CN110887891A - Micro-extraction-nano-liter electrospray ion source system in capillary and application - Google Patents
Micro-extraction-nano-liter electrospray ion source system in capillary and application Download PDFInfo
- Publication number
- CN110887891A CN110887891A CN201911082613.3A CN201911082613A CN110887891A CN 110887891 A CN110887891 A CN 110887891A CN 201911082613 A CN201911082613 A CN 201911082613A CN 110887891 A CN110887891 A CN 110887891A
- Authority
- CN
- China
- Prior art keywords
- nano
- micro
- needle
- electrospray
- liter
- 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.)
- Pending
Links
Images
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/62—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating the ionisation of gases, e.g. aerosols; by investigating electric discharges, e.g. emission of cathode
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N1/00—Sampling; Preparing specimens for investigation
- G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
- G01N1/34—Purifying; Cleaning
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N1/00—Sampling; Preparing specimens for investigation
- G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
- G01N1/40—Concentrating samples
- G01N1/4055—Concentrating samples by solubility techniques
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
- H01J49/00—Particle spectrometers or separator tubes
- H01J49/02—Details
- H01J49/10—Ion sources; Ion guns
- H01J49/16—Ion sources; Ion guns using surface ionisation, e.g. field-, thermionic- or photo-emission
- H01J49/165—Electrospray ionisation
- H01J49/167—Capillaries and nozzles specially adapted therefor
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N1/00—Sampling; Preparing specimens for investigation
- G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
- G01N1/40—Concentrating samples
- G01N1/4055—Concentrating samples by solubility techniques
- G01N2001/4061—Solvent extraction
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Analytical Chemistry (AREA)
- Physics & Mathematics (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Biochemistry (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Engineering & Computer Science (AREA)
- Electrochemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Biomedical Technology (AREA)
- Molecular Biology (AREA)
- Plasma & Fusion (AREA)
- Other Investigation Or Analysis Of Materials By Electrical Means (AREA)
Abstract
The invention discloses a micro-extraction-nano-liter electrospray ion source system in a capillary and application thereof, wherein the system comprises a micro-scale sampling probe, a nano-liter electrospray needle and a high-voltage power supply, realizes the online combination of three technologies of solid-liquid micro-extraction, Patern oa-B ü chi online photochemical reaction and normal-pressure open field nano-liter electrospray mass spectrometry, can be used as a novel nano-liter electrospray ion source for mass spectrometry, has extremely high sensitivity, and can be used for in-situ, direct, micro-scale lipid analysis and omics research of complex biological samples.
Description
The technical field is as follows:
the invention relates to the field of chemistry, in particular to a micro-extraction-nano-liter electrospray ion source system in a capillary and application thereof.
Background art:
lipids are important active substances of organisms, not only main constituent substances of cell membranes, but also mediator molecules for cell energy storage and signal transmission. The generation and development of various diseases such as Alzheimer disease, atherosclerosis, diabetes and the like are closely related to abnormal lipid metabolism. The lipid components of organisms are complex and diverse, consisting of thousands of molecules with different chemical structures, different physicochemical properties, and different substance concentrations. Lipidomics are an important method for studying the structure, composition and function of lipids in organisms, and also an important field of analytical chemistry and biological research in recent years. Various analysis technologies such as chromatography, electrophoresis, nuclear magnetic resonance spectrum, mass spectrometry and the like are widely applied to lipidomics research, wherein the mass spectrometry is becoming one of the strongest powerful tools for lipidomics research due to the advantages of high sensitivity, good resolution, ideal selectivity, excellent specificity, rich information and the like. A series of information such as the type of lipid, the composition of fatty acid chains, the degree of unsaturation, the position of the C ═ C double bond, and isomers can be obtained by mass spectrometry. Electrospray and matrix-assisted laser desorption/ionization are two common ionization techniques for lipid analysis and omics research by mass spectrometry, and a direct electrospray mass spectrometry shotgun method, a liquid chromatography-mass spectrometry combined method and a matrix-assisted laser desorption/ionization mass spectrometry rule are three common methods for lipid omics research by mass spectrometry. However, both the direct electrospray shotgun method and the liquid chromatography-mass spectrometry combined method can only analyze the extract of a biological sample, and require a large amount of biological sample to be consumed, and are difficult to perform in-vivo and in-situ lipidomics research. Matrix-assisted laser desorption/ionization mass spectrometry requires analysis under vacuum conditions, which limits its analysis of living organisms and cells.
