Sliding band capacitor inductive coupling in a low temperature nuclear magnetic resonance probe and methods of use

In various embodiments of the invention, a cooled nuclear magnetic resonance (NMR) probe can utilize a sliding band capacitor which can be moved relative to a parent coil inner conductance tapered skirt to adjust the frequency of the parent coil to allow the parent coil to detect the resonance of at least two nuclei without requiring leads between the parent coil and a lock coil. In this manner a cooled NMR probe can be provided without the disadvantages of prior art cooled NMR probes. In an embodiment of the invention, the sliding band capacitor comprises a diamagnetic insulator with a first volume magnetic susceptibility, at least one paramagnetic metal with a second volume magnetic susceptibility and at least one diamagnetic metal with a third volume magnetic susceptibility, where the sum of the first volume magnetic susceptibility, the second volume magnetic susceptibility and the third volume magnetic susceptibility is approximately zero.

RELATED APPLICATION

The present invention is related to U.S. application Ser. No. 18/599,758, filed on Mar. 8, 2024, by inventor: Anthony Siaw, and entitled “INDUCTIVE TUNING WITH A SLIDING BAND CAPACITOR IN A LOW TEMPERATURE NUCLEAR MAGNETIC RESONANCE PROBE AND METHODS OF USE”, which application is hereby incorporated by reference in its entirety and for all purposes.

FIELD OF THE INVENTION

The present invention relates to methods and devices to monitor one or more nuclei in high resolution low temperature nuclear magnetic resonance probes utilizing radio frequency signals.

BACKGROUND OF THE INVENTION

Structural elucidation of a compound, whether a synthesis product or an extract from a natural source generally requires a number of analytical techniques. Infrared spectroscopy, mass spectrometry, and Nuclear Magnetic Resonance (NMR) spectroscopy can provide extensive chemical information. NMR can provide structural information and also information on both intermolecular and intramolecular dynamics. Applications of NMR range from determination of three-dimensional structures of large proteins to the analysis of very small amounts of products from combinatorial syntheses. Furthermore, NMR is a nondestructive analytical method.

NMR generally uses induction to detect the oscillating magnetic moment from nuclei precessing in a magnetic field. Because the signal from these precessing nuclei is inherently weak research efforts have been focused on improving the signal to noise ratio (SNR) obtained in NMR experiments. There are two general ways to increase the SNR. One way is to increase the size of the magnetic field. While more powerful magnets, are increasingly being employed, currently superconducting magnets with up to 1.2 GHz are commercially available, there is an upper limit of the critical field of a superconducting magnet. The other way is to decrease the noise by cooling the coils and electronics used to detect the signal.

High resolution NMR probes typically have an ‘inner coil’ for irradiation and detection of a first nuclear species, and a second larger coil, coaxial with the inner coil, for irradiation of one or more other nuclear species. The two coils are typically oriented 900 with respect to each other to minimize coupling between the two coils. Capacitive coupling has previously been used to form double-tuned high resolution NMR probes for 1H-2H, 13C-15N and 1H-19F.

The magnetic coupling loops, coupling resonators, variable tuning capacitors, pulse field gradients, Faraday shields and loop gap shields can all be detrimental to the performance of the probe in some manner. The RF homogeneity of the parent coil can be impacted by the presence of additional metallic objects and the presence of magnetic coupling loops or resonators that couple to the sample inductor. All of the above, shields, coupling loops, variable capacitors, resonators, pulse field gradients etc., can dilute the SNR of the NMR experiment even if only in a minor manner. From the above it can be deduced that the fewer the number of objects in the sample region of the NMR probe the better the SNR.

In U.S. Pat. No. 4,654,593 to Ackerman, a method for NMR imaging uses a nonmagnetic moving object positioned in the field of a Radio Frequency (RF) excitation coil and a magnetic field where the object is of a low conductivity so as to be substantially transparent to electromagnetic radiation at the NMR frequency and the nonmagnetic object is subjected to periodic motion while transverse magnetization is generated, and a short duration phase-encoding magnetic field gradient pulse is applied in a specified direction to the moving nonmagnetic object, where the magnetic field gradient is turned off and a free induction decay signal is detected. In U.S. Pat. No. 5,227,724 to Cory et al., a method for measuring the distribution of the extent of molecular transport along two orthogonal directions, and further for measuring the anisotropy of molecular transport is disclosed. In U.S. Statutory Invention Registration. No. H1218 to Cory et al., a method of NMR imaging where spatial coupling of the sample with a receiver device is varied using pulsed magnetic field gradients and the sample is moved relative to the receiver device, or the spatial coupling of the receiver device and the sample is electronically altered, is disclosed. Kuhns et al. describe the use of inductive coupling for series linked tuning of resonant circuits, J. Magnetic Resonance, “Inductive Coupling and Tuning in NMR Probes: Applications”, 78 (1988) 69-76. Hoult and Tomanek describes the use of mutually inductive coils and investigates field strength, losses and signal to noise ratio, “Use of Mutually Inductive Coupling in probe Design”, Concepts in Magnetic Resonance, 15(4) (2002) 262-285, Wiley Periodicals, Inc.

SUMMARY OF THE INVENTION

A limitation of using a variable capacitor with associated leads to adjust the parent coil resonance is that the leads can act as inductors and thereby reduce the amplitude of the parent coil flux. In an embodiment of the present invention, the limitation can be addressed by using a sliding band capacitor in which over ninety (90) percent of the high frequency resonating nucleus current is in the parent coil. In an embodiment of the present invention, the performance of cooled NMR probes with a low inductance coil that have high Q values can be improved by incorporating a sliding band capacitor to adjust the parent coil resonance. However, a further problem relates to a low temperature probe in which the properties of the sliding band capacitor must be retained at cryo-cooled temperatures. Further, the sliding band capacitor can comprise a paramagnetic material used to compensate for diamagnetic materials in the sliding band capacitor and thereby ensure that the B0 homogeneity in the sample region is not degraded.

In an embodiment of the present invention, the performance of a low inductance low temperature probe that has a high Q value can be improved by incorporating a sliding band capacitor, that doesn't perturb the magnetic field near the sample, at cryo-cooled temperatures. This can be accomplished by carefully choosing (i) the diamagnetic material used to support and insulate the sliding band capacitor, (ii) a paramagnetic metal to compensate for diamagnetic materials and (iii) a high conductance metal to surround the paramagnetic material to ensure high conductance and that the RF does not penetrate and result in the amplitude of the parent coil flux being degraded.

In an embodiment of the present invention, the low temperature probe is in the presence of three or more materials in which the sum of the magnetic susceptibility is approximately zero. In an embodiment of the present invention, the three or more materials comprise a diamagnetic support, a paramagnetic metal, and a diamagnetic metal, where the diamagnetic metal surrounds the paramagnetic metal i.e., the diamagnetic metal is contacting the paramagnetic metal and has a conductivity of greater than 4×10−7 S/m. In this range approximately zero means a volume magnetic susceptibility of less than 1×10−4 at 300° K and less than 1×10−5 at 80° K. In various embodiments of the present invention, the paramagnetic metal of the three or more materials can be selected from a metal in Table II. In various embodiments of the present invention, the diamagnetic metal of the three or more metals can be selected from a metal in Table I.

In an embodiment of the present invention, the sliding band capacitor comprises a thin titanium sheet (the paramagnetic metal) which is then surrounded by a thin copper sheet (the diamagnetic metal), where the diamagnetism due to the diamagnetic support and the amount, thickness and positioning of the thin copper sheet is offset by the paramagnetism of the thin titanium sheet such that the sum of the magnetic susceptibility of the three or more metals is approximately zero. In an alternative embodiment of the invention, the sliding band capacitor comprises a thin titanium sheet which is then surrounded by a thin silver sheet, where the diamagnetism due to the diamagnetic support and to the amount, thickness and positioning of the thin silver sheet is offset by the paramagnetism of the thin titanium sheet such that the sum of the magnetic susceptibility of the three or more metals is approximately zero.

In an additional embodiment of the invention, the sliding band capacitor comprises a thin aluminum sheet which is surrounded by a thin copper sheet, where the diamagnetism due to the diamagnetic support and the amount, thickness and positioning of the thin copper sheet is offset by the paramagnetism of the thin aluminum sheet such that the sum of the magnetic susceptibility of the three or more metals is approximately zero. In an alternative embodiment of the present invention, the sliding band capacitor comprises a thin aluminum sheet which is surrounded by a thin silver sheet, where the diamagnetism due to the diamagnetic support and the amount, thickness and positioning of the thin silver sheet is offset by the paramagnetism of the thin aluminum sheet such that the sum of the magnetic susceptibility of the three or more metals is approximately zero.

