CN107308924A - A kind of polyether-ether-ketone capillary electric chromatographic column of poly-dopamine modification and its application - Google Patents

A kind of polyether-ether-ketone capillary electric chromatographic column of poly-dopamine modification and its application Download PDF

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CN107308924A
CN107308924A CN201710438672.4A CN201710438672A CN107308924A CN 107308924 A CN107308924 A CN 107308924A CN 201710438672 A CN201710438672 A CN 201710438672A CN 107308924 A CN107308924 A CN 107308924A
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ether
polyether
ketone
poly
dopamine
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陈子林
周韦
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Wuhan University WHU
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/281Sorbents specially adapted for preparative, analytical or investigative chromatography
    • B01J20/286Phases chemically bonded to a substrate, e.g. to silica or to polymers
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D15/00Separating processes involving the treatment of liquids with solid sorbents; Apparatus therefor
    • B01D15/08Selective adsorption, e.g. chromatography
    • B01D15/26Selective adsorption, e.g. chromatography characterised by the separation mechanism
    • B01D15/38Selective adsorption, e.g. chromatography characterised by the separation mechanism involving specific interaction not covered by one or more of groups B01D15/265 - B01D15/36
    • B01D15/3861Selective adsorption, e.g. chromatography characterised by the separation mechanism involving specific interaction not covered by one or more of groups B01D15/265 - B01D15/36 using an external stimulus
    • B01D15/3885Using electrical or magnetic means
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N33/00Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
    • G01N33/48Biological material, e.g. blood, urine; Haemocytometers
    • G01N33/50Chemical analysis of biological material, e.g. blood, urine; Testing involving biospecific ligand binding methods; Immunological testing
    • G01N33/88Chemical analysis of biological material, e.g. blood, urine; Testing involving biospecific ligand binding methods; Immunological testing involving prostaglandins or their receptors
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2220/00Aspects relating to sorbent materials
    • B01J2220/50Aspects relating to the use of sorbent or filter aid materials
    • B01J2220/52Sorbents specially adapted for preparative chromatography
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2220/00Aspects relating to sorbent materials
    • B01J2220/50Aspects relating to the use of sorbent or filter aid materials
    • B01J2220/54Sorbents specially adapted for analytical or investigative chromatography
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2220/00Aspects relating to sorbent materials
    • B01J2220/80Aspects related to sorbents specially adapted for preparative, analytical or investigative chromatography
    • B01J2220/86Sorbents applied to inner surfaces of columns or capillaries

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Abstract

The invention discloses a kind of polyether-ether-ketone capillary electric chromatographic column of poly-dopamine modification and its application.Its preparation method is as follows:The dopamine solution of pre-oxidation is passed through in polyether-ether-ketone pipe, the surface not only amino with positively charged but also the poly-dopamine coating with electronegative phenolic hydroxyl group is formed, to realize the adjustability of EOF.Modification of the poly-dopamine to inertia polyether-ether-ketone pipe can strengthen the adjustability of its EOF, expand its application in capillary electric chromatogram.Preparation method of the present invention is simple, and the coating uniform of formation is fine and close, and thickness is controllable, without obscission after long-time use.Polyether-ether-ketone capillary port stability and durability are good, Swelling will not occur when being connected with mass spectrum, it is adaptable to several amino acids, the separation and detection of aldehydes matter and plant hormone.

Description

A kind of polyether-ether-ketone capillary electric chromatographic column of poly-dopamine modification and its application
Technical field
The invention belongs to chromatographic technology field, and in particular to a kind of electric color of polyether-ether-ketone capillary of poly-dopamine modification Compose post and preparation method and application.
Background technology
Capillary electrophoresis-laser-induced fluorescence technology is one grown up on the basis of LC-MS-MS New analytical technology, it is combined, and capillary electrophoresis separation efficiency high, analyze speed be fast, sample consumption is few and Mass Spectrometer Method Utensil has the advantages that both high sensitivity and strong structure analytic ability, has become the novel micro for enjoying analytical chemist to pay close attention to Analytical technology.At present, the Fused-silica capillary column of pi parcel with good toughness, optics permeability, heat because pass It is current the features such as leading the silicone hydroxyl of ability and inside stable EOF can be provided and be conducive to the fixation of chromatographic material Most-often used piping material in Capillary Electrophoresis.But it has pi coating in organic solvent and alkaline solution Unstable the problem of, particularly in capillary electrophoresis-laser-induced fluorescence, high temperature, high voltage, the organic solvent of mass spectrum spraying port Under conditions of content is high, the capillary is easily swelled to be acted on aminolysis, and so as to cause the blocking of port, spraying is not Stable a series of problems, such as, impact analysis result sets infringement equipment.( Yamamoto, M.; Ly, R.; Gill, B.; Zhu, Y.; Moran-Mirabal, J.; Britz-McKibbin, P. Anal. Chem. 2016, 88, 10710- 10719)。
Polyetheretherketonematerials materials are because heat endurance is good, and chemical stability is strong, is commonly used for high performance liquid chromatography, gas-chromatography In pipeline Deng instrument, but because optics permeability is poor, EOF ability of regulation and control difference and chemical inertness are unfavorable for by force chromatogram The shortcomings of modification of material, it is rarely used at present in Capillary Electrophoresis.
The content of the invention
To overcome problems of the prior art, it is adjustable that the present invention provides a kind of stable EOF, direction and size The polyether-ether-ketone capillary electric chromatographic column of poly-dopamine modification, capillary electric chromatogram-mass spectrometry separation for many kinds of substance Analysis.
Concrete technical scheme is as follows:
A kind of polyether-ether-ketone capillary electric chromatographic column of poly-dopamine modification, is prepared by the following method and obtains:
1)1 ~ 2 mg/mL dopamine alkaline solution is prepared, the pH of the solution is 8.5 ~ 9, logical oxygen makes its pre-oxidation to brown;
2)By step 1)Dopamine alkaline solution flowing after the pre-oxidation of gained passes through clean polyether-ether-ketone using peristaltic pump Capillary column, the flow velocity of peristaltic pump is 0.01-0.1 mL/h, and the time of poly-dopamine modification is 1 ~ 24 hour, is placed in 60 DEG C of bakings 3 h of drying, are modified polyether-ether-ketone inside pipe wall in case.
The process of the poly-dopamine modification reaction of the present invention is as shown in Figure 1.The present invention is based on the bionical poly-dopamine of extra large freshwater mussel Modification method.Dopamine can be in briny environment(Alkalescent)Under the conditions of occur polymerization ([2] Lee, H.; Dellatore, S.M.; Miller, W.M.;Messersmith, P.B. Science 2007,318,426-430), in the polyethers being immersed Ether ketone capillary inner surface forms one layer of stable structure with catechol and amino, and on the one hand the active group can be Polyether-ether-ketone pipe provides direction and the adjustable EOF of size, can also solve the problem of its chemical inertness is stronger.
The polyether-ether-ketone capillary electric chromatographic column of described poly-dopamine modification is in capillary electrophoresis-laser-induced fluorescence analysis Application.
The polyether-ether-ketone capillary electric chromatographic column of described poly-dopamine modification is analyzed in amino acid, phenols and plant hormone Application in the capillary electrophoresis-laser-induced fluorescence separation analysis of thing.
The polyether-ether-ketone capillary electric chromatographic column of poly-dopamine modification in the present invention, has the following advantages that:
(1)The vitreous silica capillary of conventional pi parcel is replaced using polyether-ether-ketone pipe capillary is used for capillary electricity Swimming-mass spectrometry analysis, can solve pi coating and easily be swelled in organic solvent and easy in the basic conditions Occur the shortcoming of aminolysis, a stable port is provided for the GC-MS.
(2)Polyether-ether-ketone pipe surface is smooth and chemical inertness is high, the method coated using physics and common covalent modification Method is difficult to chromatographic material being coated to its inner surface;The present invention will be poly- more with a large amount of amino and hydroxyl by poly-dopamine method Bar amine layer modifies the inner surface in polyether-ether-ketone pipe, can effectively solve the problem of chemical inertness is strong.
(3)The modification of poly-dopamine layer, can provide stable for polyether-ether-ketone pipe, direction and the adjustable EOF of size, It is conducive to separate the application in analyzing.Using the capillary after the modification, realize to several amino acids, phenols and plant The good separating effect of hormone.
Brief description of the drawings
Fig. 1 is the process schematic of poly-dopamine modification reaction in polyether-ether-ketone pipe.
Fig. 2 is that the polyether-ether-ketone pipe that poly-dopamine is modified is used for the schematic diagram that CE-MS is separated.
Fig. 3 is the polyether-ether-ketone capillary electric chromatographic column of poly-dopamine modification prepared by embodiment 1 and unmodified and melting The comparison that quartz capillary EOF changes with pH value.
Fig. 4 is the polyether-ether-ketone capillary electric chromatographic column of poly-dopamine modification prepared by embodiment 1 in positive EOF bar To the separating effect figure of three Plant Hormones under part.
Fig. 5 is the polyether-ether-ketone capillary electric chromatographic column of poly-dopamine modification prepared by embodiment 1 in reverse EOF bar To the separating effect figure of three kinds of amino acid under part.
Fig. 6 is the polyether-ether-ketone pipe capillary electric chromatogram of poly-dopamine modification prepared by embodiment 1 in positive EOF bar To the separating effect figure of two kinds of aldehydes matters under part.
Embodiment
By combination accompanying drawing described further below it will be further appreciated that the features and advantages of the invention.The implementation provided Example is only the explanation to the inventive method, without limiting remaining content that the present invention is disclosed in any way.
【Embodiment 1】
1)The mg of dopamine 10 is weighed, is dissolved in 10 mmol/L Tris-HCl buffer solutions, pH to 8.5 is adjusted, solution is shaken, To solution in palm fibre.
2)With the mL/min of flow velocity 0.03 by step 1)The solution of gained passes through 50 clean cm(360 μm of external diameter, internal diameter 50 μm)Polyether-ether-ketone pipe, modifies 3 h at room temperature, and water washing, nitrogen blows away solvent, is placed in 60 DEG C of h of drying in oven 3, obtains The polyether-ether-ketone capillary electric chromatographic column of poly-dopamine modification.
As shown in Fig. 2 the polyether-ether-ketone capillary electric chromatographic column that poly-dopamine made from embodiment 1 is modified is connected to capillary Electrophoresis tube-mass spectrum(Using coaxial threeway sheath stream interface)In device, capillary electric chromatogram-mass spectrometry analysis, progressive is realized It can test, it is as follows:
The polyether-ether-ketone capillary electric chromatographic column and unmodified and vitreous silica capillary of poly-dopamine modification prepared by embodiment 1 The result that pipe EOF changes with pH value is compared, and its result is as shown in figure 3, the polyether-ether-ketone hair modified without poly-dopamine The EOF of forward direction is presented in tubule in the range of pH=3-9, all, and in pH=7-9, change of the EOF little with pH value And change, show weaker EOF adjustability.And after poly-dopamine modification, the pipeline is in pH<When 5, EOF is in Reversely, as pH >=5, EOF is constantly raised in forward direction, and EOF with the rise of pH value.Gather compared to unmodified Ether ether ketone pipe and conventional vitreous silica capillary, all show stronger EOF adjustability.
In separation and detection that the device is used for various plants hormone, amino acid and aldehydes matter.As shown in figure 4, Buffer solution is 5 mM ammonium acetate aqueous solutions(pH=7), voltage is added under conditions of+15 kV, to realize in positive EOF bar To the baseline separation of three Plant Hormones under part, managed compared to unmodified PEEK, separating effect lifting is obvious.Such as Fig. 5 institutes Show, be 20 Mm ammonium acetate aqueous solutions in buffer solution(pH=3), voltage is added under conditions of -15 kV, to realize in reverse electricity To the baseline separation of three kinds of amino acid under the conditions of seepage flow.As shown in fig. 6 ,+15 kV voltage is being added using the pipeline, between pair In the separation of two kinds of aldehydes matters of benzenediol and metanitrophenol, discovery is being added without acetonitrile(ACN)Under conditions of, resorcinol Due to having certain hydrophobic interaction with poly-dopamine layer, the phenomenon of hangover is generated, in the slow of 20 Mm ammonium acetates (pH=7) The ACN of addition 5% in fliud flushing, conditions of streaking is obviously improved.Continue raising ACN addition, the separation of two kinds of materials can be reduced Degree.Managed compared to unmodified empty PEEK, the PEEK pipes of poly-dopamine modification have the work that improves significantly to separating effect With.
Embodiment 2
1)The mg of dopamine 20 is weighed, is dissolved in 10 mmol/L Tris-HCl buffer solutions, pH to 9 is adjusted, solution is shaken, extremely Solution is in light brown.
2)With the mL/min of flow velocity 0.08 by step 1)The solution of gained passes through 50 clean cm(360 μm of external diameter, internal diameter 50 μm)Polyether-ether-ketone pipe, modifies 24 h at room temperature, and water washing, nitrogen blows away solvent, is placed in 60 DEG C of h of drying in oven 3, obtains Obtain the polyether-ether-ketone capillary electric chromatographic column of poly-dopamine modification.

