CN106496641A - A kind of preparation method and its usage of daiamid/rare-earth fluorescent blotting membrane - Google Patents
A kind of preparation method and its usage of daiamid/rare-earth fluorescent blotting membrane Download PDFInfo
- Publication number
- CN106496641A CN106496641A CN201610880214.1A CN201610880214A CN106496641A CN 106496641 A CN106496641 A CN 106496641A CN 201610880214 A CN201610880214 A CN 201610880214A CN 106496641 A CN106496641 A CN 106496641A
- Authority
- CN
- China
- Prior art keywords
- rare
- polyamide
- blotting membrane
- amide
- earth fluorescent
- 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
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
- C08L1/08—Cellulose derivatives
- C08L1/10—Esters of organic acids, i.e. acylates
- C08L1/12—Cellulose acetate
-
- 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
- B01J20/24—Naturally occurring macromolecular compounds, e.g. humic acids or their derivatives
-
- 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
- B01J20/262—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon to carbon unsaturated bonds, e.g. obtained by polycondensation
-
- 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
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
- B01J20/28033—Membrane, sheet, cloth, pad, lamellar or mat
-
- 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
- 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
- C08J2301/00—Characterised by the use of cellulose, modified cellulose or cellulose derivatives
- C08J2301/08—Cellulose derivatives
- C08J2301/10—Esters of organic acids
- C08J2301/12—Cellulose acetate
-
- 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
- C08J2305/00—Characterised by the use of polysaccharides or of their derivatives not provided for in groups C08J2301/00 or C08J2303/00
- C08J2305/08—Chitin; Chondroitin sulfate; Hyaluronic acid; Derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/16—Applications used for films
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Analytical Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Polymers & Plastics (AREA)
- Medicinal Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Materials Engineering (AREA)
- Water Supply & Treatment (AREA)
- Environmental & Geological Engineering (AREA)
- Hydrology & Water Resources (AREA)
- Investigating, Analyzing Materials By Fluorescence Or Luminescence (AREA)
- Investigating Or Analysing Materials By The Use Of Chemical Reactions (AREA)
Abstract
The invention provides a kind of preparation method and its usage of daiamid/rare-earth fluorescent blotting membrane, the preparation method comprises the steps：Prepare the coordination compound of europium；Prepare casting solution；Prepare daiamid/rare-earth fluorescent blotting membrane；The removing of template molecule in daiamid/rare-earth fluorescent blotting membrane.In the present invention, printing process occurs in membrane material surface and inside, it is to avoid conventional template molecule is only in the inadequate problem of surface barrier force.Shitosan is added, the molecularly imprinted polymer is embedded in film, it is to avoid polymer comes off in membrane cleaning process.Daiamid/rare-earth fluorescent trace the composite membrane obtained using the present invention has heat stability good, superior bisphenol-A molecular recognition performance.Molecular engram membrane technology is combined with detection technique of fluorescence, the new method of BPA contents in a kind of easy to operate, quick, sensitive and high throughput testing food is established.
Description
Technical field
The invention belongs to material is prepared and separation technology field, a kind of system of polyamide-amide/rare-earth fluorescent blotting membrane is refered in particular to
Preparation Method and application thereof.
Background technology
Bisphenol-A (BPA) as a kind of industrial chemicals, mainly for the production of polycarbonate plastic, epoxy resin, fire retardant,
Antioxidant, coating and pesticide etc., it is various with direct body contact's that downstream product is widely used in packaging for foodstuff, plastic etc.
In daily living article, therefore bisphenol-A can be entered in surrounding medium by all means.Meanwhile, bisphenol-A or one kind have
Have the environmental estrogens of stronger bio-toxicity and endocrine, and be difficult to degrade, easily accumulate in vivo, can and people
The endogenous hormones estradiol competition binding estrogen receptor of body, even if will also result in a lot of diseases of human body under conditions of trace
Occur, including the cancer relevant with hormone such as diabetes, carcinoma of prostate and breast carcinoma.Therefore, in the urgent need to Accurate Determining food
The content of middle BPA, to ensure human health.
At present, detection food in BPA contents assay method mainly have gas chromatography, high performance liquid chromatography and it
Various multiple techniques.As bisphenol-A has stronger polarity, easily adsorbed by complicated sample matrices, therefore entered
Before row chromatography, need to carry out extracting and developing and enrichment to which.Conventional sample pretreating method has liquid-liquid extraction, consolidates
Mutually extraction, matrix solid phase dispersion, accelerated solvent extraction, solid-phase microextraction, and liquid-liquid micro-extraction etc..Although these extracting process
The separation problem analysis of bisphenol-A is to some extent solved, but there is also deficiency, be mainly reflected in：Do not inhale with specificity
Attached performance, while target analytes are extracted, the close mutual interference thing of some structures and property can also be extracted.Work as target
Analyte concentration is very low, and when mutual interference thing concentration is larger, this competitive Adsorption effect can be to subsequent separation detection, such as thing
Matter separating degree, analytical precision and accuracy have a negative impact.Therefore, we be badly in need of one kind can quick, easy to operate,
Method with high-sensitivity detection trace BPA.
