JP4156646B2 - NMR probe for multiple resonance - Google Patents

Description

  The present invention relates to a multi-resonance NMR probe used in an NMR apparatus, and in particular, for multi-resonance in which at least three high-frequency frequencies that can be co-tuned simultaneously have at least three frequencies, and at least two of them have a wide tuning range. It relates to an NMR probe.

  There are a wide variety of nuclides that can be observed by NMR. Depending on the nuclide, the resonance frequency varies greatly. Specifically, nuclides as shown in FIG. 1 are the main observation targets of NMR. In the figure, the chemical symbol on the left represents the type of observation nucleus, and the numerical value on the right represents the resonance frequency of the observation nucleus when placed in a static magnetic field of 18 Tesla (T), in units of megahertz (MHz).

  The NMR apparatus includes an NMR probe as one of its important components. The NMR probe includes a sample coil and a tuning circuit combined with the sample coil, and irradiates a sample placed in a static magnetic field with a high frequency pulse and detects an NMR signal generated from the sample by this irradiation. Used. As one of the NMR probes having such a role, an irradiation system high frequency that is a relatively high frequency, an observation system high frequency that is a relatively low frequency, and an NMR lock high frequency that is used to compensate for a drift of a static magnetic field. Have been developed for multiple resonance NMR probes with multiple tuning circuits.

FIG. 2 shows an example of a conventional multiple resonance NMR probe. Among these, FIG. 2A is an example of an NMR probe for multi-resonance having three frequencies (f ₁ , f ₂ , f ₃ ) that can be simultaneously tuned, and one of the frequencies (f ₁ ) is 1 to Broadband tuning of about 3 octaves and the remaining two frequencies (f ₂ , f ₃ ) are single-tuned. Specifically, f ₁ is an observation system high frequency that can be tuned to the resonance frequency of ³¹ P nuclei to ¹⁵ N nuclei, f ₂ is an irradiation system high frequency that can be tuned to the resonance frequency of ¹ H nuclei, and f ₃ is ² It corresponds to an NMR lock type high frequency that can be tuned to the resonance frequency of the D nucleus.

FIG. 2B shows an example of a multiple resonance NMR probe having four frequencies (f ₁ , f ₂ , f ₃ , f ₄ ) that can be simultaneously tuned simultaneously, and all four frequencies are single-tuned. It is what. Specifically, f ₁ is a first observation system high frequency that can be tuned to the resonance frequency of ¹³ C nuclei, f ₂ is an irradiation system high frequency that can be tuned to the resonance frequency of ¹ H nuclei, and f ₃ is ¹⁵ N the second observation system frequency can be tuned to the resonant frequency of the nuclei, f _4, it corresponds to a tunable NMR rock frequency to the resonant frequency of the ^{2 D} nucleus. The combination of the high-frequency is not necessarily _absolute, as another example of a combination of _{f 1 / f 2 / f 3} / f 4, for example, the resonant frequency of the _{f 1} ¹³ C nuclei, the _{f 2} ¹⁹ F nuclear resonance frequency, the resonance frequency of the ¹ H nuclei to _{f 3,} the resonant frequency of ² D nucleus _{f 4,} may be assigned respectively.

Japanese Patent Laid-Open No. 07-120419

By the way, as a sample that has been conventionally measured by NMR,
(1) A sample containing ¹³ C nuclei, ¹ H nuclei, and ¹⁵ N nuclei and made into a solution in a deuterium ( ² D) nuclear solvent.
(2) A sample containing ⁷⁹ Br nuclei, ¹³ C nuclei, and ¹ H nuclei and made into a solution in a deuterium ( ² D) nuclear solvent.
(3) A sample containing ¹⁵ N nuclei, ¹ H nuclei, ³¹ P nuclei, and ( ¹³ C nuclei) and made into a solution in a deuterium ( ² D) nuclear solvent.
There was. As is clear from these examples, measurement samples for measuring heterogeneous species such as ³¹ P nucleus to ¹⁵ N nucleus (sometimes ¹⁵ N nucleus to ¹⁰³ Rh nucleus) and ¹ H nucleus are known / unknown. Regardless, there are many.

  If you want to measure such a sample, it is impossible to cover all the nuclei observations with a single NMR probe with the conventional technology, and even if it is troublesome, you can tune to the resonance frequency of a given nucleus. A plurality of NMR probes were prepared, and each time, the NMR probe was attached to the NMR magnet, the resolution was increased, and the measurement conditions were adjusted and measurement was repeated. In addition, the time and effort required to do so are not stupid, and the NMR probe has different resolution, irradiation efficiency, and detection efficiency for each probe. There was a problem that the data had to be corrected.

  In view of the above points, an object of the present invention is to provide a multiple resonance NMR probe capable of simultaneously observing a plurality of types of nuclei with a single NMR probe, and to solve the above-described disadvantages.

In order to achieve this object, the NMR probe for multiple resonance according to the present invention comprises:
In a multi-resonance NMR probe that irradiates a sample set in a static magnetic field with a plurality of high frequencies of different frequencies and detects a plurality of nuclear magnetic resonance signals emitted from the sample in response to the irradiation high frequency,
The NMR probe for multiple resonance includes two sample coils, and is set so that the high-frequency magnetic field axis generated in the first coil and the high-frequency magnetic field axis generated in the second coil are in different directions,
The first coil double-tunes a narrow band corresponding to the resonance frequency of ¹⁹ F nucleus or ¹ H nucleus and a broadband corresponding to the resonance frequency of ¹⁵ N nucleus to ³¹ P nucleus, and the second coil is ² D corresponding to the narrow band and ¹⁵ resonance frequency of N nuclei ~ ³¹ P nuclei corresponding to the resonant frequency of the wideband or ² D nucleus and corresponds to the resonant frequency of the narrowband and ¹⁹⁹ Hg nuclei ~ ³¹ P nuclei corresponding to the resonant frequency of the nuclei It is characterized by the double tuning of a wide band.

  Further, the first coil is an inner coil, and the second coil is an outer coil.

According to the NMR probe for multiple resonance according to the present invention,
In a multi-resonance NMR probe that irradiates a sample set in a static magnetic field with a plurality of high frequencies of different frequencies and detects a plurality of nuclear magnetic resonance signals emitted from the sample in response to the irradiation high frequency,
The NMR probe for multiple resonance includes two sample coils, and is set so that the high-frequency magnetic field axis generated in the first coil and the high-frequency magnetic field axis generated in the second coil are in different directions,
The first coil double-tunes a narrow band corresponding to the resonance frequency of ¹⁹ F nucleus or ¹ H nucleus and a broadband corresponding to the resonance frequency of ¹⁵ N nucleus to ³¹ P nucleus, and the second coil is ² D corresponding to the narrow band and ¹⁵ resonance frequency of N nuclei ~ ³¹ P nuclei corresponding to the resonant frequency of the wideband or ² D nucleus and corresponds to the resonant frequency of the narrowband and ¹⁹⁹ Hg nuclei ~ ³¹ P nuclei corresponding to the resonant frequency of the nuclei Because it is characterized by double tuning the wideband to
A multi-resonance NMR probe capable of simultaneously observing a plurality of types of nuclei with one NMR probe can be provided.

Embodiments of the present invention will be described below with reference to the drawings. FIG. 3 shows an embodiment of the NMR probe for multiple resonance according to the present invention. As shown in FIG. 3, the multi-resonance NMR probe according to the present invention has four frequencies (f ₁ , f ₂ , f ₃ , f ₄ ) that can be simultaneously tuned, and one of the frequencies (f ₁ ). There wideband tuning of about 1 to 3 octaves, 1 frequency _{(f 2)} 1 to 2 octaves about wideband tuning, but the remaining 2 frequency _(f 3, f ₄₎ is a single-tuned respectively. Specifically, f ₁ is a first observation system high frequency that can be tuned to the resonance frequency of ³¹ P nucleus to ¹⁵ N nucleus, and f ₂ is a _second frequency that can be tuned to the resonance frequency of ³¹ P nucleus to ¹⁹⁹ Hg nucleus. F _{3 corresponds} to an irradiation system high frequency that can be tuned to the resonance frequency of ¹ H nucleus or ¹⁹ F nucleus, and f ₄ corresponds to an NMR lock type high frequency that can be tuned to the resonance frequency of ² D nucleus. .

In such a configuration, in the present embodiment, meticulous measures are taken in order to prevent f ₁ and f ₂ having close frequencies from interfering with each other. FIG. 4 shows the shape of the sample coil portion of the multiple resonance NMR probe according to the present invention. As is clear from FIG. 4, the sample coil portion is composed of two saddle-type coils L _A and L _B arranged concentrically, so that the directions of the high-frequency magnetic fields generated by the respective coils are in different directions. It is configured.

FIG. 5 shows the relationship between the direction of the high-frequency magnetic field generated by the two large and small saddle coils L _A and L _B and the isolation between the two coils. FIG. 5A is a schematic diagram showing the direction of the high-frequency magnetic field generated by the two large and small saddle-type coils L _A and L _B , and FIG. 5B shows the generation of the two large and small saddle-type coils L _A and L _B. It is a figure which shows the relationship between the angle (theta) which the magnetic field axis of the high frequency magnetic field to make, and the isolation I between two coils. FIG 5 (b) As is apparent from the two large and small saddle coil L _A, when L _B is changing the angle θ formed by the magnetic field axis of the high-frequency magnetic field generated, the value I of isolation between the two coils The value I of the isolation takes a minimum value at a predetermined angle θ ₀ that varies depending on the angle θ and θ is approximately 90 °.

At this time, 6.4Mmfai the diameter of the saddle type coil _{L A, 10.5mmφ} the diameter of the saddle type coil _{L B,} two coils _L A, assuming equal the coil length _{L B,} between the two coils cross A practical isolation value that can eliminate the talk was about 10 dB, and more preferably about 20 dB. Therefore, this 20dB stipulates that isolation I ₀ indicating a practical level, were examined angle theta which satisfies I _0, theta is, θ ₀ ± 10 °, more preferably about, theta ₀ ± 3 It was found to be about °. Since the value of the optimum angle θ ₀ can be accurately determined using a network analyzer or a predetermined jig, the azimuth angle of the high-frequency magnetic field of the two coils is determined at the angle θ ₀ thus determined. The two large and small saddle-type coils L _A and L _B are arranged so as to match.

Further, the inductance value of the saddle type coil L _A (inner coil) is set to about 60 nH, the inductance value of the saddle type coil L _B (outer coil) is set to about 150 nH, and the inductance values of both coils are intentionally set to be unbalanced. By doing so, the two frequencies f ₁ and f ₂ are configured to be difficult to crosstalk. The coupling inductance κ between the two coils is equivalent to κ in the tank circuit shown in FIG. This coupling inductance κ is
_{κ = β√ (L A × L} B)
It is represented by The degree of coupling beta, is a device constant determined and the angle θ formed by the high frequency magnetic field axis of the high-frequency magnetic field axis and the coil L _B of the coil L _A, by the value of the distance between the coils L _A · coil L _B. The angle formed with the high-frequency magnetic field axis of the high-frequency magnetic field axis and the coil _{L B} of the coil _{L A} and sets the θ ₀ ± 3 °, set to 6.4mm and 10.5mm in diameter of the coil _{L A} and the coil _{L B,} respectively to, by the distance between the coils _{L a} · coil _{L B} and 2.05 mm, it was possible to reduce the value of the connection degree β up to about 0.1. As a result, the value of the coupling inductance κ is is about 9.5NH, could be realized Kappa«L _A, the Kappa«L _B conditions. The value of the coupling inductance κ is, the inductance L _A of the _coil, so much smaller than the value of L _B, when a high-frequency f ₁ to the coil L _A, and when a high-frequency f ₂ in the coil L _B, the value of the high frequency current induced in the point of attachment of the coil L _a and the coil L _B is very small, even when taking the frequency f ₁ and f ₂ are close, less resonant of interfering with each other between the two coils The system could be realized.

  In the above example, the value of the inductance ratio between the inner coil and the outer coil is determined to be approximately 1: 2.5. However, the value of this ratio is approximately 1: 3 or 1: 4. There may be. Conversely, it is possible to obtain a resonance system with little interference even at about 1: 1 or 1: 2, but in that case, spurious components called ghosts may appear in each band, which is not preferable. .

Further, in the above example, by setting the diameter of the coil _{L A} and the coil _{L B} respectively 6.4mm and 10.5 mm, the coil _{L A} · coil _{L B} distance by a 2.05 mm, the degree of coupling Although the value of β was reduced to about 0.1, if the distance between the two coils was more than 2.05 mm, the sensitivity of the NMR apparatus was sacrificed by moving the outer coil away from the measurement sample. The value of the coupling degree β can be made smaller than about 0.1, and the crosstalk can be further reduced. This means that the degree of coupling β includes not only the inductive element but also the element of the coupling capacitance generated between the coils. That is, if the inter-coil distance is appropriately determined together with the inter-coil angle, the coil shape, etc., it means that the coupling degree β can be set to 0.1 or less.

FIG. 7 shows a circuit configuration including a separation circuit as an embodiment of the NMR probe for multiple resonance according to the present invention. From the input terminal A, a high frequency f ₃ (irradiation system) having a frequency corresponding to the resonance frequency of ¹ H nucleus or ¹⁹ F nucleus, and from the input terminal B, resonance of ¹⁵ N nucleus to ³¹ P nucleus. frequency f ₁ with a frequency corresponding to the frequency _(first observation system), is injected toward the coil L _a, respectively. Frequency f ₃ which is injected from the input terminal A is supplied to the coil L _A through a high-pass filter HPF, a coil L _A, element 2, tuning variable capacitor 4, matching variable capacitor 3, and the resonant frequency constituted by the element 1 It resonates the LC resonator f _3. The high frequency _{f 1,} which is injected from the input terminal B is supplied to the coil _{L A} through band reject filter BRF1, coil _{L A,} element 1, the desorption device ST1, tuning variable capacitor 2, matching variable capacitor 1, and Resonance is caused by the LC resonator having the resonance frequency f ₁ constituted by the element 2.

Further, from the input terminal C, a high frequency f ₂ (second observation system) having a frequency corresponding to the resonance frequency of ¹⁹⁹ Hg nucleus to ³¹ P nucleus, and from the input terminal D, resonance of ² D nucleus frequency f ₄ having a frequency (NMR lock frequency) corresponding to the frequency _(rock) is injected toward the coil L _B, respectively. Frequency _{f 2} which is injected from the input terminal C is supplied directly to the coil _{L B,} the coil _{L B,} the element 3, the desorption device ST2, tuning variable capacitor 6, matching variable capacitor 5, and the resonance frequency _{f 2} which is constituted by the element 4 Resonate with the LC resonator. The high frequency f ₄ which is injected from the input terminal D is supplied to the coil L _B through the band-pass filter BPF1, the coil L _B, the element 4, the tuning capacitor 8, is constituted by the matching capacitor 7, and the element 3 and it resonates the LC resonator of the resonance frequency _{f 4.}

In the example of FIG. 7, f ₂ is a high frequency having a frequency corresponding to the resonance frequency of ¹⁹⁹ Hg nucleus to ³¹ P nucleus, but this is a frequency corresponding to the resonance frequency of ¹⁵ N nucleus to ⁶ Li nucleus. It is good also as a high frequency with. In the example of FIG. 7, _{f 1} and _{f 3} in the inner coil _{L A,} has been assigned a _{f 2} and _{f 4} to the outer coil _{L B,} which, in accordance with the sensitivity and applications of measuring, combinations thereof It can also be changed to another combination.

In such a configuration, the high-pass filter HPF has an element having a characteristic that blocks transmission of a high frequency having a frequency lower than the resonance frequency of the ¹ H nucleus, and the band reject filter BRF1 has the element having such characteristics as to prevent the band of high frequency transmission is close to the resonant frequency of the ^{1 H} nucleus and also to a band-pass filter BPF1 transmits only the band of high frequency close to the resonance frequency of the ^{2 D} nuclear Each element has the same characteristics. Specific examples of these elements are collectively shown in FIG.

Further, one of the combinations of three types of elements as shown in FIG. 9A is selected and used for the detachable elements ST1 and ST2. For element 1, one selected from the combination of two types of reactance elements as shown in FIG. 9B was used. At this time, as the circuit operation of the element 1, the constants of the capacitor and the coil were determined so that the capacitive operation was performed for f _{1 and the} ground operation was performed for f ₃ . For element 2, one selected from the combination of two types of reactance elements as shown in FIG. 9C was used. At this time, as the circuit operation of the element 2, the constants of the capacitor and the coil were determined so that an appropriate impedance for f _{1 and} a high impedance or a helical resonator for f ₃ were obtained. For the element 3, a reactance element as shown in FIG. In this case, the circuit operation of the element 3, the high impedance to f _2, so that the ground work for f _4, to determine the constants of the capacitor and the coil. Further, as the element 4, a reactance element as shown in FIG. In this case, the circuit operation of the element 4, the ground work for f _2, to operate the capacitive for f _4, to determine the constants of the capacitor.

In the above-described example, the multi-resonance NMR probe has been described in which the high frequency capable of coexisting simultaneously is four frequencies, and two of them have a wide tuning range. It is not limited to the above example. For example, ¹ without performing decoupling of ^H nuclei used in measuring NMR, channels 3 NMR probe and for multiple resonance frequencies types not provided irradiation system frequency f _3, it runs the external locking, locking 3 frequency type multi-resonance NMR probe that is not provided with a system high-frequency f ₄ channel, or a 3 frequency type multi-resonance type that is used for measurement of a solid sample with a wide spectral line width and does not have a lock mechanism originally. Needless to say, an NMR probe for multi-resonance, such as an NMR probe, that has three high-frequency frequencies that can be simultaneously tuned and two of which have a wide tuning range, falls within the scope of the present invention.

In recent ^years, 99 ^Ru, 183 ^W, although ¹⁰³ NMR measurement of the organometallic compound and the like Rh are being actively made, the resonant frequencies of these nuclides are very low. These nuclides can be dealt with by increasing the number of turns of the coil and increasing the value of the inductance constituting the LC resonance circuit.

  As described above, according to the multi-resonance NMR probe of the present invention, since there are two channels capable of broadband tuning of about 1 to 3 octaves, one heteronuclear correlation across three nuclei and four nuclei can be obtained. It became possible to measure with this probe.

In addition, since the conditions for isolation between the two coils have been established, two very close nuclides (for example, ¹³ C and ²⁷ Al, ¹¹ B and ¹¹⁹ Sn, ⁷ Li, which have a resonance frequency difference of only a few percent). even for the like ^{31 P),} it made it possible to simultaneously irradiate a high frequency.

It is a figure which shows an example of the nuclide measured by NMR, and its resonant frequency. It is a figure which shows the conventional NMR probe for multiple resonance. It is a figure which shows one Example of the NMR probe for multiple resonances concerning this invention. It is a figure which shows one Example of the sample coil part of the NMR probe for multiple resonances concerning this invention. It is a figure which shows the relationship between direction of a sample coil, and isolation. It is a figure which shows the coupling inductance between sample coils. It is a figure which shows one Example of the circuit structure of the NMR probe for multiple resonances concerning this invention. It is a figure which shows one Example of the circuit element used for the NMR probe for multiple resonances concerning this invention. It is a figure which shows one Example of the circuit element used for the NMR probe for multiple resonances concerning this invention.

Explanation of symbols

1: matching variable capacitor, 2: tuning variable capacitor, 3: matching variable capacitor, 4: tuning variable capacitor, 5: matching variable capacitor, 6: tuning variable capacitor, 7: matching capacitor, 8: tuning capacitor, A: input terminal, B: input terminal, C: Input terminal, D: Input terminal, L _A : Sample coil (inner coil), L _B : Sample coil (outer coil), ST1: Desorption element, ST2: Desorption element, HPF: High-pass filter, BRF1: Band Reject filter, BPF1: Band pass filter

Claims (2)

In a multi-resonance NMR probe that irradiates a sample set in a static magnetic field with a plurality of high frequencies of different frequencies and detects a plurality of nuclear magnetic resonance signals emitted from the sample in response to the irradiation high frequency,
The NMR probe for multiple resonance includes two sample coils, and is set so that the high-frequency magnetic field axis generated in the first coil and the high-frequency magnetic field axis generated in the second coil are in different directions,
The first coil double-tunes a narrow band corresponding to the resonance frequency of ¹⁹ F nucleus or ¹ H nucleus and a broadband corresponding to the resonance frequency of ¹⁵ N nucleus to ³¹ P nucleus, and the second coil is ² D corresponding to the narrow band and ¹⁵ resonance frequency of N nuclei ~ ³¹ P nuclei corresponding to the resonant frequency of the wideband or ² D nucleus and corresponds to the resonant frequency of the narrowband and ¹⁹⁹ Hg nuclei ~ ³¹ P nuclei corresponding to the resonant frequency of the nuclei A multi-resonance NMR probe characterized by double-tuning a wide band. 2. The NMR probe for multiple resonance according to claim 1, wherein the first coil is an inner coil, and the second coil is an outer coil.

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