Atmospheric open mass spectrometry (AMS) is a new mass spectrometry technology developed in the beginning of the 21 st century that can directly analyze samples under atmospheric and open conditions without or with little sample pretreatment and without chromatographic separation, and it has brought new opportunities for in-situ, in-vivo, microscale lipid analysis and omics research. The Cooks group reports the application of desorption electrospray ionization mass spectrometry (DESI-MS) technology in identifying human brain astrocytoma subtypes, and the Hiraoka group reports the application of probe electrospray ionization mass spectrometry (PESI-MS) technology in renal cancer lipid analysis. In addition, the studies of various atmospheric open mass spectrometry techniques such as EASI-MS, LAESI-MS, LDIDD-MS and the like in lipid analysis have been reported successively.
Although the atmospheric open mass spectrometry provides a new technical means for rapidly and directly characterizing the biological lipid, the establishment of a systematic and complete lipidomics method by the atmospheric open mass spectrometry is still a difficult task. DESI-MS, EASI-MS, LAESI-MS and LDIDD-MS are all surface analysis methods, which are not favorable for deep layer analysis of biological samples. PESI-MS, which utilizes a non-adsorbent probe for sample extraction and analysis, generally has limited sensitivity, selectivity, and the types of lipids that can be detected. Therefore, it would be of great importance to develop a highly sensitive, in situ, microscale lipid analysis and omics research method that can be used for the direct analysis of complex biological samples.
The invention content is as follows:
the invention aims to provide a micro-extraction-nano-liter electrospray ion source system in a capillary and application thereof, the system realizes the online combination of three technologies of solid-liquid micro-extraction, Patern oa-B ü chi (PB for short) online photochemical reaction and normal-pressure open field nano-liter electrospray mass spectrometry, can be used as a novel nano-liter electrospray ion source for mass spectrometry, has extremely high sensitivity, and can be used for in-situ, direct and micro-scale lipid analysis and omics research of complex biological samples.
The invention is realized by the following technical scheme:
a micro-extraction-nanoliter electrospray ion source system in a capillary comprises a micro-scale sampling probe, a nanoliter electrospray ion source and a high-voltage power supply, wherein the micro-scale sampling probe directly performs micro-scale sampling on a biological tissue sample, directly brings the collected micro-scale sample into a nanoliter electrospray ion needle to which an extraction/spray solvent and/or a Patern OA-B ü chi (PB) photochemical reaction reagent are/is added, performs solid-liquid microextraction in the capillary of the nanoliter electrospray ion needle, and then directly performs field nanoliter electrospray mass spectrometry under the normal-pressure open condition.
In particular, the system for the microextraction-nanoliter electrospray ion source in a capillary also comprises an ultraviolet lamp for the photochemical reaction Patern oa-B ü chi.
The ultraviolet lamp is an ultraviolet lamp with the wavelength of 254 nm.
The micro-scale sampling probe is a metal needle with the tip diameter ranging from 1 to 10 mu m, and is preferably a tungsten needle subjected to surface treatment; the nano-liter electric spraying needle is a metal-coated glass nano-liter electric spraying needle or a quartz nano-liter electric spraying needle; the inner diameter of a capillary tube of the nano-liter spray needle is within the range of 1-2 mm, and the inner diameter of the tip of the nano-liter spray needle is within the range of 1-10 mu m; the high-voltage power supply is a field-induced high-voltage power supply, a high-voltage electric field is applied to a mass spectrum inlet and can be adjusted within 0-5 kV, the microscale sampling probe is grounded, a high-voltage electric field is formed between the nanoliter electrospray needle and the mass spectrum inlet, and the solvent containing a target compound in the nanoliter electrospray needle is induced to generate electrospray ionization so as to perform mass spectrum analysis; and the high-voltage electric field is not contacted with the sample, and the fast positive and negative switching can be directly carried out under the condition of normal pressure opening.
A mass spectrum analysis device comprises the capillary internal micro-extraction-nano-liter electric spray ion source system and a bracket which is used for fixing the nano-liter electric spray needle tip of the capillary internal micro-extraction-nano-liter electric spray ion source system to be aligned with a mass spectrum inlet and is 5-15mm away from the mass spectrum inlet, wherein a micro-scale sampling probe of the capillary internal micro-extraction-nano-liter electric spray ion source system directly carries out micro-scale sampling on a biological tissue sample, directly brings the collected micro-biological sample into a nano-liter electric spray needle, carries out solid-liquid micro-extraction in the capillary of the nano-liter electric spray needle, can simultaneously carry out Patern I-B ü chi on-line electro-photochemical reaction, then directly carries out nano-liter electric spray mass spectrum analysis under the normal pressure open condition, and simultaneously records a positive ion mass spectrum and a negative ion mass spectrum.
The invention also protects the application of the mass spectrometric analysis device for direct analysis of biological samples and omics studies, preferably for lipid analysis and lipidomics studies.
The lipid comprises more than one of fatty acyl, glyceride, glycerophospholipid, sphingolipid, sterol lipid, pregnenolone lipid, glycolipid, and polyketide.
A method for the direct analysis of biological samples by means of the mass spectrometer comprises the steps of sampling by means of a microscale sampling probe, carrying out solid-liquid microextraction in a capillary of a nanoliter electrospray needle, and carrying out electrospray ionization and mass spectrometry directly by the nanoliter electrospray needle after an online photochemical reaction.
The method specifically comprises the following steps that a microscale sampling probe directly performs microscale sampling on a biological tissue sample, the collected microscale biological sample is directly inserted into a nanoliter electrospray needle which is added with an extraction/spray solvent or/and a Patern oa-B ü chi (PB) photochemical reaction reagent, solid-liquid microextraction is performed in a capillary tube of the nanoliter electrospray needle, a target compound in the biological sample is desorbed, extracted and enriched, the solvent which is enriched in the nanoliter electrospray needle and is enriched in the target compound can be simultaneously irradiated by an ultraviolet lamp to perform a Patern oa-B ü chi online photochemical reaction, then the nanoliter electrospray needle containing the microscale sampling probe is placed on a bracket for fixation, the tip of the nanoliter electrospray needle is aligned to a mass spectrum inlet and is 5-15mm away from the mass spectrum inlet, the microscale electrospray needle is grounded, a high-voltage electric field which can quickly perform polarity conversion is applied to the mass spectrum inlet, and positive and negative ion mass spectra are recorded simultaneously.
The extraction/spray solvent is typically 0.5-5 μ L, preferably 5 μ L, of methanol spray solvent, which desorbs the enriched components, moves towards the tip under the action of a high voltage electric field and forms a taylor cone at the tip, then generates charged spray droplets, further desolventizes to form gas phase ions, ionizes the components, and enters mass spectrometry for analysis.
Typically, the Patern oa-B ü chi (PB) photochemical reaction reagent is benzophenone.
The invention has the following beneficial effects:
the invention directly carries out microscale sampling on a biological tissue sample by adopting a microscale sampling probe of a capillary-in-micro-extraction-nanoliter electrospray ion source system, and directly inserts the microscale sampling probe into a nanoliter electrospray needle, carries out solid-liquid micro-extraction in the capillary of the nanoliter electrospray ion source system, can simultaneously carry out Patern OA-B ü chi online photochemical reaction, then directly carries out field nanoliter electrospray mass spectrometry under the condition of normal pressure opening, simultaneously records a positive ion mass spectrogram and a negative ion mass spectrogram, integrates the solid-liquid micro-extraction and normal pressure open field nanoliter electrospray mass spectrometry technology, realizes the online combination of the solid-liquid micro-extraction, Patern OA-B ü chi online photochemical reaction and normal pressure open field nanoliter electrospray mass spectrometry, can act as a novel nanoliter electrospray ion source to carry out mass spectrometry, has extremely high sensitivity and ideal reproducibility, and can be used for high-sensitivity, in-situ and microscale analysis and research of direct analysis of complex biological samples.
Description of the drawings:
FIG. 1 is a technical schematic of the present invention;
FIG. 2 is a chromatogram of positive and negative ion patterns obtained by analyzing mouse liver samples by using an in-capillary micro-extraction-nano-liter electrospray ion source in example 4 of the present invention.
FIG. 3 is a mass spectrum of positive and negative ion modes obtained by analyzing mouse liver samples using an in-capillary micro-extraction-nano-liter electrospray ion source system in example 4 of the present invention.
FIG. 4 is a mass spectrum of positive and negative ion modes obtained by analyzing muscle samples of zebra fish exposed to perfluorinated compounds using an in-tube capillary micro-extraction-nano-liter electrospray ion source system in example 5 of the present invention.
The specific implementation mode is as follows:
the following is a further description of the invention and is not intended to be limiting.
Example 1: micro-extraction-nano-liter electrospray ion source system in capillary
A capillary micro-extraction-nano-liter electrospray ion source system comprises a micro-scale sampling probe, a nano-liter electrospray needle and a high-voltage power supply; the micro-scale sampling probe directly carries out micro-scale sampling on a biological tissue sample, directly brings the collected trace sample into a nano-liter electrospray needle, carries out solid-liquid micro-extraction in a capillary tube of the nano-liter electrospray needle, and then directly carries out field nano-liter electrospray mass spectrometry under the open condition of normal pressure. The micro-scale sampling probe is a tungsten needle with the tip diameter within the range of 1 mu m and subjected to surface treatment.
Example 2: micro-extraction-nano-liter electrospray ion source system in capillary
The system comprises a microscale sampling probe, a nanoscale electrospray needle, an ultraviolet lamp with a wavelength of 254nm and a high-voltage power supply, wherein the ultraviolet lamp can be used for Patern oa-B ü chi photochemical reaction, the microscale sampling probe directly carries out microscale sampling on a biological tissue sample, the collected microscale sample is directly brought into the nanoscale electrospray needle, solid-liquid microextraction is carried out in a capillary tube of the nanoscale electrospray needle, and the PB online photochemical reaction is directly carried out field-induced nanoscale electrospray mass spectrometry under the condition of normal pressure opening.
Example 3: method for direct analysis of biological samples
The method comprises the steps of using a micro-scale sampling probe for direct sampling of a biological tissue sample, picking up and adhering a certain trace amount of biological tissue sample (with a volume of no more than 0.5mm x 0.5mm) to the probe tip through the probe tip, and then inserting the probe together with the biological tissue sample adhered to the probe tip into a nanoliter spray needle containing a certain amount of an extraction/spray solvent (optionally containing a certain amount of PB reagent, usually 0.05-0.5mg/mL benzophenone at the tip), subjecting the biological tissue sample to solid-liquid microextraction in the capillary of the nanoliter spray needle, subjecting the compound in the biological tissue sample to extraction, desorption, enrichment in a desorption/desorption solvent, optionally using 254nm wavelength, irradiating the nanoliter spray needle with a high-pressure electrospray induction probe, subjecting the extracted, desorbed and adsorbed ions to a high-voltage electrospray induction under normal pressure condition, and simultaneously subjecting the nanoliter spray needle to a nanoliter spray induction sampling under normal pressure condition, wherein the nanoliter spray needle is placed in a nanoliter spray needle under normal pressure, and the nanoliter spray induction probe under normal pressure conditions of a negative electrospray induction probe induction.
Example 4: lipid analysis and omics studies on mouse liver samples
The mass spectrometer comprises the micro-extraction-nano-liter electrospray ion source system in the capillary and a bracket which is used for fixing the tip of a nano-liter electrospray needle of the micro-extraction-nano-liter electrospray ion source system in the capillary, is aligned to a mass spectrum inlet and is 10mm away from the mass spectrum inlet in embodiment 1.
The method comprises the following steps: a microscale sampling probe with a tip of 1 μm is used for directly sampling mouse liver samples, and a certain trace amount of liver tissue sample (with a volume of about 0.5mm × 0.5mm × 0.5mm) is picked up and adhered by the probe tip. The probe was then inserted into a nanoliter electrospray needle containing 5 μ L methanol/chloroform (v: v ═ 9:1) along with the liver tissue sample to which the probe tip was attached. In the capillary of a nanoliter electrospray needle, a solvent is used for carrying out solid-liquid microextraction on a mouse liver sample, and a lipid compound is extracted and enriched into a desorption/spray solvent. Then, a sampling probe and a nano-liter electrospray needle are placed at a mass spectrum inlet, the tip of the spray needle is 10mm away from the mass spectrum inlet, meanwhile, a metal wire is used for grounding the micro-scale sampling probe, a high-voltage electric field capable of performing rapid polarity conversion is applied to the inlet end of the mass spectrum, the voltage is +/-3.0 kV, the solvent in the nano-liter electrospray needle is guided to generate field electrospray ionization under normal pressure and open conditions, mass spectrum analysis is carried out, and a chromatogram map (figure 2) and a mass spectrum map (figure 3) of positive ions and negative ions are recorded. Because the consumption of the sample in the nanoliter electrospray ionization mass spectrometry is low, the signal duration can reach 30min, and the signal duration is long enough to complete the secondary mass spectrometry of most lipid compounds, so that the aim of identifying the compounds is fulfilled.
Example 5: correlation study for zebra fish perfluorinated compound exposure and lipid metabolism
The mass spectrometer comprises the micro-extraction-nano-liter electrospray ion source system in the capillary and a bracket which is used for fixing the tip of a nano-liter electrospray needle of the micro-extraction-nano-liter electrospray ion source system in the capillary, is aligned to a mass spectrum inlet and is 10mm away from the mass spectrum inlet in embodiment 1.
The method comprises the following steps: one zebrafish was exposed to an aqueous solution containing perfluorocompounds (PFOS at a concentration of 10ng/mL, PFHpA, PFOA, PFNA, PFDA, PFUnDA, PFDoDA) for 5 days. The zebrafish was then used to study the correlation of perfluorochemical exposure with lipid metabolism. The muscle on the back of zebra fish was directly sampled with a tungsten probe having a tip diameter of about 1 μm, a trace amount of fish tissue sample was adhered through the probe tip, and then the probe was inserted into a nanoliter electrospray needle containing 2 μ L of methanol/chloroform (v: v ═ 9:1) together with the fish tissue sample adhered to the probe tip. In a capillary of a nanoliter electrospray needle, carrying out solid-liquid microextraction on lipid and perfluorinated compounds in a zebra fish meat sample by using methanol/chloroform, and extracting the lipid compounds and the perfluorinated compounds into a solvent. And then, placing the tungsten probe and the nano-liter electrospray needle at the mass spectrum inlet together, enabling the tip of the spray needle to be about 10mm away from the mass spectrum inlet, grounding the tungsten probe by using a metal wire, applying a high-voltage electric field capable of performing rapid polarity conversion at the inlet end of the mass spectrum, enabling the voltage to be +/-3.0 kV, guiding the solvent in the nano-liter electrospray needle to perform field electrospray ionization under the open condition of normal pressure, performing mass spectrum analysis, and recording mass spectrograms of positive ions and negative ions. The signals of most phospholipids and triglycerides are recorded on the positive ion spectrum and the signals of perfluorinated compounds are recorded on the negative ion spectrum (fig. 4).
Claims (10)
1. A micro-extraction-nanoliter electrospray ion source system in a capillary is characterized by comprising a micro-scale sampling probe, a nanoliter electrospray needle and a high-voltage power supply, wherein the micro-scale sampling probe directly performs micro-scale sampling on a biological tissue sample, directly brings the collected micro-scale sample into the nanoliter electrospray needle to which an extraction/spray solvent and/or a Patern oa-B ü chi photochemical reaction reagent are/is added, performs solid-liquid micro-extraction in the capillary of the nanoliter electrospray needle, and then directly performs field nanoliter electrospray mass spectrometry under the normal-pressure open condition.
2. The system according to claim 1, characterized in that it further comprises UV lamps for the photochemical reaction of Patern oa-B ü ch, said UV lamps having a wavelength of 254 nm.
3. The system of claim 1 or 2, wherein the micro-extraction-nano-liter electrospray ion source system is characterized in that the micro-scale sampling probe is a metal needle with a tip diameter ranging from 1 to 10 μm; the nano-liter electric spraying needle is a metal-coated glass nano-liter electric spraying needle or a quartz nano-liter electric spraying needle; the inner diameter of a capillary tube of the nano-liter spray needle is within the range of 1-2 mm, and the inner diameter of the tip of the nano-liter spray needle is within the range of 1-10 mu m; the high-voltage power supply is a field-induced high-voltage power supply, a high-voltage electric field is applied to a mass spectrum inlet and can be adjusted within 0-5 kV, the microscale sampling probe is grounded, a high-voltage electric field is formed between the nanoliter electrospray needle and the mass spectrum inlet, and the solvent containing a target compound in the nanoliter electrospray needle is induced to generate electrospray ionization so as to perform mass spectrum analysis; and the high-voltage electric field is not contacted with the sample, and the fast positive and negative switching can be directly carried out under the condition of normal pressure opening.
4. A mass spectrometry device, comprising the capillary micro-extraction-nano-liter electrospray ion source system of claim 1 or 2, a bracket for fixing the capillary micro-extraction-nano-liter electrospray ion source system, wherein the tip of a nano-liter electrospray needle of the capillary micro-extraction-nano-liter electrospray ion source system is aligned with a mass spectrum inlet and is 5-15mm away from the mass spectrum inlet, a micro-scale sampling probe of the capillary micro-extraction-nano-liter electrospray ion source system directly carries out micro-scale sampling on a biological tissue sample and directly brings the collected micro-biological sample to the nano-liter electrospray needle, solid-liquid micro-extraction is carried out in the capillary of the nano-liter electrospray ion needle, Patern-B ü chi on-line photochemical reaction can be simultaneously carried out, then field-nano-liter electrospray mass spectrometry is directly carried out under the open condition of normal pressure, and positive and negative ion mass spectrograms are recorded simultaneously.
5. Use of the mass spectrometer arrangement according to claim 4 for direct analysis of biological samples and omics studies.
6. Use according to claim 5, for lipid analysis and lipidomics studies; the lipid comprises more than one of fatty acyl, glyceride, glycerophospholipid, sphingolipid, sterol lipid, pregnenolone lipid, glycolipid, and polyketide.
7. A method for direct analysis of a biological sample using the mass spectrometry apparatus of claim 4, comprising the steps of: after sampling is carried out by utilizing a microscale sampling probe, solid-liquid microextraction is carried out in a capillary of the nano-liter electrospray needle, and PB online photochemical reaction, the nano-liter electrospray needle can directly carry out electrospray ionization and mass spectrometry.
8. The method for the direct analysis of biological samples according to claim 7, characterized in that it comprises in particular the following steps:
the microscale sampling probe directly carries out microscale sampling on a biological tissue sample, the collected microscale biological sample is directly inserted into a nanoliter electrospray needle which is added with an extraction/spray solvent or/and a Patern oa-B ü chi photochemical reaction reagent, solid-liquid microextraction is carried out in a capillary tube of the nanoliter electrospray needle, a target compound in the biological sample is desorbed, extracted and enriched, an ultraviolet lamp can be simultaneously used for irradiating the solvent which is enriched with the target compound in the nanoliter electrospray needle to carry out the online photochemical reaction of the Patern oa-B ü chi, then the nanoliter electrospray needle containing the microscale sampling probe is placed on a bracket for fixing, the tip of the nanoliter electrospray needle is aligned to a mass spectrum inlet and is 5-15mm away from the mass spectrum inlet, the microscale sampling probe is grounded, a high-voltage electric field which can rapidly carry out polarity conversion is applied to the mass spectrum inlet, and field nanoliter electrospray mass spectrum analysis is directly carried out under the condition of normal pressure opening, and positive and negative ion mass spectra are recorded.
9. The method for direct analysis of biological samples according to claim 8, wherein the extraction/spray solvent is typically 0.5-5 μ L of methanol spray solvent.
10. The method according to claim 8, wherein the photochemical reaction reagent is benzophenone, oa-B ü chi.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911082613.3A CN110887891A (en) | 2019-11-07 | 2019-11-07 | Micro-extraction-nano-liter electrospray ion source system in capillary and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911082613.3A CN110887891A (en) | 2019-11-07 | 2019-11-07 | Micro-extraction-nano-liter electrospray ion source system in capillary and application |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN110887891A true CN110887891A (en) | 2020-03-17 |
Family
ID=69747028
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201911082613.3A Pending CN110887891A (en) | 2019-11-07 | 2019-11-07 | Micro-extraction-nano-liter electrospray ion source system in capillary and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110887891A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111830117A (en) * | 2020-07-20 | 2020-10-27 | 中山大学 | Laser-ionized solid phase microextraction-time-of-flight mass spectrometry combined system |
| CN111834193A (en) * | 2020-07-20 | 2020-10-27 | 中山大学 | Laser analysis ionization method based on optical fiber conduction |
| CN114695069A (en) * | 2022-03-17 | 2022-07-01 | 中国计量科学研究院 | Nano-liter photoionization mass spectrum ion source device and operation method thereof |
| WO2024022312A1 (en) * | 2022-07-25 | 2024-02-01 | 清华大学 | Capillary electrophoresis-based lipidome analysis system as well as use thereof, and lipidome analysis method |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20040229377A1 (en) * | 2003-04-14 | 2004-11-18 | National Cheng Kung University | Microfluidic chip system integrated with nano-electrospray interface and method using thereof |
| US20090266982A1 (en) * | 2008-04-24 | 2009-10-29 | Canon Kabushiki Kaisha | Mass spectrometry substrate and mass spectrometry method |
| CN104062348A (en) * | 2014-07-07 | 2014-09-24 | 南昌大学第二附属医院 | Method for directly analyzing lung cancer tissue sample based on tissue electro-spray ionization mass spectrometry |
| CN104134606A (en) * | 2014-07-30 | 2014-11-05 | 中山大学 | Microextraction probe electrospray ion source and manufacturing method and application of microextraction probe electrospray ion source |
| CN104771934A (en) * | 2014-12-31 | 2015-07-15 | 中国广州分析测试中心 | Solid phase micro-extraction apparatus |
| CN106404945A (en) * | 2016-08-30 | 2017-02-15 | 中山大学 | Slug flow microextraction-paper spray mass spectrometry technology |
| US20180294148A1 (en) * | 2015-05-29 | 2018-10-11 | Purdue Research Foundation | Methods for analyzing a tissue sample |
| US20190277735A1 (en) * | 2016-06-03 | 2019-09-12 | Purdue Research Foundation | Systems and methods for analyzing an analyte extracted from a sample using an adsorbent material |
-
2019
- 2019-11-07 CN CN201911082613.3A patent/CN110887891A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20040229377A1 (en) * | 2003-04-14 | 2004-11-18 | National Cheng Kung University | Microfluidic chip system integrated with nano-electrospray interface and method using thereof |
| US20090266982A1 (en) * | 2008-04-24 | 2009-10-29 | Canon Kabushiki Kaisha | Mass spectrometry substrate and mass spectrometry method |
| CN104062348A (en) * | 2014-07-07 | 2014-09-24 | 南昌大学第二附属医院 | Method for directly analyzing lung cancer tissue sample based on tissue electro-spray ionization mass spectrometry |
| CN104134606A (en) * | 2014-07-30 | 2014-11-05 | 中山大学 | Microextraction probe electrospray ion source and manufacturing method and application of microextraction probe electrospray ion source |
| CN104771934A (en) * | 2014-12-31 | 2015-07-15 | 中国广州分析测试中心 | Solid phase micro-extraction apparatus |
| US20180294148A1 (en) * | 2015-05-29 | 2018-10-11 | Purdue Research Foundation | Methods for analyzing a tissue sample |
| US20190277735A1 (en) * | 2016-06-03 | 2019-09-12 | Purdue Research Foundation | Systems and methods for analyzing an analyte extracted from a sample using an adsorbent material |
| CN106404945A (en) * | 2016-08-30 | 2017-02-15 | 中山大学 | Slug flow microextraction-paper spray mass spectrometry technology |
Non-Patent Citations (4)
| Title |
|---|
| DENG JIEWEI等: "Biocompatible Surface-Coated Probe for in Vivo, in Situ, and Microscale Lipidomics of Small Biological Organisms and Cells Using Mass Spectrometry", 《ANALYTICAL CHEMISTRY》 * |