Molecular engram film (Molecularly Imprinted Membrane, MIM) is the one of separation function Material Field
Significant research direction is planted, the class film that it refers to comprising or is made up of molecularly imprinted polymer, by polymerization
Thing reaches the purpose of molecular recognition to the memory recognition performance of template molecule, and its molecule space identification ability is strong, can achieve Gao Xuan
Selecting property is separated；Basic ideas are addition microspheres in polymerisation medium, remove microsphere, trace polymerization layer net after film forming
The hole matched with microsphere size has been left with shape structure, has been existed between the blotting membrane and microsphere of generation
Interact, when using it for the mixture that separation microsphere is constituted with other materials, blotting membrane can recognize that microsphere,
So as to effectively object is separated from mixture.
Molecular engram membrane technology is combined with highly sensitive detection technique of fluorescence, is prepared with fluorescent characteristic
Fluorescence MIM, MIM can determine combined BPA contents according to changing for fluorescence signal while specific isolation BPA, and two
The combination of person can meet the demand of anti-interference, high sensitivity, high specific and high stability simultaneously, therefore in food samples
The analysis context of detection of BPA has broad application prospects.
Content of the invention
The present invention be with cellulose acetate (CA) as substrate, shitosan (CHI) be functional polymer, polyamide-amide wrap up
Rare Earth Europium Complex (PAMAM-Eu (TTA)3Phen it is) additive, synthesis has single-minded evident characteristics to bisphenol-A (BPA) molecule
Polyamide-amide/rare-earth fluorescent blotting membrane, and in aqueous solution bisphenol-A selective enumeration method identification and separate, the polyamides
Amine-amine/rare-earth fluorescent blotting membrane has higher selectivity and adsorptivity to bisphenol-A molecule.
The technical scheme is that：
A kind of preparation method of polyamide-amide/rare-earth fluorescent blotting membrane, comprises the steps：
Step 1,0.225～0.675g thenoyltrifluoroacetone (TTA) is dissolved in the ethanol of 10～30mL, with 1～
4mol/L NaOH solutions adjust pH=8.0, obtain mixed liquor A；
Step 2, the europiumsesquioxide (Eu for weighing 0.06～0.18g2O3), Deca 1～3mL concentrated hydrochloric acid makes europiumsesquioxide
Dissolving, adds the deionized water of 3～10mL, instills in the mixed liquor A in step 1, is warming up to 60 DEG C, magnetic agitation 0.5h,
Obtain mixed liquid B；
Step 3,0.06～0.18g o-phenanthrolines (Phen) are dissolved in the ethanol of 3～10mL, this ethanol solution is instilled
To in the mixed liquid B of step 2, under magnetic stirring, 60 DEG C of back flow reaction 3h, are cooled to room temperature after completion of the reaction, sucking filtration, then
With ethanol and water washing, 24h is vacuum dried at last 60 DEG C, obtains the coordination compound of europium；
Step 4, the coordination compound for taking the europium that step 3 is obtained, polyamide-amide are added in dimethyl sulfoxide (DMSO), are warming up to
40 DEG C, mechanical agitation 24h, to being completely dissolved, obtains mixed liquor C；
Membrane matrix cellulose acetate (CA), functional polymer shitosan is added in step 5, the mixed liquor C obtained to step 4
(CHI) and template molecule bisphenol-A (BPA), stirring and evenly mixing at 40 ± 5 DEG C, 3～4h of mechanical agitation obtain casting film to being uniformly dissolved
Liquid；
Step 6, the casting solution for obtaining step 5 are incubated standing at 40 ± 5 DEG C, to the bubble that stirring is produced is sloughed, so
Take the glass plate of a cleaning afterwards, casting solution is laid on glass plate, certain thickness is scraped with Glass rod, slow by which after 30s
In immersion deionized water, 30min is soaked, take out glass plate and peeled, obtain polyamide-amide/rare-earth fluorescent blotting membrane；
Step 7, the polyamide-amide/rare-earth fluorescent blotting membrane for obtaining step 6 are mixed molten using ferric chloride deionized water
Liquid is extracting solution, to remove template molecule bisphenol-A, is washed with water and washs to neutrality, will be glimmering for final obtained polyamide-amide/rare earth
Light blotting membrane is immersed in deionized water and stores.
In step 1～3, the thenoyltrifluoroacetone that used, europiumsesquioxide, the mass ratio of o-phenanthroline are
3.75:1:1, in step 2, the mass fraction of the concentrated hydrochloric acid is 36.5%.
In step 4, the coordination compound of described europium, polyamide-amide, dimethyl sulfoxide are 6 according to mass ratio:7:5129.
In step 5, in the casting solution of described film, the mass fraction of polymer cellulose acetate (CA) is 13%, work(
The mass fraction of energy polymer shell polysaccharide (CHI) for casting solution 1.0%, the mass fraction of template molecule bisphenol-A (BPA) is casting
The 0.3% of film liquid.
