CN110215738A - A kind of preparation method of the hydrophilic pre-treatment material of graphene polymer - Google Patents
A kind of preparation method of the hydrophilic pre-treatment material of graphene polymer Download PDFInfo
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Abstract
The invention belongs to analytical chemistry fields, relate more specifically to a kind of preparation method of hydrophilic pre-treatment material of graphene polymer.Specific step is as follows: (1) functional monomer 4- amino -3- diazanyl -5- sulfydryl -1,2, the grapheme material (GO/CS) of 4- triazole (AHMT) and modification chitosan being suspended in solvent, and vibrate 10-70h at room temperature.(2) resulting material is subjected to centrifugation 5min after the reaction was completed, and is rinsed with 5% hydrochloric acid, the material after washing is dried in vacuo to get the hydrophilic pre-treatment material of graphene polymer of the invention.
Description
Technical field
The invention belongs to analytical chemistry fields, more particularly to a kind of preparation of the hydrophilic pre-treatment material of graphene polymer
Method.
Background technique
Protein post-translational modification has complexity and diversity, is the pith of proteomics, more commonly used
Classification has phosphorylation (Phosphorylation), methylation (Methylation), acetylation (Acetylation), ubiquitination
(Ubiquitination), it glycosylates [1] such as (Glycosylation).And the glycosylation of protein is that protein is most important, most
The protein of one of universal posttranslational modification, more than half in human body all has glycosylation modified [2], in various tissues and thin
Glycoprotein in born of the same parents after widely distributed modification, participate in regulating cell grow, identify, sticking, migrating and the folding of protein,
Many physiology courses [3-4] such as transhipment, while generation, development and the glycosylation of protein of a variety of major diseases of the mankind are extremely close
Cut phase is closed.Therefore, the research of glycoproteomics examines disease while providing important information for biology mechanism study
The discovery of disconnected marker and therapeutic targets is also most important [5].However, glycoprotein has microheterogeneity [6], and most of
Glycoprotein be low abundance proteins, during Mass Spectrometer Method be easy covered by other non-glycoprotein.Therefore, to containing not
Glycoprotein with glycan structure carries out high efficiency and highly selective separation and concentration, is the pass for realizing highly sensitive glycoprotein identification
Where key.All multi-methods are had been developed for the separation and concentration of glycoprotein at present, such as the affine method of agglutinin, hydrazine chemical method, hydrophilic
Interaction method, boric acid are affine method, volume exclusion method etc..
Hydrophilic interaction chromatography (HILIC) is using polar stationary phase (such as silica gel, derivative silica gel), organic solvent
(such as acetonitrile)-water is a kind of chromatogram mode of mobile phase, has mobile phase similar with reversed phase liquid chromatography, and compound is washed
De- sequence is similar to normal-phase chromatography.HILIC can effectively retain in reverse-phase chromatography and retain not exclusively or not retain highly polar
Compound, and there is good separating effect, be solve all kinds of highly polar compounds and hydrophilic compounds separation problem can
By means.The flow visualizing that this method uses is relatively easy, and separation condition is mild, applied widely, sample loss is few, energy
It is enough enriched with the glycopeptide of various structures, therefore has obtained quick development [7] in fields such as Pharmaceutical Analysis, Food Sciences.
Graphene (Graphene) material is a kind of monatomic thickness, and the Novel Carbon Nanomaterials of sp2 hydridization are unique
Physicochemical property causes every field scientist and pays close attention to it, shows huge application potential [8-10].The oxidation of its derivative
Graphene (Graphene oxide, GO) is [11] prepared by way of strong oxidizer and strong acid graphite oxide is added, greatly
The oxygen-containing group of amount improves the chemical stability and hydrophily of GO, provides reaction to prepare graphene oxide groundmass composite material
Site [12-14] is the carbon material that a kind of good biocompatibility, large specific surface area, pH tolerance range be wide, surface is easily modified,
Analysis detection, drug delivery, bio-imaging, biosensor, Clinics and Practices of cancer etc. are all widely used.
