CN117066505A - Laser desorption/ionization mass spectrometry method for detecting vitamins - Google Patents
Laser desorption/ionization mass spectrometry method for detecting vitamins Download PDFInfo
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- 229940088594 vitamin Drugs 0.000 title claims abstract description 26
- 229930003231 vitamin Natural products 0.000 title claims abstract description 26
- 235000013343 vitamin Nutrition 0.000 title claims abstract description 26
- 239000011782 vitamin Substances 0.000 title claims abstract description 26
- 238000003795 desorption Methods 0.000 title claims abstract description 21
- 238000000034 method Methods 0.000 title claims abstract description 16
- 238000004949 mass spectrometry Methods 0.000 title claims abstract description 13
- 239000002086 nanomaterial Substances 0.000 claims abstract description 108
- 239000011258 core-shell material Substances 0.000 claims abstract description 72
- OVBPIULPVIDEAO-LBPRGKRZSA-N folic acid Chemical compound C=1N=C2NC(N)=NC(=O)C2=NC=1CNC1=CC=C(C(=O)N[C@@H](CCC(O)=O)C(O)=O)C=C1 OVBPIULPVIDEAO-LBPRGKRZSA-N 0.000 claims abstract description 68
- OVBPIULPVIDEAO-UHFFFAOYSA-N N-Pteroyl-L-glutaminsaeure Natural products C=1N=C2NC(N)=NC(=O)C2=NC=1CNC1=CC=C(C(=O)NC(CCC(O)=O)C(O)=O)C=C1 OVBPIULPVIDEAO-UHFFFAOYSA-N 0.000 claims abstract description 34
- 238000001514 detection method Methods 0.000 claims abstract description 34
- 239000011724 folic acid Substances 0.000 claims abstract description 34
- 229960000304 folic acid Drugs 0.000 claims abstract description 34
- 235000019152 folic acid Nutrition 0.000 claims abstract description 34
- 239000000126 substance Substances 0.000 claims abstract description 29
- JMGZEFIQIZZSBH-UHFFFAOYSA-N Bioquercetin Natural products CC1OC(OCC(O)C2OC(OC3=C(Oc4cc(O)cc(O)c4C3=O)c5ccc(O)c(O)c5)C(O)C2O)C(O)C(O)C1O JMGZEFIQIZZSBH-UHFFFAOYSA-N 0.000 claims abstract description 28
- IVTMALDHFAHOGL-UHFFFAOYSA-N eriodictyol 7-O-rutinoside Natural products OC1C(O)C(O)C(C)OC1OCC1C(O)C(O)C(O)C(OC=2C=C3C(C(C(O)=C(O3)C=3C=C(O)C(O)=CC=3)=O)=C(O)C=2)O1 IVTMALDHFAHOGL-UHFFFAOYSA-N 0.000 claims abstract description 28
- FDRQPMVGJOQVTL-UHFFFAOYSA-N quercetin rutinoside Natural products OC1C(O)C(O)C(CO)OC1OCC1C(O)C(O)C(O)C(OC=2C(C3=C(O)C=C(O)C=C3OC=2C=2C=C(O)C(O)=CC=2)=O)O1 FDRQPMVGJOQVTL-UHFFFAOYSA-N 0.000 claims abstract description 28
- 235000005493 rutin Nutrition 0.000 claims abstract description 28
- ALABRVAAKCSLSC-UHFFFAOYSA-N rutin Natural products CC1OC(OCC2OC(O)C(O)C(O)C2O)C(O)C(O)C1OC3=C(Oc4cc(O)cc(O)c4C3=O)c5ccc(O)c(O)c5 ALABRVAAKCSLSC-UHFFFAOYSA-N 0.000 claims abstract description 28
- 229960004555 rutoside Drugs 0.000 claims abstract description 28
- 238000006243 chemical reaction Methods 0.000 claims abstract description 18
- 238000001819 mass spectrum Methods 0.000 claims abstract description 18
- 150000003722 vitamin derivatives Chemical class 0.000 claims abstract description 14
- 239000000463 material Substances 0.000 claims abstract description 12
- IKGXIBQEEMLURG-BKUODXTLSA-N rutin Chemical compound O[C@H]1[C@H](O)[C@@H](O)[C@H](C)O[C@@H]1OC[C@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](OC=2C(C3=C(O)C=C(O)C=C3OC=2C=2C=C(O)C(O)=CC=2)=O)O1 IKGXIBQEEMLURG-BKUODXTLSA-N 0.000 claims abstract 5
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 69
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 21
- 239000002245 particle Substances 0.000 claims description 15
- 239000011159 matrix material Substances 0.000 claims description 13
- 239000000523 sample Substances 0.000 claims description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 150000002500 ions Chemical class 0.000 claims description 7
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- 238000005070 sampling Methods 0.000 claims description 7
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- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 6
- AZMMUMQYPBKXHS-UHFFFAOYSA-N gold sodium Chemical compound [Na].[Au] AZMMUMQYPBKXHS-UHFFFAOYSA-N 0.000 claims description 6
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 5
- 238000000752 ionisation method Methods 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000012488 sample solution Substances 0.000 claims description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims description 3
- 230000009467 reduction Effects 0.000 claims description 3
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- IKGXIBQEEMLURG-NVPNHPEKSA-N rutin Chemical compound O[C@@H]1[C@H](O)[C@@H](O)[C@H](C)O[C@H]1OC[C@@H]1[C@@H](O)[C@H](O)[C@@H](O)[C@H](OC=2C(C3=C(O)C=C(O)C=C3OC=2C=2C=C(O)C(O)=CC=2)=O)O1 IKGXIBQEEMLURG-NVPNHPEKSA-N 0.000 description 23
- 239000010931 gold Substances 0.000 description 19
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- 238000004458 analytical method Methods 0.000 description 10
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- 238000012512 characterization method Methods 0.000 description 6
- 238000002425 crystallisation Methods 0.000 description 6
- 230000008025 crystallization Effects 0.000 description 6
- NZNMSOFKMUBTKW-UHFFFAOYSA-N Cyclohexanecarboxylic acid Natural products OC(=O)C1CCCCC1 NZNMSOFKMUBTKW-UHFFFAOYSA-N 0.000 description 5
- AFVLVVWMAFSXCK-VMPITWQZSA-N alpha-cyano-4-hydroxycinnamic acid Chemical compound OC(=O)C(\C#N)=C\C1=CC=C(O)C=C1 AFVLVVWMAFSXCK-VMPITWQZSA-N 0.000 description 5
- 238000010586 diagram Methods 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 230000005588 protonation Effects 0.000 description 4
- 239000002243 precursor Substances 0.000 description 3