DETAILED DESCRIPTION OF THE INVENTION

Definitions

The transitional term ‘comprising’ is synonymous with ‘including’, ‘containing’, or ‘characterized by’, is inclusive or open-ended and does not exclude additional, unrecited elements or method steps.

The transitional phrase ‘consisting of’ excludes any element, step, or ingredient not specified in the claim, but does not exclude additional components or steps that are unrelated to the invention such as impurities ordinarily associated with a composition.

The transitional phrase ‘consisting essentially of’ limits the scope of a claim to the specified materials or steps and those that do not materially affect the basic and novel characteristic(s) of the claimed invention.

The phrase ‘the NMR instrument’ includes the magnet field characteristics of the NMR, e.g., the maximum magnet field intensity. The phrase ‘the NMR probe’ includes the size characteristics of the low temperature probe.

The Quality Factor (Q) is defined as the ratio of the energy stored in a component to the energy dissipated by the component. The unloaded Q (Qu) is the measured Q without the load.

The phrases ‘low temperature probe’, ‘ultra-low temperature probe’, ‘cryo-cooled probe’, ‘liquid nitrogen cooled probe’, or ‘low temperature cryo-cooled probe’, mean an NMR probe that is adapted to be cooled to be used at temperatures below approximately 100° K. In this circumstance, approximately means plus or minus twenty (20) percent.

A thin foil is approximately cuboid and contains six surfaces of which four (4) of the surfaces are referred to as edges and two (2) of the surfaces are referred to as faces.

The term ‘opposing edge’ when used to refer to two articulated edges (each having approximately the same dimensions and area) means the edges formed (when the foil is adapted to form a ring) are in close proximity and/or touching. The term ‘opposing face’ when used to refer to two articulated faces means the faces are in close proximity and/or touching. In this circumstance, approximately means plus or minus five (5) percent tolerance.

The word ‘exposed’ means an edge or a face of a metal that otherwise is not covered. Two opposing edges of a metal are not exposed. That is a titanium foil has an exposed top edge, an exposed bottom edge and two exposed faces, see FIG. 2.

The phrase ‘exposed edges of a ring’ of a paramagnetic metal foil ring refers to the top edge and the bottom edge. The phrase ‘exposed faces of a ring’ of a paramagnetic metal foil ring refers to the two faces.

A ‘paramagnetic metal ring’ means a paramagnetic metal foil adapted to form the top edge, the bottom edge and the two faces. A thin foil that is adapted to form a ring retains a rectangular cross section, see FIG. 2.

A ‘face is aligned with another face’ when each face has the same dimensions and area as an opposing face, and the face meets the opposing face such that the two faces are touching over approximately the area of the two faces. In this circumstance, approximately means plus or minus ten (10) percent tolerance.

A ‘face of a foil ring’ of a paramagnetic metal foil ring means the largest area of the foil and excludes the two opposing edges, the top edge and the bottom edge. A ‘surface of a titanium foil ring’ means largest area of the foil and excludes the two opposing edges, the top edge and the bottom edge. In a titanium foil with dimensions 41.32 mm×10 mm×60 μm, the surface area of the side of a titanium foil ring is 4.13×10−4 M2.

A ‘top edge of a foil ring’ of a paramagnetic metal foil ring means the edge of the ring that is closest to the spacer plates 250. A ‘top edge of a titanium foil ring’ means the edge of the ring that is closest to the spacer plates 250. In a titanium foil with dimensions 41.32 mm×10 mm×60 μm, the surface area of the top edge of a titanium foil ring is 1.0495×10−6 m2.

A ‘bottom edge of a foil ring’ of a paramagnetic metal foil ring means the edge of the ring that is furthest from the spacer plates 250. A ‘bottom edge of a titanium foil ring’ means the edge of the ring that is furthest from the spacer plates 250. In a titanium foil with dimensions 41.32 mm×10 mm×60 μm, the surface area of bottom edge of a titanium foil ring is 1.0495×10−6 m2.

An ‘optimal Q value’ means the theoretically calculated Q value of a paramagnetic metal foil ring smoothly aligned with a diamagnetic metal foil in which for the calculation one hundred (100) percent of the paramagnetic metal is covered with the diamagnetic metal.

A ‘paramagnetic metal foil ring is enclosed by a diamagnetic metal’ means a paramagnetic metal foil ring smoothly aligned with a diamagnetic metal foil such that the measured Q value is greater than approximately ninety-five (95) percent of the optimal Q value. For example, a titanium foil ring is enclosed by copper when approximately ninety-nine (99) percent the surface area of the top edge of a titanium foil ring is approximately smoothly aligned with a copper surface and approximately ninety-nine (99) percent the surface area of the side of a titanium foil ring is approximately smoothly aligned with a copper surface. In this circumstance, approximately means plus or minus one (1) percent. Unexpectedly, for a titanium ring sliding band capacitor 5012 positioned below the rectangular coil window 750, exposing the top edge of the titanium foil has a dramatic effect on the Q value, e.g., FIG. 11A shows that the Q @500 MHz drops to 893.8 compared with FIG. 11B with a Q @500 MHz of 1069.2 (calculations based on coil ID=10 mm, sapphire thickness 0.4 mm, copper foil thickness 25.4 μm, and titanium foil is 41.32 mm×10 mm×60 μm). In contrast, exposing the bottom titanium ring edge of a sliding band capacitor 5012 positioned below the rectangular coil window 750 has a minimal effect on the Q value. This is because when the sliding band capacitor 5012 is positioned below the rectangular coil window 750, most of the current flows in the top edge and not in the bottom edge of the titanium ring. However, we note that exposing the bottom titanium ring edge of a sliding band capacitor 5012 positioned above the rectangular coil window 750 will have a significant effect, while exposing the bottom edge of a titanium ring sliding band capacitor 5012 positioned above the rectangular coil window 750 has a minimal effect on the Q value. This is because when the sliding band capacitor 5012 is positioned above the rectangular coil window 750, most of the current flows in the bottom edge and not in the top edge of the titanium ring. We also note that the tapered skirt 730 would need to be inverted in order for the sliding band capacitor 5012 to effectively function when positioned above the rectangular coil window 750. In the zoom 710 in FIG. 11A the top edge of the titanium 220 is exposed between the sapphire 230 and the copper 210 (the tapered skirt 730 is adjacent the sapphire 230). In the zoom 720 in FIG. 11B the sapphire 230 is sandwiched between the tapered skirt 730 and the copper 210.

A ‘paramagnetic metal foil ring is surrounded by a diamagnetic metal’ means a paramagnetic metal foil ring smoothly aligned with a diamagnetic metal foil such that the measured Q value is greater than approximately ninety (90) percent of the optimal Q value. For example, a titanium foil ring is surrounded by copper when approximately ninety-nine (99) per cent the surface area of the top edge of a titanium foil ring is approximately smoothly aligned with a copper surface and approximately ninety-five (95) percent the surface area of the side of a titanium foil ring is approximately smoothly aligned with a copper surface. In this circumstance, approximately means plus or minus one (1) percent.

A ‘paramagnetic metal foil ring is contacted by a diamagnetic metal’ means a paramagnetic metal foil ring smoothly aligned with a diamagnetic metal foil such that the measured Q value is greater than approximately eighty (80) percent of the optimal Q value. For example, a titanium foil ring is contacted by copper when approximately ninety-nine (99) percent the surface area of the top edge of a titanium foil ring is approximately smoothly aligned with a copper surface and approximately ninety (90) percent the surface area of the side of a titanium foil ring is approximately smoothly aligned with a copper surface. In this circumstance, approximately means plus or minus one (1) percent.

A ‘titanium metal alloy’ means titanium alloyed with one or more metals selected from Table II, where the titanium composition is greater than eighty (80) percent. In this circumstance, approximately means plus or minus twenty (20) percent. In an alternative embodiment of the invention, titanium metal alloy means titanium alloyed with one or more metals, where the titanium composition is greater than ninety (90) percent. In this circumstance, approximately means plus or minus ten (10) percent. In another alternative embodiment of the invention, a titanium metal alloy means titanium alloyed with one or more metals, where the titanium composition is greater than ninety-five (95) percent. In this circumstance, approximately means plus or minus five (5) percent. In a further alternative embodiment of the invention, a titanium metal alloy means titanium alloyed with one or more metals, where the titanium composition is greater than ninety-eight (98) percent. In this circumstance, approximately means plus or minus one (1) percent.

In an embodiment of the invention, a sliding band capacitor has a sum volume magnetic susceptibility of less than approximately 1×10−6 such that the Q is maximized. In an alternative embodiment of the invention, a sliding band capacitor has a sum volume magnetic susceptibility of less than approximately 5×10−7 such that the Q is maximized. In an alternative embodiment of the invention, a sliding band capacitor has a sum volume magnetic susceptibility of less than approximately 1×10−7 such that the Q is maximized. In these circumstances, approximately means plus or minus ten (10) percent.

The phrase ‘high conductance metal’ means a conductance of greater than approximately 2×107 S/m at 20° C. In this circumstance, approximately means plus or minus 1×107 S/m at 20° C. The conductance's of some suitable diamagnetic metals are given in Table I.

The phrase ‘low inductance probe’ means a probe with a parent coil inductance of less than approximately 1×10−7 H. In this circumstance, approximately means plus or minus twenty (20) percent.

The phrase ‘stable paramagnetic metal’ means a paramagnetic metal that is not readily oxidized at approximately 300° K and/or approximately 100° K and/or that undergoes radioactive decay. The properties of some suitable stable paramagnetic metals are given in Table II.

The phrase ‘radioactive decay’ means an element that loses energy through radiation, e.g., undergoes one or more of alpha decay, beta decay, gamma decay and/or neutron decay. For example, all elements of atomic number 83 or greater undergo radioactive decay.

A ‘cell’ means a vessel such as a sample tube used to contain one or more of a homogeneous or heterogeneous liquid, gas or solid sample.

A ‘parent circuit’ means the circuit comprising the parent coil 1010 and sliding band capacitor 5012.

Coupling to various coils of different sizes and functions can be used to optimize the circuit. A parent coil, a coupling coil, a lock coil, and a detector coil can be solenoidal coils.

The word ‘excitation’ describes the disruption of the alignment of spins of nuclei in a sample in a static magnetic field (B0) which occurs by applying an RF pulse at the Larmor frequency of the spins perpendicular to the magnetic field (B1).

The word ‘performance’ means the SNR of a circuit with respect to the parent mode(s).

The word ‘mode’ means a resonance in the circuit.

The words or phrases ‘coupling’, ‘coupling modes’, ‘detecting’ or ‘detecting modes’ means selecting the sliding band capacitor 5012 and adjusting the resonance frequency by moving the position of the sliding band capacitor 5012 relative to the parent coil 1010. The critical coupling is necessary for matching the resistance to a fifty (50) Ohm coax. In various embodiments of the invention, the resistance can be matched to other resistance coax. In an embodiment of the invention, the resistance can be coupled to seventy-five (75) Ohm coax. In various embodiments of the invention, seventy-seven (77) Ohm coax gives minimum loss.

The phrases ‘parent coil’ or ‘sample coil’ means the inductor constructed to observe the parent resonance. Elements 140 (copper rods), 250 (plates) and 730 (tapered skirt) comprise the parent coil 1010.

The phrase ‘sample coupling coil’ refers to an inductive coil 3087, 3088. A sample coupling coil can be used for detecting the fluctuating signal that is in resonance with a signal from a sample. In circumstances where there is no lower threshold, a first distance is defined between the sample coupling coil and the one or more inductive coupling loops. A resonant circuit is an electric circuit which has oscillating currents which are stored as energy (i.e. electric field and magnetic field) and the complex impedance of the sliding band capacitor and inductor are each near zero. The only losses in the circuit are from the pure resistive parts of the components, the inductor 1010 and the sliding band capacitor 5012. Inductive coupling is the near field wireless transmission of electrical energy between two magnetically coupled coils.

The phrases ‘tapered skirt’ or ‘tapered inner conductance skirt’ 730 means a thin metal volume in which the volume is tapered such that the surface area changes in the vertical plane as shown in FIG. 7 and FIG. 8. Elements 140 (copper rods), 250 (plates) and 730 (tapered skirt) comprise the parent coil 1010. The tapered skirt 730 comprises a material selected from the group consisting of Cu, Cu plated with Pd, or a Cu Al Cu coil. The movement of the sliding band capacitor 5012, relative the tapered skirt changes the capacitance of the parent circuit and can be used to tune the parent coil 1010 to a specific frequency.

FIG. 1 shows a prior art cooled NMR probe 100 comprising two (2) polyethyl ether ketone blocks 130 that space four (4) copper palladium plated rods 140 and a quartz cylinder 150, two (2) spacer plates 250, and a variable capacitor 160. In FIG. 1 the leads 1030, 1031 connect the variable capacitor 160 to adjust the capacitance in the parent coil (not shown). FIG. 3A shows a prior art circuit that can be used with the probe shown in FIG. 1. In FIG. 3A the parent coil 1010 and the capacitor 1012 are located near the sample and the lock inductor coils 1070, 1071 are used to detect the parent resonance by adjusting the variable capacitors 1086, 1088, 1022, and 1087 to match with one of the two fifty-ohm ports 3080, 3081. Variable capacitor 1089 and fixed capacitor 1025 and the ground points are also shown 1090. However, the leads 1030, 1031 act like inductors (see e.g., 1030 and 1031 in FIG. 3B) that dilute the SNR of the parent coil 1010. This is because the flux generated by the current in these leads 1030 and 1031 reduces the flux in the parent coil 1010. Note that the SNR for the parent coil 1010 in FIG. 3B will be maximized when the majority of the capacitance in the circuit is in the variable capacitor 1012 and when the capacitance in the variable capacitors 1086, 1088, 1022, and 1087 is minimized.

FIG. 7 shows a schematic of a parent coil 1010 and sliding band capacitor 5012, together 700. In FIG. 7, two (2) polyethyl ether ketone blocks 130 space four (4) copper rods 140 and a quartz cylinder 150. In FIG. 7, the copper rods 140, the two (2) spacer plates 250 and a tapered inner conductance skirt 730 comprise the parent coil 1010. In FIG. 7, a sliding band capacitor 5012.

FIG. 8 shows the movement of a sliding band capacitor 5012, relative to a tapered inner conductance skirt 730. In an embodiment of the present invention, with the sliding band capacitor 5012 in the lower position (see FIG. 8B) relative to the tapered skirt 730, the capacitance of the sliding band capacitor 5012 is decreased allowing the parent coil 1010 to tune to a higher frequency. In an embodiment of the present invention, with the sliding band capacitor 5012 in the upper position (see FIG. 8A) relative to the tapered skirt 730, the capacitance of the sliding band capacitor 5012 is increased allowing the parent coil 1010 to tune to a lower frequency. That is, moving the position of the sliding band capacitor 5012 relative to the tapered skirt 730 changes the capacitance of the sliding band capacitor 5012. However, there is no significant change in the inductance of the parent coil 1010 with movement of the sliding band capacitor 5012, since the current path change is minimal. It is noted that the tapered skirt 730 contains a region at the top of the skirt 730 where there is no taper and as a result moving the position of the sliding band capacitor 5012 relative to the tapered skirt 730 changes the inductance of the parent coil 1010 with no significant change in the capacitance of the sliding band capacitor 5012.

The phase ‘sliding band capacitor’ 5012 refers to a capacitance device, with at least one paramagnetic metal and at least one high conductance diamagnetic metal, where the paramagnetic metal is enclosed or surrounded by the high conductance diamagnetic metal such that the sliding band capacitor’ 5012 has a very low volume magnetic susceptibility.

The sliding band capacitor 5012 can be used to adjust the resonance of the parent coil 1010 and localize the energy in the parent coil 1010. FIG. 5 shows a circuit with a power supply 1063, ammeters 1062, 1064, 1066, 1067, a parent coil 1010, a sliding band capacitor 5012, resistors 1052, 1054, 1056, 1058, capacitors 1086, 1024, 1025, 1087, variable capacitors 1022, 1026, lock inductors 1070, 1071, coupling loops 3087, 3088, and grounds 1090, that can be used with the probe shown in FIG. 7. In FIG. 5 the parent coil 1010 and the sliding band capacitor 5012 are located near the sample and the lock coils 1070, 1071 are used to detect the parent resonance by inductively coupling with the variable capacitors 1022, and/or 1026 to match with one of the two fifty-ohm ports 3080, 3081. A resonator 1088 and fixed capacitor 1025 and the ground points are also shown 1090. One advantage of using a sliding band capacitor 5012 is that it eliminates the need to have leads (see 1030, 1031 FIG. 1 and FIG. 3B connecting the parent coil 1010 to lock inductors 1070, 1071) and thereby reducing the number of inductors in the circuit, thereby keeping the majority of the high frequency circulating current in the parent coil 1010. The sliding band capacitor 5012 is particularly useful when the sample inductor has a low inductance value. In this situation the leads (1030 and 1031 in FIG. 3B) going from the parent coil (1010 in FIG. 3B) to the variable capacitors (1086, 1088, 1022, and 1087 in FIG. 3B) can have an inductance on the order of the sample inductor (1010 in FIG. 3B) itself. Hence minimizing the current in these leads by maximizing the circulating current in the parent coil 1010 with the sliding band capacitor 5012 is critical to maximizing the SNR. If the parent coil 1010 is of high inductance and the leads are of low inductance then using a sliding band capacitor 5012 can be less critical. The sliding band capacitor 5012 will help improve the SNR but not nearly as much as when the parent coil 1010 has a large inductance value. That is, it is all about the CFF, i.e. it is desirable that all the energy is in the parent coil 1010 and not in the leads or auxiliary inductors of the circuit for the mode of interest. The sliding band capacitor 5012 is closer to the parent coil 1010 than any other reactive component, such as another capacitor or another inductive component. However, because the sliding band capacitor 5012 is made of materials in which the sum of the magnetic susceptibility is zero, the sliding band capacitor 5012 does not need to be compensated as the mechanical movement of the sliding band capacitor (see FIG. 8) will not disturb the magnetic field experienced (see FIG. 9) by the sample.

In the last 20 years cooling the coils has been the major focus of NMR research. For example, to provide improved sensitivity the electronics for signal detection can be cryo-cooled. However, the SNR of the RF homogeneity of the parent coil can be degraded by magnetic coupling to the coil with even small k (coupling constant) values. Further, the leads connecting a variable capacitor to the parent coil have an inductance. The inductance of these leads does not produce a flux in the B1 field that penetrates the sample. Hence the filling factor is reduced because not all the inductance of the circuit produces flux which couples to the sample. Even in a situation where the parent circuit has chip capacitors across the parent coil to minimize circuit losses the leads to the variable capacitor will produce signal degradation. Accordingly, increasing the signal to noise would address (i) removing the leads and (ii) introducing a sliding band capacitor, where the sliding band capacitor does not affect the parent coil field. Further, appropriately choosing the materials in the sliding band capacitor can allow the sum of the magnetic susceptibility of the components to be minimized to zero at cryo-cooled. Finally, the materials used to construct the sliding band capacitor should allow transfer of the cryo-cooled temperatures surrounding the outside of the sliding band capacitor to the parent coil, i.e., the sliding band capacitor must be made of materials that are good heat conductors so that the cryo-cooled temperature is readily transmitted to the parent coil.

TABLE I

Characteristics of some high conductance diamagnetic metals.

Thermal

Volume

TABLE II

Characteristics of stable low volume magnetic susceptibility

Volume
Volume

* In Tables I and II Volume Magnetic Susceptibility is in S.I. Units and is a dimensionless quantity. Absent express recitation to the contrary, Volume Magnetic Susceptibility is in S.I. Units and as such is a dimensionless quantity; ≠=90% Ti, 6% Al, 4% V, see Data Handbook, Appendix A6, Properties of Solids at Low Temperatures, p579. Based on the reported diamagnetism of Ti—Al—V≠, in Table II, a suitable Titanium alloy would comprise greater than 92% titanium.

Titanium is highly reactive to trace amounts of water and metal oxides. The Hunter process generates titanium from the titanium tetrachloride salt by reduction with liquid sodium metal. Alternatively, liquid calcium can be used as the reductant. Titanium tetraiodide can also be decomposed to generate titanium metal. The Kroll process reduces titanium tetrachloride using liquid magnesium in a stainless-steel vessel at above 800° C. to generate a porous metallic titanium sponge. The sponge can be further purified by leaching, vacuum distillation. The Kroll process replaced the Hunter process for almost all commercial production. Alternatively, titanium oxide in a solution of molten calcium chloride can be electrolytically reduced to give titanium metal. Using an electron beam furnace and vacuum arc remelting furnace, a high purity titanium can be obtained. The precise method used to generate the titanium metal will affect the purity and composition of the resulting titanium foil, see Tables III and IV.

TABLE III

Characteristics of some Titanium foils (ppm).

*
Fe
Ni
Cr
A1
V
Mn
S
Zn
Zr
Si
Sn
Cu
O

TABLE IV

Characteristics of some Titanium foils.

**
Ti
Fe
C
N
H
Other
O

In an embodiment of the present invention, the low temperature probe is surrounded by a 12.28 (ID) sapphire ring which is surrounded by at least two 0.03 mm titanium foils which are then enclosed or surrounded by a 0.025 mm copper foil, where the diamagnetism due to the 12.28 (ID) sapphire ring and the diamagnetism due to the 0.025 mm copper foil offsets the paramagnetism of the at least two 0.03 mm titanium foils. In an alternative embodiment of the present invention, the low temperature probe is surrounded by a sapphire ring which is surrounded by an aluminum foil which is then encased by a silver foil, where the diamagnetism due to the sapphire ring and the diamagnetism due to the silver foil offsets the paramagnetism of the aluminum foil.

In an embodiment of the present invention, the low temperature probe is surrounded by a 12.28 (ID) sapphire ring which is in turn surrounded by at least two metal layers, where the sum of the magnetic susceptibility of the sapphire ring and the at least two metal layers is less than 1×10−4 at 300° K and less than 1×10−5 at 80° K, where a first metal of the at least two metal layers is a diamagnetic metal, where a second metal of the at least two metal layers is a paramagnetic metal, where the first metal is located on the surface facing away from the low temperature probe and has a conductivity of greater than 4×10−7 S/m. In an embodiment of the invention, the at least two metal layers comprise copper and titanium, where a thin copper foil encloses or surrounds two or more thin titanium foils, where the diamagnetism due to the sapphire ring and the layers of thin copper foil is offset the paramagnetism of the two or more thin titanium foil(s). In an alternative embodiment of the present invention, the low temperature probe is surrounded by a 12.28 (ID) sapphire ring which is surrounded by a 0.025 mm copper foil which in turn is surrounded by two or more 0.03 mm titanium foils, which are then surrounded on all sides by the 0.025 mm copper foil, where the diamagnetism due to the 12.28 (ID) sapphire ring and the 0.025 mm copper foil offsets the paramagnetism of the two or more 0.03 mm titanium foils.

In an embodiment of the present invention, a 13.05 mm (OD) 12.28 mm (ID)×10 mm L sapphire ring (AdValue Tech, AZ, USA) can enclose the low temperature probe. In an embodiment of the present invention, a 0.025 mm copper foil (Basic Copper, NC, USA) can surround an annealed 0.03 mm titanium foil (Goodfellow, UK). In an embodiment of the present invention, the Ti foil is grade 1 (ASTM B265 Chemistry only) and has a titanium content greater than approximately 98%. In this circumstance, approximately means that the efficiency is plus or minus two (2) percent. In an embodiment of the present invention, the Cu foil is >99.9% Cu, with an electrical conductivity of 101% International Annealed Copper Standard (IACS), where 100% IACS is equivalent to a conductivity of 5.8×107 Siemens per meter (S/m) at 20° C. In an embodiment of the present invention, after the titanium foil is surrounded by the copper foil, the exposed edge of the copper foil edge can be soldered using 42Sn58Bi solder wire (Indium Corporation, NY, USA) and Superior 30 flux (Superior Flux & Mfg. Co., Ohio, USA).

In an embodiment of the present invention, the sliding band capacitor metals can have a high thermal conductivity. The thermal conductivity of fused quartz is 1.4 W/(m·C) at 20° C., but is significantly reduced at 80° K [8.4 W/(m·K)]. The thermal conductivity of sapphire is 23 W/(m·C) at 23° C. and remains excellent at 80° K. The thermal conductivity of titanium is 1.8 W/(cm·K) at 25° C. and remains good at 80° K [11.4 W/k·K at 240° C.]. The thermal conductivity of aluminum is 237 W/(m·K) at 25° C., and remains good at 80° K.

In an embodiment of the present invention, the outer surface of the sliding band capacitor material can have a high conductivity. If the sliding band capacitor had a low conductivity, then it would result in a low Q.

The word ‘near’ refers to the position of the sample relative to the parent coil. The SFF is maximized by having the parent coil as close to the sample as physically possible.

The issue in prior art low temperature probes (see FIG. 3A and FIG. 3B) is that the leads 1030, 1031 from the parent coil 1010 to the variable tune capacitors 1086, 1022 and 1087 can constitute a significant portion of the inductance observed. These losses result in sample filling factor losses (SFF) because the Bi flux from the leads does not go thru the sample (see Equation 3).

The phrase ‘Circuit Fill Factor (CFF)’ means for a specific mode, k, the definition of CFFk,a referred to a reference inductor, a is given by Equation 3.

