CN117443198A - Membrane with detection function and preparation method and application thereof - Google Patents
Membrane with detection function and preparation method and application thereof Download PDFInfo
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- CN117443198A CN117443198A CN202210843359.XA CN202210843359A CN117443198A CN 117443198 A CN117443198 A CN 117443198A CN 202210843359 A CN202210843359 A CN 202210843359A CN 117443198 A CN117443198 A CN 117443198A
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- film
- thiol
- membrane
- gold
- gold complex
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- 239000012528 membrane Substances 0.000 title claims abstract description 79
- 238000001514 detection method Methods 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000010931 gold Substances 0.000 claims abstract description 109
- 229910052737 gold Inorganic materials 0.000 claims abstract description 109
- SNGREZUHAYWORS-UHFFFAOYSA-N perfluorooctanoic acid Chemical compound OC(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F SNGREZUHAYWORS-UHFFFAOYSA-N 0.000 claims abstract description 42
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 51
- 239000002105 nanoparticle Substances 0.000 claims description 49
- 238000000034 method Methods 0.000 claims description 30
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- 238000005266 casting Methods 0.000 claims description 20
- 239000002904 solvent Substances 0.000 claims description 18
- 239000003638 chemical reducing agent Substances 0.000 claims description 13
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- 238000011068 loading method Methods 0.000 claims description 12
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- 230000008859 change Effects 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 10
- 229920001661 Chitosan Polymers 0.000 claims description 9
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 9
- 230000015271 coagulation Effects 0.000 claims description 9
- 238000005345 coagulation Methods 0.000 claims description 9
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethanethiol Chemical compound CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 claims description 8
- 229920001690 polydopamine Polymers 0.000 claims description 8
- SUVIGLJNEAMWEG-UHFFFAOYSA-N propane-1-thiol Chemical compound CCCS SUVIGLJNEAMWEG-UHFFFAOYSA-N 0.000 claims description 8
- 239000004793 Polystyrene Substances 0.000 claims description 7
- 229920002492 poly(sulfone) Polymers 0.000 claims description 7
- 229920002223 polystyrene Polymers 0.000 claims description 7
- ZJLMKPKYJBQJNH-UHFFFAOYSA-N propane-1,3-dithiol Chemical compound SCCCS ZJLMKPKYJBQJNH-UHFFFAOYSA-N 0.000 claims description 7
- DHBXNPKRAUYBTH-UHFFFAOYSA-N 1,1-ethanedithiol Chemical compound CC(S)S DHBXNPKRAUYBTH-UHFFFAOYSA-N 0.000 claims description 6
- -1 2, 3-dimercaptobenzimidazole Chemical compound 0.000 claims description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- 239000002033 PVDF binder Substances 0.000 claims description 6
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- 230000001112 coagulating effect Effects 0.000 claims description 6
- WQABCVAJNWAXTE-UHFFFAOYSA-N dimercaprol Chemical compound OCC(S)CS WQABCVAJNWAXTE-UHFFFAOYSA-N 0.000 claims description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 6
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 6
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 claims description 5
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 5
- 230000015572 biosynthetic process Effects 0.000 claims description 5
- SCBKKGZZWVHHOC-UHFFFAOYSA-N 2,2-bis(sulfanyl)propanoic acid Chemical compound CC(S)(S)C(O)=O SCBKKGZZWVHHOC-UHFFFAOYSA-N 0.000 claims description 4
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- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 4
- 229920002125 Sokalan® Polymers 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- WQAQPCDUOCURKW-UHFFFAOYSA-N butanethiol Chemical compound CCCCS WQAQPCDUOCURKW-UHFFFAOYSA-N 0.000 claims description 4
- UFULAYFCSOUIOV-UHFFFAOYSA-N cysteamine Chemical compound NCCS UFULAYFCSOUIOV-UHFFFAOYSA-N 0.000 claims description 4
- XUJNEKJLAYXESH-UHFFFAOYSA-N cysteine Natural products SCC(N)C(O)=O XUJNEKJLAYXESH-UHFFFAOYSA-N 0.000 claims description 4
- 235000018417 cysteine Nutrition 0.000 claims description 4
