CN106422415B - A kind of hydrophilic solid phase microextraction integral post of mucopolysaccharide functionalization - Google Patents
A kind of hydrophilic solid phase microextraction integral post of mucopolysaccharide functionalization Download PDFInfo
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- CN106422415B CN106422415B CN201610816758.1A CN201610816758A CN106422415B CN 106422415 B CN106422415 B CN 106422415B CN 201610816758 A CN201610816758 A CN 201610816758A CN 106422415 B CN106422415 B CN 106422415B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D15/00—Separating processes involving the treatment of liquids with solid sorbents; Apparatus therefor
- B01D15/08—Selective adsorption, e.g. chromatography
- B01D15/10—Selective adsorption, e.g. chromatography characterised by constructional or operational features
- B01D15/22—Selective adsorption, e.g. chromatography characterised by constructional or operational features relating to the construction of the column
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Abstract
It is that dehydrated in situ polycondensation is made under catalyst solution effect by mucopolysaccharide, the matrix monomer solution with amide groups, the matrix monomer solution with aldehyde radical the invention discloses a kind of hydrophilic solid phase microextraction integral post of mucopolysaccharide functionalization.In the preparation process of integral post, the addition of mucopolysaccharide plays a dual role of overall structure crosslinking and hydrophile function.When carrying out solid phase microextraction using the integral post, when for ethane nitrile content in the range of 40% ~ 95%, which can still embody polarity check object apparent hydrophilic extracting and enriching ability in sample introduction sample solution.Present invention process is simple, it is easily operated, do not need expensive instrument, be easy to spread, and it can realize that the efficiently concentrating extraction of the various polarities compound such as melamine, aminoglycoside antibiotics and highly sensitive detection, applicable analysis object range are wide based on efficient hydrophilic extraction pattern.
Description
Technical field
The invention belongs to integral post preparation fields, and in particular to a kind of hydrophilic solid phase microextraction of mucopolysaccharide functionalization is whole
Column.
Background technology
Integral post is a kind of novel color carrying out in-situ polymerization preparation using organic and inorganic or hybrid inorganic-organic method
Compose stationary phase.It is excellent since it is excellent with permeability, space availability ratio is high, preparation method is easy, back pressure is low, mass transfer velocity is fast etc.
Point is used widely in solid phase microextraction field.In recent years, the particular characteristic that integral post is improved by specific functionization, at
For an important research direction of integral post preparation field.Large biological molecule（Such as protein, polysaccharide, cellulose）Due to having
Unique biological and chemical property, is therefore widely used in the functionalization of integral post.So far, large biological molecule functionalization
The preparation of integral post is mainly coated on matrix integral post surface by large biological molecule or the modes such as chemical bonding are realized.Example
Such as, Lu et al.（Junyu Lu, et al. J. Sep. Sci., 2011, 34, 2329-2336）Using mercaptopropyi front three
Oxysilane prepares monolithic silica column as function monomer, and fixes gold nano grain on its surface；By gold nano grain and
The interaction of amino, realizes bovine serum albumin(BSA) on protein（BSA）Functionalization on monolithic silica column surface.This project
Group（Wang Jiabin etc., chromatography, 2011,29 (12), 1222-1229）N- acryloyl succinimides are used in previous work
（NAS）For matrix monomer, ethylene glycol dimethacrylate（EDMA）For crosslinking agent, in-situ polymerization prepares poly-（NAS-co-
EDMA）Capillary monolithic column, then by chemical bonding by large biological molecule cellulose-three（4- methyl benzoic acid esters）Covalent bond
It closes in integral post, realizes the preparation of cellulose functionalized integral post.In these work, large biological molecule functionalization is whole
The preparation thinking of column mainly carries out secondary function derivative on active matrix integral post surface, thus its preparation process it is complicated,
Preparation time is tediously long, is prepared into that power is relatively low, limits the promotion and application of large biological molecule functionalization entirety column technology.