Claims (3)

1. a kind of polyether-ether-ketone capillary electric chromatographic column of poly-dopamine modification, it is characterised in that be prepared by the following method Arrive:
1)1 ~ 2 mg/mL dopamine alkaline solution is prepared, the pH of the solution is 8.5 ~ 9, logical oxygen makes its pre-oxidation to brown;
2)By step 1)Dopamine alkaline solution flowing after the pre-oxidation of gained passes through clean polyether-ether-ketone using peristaltic pump Capillary column, the flow velocity of peristaltic pump is 0.01-0.1 mL/h, and the time of poly-dopamine modification is 1 ~ 24 hour, is placed in 60 DEG C of bakings 3 h of drying, are modified polyether-ether-ketone inside pipe wall in case.
2. the polyether-ether-ketone capillary electric chromatographic column of poly-dopamine modification according to claim 1 is in Capillary Electrophoresis-matter Compose the application in combination analysis.
3. application according to claim 2, it is characterised in that refer to the polyether-ether-ketone capillary electricity of described poly-dopamine modification Application of the chromatographic column in the capillary electrophoresis-laser-induced fluorescence separation analysis of amino acid, phenols and plant hormone analyte.
CN201710438672.4A 2017-06-12 2017-06-12 A kind of polyether-ether-ketone capillary electric chromatographic column of poly-dopamine modification and its application Pending CN107308924A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115181314A (en) * 2022-07-26 2022-10-14 季华实验室 Method for surface modification of polyether-ether-ketone based on backbone grafting method
CN115216049A (en) * 2022-07-27 2022-10-21 季华实验室 Method for surface modification of polyether-ether-ketone based on grafting to main chain method

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Publication number Priority date Publication date Assignee Title
CN101913278A (en) * 2010-06-30 2010-12-15 中国科学技术大学 Preparation method of polydopamine-g-polyethylene oxide capillary coating for separating protein by capillary electrophoresis
CN103191705A (en) * 2013-04-15 2013-07-10 武汉大学 Preparation method of open tubular capillary electrochromatographic column
CN104359996A (en) * 2014-12-02 2015-02-18 武汉大学 Modified carbon fiber-filled polyether-ether-ketone pipe solid phase microextraction column and preparation method thereof
CN105214340A (en) * 2015-09-14 2016-01-06 武汉长林医药科技有限公司 A kind of method of fixing covalent organic framework material and application thereof
CN106076296A (en) * 2016-05-31 2016-11-09 江西中医药大学 Based on nickel foam adsorbent that poly-dopamine is modified and its preparation method and application

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Publication number Priority date Publication date Assignee Title
CN101913278A (en) * 2010-06-30 2010-12-15 中国科学技术大学 Preparation method of polydopamine-g-polyethylene oxide capillary coating for separating protein by capillary electrophoresis
CN103191705A (en) * 2013-04-15 2013-07-10 武汉大学 Preparation method of open tubular capillary electrochromatographic column
CN104359996A (en) * 2014-12-02 2015-02-18 武汉大学 Modified carbon fiber-filled polyether-ether-ketone pipe solid phase microextraction column and preparation method thereof
CN105214340A (en) * 2015-09-14 2016-01-06 武汉长林医药科技有限公司 A kind of method of fixing covalent organic framework material and application thereof
CN106076296A (en) * 2016-05-31 2016-11-09 江西中医药大学 Based on nickel foam adsorbent that poly-dopamine is modified and its preparation method and application

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115181314A (en) * 2022-07-26 2022-10-14 季华实验室 Method for surface modification of polyether-ether-ketone based on backbone grafting method
CN115181314B (en) * 2022-07-26 2024-05-07 季华实验室 Method for carrying out surface modification on polyether-ether-ketone based on main chain grafting method
CN115216049A (en) * 2022-07-27 2022-10-21 季华实验室 Method for surface modification of polyether-ether-ketone based on grafting to main chain method
CN115216049B (en) * 2022-07-27 2024-05-07 季华实验室 Method for carrying out surface modification on polyether-ether-ketone based on grafting to main chain method

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Application publication date: 20171103