CN1696705A - High performance spectrmeter for liquid chromatography and magnetic resonance imaging - Google Patents
High performance spectrmeter for liquid chromatography and magnetic resonance imaging Download PDFInfo
- Publication number
- CN1696705A CN1696705A CN 200510026402 CN200510026402A CN1696705A CN 1696705 A CN1696705 A CN 1696705A CN 200510026402 CN200510026402 CN 200510026402 CN 200510026402 A CN200510026402 A CN 200510026402A CN 1696705 A CN1696705 A CN 1696705A
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- magnetic resonance
- magnet
- chromatographic column
- nuclear magnetic
- liquid chromatography
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- 238000004811 liquid chromatography Methods 0.000 title claims description 3
- 238000002595 magnetic resonance imaging Methods 0.000 title description 2
- 239000000523 sample Substances 0.000 claims abstract description 31
- 238000005481 NMR spectroscopy Methods 0.000 claims abstract description 29
- 238000001228 spectrum Methods 0.000 claims abstract description 9
- 238000004128 high performance liquid chromatography Methods 0.000 claims description 13
- 238000005259 measurement Methods 0.000 claims description 11
- 238000003384 imaging method Methods 0.000 claims 3
- 238000001511 high performance liquid chromatography nuclear magnetic resonance spectroscopy Methods 0.000 claims 2
- 238000012594 liquid chromatography nuclear magnetic resonance Methods 0.000 claims 1
- 230000005291 magnetic effect Effects 0.000 abstract description 9
- 239000007791 liquid phase Substances 0.000 abstract description 3
- 239000000126 substance Substances 0.000 description 23
- 239000007788 liquid Substances 0.000 description 8
- 238000004140 cleaning Methods 0.000 description 7
- 238000010586 diagram Methods 0.000 description 7
- 239000000463 material Substances 0.000 description 6
- 238000009434 installation Methods 0.000 description 5
- 238000013421 nuclear magnetic resonance imaging Methods 0.000 description 5
- 238000004587 chromatography analysis Methods 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 3
- 230000005284 excitation Effects 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 230000008878 coupling Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 230000003595 spectral effect Effects 0.000 description 2
- 239000004696 Poly ether ether ketone Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000013375 chromatographic separation Methods 0.000 description 1
- 239000010431 corundum Substances 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 238000007405 data analysis Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000003302 ferromagnetic material Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000005445 natural material Substances 0.000 description 1
- 229920002530 polyetherether ketone Polymers 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003325 tomography Methods 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
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- Investigating Or Analyzing Materials By The Use Of Magnetic Means (AREA)
Abstract
An image and spectrum analyzer is composed of high efficient liquid phase chromatograph system and nuclear magnetic resonance system. It is featured as setting chromatographic column in central hole of measuring probe placed between two gradient coils set between two cylindrical magnetic poles if normal magnet is applied or setting chromatographic column in central hole of measuring probe placed in gradient coil set in cylindrical superconductive magnet if superconductive magnet is applied.
Description
Technical Field
The invention belongs to the technical field of chemical analysis, and particularly relates to a high performance liquid chromatography nuclear magnetic resonance imaging spectrum analyzer.
Background
At present, a nuclear magnetic resonance chemical analysis instrument and a high performance liquid chromatography analysis instrument are separated and independent.
The nuclear magnetic resonance chemical analyzer comprises: bruker, Switzerland, Japan JEO, and Varian, USA.
The high performance liquid chromatography analyzer is abroad: aglient (Agilent), Waters, Inc., USA. Products of the companies are imported domestically.
The defects of the prior art are as follows: nuclear magnetic resonance and chromatography are difficult to combine. The reason is that in the prior art, the substances are separated and collected by using a chromatograph, and then the collected substances are respectively put into nuclear magnetic resonance for measurement. Such collection results in a substantial loss of material, especially in the case where nuclear magnetic resonance itself is a low sensitivity, low availability analytical instrument, and thus the amount of material chromatographically separated is essentially too small to be measured. This is why the combination of chromatography and nmr is difficult to achieve effectively.