CFF
       
        k
        ,
        a
       
      
      =
      
       
        
         L
         a
        
        ⁢
        
         i
         a
         2
        
       
       
        
         
          ∑
           
         
         
          j
          =
          1
         
         N
        
        ⁢
        
         L
         j
        
        ⁢
        
         i
         j
         2
        
       
      
     
     ,
    
   
   
    
     Equation
     ⁢
        
     3

where a is the sample inductor, i is the current in the inductor, the j indices identify specific inductors, and it is implicit that the current values are for the kth mode. The CFFk,a is a measure of the efficiency of a probe circuit. The CFFk,a determines for the kth mode of a circuit how much energy is delivered to a specific inductor, a. Here the CFFk,a is a measure of the efficiency of the parent coil in the probe circuit. It is clear that this definition does not accommodate the presence of mutual inductance. It can be concluded from Equation 2 and Equation 3, that the presence of more than one inductor in the circuit dilutes the signal to noise ratio of the multiply tuned probe circuit. For probe circuits with multiple ground points there exist the question of what is the common ground point. If the ground points are not at the same potential as the common ground point then each ground point is essentially an inductor to that common ground point and such a circuit generates the potential to dilute the CFFk,a of the circuit. Hence, eliminating the variable tune capacitors 1086, 1022 and 1087 and thereby the leads 1030, 1031 is highly desirable. Eliminating ground points 1090 that are not at the same potential is also highly desirable.

The phrase ‘electrically connected’ means a connection where electrons will flow (i.e., in a circuit with a capacitor, electrons do not flow across the capacitor).

The phrase ‘the field strength of the magnetic field in the location remains essentially constant’ means that the incremental change in the magnetic field is less than approximately 1 ppm. In this circumstance, approximate means plus or minus 0.1 ppm.

The phrase ‘the RF field symmetry is minimally affected by the position of the sliding band capacitor’ means that a 2D plot of the sliding band capacitor 1512 field lines 1910 show the right-side field lines being the approximate mirror images of the left-hand side field lines, as shown in FIG. 9. In this circumstance, approximate means that the left side and the right side are mirror images superimposable within a ten (10) percent tolerance.

An NMR probe can include a sample, a parent detection coil/associated circuitry, a lock coil/associated circuitry, a pulsed field gradient, one or more coupling coils/associated circuitry, one or more fixed capacitors, one or more variable capacitors, a stator to support the sample, and the parent detection coil and a sliding band capacitor. The sliding band capacitor comprises a diamagnetic support, a paramagnetic material that is surrounded with a high conductance diamagnetic material. A perturbation of the magnetic field or the flux generated by the parent coil will reduce the signal to noise ratio. Accordingly, minimizing the components in the sample region of the NMR probe can reduce perturbations of the magnetic field (B0), the RF homogeneity and accordingly increase the signal to noise ratio.

As known in the art, the term S11 refers to the forward reflection of a first input port, which is a measure of the impedance match. The term S22 refers to the forward reflection of a second input port, which is a measure of the impedance match.

In an embodiment of the present invention, the cryo-cooled temperature limitation problem can be solved by selecting an appropriate inductance parent coil and tuning the parent coil by adjusting a sliding band capacitor, in which the sliding band capacitor does not distort the magnetic field of the parent coil, i.e., the parent coil is surrounded by materials in which the sum of the magnetic susceptibility is zero at cryo-cooled temperatures. The RF-homogeneity of the parent coil is a concern when there are leads is close in proximity to the parent coil. Ensuring the RF-homogeneity of the parent coil is a major advantage of using the sliding band capacitor, as per embodiments of the invention.

The word ‘adjusted’ when used in the phrase ‘interaction between the parent coil 1010 and the lock coils 1070, 1071 is adjusted to a resonant condition’ means the CFF for the circuit would show greater than approximately ninety (90) percent of the energy resides in the parent coil 1010. Approximately in this range means plus or minus ten (10) percent.

Absent express recitation to the contrary, the term ‘approximately’ means a nominal value plus or minus ten (10) percent thereof.

In the NMR experiment, the relationship between SNR, Quality factor for a resonator k (Qk), Sample Fill Factor (SFF) and Circuit Fill Factor (CFFk,a) is given by Equation 2, where is a dimensionless parameter defined as the ratio of the initial energy stored in the resonator to the energy lost in one radian of the cycle of oscillation.

According to Equation 2, in order to maximize the SNR, it is necessary to maximize Qk, SFF and/or CFFk,a. To maximize Qk is maximized by increasing the surface area of the conductor forming the resonator, thus a large surface area for the conductor in the parent coil is preferred. This usually is resolved by using a low inductance coil, i.e. similar to an Alderman—Grant coil. A measure of the SFF is the square of the ratio of the sample diameter divided by the diameter of the parent coil. Coils with larger surface areas generally result in slightly higher SFF values. In addition, the SFF can be maximized by having the parent coil as close to the sample as physically possible. Further, CFFk,a can be maximized by having the fewest inductors in the circuit as possible. That is, by connecting a variable capacitor to the parent coil, the circuit shown in FIG. 3A is actually more accurately represented by the circuit shown in FIG. 3B. That is, the number of inductors in the circuit shown in FIG. 3B has been increased by two (2), being the number of leads 1030, 1031 connecting to the variable capacitors 1086, 1088, 1022 and 1087. In an embodiment of the present invention, the parent coil can be tuned using a sliding band capacitor i.e., a capacitor that is built into the resonator circuit without leads to connect the means of varying the capacitance to the parent coil. By tuning a parent coil with such a sliding band capacitor with no leads to attach the sliding band capacitor to the circuit measuring the parent coil inductance, then the number of inductors in the circuit can be decreased (by two (2)) and accordingly the CFF of the parent coil can be increased (see Equation 1).

Importantly, in the circuit shown in FIG. 5 the inductive coupling loops exhibit very little loss.

The circuit shown in FIG. 5 has several advantages, a) the coupling loops don't interfere with the coils in the sample region of the probe, b) RF distortion of the parent coil Bi field from the lock coils 1070, 1071 is eliminated by using a sliding band capacitor 1512 to couple to the resonance of the parent coil 1010, c) the sliding band capacitor 1512 doesn't have to be susceptibility corrected due to its proximity to the parent coil 1010 since the sum of the volume magnetic susceptibility is near zero, and d) the lock coils don't have to be susceptibility corrected due to their proximity to the parent coil since they are not located in the region of the probe.

To analyze the circuits shown in this paper a CFF analysis was conducted. As shown in Equation 2, the SNR depends on the CFFk,a. CFFk,a for the sample inductor (a) for the observed mode (k) and Qk is the Q of the kth mode.

In the following description, various aspects of the present invention are described. However, it will be apparent to those skilled in the art that the present invention can be practiced with only some or all aspects of the present invention. For purposes of explanation, specific numbers, materials, and configurations are set forth to provide a thorough understanding of the present invention. However, it will be apparent to one skilled in the art that the present invention can be practiced without the specific details. In other instances, well-known features are omitted or simplified in order not to obscure the present invention.

Parts of the description are presented in data processing terms, such as data, selection, retrieval, generation, and so forth, consistent with the manner commonly employed by those skilled in the art to convey the substance of their work to others skilled in the art. As is well understood by those skilled in the art, these quantities (data, selection, retrieval, generation) can take the form of electrical, magnetic, or optical signals capable of being stored, transferred, combined, and otherwise manipulated through electrical, optical, and/or biological components of a processor and its subsystems.

Various operations are described as multiple discrete steps in turn, in a manner that is helpful in understanding the present invention; however, the order of description should not be construed as to imply that these operations are necessarily order dependent.

Various embodiments are illustrated in terms of exemplary classes and/or objects in an object-oriented programming paradigm. It will be apparent to one skilled in the art that the present invention can be practiced using any number of different classes/objects, not merely those included here for illustrative purposes.

Aspects of the invention are illustrated by way of example and not by way of limitation in the figures of the accompanying drawings in which like references indicate similar elements. It should be noted that references to ‘an’ or ‘one’ embodiment in this disclosure are not necessarily to the same embodiment, and such references mean at least one.

There remain encumbrances to the employment of inductively coupled low temperature probes to the NMR technique for a variety of samples and various experimental conditions. In general, low temperature dual probe circuits do not utilize inductive coupling to achieve the double-tuned circuit but rather use capacitive coupling to achieve the desired tuning properties. Here we show the use of inductive coupling to achieve the desired tuning properties in low temperature NMR probes.