Chitosan (Chitosan, Cs) is also known as chitosan, is a kind of alkaline polysaccharide cheap and easy to get, in nature
In it is generally existing.Chitosan has the characteristics such as good biocompatibility, hypotoxicity, enzyme degradability, this is attributed in its molecule
The presence [15] of a large amount of amino.Meanwhile because containing a large amount of amino on its macromolecular chain, the polarity of chitosan is larger, can be by
Preparation for hydrophilic separation material.
4- amino -3- diazanyl -5- sulfydryl -1,2,4- triazole (AHMT) have unique triazole ring structure, have certain
Alkalinity easily occurs to protonate and the lotus that becomes positively charged in acid condition, shows electrostatic attraction or repulsive interaction.AHMT is both sexes
Ion, while there is positive charge and center of negative charge, there are preferable hydrophily [16].
This technology is modified using quick, easy, cheap method using graphene oxide as matrix, proposes one kind
Novel graphene polymeric hydrophilic pre-treatment material.The material structure is novel, and active force is clear, has stronger application prospect.
Bibliography
[1] Zhang Fengxue, Wang Xinhua proteomics research and its big to the Guangzhou enlightenment [J] the traditional Chinese medicine of Development of Chinese Medicine
Learn journal, 2004,21 (6): 486-488.
[2]Zhang Y,Jiao J,Yang P,et al.Mass spectrometry-based N-
glycoproteomics for cancer biomarker discovery[J].Clinical Proteomics,11,1
(2014-05-05),2014,11(1):18.
[3]Helenius A,Aebi M.Intracellular functions of N-linked glycans.[J]
.Science,2001,291(5512):2364-9.
[4]Prabhjit K Grewal,Satoshi Uchiyama,David Ditto,et al.The Ashwell
receptor mitigates the lethal coagulopathy of sepsis[J].Naturemedicine,2008,
14(6):648-655.
[5] Shi Zhaomei, Fan Chao, Huang Junjie wait the preparation of graphene oxide immobilization agglutinin and in glycoprotein/glycopeptide
Application [J] chromatography in enrichment, 2015,33 (2): 116-122.
[6] Wang Yali is based on the enrichment of the glycopeptide of functionalized nano material and biological mass spectrometry and new Identification technology new method
[D] Fudan University, 2014.
[7] development overview [J] chemical management of Jin little Qing, Yao Lixin, Xue Kunpeng hydrophilic Interaction Chromatography, 2014 (27):
70-71.
[8]Georgakilas V,Otyepka M,Bourlinos A B,et al.Functionalization of
graphene:covalent and non-covalent approaches,derivatives and applications.
[J].Chemical Reviews,2012,112(11):6156-214.
[9]Hong Y M,Laurent S,Wei C,et al.Graphene:Promises,Facts,
Opportunities,and Challenges in Nanomedicine[J].Chemical Reviews,2013,113(5):
3407.
[10]Allen M J,Tung V C,Kaner R B.Honeycomb carbon:a review of
graphene[J].Chemical Reviews,2010,110(1):132.
[11]Dikin D A,Stankovich S,Zimney E J,et al.Preparation and
characterization of graphene oxidepaper[J].Nature,2007,448(7152):457.
[12]Zhang LN,Deng H H,Lin F L,et al.In situ growth of porous platinum
nanoparticles on graphene oxide for colorimetric detection of cancer cells
[J].Analytical Chemistry,2014,86(5):2711-8.
[13]Qin Y,Li J,KongY,et al.In situ growth of Au nanocrystals on
graphene oxide sheets.[J].Nanoscale,2014,6(3):1281-5.
[14]Kuo T R,Wang D Y,ChiuY C,et al.Layer-by-layer thin film of
reduced graphene oxide and gold nanoparticles as an effective sample plate in
laser-induced desorption/ionization mass spectrometry.[J].Analytica Chimica
Acta,2014,809:97-103.
[15] preparation and its application study [D] the Qingdao University of Science and Technology of Wang Jintao water-solubility chitosan derivative, 2010.
[16] Guo Zhimou, Zhang Xiuli, Xu Qing, Liang Xinmiao hydrophilic Interaction Chromatography stationary phase and its answering in Chinese medicine separation
With [J] chromatography, 2009,27 (05): 675-681.
