CN109772178A - A kind of preparation method and application of the pyrimethamine molecularly imprinted composite membrane based on the two-sided load of click chemistry - Google Patents
A kind of preparation method and application of the pyrimethamine molecularly imprinted composite membrane based on the two-sided load of click chemistry Download PDFInfo
- Publication number
- CN109772178A CN109772178A CN201811542607.7A CN201811542607A CN109772178A CN 109772178 A CN109772178 A CN 109772178A CN 201811542607 A CN201811542607 A CN 201811542607A CN 109772178 A CN109772178 A CN 109772178A
- Authority
- CN
- China
- Prior art keywords
- pyrimethamine
- composite membrane
- molecularly imprinted
- imprinted composite
- preparation
- 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.)
- Granted
Links
Landscapes
- Separation Using Semi-Permeable Membranes (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention belongs to functional material preparation technical fields, disclose a kind of preparation method and application of pyrimethamine molecularly imprinted composite membrane based on the two-sided load of click chemistry；Preparation step are as follows: using dopamine as biomimetic modification material, carbon nanotube is film support materials, pyrimethamine is template molecule, methacrylic acid is function monomer, four (3- mercaptopropionic acid) pentaerythritol esters be crosslinking agent, dipentaerythritol it is amyl-/hex- acrylic acid is assistant crosslinking agent, in conjunction with two-sided suction filtration load means, based on " click chemistry " polymerization, the pyrimethamine molecularly imprinted composite membrane of two-sided load is prepared；The recycling of hardly possible present in the existing pyrimethamine molecularly imprinted polymer of two-sided load pyrimethamine molecularly imprinted composite membrane effective solution prepared by the present invention is also easy to produce the deficiencies of secondary pollution；In addition, there is good specific recognition capability and adsorbing separation ability to pyrimethamine.
Description
Technical field
The invention belongs to functional material preparation technical fields, and in particular to a kind of ethamine based on the two-sided load of click chemistry
The preparation method and application of pyrimidines molecules trace composite membrane.
Background technique
Pyrimethamine is a kind of broad-spectrum antiseptic veterinary drug, is mainly used for preventing and treating chicken coccidiasis, avian cholera and white scour of piglet etc..This
Outside, pyrimethamine also has a wide range of applications in culture fishery, appropriate to use the disease resistance that enhance aquatic livestock.And
Pyrimethamine is accumulative with height in aquatic products body, exceeds a certain range, the hemopoietic system of people is destroyed after people is edible, is made
At haemolytical anaemia, or even there is the possibility for causing potential carcinogenicity, while Central nervous system has direct toxic effect.
2017, the carcinogenic substance inventory edit reference that international cancer research institution, the World Health Organization announces, pyrimethamine was three
In class carcinogenic substance inventory.Therefore develop it is a kind of can in efficient selective separation solution the method for pyrimethamine have it is particularly significant
Society and economy value.
Molecular engram film is a kind of new separation material developed based on membrane separation technique and molecular imprinting technology,
In the presence of template molecule (target molecule), the process being polymerize using function monomer in film surface is poly- in film surface
It closes and constructs the molecular recognition site that size and active force and target molecule match in object.In external driving force (pressure, concentration
Difference etc.) effect under so that the mixed solution containing different kinds of molecules is penetrated through molecular engram film, due to molecular engram recognition site
In the presence of target molecule can be by Selective recognition and absorption, rather than target molecule can then pass through molecular engram film
The other side is diffused to, with this to the Selective Separation between size, property similar molecules.
Molecular imprinting technology mainly utilizes conventional free radical polymerization, atom transfer radical polymerization, reversible addition-disconnected at present
The building that the polymerization methods such as chain transfer polymerization realize molecular engram recognition site is split, but since the above method often has energy consumption
High, reaction time length, polymerization process are difficult to the features such as controlling, and limit the combination of membrane separation technique and molecular imprinting technology
System." click chemistry " occurred in recent years is a kind of novel polymerization, have be swift in response, yield is high, selectivity is high, production
Many advantages, such as object is to oxygen and insensitive water is especially suitable for condition and requires harsh membrane surface molecule printing process.
Summary of the invention
In view of the deficiency of the prior art, it is an object of the invention to overcome technology existing in the prior art to lack
It falls into, the problems such as conventional molecular blotting membrane preparation time is long, temperature is high, selectivity is low is solved, so as to the thermal stability of basilar memebrane
It is required that being greatly reduced, preparation time substantially shortens, and the Selective Separation efficiency of target molecule (pyrimethamine) is substantially improved.
The present invention achieves the above technical objects by the following technical means.
A kind of preparation method based on two-sided load technology pyrimethamine molecularly imprinted composite membrane, comprising the following steps:
S1. the preparation of dopamine modified substrate film: three (methylol) aminomethane hydrochlorides and Dopamine hydrochloride are dissolved
Mixed solution is obtained in water, adjusts solution ph, basilar memebrane is immersed in mixed solution, when vibrating one section at room temperature
Between, dopamine modified substrate film is obtained after washing, drying；
S2. the preparation of two-sided carbon nanotube loaded film: by carbon nanotube, N, N- dimethyl-N-(3- sulfopropyl) -1- 18
Alkane ammonium inner salt is mixed with glycerol, carries out first time grinding, and the aqueous solution of kappa-carrageenan is added, and is carried out second and is ground；Then from
The heart takes supernatant liquor, and supernatant liquor is diluted with water and obtains dilution；The dilution vacuum filtration of certain volume is made in S1
After dry, dilution is filtered by vacuum in dopamine modified substrate film again for the upper surface of standby dopamine modified substrate film
Lower surface obtains two-sided carbon nanotube loaded film after drying again；
The preparation of the modified two-sided carbon nanotube loaded film of S3.KH570: the mixed solution of second alcohol and water is configured first, then
The two-sided carbon nanotube loaded film of S2 preparation is added, adds a certain amount of 3- (isobutene acyl-oxygen) propyl trimethoxy silicane,
It is heated to reflux, then is washed through alcohol, is dried to obtain the modified two-sided carbon nanotube loaded film of KH570；
S4. the preparation of pyrimethamine molecularly imprinted composite membrane: first mixing ethyl alcohol and dimethyl sulfoxide, and pyrimethamine is added
It is molten, add after mixing methacrylic acid, dipentaerythritol it is amyl-/hex- acrylic acid, four (3- mercaptopropionic acid) pentaerythrites
Ester and 2,2- dimethoxy -2- phenyl acetophenone, obtains mixed solution, finally by the modified two-sided carbon nanometer of the KH570 of S3 preparation
Pipe loaded film immerses in mixed solution, using sealing after nitrogen purification, trace polymerization reaction is carried out under ultraviolet light, through alcohol
Wash, dry after obtain trace polymerization film, template molecule is eluted using eluent, then wash, wash through alcohol, dry after obtain
Pyrimethamine molecularly imprinted composite membrane.
