CN102426187A - Graphene matrix and application of graphene matrix in matrix-assisted laser desorption/ionization-time of flight-mass spectrometry detection - Google Patents
Graphene matrix and application of graphene matrix in matrix-assisted laser desorption/ionization-time of flight-mass spectrometry detection Download PDFInfo
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Abstract
The present invention discloses a graphene matrix and an application of the graphene matrix in matrix-assisted laser desorption/ionization-time of flight-mass spectrometry (MALDI-TOF-MS) detection. According to the present invention, in the MALDI-TOF-MS, the graphene is adopted as an assisted matrix, such that the analysis and the detection of the materials including from the small molecule compounds to the biological macromolecules can be efficiently and rapidly achieved; importantly the background interference of the molecular ion peak of the traditional organic matrix can be effectively eliminated so as to achieve the analysis and the detections of amino acids, lipid compounds, peptides, proteins, oligonucleotides, and other structural molecules; the MALDI-TOF-MS adopting the graphene as the matrix is the desorption ionization method, which does not require addition of any organic matrixes, such that the decomposition of the analyte can be avoided, and good reproducibility and high salt tolerance are provided; the efficient and rapid detection method is provided for the natural products and the biological metabolites; the method further can be used for the detection of the common biological macromolecules, and can be popularized and applied in all the MALDI-TOF mass spectrometry so as to achieve the deep application of the graphene.
Description
Technical field
The present invention relates to analyzing and testing, specifically is a kind of Graphene matrix and the application in substance assistant laser desorpted ionized flight time mass spectrum detects thereof.
Background technology
Ground substance assistant laser desorption ionization flight time mass spectrum is a kind of novel soft ionization biological mass spectrometry that development in recent years is got up, and it is in theory or all is very simple with efficiently in design.Instrument mainly is made up of two parts: substance assistant laser desorpted ionized ion gun (MALDI) and time of flight mass analyzer (TOF).The principle of MALDI is with laser radiation sample and substrate formed cocrystallization film; Matrix absorbs energy delivery and gives biomolecule from laser; And in the ionization process proton translocation is obtained proton to biomolecule or from biomolecule, and make the process of biomolecule ionization.Therefore it is a kind of soft ionization technology, is applicable to the mensuration of potpourri and biomacromolecule.The principle of TOF is that ion quickens to fly over dirft tube under electric field action, and the mass-to-charge ratio (M/Z) of promptly measuring ion to be detected was directly proportional with the flight time of ion according to the flight time that arrives detecting device is different, detects ion.That MALDI-TOF-MS has is highly sensitive, accuracy is high and characteristics such as resolution height, for fields such as life science provide a kind of strong analytical test means, and is just playing the part of more and more important effect.
1988, Tanaka and Hillenkamp proposed the MALDI technology separately, and the successful part of this method is in mass spectrum, to have introduced matrix (Matrix).In MALDI-TOF MS; Matrix plays absorption, transmit laser energy, make the decisive role of sample ionsization; And the introducing of auxiliary matrix also solved non-volatile and the desorption ionization problem of biomacromolecule in mass spectrum thermal instability, and it can successfully be detected.At present, the matrix commonly used of selling on the market is α--cyanic acid-4-hydroxycinnamic acid (CHCA), 2,5-dihydroxy-benzoic acid (DHB), sinapic acid (SA), nano silicon film, diamond-like materials and their derivant thereof etc.The existence of matrix is for energy delivery and keep the integrality of molecule and important, but the introducing of matrix causes the existence at matrix peak in the low-molecular-weight zone inevitably, therefore big limitations the application of this method in micromolecule is analyzed.Therefore, the selection of matrix species, the size of concentration, the selection factor of the scale of sample and matrix makes specimen preparation complicated more, is difficult to realize the express-analysis to micromolecular compound.
Xiong Shaoxiang etc. utilize substance assistant laser desorpted ionized flying time mass spectrum analysis de-acetyl chitin catabolite-shitosan, and the factor that matrix, method for making sample etc. is influenced MALDI-TOFMS mensuration result is studied.Experiment finds that with 2,5-dihydroxy-benzoic acid (DHB) is a matrix, and secondary crystallization legal system appearance is analyzed shitosan, has both obtained the molecular weight information of shitosan, can infer the deacetylation of shitosan again; It is matrix that Zhuo Hui admire to wait with dihydroxy-benzoic acid (DHB), uses MALDI-TOF MS technology, adopts the comparison method, studies the rule that under acetonitrile effect HTF cracking becomes various small peptide, tentatively illustrates its splitting mechanism.Under the acetonitrile effect, HTF possibly pass through protein unfolding approach, forms different poly attitude HTF or polypeptide pyrolysis product.Infer that the cause that is used for congenital glycosylation of clinical diagnosis disorderly (CDG) and the low accuracy rate of chronic alcohol abuse (CAA) disease at present possibly be to receive HTF pyrolysis product or polymeric interference; Liu Nian etc. are matrix with sinapic acid (SA), through inquiring into the principal element that influences the mass spectrum imaging experiment, have set up the biological tissue's mass spectrum imaging method of optimizing based on substance assistant laser desorpted ionized flight time mass spectrum.