In step 6, the described standing and defoaming time is 24～48h, and the thickness of film is 2.0mm.
In step 7, in ferric chloride deionized water mixed solution, FeCl3Mass ratio with deionized water is 1:12500.
Prepared polyamide-amide/rare-earth fluorescent blotting membrane is used for the bisphenol-A in adsorbing separation aqueous solution.
The preparation method of corresponding non-blotting membrane (NIM) is same as described above, but is not added with template molecule bisphenol-A.
Rare earth compounding (i.e. the coordination compound of europium) described in above-mentioned technical scheme, its act as additive, detect mould
Plate bisphenol-A molecule.
Polyamide-amide dendrimer described in above-mentioned technical scheme, its act on additive, wrap up rare earth compounding,
Light stability and the heat stability of rare earth compounding is improved, has had both the advantage of organic and inorganic material.
Ethanol described in above-mentioned technical scheme, its act as solvent, and dissolving thenoyltrifluoroacetone and adjacent phenanthrene are coughed up
Quinoline.
Dimethyl sulfoxide described in above-mentioned technical scheme, which act as solvent, dissolves cellulose acetate, shitosan and adds
Plus agent, to prepare casting solution.
Cellulose acetate (CA) described in above-mentioned technical scheme, which act as membrane matrix.
Shitosan (CHI) described in above-mentioned technical scheme, which act as functional polymer, passes through hydrogen with template molecule
The effect of key, adsorbs template molecule.
Bisphenol-A (BPA) described in above-mentioned technical scheme, which act as template molecule.
Deionized water described in above-mentioned technical scheme, which act as non-solvent, so as to there is inversion of phases, film forming.
Ferric chloride deionized water mixed extract described in above-mentioned technical scheme, its act as blocking template molecule
Hydrogen bond action and between functional polymer, so as to eluted template molecule.
Polyamide-amide/rare-earth fluorescent blotting membrane is used for the bisphenol-A in adsorbing separation aqueous solution, and concrete grammar is according to following
Step is carried out：
(1) Staticadsorption experiment
Respectively take a piece of trace and non-blotting membrane is added in the bisphenol-A aqueous solution containing variable concentrations accordingly, in 25 DEG C of perseverances
Stand in incubator, after 4.0h, investigate the adsorbance of trace and non-blotting membrane, if the mixed liquor volume for adding is V (L), matched somebody with somebody molten
The initial concentration of liquid is C0(mg L-1), after certain time absorption, its equilibrium concentration is Ce(mg L-1), by below equation
Calculate the equilibrium adsorption capacity (Q of membranee,mg g-1) be：
(2) optimization of BPA conditions is detected based on fluorescence MIM multi-function microplate readers
Respectively take a piece of trace and non-blotting membrane add in the BPA solution containing variable concentrations accordingly (final concentration of 5,10,
15,20,25,30mg/L), after BPA is added, different time points (0,30,60,90,120,150min) are examined with multi-function microplate reader
The fluorescence intensity of mixed liquor is surveyed, to find out the optimum fluorescence MIM concentration of detection low concentration BPA and detection time.
(3) specificity analyses
Under the conditions of (2) multi-function microplate reader detection BPA optimal detections, fluorescence MIM or NIM are with concentration for 25mg/L's
BPA or its analog (BPC, BPZ, 4,4- dihydroxybiphenyls, tetrabromobisphenol A) mixing, with multi-function microplate reader determine BPA or its
After analog addition, the fluorescence intensity of mixed liquor, calculates fluorescence change I0/I.
Beneficial effect：
(1) printing process occurs in membrane material surface and inside, it is to avoid conventional template molecule is only in surface barrier force
Inadequate problem.
(2) shitosan is added, the molecularly imprinted polymer is embedded in film, it is to avoid polymer is de- in membrane cleaning process
Fall.
(3) polyamide-amide/rare-earth fluorescent trace composite membrane obtained using the present invention has heat stability good, superior
Bisphenol-A molecular recognition performance.
(4) molecular engram membrane technology is combined with detection technique of fluorescence, is established a kind of easy to operate, quick, sensitive
New method with BPA contents in high throughput testing food.
Specific embodiment
Above-mentioned polyamide-amide/rare-earth fluorescent blotting membrane is applied to the bisphenol-A in adsorbing separation aqueous solution, with reference to tool
The present invention will be further described for body embodiment.