In an embodiment of the present invention, two pieces of grade 1, 30 μm titanium foil 220 can be used as a diamagnetic metal to compensate for a piece of 25.4 μm copper foil 210. The two pieces of titanium foil 220 are positioned above each other on the copper foil 210 such that they are aligned with position 240, as shown in FIG. 2A. In an alternative embodiment of the present invention, one piece of grade 1, 60 μm titanium foil 220 can be used as a diamagnetic metal to compensate for a piece of 25.4 μm copper foil 210. The single titanium foil 220 can be positioned on the copper foil 210 such that they it is aligned with position 240, as shown in FIG. 2A. The copper foil 210 can be cut into a shape with edges 211, 212, 213, and 214, as shown in FIG. 2A and FIG. 2B. The copper foil 210 can be folded such that edge 212 aligns with position 240, as shown in FIG. 2C and FIG. 2D. The reverse side of the copper foil 210 can be folded around a 13.05 mm OD×12.28 mm ID×10 mm L sapphire ring 230 (AdValueTech), as shown in FIG. 2E, FIG. 2F, and FIG. 2G. In FIG. 2F, the edge 211 contacts the edge of the two titanium foils 210, where the edge 213 extends the copper foil at single thickness (i.e., without covering the two titanium foils 210). The length of edge 212 is measured and cut to allow edge 214 to align with edge 211, as shown in FIG. 2H. In an embodiment of the present invention, the edge 213 can be sealed with a small amount of 42Sn58Bi solder using Superior 30 flux, as shown in FIG. 2I.

In order to tune the circuit shown in FIG. 3B from 1H to 19F the variable capacitors 1086 and 1022 have to be increased in value to lower the frequency from 500.0 MHz to 470.3 MHz. However, this will cause more current to flow in the leads 1030, 1031 in FIG. 3B because the impedance to ground is lowered. The match at 3081 port 1 for 1H can be adjusted slightly using the variable capacitors 1087 but it has almost no effect on the current flowing in the leads or the match. The result of tuning to 19F is to cause more energy in the circuit to be removed from the parent coil and placed in the leads 1030, 1031 going to the variable capacitors (see FIG. 3B) as shown in FIG. 4C (a two-port plot overlay simulation showing the signal intensity DB(S11/S22) versus the frequency for 3090 2H (76.8 MHz, −37.5 dB), 3094 (255.2 MHz, −26.85 dB), 3095 19F (470.3 MHz, −47.77 dB) and 3096 (898.9 MHz, −11.4 dB), based on the circuit shown in FIG. 3B adjusted to detect 19F (i.e., after the frequency has been adjusted using the variable capacitors 1086, 1022, 1087). FIG. 4D is a CFF plot versus the frequency for the circuit shown in FIG. 3B adjusted to detect 19F (i.e., adjusted as in FIG. 4C) showing 3090 2H (76.8 MHz, CFF=0.0727), 3094 (255.2 MHz, CFF=0.00903), 3095 19F (470.3 MHz, CFF=0.6632) and 3096 (898.9 MHz, CFF=0.2634), where the inductance in leads 1030, 1031 in FIG. 3 results in resonances 3094, 3096.

The energy in the parent coil 1010 has dropped from ˜76% (3092 in FIG. 4B) to −66% (3095 in FIG. 4D) while the energy in the leads has increased from ˜15% (3091 and 3093 in FIG. 4B) to −26% (3094 and 3096 in FIG. 4D). The circuit (see FIG. 3B) when tuned to 19F (see FIG. 4D) is less efficient than when the circuit (see FIG. 3B) is tuned to 1H (see FIG. 4B). In an embodiment of the present invention, in order to eliminate the loss associated with the leads (1030, 1031 in FIG. 3B), a sliding band capacitor 5012 (in FIG. 5) replaces the variable capacitors 1086, 1022 and 1087 (in FIG. 3B) and can be used to tune the circuit in the parent coil.

For the calculations based on the circuit shown in FIG. 5, the parent coil 1010 has an inductance of 15 nH, the lock inductors 1070, 1071 are assigned inductances of 90 nH, the inductors 3087, 3088 are assigned inductances of 30 nH, the inductor 1088 is assigned an inductances of 50 nH, 1090 signifies ground, resistors 1052, 1054, 1056, 1058 have resistances of 1×10−9 Ohms, and capacitors 1022, 1086, 1024, 1025, 1087, and 1026 have capacitances of 47.4 pF, 113.3 pF, 3.7 pF, 21.94 pF, 2.43 pF and 1.422 pF respectively. FIG. 5 is a circuit for a probe in which a sliding band capacitor 5012 comprising zero sum volume magnetic susceptibility materials is used to adjust the resonance of the parent coil. In the process of using the sliding band capacitor 5012 in FIG. 5 it is still necessary to impedance match the circuit to a load (50 Ohms). In FIG. 5 magnetic coupling is used to do this by implementing Secondary Magnetic Coupling. FIG. 6A is a two-port plot overlay simulation showing the signal intensity DB(S11/S22) versus the frequency for 2H 3090 (76.8 MHz, −42.3 dB), and 3092 1H (500 MHz, −43.4 dB) based on the circuit shown in FIG. 5 tuned to 1H. FIG. 6B is a CFF plot versus the frequency for 2H 3090 (76.8 MHz, CFF=0.0805) and 1H 3092 (500 MHz, CFF=0.918) and based on the circuit shown in FIG. 5 tuned to 1H (i.e., for the frequency as adjusted in FIG. 6A). FIG. 6C is a two-port plot overlay simulation showing the signal intensity DB(S11/S22) versus the frequency for 2H 3090 (76.8 MHz, −45.38 dB) and 19F 3095 (470.3 MHz, −48.18 dB) and based on the circuit shown in FIG. 5 tuned to 19F (i.e., after the frequency has been adjusted using the sliding band capacitor 5012). FIG. 6D is a CFF plot versus the frequency for 2H 3090 (76.8 MHz, CFF=0.0805) and 19F 3095 (470.3 MHz, CFF=0.9177) based on the circuit shown in FIG. 5 tuned to 19F (i.e., for the frequency as adjusted in FIG. 6C). Unexpectedly, by eliminating the leads we have eliminated spurious resonances in the S11/S22 plot (see resonances 3091, 3093 in FIG. 4B and resonances 3094, 3096 in FIG. 4D) and importantly increased the energy in the parent coil. Unexpectedly, the energy in the parent coil increases from 76.35% (3092 in FIG. 4B) to 91.8% (3095 in FIG. 6B) for 1H observe. For 19F the energy in the parent coil has increased from 66.32% (3095 in FIG. 4D) to 91.77% (3095 in FIG. 6D).

In a circuit using leads to a variable capacitor the performance when tuned to 1H is higher by a factor of 1.1 compared to the performance when tuned to 19F. Unexpectedly, when a sliding band capacitor 5012 is used in the circuit instead of a circuit using leads to a variable capacitor the performance when tuned to 19F is higher by a factor of 1.1 compared to the performance when tuned to 1H. In an embodiment of the present invention, using a sliding band capacitor 5012 becomes more important for circuits using low inductance sample coils.

The circuit shown in FIG. 5 is inductively coupled double tuned circuits, however, in various embodiments of the invention, a sliding band capacitor made of materials with a sum volume magnetic susceptibility of zero can be employed with capacitive coupled circuits as shown in FIG. 10.

Further Embodiments

Embodiment P1. A NMR probe adapted to detect a resonance of at least a nucleus from a sample, including a parent coil circuit comprising a parent coil, where the parent coil comprises a tapered inner conductance skirt, a cell adapted for holding the sample at a temperature, and a sliding band capacitor adapted to adjust a frequency of the parent coil, where the sliding band capacitor comprises a diamagnetic insulator with a first volume magnetic susceptibility, at least one paramagnetic metal with a second volume magnetic susceptibility and at least one diamagnetic metal with a third volume magnetic susceptibility, where a sum of the first volume magnetic susceptibility and the second volume magnetic susceptibility and the third volume magnetic susceptibility is approximately zero, where the NMR probe is adapted to introduce the sample into a magnetic field of a NMR instrument, where the sliding band capacitor is adapted to physically move relative to the tapered inner conductance skirt to adjust a capacitance of the sliding band capacitor to allow the parent coil to detect the resonance of at least the nucleus from the sample.

Embodiment P2. The NMR probe of embodiment P1, where the at least one paramagnetic metal is adapted to form a paramagnetic metal ring.

Embodiment P3. The NMR probe of embodiment P2, where the paramagnetic metal ring is enclosed by the at least one diamagnetic metal.

Embodiment P4. The NMR probe of embodiment P2, where the paramagnetic metal ring is surrounded by the at least one diamagnetic metal.

Embodiment P5. The NMR probe of embodiment P1, where the at least one paramagnetic metal is selected from the group consisting of aluminum, palladium, platinum, rhodium, tantalum, titanium and tungsten.

Embodiment P6. The NMR probe of embodiment P2, where the paramagnetic metal ring comprises a titanium composition by volume a lower limit of greater than approximately eighty (80) percent, and an upper limit of greater than approximately ninety-eight (98) percent.

Embodiment P7. The NMR probe of embodiment P1, where a RF field symmetry of the magnetic field is minimally affected by a position of the sliding band capacitor moving relative to the tapered inner conductance skirt.

Embodiment P8. The NMR probe of embodiment P1, where the sum is a lower limit of approximately 1×10−6 at 80° K, and an upper limit of approximately 1×10−5 at 80° K.

Embodiment P9. The NMR probe of embodiment P1, where the temperature of the sliding band capacitor is approximately 300° K when the sample is introduced into the NMR instrument, where the temperature of the sliding band capacitor prior to detection of the resonance is reduced to a lower limit of approximately 15° K, and an upper limit of approximately 80° K.

Embodiment P10. The NMR probe of embodiment P1, where the at least one diamagnetic metal has an electrical conductance at 300° K of a lower limit of approximately 1×107 S/m, and an upper limit of approximately 1×108 S/m.

Embodiment P11. The NMR probe of embodiment P1, where the at least one diamagnetic metal is selected from the group consisting of copper, gold, nickel, silver, and zinc.

Embodiment P12. The NMR probe of embodiment P1, where the at least one diamagnetic metal is an alloy, where the alloy comprises copper and silver.

Embodiment P13. The NMR probe of embodiment P1, where the at least one diamagnetic metal is copper.

Embodiment P14. The NMR probe of embodiment P1, where the diamagnetic insulator is selected from the group consisting of sapphire, quartz, diamond, boron nitride, silicon nitride, and alumina.

Embodiment P15. The NMR probe of embodiment P1, where the at least one paramagnetic metal is an alloy, where the alloy comprises aluminum and titanium.

Embodiment P16. The NMR probe of embodiment P1, where the at least one paramagnetic metal is titanium.

Embodiment P17. The NMR probe of embodiment P1, where the nucleus is selected from the group consisting of 1H, 19F, and 13C.

Embodiment P18. A NMR probe adapted to detect a resonance of at least a nucleus from a sample, including a parent coil circuit comprising a parent coil, where the parent coil comprises a tapered inner conductance skirt, a cell adapted for holding the sample, and a sliding band capacitor adapted to adjust a frequency of the parent coil, where the sliding band capacitor comprises a sapphire insulator with a first volume magnetic susceptibility, at least one paramagnetic metal with a second volume magnetic susceptibility and at least one diamagnetic metal with a third volume magnetic susceptibility, where a sum of the first volume magnetic susceptibility and the second volume magnetic susceptibility and the third volume magnetic susceptibility is approximately zero, where the at least one paramagnetic metal is shaped in a form of a paramagnetic metal ring, where the paramagnetic metal ring is enclosed or surrounded by the at least one diamagnetic metal, where the sliding band capacitor is at a temperature, where the temperature of the sliding band capacitor is approximately 300° K when the sample is introduced into a NMR instrument, where the temperature of the sliding band capacitor prior to detection of the resonance is reduced to a lower limit of approximately 15° K, an upper limit of approximately 80° K, where the NMR probe is adapted to introduce the sample into a magnetic field of the NMR instrument, where the sliding band capacitor is adapted to physically move relative to the tapered inner conductance skirt to adjust a capacitance of the sliding band capacitor to allow the parent coil to detect the resonance of at least the nucleus from the sample.

Embodiment P19. The NMR probe of embodiment P18, where the paramagnetic metal ring comprises a titanium composition by volume a second lower limit of greater than approximately eighty (80) percent, and a second upper limit of greater than approximately ninety-eight (98) percent.

Embodiment P20. A method of detecting a resonance of at least a nucleus from a sample using a cooled NMR probe, including selecting a parent coil circuit comprising a parent coil, where the parent coil comprises a tapered inner conductance skirt, selecting the sample, loading the sample into the NMR probe, introducing the NMR probe into a magnetic field of a NMR instrument, where the parent coil circuit is in electrical contact with the tapered inner conductance skirt, where a capacitance of the parent coil circuit is adapted to be adjusted by moving a sliding band capacitor relative to the tapered inner conductance skirt, where the sliding band capacitor comprises a diamagnetic insulator with a first volume magnetic susceptibility, at least one paramagnetic metal with a second volume magnetic susceptibility and at least one diamagnetic metal with a third volume magnetic susceptibility, where a sum of the first volume magnetic susceptibility and the second volume magnetic susceptibility and the third volume magnetic susceptibility is approximately zero, where the at least one paramagnetic metal is adapted to form a paramagnetic metal ring, where the paramagnetic metal ring is enclosed or surrounded by the at least one diamagnetic metal, where the sliding band capacitor is adapted to be cooled to a temperature, spinning the sample, and exciting the sample with a RF field at a Larmor frequency, where the NMR probe is adapted to introduce the sample into the magnetic field of the NMR instrument, where the sliding band capacitor is adapted to physically move relative to the tapered inner conductance skirt to adjust the capacitance of the sliding band capacitor to allow the parent coil to detect the resonance of at least the nucleus from the sample.

Embodiment P21. The method of embodiment P20, where the temperature is approximately 300° K when the sample is introduced into the NMR instrument, where the temperature prior to detection of the resonance is reduced to a lower limit of approximately 30° K, and an upper limit of approximately 80° K.

Embodiment P22. The method of embodiment P20, where the at least one paramagnetic metal is an alloy, where the alloy comprises aluminum and titanium.

Embodiment P23. The method of embodiment P20, where the paramagnetic metal ring comprises a titanium composition by volume a lower limit of greater than approximately eighty (80) percent, and an upper limit of greater than approximately ninety-eight (98) percent.

Embodiment P24. The NMR probe of embodiment P2, where the paramagnetic metal ring is contacted by the at least one diamagnetic metal.

Embodiment P25. The NMR probe of embodiment P2, where greater than approximately ninety-eight (98) percent of a surface area of a top edge of the paramagnetic metal ring is aligned with the at least one diamagnetic metal and approximately ninety (90) percent of a surface area of a side of a titanium foil ring is aligned with the at least one diamagnetic metal, where an exposed portion of the side is adjacent a bottom edge.

Embodiment P26. The NMR probe of embodiment P1, where the sliding band capacitor is adapted to be cooled to a lower limit of approximately 5° K, and an upper limit of approximately 100° K.

Embodiment P27. The NMR probe of embodiment P18, where a measured Q value at 500 MHz is greater than 1000.

Embodiment P28. The NMR probe of embodiment P18, where the paramagnetic metal ring is enclosed by the at least one diamagnetic metal.

Embodiment P29. The NMR probe of embodiment P28, where a measured Q value of the paramagnetic metal ring is greater than approximately ninety-five (95) percent of an optimal Q value.

Embodiment P30. The NMR probe of embodiment P29, where approximately ninety-nine (99) percent of the surface area of a top edge of the paramagnetic metal ring is approximately smoothly aligned with the at least one diamagnetic metal.

Embodiment P31. The NMR probe of embodiment P29, where approximately ninety-nine (99) percent of the surface area of a side of the paramagnetic metal ring is approximately smoothly aligned with the at least one diamagnetic metal.

Embodiment P32. The NMR probe of embodiment P18, where the paramagnetic metal ring is surrounded by the at least one diamagnetic metal.

Embodiment P33. The NMR probe of embodiment P32, where a measured Q value of the paramagnetic metal ring is greater than approximately ninety (90) percent of an optimal Q value.

Embodiment P34. The NMR probe of embodiment P33, where approximately ninety-nine (99) percent of the surface area of a top edge of the paramagnetic metal ring is approximately smoothly aligned with the at least one diamagnetic metal.

Embodiment P35. The NMR probe of embodiment P33, where approximately ninety-nine (99) percent of the surface area of a side of the paramagnetic metal ring is approximately smoothly aligned with the at least one diamagnetic metal.

Embodiment P36. The NMR probe of embodiment P18, where the at least one paramagnetic metal is selected from the group consisting of aluminum, palladium, platinum, rhodium, tantalum, titanium and tungsten.

Embodiment P37. The NMR probe of embodiment P18, where a RF field symmetry of the magnetic field is minimally affected by a position of the sliding band capacitor moving relative to the tapered inner conductance skirt.

Embodiment P38. The NMR probe of embodiment P18, where the sum is a lower limit of approximately 1×10−6 at 80° K, and an upper limit of approximately 1×10−5 at 80° K.

Embodiment P39. The NMR probe of embodiment P18, where the at least one diamagnetic metal has a conductance at 300° K of a lower limit of approximately 1×107 S/m, and an upper limit of approximately 1×108 S/m.

Embodiment P40. The NMR probe of embodiment P18, where the at least one diamagnetic metal is selected from the group consisting of copper, gold, nickel, silver, and zinc.

Embodiment P41. The NMR probe of embodiment P18, where the at least one diamagnetic metal is an alloy, where the alloy comprises copper and silver.