Preferably, the amount ratio of (methylol) aminomethane hydrochloride, Dopamine hydrochloride and water is three described in step S1
0.1211g:0.2g:100mL；The pH value for adjusting solution is 8.5.
Preferably, in step S1, oscillation a period of time for 3~for 24 hours.
Preferably, in step S2, the carbon nanotube, N, in N- dimethyl-N-(3- sulfopropyl) -1- octadecane ammonium
The amount ratio of salt, glycerol and kappa-carrageenan is 0.01~0.50g:0.42g:4mL:0.01g.
Preferably, in step S2, the first time milling time is 0~30min；Second of milling time be
0~60min；The revolving speed of the centrifugation is 4250rpm, time 15min；The extension rate that supernatant liquor is diluted with water
It is 1~40 times.
Preferably, in step S2, diameter and the suction filtration dilution volume of the dopamine modified substrate film upper and lower surface
Than being 25mm:(0.1~5.0) mL.
Preferably, in step S3, the volume ratio of second alcohol and water is 4:1 in the mixed solution；3- (the isobutene
Acyl-oxygen) volume ratio of propyl trimethoxy silicane and mixed solution is 1~5:100.
Preferably, in step S3, the temperature that is heated to reflux is 60~120 DEG C；The time that is heated to reflux is 12
~for 24 hours.
Preferably, in step S4, the amount ratio of the pyrimethamine, ethyl alcohol and dimethyl sulfoxide is 0.5~4mmol:
75mL:5~30mL.
Preferably, in step S4, the pyrimethamine, methacrylic acid, dipentaerythritol be amyl-/hex- acrylic acid, four
The amount ratio of (3- mercaptopropionic acid) pentaerythritol ester and 2,2- dimethoxy -2- phenyl acetophenone is 0.5~4mmol:4mmol:
1mmol:2mmol:10~80mg.
Preferably, in step S4, the wavelength of the ultraviolet light is 365nm；The time of the described trace polymerization reaction is
1-12h。
Preferably, in step S4, the sealing means are to be sealed with vacuum stopper, degreasing adhesive tape and preservative film；Institute
The eluent stated is the mixed solution of methanol and acetic acid, and the volume ratio of methanol and acetic acid is 95:5；The type of elution is,
It vibrates at room temperature, changes within every 3 hours an eluent, elution process continues 3 days.
Three (methylol) aminomethane hydrochloride as described in the above technical scheme, it acts as buffers.
Dopamine hydrochloride as described in the above technical scheme, it acts as basilar memebrane biomimetic modification reagents.
Carbon nanotube as described in the above technical scheme, it acts as basilar memebrane support materials.
N as described in the above technical scheme, N- dimethyl-N-(3- sulfopropyl) -1- octadecane ammonium inner salt, it acts as carbon
Nanotube crosslinking agent.
Glycerol as described in the above technical scheme, it acts as carbon nanotube crosslinking agents.
Kappa-carrageenan as described in the above technical scheme, it acts as carbon nanotube crosslinking agents.
3- (isobutene acyl-oxygen) propyl trimethoxy silicane as described in the above technical scheme, it acts as film activation modifications
Reagent.
Pyrimethamine as described in the above technical scheme, it acts as template molecules.
Ethyl alcohol as described in the above technical scheme, it acts as solvents.
Dimethyl sulfoxide as described in the above technical scheme, it acts as solvents.
Methacrylic acid as described in the above technical scheme, it acts as function monomers.
Dipentaerythritol as described in the above technical scheme is amyl-/hex- acrylic acid, it acts as assistant crosslinking agents.
Four (3- mercaptopropionic acid) pentaerythritol ester as described in the above technical scheme, it acts as crosslinking agents.
2,2- dimethoxy -2- phenyl acetophenone as described in the above technical scheme, it acts as photoinitiators.
It is phonetic the invention also includes pyrimethamine molecularly imprinted composite membrane is applied to ethamine in mixed solution containing pyrimethamine
The selective absorption and separation of pyridine, are applied particularly to second in the mixed solution of pyrimethamine, Diverdine, bisphenol-A and sulphadiazine
The selective absorption and separation of amic metadiazine.
Material properties test:
(1) adsorption isotherm experiment
Weigh 8 parts of pyrimethamine molecularly imprinted composite membranes, be respectively put into test tube, be separately added into 10mL concentration be 5,10,
25, the mixed solution of the pyrimethamine of 50,75,100,150 and 200mg/L, Diverdine, bisphenol-A and sulphadiazine, in room temperature item
After the completion of absorption, it is phonetic to measure ethamine unadsorbed in solution by ultraviolet-visible spectrophotometer by standing adsorption 180min under part
Pyridine, Diverdine, bisphenol-A and sulphadiazine concentration, and adsorbance (Q is calculated according to resulte, mg/g):
Q=(C0-Ce)×V/m (1)
Wherein C0(mg/L) and CeIt (mg/L) is respectively the concentration for adsorbing same molecule in the solution of front and back, V (mL) is that absorption is molten
The volume of liquid, m (g) by addition pyrimethamine molecularly imprinted composite membrane quality.