Embodiment 1
(1) weigh 0.225g thenoyltrifluoroacetone (TTA) to be dissolved in 10ml ethanol, stir to being uniformly dissolved, use
1mol/L NaOH solutions adjust PH=8.0；
(2) 0.06g Eu are weighed2O3, Deca 1mL concentrated hydrochloric acid (mass fraction is 36.5%) is allowed to just dissolve, adds
3mL water is allowed to be completely dissolved, and this saline solution is instilled the ethanol solution in step (1), 60 DEG C is warming up to, magnetic agitation 0.5h；
(3) 0.06g o-phenanthrolines (Phen) are weighed to be dissolved in the ethanol of 3mL, this ethanol solution is instilled above-mentioned mixed liquor
In, it is added in the round-bottomed flask equipped with reflux condenser, 60 DEG C of magnetic agitation, flow back 3h, is cooled to room temperature, sucking filtration, then
Respectively with 6mL ethanol and 6mL water washings three times, 24h is vacuum dried at last 60 DEG C, obtains the coordination compound of europium；
(4) 8.5484g dimethyl sulfoxides (DMSO) are weighed for solvent, 0.01g rare earth compoundings and 0.0116g polyamides is weighed
Amine-amine is added in dimethyl sulfoxide (DMSO), is warming up to 40 DEG C, mechanical agitation 24h, to being completely dissolved；
(5) 1.3g cellulose acetate (CA), 0.1g shitosans (CHI) and 0.03g template molecule bisphenol-As (BPA) are added
In the solution obtained to step (4), at 40 DEG C, mechanical agitation 4h obtains casting solution to being uniformly dissolved；
(6) casting solution that step (5) is obtained, insulation at 40 DEG C stand, and slough the bubble that stirring is produced, then take one clean
Net glass plate, casting solution is laid on glass plate, is scraped certain thickness 2.0mm with Glass rod, is slowly dipped in after 30s
In deionized water, immersion 30min after take out, obtain final product polyamide-amide/rare-earth fluorescent blotting membrane, by polyamide obtained above-
Amine/rare-earth fluorescent blotting membrane is immersed in ferric chloride deionized water mixed solution, and (ferric chloride is 1 with water quality ratio:12500)
In, to remove template molecule bisphenol-A, it is washed with water and washs to neutrality, be stored in deionized water.The preparation method of non-blotting membrane with
Above-mentioned identical, but it is not added with template molecule bisphenol-A.
(7) obtained blotting membrane is carried out Staticadsorption experiment
Prepare 100mg L-1Bisphenol-A (BPA) solution, solvent is deionized water, respectively takes a piece of blotting membrane and non-blotting membrane
Quality is 0.02g, is separately added in bisphenol-A (BPA) solution of 10mL preparations, after standing 4.0h in 25 DEG C of calorstats, with ultraviolet
In spectrophotometer measurement solution, the content of bisphenol-A, as a result shows, the adsorbance of trace blend film is 4.49mg g-1Substantially high
Adsorbance 1.51mg g in non-blotting membrane-1.
(8) obtained blotting membrane is detected the optimization of BPA conditions
The trace and non-blotting membrane for respectively taking a piece of same volume is added in the BPA solution containing variable concentrations accordingly (eventually
Concentration is 5,10,15,20,25,30mg/L), after BPA is added, different time points (0,30,60,90,120,150min) are used many
Function microplate reader detects the fluorescence intensity of mixed liquor, as a result shows, detects that optimum fluorescence BPA concentration is using this method
25mg/L, detection time are 150min after addition BPA.
(9) specificity analyses
Under the conditions of (8) multi-function microplate reader detection BPA optimal detections, fluorescence MIM or NIM are with concentration for 25mg/L's
BPA or its analog (BPC, BPZ, 4,4- dihydroxybiphenyls, tetrabromobisphenol A) mixing, with multi-function microplate reader determine BPA or its
After analog addition, the fluorescence intensity of mixed liquor, calculates fluorescence change I0/ I, as a result shows, BPA has most strong to fluorescence MIM
Fluorescent quenching ability, meanwhile, the fluorescence change (I of MIM0/ I) big compared with NIM, illustrate that the former has spy to template molecule BPA
Different in nature absorbability.
Fluorescence MIM and NIM become drawing paper I with BPA and the like mixed fluorescence0/I
| Fluorescence change | BPA | BPC | BPZ | 4,4- dihydroxybiphenyls | Tetrabromobisphenol A |
| MIM(I0/I) | 1.56 | 0.98 | 1.02 | 0.96 | 1.00 |
| NIM(I0/I) | 0.82 | 1.32 | 0.76 | 0.78 | 0.74 |
Embodiment 2
(1) weigh 0.3375g thenoyltrifluoroacetone (TTA) to be dissolved in 15ml ethanol, stir to being uniformly dissolved, use
2mol/LNaOH solution adjusts PH=8.0；
(2) 0.09g Eu are weighed2O3, the appropriate concentrated hydrochloric acid of Deca (36.5%) is allowed to just dissolve, and adding 5mL water makes
Be completely dissolved, this saline solution is instilled the ethanol solution in step (1), 60 DEG C is warming up to, magnetic agitation 0.5h；
(3) 0.09g o-phenanthrolines (Phen) are weighed to be dissolved in the ethanol of 5mL, this ethanol solution is instilled above-mentioned mixed liquor
In, it is added in the round-bottomed flask equipped with reflux condenser, 60 DEG C of magnetic agitation, flow back 3h, is cooled to room temperature, sucking filtration, then
Respectively with 10mL ethanol and 10mL water washings three times, 24h is vacuum dried at last 60 DEG C, obtains the coordination compound of europium；
(4) 25.645g dimethyl sulfoxides (DMSO) are weighed for solvent, weigh the coordination compound and 0.035g polyamide of 0.03g europiums-
Amine is added in dimethyl sulfoxide (DMSO), is warming up to 40 DEG C, mechanical agitation 24h, to being completely dissolved；
(5) 3.9g cellulose acetate (CA), 0.3g shitosans (CHI) and 0.09g template molecule bisphenol-As (BPA) are added
In the solution obtained to step (4), at 40 DEG C, mechanical agitation 4h obtains casting solution to being uniformly dissolved；
(6) casting solution that step (5) is obtained, insulation at 40 DEG C stand, and slough the bubble that stirring is produced, then take one clean
Net glass plate, casting solution is laid on glass plate, is scraped certain thickness 2.0mm with Glass rod, is slowly dipped in after 30s
In deionized water, immersion 30min after take out, obtain final product polyamide-amide/rare-earth fluorescent blotting membrane, by polyamide obtained above-
Amine/rare-earth fluorescent blotting membrane is immersed in ferric chloride deionized water mixed solution, and (ferric chloride is 1 with water quality ratio:12500)
In, to remove template molecule bisphenol-A, it is washed with water and washs to neutrality, be stored in deionized water.The preparation method of non-blotting membrane with
Above-mentioned identical, but it is not added with template molecule bisphenol-A.
(7) obtained blotting membrane is carried out Staticadsorption experiment
Prepare 100mg L-1Bisphenol-A (BPA) solution, solvent is deionized water, respectively takes a piece of blotting membrane and non-blotting membrane
Quality is 0.02g, is separately added in bisphenol-A (BPA) solution of 10mL preparations, after standing 4.0h in 25 DEG C of calorstats, with ultraviolet
In spectrophotometer measurement solution, the content of bisphenol-A, as a result shows, the adsorbance of trace blend film is 4.85mg g-1Substantially high
Adsorbance 2.21mg g in non-blotting membrane-1.
(8) obtained blotting membrane is detected the optimization of BPA conditions
The trace and non-blotting membrane for respectively taking a piece of same volume is added in the BPA solution containing variable concentrations accordingly (eventually
Concentration is 5,10,15,20,25,30mg/L), after BPA is added, different time points (0,30,60,90,120,150min) are used many
Function microplate reader detects the fluorescence intensity of mixed liquor, as a result shows, detects that optimum fluorescence BPA concentration is using this method
25mg/L, detection time are 150min after addition BPA.
(9) specificity analyses
Under the conditions of (8) multi-function microplate reader detection BPA optimal detections, fluorescence MIM or NIM are with concentration for 25mg/L's
BPA or its analog (BPC, BPZ, 4,4- dihydroxybiphenyls, tetrabromobisphenol A) mixing, with multi-function microplate reader determine BPA or its
After analog addition, the fluorescence intensity of mixed liquor, calculates fluorescence change I0/ I, as a result shows, fluorescence MIM has most strong glimmering
Optical quenching ability, meanwhile, the fluorescence change (I of MIM0/ I) big compared with NIM, illustrate that the former has specificity to template molecule BPA
Absorbability.
Fluorescence MIM and NIM and BPA and the like mixed fluorescence change I0/I
| Fluorescence change | BPA | BPC | BPZ | 4,4- dihydroxybiphenyls | Tetrabromobisphenol A |
| MIM(I0/I) | 1.82 | 1.07 | 1.09 | 1.06 | 1.04 |
| NIM(I0/I) | 1.03 | 1.46 | 0.89 | 0.98 | 0.86 |
Embodiment 3
(1) weigh 0.675g thenoyltrifluoroacetone (TTA) to be dissolved in 30mL ethanol, stir to being uniformly dissolved, use
4mol/L NaOH solutions adjust PH=8.0；
(2) 0.18g Eu are weighed2O3, the appropriate concentrated hydrochloric acid of Deca (36.5%) is allowed to just dissolve, and adding 10mL water makes
Be completely dissolved, this saline solution is instilled the ethanol solution in step (1), 60 DEG C is warming up to, magnetic agitation 0.5h；
(3) 0.18g o-phenanthrolines (Phen) are weighed to be dissolved in the ethanol of 10mL, this ethanol solution is instilled above-mentioned mixed liquor
In, it is added in the round-bottomed flask equipped with reflux condenser, 60 DEG C of magnetic agitation, flow back 3h, is cooled to room temperature, sucking filtration, then
Respectively with 20mL ethanol and 20mL water washings three times, 24h is vacuum dried at last 60 DEG C, obtains the coordination compound of europium；
(4) 76.935g dimethyl sulfoxides (DMSO) are weighed for solvent, weigh the coordination compound and 0.105g polyamide of 0.09g europiums-
Amine is added in dimethyl sulfoxide (DMSO), is warming up to 40 DEG C, mechanical agitation 24h, to being completely dissolved；
(5) 11.7g cellulose acetate (CA), 0.9g shitosans (CHI) and 0.27g template molecule bisphenol-As (BPA) are added
In the solution obtained to step (4), at 40 DEG C, mechanical agitation 4h obtains casting solution to being uniformly dissolved；
(6) casting solution that step (5) is obtained, insulation at 40 DEG C stand, and slough the bubble that stirring is produced, then take one clean
Net glass plate, casting solution is laid on glass plate, is scraped certain thickness 2.0mm with Glass rod, is slowly dipped in after 30s
In deionized water, immersion 30min after take out, obtain final product polyamide-amide/rare-earth fluorescent blotting membrane, by polyamide obtained above-
Amine/rare-earth fluorescent blotting membrane is immersed in ferric chloride deionized water mixed solution, and (ferric chloride is 1 with water quality ratio:12500)
In, to remove template molecule bisphenol-A, it is washed with water and washs to neutrality, be stored in deionized water.The preparation method of non-blotting membrane with
Above-mentioned identical, but it is not added with template molecule bisphenol-A.
(7) obtained blotting membrane is carried out Staticadsorption experiment
Prepare 100mg L-1Bisphenol-A (BPA) solution, solvent is deionized water, respectively takes a piece of blotting membrane and non-blotting membrane
Quality is 0.02g, is separately added in bisphenol-A (BPA) solution of 10mL preparations, after standing 4.0h in 25 DEG C of calorstats, with ultraviolet
In spectrophotometer measurement solution, the content of bisphenol-A, as a result shows, the adsorbance of trace blend film is 5.79mg g-1Substantially high
Adsorbance 2.27mg g in non-blotting membrane-1.
(8) obtained blotting membrane is detected the optimization of BPA conditions
The trace and non-blotting membrane for respectively taking a piece of same volume is added in the BPA solution containing variable concentrations accordingly (eventually
Concentration is 5,10,15,20,25,30mg/L), after BPA is added, different time points (0,30,60,90,120,150min) are used many
Function microplate reader detects the fluorescence intensity of mixed liquor, as a result shows, detects that optimum fluorescence BPA concentration is using this method
25mg/L, detection time are 150min after addition BPA.
(9) specificity analyses
Under the conditions of (8) multi-function microplate reader detection BPA optimal detections, fluorescence MIM or NIM are with concentration for 25mg/L's
BPA or its analog (BPC, BPZ, 4,4- dihydroxybiphenyls, tetrabromobisphenol A) mixing, with multi-function microplate reader determine BPA or its
After analog addition, the fluorescence intensity of mixed liquor, calculates fluorescence change I0/ I, as a result shows, fluorescence MIM has most strong glimmering
Optical quenching ability, meanwhile, the fluorescence change (I of MIM0/ I) big compared with NIM, illustrate that the former has specificity to template molecule BPA
Absorbability.
Fluorescence MIM and NIM and BPA and the like mixed fluorescence change I0/I
| Fluorescence change | BPA | BPC | BPZ | 4,4- dihydroxybiphenyls | Tetrabromobisphenol A |
| MIM(I0/I) | 2.02 | 1.46 | 1.98 | 1.74 | 1.84 |
| NIM(I0/I) | 1.43 | 1.88 | 1.68 | 1.08 | 0.96 |
Claims (7)
1. the preparation method of a kind of polyamide-amide/rare-earth fluorescent blotting membrane, it is characterised in that comprise the steps：
Step 1,0.225～0.675g thenoyltrifluoroacetone is dissolved in the ethanol of 10～30mL, with 1～4mol/LNaOH
Solution adjusts pH=8.0, obtains mixed liquor A；
Step 2, the europiumsesquioxide for weighing 0.06～0.18g, Deca 1～3mL concentrated hydrochloric acid dissolve europiumsesquioxide, add
The deionized water of 3～10mL, instills in the mixed liquor A in step 1, is warming up to 60 DEG C, and magnetic agitation 0.5h obtains mixed liquid B；
Step 3,0.06～0.18g o-phenanthrolines are dissolved in the ethanol of 3～10mL, this ethanol solution is added dropwise to step 2
In mixed liquid B, under magnetic stirring, 60 DEG C of back flow reaction 3h, are cooled to room temperature after completion of the reaction, sucking filtration, then with ethanol and
Water washing, is vacuum dried 24h at last 60 DEG C, obtains the coordination compound of europium；
Step 4, the coordination compound for taking the europium that step 3 is obtained, polyamide-amide are added in dimethyl sulfoxide, are warming up to 40 DEG C, and machinery is stirred
24h is mixed, to being completely dissolved, mixed liquor C is obtained；
Membrane matrix cellulose acetate, functional polymer shitosan and template point is added in step 5, the mixed liquor C obtained to step 4
Sub- bisphenol-A, stirring and evenly mixing at 40 ± 5 DEG C, 3～4h of mechanical agitation obtain casting solution to being uniformly dissolved；
Step 6, the casting solution for obtaining step 5 are incubated standing at 40 ± 5 DEG C, to the bubble for sloughing stirring generation, Ran Houqu
The glass plate of one cleaning, casting solution is laid on glass plate, is scraped certain thickness with Glass rod, is slowly dipped in after 30s
In deionized water, 30min is soaked, take out glass plate and peeled, obtain polyamide-amide/rare earth blotting membrane；
Step 7, the polyamide-amide/rare earth blotting membrane for obtaining step 6 adopt ferric chloride deionized water mixed solution for extraction
Liquid, to remove template molecule bisphenol-A, is washed with water and washs to neutrality, will final obtained polyamide-amide/rare-earth fluorescent blotting membrane
It is immersed in deionized water and stores.
