CN104109187B - A kind of guanidine radicals functionalization graphene material and its preparation method and application - Google Patents
A kind of guanidine radicals functionalization graphene material and its preparation method and application Download PDFInfo
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Abstract
The invention discloses a kind of guanidine radicals functionalization graphene material and its preparation method and application.Chloride graphene is obtained by the way that the carboxyl of surface of graphene oxide is acylated；Then reacted with alkyl diamine, obtain amination graphene；Finally using methoxyl group isourea or its salt as guanidinated reagent, heating response, obtains guanidine radicals functionalization graphene in the basic conditions.By means of the specificity interaction between guanidine radicals and phosphate, guanidine radicals of the invention is grapheme modified can be as SPE materials application in the selective enrichment of Phosphorylated Peptide.
Description
Technical field
The present invention relates to a kind of functionalized carbon nano material, and in particular to a kind of guanidine radicals functionalization graphene material, the material
The preparation method of material and its application in phosphorylation peptide gathering.
Background technology
Protein phosphorylation is the posttranslational modification process played a significant role in life process, to phosphorylated protein and its
The effective detection of obtained Phosphorylated Peptide is digested for studying protein phosphorylation process and its biological significance with very heavy
The value wanted.However, signal inhibitory action that content is few, Mass Spectrometer Method sensitivity is low and high abundance non-phosphorylating peptide is brought etc.
Factor, the direct Mass Spectrometer Method to Phosphorylated Peptide brings very big difficulty.Therefore, by advance separation and enrichment means come
Improving the detection sensitivity of Phosphorylated Peptide is extremely necessary, and is used for the exploitation of the SPE material of enriching phosphated peptide
Also receive more and more attention.
The Phosphorylated Peptide SPE material more commonly used at present includes immobilized metal affinity chromatography (IMAC) material
Material and metal oxide affinity chromatography (MOAC) material.High volence metal ion is passed through the chela that is bonded on material substrate surface by IMAC
Mixture is fixed on material substrate surface, obtains being coordinated undersaturated immobilized metal, and utilize itself and phosphate group
Coordination interaction adsorbs Phosphorylated Peptide, so as to realize the extract and separate to Phosphorylated Peptide and enrichment.But this method is scarce
Point is that selectivity is not high, and the acid peptide fragment of some non-phosphorylatings can also be come out by enrichment simultaneously, and the mass spectrum of Phosphorylated Peptide is examined
Survey is interfered.MOAC then utilizes TiO2、ZrO2Come Deng the Lewis soda acids interaction between metal oxide and Phosphorylated Peptide
Extract and enriching phosphated peptide.But because material is stronger to the absorption affinity of multi-phosphopeptide, cause multi-phosphopeptide to be difficult to from material
Material surface desorption gets off and influences its follow-up Mass Spectrometer Method, thus MOAC methods multi-phosphopeptide enrichment context of detection still
It there are certain defect.
Electrostatic attraction is another noncovalent interaction that can apply to phosphorylation peptide gathering.By positively charged base
Group is modified onto enrichment material substrate surface, it is possible to use the electrostatic attraction between positive charged group and negatively charged phosphate group
Power carrys out extracting and enriching Phosphorylated Peptide.Document (C.K.Chang, C.C.Wu, Y.S.Wang and H.C.Chang.Selective
extraction and enrichment of multiphosphorylated peptides using polyarginine-
Coated diamond nanoparticles.Analytical Chemistry, 2008,80,3791-3797) in report
Preoxidized Nano diamond particle surface is arrived into poly arginine modification, and by means of on guanidine radicals on arginine and Phosphorylated Peptide
The electrostatic attraction of phosphate group, many phosphorus are enriched with using prepared poly arginine modified nano gold hard rock particle as fiber material
It is acidified peptide.But prepare the raw material nano diamond particles needed for the SPE material and poly arginine cost is higher, be unfavorable for
Large-scale application.Meanwhile, this method only has accumulation ability to multi-phosphopeptide, and can not be applied individually to any mono-phosphorylated peptide
It is enriched with while with multi-phosphopeptide.