(2) dynamic absorption is tested
9 parts of pyrimethamine molecularly imprinted composite membranes are weighed respectively, are put into test tube, and being separately added into 10mL concentration is 50mg/L
Pyrimethamine, Diverdine, bisphenol-A and sulphadiazine mixed solution, at room temperature standing adsorption 0,5,10,15,30,
60, after the completion of absorption, it is phonetic to measure ethamine unadsorbed in solution by ultraviolet-visible spectrophotometer by 90,120 and 180min
Pyridine, Diverdine, bisphenol-A and sulphadiazine concentration, and adsorbance (Q is calculated according to resultt, mg/g):
Qt=(C0-Ct)×V/m (2)
Wherein C0(mg/L) and CtIt (mg/L) is respectively the concentration for adsorbing same molecule in the solution of front and back, V (mL) is that absorption is molten
The volume of liquid, m (g) by addition pyrimethamine molecularly imprinted composite membrane quality.
(3) selectively penetrating is tested
Prepared pyrimethamine molecularly imprinted composite membrane is placed among H-shaped glass tube, realizes that H-shaped glass tube is made
Standby pyrimethamine molecularly imprinted composite membrane is separated into identical two chambers, and 100mL concentration is added in a wherein chamber
For the mixed solution of the pyrimethamine of 50mg/L, Diverdine, bisphenol-A and sulphadiazine, while 100mL is added in another chamber
Pure solvent takes 5mL solution (to seep from pure solvent chamber respectively in 0,5,10,15,30,60,90,120,180,360 and 720min
Transparent liquid) and backfill 5mL pure solvent guarantees that two chamber solution no pressures are poor immediately, is measured and is sampled by ultraviolet-visible spectrophotometer
The concentration of pyrimethamine, Diverdine, bisphenol-A and sulphadiazine in penetrating fluid.
It advantages of the present invention and has the technical effect that
(1) compared to existing pyrimethamine molecularly imprinted polymer, pyrimethamine molecular engram prepared by the present invention is multiple
Close film and have many advantages, such as to be easily recycled, convenient for later separation, it is without secondary pollution to separate substance, can be applied to continuous process, have
Effect solves the recycling of hardly possible present in existing pyrimethamine molecularly imprinted polymer, is also easy to produce the deficiencies of secondary pollution；In addition,
Pyrimethamine molecularly imprinted composite membrane prepared by the present invention, can be phonetic from ethamine to pyrimethamine selectivity with higher
Pyridine, Diverdine, bisphenol-A and sulphadiazine mixed solution in efficiently separate pyrimethamine molecule.
(2) compared to existing molecular engram film, the present invention is based on the two-sided loading process of carbon nanotube, in conjunction with trace polymerization skill
Art, preparation have synthesized efficient, stable pyrimethamine molecularly imprinted composite membrane；The pyrimethamine molecularly imprinted composite membrane of preparation has
Selective advantage high, stability is strong, regenerability is stable makes its selectivity point to pyrimethamine in COMPLEX MIXED system
It is substantially improved from efficiency；Further, since the unique design of two-sided crosslinking load carbon nanotube, prepared pyrimethamine molecule print
Mark composite membrane mechanical strength, chemical stability, in terms of also have biggish promotion.
Detailed description of the invention
A, b and c are respectively the adsorption isothermal curve of pyrimethamine molecularly imprinted composite membrane, dynamics in embodiment 1 in Fig. 1
Adsorption curve and penetrating fluid concentration curve.
A, b and c are respectively the adsorption isothermal curve of pyrimethamine molecularly imprinted composite membrane, dynamics in embodiment 2 in Fig. 2
Adsorption curve and penetrating fluid concentration curve.
A, b and c are respectively the adsorption isothermal curve of pyrimethamine molecularly imprinted composite membrane, dynamics in embodiment 3 in Fig. 3
Adsorption curve and penetrating fluid concentration curve.
Specific embodiment
The present invention will be further described with specific embodiment with reference to the accompanying drawings of the specification.
Embodiment 1:
The preparation of S1, dopamine modified substrate film:
(methylol) aminomethane hydrochloride of 0.1211g tri- and 0.2g Dopamine hydrochloride are dissolved in 100mL water and obtained
Mixed solution, adjusting solution ph using the weak solution of hydrochloric acid and sodium hydroxide is 8.5, basilar memebrane (diameter 25mm) is immersed mixed
It closes in solution, vibrates 3h at room temperature, obtain dopamine modified substrate film after washing, drying.
The preparation of S2, two-sided carbon nanotube loaded film:
By 0.01g carbon nanotube, 0.42gN, N- dimethyl-N-(3- sulfopropyl) -1- octadecane ammonium inner salt and 4mL glycerol
Mixing is added the aqueous solution that 4mL contains 0.01g kappa-carrageenan, takes supernatant liquor after being centrifuged 15min with the revolving speed of 4250rpm, will
The supernatant vacuum filtration of 0.4mL is true by the dilution of 0.1mL after the obtained dopamine modified substrate film surface of S1, drying
Empty pump filters the another side in above-mentioned basilar memebrane, obtains two-sided carbon nanotube loaded film after drying again.
The preparation of the modified two-sided carbon nanotube loaded film of S3, KH570:
The preparation-obtained two-sided carbon nanotube loaded film of S2 is dispersed in the mixed solution of ethyl alcohol containing 80mL and 20mL water
In, it is added 3- (isobutene acyl-oxygen) propyl trimethoxy silicane of 1mL, after 60 DEG C of reflux 12h, is washed through alcohol and be dried to obtain KH570
Modified two-sided carbon nanotube loaded film.