Summary of the invention
The object of the present invention is to provide a kind of hydrophilic pre-treatment material preparation methods of graphene polymer, and specific steps are such as
Under:
(1) by function monomer 4- amino -3- diazanyl -5- sulfydryl -1,2, the grapheme material of 4- triazole and modification chitosan
It is suspended in solvent, and vibrates 10-70h at room temperature；
(2) after reaction, resulting material is subjected to centrifugation 5min, and is rinsed with 5% hydrochloric acid, product is dry after washing
It is dry to get the hydrophilic pre-treatment material of graphene polymer of the invention.
In one embodiment of the invention, material described in step 1 is the grapheme material for modifying chitosan, is
Laboratory is made by oneself, preparation and the equal reference literature of characterizing method (Analytica Chimica Acta 850 (2014) 49-56), and
Some changes are carried out on this basis；Solvent is 5% hydrochloric acid solution.
In another embodiment of the present invention, 4- amino -3- diazanyl -5- sulfydryl -1,2,4- triazole and modification shell are poly-
The grapheme material of sugar and the weight ratio of solvent are 1:0.01~0.5:20~200.Preferably 1:0.05:100.
In another embodiment of the present invention, the parameter being centrifuged in step (2) is 16000r/min, 5min.
Specific embodiment
It is illustrated the present invention below by further.It should be pointed out that following explanation is only to want to the present invention
Ask the technical solution of protection for example, not to any restrictions of these technical solutions.Protection scope of the present invention is with institute
Subject to the content that attached claims are recorded.
Embodiment 1
(1) weigh 4- amino -3- diazanyl -5- sulfydryl -1,2,4- triazole (AHMT) (100mg) and be dissolved in 5% hydrochloric acid
In (10mL), then the grapheme material (GO/Cs) (5mg) for modifying chitosan is added thereto and is vibrated at room temperature
24h。
(2) 5min is centrifuged in 16000rpm after the reaction was completed and cleaned with 5% hydrochloric acid to remove excessive reactant, vacuum
With spare, obtained material is the hydrophilic pre-treatment material of graphene polymer of the invention for drying.
Embodiment 2
Glycoprotein enrichment selectivity experiment is carried out, using molar ratio as horseradish peroxidase (HRP): bovine serum albumin(BSA)
(BSA) protein mixed solution of=1:10 (being equivalent to HRP 5ug, BSA 75ug) is as investigation object.It is separately added into graphene
The 80%ACN of polymeric hydrophilic pre-treatment material (1.5mg) powder and 200 μ L, vortex 30s.16000rpm is centrifuged 5min, discards
Supernatant.Three pipe vortex 30s simultaneously hatch 1h in shaking table, and 16000rpm is centrifuged 5min, discards supernatant liquid.With the 85% of 200 μ L
ACN/1%TFA is cleaned again.Vortex 5min, shaking table are incubated for 1h, and 16000rpm is centrifuged 5min, discards supernatant liquid.200 μ are taken again
The 70%ACN/1%FA of L is added separately in three pipes, vortex 5min, and shaking table is incubated for 1h, sonic oscillation 5min, 16000rpm centrifugation
5min leaves and takes supernatant, respectively at drying for standby in freeze drier, is characterized with 12%SDS-PAGE gel electrophoresis.
In addition, the present invention also sets following comparative example, it is specific as follows:
Comparative example 1: solvent is 20% hydrochloric acid, other are the same as embodiment 1；
Comparative example 2:4- amino -3- diazanyl -5- sulfydryl -1,2, the grapheme material and solvent of 4- triazole and modification chitosan
Weight ratio be 1:10:100, other are the same as embodiment 1；
Comparative example 3: using the centrifugal condition of 5000r/min revolving speed after the reaction was completed, and centrifugation 5min carries out washing for excess raw material
It washs, other are the same as embodiment 1.
Gray analysis is carried out to the analysis band in obtained gel electrophoresis.
Concrete outcome is as shown in Table 1, the results showed that the obtained HRP enrichment selectivity of the material preparation condition of embodiment 1
It is higher.
Table 1.HRP gray analysis result
The content of present invention merely illustrates claimed some specific embodiments, one of them or more skill
Documented technical characteristic can be combined with arbitrary one or more technical solutions in art scheme, these are combined and obtain
Technical solution also in the application protection scope, the technical solution just as obtained from these are combined is disclosed in the present invention
It is specifically recorded in content the same.
Claims (7)
1. a kind of preparation method of the hydrophilic pre-treatment material of graphene polymer, the specific steps are as follows:
(1) by function monomer 4- amino -3- diazanyl -5- sulfydryl -1,2, the graphene material of 4- triazole (AHMT) and modification chitosan
Material (GO/CS) is suspended in solvent, and vibrates 10-70h at room temperature；
(2) after reaction, resulting material is subjected to centrifugation 5min, and is rinsed with 5% hydrochloric acid, the material after washing is carried out
Vacuum drying is to get the hydrophilic pre-treatment material of graphene polymer of the invention.
2. a kind of preparation method of the hydrophilic pre-treatment material of graphene polymer according to claim 1, which is characterized in that
Solvent is hydrochloric acid solution, concentration of hydrochloric acid solution 1%-50% in step 1.
3. a kind of preparation method of the hydrophilic pre-treatment material of graphene polymer according to claim 2, which is characterized in that
Solvent is hydrochloric acid solution, concentration of hydrochloric acid solution 5% in step 1.
4. a kind of preparation method of the hydrophilic pre-treatment material of graphene polymer according to claim 1, which is characterized in that
Function monomer 4- amino -3- diazanyl -5- sulfydryl -1 in step 1,2, the grapheme material and solvent of 4- triazole and modification chitosan
Weight ratio be 1:0.01~0.5:20~200.
5. a kind of preparation method of the hydrophilic pre-treatment material of graphene polymer according to claim 4, which is characterized in that
4- amino -3- diazanyl -5- sulfydryl -1 in step 1,2, the weight ratio of the grapheme material of 4- triazole and modification chitosan and solvent
For 1:0.05:100.
6. a kind of preparation method of the hydrophilic pre-treatment material of graphene polymer according to claim 1, it is characterised in that
Reaction temperature is room temperature, and the reaction time is 24 hours.
7. a kind of preparation method of the hydrophilic pre-treatment material of graphene polymer according to claim 1, its feature of step 2
It is that the revolving speed being centrifuged is 16000r/min.
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Citations (5)
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| CN104148037A (en) * | 2014-08-08 | 2014-11-19 | 华东理工大学 | Arginine bonded type hydrophilic chromatography stationary phase and preparation method thereof |
| CN105310998A (en) * | 2015-11-03 | 2016-02-10 | 吉林大学 | Microcapsule containing functionalized graphene in capsule wall and preparation method of microcapsule |
| WO2016045032A1 (en) * | 2014-09-25 | 2016-03-31 | 深圳粤网节能技术服务有限公司 | Solid phase extraction column, preparation method therefor, and chemical sample pre-processing method based on solid phase extraction column |
| CN105669827A (en) * | 2014-11-20 | 2016-06-15 | 中国科学院高能物理研究所 | Application of oxidized graphene as protein adsorption medium material and protein separation method |
| CN108927116A (en) * | 2018-07-20 | 2018-12-04 | 大连医科大学 | A kind of preparation method for the stannic oxide/graphene nano material that phenyl boric acid functionalization is chitosan-modified |
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2019
- 2019-07-15 CN CN201910637334.2A patent/CN110215738B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104148037A (en) * | 2014-08-08 | 2014-11-19 | 华东理工大学 | Arginine bonded type hydrophilic chromatography stationary phase and preparation method thereof |
| WO2016045032A1 (en) * | 2014-09-25 | 2016-03-31 | 深圳粤网节能技术服务有限公司 | Solid phase extraction column, preparation method therefor, and chemical sample pre-processing method based on solid phase extraction column |
| CN105669827A (en) * | 2014-11-20 | 2016-06-15 | 中国科学院高能物理研究所 | Application of oxidized graphene as protein adsorption medium material and protein separation method |
| CN105310998A (en) * | 2015-11-03 | 2016-02-10 | 吉林大学 | Microcapsule containing functionalized graphene in capsule wall and preparation method of microcapsule |
| CN108927116A (en) * | 2018-07-20 | 2018-12-04 | 大连医科大学 | A kind of preparation method for the stannic oxide/graphene nano material that phenyl boric acid functionalization is chitosan-modified |
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