But as the above, above-mentioned matrix be prone to produce the small molecular ion peak and analysis result (especially to micromolecular compound) is produced disturbs, and for pure sample, and MALDI-FOF MS can analytic sample be low to moderate and flies mole (femtomole, 10
-15) to atropic mole (attomole, 10
-18) sample.But when the actual analysis sample, sample source all is very complicated system such as blood, cytolysis thing, tissue, nutrient solution etc., wherein contains impurity such as amounts of protein, salt, surfactant, antiseptic; In addition; The hydrophobicity of sample itself and soda acid character also greatly influence Ionization Efficiency, thus traditional matrix (matrix, like α--cyanic acid-4-hydroxycinnamic acid (CHCA), 2; 5-dihydroxy-benzoic acid (DHB), sinapic acid (SA)) MALDI-TOF MS be difficult to analyze such complicated sample; Simultaneously the operator is also had very high requirement, and the operator needs the tediously long time remove to grope optimum experimental condition, waste time and energy.Therefore limit this technology to the analysis of low molecular weight compound and to the monitoring of biocatalytic reaction systems such as micromolecule metabolin, be badly in need of development of new matrix.
The application of Graphene matrix in MALDI-TOF MS mass spectrophotometry do not appear in the newspapers as yet.
Summary of the invention
The object of the present invention is to provide Graphene or functionalization graphene matrix.
The technical scheme that realizes the object of the invention is:
A kind of preparation method of Graphene matrix comprises the steps:
(1) graphite (1.5 g, 325 orders) is joined the dense H of 12 ml
2SO
4, 2.5 g K
2S
2O
8With 2.5 g P
2O
5Potpourri in, heat above-mentioned mixed system to 80
oC keeps this temperature, magnetic agitation 5 hours.Cooling reaction system is to room temperature subsequently;
(2) with in the potpourri impouring 500ml deionized water, hold over night;
(3) with the above-mentioned 0.2 micron membrane filtration of thing warp that leaves standstill, washing is also dried naturally, gets pre-oxidation graphite;
(4) graphite with this pre-oxidation joins 0
oThe dense H of C
2SO
4In (120 ml);
(5) slowly add 15 g KMnO subsequently
4, and the control temperature of reaction is 20
oC stirs.Potassium permanganate finishes, and the control reaction system is 35
oC stirred 4 hours, subsequently, added 250 ml deionized waters, and controlled temperature 50 through peripheral ice bath
oBelow the C.Stir after 1.5 hours, add 700 ml deionized waters again, after half an hour, dropwise splash into 20 ml, 30% H
2O
2, reaction system changes pale brown look into by brown rapidly.Remove stirring apparatus;
(6) filter this pale brown potpourri, to remove metallic ion, use 1 L deionized water cyclic washing subsequently again, get brown solid, after the drying at room temperature with HCl 1 L washing in 1: 10;
(7) above-mentioned brown solid is processed aqueous dispersions (0.5% w/w), dialyse continuously a week, filter at last, washing disperseed ultrasonic 1 hour again, filtered 60
oC vacuum drying 24 hours can prepare graphene oxide;
(8) above-mentioned graphene oxide is processed 1 mg/ml dispersion liquid (100 ml), add hydrazine hydrate (1 ml), after ultrasonic 30 minutes again 100
oC refluxed 24 hours, filtered washing, 60
oC vacuum drying 24 hours can prepare graphene nanometer sheet matrix.
The another kind of preparation method of Graphene matrix comprises the steps:
(1) the CNT sample is placed 400 ℃ of calcinings of air 1 hour, place the tubular furnace that is connected with argon hydrogen combination gas then in 900 ℃ of heating 1 hour;
(2) CNT of the first step being handled well joins in the concentrated hydrochloric acid of 12 mol/L and refluxed 4 hours at 100 ℃, refilter and with washed with de-ionized water to neutral, 800 ℃ of oven dry;
(3) alkali metallic sodium is mixed by mass ratio with CNT at 2: 1, handle through the alkali metal fusion method subsequently;
(4) the product filtration is cleaned,, got the graphene nano carrying substrates in 80 ℃ of oven dry.
Except that graphene nanometer sheet and nano belt, described Graphene can also be various Graphene products such as graphene nano particle, graphene nano fiber.