The content of the invention
It is an object of the invention to provide a kind of Phosphorylated Peptide SPE based on guanidine radicals-phosphate electrostatic interaction
Material and corresponding phosphorylation peptide gathering method, are enriched with and to polyphosphoric acid while realizing to monophosphate peptide and multi-phosphopeptide
Change the selective enrichment of peptide.
To achieve these goals, the present invention takes following technical scheme：
A kind of guanidine radicals functionalization graphene material, it is characterised in that guanidine radicals, guanidine radicals and graphite are modified with graphene-based bottom
The connected chemical constitution in alkenyl bottom is shown below：
Wherein G represents graphene-based bottom, and n is 2~8 integer.
Described guanidine radicals functionalization graphene, its microstructure is the irregular laminated structure of 1~5 μm of diameter, its surface
There is obvious fold.
Described guanidine radicals functionalization graphene, the content when weight/mass percentage composition of its N element is 5%~15%, n=6
For 7%~10%.
The synthetic method of the guanidine radicals functionalization graphene material of the present invention, comprises the following steps：
(1) using graphene oxide as raw material, it will be aoxidized using the acylating reagent such as thionyl chloride or POCl3 or oxalyl chloride
Graphenic surface carboxyl is acylated, and obtains chloride graphene, reaction equation is as follows：
(2) alkyl diamine of the chloride graphene for obtaining step (1) and C2~C8 reacts, and obtains amino graphite
Alkene, reaction equation is as follows；
(3) amination graphene for obtaining step (2) is dispersed in water, and adds methoxyl group isourea or its salt is used as guanidine radicals
Change heating response after reagent, regulation reaction solution pH to 10~12, obtain guanidine radicals functionalization graphene, reaction equation is as follows：
Further, when used acylating reagent is thionyl chloride during above-mentioned steps (1) acylation reaction, it can add
DMF is as the catalyst of acylation reaction, and the volume ratio of thionyl chloride and DMF is 20:1
~40:1, acylation reaction temperature is generally 60~80 DEG C, and the reaction time is 24~48 hours；Tried when using POCl3 to be acylated
During agent, reaction temperature can be 50~80 DEG C, and the reaction time is 24~48 hours；When using oxalyl chloride for acylating reagent, instead
It can be 20~50 DEG C to answer temperature, and the reaction time is 24~48 hours.
It is preferred that, above-mentioned steps (2) ammoxidation is that the alkyl diamine that chloride graphene is put into C2~C8 is molten
Heating response in agent, reaction temperature is 40~65 DEG C, and the reaction time is 24~60 hours.
It is preferred that, the concentration of methoxyl group isourea is 0.25~1.5mol/L in above-mentioned steps (3) guanidinated reaction solution；First
Epoxide isourea salt can be hydrochloride, sulfate, disulfate and/or the acetate of methoxyl group isourea.
It is preferred that, above-mentioned steps (3) by add appropriate sodium hydroxide or potassium hydroxide adjust the pH of reaction solution for 10~
12。
It is preferred that, the temperature of above-mentioned steps (3) guanidinated reaction is 40~70 DEG C, and the reaction time is 24~48 hours.
The guanidine radicals functionalization graphene of the present invention can be as SPE materials application in the SPE of Phosphorylated Peptide.
Thus, the invention provides a kind of solid phase extraction method of Phosphorylated Peptide, in the acetonitrile-water buffer solution containing acetic acid
(preferably, acetate concentration is 0.05~0.2mol/L, the volumn concentration of acetonitrile for 40%~80%) in, use the guanidine
Base functionalization graphene being capable of the mono-phosphorylated peptide of Sync enrichment and multi-phosphopeptide；Or, it is slow in the acetonitrile-water containing trifluoroacetic acid
Fliud flushing (preferably, trifluoroacetic acid volumn concentration is 0.015%~0.2%, the volumn concentration of acetonitrile for 40%~
80%) in, multi-phosphopeptide can be optionally enriched with using the guanidine radicals functionalization graphene.
