CN106046391B - A kind of netted ion imprinted polymer, preparation method and application - Google Patents
A kind of netted ion imprinted polymer, preparation method and application Download PDFInfo
- Publication number
- CN106046391B CN106046391B CN201610621212.0A CN201610621212A CN106046391B CN 106046391 B CN106046391 B CN 106046391B CN 201610621212 A CN201610621212 A CN 201610621212A CN 106046391 B CN106046391 B CN 106046391B
- Authority
- CN
- China
- Prior art keywords
- imprinted polymer
- gelatin
- hydroxyquinoline
- ion imprinted
- netted
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08H—DERIVATIVES OF NATURAL MACROMOLECULAR COMPOUNDS
- C08H1/00—Macromolecular products derived from proteins
-
- 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
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/26—Synthetic macromolecular compounds
- B01J20/268—Polymers created by use of a template, e.g. molecularly imprinted polymers
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
- C08J3/243—Two or more independent types of crosslinking for one or more polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/02—Chemical treatment or coating of shaped articles made of macromolecular substances with solvents, e.g. swelling agents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2389/00—Characterised by the use of proteins; Derivatives thereof
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Medicinal Chemistry (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Biochemistry (AREA)
- Water Supply & Treatment (AREA)
- Environmental & Geological Engineering (AREA)
- Hydrology & Water Resources (AREA)
- Analytical Chemistry (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Peptides Or Proteins (AREA)
Abstract
The invention discloses netted ion imprinted polymer, preparation method and its applications of a kind of Selective recognition lead ion, belong to field of new materials.It is used as function monomer using Mannich reaction synthesis 8-hydroxyquinoline grafted gelatin polypeptide, active group more enriches, contraction/swelling behavior is good, the advantages that film forming is high.On this basis, propose that a kind of secondary three step of swelling-chemical crosslinking of physical film deposition-prepares the technology of preparing of ion imprinted polymer.It is swollen the size of vessel used by control, the spontaneous distortion/folding of membrane material is completed in specific small space, obtains the imprinted polymer of various patterns.Finally, forming netted lead ion imprinted polymer films after Geniposide/transglutaminase double cross connection.Since function monomer is rich in various active group, double cross-linking systems and unique reticular structure, this ion imprinted polymer shows quick adsorption dynamics adsorption kinetics, high-adsorption-capacity and Selective recognition performance to lead ion.
Description
Technical field
The invention belongs to field of new materials, more particularly, to a kind of netted ion imprinted polymer, preparation method and
Using.
Background technique
In recent years, heavy metal pollution event in China's emerged one after another, and traces it to its cause and mostlys come from the random row of heavy metal
It puts and leaks.5 years from 2006 to 2010 year, there are nearly 20 great lead contamination accidents in China.It is high-incidence in accident
2009, the lead contamination accident placed on record is up to 178.Lead is accumulated in the body can damage renal function, while destroy mind
Through system, to budding children are in, lead poisoning is more likely to lead to intelligence decline and abnormal behavior.In fact, blood lead concentration is simultaneously
None safe dose.Although WHO thinks that blood lead concentration can be considered as normal value, lot of documents lower than 100 μ g/dL
Although showing blood lead concentration already below 75 μ g/dL, the intellectual development for influencing children is remained to.Therefore, a kind of environment is established
The detection technique of trace lead ion is imperative in complex samples.
Currently, laboratory mostly uses atomic absorption spectrum and inductive coupling plasma mass spectrometry as technological means, realize
The detection of lead ion in sample.Then, the Sample pretreatment of method is excessively cumbersome, high-temperature strong acid is needed to clear up, and technology content is quite
Height, instrument price is expensive, is not suitable for laboratories and carries out corresponding detection technique.Develop a kind of inexpensive, efficient pre-treatment
Technology is very necessary.
Ionic imprinting technique refers to the system obtained on space and binding site with the polymer of trace ion exact matching
Standby technology has the characteristics that high-efficient, at low cost, selectivity is good, practical, can play the effect of similar biological antibody,
Realize the highly selective identification of lead ion.However, since heavy metal lacks corresponding active group, thus the selection of function monomer
It is most important.Conventional use of 4-vinylpyridine and methacrylic acid organic monomer need to dissolve in organic solvent, virtually
The dissolubility for reducing template ion reduces corresponding recognition site.Secondly, the active group of these organic monomers is more single
One, thus it is poor to the Selective recognition ability of template ion, and application prospect is dull.Therefore, a kind of high water solubility, activity are developed
Radical species monomer abundant is the core link for promoting ion imprinted polymer performance.