Mucopolysaccharide is a kind of nitrogenous inhomogenous polysaccharide, repeats to couple by different dissacharide units；One of them at
It is N- acetylaminohexoses to divide, another is then for uronic acid or sugared.Common mucopolysaccharide mainly has：It is chondroitin sulfate, transparent
Matter acid, hyaluronate, heparin, dermatan sulfate, heparitin sulfate and keratan sulfate etc..These polysaccharide are all that straight chain is miscellaneous more
Sugar is the main component for constituting iuntercellular connective tissue, and it is various intracellular to be widely present in mammal.Unique point of mucopolysaccharide
Minor structure makes it show very strong polarity and elecrtonegativity, therefore possesses very strong hydrophilicity, embodies good moisturizing, profit
The effects that cunning, anticoagulation, reducing blood lipid, is used widely in fields such as biological medicine, cosmetics, organizational projects.However, with viscous
Polysaccharide is that functionalization substance preparation integral post has not been reported.
Invention content
The purpose of the present invention is to provide a kind of hydrophilic solid phase microextraction integral posts of mucopolysaccharide functionalization, big for biology
There is complicated secondary variation in molecular function integral post preparation field, can be in acid using the N- acetylaminos on mucopolysaccharide
Or the characteristic of urea aldehyde polycondensation reaction is participated under conditions of base catalysis, by mucopolysaccharide, urea liquid, formalin, catalyst solution
Mixing, prepares mucopolysaccharide functionalization integral post, wherein mucopolysaccharide plays entirety simultaneously by a step original position ureaformaldehyde dehydrating polycondensation
Structure is crosslinked and the double action of hydrophile function.Have benefited from the ultrahydrophilic of the mucopolysaccharide of bonding, the integral post is to polarity
Analysis object embodies apparent hydrophilic extracting and enriching ability.
To achieve the above object, the present invention adopts the following technical scheme that：
A kind of hydrophilic solid phase microextraction integral post of mucopolysaccharide functionalization, is by mucopolysaccharide, with the matrix monomer of amide groups
The dehydrated in situ polycondensation under catalyst solution effect of solution, the matrix monomer solution with aldehyde radical is made；Wherein, mucopolysaccharide plays whole
Body structure is crosslinked and the double action of hydrophile function.
It is the sum of by weight percent 100% meter, mass percent is shared by each component：Mucopolysaccharide 0.1 ~ 1%, band amide groups
Matrix monomer solution 40 ~ 55%, the matrix monomer solution 36 ~ 50% with aldehyde radical, catalyst solution 8 ~ 10%.
Wherein, the mucopolysaccharide includes hyaluronic acid, hyaluronate, chondroitin sulfate, heparin, dermatan sulfate, sulphur
Any one in acids heparin, keratan sulfate；
The matrix monomer solution with amide groups is the aqueous solution of urea, a concentration of 1 g/mL；
The matrix monomer solution with aldehyde radical is the aqueous solution of formaldehyde, and wherein the mass concentration of formaldehyde is 33% ~ 37%；
The catalyst is the aqueous solution of hydrochloric acid, sulfuric acid, phosphoric acid or sodium hydroxide, a concentration of 0.20 mol/L.
The preparation method of the hydrophilic solid phase microextraction integral post of mucopolysaccharide functionalization, includes the following steps：
1）The cleaning of blank pipe：Blank pipe is connected into liquid phase pump, 10 are rinsed under 0.5 mL/min flow velocitys with Chromatographic Pure Methanol
Then min leads to nitrogen, is placed in 60 DEG C of baking oven and dries 10min, for use；
2）Rapid polycondensation in pipe：By mucopolysaccharide and the matrix monomer solution with amide groups, the matrix monomer solution with aldehyde radical,
Catalyst solution uniformly mixes, 1 ~ 2 min of quick sonic oscillation, then mixture is quickly filled in the blank pipe of clean dry, two
End seal closes and is dipped in 10 min of heated at constant temperature in 70 DEG C of water-baths；
3）The flushing of integral post：It waits after the completion of reacting, using water as mobile phase, integral post is rinsed on liquid chromatography pump
1h, to remove in column bed remaining solvent and reaction remaining reagent to get to the hydrophilic solid phase microextraction of mucopolysaccharide functionalization
Integral post.
Blank pipe used is Teflon（PTFE）Pipe or polyether-ether-ketone（PEEK）Pipe.
The remarkable advantage of the present invention is：
1）Natural macromolecular substance（Such as protein, polysaccharide, cellulose etc.）Usually coated by integral post surface
Or the modes such as chemical bonding, realize its functionalization to integral material.The present invention carries acetylamino base using mucopolysaccharide itself
Group, can directly participate in integral post preparation polycondensation reaction, and the use of mucopolysaccharide can also be played in integral post preparation process it is whole
The crosslinked effect of body structure；Further, since mucopolysaccharide itself has strongly hydrophilic, it also gives the superior hydrophilic extraction of integral post
Take performance.Therefore, the addition of mucopolysaccharide plays crosslinking and hydrophilic double action.
2）The preparation of the hydrophilic solid phase microextraction integral post of mucopolysaccharide functionalization of the present invention only needs an one-step polycondensation, and method is easy,
Reaction speed is fast, eliminates the step that cumbersome integral material surface second derives, substantially increases large biological molecule functionalization
The preparation efficiency of integral post, the preparation for large biological molecule functionalization integral post provide a kind of new technology, will be to biological big point
The promotion and application of subfunction integral post bring prodigious help.
3）Usually used quartz capillary is compared, the present invention manages the tubing of column as a whole using PTFE tube or PEEK
Material, both materials have the characteristics that high mechanical strength, flexibility are good, and integral post is made to be not easy when preparing and analyzing detection application
Situations such as fractureing improves the adaptability and ease for use of integral post, extends its service life.
4）It is molten in wide sample when gained mucopolysaccharide functionalization integral post of the invention is applied to hydrophilic solid phase microextraction
Liquid ethane nitrile content range（40-95%）It is interior, apparent hydrophilic extracting and enriching ability can be embodied to polarity check object, it can be real
Efficiently concentrating extraction and the highly sensitive detection of the various polarities compounds such as existing melamine, aminoglycoside antibiotics.
Description of the drawings
Fig. 1 is the hydrophilic solid phase microextraction integral post of functionalization of the Sodium Hyaluronate of percentage containing different quality to melamine
Breakthrough curve；
In figure A be Sodium Hyaluronate mass percent be 0% integral post to the breakthrough curve of 1mg/mL toluene（Characterize body
It is the dead time）, B be Sodium Hyaluronate mass percent be 0% integral post to the breakthrough curves of 1mg/mL melamines, C is
For the integral post that bright matter acid sodium mass percent is 0.3% to the breakthrough curve of 1mg/mL melamines, D is Sodium Hyaluronate quality
For the integral post that percentage is 0.6% to the breakthrough curve of 1mg/mL melamines, E is that Sodium Hyaluronate mass percent is 0.8%
Integral post to the breakthrough curves of 1mg/mL melamines.
Fig. 2 is using the functionalization integral post that Sodium Hyaluronate mass percent is 0.8% as solid phase microextraction medium, structure
It build line In-tube SPME-high performance liquid chromatography in（In-tube SPME-HPLC）Combined system, on-line preconcentration detect milk powder
Melamine is added in sample（MEL）Chromatogram；
A is 20 ng/mL melamines of addition in figure（MEL）Powdered milk sample chromatogram, B is blank powdered milk sample
Chromatogram.
Fig. 3 is using the functionalization integral post that chondroitin sulfate mass percent is 0.8% as solid phase microextraction medium, structure
It build line In-tube SPME-high performance liquid chromatography in（In-tube SPME-HPLC）Combined system, on-line preconcentration detect milk powder
When the melamine added in sample, influence of the ethane nitrile content to melamine rich efficiency in sample solution.
Specific implementation mode
In order to make content of the present invention easily facilitate understanding, With reference to embodiment to of the present invention
Technical solution is described further, but the present invention is not limited only to this.
（1）The PTFE tube that internal diameter is 750 μm is connected into liquid phase pump, with Chromatographic Pure Methanol under the flow velocity of 0.5 mL/min
10 min, the removal remaining organic impurities of PTFE tube inner wall etc. are rinsed, then leads to nitrogen, is placed in 60 DEG C of baking ovens and dries
10min, for use；
（2）Respectively Sodium Hyaluronate or chondroitin sulfate, a concentration of 1 g/mL are weighed by table 1,2 integral post composition and ratios
The hydrochloric acid solution or sulfuric acid solution of urea liquid, the formalin that mass concentration is 35%, a concentration of 0.2 mol/L, uniformly by it
Mixing, 1 ~ 2 min of quick sonic oscillation, then mixture quickly filled in the PTFE tube of clean dry are closed at both ends and be dipped in
Heated at constant temperature 10min in 70 DEG C of water-baths；
（3）The flushing of integral post：It waits after the completion of reacting, using water as mobile phase, it is whole that PTFE tube is rinsed on liquid chromatography pump
Scapus about 1 hour, to remove in column bed remaining solvent to get whole to the corresponding hydrophilic solid phase microextraction of Sodium Hyaluronate functionalization
Scapus or the hydrophilic solid phase microextraction integral post of chondroitin sulfate functionalization.
The hydrophilic solid phase microextraction integral post composition of 1 Sodium Hyaluronate functionalization of table
The hydrophilic solid phase microextraction integral post composition of 2 chondroitin sulfate functionalization of table
Application Example 1
With 1 mg/mL toluene solutions（ACN/H2O=95%/5%, v/v）For mobile phase, micro-injection flow rate pump is 10 μ L/
Min, ultraviolet detection wavelength are 214 nm, and the dead time that breakthrough curve is carried out to the integral post e of preparation tests；And with 1 mg/mL
Melamine solution（ACN/H2O=95%/5%, v/v）For mobile phase, micro-injection flow rate pump is 10 μ L/min, ultraviolet detection wave
A length of 214 nm carries out breakthrough curve experiment respectively to integral post e, f, g, b of preparation.
Fig. 1 is the hydrophilic solid phase microextraction integral post of functionalization of the Sodium Hyaluronate of percentage containing different quality to melamine
Breakthrough curve.As seen from Figure 1, with mucopolysaccharide（Sodium hyaluronate）The increase of content, the break through of melamine
Constantly extend（31min is increased to by 7.5min）, the enriching quantity of corresponding melamine is respectively 2.04 × 103 μg/mL（Column
E, Sodium Hyaluronate mass percent are 0%）、6.52×103 μg/mL（Column f, Sodium Hyaluronate mass percent are 0.3%）、
1.30×104 μg/mL（Column g, Sodium Hyaluronate mass percent are 0.6%）、2.12×104 μg/mL（Column b, Sodium Hyaluronate
Mass percent is 0.8%）, this embodies mucopolysaccharide（Sodium Hyaluronate）Functionalization solid phase microextraction integral post is superior hydrophilic
Extracting and enriching performance.
Application Example 2
With the mucopolysaccharide of preparation（Sodium Hyaluronate）The hydrophilic solid phase microextraction integral post b structures solid phase in spool of functionalization
Micro-extraction-high performance liquid chromatography（In-tube SPME-HPLC）Combination analysis system, to 20 ng/mL melamines of mark-on
（MEL）Powdered milk sample（A）With blank powdered milk sample（B）It is detected.Sample introduction sample and load sample liquid group become ACN/H2O=
50%/50%（v/v）, 0.2 mL/min of sample introduction flow velocity, 500 μ L of sampling volume；Eluent forms ACN/H2O=10%/90%（v/
v）, 0.1 mL/min of elution flow rate, 150 μ L of elution volume；Detach mobile phase A CN/H2O=10%/90%（v/v）, detach flow velocity：
0.8 mL/min, 30 DEG C of column oven temperature, 214 nm of Detection wavelength.
Fig. 2 is to detect milk powder using online In-tube SPME-high performance liquid chromatography combination analysis system on-line preconcentration
The chromatogram of melamine is added in sample.From Figure 2 it can be seen that under the conditions of the combined system, mucopolysaccharide（Sodium Hyaluronate）Work(
Solid phase microextraction integral post can be changed and eliminate the interference of a large amount of non-polar material confrontation separation detections in milk powder matrix, and realize milk
The efficiently concentrating extraction and highly sensitive detection of the micro melamine of mark-on, show mucopolysaccharide in powder sample（Sodium Hyaluronate）
The excellent impurity removal ability of functionalization solid phase microextraction integral post and powerful hydrophilic extracting and enriching performance.
