CN111413395A - Application of porous silicon nanowire combined with MA L DI-TOF MS in metabolic small molecule detection - Google Patents
Application of porous silicon nanowire combined with MA L DI-TOF MS in metabolic small molecule detection Download PDFInfo
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Abstract
The invention provides an application of a porous silicon nanowire and MA L DI-TOF MS in metabolic small molecule detection, and an analysis method of the porous silicon nanowire as a MA L DI-TOF MS matrix is suitable for performing mass spectrometry on small molecules with the molecular weight less than 1000, so that the detection difficulty of small molecule samples is greatly simplified, the detection sensitivity of MA L DI-TOF MS of the small molecule samples is improved, and simultaneously, the elimination of mass spectrum peak interference generated by the existing matrix and the enhancement processing of mass spectrum signals of the small molecule samples can be realized.
Description
Technical Field
The invention belongs to the technical field of mass spectrometry detection, and particularly relates to an application of a porous silicon nanowire combined with MA L DI-TOF MS in metabolic small molecule detection.
Background
Since metabolic alterations can directly participate in the transformation process or support the biological process of tumor growth, small molecule metabolites can become a unique source of cancer-specific information, and thus, the application of metabolomics in clinical tumor research has become a research hotspot in recent years. During this period, mass spectrometry also plays an increasingly important role.
Although the MA L DI-TOF MS is various, the organic small molecular matrix is difficult to be used for analyzing compounds with small molecular weight (less than 10000 Da), and the main reason is that the organic small molecular matrix is cracked and associated between molecules, so that a serious matrix background interference phenomenon is generated.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides the application of the porous silicon nanowire and MA L DI-TOFMS in metabolic small molecule detection, and the analysis method of the porous silicon nanowire as the MA L DI-TOF MS matrix is suitable for performing mass spectrometry on small molecules with the molecular weight less than 1000, so that the detection difficulty of small molecule samples is greatly simplified, the detection sensitivity of MA L DI-TOF MS of the small molecule samples is improved, and simultaneously the elimination of mass spectrum peak interference generated by the existing matrix and the enhancement processing of mass spectrum signals of the small molecule samples can be realized.
In order to achieve the purpose, the technical scheme adopted by the invention for solving the technical problems is as follows:
application of porous silicon nanowires in combination with MA L DI-TOF MS in metabolic small molecule detection.
Further, the molecular weight of the metabolized small molecule is less than 1000.
Further, the metabolic small molecule is a body fluid metabolite, and the body fluid metabolite can be serum, plasma, urine, sweat, semen, hydrocephalus, synovial fluid and the like.
Further, the MA L DI-TOF MS detection is used for mass spectrum imaging of the substance to be detected.
Further, a body fluid sample containing the metabolite is dripped onto a metal target sheet of MA L DI-TOF MS, after the sample is air-dried, the porous silicon nanowire is dripped, and after the air-drying is continued, the MA L DI-TOF MS detection is carried out.
Furthermore, the concentration of the porous silicon nanowire is 0.8-1.5mg/ml, and the volume ratio of the porous silicon nanowire to the sample to be detected is 1-4: 1.
Further, the concentration of the porous silicon nanowire is 1mg/ml, and the volume ratio of the porous silicon nanowire to the sample to be detected is 2: 1.
Further, the porous silicon nanowire is prepared by the following method:
pretreatment: removing an oxide layer on the surface of the silicon wafer;
silver deposition: soaking the pretreated silicon wafer in silver-containing liquid for silver deposition;
etching: and cleaning the silicon wafer deposited with the silver by using deionized water, soaking the silicon wafer in etching solution for 50-70min, and then removing the silver on the surface of the silicon wafer to obtain the silicon nanowire.
Further, the silver deposition process is specifically as follows: soaking the pretreated silicon wafer in a mixed solution containing 4.5-5.0M hydrofluoric acid and 0.003-0.008M silver nitrate for 40-80 s; preferably, the concentration of hydrofluoric acid is 4.8M, the concentration of silver nitrate is 0.005M, and the soaking time is 60 s.