Embodiment P42. The NMR probe of embodiment P18, where the at least one diamagnetic metal is copper.

Embodiment P43. The NMR probe of embodiment P18, where the diamagnetic insulator is selected from the group consisting of sapphire, quartz, diamond, boron nitride, silicon nitride, and alumina.

Embodiment P44. The NMR probe of embodiment P18, where the at least one paramagnetic metal is an alloy, where the alloy comprises aluminum and titanium.

Embodiment P45. The NMR probe of embodiment P18, where a first paramagnetic metal of the at least one paramagnetic metal is titanium.

Embodiment P46. The NMR probe of embodiment P18, where the resonance is selected from the group consisting of 1H, 19F, and 13C.

Embodiment P47. The method of embodiment P20, where a measured Q value at 500 MHz is greater than 1000.

Embodiment P48. The method of embodiment P20, where the paramagnetic metal ring is enclosed by the at least one diamagnetic metal.

Embodiment P49. The method of embodiment P48, where a measured Q value of the paramagnetic metal ring is greater than approximately ninety-five (95) percent of an optimal Q value.

Embodiment P50. The method of embodiment P49, where approximately ninety-nine (99) percent of the surface area of a top edge of the paramagnetic metal ring is approximately smoothly aligned with the at least one diamagnetic metal.

Embodiment P51. The method of embodiment P49, where approximately ninety-nine (99) percent of the surface area of a side of the paramagnetic metal ring is approximately smoothly aligned with the at least one diamagnetic metal.

Embodiment P52. The method of embodiment P20, where the paramagnetic metal ring is surrounded by the at least one diamagnetic metal.

Embodiment P53. The method of embodiment P52, where a measured Q value of the paramagnetic metal ring is greater than approximately ninety (90) percent of an optimal Q value.

Embodiment P54. The method of embodiment P53, where approximately ninety-nine (99) percent of the surface area of a top edge of the paramagnetic metal ring is approximately smoothly aligned with the at least one diamagnetic metal.

Embodiment P55. The method of embodiment P53, where approximately ninety-five (95) percent of the surface area of a side of the paramagnetic metal ring is approximately smoothly aligned with the at least one diamagnetic metal.

Embodiment P56. The method of embodiment P20, where the at least one paramagnetic metal is selected from the group consisting of aluminum, palladium, platinum, rhodium, tantalum, titanium and tungsten.

Embodiment P57. The method of embodiment P20, where the paramagnetic metal ring comprises a titanium composition by volume a lower limit of greater than approximately eighty (80) percent, and an upper limit of greater than approximately ninety-eight (98) percent.

Embodiment P58. The method of embodiment P20, where a RF field symmetry of the magnetic field is minimally affected by a position of the sliding band capacitor moving relative to the tapered inner conductance skirt.

Embodiment P59. The method of embodiment P20, where the sum is a lower limit of approximately 1×10−6 at 80° K, and an upper limit of approximately 1×10−5 at 80° K.

Embodiment P60. The method of embodiment P20, where the at least one diamagnetic metal has a conductance at 300° K of a lower limit of approximately 1×107 S/m, and an upper limit of approximately 1×108 S/m.

Embodiment P61. The method of embodiment P20, where the at least one diamagnetic metal is selected from the group consisting of copper, gold, nickel, silver, and zinc.

Embodiment P62. The method of embodiment P20, where the at least one diamagnetic metal is an alloy, where the alloy comprises copper and silver.

Embodiment P63. The method of embodiment P20, where the at least one diamagnetic metal is copper.

Embodiment P64. The method of embodiment P20, where the diamagnetic insulator is selected from the group consisting of sapphire, quartz, diamond, boron nitride, silicon nitride, and alumina.

Embodiment P65. The method of embodiment P20, where the diamagnetic insulator is alumina.

Embodiment P66. The method of embodiment P20, where the diamagnetic insulator is sapphire.

Embodiment P67. The method of embodiment P20, where the at least one paramagnetic metal is selected from the group consisting of aluminum and titanium.

Embodiment P68. The method of embodiment P20, where the at least one paramagnetic metal is an alloy, where the alloy comprises aluminum and titanium.

Embodiment P69. The method of embodiment P20, where the tapered skirt comprises a metal or an alloy.

Embodiment P70. The method of embodiment P69, where the metal is copper.

Embodiment P71. The method of embodiment P69, where the alloy is selected from the group consisting of Cu plated with Pd, and a Cu—Al—Cu alloy.

Embodiment P72. The method of embodiment P20, where a first paramagnetic metal of the at least one paramagnetic metal is titanium.

Embodiment P73. The method of embodiment P20, where the resonance is selected from the group consisting of 1H, 19F, and 13C.

Embodiment P74. A NMR probe adapted to detect a resonance of at least a nucleus from a sample, including, a parent coil circuit comprising a parent coil, where the parent coil comprises a tapered inner conductance skirt, a cell adapted for holding the sample, and a sliding band capacitor adapted to adjust a frequency of the parent coil, where the sliding band capacitor comprises a sapphire insulator with a first volume magnetic susceptibility, at least one paramagnetic metal with a second volume magnetic susceptibility and at least one diamagnetic metal with a third volume magnetic susceptibility, where a sum of the first volume magnetic susceptibility and the second volume magnetic susceptibility and the third volume magnetic susceptibility is approximately zero, where the at least one paramagnetic metal is shaped in a form of a paramagnetic metal ring, where the paramagnetic metal ring is enclosed or surrounded by the at least one diamagnetic metal, where the paramagnetic metal ring is contacted by the at least one diamagnetic metal, where greater than approximately ninety-eight (98) percent of a surface area of a top edge of the paramagnetic metal ring is aligned with the at least one diamagnetic metal and approximately ninety (90) percent of a surface area of a side of a titanium foil ring is aligned with the at least one diamagnetic metal, where an exposed portion of the side is adjacent a bottom edge, where the sliding band capacitor is adapted to be cooled to between a lower limit of approximately 5° K, and an upper limit of approximately 100° K, where the sliding band capacitor is adapted to physically move relative to the tapered inner conductance skirt to adjust a capacitance of the parent coil circuit to allow the parent coil to detect the resonance of at least the nucleus from the sample.

Embodiment P75. A NMR probe adapted to detect a resonance of at least a nucleus from a sample, including, a parent coil circuit comprising a parent coil, where the parent coil comprises a tapered inner conductance skirt, a cell adapted for holding the sample at a temperature, and a sliding band capacitor comprising a diamagnetic insulator with a first volume magnetic susceptibility, at least one paramagnetic metal with a second volume magnetic susceptibility, and at least one diamagnetic metal with a third volume magnetic susceptibility, where a sum of the first volume magnetic susceptibility and the second volume magnetic susceptibility and the third volume magnetic susceptibility is approximately zero, where the NMR probe is adapted to introduce the sample into a magnetic field of a NMR instrument, where the at least one paramagnetic metal is adapted to form a paramagnetic metal ring, where paramagnetic metal ring is aligned with the at least one diamagnetic metal such that the measured Q value is greater than approximately ninety-five (95) percent of the optimal Q value, where the sliding band capacitor is adapted to be cooled to between, a lower limit of approximately 5° K, and an upper limit of approximately 100° K, where the sliding band capacitor is adapted to physically move relative to the tapered inner conductance skirt to adjust a capacitance of the parent coil circuit to allow the parent coil to detect the resonance of at least the nucleus from the sample.

Abbreviations: Circuit Fill Factor=CFF; Circuit Fill Factor for a specific mode, k, referred to a reference inductor, a=CFFk,a; Magnetic Field=B1; Nuclear Magnetic Resonance=NMR; Quality Factor=Q; Quality factor for a resonator k=Qk; Radio Frequency=RF; Sample Fill Factor=SFF; Signal to Noise Ratio=SNR; Static Magnetic Field=B0; Unloaded Q=Qu.

While the systems, methods, and devices have been illustrated by the described examples, and while the examples have been described in considerable detail, it is not the intention of the applicants to restrict or in any way limit the scope of the appended claims to such detail. It is, of course, not possible to describe every conceivable combination of components or methodologies for purposes of describing the systems, methods, and devices provided herein. Additional advantages and modifications will readily be apparent to those skilled in the art. Therefore, the invention, in its broader aspects, is not limited to the specific details, the representative system, method or device, and illustrative examples shown and described. Accordingly, departures may be made from such details without departing from the spirit or scope of the applicant's general inventive concept. Thus, this application is intended to embrace alterations, modifications, and variations that fall within the scope of the appended claims. Furthermore, the preceding description is not meant to limit the scope of the invention. Rather, the scope of the invention is to be determined by the appended claims and their equivalents.