The preparation of S4, pyrimethamine molecularly imprinted composite membrane:
0.5mmol pyrimethamine is dissolved in the mixed solution of ethyl alcohol containing 75mL and 5mL dimethyl sulfoxide, is divided after mixing
Not Jia Ru 4mmol methacrylic acid, 1mmol dipentaerythritol it is amyl-/hex- acrylic acid, 2mmol tetra- (3- mercaptopropionic acid) Ji Wusi
The modified two-sided carbon nanotube of the preparation-obtained KH570 of S3 is added in alcohol ester and 10mg 2,2- dimethoxy -2- phenyl acetophenone
Loaded film reacts 1h using sealing after nitrogen purification under 365nm ultraviolet light, and alcohol obtains trace polymerization film after washing drying, utilizes
The mixed solution (v/v=95:5) of methanol and acetic acid elutes template molecule, alcohol washes, washes, dry after to obtain ethamine phonetic
Pyridine molecularly imprinted composite membrane.
Fig. 1 (a) is the adsorption isothermal curve of prepared pyrimethamine molecularly imprinted composite membrane, prepared pyrimethamine
Molecularly imprinted composite membrane is in the mixed solution that concentration is 5,10,25,50,75,100,150 and 200mg/L to pyrimethamine, enemy
Bacterium is net, shown in bisphenol-A and sulphadiazine 180min adsorbance such as table 1 (a).It is above-mentioned the experimental results showed that prepared pyrimethamine
Molecularly imprinted composite membrane is higher than Diverdine, bis-phenol to the adsorbance of pyrimethamine in the mixed solution that concentration is 5~200mg/L
A and sulphadiazine, i.e., have the effect of being selectively adsorbing and separating to pyrimethamine.
Table 1 (a) pyrimethamine molecularly imprinted composite membrane isotherm adsorption data accorded
Fig. 1 (b) is the dynamic absorption curve of prepared pyrimethamine molecularly imprinted composite membrane, and prepared ethamine is phonetic
Pyridine molecularly imprinted composite membrane concentration be 50mg/L mixed solution in pyrimethamine, Diverdine, bisphenol-A and sulphadiazine 0,
5, shown in 10,15,30,60,90,120 and 180min adsorbance such as table 1 (b).It is above-mentioned the experimental results showed that prepared ethamine is phonetic
It is phonetic that pyridine molecularly imprinted composite membrane is higher than Diverdine, bisphenol-A and sulfanilamide (SN) to the adsorbance of pyrimethamine before reaching equilibrium adsorption capacity
Pyridine has the effect of being selectively adsorbing and separating to pyrimethamine.
Table 1 (b) pyrimethamine molecularly imprinted composite membrane dynamic absorption data
Fig. 1 (c) is prepared pyrimethamine molecularly imprinted composite membrane penetrating fluid obtained in selectively penetrating experiment
Concentration curve, using concentration for 50mg/L mixed solution as stoste, with prepared pyrimethamine molecularly imprinted composite membrane be seep
Saturating medium, pyrimethamine, Diverdine, bis-phenol in penetrating fluid in 0,5,10,15,30,60,90,120,180,360 and 720min
Shown in the concentration of A and sulphadiazine such as table 1 (c).It is above-mentioned the experimental results showed that prepared pyrimethamine molecularly imprinted composite membrane
Diverdine, bisphenol-A and sulphadiazine are lower than to the infiltration capacity of pyrimethamine, i.e., there is the effect of Selective Separation to pyrimethamine
Fruit.
Table 1 (c) pyrimethamine molecularly imprinted composite membrane selectively penetrating data
Embodiment 2:
The preparation of S1, dopamine modified substrate film:
(methylol) aminomethane hydrochloride of 0.1211g tri- and 0.2g Dopamine hydrochloride are dissolved in 100mL water and obtained
Mixed solution, adjusting solution ph using the weak solution of hydrochloric acid and sodium hydroxide is 8.5, basilar memebrane (diameter 25mm) is immersed mixed
It closes in solution, vibrates 6h at room temperature, obtain dopamine modified substrate film after washing, drying.
The preparation of S2, two-sided carbon nanotube loaded film:
By 0.12g carbon nanotube, 0.42gN, N- dimethyl-N-(3- sulfopropyl) -1- octadecane ammonium inner salt and 4mL glycerol
20min is ground after mixing, continues to grind 40min after the aqueous solution that 4mL contains 0.01g kappa-carrageenan is added, with turning for 4250rpm
Supernatant liquor is taken after speed centrifugation 15min and is diluted with water to the 1/20 of original content, by the dilution vacuum filtration of 0.4mL in S1 institute
After drying the another side in above-mentioned basilar memebrane is filtered by vacuum in the dilution of 0.4mL by obtained dopamine modified substrate film surface,
Two-sided carbon nanotube loaded film is obtained after drying again.
The preparation of the modified two-sided carbon nanotube loaded film of S3, KH570:
The preparation-obtained two-sided carbon nanotube loaded film of S2 is dispersed in the mixed solution of ethyl alcohol containing 80mL and 20mL water
In, it is added 3- (isobutene acyl-oxygen) propyl trimethoxy silicane of 3mL, after 80 DEG C of reflux 16h, is washed through alcohol and be dried to obtain KH570
Modified two-sided carbon nanotube loaded film.
The preparation of S4, pyrimethamine molecularly imprinted composite membrane:
1mmol pyrimethamine is dissolved in the mixed solution of ethyl alcohol containing 75mL and 10mL dimethyl sulfoxide, is divided after mixing
Not Jia Ru 4mmol methacrylic acid, 1mmol dipentaerythritol it is amyl-/hex- acrylic acid, 2mmol tetra- (3- mercaptopropionic acid) Ji Wusi
The modified two-sided carbon nanotube of the preparation-obtained KH570 of S3 is added in alcohol ester and 20mg 2,2- dimethoxy -2- phenyl acetophenone
Loaded film reacts 4h using sealing after nitrogen purification under 365nm ultraviolet light, and alcohol obtains trace polymerization film after washing drying, utilizes
The mixed solution (v/v=95:5) of methanol and acetic acid elutes template molecule, alcohol washes, washes, dry after to obtain ethamine phonetic
Pyridine molecularly imprinted composite membrane.