2. a kind of preparation method of polyamide-amide/rare-earth fluorescent blotting membrane according to claim 1, it is characterised in that step
In rapid 1～3, the thenoyltrifluoroacetone that used, europiumsesquioxide, the mass ratio of o-phenanthroline are 3.75:1:1, step 2
In, the mass fraction of the concentrated hydrochloric acid is 36.5%.
3. a kind of preparation method of polyamide-amide/rare-earth fluorescent blotting membrane according to claim 1, it is characterised in that step
In rapid 4, the coordination compound of described europium, polyamide-amide, dimethyl sulfoxide are 6 according to mass ratio:7:5129.
4. a kind of preparation method of polyamide-amide/rare-earth fluorescent blotting membrane according to claim 1, it is characterised in that step
In rapid 5, in the casting solution of described film, the mass fraction of polymer cellulose acetate is 13%, functional polymer shitosan
Mass fraction be the 1.0% of casting solution, the mass fraction of template molecule bisphenol-A for casting solution 0.3%.
5. a kind of preparation method of polyamide-amide/rare-earth fluorescent blotting membrane according to claim 1, it is characterised in that step
In rapid 6, the described standing and defoaming time is 24～48h, and the thickness of film is 2.0mm.
6. a kind of preparation method of polyamide-amide/rare-earth fluorescent blotting membrane according to claim 1, it is characterised in that step
In rapid 7, in ferric chloride deionized water mixed solution, FeCl3Mass ratio with deionized water is 1:12500.
7. the purposes of polyamide-amide/rare-earth fluorescent blotting membrane prepared by method described in claim 1～6 any one, which is special
Levy and be, the polyamide-amide/rare-earth fluorescent blotting membrane is used for the bisphenol-A in adsorbing separation aqueous solution.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610880214.1A CN106496641B (en) | 2016-10-09 | 2016-10-09 | A kind of preparation method and its usage of polyamide-amide/rare-earth fluorescent blotting membrane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610880214.1A CN106496641B (en) | 2016-10-09 | 2016-10-09 | A kind of preparation method and its usage of polyamide-amide/rare-earth fluorescent blotting membrane |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106496641A true CN106496641A (en) | 2017-03-15 |
| CN106496641B CN106496641B (en) | 2019-02-05 |
Family
ID=58294469
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610880214.1A Expired - Fee Related CN106496641B (en) | 2016-10-09 | 2016-10-09 | A kind of preparation method and its usage of polyamide-amide/rare-earth fluorescent blotting membrane |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106496641B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107022096A (en) * | 2017-06-01 | 2017-08-08 | 厦门大学 | Preparation with the high photopermeability multiple cellulose acetate film of near ultraviolet excitated function |
| CN112973457A (en) * | 2021-02-01 | 2021-06-18 | 江苏大学 | Preparation method of cellulose acetate boron affinity imprinted membrane and application of cellulose acetate boron affinity imprinted membrane in selective separation of shikimic acid |
| CN113533291A (en) * | 2021-08-24 | 2021-10-22 | 常州工学院 | Rare earth ion fluorescence detection method for bisphenol S |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005232205A (en) * | 2004-02-17 | 2005-09-02 | Japan Science & Technology Agency | Molecularly imprinted cellulose and its manufacturing method |
| CN102350319A (en) * | 2011-07-15 | 2012-02-15 | 江苏大学 | Preparation method of fly ash superbead magnetic composite material surface imprinting adsorbent |
| CN104672476A (en) * | 2015-01-26 | 2015-06-03 | 江苏大学 | Preparation method of rare-earth fluorescent molecularly imprinted membrane and application of rare-earth fluorescent molecularly imprinted membrane |
| CN104759263A (en) * | 2015-03-25 | 2015-07-08 | 江苏大学 | A preparing method of a multiwalled carbon nanotube doped salicylic acid blend imprinted membrane |
-
2016
- 2016-10-09 CN CN201610880214.1A patent/CN106496641B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005232205A (en) * | 2004-02-17 | 2005-09-02 | Japan Science & Technology Agency | Molecularly imprinted cellulose and its manufacturing method |
| CN102350319A (en) * | 2011-07-15 | 2012-02-15 | 江苏大学 | Preparation method of fly ash superbead magnetic composite material surface imprinting adsorbent |
| CN104672476A (en) * | 2015-01-26 | 2015-06-03 | 江苏大学 | Preparation method of rare-earth fluorescent molecularly imprinted membrane and application of rare-earth fluorescent molecularly imprinted membrane |
| CN104759263A (en) * | 2015-03-25 | 2015-07-08 | 江苏大学 | A preparing method of a multiwalled carbon nanotube doped salicylic acid blend imprinted membrane |
Non-Patent Citations (2)
| Title |
|---|
| KOHEI TAKEDA等: "Hybrid molecularly imprinted membranes for targeted bisphenol derivatives", 《JOURNAL OF MEMBRANE SCIENCE》 * |
| 钟剑: "基于荧光分子印迹聚合物的痕量双酚A快速检测新方法", 《中国优秀硕士学位论文全文数据库 工程科技I辑》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107022096A (en) * | 2017-06-01 | 2017-08-08 | 厦门大学 | Preparation with the high photopermeability multiple cellulose acetate film of near ultraviolet excitated function |
| CN107022096B (en) * | 2017-06-01 | 2020-03-27 | 厦门大学 | Preparation of high-light-permeability composite cellulose acetate membrane with near-ultraviolet excitation function |
| CN112973457A (en) * | 2021-02-01 | 2021-06-18 | 江苏大学 | Preparation method of cellulose acetate boron affinity imprinted membrane and application of cellulose acetate boron affinity imprinted membrane in selective separation of shikimic acid |
| CN113533291A (en) * | 2021-08-24 | 2021-10-22 | 常州工学院 | Rare earth ion fluorescence detection method for bisphenol S |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106496641B (en) | 2019-02-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Lu et al. | Multi-template imprinted polymers for simultaneous selective solid-phase extraction of six phenolic compounds in water samples followed by determination using capillary electrophoresis | |
| Deng et al. | Pretreatment techniques and analytical methods for phenolic endocrine disrupting chemicals in food and environmental samples | |
| Lamaoui et al. | Study of solvent effect on the synthesis of magnetic molecularly imprinted polymers based on ultrasound probe: Application for sulfonamide detection | |
| Zhai et al. | Chip-based molecularly imprinted monolithic capillary array columns coated GO/SiO2 for selective extraction and sensitive determination of rhodamine B in chili powder | |
| Xin-Ran et al. | An ion imprinted polymers grafted paper-based fluorescent sensor based on quantum dots for detection of Cu2+ ions | |
| Li et al. | Simultaneous solid-phase extraction and determination of three bisphenols in water samples and orange juice by a porous β-cyclodextrin polymer | |
| CN106496641A (en) | A kind of preparation method and its usage of daiamid/rare-earth fluorescent blotting membrane | |
| CN110813253B (en) | Preparation method and application of hydrophilic metal organic framework surface bisphenol A molecular imprinting high-selectivity nanocomposite | |
| Li et al. | Metal organic framework/chitosan foams functionalized with polyethylene oxide as a sorbent for enrichment and analysis of bisphenols in beverages and water | |
| CN104292381A (en) | Preparation and application of fluorescence ion imprinting probe | |
| CN106483218B (en) | A kind of molecular engram solid phase extraction-liquid chromatogram detects metrifonate and Azodrin method simultaneously | |
| CN107118354A (en) | A kind of preparation method and application of the compound separating medium of ochratoxin metal organic framework molecular engram | |
| CN103301820B (en) | Core-shell type Rhodamine B molecular imprinting solid-phase extraction magnetic material, and preparation method and application thereof | |
| CN106883411A (en) | The preparation and the application as solid extracting agent of the structure mesoporous molecularly imprinted polymer of superparamagnetic core-shell | |
| CN108051520A (en) | A kind of method of aflatoxin B1 in detection tealeaves | |
| CN106432577A (en) | High selectivity tetracycline antibiotics molecularly imprinted polymer preparation method and application | |
| Huang et al. | Chip-based dual-molecularly imprinted monolithic capillary array columns coated Ag/GO for selective extraction and simultaneous determination of bisphenol A and nonyl phenol in fish samples | |
| Sorribes-Soriano et al. | Development of a molecularly imprinted monolithic polymer disk for agitation-extraction of ecgonine methyl ester from environmental water | |
| CN109331795A (en) | A kind of magnetic nanometer composite material and its preparation and application | |
| CN107144563A (en) | Novel technology for manufacturing and applying colorimetric test paper for rapidly detecting, enriching and separating heavy metal mercury ions | |
| CN108088828B (en) | Double-column aromatic mercury ion fluorescent sensor and preparation and application thereof | |
| CN105498721A (en) | Aflatoxin molecularly imprinted material and preparation method thereof | |
| CN110483746B (en) | Synthesis of novel covalent organic framework material and application of novel covalent organic framework material in metal ion recognition and dye adsorption | |
| CN102911306B (en) | Bisphenol-A and nonylphenol double-template molecularly imprinted polymeric microspheres | |
| Huang et al. | One-pot preparation of magnetic molecularly imprinted adsorbent with dual template molecules for simultaneously specific capture of sulfonamides and quinolones in water and milk samples |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | 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 | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20190205 Termination date: 20191009 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |