JPH034114B2 - - Google Patents
Info
- Publication number
- JPH034114B2 JPH034114B2 JP2672385A JP2672385A JPH034114B2 JP H034114 B2 JPH034114 B2 JP H034114B2 JP 2672385 A JP2672385 A JP 2672385A JP 2672385 A JP2672385 A JP 2672385A JP H034114 B2 JPH034114 B2 JP H034114B2
- Authority
- JP
- Japan
- Prior art keywords
- pulse
- microwave
- sample
- resonance
- microwaves
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- 238000005481 NMR spectroscopy Methods 0.000 claims description 23
- 238000004435 EPR spectroscopy Methods 0.000 claims description 17
- 238000005259 measurement Methods 0.000 claims description 15
- 238000001514 detection method Methods 0.000 claims description 10
- 230000003068 static effect Effects 0.000 claims description 7
- 230000006698 induction Effects 0.000 claims description 4
- 230000001131 transforming effect Effects 0.000 claims description 3
- 230000005284 excitation Effects 0.000 claims 1
- 230000001678 irradiating effect Effects 0.000 claims 1
- 230000005311 nuclear magnetism Effects 0.000 claims 1
- 239000000523 sample Substances 0.000 description 18
- 238000010586 diagram Methods 0.000 description 3
- 238000005070 sampling Methods 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 230000010355 oscillation Effects 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001362 electron spin resonance spectrum Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01R—MEASURING ELECTRIC VARIABLES; MEASURING MAGNETIC VARIABLES
- G01R33/00—Arrangements or instruments for measuring magnetic variables
- G01R33/20—Arrangements or instruments for measuring magnetic variables involving magnetic resonance
- G01R33/62—Arrangements or instruments for measuring magnetic variables involving magnetic resonance using double resonance
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01R—MEASURING ELECTRIC VARIABLES; MEASURING MAGNETIC VARIABLES
- G01R33/00—Arrangements or instruments for measuring magnetic variables
- G01R33/20—Arrangements or instruments for measuring magnetic variables involving magnetic resonance
- G01R33/60—Arrangements or instruments for measuring magnetic variables involving magnetic resonance using electron paramagnetic resonance
Landscapes
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Magnetic Resonance Imaging Apparatus (AREA)
Description
【発明の詳細な説明】
［産業上の利用分野］
本発明は、１つの試料について核磁気共鳴
（NMR）測定と電子スピン共鳴（ESR）測定を
同時に行うことのできるNMR−ESR同時測定装
置に関する。[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to an NMR-ESR simultaneous measurement device that can simultaneously perform nuclear magnetic resonance (NMR) measurement and electron spin resonance (ESR) measurement on one sample. .
［従来技術］
同一試料についてNMR測定とESR測定を行う
必要がある場合、従来は一方の測定を終えてから
他方の測定を行わねばならなかつた。[Prior Art] When it is necessary to perform NMR measurement and ESR measurement on the same sample, conventionally, one measurement had to be completed before the other measurement was performed.
［発明が解決しようとする問題点］
従つて変質の速い試料では２つの測定の間に試
料が変化してしまうし、試料の温度が変わるおそ
れもあり、厳密に同一試料について同一環境条件
での測定結果でなくなつてしまうという問題があ
つた。[Problems to be solved by the invention] Therefore, in the case of a sample that undergoes rapid deterioration, the sample may change between two measurements, and the temperature of the sample may also change, making it difficult to precisely measure the same sample under the same environmental conditions. There was a problem that the measurement results were lost.
本発明はこの点に鑑みてなされたものであり、
同一試料についてNMR測定とESR測定を同時に
同一条件で行うことのできる装置を提供すること
を目的としている。 The present invention has been made in view of this point,
The objective is to provide an apparatus that can perform NMR measurements and ESR measurements on the same sample at the same time under the same conditions.
［問題点を解決するための手段］
この目的を解決するため、本発明にかかる
NMR−ESR同時測定装置は、静磁場を発生する
手段と、マイクロ波を発生するための手段と、該
マイクロ波をパルス変調するための手段と、前記
静磁場中に配置される試料に該変調手段によつて
パルス変調されたマイクロ波を照射するための手
段と、該マイクロ波照射後試料から発生する電子
スピン共鳴に基づく自由誘導減衰信号（FID信
号）を検出する第１の検出手段と、該マイクロ波
照射後試料から発生する核磁気共鳴に基づくFID
信号を検出する第２の検出手段と、該第１及び第
２の検出手段から得られるFID信号を夫々記憶し
フーリエ変換する手段とを備え、前記パルス変調
手段は前記マイクロ波をESR観測用励起パルス
としてのパルス幅を有し且つNMR測定用共鳴周
波数に相当する繰返し周波数を持つマイクロ波パ
ルス列として取出すと共に、該パルス列の長さを
NMR測定における観測パルスのパルス幅に設定
するようにしたことを特徴としている。[Means for solving the problem] In order to solve this object, the present invention
The NMR-ESR simultaneous measurement device includes a means for generating a static magnetic field, a means for generating microwaves, a means for pulse-modulating the microwaves, and a means for pulse-modulating the microwaves, and applying the modulation to a sample placed in the static magnetic field. a first detection means for detecting a free induction decay signal (FID signal) based on electron spin resonance generated from the sample after the microwave irradiation; FID based on nuclear magnetic resonance generated from the sample after microwave irradiation
It includes a second detection means for detecting a signal, and means for storing and Fourier transforming the FID signals obtained from the first and second detection means, and the pulse modulation means excites the microwave for ESR observation. It is extracted as a microwave pulse train with a pulse width and a repetition frequency corresponding to the resonance frequency for NMR measurement, and the length of the pulse train is
The feature is that it is set to the pulse width of the observation pulse in NMR measurement.
［作用］
前記パルス列に含まれる各マイクロ波パルスの
間の期間に第１の検出手段から電子スピン共鳴に
基づくFID信号が繰返し得られると共に、このマ
イクロ波パルス繰返し周波数がNMR測定用共鳴
周波数に設定され且つそのパルス列の長さが
NMR測定における観測パルス（90゜パルス）のパ
ルス幅に設定されているため、パルス列の照射後
の期間に核磁気共鳴に基づくFID信号が第２の検
出手段から得られ、夫々のFID信号は記憶され、
フーリエ変換される。[Operation] FID signals based on electron spin resonance are repeatedly obtained from the first detection means during the period between each microwave pulse included in the pulse train, and this microwave pulse repetition frequency is set as the resonance frequency for NMR measurement. and the length of the pulse train is
Since the pulse width is set to the observation pulse (90° pulse) in NMR measurement, FID signals based on nuclear magnetic resonance are obtained from the second detection means during the period after irradiation with the pulse train, and each FID signal is stored in memory. is,
Fourier transformed.
［実施例］
以下、図面に基づき本発明の一実施例を詳説す
る。[Example] Hereinafter, an example of the present invention will be described in detail based on the drawings.
第１図は本発明の一実施例を示すブロツク図で
ある。図において１は静磁場を発生するための磁
石で、この静磁場内にはESR−NMR同時測定用
プローブ２が配置されている。このプローブ２に
はESR用マイクロ波照射コイル３及びNMR用鞍
型検出コイル４が備えられており、コイル３は試
料管５の内部に挿入され、コイル４は試料管５の
周囲に配置される。 FIG. 1 is a block diagram showing one embodiment of the present invention. In the figure, 1 is a magnet for generating a static magnetic field, and a probe 2 for simultaneous ESR-NMR measurement is placed within this static magnetic field. This probe 2 is equipped with a microwave irradiation coil 3 for ESR and a saddle-shaped detection coil 4 for NMR. The coil 3 is inserted into the sample tube 5, and the coil 4 is arranged around the sample tube 5. .
６はESR用マイクロ波を発生するマイクロ波
発振器であり、該発振器６から発生したマイクロ
波は、NMR用パルス発振器７から発生した高周
波が供給される変調器８においてパルス変調を受
け、更にパルスプログラマ９によつて所定期間開
かれるゲート１０を介してマイクロ波パルス列と
して取出され、増幅器１１及びサーキユレータ１
２を介して前記コイル３へ供給される。 6 is a microwave oscillator that generates microwaves for ESR, and the microwaves generated from the oscillator 6 undergo pulse modulation in a modulator 8 to which the high frequency generated from the pulse oscillator 7 for NMR is supplied, and is further passed through a pulse programmer. 9 is opened for a predetermined period of time as a microwave pulse train, and the amplifier 11 and circulator 1
2 to the coil 3.
１３はマイクロ波パルス列中のパルとパルスの
間の期間にコイル３から反射されて来るマイクロ
波を検出するためのマイクロ波検出器であり、こ
の検出器１３から得られた電子スピン共鳴に基づ
くFID信号は増幅器１４及び高速サンプリング回
路１５を介してコンピユータ１６へ送られ、付属
するメモリ１７Ｅへ格納される。 13 is a microwave detector for detecting the microwave reflected from the coil 3 during the period between pulses in the microwave pulse train, and the FID based on electron spin resonance obtained from this detector 13 The signal is sent via amplifier 14 and high speed sampling circuit 15 to computer 16 and stored in attached memory 17E.
一方、マイクロ波パルス列照射後前記コイル４
に誘起される核磁気共鳴に基づく共鳴信号は、増
幅器１８を介して復調回路１９へ送られる。復調
によつて得られた核磁気共鳴に基づくFID信号は
Ａ−Ｄ変換器２０を介してコンピユータ１６へ送
られ、付属するメモリ１７Ｍへ格納される。 On the other hand, after the microwave pulse train irradiation, the coil 4
A resonance signal based on nuclear magnetic resonance induced by the oscilloscope is sent to a demodulation circuit 19 via an amplifier 18. The FID signal based on nuclear magnetic resonance obtained by demodulation is sent to the computer 16 via the AD converter 20 and stored in the attached memory 17M.
上述の如き構成において、静磁場の強度が例え
ば0.33T（テスラ）の場合、電子スピン共鳴の共
鳴周波数は9.4GHz、水素核の核磁気共鳴周波数
は約13MHzとなるため、発振器６の発振周波数は
9.4GHzに、発振器７の発振周波数は13MHzに
夫々設定される。 In the above configuration, when the strength of the static magnetic field is, for example, 0.33T (Tesla), the resonance frequency of electron spin resonance is 9.4GHz, and the nuclear magnetic resonance frequency of hydrogen nuclei is approximately 13MHz, so the oscillation frequency of oscillator 6 is
The oscillation frequency of the oscillator 7 is set to 9.4GHz and 13MHz, respectively.
第２図ａは上記発振器７の出力信号を示し、周
波数は上述の通り13MHz（周期約77ナノ秒）であ
る。第２図ｂは変調器８の出力信号を示し、発振
器６から発生した9.4GHzのマイクロ波が発振器
７の出力信号によつてパルス変調されている。 FIG. 2a shows the output signal of the oscillator 7, and the frequency is 13 MHz (period: about 77 nanoseconds) as described above. FIG. 2b shows the output signal of the modulator 8, in which the 9.4 GHz microwave generated from the oscillator 6 is pulse-modulated by the output signal of the oscillator 7.
この第２図ｂで示されるパルス変調されたマイ
クロ波はゲート１０へ送られるが、ゲート１０は
パルスプログラマ９から送られる第２図ｃに示す
ゲート信号によつてON−OFFされるため、第２
図ｄに示すように所定の時間幅ｔを有するマイク
ロ波パルス列が該ゲートから取出され、サーキユ
レータ１２及びコイル３を介して試料に照射され
る。この時間幅ｔのパルス列Ａが、NMR測定用
観測パルス（90゜パルス）である。この時間幅ｔ
は試料に照射されるパルス電力（エネルギー）に
よつて決定される。 The pulse-modulated microwave shown in FIG. 2b is sent to the gate 10, but since the gate 10 is turned on and off by the gate signal shown in FIG. 2
As shown in FIG. d, a microwave pulse train having a predetermined time width t is taken out from the gate and irradiated onto the sample via the circulator 12 and the coil 3. This pulse train A with a time width t is an observation pulse (90° pulse) for NMR measurement. This time width t
is determined by the pulse power (energy) applied to the sample.
前記マイクロ波パルス列Ａに含まれるマイクロ
波パルスａ１〜anのパルス幅は電子スピン共鳴
を励起するのに適した値に設定されており、従つ
て第２図ｅに示すように、各マイクロ波パルス照
射後次のマイクロ波パルスが照射されるまでの期
間に電子スピン共鳴に基づくFID信号が検出器１
３から繰返し得られ、得られたFID信号は高速サ
ンプリング回路１５を介してコンピユータ１６へ
送られ、メモリ１７Ｅへ積算される。 The pulse width of the microwave pulses a1 to an included in the microwave pulse train A is set to a value suitable for exciting electron spin resonance, and therefore, as shown in FIG. 2e, each microwave pulse After irradiation, until the next microwave pulse is irradiated, an FID signal based on electron spin resonance is detected on detector 1.
3, and the obtained FID signal is sent to the computer 16 via the high-speed sampling circuit 15 and integrated into the memory 17E.
一方、上記パルス列Ａに含まれるマイクロ波パ
ルスの繰返し周波数が水素核の共鳴周波数の13M
Hzであるため、この周波数成分の高周波磁界照射
を受けた水素核の共鳴子は、パルス列Ａの時間幅
ｔに対応する角度即ち90゜倒される。倒された共
鳴子はパルス列Ａ照射後の期間Ｔに回復し、その
回復過程を示すFID信号がコイル４に誘起され、
復調回路１９において第２図ｆに示すように取出
される。取出されたFID信号はＡ−Ｄ変換器２０
を介してコンピユータ１６へ送られ、メモリ１７
Ｎに格納される。 On the other hand, the repetition frequency of the microwave pulse included in the pulse train A is 13M, which is the resonance frequency of hydrogen nuclei.
Hz, the resonator of the hydrogen nucleus that is irradiated with the high-frequency magnetic field of this frequency component is tilted at an angle corresponding to the time width t of the pulse train A, that is, 90 degrees. The collapsed resonator recovers during the period T after irradiation with the pulse train A, and an FID signal indicating the recovery process is induced in the coil 4.
The signal is extracted in the demodulation circuit 19 as shown in FIG. 2f. The extracted FID signal is sent to the A-D converter 20
is sent to the computer 16 via the memory 17
Stored in N.
測定後、メモリ１７Ｅに格納されている電子ス
ピン共鳴に基づくFID信号をフーリエ変換すれば
ESRスペクトルが得られ、メモリ１７Ｎに格納
されている核磁気共鳴に基づくFID信号をフーリ
エ変換すればNMRスペクトルが得られる。この
２つのスペクトルは実質的に同時刻に行われた測
定によつて得られており、温度等の測定環境も全
く同一の状態で得られていることは言うまでもな
い。 After measurement, if the FID signal based on electron spin resonance stored in the memory 17E is Fourier transformed,
An ESR spectrum is obtained, and an NMR spectrum is obtained by Fourier transforming the FID signal based on nuclear magnetic resonance stored in the memory 17N. It goes without saying that these two spectra were obtained by measurements performed at substantially the same time, and were obtained under exactly the same measurement environment such as temperature.
［発明の効果］
以上詳述した如く、本発明によれば同一試料に
ついてNMR測定とESR測定を同時に同一環境で
行うことのできる装置が実現される。[Effects of the Invention] As described in detail above, according to the present invention, an apparatus capable of performing NMR measurement and ESR measurement on the same sample at the same time in the same environment is realized.
第１図は本発明の一実施例の構成を示すブロツ
ク図であり、第２図はその動作を説明するための
波形図である。
１：磁石、３：ESR用マイクロ波照射コイル、
４：NMR用鞍型検出コイル、５：試料管、６：
マイクロ波発振器、７：NMR用パルス発振器、
８：変調器、９：パルスプログラマ、１０：ゲー
ト、１２：サーキユレータ、１３：マイクロ波検
出器、１５：高速サンプリング回路、１６：コン
ピユータ、１７：メモリ、１９：復調回路、２
０：Ａ−Ｄ変換器。
FIG. 1 is a block diagram showing the configuration of an embodiment of the present invention, and FIG. 2 is a waveform diagram for explaining its operation. 1: Magnet, 3: Microwave irradiation coil for ESR,
4: Saddle type detection coil for NMR, 5: Sample tube, 6:
Microwave oscillator, 7: NMR pulse oscillator,
8: Modulator, 9: Pulse programmer, 10: Gate, 12: Circulator, 13: Microwave detector, 15: High speed sampling circuit, 16: Computer, 17: Memory, 19: Demodulation circuit, 2
0: A-D converter.
Claims (1)
するための手段と、該マイクロ波をパルス変調す
るための手段と、前記静磁場中に配置される試料
に該変調手段によつてパルス変調されたマイクロ
波を照射するための手段と、該マイクロ波照射後
試料から発生する電子スピン共鳴に基づく自由誘
導減衰信号を検出する第１の検出手段と、該マイ
クロ波照射後試料から発生する核磁気共鳴に基づ
く自由誘導減衰信号を検出する第２の検出手段
と、該第１及び第２の検出手段から得られる自由
誘導減衰信号を夫々記憶しフーリエ変換する手段
とを備え、前記パルス変調手段は前記マイクロ波
を電子スピン共鳴観測用励起パルスとしてのパル
ス幅を有し且つ核磁気共鳴観測用共鳴周波数に相
当する繰返し周波数を持つマイクロ波パルス列と
して取出すと共に、該パルス列の長さを核磁気共
鳴観測における観測パルスのパルス幅に設定する
ようにしたことを特徴とするNMR−ESR同時測
定装置。1 means for generating a static magnetic field, means for generating microwaves, means for pulse modulating the microwaves, and a means for generating pulse modulation of the microwaves by the modulating means on a sample placed in the static magnetic field. means for irradiating the sample with microwaves, first detection means for detecting a free induction decay signal based on electron spin resonance generated from the sample after the microwave irradiation, and nuclear magnetism generated from the sample after the microwave irradiation. The pulse modulation means comprises a second detection means for detecting a free induction decay signal based on resonance, and a means for storing and Fourier transforming the free induction decay signals obtained from the first and second detection means, respectively. The microwave is extracted as a microwave pulse train having a pulse width as an excitation pulse for electron spin resonance observation and a repetition frequency corresponding to the resonance frequency for nuclear magnetic resonance observation, and the length of the pulse train is measured for nuclear magnetic resonance observation. A simultaneous NMR-ESR measurement device characterized in that the pulse width is set to the pulse width of an observation pulse in .
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2672385A JPS61186843A (en) | 1985-02-14 | 1985-02-14 | Nmr-esr simultaneous measuring instrument |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2672385A JPS61186843A (en) | 1985-02-14 | 1985-02-14 | Nmr-esr simultaneous measuring instrument |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS61186843A JPS61186843A (en) | 1986-08-20 |
| JPH034114B2 true JPH034114B2 (en) | 1991-01-22 |
Family
ID=12201247
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2672385A Granted JPS61186843A (en) | 1985-02-14 | 1985-02-14 | Nmr-esr simultaneous measuring instrument |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS61186843A (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| ES2058714T3 (en) * | 1987-06-23 | 1994-11-01 | Nycomed Innovation Ab | IMPROVEMENTS INTRODUCED IN IMAGE FORMATION BY MAGNETIC RESONANCE. |
| JP5665914B2 (en) * | 2013-05-13 | 2015-02-04 | 株式会社東芝 | Magnetic resonance measuring device |
-
1985
- 1985-02-14 JP JP2672385A patent/JPS61186843A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS61186843A (en) | 1986-08-20 |
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