- WXTMDXOMEHJXQO-UHFFFAOYSA-N 2,5-dihydroxybenzoic acid Chemical compound OC(=O)C1=CC(O)=CC=C1O WXTMDXOMEHJXQO-UHFFFAOYSA-N 0.000 description 2
- 230000006978 adaptation Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
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- 238000006731 degradation reaction Methods 0.000 description 2
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- 239000000377 silicon dioxide Substances 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 238000002198 surface plasmon resonance spectroscopy Methods 0.000 description 2
- AFVLVVWMAFSXCK-UHFFFAOYSA-N α-cyano-4-hydroxycinnamic acid Chemical compound OC(=O)C(C#N)=CC1=CC=C(O)C=C1 AFVLVVWMAFSXCK-UHFFFAOYSA-N 0.000 description 2
- XJGFWWJLMVZSIG-UHFFFAOYSA-N 9-aminoacridine Chemical compound C1=CC=C2C(N)=C(C=CC=C3)C3=NC2=C1 XJGFWWJLMVZSIG-UHFFFAOYSA-N 0.000 description 1
- 206010002065 Anaemia megaloblastic Diseases 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 208000024172 Cardiovascular disease Diseases 0.000 description 1
- 241000282412 Homo Species 0.000 description 1
- 208000002720 Malnutrition Diseases 0.000 description 1
- 208000000682 Megaloblastic Anemia Diseases 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 238000004224 UV/Vis absorption spectrophotometry Methods 0.000 description 1
- 206010000210 abortion Diseases 0.000 description 1
- 231100000176 abortion Toxicity 0.000 description 1
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- 230000003110 anti-inflammatory effect Effects 0.000 description 1
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- 239000003963 antioxidant agent Substances 0.000 description 1
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- 239000007864 aqueous solution Substances 0.000 description 1
- 239000012472 biological sample Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 201000011529 cardiovascular cancer Diseases 0.000 description 1
- 238000002288 cocrystallisation Methods 0.000 description 1
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- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 230000005496 eutectics Effects 0.000 description 1
- 230000001605 fetal effect Effects 0.000 description 1
- 229930182486 flavonoid glycoside Natural products 0.000 description 1
- 150000007955 flavonoid glycosides Chemical class 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
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- 230000001071 malnutrition Effects 0.000 description 1
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- 238000000816 matrix-assisted laser desorption--ionisation Methods 0.000 description 1
- 231100001016 megaloblastic anemia Toxicity 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 230000007102 metabolic function Effects 0.000 description 1
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- 239000002207 metabolite Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
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- 238000002156 mixing Methods 0.000 description 1
- 210000005036 nerve Anatomy 0.000 description 1
- 208000015380 nutritional deficiency disease Diseases 0.000 description 1
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- 239000005017 polysaccharide Substances 0.000 description 1
- 102000004196 processed proteins & peptides Human genes 0.000 description 1
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- 102000004169 proteins and genes Human genes 0.000 description 1
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- 238000010998 test method Methods 0.000 description 1
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- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/18—Non-metallic particles coated with metal
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- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/05—Metallic powder characterised by the size or surface area of the particles
- B22F1/054—Nanosized particles
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- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
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- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y15/00—Nanotechnology for interacting, sensing or actuating, e.g. quantum dots as markers in protein assays or molecular motors
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- 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
- G01N27/64—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 using wave or particle radiation to ionise a gas, e.g. in an ionisation chamber
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Abstract
The invention discloses a laser desorption/ionization mass spectrometry method for detecting vitamin substances. The method is realized by introducing SiO with nano-scale roughness 2 the@Au core-shell nanomaterial is used for laser absorption, light-heat conversion and transmission in a mass spectrum ion source, and remarkably improves high desorption/ionization efficiency and detection sensitivity of vitamin substances such as folic acid, rutin and the like. Presence of m/z for conventional organic matrices<500 spectrum peak background interference and dessert effect, which are unfavorable for small molecule metabolismThe core-shell nano material can be used for high-sensitivity detection of vitamin substances such as folic acid, rutin and the like, so that the background interference of spectrum peaks is greatly reduced, and the preparation of the material is simple. Based on the method, the core-shell nano material is successfully used for rapidly analyzing vitamin samples such as folic acid, rutin and the like, and has wide universality and application prospect.