Application Example 3
With the mucopolysaccharide of preparation（Chondroitin sulfate）The hydrophilic solid phase microextraction integral post j of functionalization builds online In-tube
SPME-HPLC combination analysis systems investigate influence of the ethane nitrile content to analysis object melamine peak area in sample solution.Into
All product and load sample liquid group become ACN/H2O=40%/60%~95%/5%（v/v）, 0.2 mL/min of sample introduction flow velocity, sampling volume
500 μL；Eluent forms ACN/H2O=10%/90%（v/v）, 0.1 mL/min of elution flow rate, 150 μ L of elution volume；Separation
Mobile phase A CN/H2O=10%/90%（v/v）, detach flow velocity：0.8 mL/min, 30 DEG C of column oven temperature, Detection wavelength 214
nm。
When Fig. 3 is that on-line preconcentration detects the melamine added in powdered milk sample, ethane nitrile content is to trimerization in sample solution
The influence of cyanamide bioaccumulation efficiency.As shown in figure 3, as the ethane nitrile content in sample solution by 40% increases to 95%, melamine
Peak area be continuously increased, when ethane nitrile content increases to 95%, the peak area of melamine is maximum, illustrates prepared viscous more
Sugar（Chondroitin sulfate）Functionalization solid phase microextraction integral post can embody significantly within the scope of wide ethane nitrile content
Hydrophilic extracting and enriching ability.
The foregoing is merely presently preferred embodiments of the present invention, all equivalent changes done according to scope of the present invention patent with
Modification should all belong to the covering scope of the present invention.
Claims (5)
1. a kind of hydrophilic solid phase microextraction integral post of mucopolysaccharide functionalization, it is characterised in that：The integral post is by mucopolysaccharide, band
The dehydrated in situ polycondensation under catalyst solution effect of the matrix monomer solution of amide groups, the matrix monomer solution with aldehyde radical is made；
Wherein, mucopolysaccharide plays a dual role of overall structure crosslinking and hydrophile function；
The mucopolysaccharide is Sodium Hyaluronate or chondroitin sulfate；
The matrix monomer solution with amide groups is the aqueous solution of urea；
The matrix monomer solution with aldehyde radical is the aqueous solution of formaldehyde；
The catalyst is the aqueous solution of hydrochloric acid or sulfuric acid.
2. the hydrophilic solid phase microextraction integral post of mucopolysaccharide functionalization according to claim 1, it is characterised in that：By quality percentage
The sum of number is counted for 100%, and mass percent is shared by each component：Mucopolysaccharide 0.1 ~ 1%, the matrix monomer solution 40 with amide groups ~
55%, the matrix monomer solution 36 ~ 50% with aldehyde radical, catalyst solution 8 ~ 10%.
3. the hydrophilic solid phase microextraction integral post of mucopolysaccharide functionalization according to claim 1 or claim 2, it is characterised in that：The band
A concentration of 1 g/mL of the matrix monomer solution of amide groups；
The mass concentration of formaldehyde is 33% ~ 37% in the matrix monomer solution with aldehyde radical；
A concentration of 0.20 mol/L of the catalyst.
4. a kind of method preparing the hydrophilic solid phase microextraction integral post of mucopolysaccharide functionalization as described in claim 1, feature exist
In：Include the following steps：
1）The cleaning of blank pipe：Blank pipe is rinsed with Chromatographic Pure Methanol, then leads to nitrogen, is placed in 60 DEG C of baking ovens and dries, for use；
2）Rapid polycondensation in pipe：By mucopolysaccharide and the matrix monomer solution with amide groups, the matrix monomer solution with aldehyde radical, catalysis
Agent solution uniformly mixes, 1 ~ 2 min of quick sonic oscillation, then mixture is quickly filled in the blank pipe of clean dry, two end seals
It closes and is dipped in 10 min of heated at constant temperature in 70 DEG C of water-baths；
3）The flushing of integral post：It waits after the completion of reacting, using water as mobile phase, integral post is washed off into column on liquid chromatography pump
Remaining solvent is to get to the hydrophilic solid phase microextraction integral post of the mucopolysaccharide functionalization in bed.
5. the preparation method of the hydrophilic solid phase microextraction integral post of mucopolysaccharide functionalization according to claim 4, it is characterised in that：
Blank pipe used is teflon pipe or polyether-ether-ketone pipe.
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| CN1176940C (en) * | 2000-11-20 | 2004-11-24 | 中国科学院化学研究所 | High-effective affinity chromatography filler and its preparation method |
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