After enrichment is completed, the Phosphorylated Peptide that material surface is adsorbed can not be eluted, and will directly be adsorbed with phosphorus
The material of acidifying peptide is scattered in matrix solution, is analyzed using substance assistant laser desorpted ionization massspectrum.
The present invention is interacted by means of the specificity between guanidine radicals and phosphate, and guanidine radicals modification is arrived into graphene-based bottom table
Face, and by the grapheme modified selective enrichment applied to Phosphorylated Peptide of the guanidine radicals of gained.Used graphene oxide modification
Substrate has that specific surface area is big, surface functional group abundant and is easy to modification, compatible with substance assistant laser desorpted ionization massspectrum
Etc. advantage.Synthesize raw material used in the grapheme modified material of guanidine radicals easily prepared and cheap, thus be suitable for extensive
Synthesis and application.Meanwhile, under different enrichment conditions, the material can be realized to mono-phosphorylated peptide and multi-phosphopeptide
Sync enrichment or the selective enrichment to multi-phosphopeptide, thus different Phosphorylated Peptide analysis requirements can be met.
Brief description of the drawings
Fig. 1 is the FTIR technique figure of the guanidine radicals functionalization graphene material prepared by the present invention；
Fig. 2 is the transmission electron microscope photo of the guanidine radicals functionalization graphene material prepared by the present invention；
Fig. 3 is mono-phosphorylated peptide and polyphosphoric acid in guanidine radicals functionalization graphene material Sync enrichment skim milk enzymolysis liquid
The mass spectrometry results of peptide；
Fig. 4 is the mass spectrum point that guanidine radicals functionalization graphene material selectivity is enriched with multi-phosphopeptide in skim milk enzymolysis liquid
Analyse result.
Embodiment
Below in conjunction with the accompanying drawings, by embodiment, it is expanded on further technical scheme, but the protection model of the application
Enclose and do not limited by the actual conditions of these embodiments.
Embodiment 1：
The synthesis of guanidine radicals functionalization graphene material, including acylation, amination, guanidinated three steps, it is specific to prepare
Method is as follows：
(1) 120mg graphene oxides, 30mL thionyl chlorides and 1.5mL N, N- diformazans are added into 100mL round-bottomed flasks
Base formamide, ultrasound makes graphene oxide fully scatter in the solution, and then heating stirring is reacted 24 hours at 70 DEG C.
Reaction system is naturally cooled to room temperature by reaction after terminating, and is centrifuged and is removed reaction solution, and gained precipitation uses dry N, N-
Dimethylformamide washed once；
(2) acylate obtained by step (1) is directly thrown into the hexamethylene diamine of the advance heating and meltings of 30mL, at 55 DEG C
Heating stirring is reacted 48 hours.After reaction terminates, add 25mL ethanol dilute reaction solution and it is naturally cooled to room temperature, centrifuge
The mixed solvent of hexamethylene diamine and ethanol is separated off, after being precipitated successively using water and ethanol washing, is placed in vacuum drying chamber and does
It is dry；
(3) amination graphene into 100mL round-bottomed flasks obtained by addition 50mg steps (2), 3.0781g methoxyl groups
Isourea sulfate and 50mL water.After ultrasound makes amination graphene fully dispersed, the pH of sodium hydrate regulator solution is added to 11,
Then heating stirring is reacted 24 hours at 60 DEG C.Reaction naturally cools to room temperature after terminating, add 1.65mL trifluoroacetic acids whole
Only react, centrifuge and remove reaction solution, successively using water and ethanol washing precipitation, be placed in drying in vacuum drying chamber.
The FTIR technique of prepared guanidine radicals functionalization graphene is as shown in figure 1, transmission electron microscope shines
Piece is as shown in Figure 2.C element weight/mass percentage composition is 70.41% in the material, and the weight/mass percentage composition of H element is 3.99%, N
Element weight/mass percentage composition is 8.60%.
Embodiment 2：
Mono-phosphorylated peptide and multi-phosphopeptide in guanidine radicals functionalization graphene material Sync enrichment skim milk enzymolysis liquid,
It is comprised the following steps that：
After 30 μ L skim milks are mixed with 970 μ L50mmol/L ammonium bicarbonate soln, centrifuged under 14000rpm
25min.Supernatant is taken, 100 DEG C of water-bath 5min make protein denaturation therein, then add the pancreas egg that 30 μ L concentration are 1mg/mL
White enzyme solutions, digest 20 hours in 37 DEG C of water-baths, obtain skim milk enzymolysis liquid.20 μ L skim milk enzymolysis liquids are diluted in 180 μ
In the acetonitrile-water buffer solution (ethane nitrile content is 60% (v/v)) of L acetic acid containing 0.1mol/L, then to the skim milk enzymolysis liquid
The guanidine radicals functionalization graphene material (dispersion liquid concentration 4mg/mL) that 200 μ g are dispersed in water is added in dilution.Rotation mixing
After 30min, centrifuge and remove supernatant, and (ethane nitrile content is 60% with the acetonitrile-water buffer solution of the acetic acid containing 0.1mol/L
(v/v)) detergent 3 times.Finally, the material for being adsorbed with Phosphorylated Peptide is scattered in 5 μ L and contains 47.5% acetonitrile (v/v), 5%
In phosphoric acid (v/v), 30mg/mL2, the matrix solution of 5- dihydroxy-benzoic acids, and ionize-fly using substance assistant laser desorpted
Row time mass spectrum is detected.
Mass spectrogram after skim milk enzymolysis liquid is enriched is as shown in figure 3, existing single phosphorus in the Phosphorylated Peptide being enriched to
Peptide is acidified, also there is multi-phosphopeptide.
Embodiment 3：
Multi-phosphopeptide in guanidine radicals functionalization graphene material selectivity enrichment skim milk enzymolysis liquid, its specific steps
It is as follows：
After 30 μ L skim milks are mixed with 970 μ L50mmol/L ammonium bicarbonate soln, centrifuged under 14000rpm
25min.Supernatant is taken, 100 DEG C of water-bath 5min make protein denaturation therein, then add the pancreas egg that 30 μ L concentration are 1mg/mL
White enzyme solutions, digest 20 hours in 37 DEG C of water-baths, obtain skim milk enzymolysis liquid.20 μ L skim milk enzymolysis liquids are diluted in and contained
In the 180 μ L acetonitrile-waters buffer solutions (ethane nitrile content is 66% (v/v)) of 0.05% trifluoroacetic acid (v/v), then to the degreasing ox
The guanidine radicals functionalization graphene material (dispersion liquid concentration 4mg/mL) that 200 μ g are dispersed in water is added in milk enzymolysis liquid dilution.
Rotation mixing 30min after, centrifuge remove supernatant, and with contain 0.05% trifluoroacetic acid (v/v) acetonitrile-water buffer solution
(ethane nitrile content is 66% (v/v)) detergent 3 times.Finally, the material for being adsorbed with Phosphorylated Peptide is scattered in into 5 μ L to contain
In 47.5% acetonitrile (v/v), 5% phosphoric acid (v/v), 30mg/mL2, the matrix solution of 5- dihydroxy-benzoic acids, and it is auxiliary using matrix
Laser desorption ionization-flight time mass spectrum is helped to be detected.
Mass spectrogram after skim milk enzymolysis liquid is enriched is as shown in figure 3, the Phosphorylated Peptide being enriched to is polyphosphoric acid
Change peptide.
