4a, ... of the coil 1 with respect to a circumferential direction CT of the turns 4, 4a, ... is elliptic, in the depicted example circular.
- the circumference of the individual turns 4, 4a, ... with respect to the circumferential direction CT of the turns 4, 4a, ... varies with respect to the coil axis C.
- an extension direction E which extends from a beginning of the coil 1 being provided by a first turn 4 of the coil 1 to an end of the coil 1 being provided by a last turn 4f of the coil 1
- the circumference of the turns 4, 4a, ... becomes increasingly larger and then increasingly smaller.
- the circumference of the turns 4, 4a, ... in the region of the beginning of the coil 1 and the circumference of the turns 4e, 4f in the region of the end of the coil 1 is smaller than the circumference of the turns 4c, 4d in a middle region of the coil 1 , and wherein the circumference of the turn or turns 4c, 4d in the middle region is largest.
- High frequency finite element simulation was carried out to compare the RF performance of the straight solenoid coil T with cylindrical rotors 3' known in the state of the art and the spherical solenoid coil 1 with spherical rotors 3 according to the invention.
- the simulation model includes a 3.9 millimeter diameter spherical rotor 3 and a 7-turn spherical solenoid coil 1 , see figure 9a, and the magnetic field strength along the coil axis C is between 24.5 to 27.5 A/m within the spherical rotor 3, see figure 5b.
- Figure 6a depicts the comparison standard, which is here a 2.2 millimeter diameter commercial cylindrical rotor 3' with 30 microliter of sample volume and a 8-turn solenoid coil T.
- Figure 6b depicts the magnetic field strength along the coil axis, wherein the field strength is 36 A/m at the sample center and drops down to 15 A/m at the ends.
- the field was down- scaled to count for the orientation along the magic angle.
- the 3.9 millimeter diameter spherical rotor 3 is used to keep the same sample volume as in the cylindrical rotor 3'.
- the gaps G between coil 1 , T and sample in both simulations are kept the same, namely 0.6 millimeter.
- the number of turns 4, 4a, ... ; 4', 4a', ... and wire diameter dt in each coil 1 , T was optimized, see tables S1 and S2 below.
- An average magnetic field over the sample area was calculated, assuming a perfectly tuned and matched circuit with 5 mW RF input power.
- the highest magnetic field for the cylindrical rotor is 57.3 A/m with a 7 millimeter 8 turn coil and wire diameter of 0.6 mm, see table 1 below.
- the Bruker coil with 7 millimeter length, 7 turns and 0.5 millimeter wire diameter shows a slightly lower field.
- the spherical solenoid coil with the same winding and wire diameter shows a similar magnetic field as the straight solenoid coil. While the coil with 9 turns and 0.4 millimeter wire diameter shows a higher magnetic field of 63.1 A/m, the impedance is too high for matching the circuit.
- the straight solenoid coil shows a strong central field of 36 A/m, and drops to 15 A/m at the end of sample, see figure 6b.
- the spherical coil 1 according to the invention shows a comparable RF field to a straight solenoid coil T known from the state of the art, however with better homogeneity.
- the rotor 3, 3' comprises a sample chamber 5, 5' that is configured to receive a sample.
- the sample chamber 5, 5' can have various designs. For instance, it can be cylindrical as depicted in figures 7a to 8b or it can have an ellipsoidal shape, in particular a spherical shape as depicted in figures 9a and 9b.
- Most spherical rotors reported so far have been machined with a cylindrical sample chamber [18-21], although this design provides stable spinning due to the large moment of inertia from the thick rotor wall, it sacrifices sample volume and NMR filling factor.
- FIGS 7a and 7b depict a spherical rotor 3' (rotor a) in the form of a high-precision 9.525 mm diameter yttria-stabilized zirconia (ZrCh) ball with a 2.54 mm diameter through hole and longitudinal turbine grooves that was purchased from O'Keefe Ceramics (Woodland Park, CO) and that is known from previous publications [18, 19, 22],
- the rotor 3' comprises turbine grooves 18 in the form of twelve 60° notched grooves, and wherein the through hole delimits a sample chamber 5' that can only hold 39 microliter of sample.
- zirconia is a commonly used material for cylindrical rotors because it is less easy to crash.
- sapphire/ruby as the rotor material was further explored, considering their machining feasibility to obtain larger sample volume.
- Other advantages of sapphire/ruby include the high thermal conductivity and superior microwave transmission property, which are important for the application in dynamic nuclear polarization (DNP) NMR experiments. More importantly, the single crystal AI2O3 in sapphire/ruby is sensitive to the magic angle offset, allowing the magic angle adjust in situ [23],
- Rotor b depicted in figures 8a and 8b is a high-precision 9.525 mm diameter ruby (99% AI2O3 + 1% CT2O3) spherical rotor 3' with a 5.08 mm diameter through hole that was purchased from Saphirwerk AG (Brugg, Switzerland). It furthermore comprises twelve semispherical grooves 18 on the equator. Said grooves are 0.23 millimeter deep.
- the sample chamber 5' being formed by the through hole and with two flat-end caps defines a sample volume of 131 microliter.
- Rotor c depicted in figures 9a and 9b is a high-precision 9.525 mm diameter ruby spherical rotor 3 according to the invention which is further hollowed out to limit a sample chamber 5 having a volume of 219 microliter.