Fig. 2 (a) is the adsorption isothermal curve of prepared pyrimethamine molecularly imprinted composite membrane, prepared pyrimethamine
Molecularly imprinted composite membrane is in the mixed solution that concentration is 5,10,25,50,75,100,150 and 200mg/L to pyrimethamine, enemy
Bacterium is net, shown in bisphenol-A and sulphadiazine 180min adsorbance such as table 2 (a).It is above-mentioned the experimental results showed that prepared pyrimethamine
Molecularly imprinted composite membrane is higher than Diverdine, bis-phenol to the adsorbance of pyrimethamine in the mixed solution that concentration is 5~200mg/L
A and sulphadiazine, i.e., have the effect of being selectively adsorbing and separating to pyrimethamine.
Table 2 (a) pyrimethamine molecularly imprinted composite membrane isotherm adsorption data accorded
Fig. 2 (b) is the dynamic absorption curve of prepared pyrimethamine molecularly imprinted composite membrane, and prepared ethamine is phonetic
Pyridine molecularly imprinted composite membrane concentration be 50mg/L mixed solution in pyrimethamine, Diverdine, bisphenol-A and sulphadiazine 0,
5, shown in 10,15,30,60,90,120 and 180min adsorbance such as table 2 (b).It is above-mentioned the experimental results showed that prepared ethamine is phonetic
It is phonetic that pyridine molecularly imprinted composite membrane is higher than Diverdine, bisphenol-A and sulfanilamide (SN) to the adsorbance of pyrimethamine before reaching equilibrium adsorption capacity
Pyridine has the effect of being selectively adsorbing and separating to pyrimethamine.
Table 2 (b) pyrimethamine molecularly imprinted composite membrane dynamic absorption data
Fig. 2 (c) is prepared pyrimethamine molecularly imprinted composite membrane penetrating fluid obtained in selectively penetrating experiment
Concentration curve, using concentration for 50mg/L mixed solution as stoste, with prepared pyrimethamine molecularly imprinted composite membrane be seep
Saturating medium, pyrimethamine, Diverdine, bis-phenol in penetrating fluid in 0,5,10,15,30,60,90,120,180,360 and 720min
Shown in the concentration of A and sulphadiazine such as table 2 (c).It is above-mentioned the experimental results showed that prepared pyrimethamine molecularly imprinted composite membrane
Diverdine, bisphenol-A and sulphadiazine are lower than to the infiltration capacity of pyrimethamine, i.e., there is the effect of Selective Separation to pyrimethamine
Fruit.
Table 2 (c) pyrimethamine molecularly imprinted composite membrane selectively penetrating data
Embodiment 3:
The preparation of S1, dopamine modified substrate film:
(methylol) aminomethane hydrochloride of 0.1211g tri- and 0.2g Dopamine hydrochloride are dissolved in 100mL water and obtained
Mixed solution, adjusting solution ph using the weak solution of hydrochloric acid and sodium hydroxide is 8.5, basilar memebrane (diameter 25mm) is immersed mixed
It closes in solution, vibrates at room temperature for 24 hours, obtain dopamine modified substrate film after washing, drying.
The preparation of S2, two-sided carbon nanotube loaded film:
By 0.50g carbon nanotube, 0.42gN, N- dimethyl-N-(3- sulfopropyl) -1- octadecane ammonium inner salt and 4mL glycerol
30min is ground after mixing, continues to grind 60min after the aqueous solution that 4mL contains 0.01g kappa-carrageenan is added, with turning for 4250rpm
Supernatant liquor is taken after speed centrifugation 15min and is diluted with water to the 1/40 of original content, by the dilution vacuum filtration of 0.4mL in S1 institute
After drying the another side in above-mentioned basilar memebrane is filtered by vacuum in the dilution of 5.0mL by obtained dopamine modified substrate film surface,
Two-sided carbon nanotube loaded film is obtained after drying again.
The preparation of the modified two-sided carbon nanotube loaded film of S3, KH570:
The preparation-obtained two-sided carbon nanotube loaded film of S2 is dispersed in the mixed solution of ethyl alcohol containing 80mL and 20mL water
In, 3- (isobutene acyl-oxygen) propyl trimethoxy silicane of 5mL is added and is washed through alcohol after 120 DEG C of reflux for 24 hours and is dried to obtain KH570
Modified two-sided carbon nanotube loaded film.
The preparation of S4, pyrimethamine molecularly imprinted composite membrane:
4mmol pyrimethamine is dissolved in the mixed solution of ethyl alcohol containing 75mL and 30mL dimethyl sulfoxide, is divided after mixing
Not Jia Ru 4mmol methacrylic acid, 1mmol dipentaerythritol it is amyl-/hex- acrylic acid, 2mmol tetra- (3- mercaptopropionic acid) Ji Wusi
The modified two-sided carbon nanotube of the preparation-obtained KH570 of S3 is added in alcohol ester and 80mg 2,2- dimethoxy -2- phenyl acetophenone
Loaded film reacts 12h using sealing after nitrogen purification under 365nm ultraviolet light, and alcohol obtains trace polymerization film after washing drying, benefit
Template molecule is eluted with the mixed solution (v/v=95:5) of methanol and acetic acid, alcohol washes, washes, dry after obtain ethamine
Pyrimidines molecules trace composite membrane.
Fig. 3 (a) is the adsorption isothermal curve of prepared pyrimethamine molecularly imprinted composite membrane, prepared pyrimethamine
Molecularly imprinted composite membrane is in the mixed solution that concentration is 5,10,25,50,75,100,150 and 200mg/L to pyrimethamine, enemy
Bacterium is net, shown in bisphenol-A and sulphadiazine 180min adsorbance such as table 3 (a).It is above-mentioned the experimental results showed that prepared pyrimethamine
Molecularly imprinted composite membrane is higher than Diverdine, bis-phenol to the adsorbance of pyrimethamine in the mixed solution that concentration is 5~200mg/L
A and sulphadiazine, i.e., have the effect of being selectively adsorbing and separating to pyrimethamine.