The information for the Phosphorylated Peptide being enriched in Fig. 3 and Fig. 4 is as shown in table 1.
The Phosphorylated Peptide detected in the skim milk enzymolysis liquid of table 1
Note：P represents phosphorylation modification in table, and pS represents phosphorylation serine；O represents oxidative modification, and oM represents to aoxidize first
Methyllanthionine；PyroQ represents pyroglutamyl amine.
Claims (9)
1. a kind of guanidine radicals functionalization graphene material, it is characterised in that guanidine radicals, guanidine radicals and graphene are modified with graphene-based bottom
The connected chemical constitution of substrate is shown below：
Wherein G represents graphene-based bottom, and n is 2~8 integer.
2. guanidine radicals functionalization graphene material according to claim 1, it is characterised in that the quality of N element in the material
Percentage composition is 5%~15%.
3. N members in guanidine radicals functionalization graphene material according to claim 1, it is characterised in that the n=6, the material
The weight/mass percentage composition of element is 7%~10%.
4. the preparation method of any guanidine radicals functionalization graphene material of claims 1 to 3, comprises the following steps：
1) surface of graphene oxide carboxyl is acylated as acylating reagent using thionyl chloride or POCl3 or oxalyl chloride, obtained
Chloride graphene；
G-COOH→G-COCl
2) react the alkyl diamine of chloride graphene and C2~C8, obtain amination graphene；
3) amination graphene is dispersed in water, adds methoxyl group isourea or its salt as guanidinated reagent, adjust reaction solution
Heating response after pH to 10~12, obtains guanidine radicals functionalization graphene；
It is above-mentioned it is various in, G represents graphene-based bottom, and n is 2~8 integer.
5. preparation method according to claim 4, it is characterised in that step 1) using thionyl chloride as acylating reagent, N, N-
Dimethylformamide was catalyst, in 60~80 DEG C of acylation reactions 24~48 hours；Or, using POCl3 as acylating reagent,
In 50~80 DEG C of acylation reactions 24~48 hours；Or, using oxalyl chloride as acylating reagent, in 20~50 DEG C of acylation reactions 24~48
Hour.
6. preparation method according to claim 4, it is characterised in that step 2) chloride graphene is put into C2~C8
Alkyl diamine solvent in be heated to 40~65 DEG C react 24~60 hours.
7. preparation method according to claim 4, it is characterised in that step 3) guanidinated reagent be methoxyl group isourea or
Person is hydrochloride, sulfate, disulfate and/or the acetate of methoxyl group isourea, and the temperature of guanidinated reaction is 40~70 DEG C,
Time is 24~48 hours.
8. any guanidine radicals functionalization graphene material of claims 1 to 3 is used as the purposes of Phosphorylated Peptide SPE material.
9. purposes according to claim 8, it is characterised in that the guanidine radicals functionalization graphene material is placed in containing acetic acid
Acetonitrile-water buffer solution in, mono-phosphorylated peptide and multi-phosphopeptide in Sync enrichment solution；Or, by the guanidine radicals function
Graphite alkene material is placed in the acetonitrile-water buffer solution containing trifluoroacetic acid, optionally the multi-phosphopeptide in enrichment solution.
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| CN108793148B (en) * | 2018-09-13 | 2019-04-09 | 常州恒利宝纳米新材料科技有限公司 | A kind of continuous production device and method of amination graphene |
| CN110433675A (en) * | 2019-06-28 | 2019-11-12 | 浙江工业大学 | A kind of guanidine radicals functional graphene oxide/polysulfone ultrafiltration membrane and preparation method thereof |
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| WO2014088807A1 (en) * | 2012-12-04 | 2014-06-12 | 3M Innovative Properties Company | Guanidine-functionalized particles and methods of making and using |
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| WO2014088807A1 (en) * | 2012-12-04 | 2014-06-12 | 3M Innovative Properties Company | Guanidine-functionalized particles and methods of making and using |
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