The preparation method of functionalization graphene matrix comprises the steps:
(1) graphene oxide (200 mg) is distributed to 40ml thionyl chloride and 1 ml N, in the blending agent of dinethylformamide, ultrasonic 0.5 hour of room temperature refluxed 52 hours subsequently, prepared brown chloride compounds (219.2 mg)
(2) will be according to the phthalyl shitosan (phthaloyl chitosan, 1.753 g) of literature method preparation, LiCl (1.201 g) and DMAC N,N (DMAC, 120 ml) mixing is under nitrogen protection 140
oC reaction 2 hours, cool off this reaction system after, brown chloride compounds (219.2 mg) and 14 ml pyridines that back is made join in the reaction system, nitrogen protection refluxed 48 hours after the cooling, is filtered washing, vacuum drying;
(3) drying back solid stirred 6 hours in 120 ml distilled water, filtered, and solid retained is scattered in the 200 ml water again, ultrasonic 1 hour, filtered washing.The gained solid is in vacuum 65
oC dry 24 hours down gets intermedium PHCS-GO (205 g);
(4) this intermedium is scattered in the 15 ml hydrazine hydrates 80
oC reaction down removed the phthalyl protection in 16 hours.Filter, washing, vacuum drying must contain shitosan functionalization graphene (175 mg) the nanometer sheet matrix of active amine.
The another kind of preparation method of functionalization graphene nano material comprises the steps:
(1) functionalization graphene (100 mg) with method 1 preparation adds 1.5 ml water.Subsequently, add 10 ml monoethylene glycol, ultrasonic 20 minutes, dropwise add palladium bichloride ethylene glycol solution 10 ml (2.03 mg Pd/ml), regulate the pH value to 5-6, violent ultrasonic 5 minutes of reaction system, stirred overnight subsequently;
(2) subsequently, regulate pH value to 13,140 with the NaOH of 2.5 M
oC reacted 3 hours down, and entire reaction course is all taked nitrogen protection.Behind the cool to room temperature, filter;
(3) water and washing with alcohol are each three times, vacuum 65
oC dry 24 hours down gets functionalization graphene: palladium nano-particles/chitosan-modified Graphene class nanometer sheet matrix.
Described functionalization graphene matrix comprises: the Graphene that functional materials such as biomacromolecule such as functional groups such as hydroxyl, sulfydryl modify, small numerator modified, macromolecule modified, quantum dot, metal nanoparticle modification, modified metal oxide, DNA are modified.
Graphene matrix characterizes:
Detecting used instrument has:
The sign of product size and pattern is at JEM-2010F transmission electron microscope (TEM), carries out on JEOL-2010F high-resolution-ration transmission electric-lens (HRTEM) and the JSM-7401F field emission scanning electron microscope (FESEM), and the WV of Electronic Speculum is 200 kV.X-ray energy spectrum (EDS) and selected diffraction (SAED) experiment are accomplished under the JEOL-2010F high-resolution-ration transmission electric-lens.The powder x-ray diffraction of product (XRD) characterizes and on German Bruker D8-advance X-ray diffractometer, carries out, and X ray is monochromatic CuK α radiant rays (λ=1.5418), from 10 to 70 ° of 2 θ scanning angles, 0.02 ° of step-length.Carry out on Fourier's infrared spectrum (FTIR) experiment FTIR-8201 (PerkinElmer company) infrared spectrometer.IR spectroscopy is tested after through sample and KBr compressing tablet.Raman spectrum is selected the Renishaw microprobe RM1000 of Britain Lei Shaoni company type Raman spectrometer, excitation wavelength 633 nm (He/Ne laser instrument) for use.Atomic force test (Atomic force microscopic, AFM) Nanoscope III MultiMode SPM (digital display) the type scan-probe atomic force microscope of employing U.S. Wei Yike exact instrument company limited.The CE-440 elemental analyser of U.S. EAI company is adopted in ultimate analysis.
Testing result is:
Exemplary functions Graphene material characterization result is following: with palladium nano-particles/graphene composite material is example; Graphene nanometer sheet is individual layer or few range upon range of pattern that adds basically before the load; About 0.80 nm of single-layer graphene bed thickness; The Graphene size is about 1-5 μ m, and the diameter range of Pd nano particle has smaller particle size and reaches than arrowband size distribution (according to transmission electron microscope and ESEM characterization result) between 2-8 nm after the load; Raman spectrum shows that it is at 1331 cm
-1And 1590 cm
-1Have the characteristic Raman peaks, ownership is the D band and the G band of Graphene respectively; X-ray diffractogram (XRD) observes 24.7
o, four Bragg reflection peaks such as 39.6 °, 45.5 ° and 67.3 °, first is corresponding to (002) crystal face of Graphene, back three peaks are (111) of corresponding palladium successively, (200), (220) crystal face; Infrared spectrum shows that this nano material has 1545 cm
-1Characteristic peak can belong to the skeleton vibrations for Graphene.
Another object of the present invention provides Graphene or the functionalization graphene material is applied to substance assistant laser desorpted ionized flight time mass spectrum detection as matrix.
Graphene or the functionalization graphene application process in substance assistant laser desorpted ionized flight time mass spectrum detects comprises the steps:
(1) preparation of instrument and reagent: BIFLEX III type MALDI TOF mass spectrometer; Nitrogen laser, wavelength 337 nm adopt ion to postpone the working method of drawing and reflecting, and positive ion detects; The data of being gathered are utilized Flexcontrol 2.2, DAS FlexAnalysis 2.4, mass spectrum imaging software FlexImaging 1.0, software processes such as variance analysis software ClinProtools 2.0;
(2) preparation graphene film or Graphene coating on carrier, gas dries up subsequent use; Described graphene film is individual layer or layer 2-4, is to be raw material with Graphene or functionalization graphene powder, forms uniform coating through physical method at carrier surface, and thickness is about 100-500 nm; Said Graphene coating also is individual layer or layer 2-4.
(3) carrier is fixed on the MALDI target;
(4) with after sample drop is added to graphene film or coating surface after the solvent dispersion, make sample and substrate formed mixed crystal secondary crystallization, promptly make analytic sample to be measured after the solvent evaporates, carry out laser and resolve the ionization massspectrum analysis.
It is 50-8500Da. (dalton) organic micromolecule compound, biomacromolecule, polymkeric substance, C that described Graphene or functionalization graphene film can be used for molecular weight as matrix
60, some complexs Mass Spectrometer Method, and Graphene is difficult for the analyte analysis, and has good reappearance and high-wearing feature.
Described organic micromolecule compound is 50-1000Da, comprises little peptide nucleotide monomer, amino acid, lipid or saccharide compound.
Described biomacromolecule is 1000-8500Da, comprises many titaniums, protein, oligosaccharides, oligonucleotides etc.
Advantage of the present invention is:
1, speciality property is strong: Graphene (functionalization graphene) film or coating as matrix have unique physics and chemical characteristic, like high rigidity, low-friction coefficient, high-wearing feature, chemical stability, corrosion resistance, thermal conductivity, optical transmission, biocompatibility etc.;
2, adaptability is strong: carrier can be commercialization MALDI target, silicon chip, microslide, glass, sheet metal or high molecule plastic;
3, cost is low, highly versatile: the matrix after the use: graphene film or coating are after organic solvent cleans, regenerates, and be reusable;
4, highly sensitive: as effectively to get rid of the background influence that organic substrate produces, avoid the interference of substrate molecule quasi-molecular ions signal, realized accurate qualitative analysis to micromolecular compound;
5, analyst coverage is wide: can successfully realize high molecular polymer, C such as small molecular weight compounds such as amino acid, nucleotide monomer, polyethers
60, some complexs and even DNA, protein and other highly sensitive detection, sensing range: molecular weight 50-8500 Da. (dalton);
6, reappearance and high-salt tolerance: using mineral carbon alkene is that new mold base can avoid analyte to decompose, and has good reappearance and high-salt tolerance;
7, efficient, quick, easy characteristics: with the MALDI-TOF MS of Graphene (functionalization graphene) as matrix; It is a kind of new desorption ionization method that need not add any organic substrate; For natural products and biological metabolite provides efficiently, detection method fast; Equally also be applicable to the detection of common biomacromolecule, can promotion and application in all MALDI-TOF MS mass spectrums, realized that the profound level of Graphene is used.
Description of drawings
Fig. 1 is for the Graphene being matrix detection spermine (molecular ion peak 203 [M+H]
+, 205 [M+Na]
+), spermidine (molecular ion peak 168 [M+Na]
+) and putrescine (molecular ion peak 111 [M+Na]
+) wait the MALDI-TOF MS spectrogram of mixed amine;
Fig. 2 tries hard to for the atom of the Graphene of microwave assisting method preparation; Substrate: mica sheet, size: 4.0 * 4.0 μ m;
Fig. 3 is the XRD x ray diffraction analysis x: a) Graphene; B) the Pd nano particle functionalization Graphene;
Fig. 4 is the MALDI-TOF MS spectrogram (matrix: Graphene, molecular ion peak: 300.1) of annulene;
Fig. 5 is for the Graphene being the MALDI-TOF MS spectrogram that matrix detects the seizure of chlorobenzene Ullmann reaction intermediate.
Embodiment
Further set forth Graphene matrix or the application of functionalization graphene matrix in substance assistant laser desorpted ionized flight time mass spectrum detects through several typical application embodiment below.
Matrix of Graphene described in the embodiment or functionalization graphene matrix adopt foregoing preparation method to make, and no longer repeat at this.
Embodiment 1: the method that detects mixed amine samples such as spermine spermidine putrescine
(1) instrument and reagent are: BIFLEX III type MALDI TOF mass spectrometer (Bruker company); Nitrogen laser, wavelength 337 nm adopt ion to postpone to draw the working method of (delayed extraction) and reflection (reflectorn), and positive ion detects; The data of being gathered are utilized Flexcontrol 2.2, DAS Flex Analysis 2.4, mass spectrum imaging software Flex Imaging 1.0, software processes such as variance analysis software Clin Protools 2.0;
(2) preparation graphene nanometer sheet coating on carrier, gas dries up subsequent use;
(3) carrier is fixed on the MALDI target;
(4) with N; After mixed amines such as spermine spermidine putrescine after the dinethylformamide solvent disperses (etc. mol ratio) sample solution is added drop-wise to graphene film or coating surface; Make sample and substrate formed mixed crystal secondary crystallization; Promptly make analytic sample to be measured after the solvent evaporates, carry out laser and resolve ionization massspectrum analysis (Fig. 1).
Embodiment 2: the method that detects the annulene sample
(1) instrument and reagent are: BIFLEX III type MALDI TOF mass spectrometer (Bruker company); Nitrogen laser, wavelength 337 nm adopt ion to postpone to draw the working method of (delayed extraction) and reflection (reflectorn), and positive ion detects; The data of being gathered are utilized Flexcontrol 2.2, DAS Flex Analysis 2.4, mass spectrum imaging software Flex Imaging 1.0, software processes such as variance analysis software Clin Protools 2.0;
(2) preparation graphene nanometer sheet coating on carrier, gas dries up subsequent use;
(3) carrier is fixed on the MALDI target;
(4) after the annulene sample solution after xylene solvent is disperseed is added drop-wise to the Graphene coating surface, make sample and substrate formed mixed crystal secondary crystallization, promptly make analytic sample to be measured after the solvent evaporates, carry out laser parsing ionization massspectrum analysis (Fig. 4).
Embodiment 3: the method that detects shark alkene sample
(1) instrument and reagent are: BIFLEX III type MALDI TOF mass spectrometer (Bruker company); Nitrogen laser, wavelength 337 nm adopt ion to postpone to draw the working method of (delayed extraction) and reflection (reflectorn), and positive ion detects; The data of being gathered are utilized Flexcontrol 2.2, DAS Flex Analysis 2.4, mass spectrum imaging software Flex Imaging 1.0, software processes such as variance analysis software Clin Protools 2.0;
(2) preparation graphene nanometer sheet coating on carrier, gas dries up subsequent use;
(3) carrier is fixed on the MALDI target;
(4) with N; After the dinethylformamide solvent disperses back shark alkene sample solution to be added drop-wise to graphene film or coating surface; Make sample and substrate formed mixed crystal secondary crystallization, promptly make analytic sample to be measured after the solvent evaporates, carry out laser and resolve the ionization massspectrum analysis.
Embodiment 4: the method that detects the coptisine sample
(1) instrument and reagent BIFLEX III type MALDI TOF mass spectrometer (Bruker company); Nitrogen laser, wavelength 337 nm adopt ion to postpone to draw the working method of (delayed extraction) and reflection (reflectorn), and positive ion detects.The data of being gathered are utilized Flexcontrol 2.2, DAS Flex Analysis 2.4, mass spectrum imaging software Flex Imaging 1.0, software processes such as variance analysis software Clin Protools 2.0.
(2) preparation graphene nanometer sheet coating on carrier, gas dries up subsequent use;
(3) carrier is fixed on the MALDI target;
(4) with after the coptisine sample solution is added drop-wise to the graphene nanometer sheet coating surface after the tetrahydrofuran solvent dispersion, make sample and substrate formed mixed crystal secondary crystallization, promptly make analytic sample to be measured after the solvent evaporates, carry out laser and resolve the ionization massspectrum analysis.
Embodiment 5: the method that detects methyl methacrylate (PMMMA, polymkeric substance) sample
(1) instrument and reagent BIFLEX III type MALDI TOF mass spectrometer (Bruker company); Nitrogen laser, wavelength 337 nm adopt ion to postpone to draw the working method of (delayed extraction) and reflection (reflectorn), and positive ion detects.The data of being gathered are utilized Flexcontrol 2.2, DAS Flex Analysis 2.4, mass spectrum imaging software Flex Imaging 1.0, software processes such as variance analysis software Clin Protools 2.0.
(2) preparation graphene nanobelt film on carrier, gas dries up subsequent use;
(3) carrier is fixed on the MALDI target;
(4) with 1; Methyl methacrylate (PMMMA after 4-dioxane solvent disperses; Polymkeric substance) after sample solution is added drop-wise to graphene nanobelt film surface; Make sample and substrate formed mixed crystal secondary crystallization, promptly make analytic sample to be measured after the solvent evaporates, carry out laser and resolve the ionization massspectrum analysis.
Embodiment 6: the method that detects little peptide Gly-Val sample
(1) instrument and reagent BIFLEX III type MALDI TOF mass spectrometer (Bruker company); Nitrogen laser, wavelength 337 nm adopt ion to postpone to draw the working method of (delayed extraction) and reflection (reflectorn), and positive ion detects.The data of being gathered are utilized Flexcontrol 2.2, DAS Flex Analysis 2.4, mass spectrum imaging software Flex Imaging 1.0, software processes such as variance analysis software Clin Protools 2.0.
(2) preparation shitosan functionalization graphene nanometer sheet film on carrier, gas dries up subsequent use;
(3) carrier is fixed on the MALDI target;
(4) after the little peptide Gly-Val sample solution after ethyl acetate solvent is disperseed is added drop-wise to shitosan functionalization graphene nanometer sheet film surface; Make sample and substrate formed mixed crystal secondary crystallization; Promptly make analytic sample to be measured after the solvent evaporates, carry out laser and resolve the ionization massspectrum analysis.
Embodiment 7: the method that detects vitamin B1 (Zn complex) sample
(1) instrument and reagent BIFLEX III type MALDI TOF mass spectrometer (Bruker company); Nitrogen laser, wavelength 337 nm adopt ion to postpone to draw the working method of (delayed extraction) and reflection (reflectorn), and positive ion detects.The data of being gathered are utilized Flexcontrol 2.2, DAS Flex Analysis 2.4, mass spectrum imaging software Flex Imaging 1.0, software processes such as variance analysis software Clin Protools 2.0.
(2) on carrier, prepare palladium nano-particles/chitosan-modified graphene nanometer sheet coating, gas dries up subsequent use;
(3) carrier is fixed on the MALDI target;
(4) with N; After the dinethylformamide solvent disperses back vitamin B1 (Zn complex) sample solution to be added drop-wise to the graphene nanometer sheet coating surface of palladium nano-particles/chitosan-modified; Make sample and substrate formed mixed crystal secondary crystallization; Promptly make analytic sample to be measured after the solvent evaporates, carry out laser and resolve the ionization massspectrum analysis.
Embodiment 8: the method that detects the h-Mb sample
(1) instrument and reagent BIFLEX III type MALDI TOF mass spectrometer (Bruker company); Nitrogen laser, wavelength 337 nm adopt ion to postpone to draw the working method of (delayed extraction) and reflection (reflectorn), and positive ion detects.The data of being gathered are utilized Flexcontrol 2.2, DAS Flex Analysis 2.4, mass spectrum imaging software Flex Imaging 1.0, software processes such as variance analysis software Clin Protools 2.0.
(2) preparation graphene nanometer sheet film on carrier, gas dries up subsequent use;
(3) carrier is fixed on the MALDI target;
(4) with after the h-Mb sample solution is added drop-wise to graphene nanometer sheet film surface after the alcohol solvent dispersion, make sample and substrate formed mixed crystal secondary crystallization, promptly make analytic sample to be measured after the solvent evaporates, carry out laser and resolve the ionization massspectrum analysis.
Embodiment 9: the method that detects Bicr6 albumen (tumor markers in the human serum) sample
(1) instrument and reagent BIFLEX III type MALDI TOF mass spectrometer (Bruker company); Nitrogen laser, wavelength 337 nm adopt ion to postpone to draw the working method of (delayed extraction) and reflection (reflectorn), and positive ion detects.The data of being gathered are utilized Flexcontrol 2.2, DAS Flex Analysis 2.4, mass spectrum imaging software Flex Imaging 1.0, software processes such as variance analysis software Clin Protools 2.0.
(2) preparation sulfhydrylation graphene nanometer sheet film on carrier, gas dries up subsequent use;
(3) carrier is fixed on the MALDI target;
(4) with after Bicr6 albumen (tumor markers in the human serum) sample solution is added drop-wise to sulfhydrylation graphene film surface after the alcohol solvent dispersion; Make sample and substrate formed mixed crystal secondary crystallization; Promptly make analytic sample to be measured after the solvent evaporates, carry out laser and resolve the ionization massspectrum analysis.
Embodiment 10: detect DNA (sequence: the method for sample ACCCGTTAG CGG CGG TCG TCG AATC CGGG ATCG TG TCGAGGG AAGAAG ACACGATCGC)
(1) instrument and reagent BIFLEX III type MALDI TOF mass spectrometer (Bruker company); Nitrogen laser, wavelength 337 nm adopt ion to postpone to draw the working method of (delayed extraction) and reflection (reflectorn), and positive ion detects.The data of being gathered are utilized Flexcontrol 2.2, DAS Flex Analysis 2.4, mass spectrum imaging software Flex Imaging 1.0, software processes such as variance analysis software Clin Protools 2.0.
(2) preparation graphene nanometer sheet film on carrier, gas dries up subsequent use;
(3) carrier is fixed on the MALDI target;
(4) the normal hexane solvent is disperseed back DNA (sequence: after ACCCGTTAG CGG CGG TCG TCG AATC CGGG ATCG TG TCGAGGG AAGAAG ACACGATCGC) sample solution is added drop-wise to graphene nanometer sheet film surface; Make sample and substrate formed mixed crystal secondary crystallization; Promptly make analytic sample to be measured after the solvent evaporates, carry out laser and resolve the ionization massspectrum analysis.
Embodiment 11: the method that detects the Ullmann reaction intermediate
(1) instrument and reagent BIFLEX III type MALDI TOF mass spectrometer (Bruker company); Nitrogen laser, wavelength 337 nm adopt ion to postpone to draw the working method of (delayed extraction) and reflection (reflectorn), and positive ion detects.The data of being gathered are utilized Flexcontrol 2.2, DAS Flex Analysis 2.4, mass spectrum imaging software Flex Imaging 1.0, software processes such as variance analysis software Clin Protools 2.0.
(2) on carrier, prepare palladium nano-particles/chitosan-modified graphene nanometer sheet coating, gas dries up subsequent use;
(3) carrier is fixed on the MALDI target;
(4) with chlorobenzene solvent (reactant that also reacts simultaneously, 0.5 ml) and zinc powder (0.01 g, reductive agent) and acidic ion liquid [bmim (HSO as Ullmann
3C
4)] [HSO
4] (0.25 ml) mixing; And after being added drop-wise to graphene nanobelt film surface gradually; The graphene nanometer sheet of palladium nano-particles/chitosan-modified is except that as the matrix; Also can be used as the Ullmann catalysts, along with the dropping of biased sample, part Ullmann reaction product can device to be detected be captured and is carried out laser and resolve ionization massspectrum analysis (Fig. 5).
Claims (10)
1. the application of Graphene matrix in substance assistant laser desorpted ionized flight time mass spectrum detects is characterized in that: comprise the steps:
(1) preparation of instrument and reagent: BIFLEX III type MALDI TOF mass spectrometer; Nitrogen laser, wavelength 337 nm adopt ion to postpone the working method of drawing and reflecting, and positive ion detects; The data of being gathered are utilized Flexcontrol 2.2, DAS Flex Analysis 2.4, mass spectrum imaging software Flex Imaging 1.0, software processes such as variance analysis software Clin Protools 2.0;
(2) preparation graphene film or coating on carrier, gas dries up subsequent use;
(3) carrier is fixed on the MALDI target;
(4) with after sample drop is added to Graphene or functionalization graphene film or coating surface after the solvent dispersion, make sample and substrate formed mixed crystal secondary crystallization, promptly make analytic sample to be measured after the solvent evaporates, carry out laser and resolve the ionization massspectrum analysis.
2. application according to claim 1 is characterized in that: said Graphene matrix adopts the preparation method who comprises the steps to make:
(1) graphite (1.5 g, 325 orders) is joined the dense H of 12 ml
2SO
4, 2.5 g K
2S
2O
8With 2.5 g P
2O
5Potpourri in, heat above-mentioned mixed system to 80
oC keeps this temperature, magnetic agitation 5 hours, and cooling reaction system is to room temperature subsequently;
(2) with in the potpourri impouring 500ml deionized water, hold over night;
(3) with the above-mentioned 0.2 micron membrane filtration of thing warp that leaves standstill, washing is also dried naturally, gets pre-oxidation graphite;
(4) graphite with this pre-oxidation joins 0
oThe dense H of C
2SO
4In (120 ml);
(5) slowly add 15 g KMnO subsequently
4, and the control temperature of reaction is 20
oC stirs, and potassium permanganate finishes, and the control reaction system is 35
oC stirred 4 hours, subsequently, added 250 ml deionized waters, and controlled temperature 50 through peripheral ice bath
oBelow the C, stir after 1.5 hours, add 700 ml deionized waters again, after half an hour, dropwise splash into 20 ml, 30% H
2O
2, reaction system changes pale brown look into by brown rapidly, removes stirring apparatus;
(6) filter this pale brown potpourri, use 1 L deionized water cyclic washing subsequently again to remove metallic ion, get brown solid, after the drying at room temperature with 1: 10 HCl (1 L) washing;
(7) above-mentioned brown solid is processed aqueous dispersions (0.5% w/w), dialyse continuously a week, filter at last, washing disperseed ultrasonic 1 hour again, filtered 60
oC vacuum drying 24 hours can prepare graphene oxide;
(8) above-mentioned graphene oxide is processed 1 mg/ml dispersion liquid (100 ml), add hydrazine hydrate (1 ml), after ultrasonic 30 minutes again 100
oC refluxed 24 hours, filtered washing, 60
oC vacuum drying 24 hours can prepare graphene nanometer sheet.
3. application according to claim 1 is characterized in that: said Graphene matrix adopts the preparation method who comprises the steps to make:
(1) the CNT sample is placed 400 ℃ of calcinings of air 1 hour, place the tubular furnace that is connected with argon hydrogen combination gas then in 900 ℃ of heating 1 hour;
(2) CNT of the first step being handled well joins in the concentrated hydrochloric acid of 12 mol/L and refluxed 4 hours at 100 ℃, refilter and with washed with de-ionized water to neutral, 800 ℃ of oven dry;
(3) alkali metallic sodium is mixed by mass ratio with CNT at 2: 1, handle through the alkali metal fusion method subsequently; (4) the product filtration is cleaned,, got the graphene nano carrying substrates in 80 ℃ of oven dry.
4. according to claim 1 or 2 or 3 described Graphene matrix, it is characterized in that: described Graphene is graphene nanometer sheet, graphene nanobelt or graphene nano fiber.
5. the application of functionalization graphene matrix in substance assistant laser desorpted ionized flight time mass spectrum detects is characterized in that: comprise the steps:
(1) instrument and reagent: BIFLEX III type MALDI TOF mass spectrometer; Nitrogen laser, wavelength 337 nm adopt ion to postpone the working method of drawing and reflecting, and positive ion detects; The data of being gathered are utilized Flexcontrol 2.2, DAS Flex Analysis 2.4, mass spectrum imaging software Flex Imaging 1.0, software processes such as variance analysis software Clin Protools 2.0;
(2) preparation graphene film or coating on carrier, gas dries up subsequent use;
(3) carrier is fixed on the MALDI target;
(4) with after sample drop is added to Graphene or functionalization graphene film or coating surface after the solvent dispersion, make sample and substrate formed mixed crystal secondary crystallization, promptly make analytic sample to be measured after the solvent evaporates, carry out laser and resolve the ionization massspectrum analysis.
6. application according to claim 5 is characterized in that: said functionalization graphene matrix adopts the preparation method who comprises the steps to make:
(1) graphene oxide (200 mg) is distributed to 40ml thionyl chloride and 1 ml N, in the blending agent of dinethylformamide, ultrasonic 0.5 hour of room temperature refluxed 52 hours subsequently, prepared brown chloride compounds (219.2 mg)
(2) will be according to the phthalyl shitosan (phthaloyl chitosan, 1.753 g) of literature method preparation, LiCl (1.201 g) and DMAC N,N (DMAC, 120 ml) mixing is under nitrogen protection 140
oC reaction 2 hours, cool off this reaction system after, brown chloride compounds (219.2 mg) and 14 ml pyridines that back is made join in the reaction system, nitrogen protection refluxed 48 hours after the cooling, is filtered washing, vacuum drying;
(3) drying back solid stirred 6 hours in 120 ml distilled water, filtered, and solid retained is scattered in the 200 ml water again, and ultrasonic 1 hour, filter, washing, the gained solid is in vacuum 65
oC dry 24 hours down gets intermedium PHCS-GO (205 g);
(4) this intermedium is scattered in the 15 ml hydrazine hydrates 80
oC reaction down removed the phthalyl protection in 16 hours, filters, and washing, vacuum drying must contain shitosan functionalization graphene (175 mg) the nanometer sheet matrix of active amine.
7. application according to claim 5 is characterized in that: said functionalization graphene matrix adopts the preparation method who comprises the steps to make:
(1) functionalization graphene (100 mg) with method 1 preparation adds 1.5 ml water, subsequently, adds 10 ml monoethylene glycol; Ultrasonic 20 minutes, dropwise add palladium bichloride ethylene glycol solution 10 ml (2.03 mg Pd/ml), regulate the pH value to 5-6; Violent ultrasonic 5 minutes of reaction system, stirred overnight subsequently;
(2) subsequently, regulate pH value to 13,140 with the NaOH of 2.5 M
oC reacted 3 hours down, and entire reaction course is all taked nitrogen protection, behind the cool to room temperature, filtered;
(3) water and washing with alcohol are each three times, vacuum 65
oC dry 24 hours down gets functionalization graphene: palladium nano-particles/chitosan-modified Graphene class nanometer sheet matrix.
8. according to the described application of one of claim 1-7; It is characterized in that: described graphene film is individual layer or layer 2-4; Be to be raw material with Graphene or functionalization graphene powder, form uniform coating through physical method at carrier surface, thickness is about 100-500 nm.
9. according to the described application of one of claim 1-7, it is characterized in that: Graphene or functionalization graphene film are used for molecular weight 50-8500 Da. organic micromolecule compound, biomacromolecule, polymkeric substance, C as matrix
60Or the laser desorption ionization mass spectra of some complexs detects.
10. application according to claim 9 is characterized in that: described organic micromolecule compound is 50-1000 Da., comprises little peptide, nucleotide monomer, amino acid, lipid or saccharide compound; Described biomacromolecule is 1000-8500 Da., comprises polypeptide, protein, oligosaccharides or oligonucleotides.
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