Table 3 (a) pyrimethamine molecularly imprinted composite membrane isotherm adsorption data accorded
Fig. 3 (b) is the dynamic absorption curve of prepared pyrimethamine molecularly imprinted composite membrane, and prepared ethamine is phonetic
Pyridine molecularly imprinted composite membrane concentration be 50mg/L mixed solution in pyrimethamine, Diverdine, bisphenol-A and sulphadiazine 0,
5, shown in 10,15,30,60,90,120 and 180min adsorbance such as table 3 (b).It is above-mentioned the experimental results showed that prepared ethamine is phonetic
It is phonetic that pyridine molecularly imprinted composite membrane is higher than Diverdine, bisphenol-A and sulfanilamide (SN) to the adsorbance of pyrimethamine before reaching equilibrium adsorption capacity
Pyridine has the effect of being selectively adsorbing and separating to pyrimethamine.
Table 3 (b) pyrimethamine molecularly imprinted composite membrane dynamic absorption data
Fig. 3 (c) is prepared pyrimethamine molecularly imprinted composite membrane penetrating fluid obtained in selectively penetrating experiment
Concentration curve, using concentration for 50mg/L mixed solution as stoste, with prepared pyrimethamine molecularly imprinted composite membrane be seep
Saturating medium, pyrimethamine, Diverdine, bis-phenol in penetrating fluid in 0,5,10,15,30,60,90,120,180,360 and 720min
Shown in the concentration of A and sulphadiazine such as table 3 (c).It is above-mentioned the experimental results showed that prepared pyrimethamine molecularly imprinted composite membrane
Diverdine, bisphenol-A and sulphadiazine are lower than to the infiltration capacity of pyrimethamine, i.e., there is the effect of Selective Separation to pyrimethamine
Fruit.
Table 3 (c) pyrimethamine molecularly imprinted composite membrane selectively penetrating data
It is inhaled by adsorption isothermal curve and dynamics of the pyrimethamine molecularly imprinted composite membrane in FIG. 1 to FIG. 3 to pyrimethamine
Attached curve can be seen that pyrimethamine molecularly imprinted composite membrane prepared by the present invention in pyrimethamine and its analogue
To pyrimethamine adsorptive selectivity with higher in mixed solution, and can realize from analog in process of osmosis to second
Amic metadiazine efficiently separates.
Illustrate: above embodiments are only to illustrate the present invention and not limit the technical scheme described by the invention；Therefore,
Although this specification is referring to above-mentioned each embodiment, the present invention has been described in detail, the common skill of this field
Art personnel should be appreciated that and still can modify to the present invention or equivalent replacement；And all do not depart from spirit of the invention and
The technical solution and its improvement of range, should all cover in scope of the presently claimed invention.
Claims (10)
1. a kind of preparation method of the pyrimethamine molecularly imprinted composite membrane based on the two-sided load of click chemistry, which is characterized in that
Steps are as follows:
S1. dopamine modified substrate film is prepared；
S2. by carbon nanotube, N, N- dimethyl-N-(3- sulfopropyl) -1- octadecane ammonium inner salt is mixed with glycerol, carries out first
The aqueous solution of kappa-carrageenan is added in secondary grinding, carries out second and grinds；It is then centrifuged for taking supernatant liquor, and upper layer is diluted with water
Clear liquid obtains dilution；The dilution of certain volume is filtered by vacuum to the upper table of the dopamine modified substrate film prepared by S1
Dilution after dry, be filtered by vacuum in the lower surface of dopamine modified substrate film again, obtain two-sided carbon nanometer after dry by face
Pipe loaded film；
S3. the mixed solution for configuring second alcohol and water first, is then added the two-sided carbon nanotube loaded film of S2 preparation, adds
A certain amount of 3- (isobutene acyl-oxygen) propyl trimethoxy silicane, is heated to reflux, then is washed through alcohol, is dried to obtain KH570 and changes
The two-sided carbon nanotube loaded film of property；
S4. first ethyl alcohol and dimethyl sulfoxide are mixed, addition pyrimethamine is molten, adds methacrylic acid, two seasons after mixing
Penta tetrol is amyl-/hex- acrylic acid, four (3- mercaptopropionic acid) pentaerythritol esters and 2,2- dimethoxy -2- phenyl acetophenone obtains
The modified two-sided carbon nanotube loaded film of the KH570 of S3 preparation is finally immersed in mixed solution, utilizes nitrogen purification by mixed solution
After seal, under ultraviolet light carry out trace polymerization reaction, washed through alcohol, dry after obtain trace polymerization film, utilize eluent
Template molecule is eluted, then wash, wash through alcohol, dry after obtain pyrimethamine molecularly imprinted composite membrane.
2. the preparation side of the pyrimethamine molecularly imprinted composite membrane according to claim 1 based on the two-sided load of click chemistry
Method, which is characterized in that carbon nanotube described in step S2, N, N- dimethyl-N-(3- sulfopropyl) -1- octadecane ammonium inner salt,
The amount ratio of glycerol and kappa-carrageenan is 0.01 ~ 0.50g:0.42g:4mL:0.01g.
3. the preparation side of the pyrimethamine molecularly imprinted composite membrane according to claim 1 based on the two-sided load of click chemistry
Method, which is characterized in that preferred, in step S2, the first time milling time is 0 ~ 30min；Second of grinding
Time is 0 ~ 60min；The revolving speed of the centrifugation is 4250rpm, time 15min；It is described that the dilute of supernatant liquor is diluted with water
Releasing multiple is 1 ~ 40 times.
4. the preparation side of the pyrimethamine molecularly imprinted composite membrane according to claim 1 based on the two-sided load of click chemistry
Method, which is characterized in that the diameter of the dopamine modified substrate film upper and lower surface and the ratio for filtering dilution volume are 25mm:
(0.1 ~ 5.0) mL.
5. the preparation side of the pyrimethamine molecularly imprinted composite membrane according to claim 1 based on the two-sided load of click chemistry
Method, which is characterized in that in step S3, the volume ratio of second alcohol and water is 4:1 in the mixed solution；3- (the isobutene
Acyl-oxygen) volume ratio of propyl trimethoxy silicane and mixed solution is 1 ~ 5:100.
6. the preparation side of the pyrimethamine molecularly imprinted composite membrane according to claim 1 based on the two-sided load of click chemistry
Method, which is characterized in that in step S3, the temperature that is heated to reflux is 60 ~ 120 DEG C, return time 12-24h.
7. the preparation side of the pyrimethamine molecularly imprinted composite membrane according to claim 1 based on the two-sided load of click chemistry
Method, which is characterized in that in step S4, the amount ratio of the pyrimethamine, ethyl alcohol and dimethyl sulfoxide is 0.5 ~ 4mmol:75mL:
5~30mL；The pyrimethamine, methacrylic acid, dipentaerythritol be amyl-/hex- acrylic acid, four (3- mercaptopropionic acid) Ji Wusi
The amount ratio of alcohol ester and 2,2- dimethoxy -2- phenyl acetophenone is 0.5 ~ 4mmol:4mmol:1mmol:2mmol:10 ~ 80mg.
8. the preparation side of the pyrimethamine molecularly imprinted composite membrane according to claim 1 based on the two-sided load of click chemistry
Method, which is characterized in that in step S4, the wavelength of the ultraviolet light is 365nm；The time of the described trace polymerization reaction is 1 ~
12h。
9. the preparation side of the pyrimethamine molecularly imprinted composite membrane according to claim 1 based on the two-sided load of click chemistry
Method, which is characterized in that in step S4, the sealing means are to be sealed with vacuum stopper, degreasing adhesive tape and preservative film；Institute
The eluent stated is methanol and acetic acid with the mixed liquor that volume ratio is that 95:5 is formed；The type of elution are as follows: shake at room temperature
It swings, changes within every 3 hours an eluent, elution process continues 3 days.
10. the composite membrane of the preparation of preparation method described in any one is applied to pyrimethamine, enemy bacterium according to claim 1 ~ 9
Only, in the mixed solution of bisphenol-A and sulphadiazine pyrimethamine selective absorption and separation.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811542607.7A CN109772178B (en) | 2018-12-17 | 2018-12-17 | Preparation method and application of pyrimethamine molecularly imprinted composite membrane based on click chemistry double-sided loading |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811542607.7A CN109772178B (en) | 2018-12-17 | 2018-12-17 | Preparation method and application of pyrimethamine molecularly imprinted composite membrane based on click chemistry double-sided loading |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109772178A true CN109772178A (en) | 2019-05-21 |
| CN109772178B CN109772178B (en) | 2021-05-25 |
Family
ID=66497128
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811542607.7A Active CN109772178B (en) | 2018-12-17 | 2018-12-17 | Preparation method and application of pyrimethamine molecularly imprinted composite membrane based on click chemistry double-sided loading |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109772178B (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110193290A (en) * | 2019-05-30 | 2019-09-03 | 江苏大学 | A kind of preparation method and application based on click chemistry trace lincomycin molecular compound film |
| CN110501402A (en) * | 2019-09-24 | 2019-11-26 | 山东农业大学 | A kind of electrochemical sensor and its detection method of super sensitivity detection sulphathiazole |
| CN111440354A (en) * | 2020-03-27 | 2020-07-24 | 江苏大学 | Preparation method and application of bisphenol A molecularly imprinted composite membrane with through hierarchical pore structure |
| CN113318602A (en) * | 2021-05-17 | 2021-08-31 | 江苏大学 | Preparation method and application of three-dimensional macroporous PVDF (polyvinylidene fluoride) -based anti-fouling molecular imprinting membrane |
| CN113368708A (en) * | 2021-06-02 | 2021-09-10 | 江苏大学 | Preparation method and application of suction filtration type double-layer molecular imprinting nano composite membrane based on multiple nano composite imprinting system |
| CN113368706A (en) * | 2021-06-02 | 2021-09-10 | 江苏大学 | Preparation method and application of bionic suction filtration type double-layer molecularly imprinted nanofiber composite membrane based on poly-dopamine imprinting strategy |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105693959A (en) * | 2016-01-29 | 2016-06-22 | 华南师范大学 | Preparation method of magnetic molecularly imprinted polymer with hydrogen bond array |
| CN106008856A (en) * | 2016-06-30 | 2016-10-12 | 佛山科学技术学院 | Preparation method of molecularly imprinted polymer based on click chemistry |
| CN106117558A (en) * | 2016-06-30 | 2016-11-16 | 佛山科学技术学院 | A kind of method for separating and detecting of pyrimethamine |
| JP2017083293A (en) * | 2015-10-28 | 2017-05-18 | 日立化成株式会社 | Separation material and manufacturing method thereof |
| CN106902654A (en) * | 2017-03-30 | 2017-06-30 | 吉林师范大学 | A kind of preparation method and application of lithium ion trace polyethersulfone composite membrane |
| CN107344095A (en) * | 2017-08-29 | 2017-11-14 | 江苏大学 | A kind of lithium ion Blot PVDF Membrane and preparation method and its usage |
| CN108201795A (en) * | 2017-12-22 | 2018-06-26 | 江苏大学 | A kind of preparation method of Selective Separation Enoxacin molecularly imprinted composite membrane material |
-
2018
- 2018-12-17 CN CN201811542607.7A patent/CN109772178B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2017083293A (en) * | 2015-10-28 | 2017-05-18 | 日立化成株式会社 | Separation material and manufacturing method thereof |
| CN105693959A (en) * | 2016-01-29 | 2016-06-22 | 华南师范大学 | Preparation method of magnetic molecularly imprinted polymer with hydrogen bond array |
| CN106008856A (en) * | 2016-06-30 | 2016-10-12 | 佛山科学技术学院 | Preparation method of molecularly imprinted polymer based on click chemistry |
| CN106117558A (en) * | 2016-06-30 | 2016-11-16 | 佛山科学技术学院 | A kind of method for separating and detecting of pyrimethamine |
| CN106902654A (en) * | 2017-03-30 | 2017-06-30 | 吉林师范大学 | A kind of preparation method and application of lithium ion trace polyethersulfone composite membrane |