Disclosure of Invention
The invention aims to provide a high performance liquid chromatography nuclear magnetic resonance imaging spectrum analyzer capable of combining liquid chromatography and nuclear magnetic resonance.
The invention provides a high performance liquid chromatography nuclear magnetic resonance imaging spectrum analyzer, which utilizes different mechanisms of diffusion speeds of different substances in a chromatographic column in high performance liquid chromatography to enable a mixed object to have a separation function in the chromatographic column, and simultaneously utilizes a nuclear magnetic resonance tomography technology and a high resolution spectrometer technology to measure nuclear magnetic resonance chemical shift spectrums and J-J coupling spectrums at different fault positions in the chromatographic column.
The instrument consists of two parts, namely a common high performance liquid chromatography system and a nuclear magnetic resonance system. Wherein, the chromatographic column of the liquid chromatographic system is arranged in the magnet and the measuring probe of the nuclear magnetic resonance system to replace the sample position in the nuclear magnetic resonance.
Advantages of the invention
1. The method integrates the chromatogram and the nuclear magnetic resonance completely, so that the material loss does not exist, the effective utilization rate of the nuclear magnetic resonance measurement is improved, and the measurement errors of a series of high performance liquid chromatograms such as dead space and the like are eliminated.
2. The basic mechanism of chromatography can be studied by nuclear magnetic resonance imaging.
3. And comparing a solid-phase spectral line and a liquid-phase spectral line generated by the interaction of the liquid to be detected and the chromatographic column filling powder to obtain more chemical substance information.
4. Real-time measurement and on-line measurement can be realized.
Drawings
Fig. 1 is a general block diagram of the instrument under a conventional magnet.
FIG. 2 is a view showing the installation relationship of a column of the apparatus under a conventional magnet (shown in cross-section).
Fig. 3 is a general block diagram of the instrument under a superconducting magnet.
Fig. 4 is a diagram (shown in cross-sectional view) showing the installation relationship of a column of the instrument under the superconducting magnet.
Fig. 5 is a time chemical shift diagram.
Fig. 6 is a spatial chemical shift diagram.
Reference numbers in the figures: 1 is a circuit control part of nuclear magnetic resonance, 2 is a magnet, 3 is a gradient coil, 4 is a measuring probe, 5 is a chromatographic column, 6 is a high-pressure pump, 7 is a one-way valve, 8 is a cleaning solution container, 9 is a valve, 10 is a sample injector, and 11 is a superconducting magnet.
Detailed Description
The liquid phase chromatographic system is formed by connecting a chromatographic column, a high-pressure pump, a valve and a sample injector cleaning solution container through a pipeline. Wherein,
1. a magnet: the main components of nuclear magnetic resonance are divided into conventional magnets and superconducting magnets. The conventional magnet is a magnet which utilizes common magnetic steel or current to form a loop through ferromagnetic materials to obtain a high magnetic field (< 2.3T). The superconducting magnet is a magnet which is a hollow superconducting coil, utilizes zero resistance of superconducting materials at low temperature, has the capacity of flowing super-strong current and generates a super-high magnetic field (5-20T). It can and with zero resistance form a closed highly stable current without power supply.
2. Gradient coil: the main components of magnetic resonance imaging. When current flows into the gradient coil, a gradient magnetic field is generated, and different spaces can be selectively excited by using the gradient magnetic field, so that the spatial position information of the measured substance is obtained.
3. A probe: important parts of nuclear magnetic resonance. For emitting radio waves (nuclear magnetic resonance term "radio frequency magnetic field"), exciting nuclear magnetic resonance energy, and measuring the radio waves of nuclear magnetic resonance radiation. The method has the function of detecting substances in a chromatographic column, and chemical shift and J-J coupling information of the substances can be obtained according to different radio frequencies emitted by chemical substances.
4. Computer and electronic control part: important parts of nuclear magnetic resonance. The gradient coil current, the radio wave excitation and measurement of the probe are controlled by a computer, and data analysis and processing are carried out through computer software.
5. A chromatographic column: is an important part of high performance liquid chromatography, is a pipeline made of quartz or polyetheretherketone and other non-conductive, non-magnetic and non-nuclear magnetic resonance signal materials, and is filled with corundum, silica gel and other fine powder with separation property. Its function is to cause different substances to have different flow velocities and thereby spatially separate the substances. The specific location of different substances in the column can be measured by the probe and gradient coils.