- said sample chamber s is formed here by a through hole having a diameter of 5.08 millimeter and an additional spherical chamber of 7.5 millimeter.
- the shape of the sample chamber s corresponds to the shape of the rotor 3.
- the hollowed sample chamber 5 is machined using 5-axis milling technique (DMU 50, DMG MORI).
- this rotor 3 has no turbine grooves for easier machining and more robust rotor shell as it is the case with the rotors depicted in figures 7a to 8b. It has been demonstrated that the spherical rotor without grooves have similar spinning frequency as other rotor designs [19], The caps for all spherical rotors were 3D printed on Projet MJP 2500 (3D Systems) using ABS-like resin (VisiJet M2R-CL).
- Both the ring stators 6 and the mold were 3D printed on Form 3 SLA 3D printers using clear v4 resin (Formlabs Inc., Somerville, MA).
- the coil position is adjusted such that the spherical rotor is in the center of the ring stator 6, rotating around an axis of rotation R being perpendicular to the ring stator 6.
- the axis of rotation 3 is then optimized by a mechanical rotation of the ring stator 6 to obtain the highest sideband intensities in the KBr spectra.
- Figures 10a and 10b show the MAS spectra of 79Br of all three rotor types. All NMR experiments were performed at room temperature on a Bruker Avance 600 MHz spectrometer using a customized single-resonance, narrow-bore transmission line probe [21], A Bloch decay pulse sequence with inter-scan delay of 1 s was used. 79Br spectra were obtained at 150.37 MHz using a TT/2 pulse of 14 ps at 200 W incident RF power. The spinning frequency of ⁇ 4 kHz was maintained during the data acquisition with nitrogen gas at a pressure of 2 bar. Four scans are acquired in each spectrum.
- the gradually inversed spinning sidebands at higher frequencies result from the long 90° pulse (14 microsecond), which excites only a limited frequency range efficiently.
- the highest NMR sensitivity is obtained with the rotor according to the invention, rotor c, which contains 405.3 mg of KBr, whereas the lowest sensitivity is from rotor a, with 70.6 mg of KBr, see the expansion view of the center peak of figure 10a depicted in figure 10b.
- the ratio of signal integration for each spectrum is 1 :0.66: 0.15, similar to the ratio of sample mass within each rotor (1 :0.67: 0.17).
- the utility of a spherical coil tightly wrapped around the spherical rotor as an RF coil but also a part of the rotation device for MAS has been demonstrated.
- One unique advantage of this apparatus is that the coil axis C is fixed perpendicular to the external magnetic field B regardless of the axis of rotation R of the rotor 3. All the B1 field generated is along the x/y axis and experiments such as dynamic-angle spinning (DAS) and variableangle spinning can be performed without compromising the B1 field.
- DAS dynamic-angle spinning
- the present invention makes use of all the RF power and furthermore allows magic angle adjustment without coil movement.
- the capability of spherical rotor spinning within the RF coil 1 releases the high-precision requirement for stator fabrication, making it easier for the stator development of smaller rotors.
- the fluid supply device 6 in the form of the ring stator to supply spinning gas and to adjust the magic angle a being external to the coil 1 minimizes the gap G between the sample and coil 1. It has also been affirmed the NMR filling factor is greatly improved with the increased sample volume and minimized samplecoil distance.
- the hollowed spherical rotor leads to 6 times higher signal integration.
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Abstract
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Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP22154773.0A EP4224190A1 (en) | 2022-02-02 | 2022-02-02 | Improvements in mas nmr |
| PCT/EP2023/052410 WO2023148202A1 (en) | 2022-02-02 | 2023-02-01 | Improvements in mas nmr |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| EP4473327A1 true EP4473327A1 (en) | 2024-12-11 |
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Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP22154773.0A Withdrawn EP4224190A1 (en) | 2022-02-02 | 2022-02-02 | Improvements in mas nmr |
| EP23702349.4A Withdrawn EP4473327A1 (en) | 2022-02-02 | 2023-02-01 | Improvements in mas nmr |
Family Applications Before (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP22154773.0A Withdrawn EP4224190A1 (en) | 2022-02-02 | 2022-02-02 | Improvements in mas nmr |
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| Country | Link |
|---|---|
| EP (2) | EP4224190A1 (en) |
| JP (1) | JP2025504992A (en) |
| WO (1) | WO2023148202A1 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60171439A (en) * | 1984-02-16 | 1985-09-04 | Yokogawa Hokushin Electric Corp | Coil for nmr image diagnosing apparatus |
| WO2019108754A1 (en) * | 2017-12-01 | 2019-06-06 | Washington University | Systems, spherical rotors, stators, and methods of use |
-
2022
- 2022-02-02 EP EP22154773.0A patent/EP4224190A1/en not_active Withdrawn
-
2023
- 2023-02-01 EP EP23702349.4A patent/EP4473327A1/en not_active Withdrawn
- 2023-02-01 WO PCT/EP2023/052410 patent/WO2023148202A1/en not_active Ceased
- 2023-02-01 JP JP2024545892A patent/JP2025504992A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| WO2023148202A1 (en) | 2023-08-10 |
| EP4224190A1 (en) | 2023-08-09 |
| JP2025504992A (en) | 2025-02-19 |
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