Summary of the invention
Aiming at the above defects or improvement requirements of the prior art, the present invention provides a kind of nets of Selective recognition lead ion
Shape ion imprinted polymer and preparation method thereof, its object is to 8-hydroxyquinoline is prepared by Mancini reaction first to connect
The gelatin polypeptides of branch, the excellent performance by gelatin polypeptides as function monomer, and then pass through physical film deposition-swelling-change again
It learns crosslinking and a kind of netted ion imprinted polymer is prepared, thus solve the ion imprinted polymer organic monomer of the prior art
Active group is single, poorly water-soluble, the technical problem to the Selective recognition ability difference of template ion.
To achieve the above object, according to one aspect of the present invention, a kind of system of netted ion imprinted polymer is provided
Preparation Method includes the following steps：
(1) preparation of 8-hydroxyquinoline grafted gelatin polypeptide
1.1) pure Gelatin will be analyzed in the sodium hydroxide solution of 0.01~0.1mol/L, make gelatin concentration 10~
50mg/mL, reacted under the conditions of 70~100 DEG C 0.5~4 hour it is complete to gelatin hydrolysis, then with inorganic acid by the pH of solution
Value is adjusted to 7.0, and gelatin polypeptides solution is made；
1.2) in ethanol by 8-hydroxyquinoline dissolution, the gelatin polypeptides solution that step 1.1) is prepared is added, is matched
Homogeneous mixture solotion is made, wherein the mass ratio of gelatin and 8-hydroxyquinoline is 1~5:1；
1.3) acetic acid and 1~5% for accounting for its total volume 0.1~1% are added in the mixed solution that step 1.2) obtains
It after formaldehyde, is reacted 4~10 hours under the conditions of 80~100 DEG C, obtaining white precipitate is 8-hydroxyquinoline grafted gelatin polypeptide；
(2) by physical film deposition-, swelling-chemical crosslinking prepares netted ion imprinted polymer again.
Preferably, the step (2) includes following sub-step：
2.1) physical film deposition：The 8-hydroxyquinoline grafted gelatin polypeptide that lead acetate, chitosan and step (1) are prepared
It is dispersed in 5~20mL water and obtains mixed liquor, wherein the mass ratio of lead acetate, chitosan and 8-hydroxyquinoline grafted gelatin polypeptide
It is 1:1~10:1~10, then mixed liquor is poured into culture dish A, in 40~60 DEG C of fully reactings, it is thin to obtain yellow colloidal
Film；
2.2) it is swollen again：The yellow colloidal film that step 2.1) obtains is put into culture dish B, the culture dish B's
Diameter is smaller than the diameter of culture dish A, and aqueous solution, which is added, makes its swelling/folding obtain gel-like film；
2.3) it is chemically crosslinked：Geniposide and two kinds of transglutaminase friendships are added into the gel-like film that step 2.2) obtains
Join agent and carry out chemical polymerization, wherein the gross mass of chitosan and 8-hydroxyquinoline grafted gelatin polypeptide, Geniposide and turns glutamy
The mass ratio of amine enzyme is 200:1~10:1~10, it is reacted 10~20 hours at 40~60 DEG C, obtains blue network polymers,
After removing template lead acetate with pickling, netted ion imprinted polymer is obtained.
Preferably, the concentration of gelatin is 30mg/mL in the step 1.1).
Preferably, the mass ratio of gelatin and 8-hydroxyquinoline is 2.1 in the step 1.2):1.
Preferably, the dosage of acetic acid and formaldehyde is respectively the 0.5% of the mixed solution total volume in the step 1.3)
With 1%.
Preferably, the mass ratio of lead acetate, chitosan and 8-hydroxyquinoline grafted gelatin polypeptide is in the step 2.1)
1:5:5。
Preferably, chitosan and 8-hydroxyquinoline grafted gelatin polypeptide gross mass, Geniposide and turn in the step 2.3)
Glutaminase and mass ratio be 40:1:1.
Other side according to the invention provides a kind of netted ion imprinted polymer, it is characterised in that：According to institute
The preparation method stated is prepared.
Preferably, the netted ion imprinted polymer is 78mg/g to the adsorption capacity of Pb (II), and imprinting factor is
4.58。
Other side according to the invention provides the application of netted ion imprinted polymer described in one kind, application
In the Selective recognition to the Pb (II) in water sample, the efficient suction of selective extraction or Pb (II) including Pb in water sample (II)
Attached/purification.
Other side according to the invention provides a kind of selective absorbent of Pb (II), it is characterised in that：Include
The netted ion imprinted polymer.
In general, through the invention it is contemplated above technical scheme is compared with the prior art, can obtain down and show
Beneficial effect.
(1) compared with traditional ion imprinted polymer, the gelatin polypeptides of 8-hydroxyquinoline grafting prepared by the present invention are rich
Containing functional group abundant (amino, carboxyl, imino group, sulfydryl, imidazoles etc.) and gelatin egg is destroyed by basic hydrolysis technology
Three strands of peptide chain spiral winding structures of white reservation, obtain the mixtures of polypeptides of small molecule, are more advantageous to ion imprinted polymer
Preparation.Further, since gelatin structural damage, gelatin polypeptides are a kind of aqueous solutions (gelatin is solid under room temperature) under room temperature,
With good water phase compatibility, film forming characteristics and environmentally protective characteristic.
(2) good characteristic of the gelatin polypeptides based on 8-hydroxyquinoline grafting, the present invention propose a kind of physical film deposition-again
Three step of swelling-chemical crosslinking prepares the technology of preparing of ion imprinted polymer, and preparing product not only has water phase compatibility, but also
Preparation is simple, low in cost, can be realized the highly selective identification of target molecule in complex environment sample, both can be used for water sample
The selective extraction of middle Pb (II), can be used for efficient absorption/purification of Pb (II).
(3) chemical crosslinking of ion imprinted polymer is used as crosslinking agent using Geniposide and transglutaminase simultaneously.Capital
The flat crosslinking that can be realized amino and amino of Buddhist nun, maintains the three-dimensional structure in trace hole, however amino itself is also trace polymerization
The functional group of object identification, excessive crosslinking will affect the adsorption capacity of polymer, and excessively few then mechanical stability is insufficient.The present invention draws
Glutamine and lysine can be polymerize, not influence with substrate dependence by entering another transglutaminase as crosslinking agent
Other amino acid residues (especially amino), thus show the double dominant of high mechanical stability and high-adsorption-capacity.
(4) by selecting different lewis' acids for template, it can be used in the imprinted polymer for preparing any object.
(5) netted ion imprinted polymer of the present invention is 78mg/g to the adsorption capacity of Pb (II), it is selective because
Son reaches 4.58 times.
Detailed description of the invention
Fig. 1 is that embodiment 1 is prepared among the flow diagram and the ion imprinted polymer of netted ion imprinted polymer
And end-state electron microscope；
Fig. 2 is netted ion imprinted polymer and nonionic imprinted polymer (blank control) of the invention to lead ion
Adsorption effect；
Fig. 3 is the adsorption dynamics adsorption kinetics of netted ion imprinted polymer of the invention to Pb (II)；
Fig. 4 is the Selective recognition performance of netted ion imprinted polymer of the invention to various heavy metal ion.
Specific embodiment
In order to make the objectives, technical solutions, and advantages of the present invention clearer, with reference to the accompanying drawings and embodiments, right
The present invention is further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, and
It is not used in the restriction present invention.As long as in addition, technical characteristic involved in the various embodiments of the present invention described below
Not constituting a conflict with each other can be combined with each other.
A kind of netted ion imprinted polymer provided by the invention, preparation method include the following steps：
(1) preparation of 8-hydroxyquinoline grafted gelatin polypeptide
It 1.1) will be the pure Gelatin of analysis made of Raw material processing in the sodium hydroxide of 0.01~0.1mol/L using pigskin
In solution, until Gelatin is complete, wherein the concentration of gelatin is 10~50mg/mL, preferably 30mg/mL, in 70~100 DEG C of conditions
It is lower reaction 0.5~4 hour, glutin is hydrolyzed to the mixtures of polypeptides of small molecule, then with sodium hydroxide isoconcentration
The pH value of solution is adjusted to 7.0 by hydrochloric acid, obtains gelatin polypeptides aqueous solution；
1.2) 8-hydroxyquinoline is dissolved in ethanol solution, the gelatin polypeptides aqueous solution of 1.1) preparation is then added,
The mass ratio of middle gelatin and 8-hydroxyquinoline is 1~5:1, preferably 2.1:1, ultrasonic disperse uniformly obtains mixed solution；
1.3) acetic acid of total volume 0.1~1% and 1~5% formaldehyde are accounted in the mixed solution addition that step 1.2) obtains
Afterwards, wherein the dosage of acetic acid and formaldehyde is respectively preferably the 0.5% and 1% of the mixed solution total volume, pour into be connected with it is cold
In the round-bottomed flask of solidifying pipe, 80~100 DEG C of reactions, 4~10 hours, obtaining white precipitate was that 8-hydroxyquinoline grafted gelatin is more
Peptide；It is cleaned repeatedly with ethyl alcohol and aqueous solution, removes unreacted reagent.
(2) netted ion imprinted polymer is prepared：
2.1) physical film deposition：8-hydroxyquinoline grafted gelatin prepared by a certain amount of lead acetate, chitosan and step (1)
Polypeptide is dispersed in 5~20mL aqueous solution, and wherein the mass ratio of lead acetate, chitosan and 8-hydroxyquinoline grafted gelatin polypeptide is
1:1~10:1~10, preferably 1:5:5, then mixed liquor is poured into culture dish (A), 40~60 DEG C of fully reactings obtain Huang
Color gel-like film；
2.2) it is swollen again：Yellow colloidal film prepared by step (2.1), is put into culture more smaller than culture dish (A)
In ware (B), aqueous solution, which is added, makes its swelling/folding, folds the diameter ratio that degree depends on culture dish (A) and culture dish (B).
2.3) it is chemically crosslinked：In the hydrogel thin film of swelling, two kinds of crosslinking agents of Geniposide and transglutaminase are added
Chemical polymerization is carried out, wherein gross mass, Geniposide and the transglutaminase of chitosan and 8-hydroxyquinoline grafted gelatin polypeptide
Mass ratio be 200:1~10:1~10, preferably 40:1:1, it is reacted 10~20 hours at 40~60 DEG C, obtains blue net
Shaped polymer after washing away template lead acetate with hydrochloric acid, has obtained netted ion imprinted polymer.
One of the objects of the present invention is to provide a kind of novel function monomers.Gelatin has been abolished by technology for hydrolyzing
Three-dimensional molecular structure, the gelatin polypeptides of acquisition are rich in activity functional groups abundant, and have unique characteristic of science, such as：
Water phase compatibility, film forming characteristics and environmentally protective characteristic, are more suitable for preparing ion imprinted polymer.8-hydroxyquinoline is a kind of normal
Heavy metal chelating reagent.By the gelatin polypeptides of 8-hydroxyquinoline grafting prepared by Mannich reaction, active group is more
It is abundant, contraction/swelling behavior is good, be a kind of ideal monomer to prepare ion imprinted polymer, realize Lead in Aqueous Solution
Selective recognition.Based on this, the invention firstly uses Mannich reactions to synthesize 8-hydroxyquinoline grafted gelatin polypeptide as function
Can monomer, by its excellent performance, so propose a kind of simple physical film deposition-be swollen-be chemically crosslinked again three steps prepare from
The technology of preparing of sub- imprinted polymer.Control is swollen the size of vessel used, using narrow space, so that the spontaneous torsion of material
Song/folding obtains the imprinted polymer of different-shape.Finally, forming netted lead ion imprinted polymer after chemical crosslinking
Film.The double cross-linking systems of Geniposide/transglutaminase can obtain the dual excellent of high mechanical stability and high-adsorption-capacity
Gesture.Due to the various active group, double cross-linking systems and special reticular structure of function monomer, this ion imprinted polymer is to lead
Ion shows quick adsorption dynamics adsorption kinetics, extremely strong adsorption capacity and highly selective recognition performance.
Netted ion imprinted polymer prepared by the present invention is 78mg/g to the adsorption capacity of Pb (II), and imprinting factor is
4.58, it can be applied to the Selective recognition to the Pb (II) in water sample, selective extraction or Pb including Pb in water sample (II)
(II) efficient absorption/purification.
The following are embodiments：
Embodiment 1
(1) preparation of 8-hydroxyquinoline grafted gelatin polypeptide
It will be using pigskin as the pure Gelatin (0.1mol/ in the sodium hydroxide solution of 25mL of analysis made of Raw material processing
L), gelatin concentration 30mg/mL reacts 2 hours under the conditions of 80 DEG C and obtains gelatin polypeptides, then will be molten with the hydrochloric acid of isoconcentration
The pH value of liquid is adjusted to 7.0.350mg 8-hydroxyquinoline is dissolved in 25mL ethanol solution, it is molten that above-mentioned gelatin polypeptides are then added
In liquid, ultrasonic disperse is uniform；Then, it after 0.25mL acetic acid and 0.5mL formaldehyde is added in mixed solution, pours into and is connected with condenser pipe
Round-bottomed flask in, 100 DEG C reaction, 6 hours, obtain white precipitate；It is cleaned, is removed unreacted repeatedly with ethyl alcohol and aqueous solution
Reagent；
(2) netted ion imprinted polymer is prepared
A certain amount of lead acetate (20mg), chitosan (100mg) and 8-hydroxyquinoline grafted gelatin (100mg) are dispersed in
In 10mL aqueous solution, then mixed liquor is poured into culture dish (diameter 90mm), it is thin to obtain white gels for 60 DEG C of fully reactings
Film.Then, film is put into culture dish (diameter 20mm), aqueous solution, which is added, makes its swelling/folding.Finally, the capital 5mg Buddhist nun is added
Gentle 5mg transglutaminase is chemically crosslinked, and 40 DEG C are reacted 10 hours, is obtained blue network polymers, is washed away with hydrochloric acid
After template lead acetate, netted ion imprinted polymer has been obtained.
The preparation process of netted nonionic imprinted polymer (blank control) is same as above, is only added without in preparation process
Template lead acetate.Since lead acetate is as template, thus function monomer can form multi-acting force around lead acetate, pass through capital
Buddhist nun is flat/chemical crosslinking of transglutaminase, so that it may obtain a kind of thin polymer film.After washing away template ion, reserved position
The template ion of absorption again of the point property of may be selected by, here it is the preparation principles of netted ion imprinted polymer.Rather than trace
Guidance of the polymer due to lacking template ion, thus function monomer random alignment, not will form the site of specific recognition, often
For the selectivity as blank control research ion imprinted polymer.
Fig. 1 shows flow diagram and the ion blotting polymerization that embodiment 1 prepares netted ion imprinted polymer
Object centre and end-state electron microscope.As can be seen that three step preparation flows are swollen-are chemically crosslinked again by physical film deposition-, with
And the excellent performance of the gelatin polypeptides of 8-hydroxyquinoline grafting, thus can get the network structure polymer of high crimp, to lead
Ion shows quick adsorption dynamics adsorption kinetics, extremely strong adsorption capacity and highly selective recognition performance.
Embodiment 2
(1) preparation of 8-hydroxyquinoline grafted gelatin polypeptide
It using pigskin is the pure Gelatin of analysis made of Raw material processing in the sodium hydroxide solution of 15mL by 150mg
(0.01mol/L), gelatin concentration 10mg/mL react 0.5 hour under the conditions of 70 DEG C and obtain gelatin polypeptides, then with etc. it is dense
The pH value of solution is adjusted to 7.0 by the hydrochloric acid of degree.150mg 8-hydroxyquinoline is dissolved in 25mL ethanol solution, is then added
State glue polypeptid solution clearly, ultrasonic disperse is uniform；Then, it after 0.04mL acetic acid and 0.8mL formaldehyde is added in mixed solution, pours into
It is connected in the round-bottomed flask of condenser pipe, 80 DEG C of reactions 4 hours, obtain white precipitate；It is cleaned repeatedly with ethyl alcohol and aqueous solution,
Remove unreacted reagent；
(2) netted ion imprinted polymer is prepared
A certain amount of lead acetate (20mg), chitosan (20mg) and 8-hydroxyquinoline grafted gelatin (20mg) are dispersed in
In 5mL aqueous solution, then mixed liquor is poured into culture dish (diameter 90mm), 40 DEG C of fully reactings obtain yellow colloidal film.
Then, film is put into culture dish (diameter 20mm), aqueous solution, which is added, makes its swelling/folding.Finally, the capital 0.2mg Buddhist nun is added
Gentle 0.2mg transglutaminase is chemically crosslinked, and 50 DEG C are reacted 15 hours, blue network polymers is obtained, with salt pickling
After removing template lead acetate, netted ion imprinted polymer has been obtained.
Embodiment 3
(1) preparation of 8-hydroxyquinoline grafted gelatin polypeptide
250mg, which is analyzed pure Gelatin (0.015mol/L), gelatin concentration in the sodium hydroxide solution of 50mL, is
50mg/mL reacts 4 hours under the conditions of 100 DEG C, the pH value of solution is then adjusted to 7.0 with the hydrochloric acid of isoconcentration.By 50mg
8-hydroxyquinoline is dissolved in 25mL ethanol solution, and above-mentioned gelatin polypeptides aqueous solution is then added, and ultrasonic disperse is uniform；Then,
After 0.75mL acetic acid and 3.75mL formaldehyde is added in mixed solution, pours into and be connected in the round-bottomed flask of condenser pipe, 90 DEG C of reactions,
10 hours, obtain white precipitate；It is cleaned repeatedly with ethyl alcohol and aqueous solution, removes unreacted reagent；
(2) netted ion imprinted polymer is prepared
A certain amount of lead acetate (20mg), chitosan (200mg) and 8-hydroxyquinoline grafted gelatin (200mg) are dispersed in
In 20mL aqueous solution, then mixed liquor is poured into culture dish (diameter 90mm), it is thin to obtain yellow colloidal for 50 DEG C of fully reactings
Film.Then, film is put into culture dish (diameter 20mm), aqueous solution, which is added, makes its swelling/folding.Finally, the capital 20mg is added
Buddhist nun is gentle, and 20mg transglutaminase is chemically crosslinked, and 60 DEG C are reacted 20 hours, blue network polymers is obtained, with salt pickling
After removing template lead acetate, netted ion imprinted polymer has been obtained.
Embodiment 4
The netted ion imprinted polymer of 20mg and nonionic imprinted polymer prepared by embodiment 1 are added separately to 20mL
Leaded aqueous solution in, the concentration of lead is respectively 0~100 μ g/mL.After oscillation 10 hours, measured using national standard method
The content of lead in supernatant, and then ion imprinted polymer and nonionic imprinted polymer are calculated to the adsorption capacity of lead.Knot
Fruit is as shown in Fig. 2, netted ion imprinted polymer reaches 78mg/g to the adsorption capacity of lead ion, and compares non-imprinted polymer
Adsorption capacity be only 17mg/g, imprinting factor (ratio of imprinted polymer and non-imprinted polymer adsorption capacity) is 4.58,
Show prepared by the imprinted sites of specific recognition lead ion.
Embodiment 5
The netted ion imprinted polymer of 20mg and nonionic imprinted polymer prepared by embodiment 1 are added separately to 20mL
Leaded aqueous solution in, the concentration of lead is respectively 10 μ g/mL.While oscillation absorption, it is spaced in different time point acquisitions
Clear liquid using the content of lead in national standard method measurement supernatant, and then calculates ion imprinted polymer and nonionic print
The rate of adsorption of the mark polymer to lead.As a result as shown in figure 3, due to reticular structure presence and removal the remaining print of template ion
Mark site, netted ion imprinted polymer can reach adsorption equilibrium in 45 minutes, print far below lead ion reported in the literature
The dynamics time (60~100 minutes) of mark polymer, show faster adsorption efficiency.Rather than ion imprinted polymer due to
Lack matched imprinted cavity, needs can be only achieved adsorption equilibrium within 120 minutes.
Embodiment 6
The netted ion imprinted polymer of 20mg and nonionic imprinted polymer prepared by embodiment 1 are added separately to 20mL
The aqueous solution containing different heavy metals in, the concentration of heavy metal ion is respectively 10 μ g/mL.After oscillation 10 hours, using state
The content of heavy metal ion in family's standard method measurement supernatant, and then it is poly- to calculate ion imprinted polymer and nonionic trace
Object is closed to the adsorption capacity of heavy metal ion, investigates the Selective recognition ability of ion imprinted polymer.As a result as shown in figure 4,
It is non-with blank control since function monomer carries active group abundant and the remaining print identification site of imprinting polymerization process
Imprinted polymer is compared, and netted ion imprinted polymer only shows highly selective recognition capability to lead ion, thus in complexity
It, being capable of highly selective identification lead ion in the environmental samples that matrix coexists, it can the selectivity extraction for Pb (II) in water sample
It takes, and can be used for efficient absorption/purification of Pb (II).
As it will be easily appreciated by one skilled in the art that the foregoing is merely illustrative of the preferred embodiments of the present invention, not to
The limitation present invention, any modifications, equivalent substitutions and improvements made within the spirit and principles of the present invention should all include
Within protection scope of the present invention.
Claims (9)
1. a kind of preparation method of netted ion imprinted polymer, which is characterized in that include the following steps：
(1) preparation of 8-hydroxyquinoline grafted gelatin polypeptide
1.1) pure Gelatin will be analyzed in the sodium hydroxide solution of 0.01~0.1mol/L, make gelatin concentration 10~
50mg/mL, reacted under the conditions of 70~100 DEG C 0.5~4 hour it is complete to gelatin hydrolysis, then with inorganic acid by the pH of solution
Value is adjusted to 7.0, and gelatin polypeptides solution is made；
1.2) in ethanol by 8-hydroxyquinoline dissolution, the gelatin polypeptides solution that step 1.1) is prepared is added, is configured to
Homogeneous mixture solotion, wherein the mass ratio of gelatin and 8-hydroxyquinoline is 1~5:1；
1.3) formaldehyde of the acetic acid and 1~5% that account for its total volume 0.1~1% is added in the mixed solution that step 1.2) obtains
Afterwards, it is reacted 4~10 hours under the conditions of 80~100 DEG C, obtaining white precipitate is 8-hydroxyquinoline grafted gelatin polypeptide；
(2) by physical film deposition-, swelling-chemical crosslinking prepares netted ion imprinted polymer again；
2.1) physical film deposition：The 8-hydroxyquinoline grafted gelatin polypeptide dispersion that lead acetate, chitosan and step (1) are prepared
Mixed liquor is obtained in 5~20mL water, wherein the mass ratio of lead acetate, chitosan and 8-hydroxyquinoline grafted gelatin polypeptide is 1:
1~10:1~10, then mixed liquor is poured into culture dish A, in 40~60 DEG C of fully reactings, obtains yellow colloidal film；
2.2) it is swollen again：The yellow colloidal film that step 2.1) obtains is put into culture dish B, the diameter of the culture dish B
Smaller than the diameter of culture dish A, aqueous solution, which is added, makes its swelling/folding obtain gel-like film；
2.3) it is chemically crosslinked：Two kinds of crosslinking agents of Geniposide and transglutaminase are added into the gel-like film that step 2.2) obtains
Chemical polymerization is carried out, wherein gross mass, Geniposide and the transglutaminase of chitosan and 8-hydroxyquinoline grafted gelatin polypeptide
Mass ratio be 200:1~10:1~10, it is reacted 10~20 hours at 40~60 DEG C, blue network polymers is obtained, with acid
After washing away template lead acetate, netted ion imprinted polymer is obtained.
2. the preparation method of netted ion imprinted polymer as described in claim 1, it is characterised in that：In the step 1.1)
The concentration of gelatin is 30mg/mL, and the mass ratio of gelatin and 8-hydroxyquinoline is 2.1 in the step 1.2):1.
3. the preparation method of netted ion imprinted polymer as described in claim 1, it is characterised in that：In the step 1.3)
The dosage of acetic acid and formaldehyde is respectively the 0.5% and 1% of the mixed solution total volume.
4. the preparation method of netted ion imprinted polymer as described in claim 1, it is characterised in that：In the step 2.1)
The mass ratio of lead acetate, chitosan and 8-hydroxyquinoline grafted gelatin polypeptide is 1:5:5.
5. the preparation method of netted ion imprinted polymer as described in claim 1, it is characterised in that：In the step 2.3)
The mass ratio of the gross mass of chitosan and 8-hydroxyquinoline grafted gelatin polypeptide, Geniposide and transglutaminase is 40:1:1.
6. a kind of netted ion imprinted polymer, it is characterised in that：According to the described in any item preparation methods of Claims 1 to 5
It is prepared.
7. netted ion imprinted polymer as claimed in claim 6, it is characterised in that：The netted ion imprinted polymer
Adsorption capacity to Pb (II) is 78mg/g, imprinting factor 4.58.
8. a kind of application of netted ion imprinted polymer as claimed in claim 6, it is characterised in that：Applied to in water sample
Pb (II) Selective recognition, efficient absorption/purification of selective extraction or Pb (II) including Pb in water sample (II).
9. a kind of selective absorbent of Pb (II), it is characterised in that：It polymerize comprising netted ion blotting as claimed in claim 6
Object.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610621212.0A CN106046391B (en) | 2016-08-01 | 2016-08-01 | A kind of netted ion imprinted polymer, preparation method and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610621212.0A CN106046391B (en) | 2016-08-01 | 2016-08-01 | A kind of netted ion imprinted polymer, preparation method and application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106046391A CN106046391A (en) | 2016-10-26 |
| CN106046391B true CN106046391B (en) | 2018-11-30 |
Family
ID=57196004
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610621212.0A Active CN106046391B (en) | 2016-08-01 | 2016-08-01 | A kind of netted ion imprinted polymer, preparation method and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106046391B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109647360A (en) * | 2019-01-28 | 2019-04-19 | 中国科学院烟台海岸带研究所 | A kind of preparation method and applications of green multifunctional monomer ion imprinted material |
| CN111375357A (en) * | 2020-04-07 | 2020-07-07 | 华东理工大学 | Preparation method of multifunctional nano aerogel with amphipathy |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101724097A (en) * | 2009-12-14 | 2010-06-09 | 武汉理工大学 | Chitosan and metal copper ion complex protein-imprinted polymer and preparation method thereof |
| CN105001463A (en) * | 2015-07-28 | 2015-10-28 | 河南工程学院 | Preparation method and application of gelatin-chitosan composite membrane |
| KR20160049682A (en) * | 2014-10-28 | 2016-05-10 | (주)헵틸와이 | Double crosslinked biocompatible porous sheet and manufacturing method thereof |
-
2016
- 2016-08-01 CN CN201610621212.0A patent/CN106046391B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101724097A (en) * | 2009-12-14 | 2010-06-09 | 武汉理工大学 | Chitosan and metal copper ion complex protein-imprinted polymer and preparation method thereof |
| KR20160049682A (en) * | 2014-10-28 | 2016-05-10 | (주)헵틸와이 | Double crosslinked biocompatible porous sheet and manufacturing method thereof |
| CN105001463A (en) * | 2015-07-28 | 2015-10-28 | 河南工程学院 | Preparation method and application of gelatin-chitosan composite membrane |
Non-Patent Citations (1)
| Title |
|---|
| "Selective Solid-Phase Extraction of Lead Ions in Water Samples Using Three-Dimensional Ion-Imprinted Polymers";Kai Huang等;《Analytical Chemistry》;20160606;第88卷(第13期);第6820-6826页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106046391A (en) | 2016-10-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Dinc et al. | Recent advances on core–shell magnetic molecularly imprinted polymers for biomacromolecules | |
| Li et al. | Efficient preparation of surface imprinted magnetic nanoparticles using poly (2-anilinoethanol) as imprinting coating for the selective recognition of glycoprotein | |
| Rao et al. | Metal ion-imprinted polymers—novel materials for selective recognition of inorganics | |
| Xu et al. | Chitosan in molecularly-imprinted polymers: Current and future prospects | |
| Gao et al. | A highly-efficient imprinted magnetic nanoparticle for selective separation and detection of 17β-estradiol in milk | |
| Li et al. | Photolithographic boronate affinity molecular imprinting: a general and facile approach for glycoprotein imprinting. | |
| Wang et al. | Covalent organic framework-coated magnetic graphene as a novel support for trypsin immobilization | |
| CN107469653B (en) | Synthesis method of molecular imprinting composite membrane for enriching and separating norfloxacin | |
| Shoghi et al. | Nanosized aptameric cavities imprinted on the surface of magnetic nanoparticles for high-throughput protein recognition | |
| US9308582B2 (en) | Solution stable and chemically reactive metallic nanoparticles | |
| Wu et al. | Recent advances in green reagents for molecularly imprinted polymers | |
| CN103506093B (en) | Magnetic dual-template protein molecule imprinted nano particle and preparation method thereof | |
| CN106046391B (en) | A kind of netted ion imprinted polymer, preparation method and application | |
| CN104292381A (en) | Preparation and application of fluorescence ion imprinting probe | |
| CN106442436A (en) | Magnetic quantum dot printing material for detecting trace 4-nitrophenol in water, preparation method and application thereof | |
| CN102483409A (en) | Detection method and quantification method of detection target | |
| Li et al. | Preparation of surface imprinted core-shell particles via a metal chelating strategy: specific recognition of porcine serum albumin | |
| CN110139708A (en) | For extracting the molecularly imprinted polymer bead of lithium, mercury and scandium | |
| Zhang et al. | A Ce 3+-imprinted functionalized potassium tetratitanate whisker sorbent prepared by surface molecularly imprinting technique for selective separation and determination of Ce 3+ | |
| Reville et al. | Customizable molecular recognition: Advancements in design, synthesis, and application of molecularly imprinted polymers | |
| CN106432606A (en) | Magnetic Cr(VI) ionic imprinting polymer and preparation method and application thereof | |
| Chen et al. | Magnetic molecularly imprinted polymers synthesized by surface‐initiated reversible addition‐fragmentation chain transfer polymerization for the enrichment and determination of synthetic estrogens in aqueous solution | |
| Gao et al. | Fabrication of boronate‐decorated polyhedral oligomeric silsesquioxanes grafted cotton fiber for the selective enrichment of nucleosides in urine | |
| Jiang et al. | A recyclable colorimetric sensor made of waste cotton fabric for the detection of copper ions | |
| Sun et al. | Click synthesis of boronic acid-functionalized molecularly imprinted silica nanoparticles with polydopamine coating for enrichment of trace glycoproteins |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |