CN104959124B - The synthesis and its application of the double modified derivatives of chitosan bearing cyclodextrin phosphorylation - Google Patents
The synthesis and its application of the double modified derivatives of chitosan bearing cyclodextrin phosphorylation Download PDFInfo
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Abstract
The invention discloses a kind of synthetic method of the double modified derivatives of chitosan bearing cyclodextrin phosphorylation, comprise the following steps：Chitosan bearing cyclodextrin is taken to be dissolved in Loprazolam, nitrogen protection is lower to add P2O5, in being reacted under ice bath, after reaction terminates, ether is added with precipitated product, produces the double modified derivatives of chitosan bearing cyclodextrin phosphorylation.The present invention has selected chitosan as carrier, carries out the immobilized of beta cyclodextrin, and carries out phosphorylation modification, synthesizes the derivative of chitosan bearing cyclodextrin phosphorylation modification（CTS‑CD‑P）, the derivative improves MC LR enrichment adsorption efficiency by the cyclodextrin on chitosan and sulfydryl phospho-specif iotac combination Microcystin.
Description
Technical field
The invention belongs to analysizing trace organics field among water body and food-grade, it is related to specific adsorption microcystin
The method of preparation and use of the chitin modified material of element, and in particular to a kind of double modifications of chitosan bearing cyclodextrin phosphorylation are spread out
Biological synthesis and its application.
Background technology
As China's modernization is accelerated, blue-green alga bloom is harmful to as caused by earth's surface water eutrophication regular a wide range of
Occur, the most universal with the generation of Microcystis aeruginosa (Microcystis) wawter bloom wherein in blue-green alga bloom, produced Microcystin is not
Poisons in freshwater is only seriously endangered, in the food chain of freshwater environment, the frond cell containing Microcystin is swum dynamic
Thing, shell-fish, shellfish etc. ingest, and are enriched in by animal ingestion in the aquatic products and poultry meat product such as a variety of fish, can be with
Cause the mankind and poultry multiple organ injury or even trigger cancer.
Due to Microcystin（MC-LR）Concentration is relatively low in water body and food samples, needs to carry out sample before detection
Enrichment analyzed again.The method of current purification enrichment Microcystin Dings Xiang ﹑ methyl-props including affine in immunity Zhu ﹑ C18 Gu
The thin pipe ﹑ molecules print mark of olefin(e) acid butyl ester hair is poly- to close thing ﹑ active carbon fibre peacekeeping macroreticular resins etc..Or but take in these methods
Chang ﹑ requires high to technical operation, otherwise Jia lattice Ang Gui ﹑ are low to the adsorbance of Algae toxins, or to the selectivity of Microcystin
It is not high, cause the purity of the Microcystin of enriching and purifying not high.Therefore need a kind of Lian Jia ﹑ selectivitys strong at present and adsorbance
The method of high enriching and purifying Microcystin.
The content of the invention
In order to solve the above-mentioned technical problem, the present invention is according to Microcystin（MC-LR）Design feature carry out rationality set
Meter, for containing hydrophobic benzene ring structure and positively charged arginic guanidine radicals, in theory hydrophobic phenyl ring knot in MC-LR structures
Structure can carry out Host-guest reaction with the hydrophobic cavity of cyclodextrin and specifically bind, and positively charged arginic guanidine radicals can
To occur electrostatic interaction and formation hydrogen bond with negatively charged phosphate group and specifically bind, pass through the special of two chemical bonds
Property combine, material can be improved to MC-LR binding specificities.
Chitosan has biodegradability, non-toxic, and the advantage of good biocompatibility and low cost is mainly used in doctor
The field such as Yao ﹑ food and environmental protection.There are many hydroxyls and amino group on chitosan, therefore, it is possible to participate in the modification of many chitosans
Reaction, the chitosan of bearing cyclodextrin has cyclodextrin to organic matter and the tetra-inclusion complex of metal ion, in recent years applied chemistry
The method of modification synthesizes the chitosan derivatives with new biological function, is made it have new due to the introducing of new group
Function.
The present invention has selected chitosan as carrier, carries out the immobilized of beta-schardinger dextrin, and carries out phosphorylation modification, synthesizes shell
The derivative of glycan bearing cyclodextrin phosphorylation modification（CTS-CD-P）, the derivative passes through the cyclodextrin and sulfydryl on chitosan
Phospho-specif iotac combination Microcystin, improves MC-LR bioaccumulation efficiency, sets up the double modified derivatives of chitosan to Microcystis aeruginosa
The absorption of toxin and its elution process, it is intended to develop a kind of cheap, enriching and purifying microcystin that selectivity is strong and adsorbance is high
The new material and its application process of element.
The synthetic method for the double modified derivatives of chitosan bearing cyclodextrin phosphorylation that the present invention is provided, including following step
Suddenly：
Chitosan bearing cyclodextrin is taken to be dissolved in Loprazolam, nitrogen protection is lower to add P2O5, in being reacted under ice bath, react
After end, ether is added with precipitated product, produces the double modified derivatives of chitosan bearing cyclodextrin phosphorylation.
It is used as optimal technical scheme, chitosan bearing cyclodextrin, Loprazolam and P2O5Ratio be 1g：7-12 mL：1-
5g。
It is used as optimal technical scheme, chitosan bearing cyclodextrin, Loprazolam and P2O5Weight ratio be 1g:10 mL:5
g。
As optimal technical scheme, above-mentioned synthetic method is 1 ~ 3 hour in the lower reaction of ice bath stirring, reaction time.
As optimal technical scheme, above-mentioned synthetic method also includes, the step of obtained precipitated product is washed, precipitation
Product is washed with ether, acetone, methanol and ether successively.
As optimal technical scheme, chitosan bearing cyclodextrin is prepared via a method which：
Chitosan is dissolved in the glacial acetic acid that volumetric concentration is 1%, will be dissolved with list -6- tolysulfonyl-beta-schardinger dextrin
DMF is added thereto, and is well mixed, the mixed system is condensing reflux 40-60 hours at 80-100 DEG C, instead
Dialysed mixed liquor 3-4 days with bag filter after should terminating, carry out purification of target product, be then freeze-dried, obtain the solid of cotton shape,
The as immobilized beta-schardinger dextrin of chitosan.
Above-mentioned list-(p-methylphenyl sulfonyl) beta-schardinger dextrin is prepared via a method which：
1）The beta-schardinger dextrin for weighing 1 part is added in 8 parts of water, and the distilled water containing alkali is slowly added into β-CD（Cyclodextrin）
Suspension in, alkali is NaOH, KOH or ammoniacal liquor, is added dropwise while stir, and time for adding is 8 ~ 10min, and last β-CD are complete
It is dissolved in alkali, suspension becomes transparent β-CD solution.
In the organic solvent that 1 part of p-methyl benzene sulfonic chloride is dissolved into 3 parts, organic solvent is acetone, acetonitrile, three chloromethanes
Alkane, is then gradually dripped in transparent β-CD solution, is added dropwise while being stirred with glass bar, time for adding is 10 ~ 12min.
After completion of dropwise addition, transparent β-CD solution becomes turbid solution.1000r/min stirs 2.5h at 18-22 DEG C of constant temperature blender with magnetic force.
Reaction is centrifugally separating to obtain supernatant after terminating, by supernatant in placing half a day in 4 DEG C, has a large amount of white precipitates and separates out.Again
By white precipitate using distilled water as 75 DEG C of solvent at recrystallize twice, then be freeze-dried.Obtain drying the sulfonated products of high-purity
(β-CD-OTS)。
The present invention provides the double modified derivatives of chitosan bearing cyclodextrin phosphorylation that above-mentioned synthetic method is prepared.
The present invention provides the side that the double modified derivatives of above-mentioned chitosan bearing cyclodextrin phosphorylation are enriched with Microcystin
Method, comprises the following steps：
1）The double modified derivatives of chitosan bearing cyclodextrin phosphorylation are dissolved in pH 10 ~ 11 NaHCO3/ Na2CO3It is slow
Rush in solution；
2）In step 1）The sample containing Microcystin is added in obtained buffer system, mixes to place and is adsorbed；
3）To step 2）System in add concentration be 0.1-0.5mol/L glacial acetic acid to precipitate chitosan bearing cyclodextrin
The derivative of Microcystin has been adsorbed in the double modified derivatives of phosphorylation, centrifugation.
4）Trichloroacetic acid is added in concentration 50%-70% methanol aqueous solutions, constitutes the body of trichloroacetic acid in eluent, eluent
Product concentration is 0.03-0.07%, with elution step 3）Microcystis aeruginosa on the obtained derivative for having adsorbed Microcystin
Toxin.
The present invention separately provides a kind of above-mentioned chitosan bearing cyclodextrin phosphorylation double modified derivative enrichment microcystins
The method of element, comprises the following steps：
1）The double modified derivatives of the chitosan bearing cyclodextrin phosphorylation add water sample containing Microcystin or containing micro-
The sample suspension of capsule Algae toxins places absorption, and centrifugation obtains derivative;
2）Trichloroacetic acid is added in concentration 50%-70% methanol aqueous solutions, constitutes the body of trichloroacetic acid in eluent, eluent
Product concentration is 0.03-0.07%, with elution step 1）Microcystis aeruginosa on the obtained derivative for having adsorbed Microcystin
Toxin.
It is contemplated that overcome for Microcystin be enriched with high polymer material C18 Gu Ding Xiang ﹑ molecular engrams polymerization
The methods such as thing ﹑ active carbon fibre peacekeeping macroreticular resins are not high to the selectivity of Microcystin, the relatively low shortcoming of adsorbance, the present invention
Derivant material preparation method and its Microcystin enrichment there is provided a kind of double modifications of chitosan bearing cyclodextrin phosphorylation
Method.
The invention provides a kind of derivant material of the double modifications of chitosan bearing cyclodextrin phosphorylation, chitosan has life
There are many hydroxyls and amino group in Biodegradable, non-toxic, the advantage of good biocompatibility and low cost, its structure, because
This can participate in the modification reaction of many chitosans, and the method for applied chemistry modification is gathered to synthesize the shell with new biological function
Sugar derivatives, new function is made it have due to the introducing of new group.
Select chitosan as carrier in the present invention, carry out beta-schardinger dextrin（β-CD）It is immobilized, and carry out phosphorylation and repair
Decorations, synthesize the derivative of chitosan bearing cyclodextrin phosphorylation modification（CTS-CD-P）, the derivative passes through the ring on chitosan
Contain hydrophobic benzene ring structure and positively charged arginine in dextrin and sulfydryl phospho-specif iotac combination Microcystin structure
Guanidine radicals, carry out specific combination.
Embodiment
With reference to specific embodiment, the invention will be further described, so that those skilled in the art can be more preferable
Understand the present invention and can be practiced, but illustrated embodiment is not as a limitation of the invention.
Embodiment 1
First, the synthesis of the double modified derivatives of chitosan bearing cyclodextrin phosphorylation
The preparation of first step list-(6- p-methylphenyls sulfonyl) beta-schardinger dextrin
In the distilled water that 55g β-CD are added to 435mL, the distilled water dissolved with 5.2g NaOH is slowly added into β-CD's
In suspension, it is added dropwise while stirring, time for adding is 8 ~ 10min, last β-CD are completely dissolved in NaOH, and suspension becomes
Transparent β-CD solution.Again by dissolved with the 24mL acetonitriles of 7.96g p-methyl benzene sulfonic chlorides dropwise into transparent β-CD solution, one
Side is added dropwise while being stirred with glass bar, and time for adding is 10 ~ 12min.After completion of dropwise addition, transparent β-CD solution becomes muddy
Liquid.Then in 1000r/min stirrings 2.5h at 22 DEG C of constant temperature blender with magnetic force.Reaction is centrifugally separating to obtain supernatant after terminating,
By supernatant in placing half a day in 4 DEG C, have a large amount of white precipitates and separate out.Again by white precipitate using distilled water as 75 DEG C of solvent at
Recrystallization twice, then is freeze-dried.Obtain drying the beta-schardinger dextrin sulfonated bodies of high-purity（List-(6- p-methylphenyls sulfonyl) β-
Cyclodextrin）.
The synthesis of second step chitosan bearing cyclodextrin (CD-CS)
1g chitosans are dissolved in 40mL 1% glacial acetic acid, and the DMF solution that will be dissolved with 5g beta-schardinger dextrin sulfonated bodies
It is added thereto, is uniformly mixed, system condensing reflux 48h at 100 DEG C is purified 3 days in bag filter, then freezed dry
It is dry, obtain chitosan bearing cyclodextrin (CD-CS) solid of cotton shape.
The double modified derivatives of 3rd step chitosan bearing cyclodextrin phosphorylation（CTS-CD-P chitosan derivatives）Synthesis
The 0.5g chitosan bearing cyclodextrins that synthesis is obtained are dissolved in 5mL Loprazolam, then add 2.5g P2O5,
Entirely react in N2Protection under constantly stirred with glass bar, in ice bath carry out（0-5℃）, by change the reaction time or
P2O5Consumption obtain the phosphonized chitosans of different substitution degree.After the completion of reaction, adding ether precipitates product, centrifugation point
From using ether (5 times) respectively successively, acetone (3 times), methanol (3 times), the washing precipitation of ether (1 time) is then freeze-dried.
The absorption and elution of Microcystin：
Method one：0.01g CTS-CD-P chitosan derivatives are dissolved in 1mL NaHCO3/ Na2CO3（10.83）Buffer solution
In, it is to be dissolved after take 100 μ L as reaction system, then add 50 μ L MC-LR (250 μ g/mL) standard blend in the system and put
Put and adsorbed.With 100 μ L 0.3mol/L glacial acetic acid precipitate C S-CD-P chitosan derivatives, 12000r/min centrifuges 5min,
With 500 μ l 70% methanol solution（Add 0.05%TFA）Eluted, liquid-phase chromatographic analysis result display dissolving CTS-CD-P shells
Polysaccharid derivative reaches 8.98mg/g to MC-LR adsorption capacity, is as a result significantly higher than in document and utilizes molecularly imprinted polymer
（It is 153.7 μ g/g to MC-LR maximal absorptive capacities）And activated carbon fiber（It is 246 μ g/g to MC-LR maximal absorptive capacities）Absorption
Amount.
Method two：Take 0.002g CS-CD-P chitosan derivatives in 150 μ L distilled water, add 50 μ l MC-LR
Absorption 10 hours, 12000r/min centrifugation 5min, with the methanol of 500 μ l volumetric concentrations 70% are placed in (125 μ g/mL) standard, mixing
The aqueous solution（Add 0.05%TFA）Elution collection is carried out, available for the measure of liquid chromatogram, adsorbance is 3.37 mg/ after measured
g。
Embodiment 2
First, the synthesis of the double modified derivatives of chitosan bearing cyclodextrin phosphorylation
The first step and second step be the same as Example 1.
3rd step
The double modified derivatives of 3rd step chitosan bearing cyclodextrin phosphorylation（CTS-CD-P chitosan derivatives）Synthesis
The 3g chitosan bearing cyclodextrins that synthesis is obtained are dissolved in 36mL Loprazolam solution, then add 15g's
P2O5, entirely react in N2Protection under constantly stirred with glass bar, in ice bath carry out（0-5℃）, when being reacted by changing
Between or P2O5Consumption obtain the phosphonized chitosans of different substitution degree.After the completion of reaction, adding ether precipitates product, from
The heart is separated, and uses ether (5 times) respectively successively, and then acetone (3 times), methanol (3 times), (1 time) washing precipitation of ether freezes dry
It is dry.
The absorption and elution of Microcystin：
Method one：5.00 g crucian sample homogeneous samples accurately are weighed in 15 mL centrifuge tubes, add 50 μ L standards
MC-LR, (125 μ g/mL), in 1 min of quick mixing on liquid blending device (10000 r/min), makes standard equal with sample mixed
Even, supernatant is transferred to be measured in test tube by the min of homogeneous 2,5 min of centrifugation (3000 r/min)；By 0.02g CTS-CD-P
Chitosan derivatives are dissolved in 2 mL NaHCO3/ Na2CO3（10.83）In buffer solution, then add in the system homogenate fish to be measured
Meat products is mixed to place and adsorbed for 12 hours.With 1ml 0.3mol/L glacial acetic acid precipitate C S-CD-P chitosan derivatives,
12000r/min centrifuges 5min, with 2ml 70% methanol solution（Add 0.05%TFA）Eluted, liquid-phase chromatographic analysis result
Display CTS-CD-P chitosan derivatives reach 5.46mg/g. to MC-LR adsorption capacity
Method two：
The preparation of flesh of fish sample to be measured takes 0.02g CS-CD-P chitosan derivatives to distill water logging in 1mL with method two
It is molten, add homogenate fish product mixing placement to be measured and adsorbed for 12 hours, 12000r/min centrifuges 5min, dense with 2ml volumes
Spend 70% methanol aqueous solution（Add 0.05%TFA）Elution collection is carried out, available for the measure of liquid chromatogram, adsorbance is after measured
2.95mg/g。
Embodiment 3
First, the synthesis of the double modified derivatives of chitosan bearing cyclodextrin phosphorylation
The first step and second step be the same as Example 1.
3rd step
The double modified derivatives of 3rd step chitosan bearing cyclodextrin phosphorylation（CTS-CD-P chitosan derivatives）Synthesis
The 2g chitosan bearing cyclodextrins that synthesis is obtained are dissolved in 14ml Loprazolam solution, then add 2g's
P2O5, entirely react in N2Protection under constantly stirred with glass bar, in ice bath carry out（0-5℃）, when being reacted by changing
Between or P2O5Consumption obtain the phosphonized chitosans of different substitution degree.After the completion of reaction, adding ether precipitates product, from
The heart is separated, and uses ether (5 times) respectively successively, and then acetone (3 times), methanol (3 times), (1 time) washing precipitation of ether freezes dry
It is dry.
The absorption and elution of Microcystin：
Method one：Shellfish is organized to take out, blends, mix in ice-water bath after draining away the water, accurately weigh after homogeneous
The g of sample 5 adds 50 μ l MC-LR (125 μ g/mL) standard, in liquid blending device (10000 r/ in 15 mL centrifuge tubes
Min 1 min of quick mixing on), makes standard uniform with sample mixed, the min of homogeneous 2,5 min of centrifugation (3000 r/min), will
Supernatant is transferred to be measured in test tube, and 0.01g CTS-CD-P chitosan derivatives are dissolved in into 2 mL NaHCO3/ Na2CO3
（10.83）In buffer solution, then add in the system homogenate fish product to be measured and mix to place and adsorbed for 12 hours, use 5ml
0.3mol/L glacial acetic acid precipitate C S-CD-P chitosan derivatives, 12000r/min centrifugation 5min, with 3ml 70% methanol solution
（Add 0.05%TFA）Eluted, liquid-phase chromatographic analysis result shows absorption of the CTS-CD-P chitosan derivatives to MC-LR
Ability reaches 6.21mg/g.
Method two：
The preparation of shellfish meat sample product to be measured takes 0.01g CS-CD-P chitosan derivatives to distill water logging in 1mL with method two
It is molten, add homogenate fish product mixing placement to be measured and adsorbed for 12 hours, 12000r/min centrifuges 5min, dense with 3ml volumes
Spend 70% methanol aqueous solution（Add 0.05%TFA）Elution collection is carried out, available for the measure of liquid chromatogram, adsorbance is after measured
2.37mg/g。
Embodiment described above is only the preferred embodiment to absolutely prove the present invention and being lifted, protection model of the invention
Enclose not limited to this.Equivalent substitute or conversion that those skilled in the art are made on the basis of the present invention, in the present invention
Protection domain within.Protection scope of the present invention is defined by claims.
Claims (7)
1. the synthetic method of the double modified derivatives of a kind of chitosan bearing cyclodextrin phosphorylation, it is characterised in that including following step
Suddenly：
Chitosan bearing cyclodextrin is taken to be dissolved in Loprazolam, nitrogen protection is lower to add P2O5, in being reacted under ice bath, reaction terminates
Afterwards, ether is added with precipitated product, produces the double modified derivatives of chitosan bearing cyclodextrin phosphorylation；
Wherein, chitosan bearing cyclodextrin is prepared via a method which：
Chitosan is dissolved in the glacial acetic acid that volumetric concentration is 1%, will be dissolved with the N, N- of list -6- tolysulfonyl-beta-schardinger dextrin
Dimethylformamide is added thereto, and is well mixed, and the mixed system is condensing reflux 40-60 hours at 80-100 DEG C, reaction knot
Shu Houyong bag filters dialysis mixed liquor 3-4 days, carrys out purification of target product, is then freeze-dried, obtain the solid of cotton shape, be
The immobilized beta-schardinger dextrin of chitosan；
Wherein, chitosan bearing cyclodextrin, Loprazolam and P2O5Ratio be 1g：7-12 mL：1-5g.
2. synthetic method according to claim 1, it is characterised in that chitosan bearing cyclodextrin, Loprazolam and P2O5's
Ratio is 1g:10 mL:5 g.
3. synthetic method according to claim 1, it is characterised in that in the lower reaction of ice bath stirring, the reaction time is 1 ~ 3 small
When.
4. synthetic method according to claim 1, it is characterised in that also include, the step that obtained precipitated product is washed
Suddenly, precipitated product is washed with ether, acetone, methanol and ether successively.
5. the double modifications of chitosan bearing cyclodextrin phosphorylation that the synthetic method described in any one of claim 1 ~ 4 is prepared are spread out
It is biological.
6. the method that the double modified derivatives of chitosan bearing cyclodextrin phosphorylation described in claim 5 are enriched with Microcystin,
It is characterised in that it includes following steps：
1）The double modified derivatives of chitosan bearing cyclodextrin phosphorylation are dissolved in pH 10 ~ 11 NaHCO3/ Na2CO3Buffering is molten
In liquid；
2）In step 1）The sample containing Microcystin is added in obtained buffer system, mixes to place and is adsorbed；
3）To step 2）System in add concentration be 0.1-0.5mol/L glacial acetic acid to precipitate chitosan bearing cyclodextrin phosphoric acid
Change double modified derivatives, the derivative of Microcystin has been adsorbed in centrifugation；
4）Trichloroacetic acid is added in concentration 50%-70% methanol aqueous solutions, and the volume for constituting trichloroacetic acid in eluent, eluent is dense
Spend for 0.03-0.07%, with elution step 3）Microcystin on the obtained derivative for having adsorbed Microcystin
Element.
7. the method that the double modified derivatives of chitosan bearing cyclodextrin phosphorylation described in claim 5 are enriched with Microcystin,
It is characterised in that it includes following steps：
1）The double modified derivatives of the chitosan bearing cyclodextrin phosphorylation add water sample containing Microcystin or containing Microcystis aeruginosa
The sample suspension of toxin places absorption, and centrifugation obtains derivative;
2）Trichloroacetic acid is added in concentration 50%-70% methanol aqueous solutions, and the volume for constituting trichloroacetic acid in eluent, eluent is dense
Spend for 0.03-0.07%, with elution step 1）Microcystin on the obtained derivative for having adsorbed Microcystin
Element.
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| CN109052650B (en) * | 2018-08-15 | 2021-04-20 | 浙江海洋大学 | Preparation of immobilized microalgae water quality control agent |
| CN111771968A (en) * | 2020-03-09 | 2020-10-16 | 天津科技大学 | Thymol-chitosan oligosaccharide compound and preparation method and application thereof |
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| Hydroxypropyl Chitosan Bearing b-Cyclodextrin;Mani Prabaharan等;《Macromol. Biosci.》;20051231;第5卷;第965-973页 * |
| 壳聚糖及其衍生物固载环糊精的制备及应用研究进展;程德书等;《化工进展》;20081231;第27卷(第6期);第819-830页 * |
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