Further, the etching process specifically comprises: washing the silicon wafer with the deposited silver by using deionized water, then soaking the silicon wafer in a mixed solution containing 4.5-5.5M hydrofluoric acid and 0.6-1.2M hydrogen peroxide for 50-70min, and then soaking the silicon wafer in concentrated nitric acid for 50-70min to prepare a silicon nanowire; preferably, the silicon wafer after silver deposition is washed by deionized water, then is soaked in a mixed solution containing 4.8M hydrofluoric acid and 0.8M hydrogen peroxide for 60min, and then is soaked in concentrated nitric acid for 1 h.
The application of the porous silicon nanowire combined with MA L DI-TOF MS in metabolic small molecule detection has the following beneficial effects:
the invention generates amorphous SiO on the silicon nano-crystalline nucleus by the high-oxidation etching process2Layer, made hydrophilic and following H during etching with silver catalyst solution2O2The increase of the concentration and the porosity and one-dimensional characteristics of the silicon nanowire are realizedIn addition, the structure of the porous silicon nanowire is favorable for absorbing the energy excited by ultraviolet laser from the matrix-assisted laser desorption ionization time-of-flight mass spectrum, promotes desorption ionization of the substance to be detected, and does not generate cluster ions of mass spectrum peaks detectable by MS, so that small molecule metabolite signals smaller than 1000Da can be captured and analyzed, the defect that the existing matrix can not effectively analyze small molecule samples due to the fact that the existing matrix easily generates serious matrix background interference in a low molecular weight region is effectively overcome, the detection difficulty of the small molecule samples is greatly simplified, and the detection sensitivity of MA L DI-TOF MS of the small molecule samples is improved.
Drawings
FIG. 1 is a graph of characterization results for porous silicon nanowires.
Fig. 2 is a schematic diagram of porous silicon nanowires as a matrix in MA L DI-TOF MS detection.
Fig. 3 shows typical L DI signal results after mixing porous silicon nanowires as a matrix with serum samples.
FIG. 4 shows the result of glucose signal detected after mixing the porous silicon nanowire as a matrix with a serum sample.
Fig. 5 shows the creatinine signal results detected after the porous silicon nanowire is used as a matrix to be mixed with a serum sample.
Fig. 6 shows the result of glucose signal detected after the porous silicon nanowire is used as a matrix to be mixed with a serum sample.
Fig. 7 shows the result of glucose signal detected after the porous silicon nanowire is used as a matrix to be mixed with a serum sample.
Fig. 8 shows the result of glucose signal detected after the porous silicon nanowire is used as a matrix to be mixed with a serum sample.
FIG. 9 shows the results of the measurement of ten mixed amino acids at a concentration of 200 nM.
FIG. 10 shows the results of the measurement of ten mixed amino acids at a concentration of 1000 nM.
FIG. 11 shows the results of detection at a concentration of 0.25. mu.M for four mixed amino acids.
FIG. 12 shows the results of detection at a concentration of 0.25. mu.M for four mixed amino acids.
FIG. 13 shows the results of detection at a concentration of 5. mu.M for four mixed amino acids.
FIG. 14 shows the results of detection at a concentration of 25. mu.M for four mixed amino acids.
Detailed Description
Example 1 preparation of porous silicon nanowires
(1) Pretreatment of
Soaking an N-type Si (100) wafer with a resistivity of 0.008-0.02 Ω · cm in an Oxide corrosion buffer (such as BOE (buffered Oxide etch) formed by hydrofluoric acid (49%) and water or a mixture of ammonium fluoride and water) for 2 minutes to remove a native Oxide layer;
(2) silver deposition
Taking out the pretreated silicon wafer, and soaking in 4.8M hydrofluoric acid (HF) and 0.005M silver nitrate (AgNO)3) The immersion time in the silver deposition solution is 1 minute;
(3) etching of
The silicon wafer with silver deposited thereon was rinsed with deionized water to remove excess silver ions and immediately immersed in a solution of 4.8M HF and 0.8M H2O2Soaking in the etching solution for 60min, removing silver on the surface of the silicon wafer, thoroughly washing off Ag and HF residues on the surface of the silicon wafer by water in the etching time, and soaking the silicon wafer in concentrated nitric acid (HNO)3) And soaking for 1h to remove Ag residues deposited on the silicon wafer, thereby obtaining the pure silicon nanowire.