| DENG JIEWEI等: "Coupling Paternò-Büchi Reaction with Surface-Coated Probe Nanoelectrospray Ionization Mass Spectrometry for In Vivo and Microscale Profiling of Lipid C=C Location Isomers in Complex Biological Tissues", 《ANALYTICAL CHEMISTRY》 * |
| YANG YUNYUN等: "A microscale solid-phase microextraction probe for the in situ analysis of perfluoroalkyl substances and lipids in biological tissues using mass spectrometry", 《ANALYST》 * |
| 邓洁薇等: "微萃取与质谱联用在环境与生物分析中的新进展", 《第一届全国环境化学青年学者论坛论文集》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111830117A (en) * | 2020-07-20 | 2020-10-27 | 中山大学 | Laser-ionized solid phase microextraction-time-of-flight mass spectrometry combined system |
| CN111834193A (en) * | 2020-07-20 | 2020-10-27 | 中山大学 | Laser analysis ionization method based on optical fiber conduction |
| CN111834193B (en) * | 2020-07-20 | 2021-10-01 | 中山大学 | Laser analysis ionization method based on optical fiber conduction |
| CN114695069A (en) * | 2022-03-17 | 2022-07-01 | 中国计量科学研究院 | Nano-liter photoionization mass spectrum ion source device and operation method thereof |
| WO2024022312A1 (en) * | 2022-07-25 | 2024-02-01 | 清华大学 | Capillary electrophoresis-based lipidome analysis system as well as use thereof, and lipidome analysis method |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110887891A (en) | Micro-extraction-nano-liter electrospray ion source system in capillary and application | |
| US11830715B2 (en) | Mass spectrometric determination of fatty acids | |
| JP2005519669A (en) | Micro apparatus for biological tissue examination and analysis method | |
| CN105021758B (en) | Chemical derivatization-based phosphatide classification detection and quantification method | |
| CN107923826A (en) | Method for analyzing tissue sample | |
| CN113640417A (en) | Method for detecting trans-triiodothyronine by mass spectrometry | |
| CN105067697B (en) | A kind of phosphatide classification and Detection and quantitative approach based on stable isotope labeling | |
| JP6492099B2 (en) | Analysis of extracted samples using immiscible extraction solvents | |
| US9068995B2 (en) | Method for determining derivatized analytes in a separated biological fluid | |
| Kirschbaum et al. | Lipid analysis by mass spectrometry coupled with laser light | |
| Li et al. | Determination of methylmalonic acid and glutaric acid in urine by aqueous‐phase derivatization followed by headspace solid‐phase microextraction and gas chromatography‐mass spectrometry | |
| Gopaul et al. | Gas chromatography/negative ion chemical ionization mass spectrometry and liquid chromatography/electrospray ionization tandem mass spectrometry quantitative profiling of N‐acetylcysteine conjugates of valproic acid in urine: application in drug metabolism studies in humans | |
| US20080176269A1 (en) | Method for determination of DHT levels in tissue samples | |
| Sousa et al. | Methods of lipid analysis | |
| CN115236170A (en) | Lipidosome analysis system based on capillary electrophoresis, application thereof and lipidosome analysis method | |
| You et al. | 10-Ethyl-acridine-2-sulfonyl chloride: a new derivatization agent for enhancement of atmospheric pressure chemical ionization of estrogens in urine | |
| RU2687887C1 (en) | Method for determining 1-hydroxypyren in urine by chromatography-mass-spectrometric analysis | |
| Tan et al. | Nanoliter atmospheric pressure photoionization-mass spectrometry for direct bioanalysis of polycyclic aromatic hydrocarbons | |
| CN113588772A (en) | Unsaturated fatty acid carbon-carbon double bond epoxidation and positioning method based on arc plasma | |
| CN217521095U (en) | Analytical equipment based on thin layer chromatography-carbon fiber ionization mass spectrum | |
| CN116046929A (en) | Qualitative and quantitative analysis method for unsaturated lipid isomer based on microwave-assisted MMPP epoxidation technology | |
| Kałużna-Czaplińska et al. | Medical Bioanalytics: Separation Techniques in Medical Diagnostics of Neurological Diseases and Disorders on Selected Examples | |
| Mielczarek et al. | 8 Rapid Generation | |
| Domenick | Development of Ion Mobility-Mass Spectrometric Methods to Enhance Coverage of the Cellular Metabolome | |
| CN112946054A (en) | Tubular paper ionization-mass spectrometry rapid analysis method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20200317 |