| CN107344095A (en) * | 2017-08-29 | 2017-11-14 | 江苏大学 | A kind of lithium ion Blot PVDF Membrane and preparation method and its usage |
| CN108201795A (en) * | 2017-12-22 | 2018-06-26 | 江苏大学 | A kind of preparation method of Selective Separation Enoxacin molecularly imprinted composite membrane material |
Non-Patent Citations (2)
| Title |
|---|
| THAYYATH S. ANIRUDHAN: "A potentiometric sensor for the trace level determination of hemoglobin in real samples using multiwalled carbon nanotube based molecular imprinted polymer", 《EUROPEAN POLYMER JOURNAL》 * |
| 刘发强: "乙胺嘧啶分子印迹聚合物的制备及其性能研究", 《化学工程师》 * |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110193290A (en) * | 2019-05-30 | 2019-09-03 | 江苏大学 | A kind of preparation method and application based on click chemistry trace lincomycin molecular compound film |
| CN110501402A (en) * | 2019-09-24 | 2019-11-26 | 山东农业大学 | A kind of electrochemical sensor and its detection method of super sensitivity detection sulphathiazole |
| CN111440354A (en) * | 2020-03-27 | 2020-07-24 | 江苏大学 | Preparation method and application of bisphenol A molecularly imprinted composite membrane with through hierarchical pore structure |
| CN111440354B (en) * | 2020-03-27 | 2022-04-26 | 江苏大学 | Preparation method and application of bisphenol A molecularly imprinted composite membrane with through hierarchical pore structure |
| CN113318602A (en) * | 2021-05-17 | 2021-08-31 | 江苏大学 | Preparation method and application of three-dimensional macroporous PVDF (polyvinylidene fluoride) -based anti-fouling molecular imprinting membrane |
| CN113318602B (en) * | 2021-05-17 | 2022-04-26 | 江苏大学 | Preparation method and application of three-dimensional macroporous PVDF (polyvinylidene fluoride) -based anti-fouling molecular imprinting membrane |
| CN113368708A (en) * | 2021-06-02 | 2021-09-10 | 江苏大学 | Preparation method and application of suction filtration type double-layer molecular imprinting nano composite membrane based on multiple nano composite imprinting system |
| CN113368706A (en) * | 2021-06-02 | 2021-09-10 | 江苏大学 | Preparation method and application of bionic suction filtration type double-layer molecularly imprinted nanofiber composite membrane based on poly-dopamine imprinting strategy |
| CN113368708B (en) * | 2021-06-02 | 2022-04-26 | 江苏大学 | Preparation method and application of suction filtration type double-layer molecular imprinting nano composite membrane based on multiple nano composite imprinting system |
| CN113368706B (en) * | 2021-06-02 | 2022-05-20 | 江苏大学 | Preparation method and application of bionic suction filtration type double-layer molecularly imprinted nanofiber composite membrane based on poly-dopamine imprinting strategy |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109772178B (en) | 2021-05-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109772178A (en) | A kind of preparation method and application of the pyrimethamine molecularly imprinted composite membrane based on the two-sided load of click chemistry | |
| Gao et al. | Recent advances and future trends in the detection of contaminants by molecularly imprinted polymers in food samples | |
| Malik et al. | Recent applications of molecularly imprinted polymers in analytical chemistry | |
| Zhou et al. | Recent advances and trends of molecularly imprinted polymers for specific recognition in aqueous matrix: Preparation and application in sample pretreatment | |
| Torabi et al. | A critical review of covalent organic frameworks-based sorbents in extraction methods | |
| CN104231166B (en) | A kind of preparation method of bionical artemisinin molecularly imprinted composite membrane | |
| CN107519845B (en) | A kind of ion liquid modified cross-linked porous chitosan absorbent and its preparation and application | |
| CN109174023A (en) | A kind of nano-cellulose cross-linked graphene/chitosan aeroge and preparation method thereof, application | |
| CN104479072A (en) | Method for preparing magnetic molecularly-imprinted adsorbent | |
| EP2080524A4 (en) | Pharmaceutical composition containing docetaxel-cyclodextrin inclusion complex and its preparing process | |
| Xing et al. | Biomass activated carbon/SiO2-based imprinted membranes for selective separation of atrazine: a synergistic integration system | |
| CN102068965A (en) | Method for preparing chitosan separation medium suitable for protein purification | |
| Wang et al. | Multi-templates molecularly imprinted polymers for simultaneous recognition of multiple targets: From academy to application | |
| CN110256629A (en) | A kind of preparation method of Bravo magnetic molecularly imprinted polymer | |
| CN104530314A (en) | Preparation method and application of bionic temperature-sensitive molecular engram composite film | |
| CN104062275A (en) | MWCNTs-QDs-based nano fluorescence bionic sensor and preparation method thereof | |
| CN102079795A (en) | Preparation of water-soluble crosslinked chitosan and application thereof | |
| CN110498887A (en) | A method of C14H10Cl2NNaO2 molecular imprinted polymer on surface is prepared as carrier in water phase using ZIF-67 | |
| Sun et al. | Eco-friendly deep eutectic solvents skeleton patterned molecularly imprinted polymers for the separation of sinapic acid from agricultural wastes | |
| CN106176620A (en) | A kind of Graphene medicament slow-release microsphere and preparation method thereof | |
| CN106758257A (en) | A kind of Electrospun nano-fibers of surface molecule print for bilirubin adsorption and preparation method thereof | |
| CN106638093A (en) | Preparation method of water-soluble filter paper cellulose micelle having photo-responsive characteristics | |
| CN111440354B (en) | Preparation method and application of bisphenol A molecularly imprinted composite membrane with through hierarchical pore structure | |
| CN110193290A (en) | A kind of preparation method and application based on click chemistry trace lincomycin molecular compound film | |
| CN109554826B (en) | Nano electro-spinning membrane with efficient selectivity on amino acid and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |