CN106422415A - Mucopolysaccharide functionalized hydrophilic solid-phase microextraction monolithic column - Google Patents
Mucopolysaccharide functionalized hydrophilic solid-phase microextraction monolithic column Download PDFInfo
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- CN106422415A CN106422415A CN201610816758.1A CN201610816758A CN106422415A CN 106422415 A CN106422415 A CN 106422415A CN 201610816758 A CN201610816758 A CN 201610816758A CN 106422415 A CN106422415 A CN 106422415A
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- mucopolysaccharide
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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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/281—Sorbents specially adapted for preparative, analytical or investigative chromatography
Abstract
The invention discloses a mucopolysaccharide functionalized hydrophilic solid-phase microextraction monolithic column that is obtained by in-situ dehydration and polycondensation of mucopolysaccharide, matrix monomer solution with an amide group, and matrix monomer solution with an aldehyde group under the action of catalyst solution. In the preparation of the monolithic column, the addition of mucopolysaccharide has played a dual role in the cross-linking and hydrophilic function of the overall structure. When the monolithic column is applied to solid-phase microextraction and the content of acetonitrile in the sample solution is in the range of 40% to 95%, the monolithic column can still show the hydrophilic enrichment and extraction ability for polarity analysis objects. The invention has the advantages of simple process, easy operation, no need for expensive equipment, easy promotion, and efficient extraction and high sensitivity detection of various polar compounds such as melamine and aminoglycoside antibiotics can be realized based on the high efficiency hydrophilic extraction mode. The monolithic column is applicable to a wide range of analysis objects.
Description
Technical field
The invention belongs to integral post preparation field is and in particular to a kind of hydrophilic SPME of mucopolysaccharide functionalization is overall
Post.
Background technology
Integral post is a kind of new color carrying out in-situ polymerization preparation using organic and inorganic or hybrid inorganic-organic method
Spectrum fixing phase.Due to it, to have that permeability is excellent, space availability ratio is high, preparation method is simple, back pressure are low, mass transfer velocity is fast etc. excellent
Point, is used widely in SPME field.In recent years, improve the particular characteristic of integral post by specific functionization, become
An important research direction for integral post preparation field.Large biological molecule（As protein, polysaccharide, cellulose etc.）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 realized in the mode such as the coating of matrix integral post surface or chemical bonding by large biological molecule.Example
As Lu et al.（Junyu Lu, et al. J. Sep. Sci., 2011, 34, 2329-2336）Using mercaptopropyi front three
TMOS prepares monolithic silica column as function monomer, and fixes gold nano grain on its surface；By gold nano grain and
On protein, the interaction of amino is it is achieved that bovine serum albumin(BSA)（BSA）Functionalization on monolithic silica column surface.This problem
Group（Wang Jiabin etc., chromatogram, 2011,29 (12), 1222-1229）N- acryloyl succinimide is adopted in previous work
（NAS）For matrix monomer, ethylene glycol dimethacrylate（EDMA）For crosslinking agent, in-situ polymerization is prepared poly-（NAS-co-
EDMA）Capillary monolithic column, then by chemical bonding by large biological molecule cellulose-three（4- methyl benzoic acid ester）Covalent bond
Close in integral post it is achieved that the preparation of cellulose functionalized integral post.In these work, large biological molecule functionalization is overall
The preparation thinking of post mainly carries out secondary functionization on active matrix integral post surface and derives, therefore its preparation process complicated,
Preparation time is tediously long, be prepared into that power is relatively low, limits the promotion and application of large biological molecule functionalization entirety column technology.
Mucopolysaccharide is the nitrogenous heterogeneity polysaccharide of a class, repeats connection by different dissacharide units and forms；One of one-tenth
Dividing is N- acetylaminohexose, and another is then uronic acid or sugared.Common mucopolysaccharide mainly has：Chondroitin sulfate, transparent
Matter acid, hyaluronate, heparin, dermatan sulfate, heparitin sulfate and keratan sulfate etc..These polysaccharide are all that straight chain is miscellaneous many
Sugar, is the main component constituting iuntercellular connective tissue, is widely present in mammal various intracellular.Unique the dividing of mucopolysaccharide
Minor structure makes it show very strong polarity and elecrtonegativity, therefore has very strong hydrophilicity, embodies good moisturizing, profit
Cunning, anticoagulation, reducing blood lipid etc. act on, and are used widely in fields such as biological medicine, cosmetics, organizational projects.However, with viscous
Polysaccharide have not been reported for functionalization material preparation integral post.
Content of the invention
It is an object of the invention to provide a kind of hydrophilic SPME integral post of mucopolysaccharide functionalization, it is directed to biological big
There is complicated secondary variation in molecular function integral post preparation field, can be in acid using the N- acetylamino on mucopolysaccharide
Or under conditions of base catalysis participate in urea aldehyde polycondensation reaction characteristic, by mucopolysaccharide, urea liquid, formalin, catalyst solution
Mixing, prepares mucopolysaccharide functionalization integral post by a step original position ureaformaldehyde dehydrating polycondensation, wherein, mucopolysaccharide has simultaneously worked as entirety
The crosslinked double action with hydrophile function of structure.Have benefited from the ultrahydrophilic of the mucopolysaccharide of bonding, this integral post is to polarity
Analysis object embodies significantly hydrophilic extracting and enriching ability.
For achieving the above object, the present invention adopts the following technical scheme that：
A kind of hydrophilic SPME integral post of mucopolysaccharide functionalization, its be by mucopolysaccharide, the matrix monomer solution with amide groups,
The dehydrated in situ polycondensation under catalyst solution effect of matrix monomer solution with aldehyde radical is obtained；Wherein, mucopolysaccharide plays overall knot
The crosslinked double action with hydrophile function of structure.
Sum is 100% meter by weight percent, and mass percent shared by each component is：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, described mucopolysaccharide includes hyaluronic acid, hyaluronate, chondroitin sulfate, heparin, dermatan sulfate, sulphur
Any one in acids heparin, keratan sulfate；
The described matrix monomer solution with amide groups is the aqueous solution of urea, and its concentration is 1 g/mL；
The described matrix monomer solution with aldehyde radical is the aqueous solution of formaldehyde, and wherein the mass concentration of formaldehyde is 33% ~ 37%；
Described catalyst is hydrochloric acid, the aqueous solution of sulfuric acid, phosphoric acid or NaOH, and its concentration is 0.20 mol/L.
The preparation method of the hydrophilic SPME integral post of described mucopolysaccharide functionalization, comprises the following steps：
1）The cleaning of blank pipe：Blank pipe is connected liquid phase pump, rinses 10 min with Chromatographic Pure Methanol under 0.5 mL/min flow velocity, so
Lead to nitrogen afterwards, be placed in 60 DEG C of baking oven drying 10min, stand-by；
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, quick sonic oscillation 1 ~ 2 min, then mixture is quickly filled in the blank pipe of clean dry, two end seals
Close and be dipped in heated at constant temperature 10 min in 70 DEG C of water-baths；
3）The flushing of integral post：After the completion of question response, with water as mobile phase, integral post is rinsed on liquid chromatography pump 1h, with
Remove the solvent of residual and reaction remaining reagent in post bed, that is, obtain the hydrophilic SPME of described mucopolysaccharide functionalization overall
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 material（Such as protein, polysaccharide, cellulose etc.）It is generally all to be coated by integral post surface or change
Learn the modes such as bonding, realize its functionalization to integral material.The present invention utilizes mucopolysaccharide itself to carry acetamido group, can
Directly participate in the polycondensation reaction of integral post preparation, and the use of mucopolysaccharide also can play overall structure in integral post preparation process
Crosslinked effect；Further, since mucopolysaccharide has strongly hydrophilic in itself, it also gives the superior hydrophilic extractibility of integral post
Energy.Therefore, the addition of mucopolysaccharide serves crosslinked and hydrophilic double action.
2）The preparation of the hydrophilic SPME integral post of mucopolysaccharide functionalization of the present invention only needs an one-step polycondensation, and method is easy,
Reaction speed is fast, eliminates loaded down with trivial details step derived from integral material surface second, substantially increases large biological molecule functionalization
The preparation efficiency of integral post, is that the preparation of large biological molecule functionalization integral post provides a kind of new technology, will be to biological big point
The promotion and application of subfunction integral post bring very big help.
3）Contrast the quartz capillary being usually used, the present invention adopts PTFE tube or PEEK pipe as the tubing of integral post
Material, both materials have the characteristics that high mechanical strength, pliability are good, so that integral post is difficult in preparation and analysis detection application
Situations such as fracture occurs, improves adaptability and the ease for use of integral post, extend its service life.
4）When gained mucopolysaccharide functionalization integral post of the present invention is applied to hydrophilic SPME, molten in wide sample
Liquid ethane nitrile content scope（40-95%）Interior, polarity check object can be embodied with significantly hydrophilic extracting and enriching ability, can be real
Efficiently concentrating extraction and the highly sensitive detection of the existing various polarity compound such as melamine, aminoglycoside antibiotics.
Brief description
Fig. 1 is the functionalization hydrophilic SPME integral post of the Sodium Hyaluronate of percentage containing different quality to melamine
Breakthrough curve；
The breakthrough curve to 1mg/mL toluene for the integral post that in figure A is 0% for Sodium Hyaluronate mass percent（Representation system is dead
Time）, the breakthrough curve to 1mg/mL melamine for the integral post that B is 0% for Sodium Hyaluronate mass percent, C is hyalomitome
Sour sodium mass percent is 0.3% breakthrough curve to 1mg/mL melamine for the integral post, and D is Sodium Hyaluronate percent mass
The breakthrough curve to 1mg/mL melamine for the integral post for 0.6% for the number, E for Sodium Hyaluronate mass percent be 0.8% whole
The breakthrough curve to 1mg/mL melamine for the scapus.
Fig. 2 be using Sodium Hyaluronate mass percent be 0.8% functionalization integral post as SPME medium, structure
It build line In-tube SPME-high performance liquid chromatography in（In-tube SPME-HPLC）Combined system, on-line preconcentration detects milk powder
Add melamine in sample（MEL）Chromatogram；
In figure A is to add 20 ng/mL melamines（MEL）Powdered milk sample chromatogram, B is the chromatogram of blank powdered milk sample
Figure.
Fig. 3 be using chondroitin sulfate mass percent be 0.8% functionalization integral post as SPME medium, structure
It build line In-tube SPME-high performance liquid chromatography in（In-tube SPME-HPLC）Combined system, on-line preconcentration detects milk powder
During the melamine adding in sample, the impact to melamine rich efficiency for the ethane nitrile content in sample solution.
Specific embodiment
In order that content of the present invention easily facilitates understanding, with reference to specific embodiment to of the present invention
Technical scheme is described further, but the present invention is not limited only to this.
（1）The PTFE tube that internal diameter is 750 m connects liquid phase pump, with Chromatographic Pure Methanol under the flow velocity of 0.5 mL/min
Rinse 10 min, remove organic impurities of PTFE tube inwall residual etc., then lead to nitrogen, be placed in drying in 60 DEG C of baking ovens
10min, stand-by；
（2）Respectively by table 1,2 integral post composition and ratios weigh Sodium Hyaluronate or chondroitin sulfate, concentration are 1 g/mL urea
Hydrochloric acid solution or sulfuric acid solution that formalin that solution, mass concentration are 35%, concentration are 0.2 mol/L, it is uniformly mixed
Close, quick sonic oscillation 1 ~ 2 min, then mixture is quickly filled in the PTFE tube of clean dry, closed at both ends is simultaneously dipped in 70
Heated at constant temperature 10min in DEG C water-bath；
（3）The flushing of integral post：After the completion of question response, with water as mobile phase, PTFE tube integral post is rinsed on liquid chromatography pump
About 1 hour, to remove the solvent of residual in post bed, that is, obtain the hydrophilic SPME integral post of corresponding Sodium Hyaluronate functionalization
Or chondroitin sulfate functionalization hydrophilic SPME integral post.
The hydrophilic SPME integral post of table 1 Sodium Hyaluronate functionalization forms
The hydrophilic SPME integral post of table 2 chondroitin sulfate functionalization forms
Application Example 1
With 1 mg/mL toluene solution（ACN/H2O=95%/5%, v/v）For mobile phase, micro-injection flow rate pump is 10 μ L/min,
Ultraviolet detection wavelength is 214 nm, and integral post e prepared is carried out with the dead time test of breakthrough curve；And with 1 mg/mL trimerization
Cyanamide solution（ACN/H2O=95%/5%, v/v）For mobile phase, micro-injection flow rate pump is 10 μ L/min, and ultraviolet detection wavelength is
214 nm, carry out breakthrough curve experiment respectively to integral post e, f of preparation, g, b.
Fig. 1 is the functionalization hydrophilic SPME integral post 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 respectively 2.04 × 10 of its corresponding melamine3μg/mL（Post
E, Sodium Hyaluronate mass percent is 0%）、6.52×103μg/mL（Post f, Sodium Hyaluronate mass percent is 0.3%）、
1.30×104μg/mL（Post g, Sodium Hyaluronate mass percent is 0.6%）、2.12×104μg/mL（Post b, Sodium Hyaluronate
Mass percent is 0.8%）, this embodies mucopolysaccharide（Sodium Hyaluronate）Superior hydrophilic of functionalization SPME integral post
Extracting and enriching performance.
Application Example 2
Mucopolysaccharide with preparation（Sodium Hyaluronate）Functionalization hydrophilic SPME integral post b builds the micro- extraction of solid phase in spool
Take-high performance liquid chromatography（In-tube SPME-HPLC）Combination analysis system, to mark-on 20 ng/mL melamine（MEL）'s
Powdered milk sample（A）With blank powdered milk sample（B）Detected.Sample introduction sample and load sample liquid consist of ACN/H2O=50%/50%（v/
v）, sample introduction flow velocity 0.2 mL/min, sampling volume 500 μ L；Eluent forms ACN/H2O=10%/90%（v/v）, elution flow rate
0.1 mL/min, elution volume 150 μ L；Separate mobile phase A CN/H2O=10%/90%（v/v）, separate flow velocity：0.8 mL/min,
30 DEG C of column oven temperature, Detection wavelength 214 nm.
Fig. 2 is using online In-tube SPME-high performance liquid chromatography combination analysis system on-line preconcentration detection milk powder
Add the chromatogram of melamine in sample.From Figure 2 it can be seen that under the conditions of this combined system, mucopolysaccharide（Sodium Hyaluronate）Work(
The interference that SPME integral post eliminates a large amount of non-polar material confrontation separation detections in milk powder matrix can be changed, and achieve milk
In powder sample, the efficiently concentrating extraction of the micro melamine of mark-on and highly sensitive detection, indicate mucopolysaccharide（Sodium Hyaluronate）
The excellent Impurity removal ability of functionalization SPME integral post and powerful hydrophilic extracting and enriching performance.
Application Example 3
Mucopolysaccharide with preparation（Chondroitin sulfate）Functionalization hydrophilic SPME integral post j builds online In-tube
SPME-HPLC combination analysis system, investigates the impact to analysis object melamine peak area for the ethane nitrile content in sample solution.Enter
All product and load sample liquid consist of ACN/H2O=40%/60%~95%/5%（v/v）, sample introduction flow velocity 0.2 mL/min, sampling volume
500 μL；Eluent forms ACN/H2O=10%/90%（v/v）, elution flow rate 0.1 mL/min, elution volume 150 μ L；Separate
Mobile phase A CN/H2O=10%/90%（v/v）, separate flow velocity：0.8 mL/min, 30 DEG C of column oven temperature, Detection wavelength 214
nm.
When Fig. 3 detects, for on-line preconcentration, the melamine adding in powdered milk sample, in sample solution, ethane nitrile content is to trimerization
The impact of cyanamide bioaccumulation efficiency.As shown in figure 3, increasing to 95% with the ethane nitrile content in sample solution by 40%, melamine
Peak area be continuously increased, when ethane nitrile content increases to 95%, the peak area of melamine is maximum, illustrate prepared glue many
Sugar（Chondroitin sulfate）Functionalization SPME integral post can embody significantly in the range of wide ethane nitrile content
Hydrophilic extracting and enriching ability.
The foregoing is only presently preferred embodiments of the present invention, all impartial changes done according to scope of the present invention patent with
Modify, all should belong to the covering scope of the present invention.
Claims (5)
1. a kind of hydrophilic SPME integral post of mucopolysaccharide functionalization it is characterised in that：Described 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 obtained；
Wherein, mucopolysaccharide plays the crosslinked double action with hydrophile function of overall structure.
2. according to claim 1 mucopolysaccharide functionalization hydrophilic SPME integral post it is characterised in that：By percent mass
Number sum is 100% meter, and mass percent shared by each component is：Mucopolysaccharide 0.1 ~ 1%, the matrix monomer solution 40 with amide groups ~
55%th, the matrix monomer solution 36 ~ 50% with aldehyde radical, catalyst solution 8 ~ 10%.
3. the hydrophilic SPME integral post of mucopolysaccharide functionalization according to claim 1 or claim 2 it is characterised in that：Described viscous
Polysaccharide includes hyaluronic acid, hyaluronate, chondroitin sulfate, heparin, dermatan sulfate, heparitin sulfate, keratan sulfate
In any one；
The described matrix monomer solution with amide groups is the aqueous solution of urea, and its concentration is 1 g/mL；
The described matrix monomer solution with aldehyde radical is the aqueous solution of formaldehyde, and wherein the mass concentration of formaldehyde is 33% ~ 37%；
Described catalyst is hydrochloric acid, the aqueous solution of sulfuric acid, phosphoric acid or NaOH, and its concentration is 0.20 mol/L.
4. a kind of method preparing the hydrophilic SPME integral post of mucopolysaccharide functionalization as claimed in claim 1, its feature exists
In：Comprise the following steps：
1）The cleaning of blank pipe：Rinse blank pipe with Chromatographic Pure Methanol, then lead to nitrogen, be placed in drying in 60 DEG C of baking ovens, stand-by；
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, quick sonic oscillation 1 ~ 2 min, then mixture is quickly filled in the blank pipe of clean dry, two end seals
Close and be dipped in heated at constant temperature 10 min in 70 DEG C of water-baths；
3）The flushing of integral post：After the completion of question response, with water as mobile phase, integral post is washed off on liquid chromatography pump post
In bed, the solvent of residual, that is, obtain the hydrophilic SPME integral post of described mucopolysaccharide functionalization.
5. according to claim 4 mucopolysaccharide functionalization hydrophilic SPME integral post preparation method it is characterised in that：
Blank pipe used is teflon pipe or polyether-ether-ketone pipe.
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| CN107413317A (en) * | 2017-08-16 | 2017-12-01 | 江苏理工学院 | Chitin modified GMA/MAA polymer absorbants and its methods and applications |
| CN108927113B (en) * | 2018-05-22 | 2021-05-18 | 福州大学 | Nano-hydroxyapatite functionalized solid phase extraction monolithic column |
| CN108927113A (en) * | 2018-05-22 | 2018-12-04 | 福州大学 | A kind of nanometer hydroxyapatite functionalization Solid Phase Extraction integral post |
| CN110575683A (en) * | 2019-08-29 | 2019-12-17 | 福州佳宸生物科技有限公司 | hydroxyapatite functionalized monolithic column prepared by in-situ mineralization method |
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| CN114471495B (en) * | 2022-01-18 | 2023-01-10 | 福州大学 | Covalent organic framework surface functionalized solid phase extraction monolithic column |
| CN115201373A (en) * | 2022-07-13 | 2022-10-18 | 北京英太格瑞检测技术有限公司 | Method for detecting LC-MSMS (liquid chromatography-Mass Spectrometry) by hygromycin B in feed without using ion-pair reagent in mobile phase |
| CN115201373B (en) * | 2022-07-13 | 2023-07-28 | 北京英太格瑞检测技术有限公司 | Method for detecting LC-MSMS (LC-MSMS) in feed without using ion pair reagent in mobile phase |
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