The invention generates amorphous SiO on the silicon nano-crystalline nucleus by the high-oxidation etching process2Layer, made hydrophilic and following H during etching with silver catalyst solution2O2The increase of the concentration realizes the porosity and one-dimensional characteristics of the silicon nanowire, increases the surface area of the silicon nanowire, and is favorable for increasing the interaction with small molecule metabolites. In the using process, millimeter-grade nanowire solution required by thousands of samples can be produced by adopting a centimeter-sized silicon wafer, so that the material cost is greatly reduced, and the method is more beneficial to clinical application.
Scanning Electron Microscope (SEM), Transmission Electron Microscope (TEM) and ultraviolet-visible light (UV-vis) detection are carried out on the porous silicon nanowire prepared in the above way, and the detection result is shown in figure 1. Wherein, fig. 1a is a Scanning Electron Microscope (SEM) image of the porous silicon nanowire (SiNW), an inset in fig. 1a is a Transmission Electron Microscope (TEM) image of the porous silicon nanowire, and fig. 1b is an ultraviolet-visible light absorption spectrum image of the porous silicon nanowire.
As can be seen from fig. 1a, the length of the nanowires is controlled by the etching time, so that a high-density nanowire forest is formed.
As can be seen from the inset in fig. 1a, the individual silicon nanowires have an irregular porosity in the 10nm region.
As can be seen from fig. 1b, the broad absorption of porous silicon nanowires in the ultraviolet region may be due to quantum confinement of their widely distributed critical dimensions.
Example 2 matrix-assisted laser desorption ionization time-of-flight mass spectrometry
Detecting small molecular substances in serum
An experimental group is that 0.5u L serum sample is dripped on a polishing steel target plate MTP384, after air drying, 1u L porous silicon nanowire is dripped (the porous silicon nanowire is ultrasonically oscillated into deionized water to enable the concentration to be 1mg/ml), after complete drying, the sample is arranged on an Autoflex Max mass spectrometer (Bruker Daltonics company of Bremen, Germany) to carry out mass spectrum detection, a smartpeak-II laser is used for acquiring a spectrum under a 355nm reflection positive mode in the detection process, each sample with the laser frequency of 1000 hz. measures 20 different points at random, and each point is subjected to laser random dotting for 25 times, so 500 satisfactory dotting points can be obtained.
In the control group, the porous silicon nanowires were replaced with α -cyano-4-hydroxyphenylacrylic acid (CHCA) matrix, and the other procedures were the same as those in the experimental group.
A schematic diagram of porous silicon nanowires as a matrix in MA L DI-TOF MS detection is shown in FIG. 2, wherein GNS (SiO) in FIG. 22core/Au shell nanomaterial) is also a matrix.
The results of a typical L DI signal after mixing porous silicon nanowires as matrix with serum samples are shown in FIG. 3, where the curves in FIG. 3 represent CHCA × 10, GNS and SiNW, respectively, from bottom to top.
As can be seen from FIG. 3, mixed with GNThe serum sample of S or SiNW produced significant signals at 100-900Da m/z after passing through a mass spectrometer, and the serum sample mixed with GNS partially showed the following results, glucose (G L U), m/z 181.07[ G L U + H ]]+Glucose (G L U) m/z 203.05[ G L U + Na ]]+Glucose (G L U) m/z 219.026[ G L U + K ]]+(ii) a Uric Acid (UA): 169.035[ UA + H ] m/z]+(ii) a Uric Acid (UA): m/z 191.017[ UA + Na]+(ii) a Uric Acid (UA): m/z 206.99[ UA + K]+(ii) a Creatinine (CRE): 114.06[ CRE + H ] m/z]+(ii) a Creatinine (CRE): 136.048[ CRE + Na ] m/z]+(ii) a Creatinine (CRE): m/z 152.02[ CRE + K ═]+(ii) a Partial results are shown in fig. 4 to 8.
In contrast, mixtures that directly mix conventional α -cyano-4-hydroxyphenylacrylic acid (CHCA) matrices with serum samples hardly yield any signal, even if expanded 10-fold, which may be due to lipid interference
The detection was performed according to the detection method in the above experimental group, except that the serum sample was replaced with ten mixed amino acids at a concentration of 200nM, and the specific amino acids were Ser, Pro, Thr, L eu, Met, L ys, His, Phe, Try, and Val, and the detection results are shown in FIG. 9.
The amino acid concentration was changed to 1000nM, and the results are shown in FIG. 10.
As can be seen from FIGS. 9 and 10, when MA L DI-TOF MS detection was performed using the matrix provided herein, each small-molecule amino acid among the mixed amino acids was detected, and thus it was found that the matrix provided herein was effective for detecting small-molecule substances having a molecular weight of less than 1000 Da.
Thirdly, detecting signals in the mixture of four amino acids
The detection was performed according to the detection method in the above experimental group, except that the serum sample was changed to four mixed amino acids at a concentration of 0.25. mu.M, and the specific amino acids were Met, Phe, Try and Thr, and the detection results are shown in FIG. 11.
The amino acid concentration was changed to 2.5. mu.M, and the results are shown in FIG. 12.
The amino acid concentration was changed to 5. mu.M, and the results are shown in FIG. 13.
The amino acid concentration was changed to 25. mu.M, and the results are shown in FIG. 14.
As can be seen from FIGS. 11-14, when the matrix provided herein was used for MA L DI-TOF MS detection, each small-molecule amino acid among the mixed amino acids was detected, and thus it was found that the matrix provided herein was effective for detecting small-molecule substances having a molecular weight of less than 1000 Da.
Claims (10)
1. Application of porous silicon nanowires in combination with MA L DI-TOF MS in metabolic small molecule detection.
2. The use of claim 1, wherein said metabolized small molecule has a molecular weight of less than 1000.
3. Use according to claim 1 or 2, wherein the metabolising small molecule is a metabolite of a body fluid.
4. Use according to claim 1, wherein the MA L DI-TOF MS detection is used for mass spectrometric imaging of a substance to be tested.
5. The use of claim 1, wherein the metabolite-containing body fluid sample is dropped onto a metal target of MA L DI-TOF MS, after the sample is air-dried, the porous silicon nanowires are dropped, and after the air-drying is continued, the MA L DI-TOFMS detection is performed.
6. The use according to claim 1 or 5, wherein the concentration of the porous silicon nanowires is 0.8-1.5mg/ml, and the volume ratio of the porous silicon nanowires to the sample to be tested is 1-4: 1.
7. The use according to claim 6, wherein the concentration of the porous silicon nanowires is 1mg/ml, and the volume ratio of the porous silicon nanowires to the sample to be tested is 2: 1.
8. The use according to claim 1, wherein the porous silicon nanowires are prepared by:
(1) pretreatment: removing an oxide layer on the surface of the silicon wafer;
(2) silver deposition: soaking the pretreated silicon wafer in silver-containing liquid for silver deposition;
(3) etching: and cleaning the silicon wafer deposited with the silver by using deionized water, soaking the silicon wafer in etching solution for 50-70min, and then removing the silver on the surface of the silicon wafer to obtain the silicon nanowire.
9. Use according to claim 8, characterized in that the silver deposition process is in particular: soaking the pretreated silicon wafer in a mixed solution containing 4.5-5.0M hydrofluoric acid and 0.003-0.008M silver nitrate for 40-80 s.
10. The application of claim 8, wherein the etching process is specifically: washing the silicon wafer with deionized water after silver deposition, soaking in a mixed solution containing 4.5-5.5M hydrofluoric acid and 0.6-1.2M hydrogen peroxide for 50-70min, and soaking in concentrated nitric acid for 50-70min to obtain the silicon nanowire.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112458539A (en) * | 2020-09-23 | 2021-03-09 | 四川大学 | Porous silicon nanowire and preparation method thereof |
| CN113588769A (en) * | 2021-02-20 | 2021-11-02 | 上海交通大学 | Preparation method of porous alloy nano material and application of porous alloy nano material in detection of plasma metabolites |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104835719A (en) * | 2015-04-01 | 2015-08-12 | 浙江大学 | Porous SiO2 nanowire array preparation method |
| CN106814128A (en) * | 2015-11-27 | 2017-06-09 | 上海交通大学 | A kind of method of utilization Mass Spectrometer Method excretion body small molecule metabolites |
| CN106841373A (en) * | 2015-12-07 | 2017-06-13 | 中国科学院大连化学物理研究所 | Sub-micron aoxidizes application of the carbon ball as matrix in MALDI-MS |
| CN107490615A (en) * | 2016-06-13 | 2017-12-19 | 清华大学 | Array chip for MALDI-TOF-MS and preparation method and application |
| CN107655960A (en) * | 2017-09-18 | 2018-02-02 | 亿纳谱（浙江）生物科技有限公司 | Serum mass spectrometric analysis method, matrix based on gold-palladium and preparation method thereof, application |
| CN108847383A (en) * | 2018-05-29 | 2018-11-20 | 昆明理工大学 | A kind of preparation method of porous silicon nanowire array |
| CN109932410A (en) * | 2017-12-18 | 2019-06-25 | 中国科学院大连化学物理研究所 | A kind of Mass Spectrometry detection method based on papery target piece |
| CN110530965A (en) * | 2019-10-08 | 2019-12-03 | 浙江大学 | A kind of method that silicon nanowire array chip detects cell metabolite, lipid |
| CN110954590A (en) * | 2019-11-01 | 2020-04-03 | 杭州汇健科技有限公司 | Saliva sample detection method based on silicon nanowire chip |
-
2020
- 2020-04-21 CN CN202010316858.4A patent/CN111413395A/en active Pending
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104835719A (en) * | 2015-04-01 | 2015-08-12 | 浙江大学 | Porous SiO2 nanowire array preparation method |
| CN106814128A (en) * | 2015-11-27 | 2017-06-09 | 上海交通大学 | A kind of method of utilization Mass Spectrometer Method excretion body small molecule metabolites |
| CN106841373A (en) * | 2015-12-07 | 2017-06-13 | 中国科学院大连化学物理研究所 | Sub-micron aoxidizes application of the carbon ball as matrix in MALDI-MS |
| CN107490615A (en) * | 2016-06-13 | 2017-12-19 | 清华大学 | Array chip for MALDI-TOF-MS and preparation method and application |
| CN107655960A (en) * | 2017-09-18 | 2018-02-02 | 亿纳谱（浙江）生物科技有限公司 | Serum mass spectrometric analysis method, matrix based on gold-palladium and preparation method thereof, application |
| CN109932410A (en) * | 2017-12-18 | 2019-06-25 | 中国科学院大连化学物理研究所 | A kind of Mass Spectrometry detection method based on papery target piece |
| CN108847383A (en) * | 2018-05-29 | 2018-11-20 | 昆明理工大学 | A kind of preparation method of porous silicon nanowire array |
| CN110530965A (en) * | 2019-10-08 | 2019-12-03 | 浙江大学 | A kind of method that silicon nanowire array chip detects cell metabolite, lipid |
| CN110954590A (en) * | 2019-11-01 | 2020-04-03 | 杭州汇健科技有限公司 | Saliva sample detection method based on silicon nanowire chip |
Non-Patent Citations (4)
| Title |
|---|
| GAELLE PIRET ET AL.: "Matrix-Free Laser Desorption/Ionization Mass Spectrometry on Silicon Nanowire Arrays Prepared by Chemical Etching of Crystalline Silicon", 《LANGMUIR》 * |
| JINRUI GAN ET AL.: "Designer SiO2@Au nanoshells towards sensitive and selective detection of small molecules in laser desorption ionization mass spectrometry", 《NANOMEDICINE》 * |
| L.COLAIANNI ET AL.: "Laser Desorption Ionization-Mass Spectrometry Detection of Amino Acids and Peptides Promoted by Gold Nanowires", 《SENSORS LETTERS》 * |
| MIN-JUNG KANG ET AL.: "Nanowire-assisted laser desorption and ionization mass spectrometry for quantitative analysis of small molecules", 《RAPID COMMUN. MASS SPECTROM.》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112458539A (en) * | 2020-09-23 | 2021-03-09 | 四川大学 | Porous silicon nanowire and preparation method thereof |
| CN113588769A (en) * | 2021-02-20 | 2021-11-02 | 上海交通大学 | Preparation method of porous alloy nano material and application of porous alloy nano material in detection of plasma metabolites |
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Application publication date: 20200714 |