Description
Technical Field
The invention belongs to the field of analytical chemistry, and in particular relates to an application of SiO 2 An LDI-MS detection method for detecting vitamin substances by taking an Au core-shell nano material as a nano matrix in an auxiliary laser desorption/ionization process.
Background
Vitamins are a class of important trace substances necessary for humans and animals to maintain normal physiological and vital activities and to regulate metabolic functions. Most vitamins are not synthesized by living organisms or have insufficient yield, and are difficult to meet the requirements of organisms, so the vitamins must be obtained from foods frequently. If the vitamin intake is insufficient, the imbalance of metabolism and the immunity of the human body are easily caused, so that the human body is easy to suffer from various diseases and malnutrition. Among them, folic acid is a vitamin essential to the human body, and insufficient intake may lead to abortion in pregnant women, fetal nerve tube deformity, childhood megaloblastic anemia, and increase the risk of cardiovascular diseases and cancers in adults. Rutin is also known as vitamin P, is a natural flavonoid glycoside and has remarkable anti-inflammatory, antioxidant, antiallergic and antiviral effects. However, due to the structural characteristics of the substances, the substances have higher melting point, unstable structure and easy fragmentation after being irradiated by light, lack of protonation sites and the like, so that the substances have lower sensitivity in laser desorption/ionization mass spectrometry (LDI-MS) detection, and limit the detection capability of the LDI-MS in actual vitamin samples.
Although matrix assisted laser desorption/ionization mass spectrometry (MALDI-MS) has become an indispensable technical means for analyzing biological macromolecules such as polysaccharides, polymers, polypeptides, proteins, etc., the use of traditional organic matrices (such as 2, 5-dihydroxybenzoic acid, alpha-cyano-4-hydroxycinnamic acid, 9-aminoacridine, etc.) is very likely to cause background peak interference of the organic matrices below 700Da in the mass spectrum, thereby affecting the detection of small molecule metabolites. Meanwhile, the organic matrix has larger crystal particles and uneven distribution, and the problems of poor spectrogram reproducibility and the like caused by dessert effect are easy to generate. For this reason, some researchers propose to use inorganic nanomaterials instead of conventional organic matrices to overcome the above-mentioned drawbacks, and develop a surface-assisted laser desorption/ionization mass spectrometry (SALDI-MS) method, but a SALDI-MS high-efficiency analysis method suitable for vitamin substances such as folic acid has not been found in practical analysis.
Currently, a series of inorganic nanomaterials having advantages of high specific surface area, excellent light-to-heat conversion efficiency, high electric conductivity, low heat conduction, and the like have attracted extensive research interest, such as carbon nanomaterials (anal.chem., 2010,82,6208-6214;ACS Appl.Nano Mater, 2022,5,2187-2194), silicon nanomaterials (Adv.Funct.Mater., 2019,29,1903609;Adv.Funct.Mater, 2018,28,1801730), metal nanomaterials (anal.chem., 2016,88,8926-8930; j.hazard.mate., 2023,453,131304), metal oxide nanomaterials (J.Hazard.Mater., 2020,388,121817;Adv.Funct.Mater, 2021,31,2106743), metal-organic framework materials (angel.chem.int.ed., 2020,59,10831-10835;ACS Appl.Mater.Interfaces,2019,11,38255-38264), and the like. The above nanomaterials all show superior detection performance in SALDI-MS analysis compared to MALDI matrix, however nanomaterial analysis performance with a single structure or morphology is still not ideal, especially when it is applied in complex biological sample analysis. In addition, because folic acid and rutin substances are specific in structure and lack of protonation sites, a core-shell nanomaterial for high-sensitivity mass spectrometry detection of folic acid and rutin substances is urgently required to be developed, and the application capability of the SALDI-MS technology in actual samples is further expanded.
Disclosure of Invention
The invention aims to overcome the defects of the prior art, and provides a core-shell nano material which can be used for SALDI-MS analysis and is used for mass spectrum detection application of vitamin substances such as folic acid, rutin and the like.
The above object of the present invention is achieved by the following technical scheme:
the invention is realized by optimizing SiO 2 Preparation method of@Au core-shell nanomaterial to prepare SiO 2 @Au core-shell nanoparticles, the core-shell nanomaterial being compared to bare SiO 2 The nanoparticles have a nanoscale roughness. Due to SiO 2 Au nano particles on the outer layer of the@Au core-shell nano material can generate local surface plasmon resonance with 337nm or 355nm laser, so that the light-heat conversion efficiency of the material is remarkably improved, the molecules to be detected can obtain higher desorption and ionization efficiency, and meanwhile, siO (silicon dioxide) is prepared 2 The surface of the@Au core-shell nano material is rich in Na + And K + Can specifically enhance [ M+Na ] of folic acid, rutin and other substances] + And [ M+K ]] + Signal intensity, thus effectively avoiding the problems of uneven crystallization, low protonation efficiency and the like of the traditional organic matrix.
SiO according to the invention 2 the@Au core-shell nanomaterial is prepared by the following steps:
s1, preparing monodisperse SiO with smooth surface 2 Nano material: adding Tetraethoxysilane (TEOS) into the mixed solvent, stirring at room temperature for reacting for a period of time, washing with ethanol, and drying to obtain monodisperse SiO 2 A nanomaterial;
s2, preparing amino-functionalized SiO 2 Nanomaterial (SiO) 2 -NH 2 ): siO obtained in the step S1 is processed 2 Dispersing nano material in ethanol water solution, adding 3-aminopropyl triethoxysilane (APTES), reacting at a certain temperature for a period of time to obtain monodisperse SiO 2 -NH 2 A nanomaterial;
s3, at SiO 2 -NH 2 Preparation of Au nanoshell layer (SiO) on nanomaterial surface 2 @ Au): under a certain pH condition, naOH and HAuCl are added 4 ·3H 2 Adding the O mixture to the SiO which is dispersed by water ultrasonic 2 -NH 2 In the nano material, the suspension is stirred vigorously and heated for reacting for a period of time to obtain SiO 2 Seed of @ Au; si is mixed withO 2 Adding the seed at the temperature of the reaction kettle into a sodium-gold solution, and then adding NaBH with a certain concentration and volume into the solution in each cycle of reduction 4 SiO is prepared 2 @au core-shell nanomaterial.
In step S1, the surface is smooth and monodisperse SiO 2 The nanomaterial may be prepared by reference to existing methods.
Preferably, in step S1, the mixed solvent is composed of absolute ethanol, ammonia water and deionized water according to a volume ratio of 53:2.1:2.33.
Preferably, in step S1, the volume ratio of tetraethoxysilane to mixed solvent is 3:57.43.
Preferably, in step S1, the reaction time is 6 to 8 hours, more preferably 7 hours.
Preferably, in step S1, the monodisperse SiO 2 The particle size of the nanomaterial is 50 to 300nm, more preferably 150nm.
Preferably, in step S2, the aqueous ethanol solution is composed of ethanol and water according to a volume ratio of 3:1.
Preferably, in step S2, the monodisperse SiO 2 The concentration of the particles of the nanomaterial is 5 to 50mg/mL, and more preferably 20mg/mL.
Preferably, in step S2, the volume ratio of the 3-aminopropyl triethoxysilane to the ethanol aqueous solution is (0.1-0.3): (50-70), more preferably 0.2:60.
Preferably, in step S2, the reaction temperature is 85 to 110 ℃, more preferably 95 ℃; the reaction time is 0.2 to 2 hours, more preferably 1 hour.
Preferably, in step S3, the SiO 2 -NH 2 The concentration of the nanomaterial is 20 to 50mg/mL, and more preferably 33.33mg/mL.
Preferably, in step S3, the pH of the reaction system is 6.0 to 8.0, more preferably pH 7.0.
Preferably, in the step S3, the concentration of NaOH in the reaction system is 0.05-0.20M, and HAuCl 4 ·3H 2 The concentration of O is 5 to 7.5M, more preferably HAuCl 4 ·3H 2 The concentration of O was 6.35M.
Preferably, in step S3, the reaction temperature is 60 to 90 ℃, more preferably 75 ℃; the reaction time is 10 to 20 minutes, more preferably 15 minutes.
Preferably, in step S3, the SiO 2 Seed of Au with sodium gold solution (from HAuCl 4 And Na (Na) 2 CO 3 Prepared) in a volume ratio of (0.5-2) 100, more preferably, the SiO 2 The volume ratio of the @ Au seeds to the sodium-gold solution is 1:101.5.
Preferably, in step S3, the NaBH 4 The concentration of (2) is 0.05-0.2M, the volume is 1-2 mL, more preferably, the NaBH 4 Is 0.1M in volume of 1.6mL.
The invention also provides a laser desorption/ionization mass spectrometry method for detecting the vitamin substances, which comprises the following steps:
(1) Preparation of SiO 2 Suspension of Au core-shell nanomaterial and use it as a nanomatrix for assisting the laser desorption/ionization process;
(2) SiO is made of 2 Spotting the@Au nanometer matrix solution and the sample solution to be detected on a metal target plate according to the equal volume ratio, drying, and then placing into an instrument to directly perform laser desorption/ionization mass spectrum detection;
(3) Mass spectrometry detection: and carrying out ablation sampling on the mixed sample residues by adopting laser, and detecting by a mass analyzer to obtain mass spectrum signals of the vitamins in the sample.
Preferably, in step (1), the SiO 2 The particle concentration of the@Au core-shell nanomaterial is 0.05-5 mg/mL, and more preferably 1mg/mL;
preferably, in step (2), the SiO 2 The spotting volumes of the@Au nanomatrix solution and the sample solution to be measured are 0.1-3. Mu.L, and more preferably 1. Mu.L.
Preferably, in the step (3), the mass spectrum detection method is a conventional LDI-MS detection method, the molecular weight range is 100-1000 Da, the laser wavelength is 337nm or 355nm, and the detection mode is positive ions.
Preferably, in the step (3), the mass analyzer may be a quadrupole rod analyzer, an ion trap analyzer, a time-of-flight analyzer, a magnetic field analyzer, a fourier transform analyzer, or the like.
Preferably, the vitamins include, but are not limited to folic acid and rutin.
The invention also provides SiO 2 Application of@Au core-shell nanomaterial as a nanomatrix in laser desorption/ionization mass spectrometry detection of vitamin substances; the SiO is 2 The preparation steps of the @ Au core-shell nanomaterial are as described above. The vitamins include, but are not limited to folic acid and rutin.
Compared with the prior art, the invention has the following beneficial effects:
the invention provides a SiO-based material 2 Mass spectrum method for detecting vitamin substances such as folic acid, rutin and the like by adopting@Au core-shell nano material. The SiO is 2 Compared with bare SiO, the@Au core-shell nanomaterial 2 The nanoparticles have a nanoscale roughness. Due to SiO 2 Au nano particles on the outer layer of the@Au core-shell nano material can generate local surface plasmon resonance with 337nm or 355nm laser, so that the light-heat conversion efficiency of the material is remarkably improved, the molecules to be detected can obtain higher desorption and ionization efficiency, and meanwhile, siO (silicon dioxide) is prepared 2 The surface of the@Au core-shell nano material is rich in Na + And K + Can specifically enhance [ M+Na ] of folic acid, rutin and other substances] + And [ M+K ]] + The signal intensity is adopted, so that the problems of uneven crystallization, low protonation efficiency and the like of the traditional organic matrix are effectively avoided, and a higher spectrogram signal-to-noise ratio and a lower detection limit are obtained. Meanwhile, the SiO of the invention 2 The preparation method of the@Au nano material is simple, does not need complex tissue sample pretreatment, and has wide application prospect.
Drawings
FIG. 1 is a diagram of the SiO of the present invention 2 The @ Au core-shell nanomaterial is used for LDI-MS analysis flow of folic acid and other substances.
FIG. 2 is SiO 2 Nanoparticles and SiO 2 Zeta potential diagram of the @ Au core-shell nanomaterial.
FIG. 3 is SiO 2 Nano material of@Au core-shell and electron microscope characterization result of synthesized precursor material thereof, (A) SiO 2 Nanomaterial, (B) SiO 2 Nano material of seed of Au (C) 1 timeSiO after reduction reaction 2 Nano material of core-shell Au (SiO) 2 SiO after @ Au-1), (D) 2 reduction reactions 2 Nano material of core-shell Au (SiO) 2 SiO after 3 reduction reactions of @ Au-2) and (E) 2 Nano material of core-shell Au (SiO) 2 @ Au-3), scale bar 100nm.
FIG. 4 is SiO 2 Nanomaterial, siO 2 Seed of @ Au, siO 2 @Au-1、SiO 2 @Au-2 and SiO 2 Ultraviolet visible absorption spectrum results of @ Au-3.
FIG. 5 shows the SiO of the present invention in the positive ion mode 2 Mass spectrogram of @ Au core-shell nanomaterial for detecting folic acid and rutin, wherein (A) SiO 2 The concentration ratio of the@Au core-shell nano material to the analyte is 1:1, (B) SiO 2 The concentration ratio of the@Au core-shell nano material to the analyte is 10:1, (C) SiO 2 The ratio of the@Au core-shell nanomaterial to the analyte concentration is 1:10, and the analyte concentration is 1mg/mL.
FIG. 6 is a diagram of the SiO of the present invention 2 The detection limit result of the nano material of the@Au core-shell is that the nano material concentration is 1mg/mL.
FIG. 7 is a diagram of the SiO of the present invention 2 The detection limit result of the nano material of the@Au core-shell is that the concentration of the nano material is 1mg/mL.
FIG. 8 shows (A) CHCA matrix, (B) CHCA matrix and folic acid, (C) SiO 2 Nano material of@Au core-shell and (D) SiO 2 Comparison of crystallization patterns of @ Au core-shell nanomaterial and folic acid.
FIG. 9 is a view of SiO according to the present invention 2 (A) mass spectrogram and (B) signal stability of folic acid in 10 different sampling points by the @ Au core-shell nanomaterial.
FIG. 10 is a view of SiO according to the present invention 2 The @ Au core-shell nanomaterial has stability to (A) mass spectrograms and (B) signals of rutin in 10 different sampling points.
Detailed Description
The invention will be further illustrated with reference to specific examples. It is to be understood that these examples are provided for illustrative purposes only and are not meant to limit the invention. The test methods, which are not specified in the following examples, are generally carried out under conventional conditions, and the instruments involved are commercially available. Percentages and parts are by weight unless otherwise indicated.
Example 1: siO (SiO) 2 Preparation of@Au core-shell nanomaterial
S1, preparing monodisperse SiO with smooth surface 2 Nano material: 3mL of TEOS was added dropwise to a mixed solvent consisting of 53mL of absolute ethanol, 2.1mL of ammonia water and 2.33mL of deionized water, stirred at room temperature for reaction for 7h, washed with ethanol several times and dried at 60℃to obtain monodisperse SiO 2 A nanomaterial.
S2, preparing amino-functionalized SiO 2 Nanomaterial (SiO) 2 -NH 2 ): siO obtained in the step S1 is processed 2 The nanomaterial was dispersed in 60mL aqueous ethanol (3:1, v/v) to monodisperse SiO 2 The particle concentration is 20mg/mL, 200 mu LAPTES solution is added and reacted for 1h at 95 ℃ to prepare the monodisperse SiO 2 -NH 2 A nanomaterial.
S3, at SiO 2 -NH 2 Preparation of Au nanoshell layer (SiO) on nanomaterial surface 2 @ Au): naOH and HAuCl were added at pH 7.0 4 ·3H 2 The O mixture was added to 3mL of SiO with a concentration of 33.33mg/mL dispersed by water ultrasound 2 -NH 2 In the nano material solution, the concentration of NaOH in the reaction system is 0.10M, and HAuCl 4 ·3H 2 The concentration of O in the reaction system is 6.35M, the suspension is stirred vigorously and reacts for 15min at 75 ℃ to obtain SiO 2 Seed of @ Au; 1mL of SiO 2 Seed addition of 1.5mL 25mM HAuCl 4 And 100mL of 0.2mg/mL Na 2 CO 3 To the sodium gold solution prepared, 1.6mL of NaBH having a concentration of 0.1M was then added in each cycle of reduction 4 Solution to obtain SiO 2 @au core-shell nanomaterial.
According to the method, siO after 1 reduction reaction is prepared respectively 2 Nano material of core-shell Au (SiO) 2 @Au-1), siO after 2 reduction reactions 2 Nano material of core-shell Au (SiO) 2 SiO after 3 reduction reactions @ Au-2) 2 Nano material of core-shell Au (SiO) 2 @Au-3)。
Example 2: zeta potential characterization of the product of example 1
FIG. 2 is a representation of SiO 2 Nanoparticles and SiO 2 And (5) Zeta potential characterization results of the@Au core-shell nanomaterial. From the zeta potential results, it can be seen that SiO 2 The zeta potential of the nanoparticle is about-31 mV, and the SiO is enabled along with the continuous coverage of the AuNP core-shell particles 2 Zeta potential of the @ Au core-shell nanomaterial moves in a negative direction, about-36 mV, thus facilitating capture of H in the sample + 、Na + 、K + The plasma positive charge ions are arranged on the surface of the core-shell nano material, so that the ionization efficiency of the LDI ion source is improved, and the [ M+Na ] is formed] + 、[M+K] + And [ M+H ]] + And (3) the sum peak of the ion source is increased.
Example 3: electron microscope characterization of the product of example 1
FIG. 3 is a graph showing SiO 2 An electron microscope characterization diagram of an Au core-shell nano material and a synthesis precursor material thereof. The results show that SiO 2 The particle surface is very smooth, and the particle diameter is about 150nm; with NaBH 4 Continuously adding SiO 2 AuNPs with uniform size are gradually modified on the particle surface, and SiO is generated along with the increase of reduction reaction times 2 The AuNPs density of the particle surface is higher and higher, and stable SiO is formed 2 @au core-shell nanomaterial.
Example 4: characterization of UV-Vis absorption Spectrometry for the product of example 1
FIG. 4 is a graph showing SiO 2 UV-Vis absorption spectrum of Au core-shell nanomaterial and synthetic precursor material thereof. The results show that SiO 2 Nanoparticles and SiO 2 The absorbance of the @ Au-seed nanoparticle is lower at 355nm wavelength (the laser wavelength commonly used in commercial MALDI-MS instruments) and does not produce good photo-thermal conversion efficiency and mass spectrum signal response. Along with SiO 2 The surface of the particles is gradually modified with AuNPs to form SiO 2 When the nano material is coated with Au, the absorption efficiency of the nano material at 355nm wavelength is gradually increased, which is beneficial to the subsequent analysis of substances such as folic acid, rutin and the like by LDI-MS.
Example 5: siO is made of 2 LDI-MS detection of folic acid, rutin and other substances by using@Au core-shell nano material
The inventionThe SiO is explicitly described 2 The LDI-MS analysis flow of the@Au core-shell nanomaterial for folic acid, rutin and other substances can be referred to as figure 1. A mixed sample of the substance to be detected and the nano core-shell material in equal volume ratio is prepared on a mass spectrum target plate and used for the subsequent direct laser desorption/ionization process and mass spectrum detection (fig. 1-1 and fig. 1-2). The laser is adopted to carry out degradation sampling on the mixed sample residues, and the mass spectrum signal intensity of substances such as folic acid or rutin in the sample is obtained through detection of a mass analyzer (figures 1-3), and the method specifically comprises the following steps:
(1) Preparation of SiO with particle concentration of 1mg/mL 2 Suspension of Au core-shell nanomaterial and use it as a nanomatrix for assisting the laser desorption/ionization process;
(2) SiO is made of 2 The mixture of the@Au nanometer matrix solution and the sample solution to be detected is spotted on a metal target plate according to a certain proportion, the spotting volumes of the nanometer core-shell material and the sample to be detected are 1 mu L, and the mixture is dried and then put into an instrument for direct laser desorption/ionization mass spectrum detection;
(3) Detecting according to a conventional LDI-MS detection method, wherein the molecular weight range is 100-1000 Da, the laser wavelength is 337nm or 355nm, and the detection mode is positive ions; and carrying out degradation sampling on the mixed sample residues by adopting laser, and detecting by a mass analyzer to obtain a mass spectrum signal of folic acid/rutin in the sample.
Example 6: different SiO 2 Mass spectrum detection of folic acid, rutin and other substances under the condition of nano material concentration of@Au core-shell
FIG. 5 shows that the analyte concentration was fixed at 1mg/mL, siO 2 When the ratio of the concentration of the@Au core-shell nanomaterial to the concentration of the analyte is (A) 1:1, (B) 10:1 and (C) 1:10, the LDI-MS detection results are compared. The results show that when SiO 2 When the nano material of the@Au core-shell is excessive or equivalent to an analyte, the optimal detection capability of folic acid and rutin substances can be obtained, and the spectrogram signal-to-noise ratio is high. This is because when SiO 2 When the concentration of the@Au core-shell nanomaterial is too low (the analyte is far excessive), laser can be directly radiated to the molecules of the to-be-detected object, and high light-heat conversion efficiency is difficult to obtain.
Example 7: siO (SiO) 2 Nano Au core-shellDetection limit result of folic acid and rutin by material
FIGS. 6-7 illustrate the SiO of the present invention 2 The @ Au core-shell nanomaterial is used for detection limit results of folic acid and rutin substances respectively. The results show that SiO 2 The absolute detection limit of the @ Au core-shell nano-material on folic acid and rutin retinoid substances can reach 50pmol.
Example 8: siO (SiO) 2 Crystallization condition of@Au core-shell nanomaterial
FIG. 8 shows that (A) conventional alpha-cyano-4-hydroxycinnamic acid (CHCA) crystals, CHCA co-crystals after mixing with folic acid material, (C) SiO 2 Crystallization of @ Au core-shell nanomaterial and (D) SiO 2 And comparing the co-crystallization condition of the mixed@Au core-shell nanomaterial and folic acid substances. The results show that the traditional CHCA matrix has larger crystal particles, is not uniformly distributed, is easy to generate a dessert effect and has poor reproducibility. In contrast, siO 2 The nano Au material can provide satisfactory uniformity no matter self-crystallizing or forming eutectic with an analyte, and can ensure that a spectrogram can be acquired at different places to obtain uniform spectrum peak signals.
Example 9: siO (SiO) 2 Nano material of@Au core-shell is used for examining reproducibility between midpoint and point in LDI-MS analysis
FIGS. 9-10 reflect, siO 2 When the@Au core-shell nanomaterial is used for folic acid and rutin mass spectrum analysis, reproducibility among different sample points is examined. The results show that, for folic acid or rutin, siO 2 The SiO is proved by that the Relative Standard Deviation (RSD) of the nano material of the@Au core-shell is lower than 5 percent 2 the@Au core-shell nanomaterial has good reproducibility and crystallization condition in a sampling area, and the reliability and repeatability of the method are further improved.
The foregoing is merely a preferred embodiment of the present invention, and it should be noted that the above-mentioned preferred embodiment should not be construed as limiting the invention, and the scope of the invention should be defined by the appended claims. It will be apparent to those skilled in the art that various modifications and adaptations can be made without departing from the spirit and scope of the invention, and such modifications and adaptations are intended to be comprehended within the scope of the invention.
Claims (10)
1.SiO 2 Application of@Au core-shell nanomaterial as a nanomatrix in laser desorption/ionization mass spectrometry detection of vitamin substances.
2. The use according to claim 1, wherein the vitamins comprise folic acid and rutin.
3. The use according to claim 1, characterized in that the SiO 2 the@Au core-shell nanomaterial is prepared by the following steps:
s1, adding tetraethoxysilane into a mixed solvent, stirring at room temperature for reacting for a period of time, washing with ethanol, and drying to obtain monodisperse SiO 2 A nanomaterial;
s2, siO obtained in the step S1 2 Dispersing nano material in ethanol water solution, adding 3-aminopropyl triethoxy silane, reacting for a period of time at a certain temperature to obtain monodisperse SiO 2 -NH 2 A nanomaterial;
s3, under a certain pH condition, naOH and HAuCl are added 4 ·3H 2 Adding the O mixture to the SiO which is dispersed by water ultrasonic 2 -NH 2 In the nano material, the suspension is stirred vigorously and heated for reacting for a period of time to obtain SiO 2 Seed of @ Au; will be
SiO 2 Adding the seed at the temperature of the reaction kettle into a sodium-gold solution, and then adding NaBH with a certain concentration and volume into the solution in each cycle of reduction 4 SiO is prepared 2 @au core-shell nanomaterial.
4. The use according to claim 3, wherein in step S1, the mixed solvent is composed of absolute ethanol, ammonia water and deionized water in a volume ratio of 53:2.1:2.33; the volume ratio of the tetraethoxysilane to the mixed solvent is 3:57.43;
the reaction time is 6-8 h; the monodisperse SiO 2 The grain size of the nanometer material is 50-300 nm.
5. The use according to claim 3, wherein in step S2, the aqueous ethanol solution is composed of ethanol and water in a volume ratio of 3:1; the monodisperse SiO 2 The concentration of the particles of the nano material is 5-50 mg/mL; the volume ratio of the 3-aminopropyl triethoxy silane to the ethanol water solution is (0.1-0.3) (50-70); the reaction temperature is 85-110 ℃, and the reaction time is 0.2-2 h.
6. The use according to claim 3, wherein in step S3, the SiO 2 -NH 2 The concentration of the nano material is 20-50 mg/mL; the pH of the reaction system is 6.0-8.0, the concentration of NaOH is 0.05-0.20M, and HAuCl 4 ·3H 2 The concentration of O is 5-7.5M; the reaction temperature is 60-90 ℃ and the reaction time is 10-20 min; the SiO is 2 The volume ratio of the @ Au seed to the sodium-gold solution is (0.5-2): 100; the NaBH 4 The concentration of (C) is 0.05-0.2M, and the volume is 1-2 mL.
7. A laser desorption/ionization mass spectrometry method for detecting vitamins, comprising the steps of:
(1) A SiO produced according to claim 3 2 Dispersing the@Au core-shell nanomaterial to obtain a suspension, and using the suspension as a nano matrix for assisting a laser desorption/ionization process;
(2) SiO is made of 2 Spotting the@Au nanometer matrix solution and the sample solution to be detected on a metal target plate according to the equal volume ratio, drying, and then placing into an instrument to directly perform laser desorption/ionization mass spectrum detection;
(3) Mass spectrometry detection: and carrying out ablation sampling on the mixed sample residues by adopting laser, and detecting by a mass analyzer to obtain mass spectrum signals of the vitamins in the sample.
8. The method according to claim 7, wherein in step (1), the SiO 2 The particle concentration of the@Au core-shell nano material is 0.05-5 mg/mL.
9. The method according to claim 7, wherein in step (3), the molecular weight of the mass spectrum detection method is 100-1000 Da, the laser wavelength is 337nm or 355nm, and the detection mode is positive ions.
10. The method of claim 7, wherein the vitamins include folic acid and rutin.
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