6. A high-pressure pump: an important component of high performance liquid chromatography, which provides the motive force for the flow of sample in a chromatography column.
7. A valve: components of high performance liquid chromatography. The device is used for switching samples and cleaning liquids.
8. One-way valve, sample injector: an auxiliary component of high performance liquid chromatography.
9. Cleaning liquid container: and storing the cleaning liquid.
The installation of the column has 2 different forms, according to the two different types of magnets, as follows:
1. installation of a column corresponding to a conventional magnet:
the conventional magnet consists of two flat cylindrical magnets, a certain gap is arranged between the two magnets, which is generally called magnetic gap, the gradient coil is two thin plates wound by common coils, the measuring probe is in a thin-wall cylindrical shape, and the chromatographic column is in a slender cylindrical shape. The "measurement probe" is located in two sheets of the "gradient coil" which is located in the gap between the two magnets. The "chromatographic column" has the smallest diameter and is mounted in a cylindrical "measuring probe".
2. Installation of a chromatographic column corresponding to a superconducting magnet:
the superconducting magnet is a cylinder which is made of superconducting wire coils and provided with a hole in the middle, the gradient coil is a thin-wall cylinder which is made of a common coil in a winding mode, the measuring probe is also a thin-wall cylinder, and the chromatographic column is an elongated cylinder.
The "measurement probe" is located within a "gradient coil" located in a central bore of a "superconducting magnet". The diameter of the chromatographic column is the smallest, and the chromatographic column is arranged in a thin-wall cylinder measuring probe. As shown in fig. 3 and 4.
Connection relation:
the gradient current output of the circuit control part is connected with the gradient coil, and the radio frequency detection system and the measuring probe of the circuit control part form a nuclear magnetic resonance system.
The cleaning liquid container is connected with the input port of the one-way valve, the output port of the one-way valve is connected with the input port of the high-pressure pump, the output port of the high-pressure pump is connected with the input port 1 of the valve, the sample injector is connected with the input port 2 of the valve, and the output port of the valve is connected with the input port of the chromatographic column to form a liquid chromatographic system.
The specific use method is as follows:
a sample consisting of a plurality of chemical substances (a substance after chemical reaction or a plurality of mixed natural substances) is injected into the bottom of the chromatographic column by a sample injector through an opened valve, the valve is closed, and a high-pressure pump is started to slowly inject a cleaning solution into the chromatographic column. The sample flows through the column under the urging of the wash solution. Different substances in the sample are gradually separated according to different flow rates in the chromatographic column. And performing scanning excitation layer by layer on different spatial positions in the chromatographic column by using the nuclear magnetic resonance gradient coil, observing radio waves emitted by nuclear magnetic resonance of different layers, and obtaining a chromatographic nuclear magnetic resonance two-dimensional spectrogram by computer spectrum analysis software.
The spectrum of the chromatographic nuclear magnetic resonance is divided into two working modes:
1. time-chemical shift diagram: excitation is repeated for only one layer to distinguish the chromatographic material information by time. As shown in fig. 5.
2. Space-chemical shift diagram: and scanning and exciting the multilayer space to directly obtain chromatographic separation information. As shown in fig. 6.
Claims (3)
1. The high performance liquid chromatography-nuclear magnetic resonance type imaging spectrum analyzer is characterized by comprising a high performance liquid chromatography system and a nuclear magnetic resonance system, wherein a chromatographic column of the liquid chromatography system is arranged in a magnet and a measuring probe of the nuclear magnetic resonance system.
2. The hplc nmr imaging spectrometer of claim 1, wherein the magnet is a conventional magnet, the magnet comprises two flat cylindrical magnets, the gradient coil is wound as two thin plates, the measurement probe is a thin-walled cylindrical shape, the chromatographic column is an elongated cylindrical shape, the measurement probe is positioned between the two thin plates of the gradient coil, the gradient coil is positioned in the gap between the two magnets, and the chromatographic column is mounted in the measurement probe.
3. The hplc nmr imaging spectrometer of claim 1, wherein when the magnet is a superconducting magnet, the magnet is a cylinder with a hole in the middle and made of a superconducting coil, the gradient coil is made into a thin-walled cylinder, the measuring probe is a thin-walled cylinder, and the chromatographic column is an elongated cylinder; the measuring probe is positioned in a middle hole of the gradient coil, the gradient coil is positioned in a middle hole of the cylindrical superconducting magnet, and the chromatographic column is arranged in the middle hole of the measuring probe.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB200510026402XA CN100504396C (en) | 2005-06-02 | 2005-06-02 | High performance liquid chromatography and magnetic resonance imaging analyzer |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB200510026402XA CN100504396C (en) | 2005-06-02 | 2005-06-02 | High performance liquid chromatography and magnetic resonance imaging analyzer |
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| Publication Number | Publication Date |
|---|---|
| CN1696705A true CN1696705A (en) | 2005-11-16 |
| CN100504396C CN100504396C (en) | 2009-06-24 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB200510026402XA Expired - Fee Related CN100504396C (en) | 2005-06-02 | 2005-06-02 | High performance liquid chromatography and magnetic resonance imaging analyzer |
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| CN (1) | CN100504396C (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105004832A (en) * | 2015-08-11 | 2015-10-28 | 苏州优谱德精密仪器科技有限公司 | Four-spectrometer combined analytical instrument suitable for complex chemical samples |
| CN106525890A (en) * | 2016-11-29 | 2017-03-22 | 中国地质调查局油气资源调查中心 | Experimental facility for synthesis and dissociation of gas mixture hydrate |
| CN107607894A (en) * | 2017-11-06 | 2018-01-19 | 厦门大学 | It is applicable miniature malcoils and its preparation associated with HPLC NMR |
| CN108896946A (en) * | 2018-07-04 | 2018-11-27 | 中国原子能科学研究院 | Device and scaling method for the calibration of induction coil probe area |
| CN117130297A (en) * | 2023-10-25 | 2023-11-28 | 北京豪思生物科技股份有限公司 | Upper computer control method, device and equipment of liquid chromatograph |
| CN117783017A (en) * | 2024-02-26 | 2024-03-29 | 中国科学院武汉岩土力学研究所 | Rock and soil detection device and method combining nuclear magnetic resonance and hyperspectral imaging |
-
2005
- 2005-06-02 CN CNB200510026402XA patent/CN100504396C/en not_active Expired - Fee Related
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105004832A (en) * | 2015-08-11 | 2015-10-28 | 苏州优谱德精密仪器科技有限公司 | Four-spectrometer combined analytical instrument suitable for complex chemical samples |
| CN106525890A (en) * | 2016-11-29 | 2017-03-22 | 中国地质调查局油气资源调查中心 | Experimental facility for synthesis and dissociation of gas mixture hydrate |
| CN107607894A (en) * | 2017-11-06 | 2018-01-19 | 厦门大学 | It is applicable miniature malcoils and its preparation associated with HPLC NMR |
| CN107607894B (en) * | 2017-11-06 | 2019-06-04 | 厦门大学 | It is applicable in miniature malcoils and its preparation associated with HPLC-NMR |
| CN108896946A (en) * | 2018-07-04 | 2018-11-27 | 中国原子能科学研究院 | Device and scaling method for the calibration of induction coil probe area |
| CN117130297A (en) * | 2023-10-25 | 2023-11-28 | 北京豪思生物科技股份有限公司 | Upper computer control method, device and equipment of liquid chromatograph |
| CN117130297B (en) * | 2023-10-25 | 2023-12-29 | 北京豪思生物科技股份有限公司 | Upper computer control method, device and equipment of liquid chromatograph |
| CN117783017A (en) * | 2024-02-26 | 2024-03-29 | 中国科学院武汉岩土力学研究所 | Rock and soil detection device and method combining nuclear magnetic resonance and hyperspectral imaging |
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| Publication number | Publication date |
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| CN100504396C (en) | 2009-06-24 |
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Granted publication date: 20090624 Termination date: 20200602 |