- 229960003067 cystine Drugs 0.000 claims description 4
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 claims description 4
- ALPIESLRVWNLAX-UHFFFAOYSA-N hexane-1,1-dithiol Chemical compound CCCCCC(S)S ALPIESLRVWNLAX-UHFFFAOYSA-N 0.000 claims description 4
- 229920000747 poly(lactic acid) Polymers 0.000 claims description 4
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- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims 1
- 229910052799 carbon Inorganic materials 0.000 claims 1
- 150000003839 salts Chemical class 0.000 abstract description 13
- 239000002131 composite material Substances 0.000 abstract description 2
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- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 239000001509 sodium citrate Substances 0.000 description 9
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 9
- 238000009835 boiling Methods 0.000 description 8
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- SNGREZUHAYWORS-UHFFFAOYSA-M 2,2,3,3,4,4,5,5,6,6,7,7,8,8,8-pentadecafluorooctanoate Chemical compound [O-]C(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F SNGREZUHAYWORS-UHFFFAOYSA-M 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- HVYWMOMLDIMFJA-DPAQBDIFSA-N cholesterol Chemical compound C1C=C2C[C@@H](O)CC[C@]2(C)[C@@H]2[C@@H]1[C@@H]1CC[C@H]([C@H](C)CCCC(C)C)[C@@]1(C)CC2 HVYWMOMLDIMFJA-DPAQBDIFSA-N 0.000 description 2
- 230000035558 fertility Effects 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 230000036541 health Effects 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- MQHUHNALGOSWPX-QIFMNYRTSA-N (2r)-2-amino-3-[[(2r)-2-amino-2-carboxyethyl]disulfanyl]propanoic acid;(2r)-2-amino-3-sulfanylpropanoic acid Chemical compound SC[C@H](N)C(O)=O.OC(=O)[C@@H](N)CSSC[C@H](N)C(O)=O MQHUHNALGOSWPX-QIFMNYRTSA-N 0.000 description 1
- OTYYBJNSLLBAGE-UHFFFAOYSA-N CN1C(CCC1)=O.[N] Chemical compound CN1C(CCC1)=O.[N] OTYYBJNSLLBAGE-UHFFFAOYSA-N 0.000 description 1
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Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D65/00—Accessories or auxiliary operations, in general, for separation processes or apparatus using semi-permeable membranes
- B01D65/10—Testing of membranes or membrane apparatus; Detecting or repairing leaks
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention relates to the technical field of porous composite membranes, and discloses a membrane with a detection function, a preparation method and application thereof. The membrane comprises a membrane skeleton and a thiol-gold complex supported on the membrane skeleton. When the membrane is used for detection, the operation is simple, and large instruments and complicated detection steps are eliminated; the existence of perfluorooctanoic acid and salts thereof in the solution can be judged by naked eyes, the sensitivity is high, and the preparation method of the membrane is simple.
Description
Technical Field
The invention relates to the technical field of porous composite membranes, in particular to a membrane with a detection function, and a preparation method and application thereof.
Background
Perfluorinated compounds, particularly perfluorooctanoic acid and its salt derivatives, are widely used in daily life by their excellent thermal stability, chemical stability, high surface activity and unique hydrophobic and oleophobic properties. Due to their mass production and use, in addition to their extremely high durability and flowability, perfluorinated compounds are ubiquitous in aquatic environments, sediments, air, biota-nations and humans. They are environmental pollutants that are of high concern. In recent years there has been an increasing concern about perfluorinated compounds in drinking water, which may have toxic effects. Animal toxicity studies have found that there is a correlation between contact with perfluorooctanoic acid (or perfluorooctanoate) and adverse effects on fertility and many organs and systems. Epidemiological studies have also found that there is a link between exposure to perfluorooctanoic acid and health problems including increased cholesterol and liver enzymes, increased incidence of testicular and renal cancers, reduced fertility and fertility, immunosuppression, thyroid disease, and the like. Therefore, the drinking water quality standards set by the national health organization (WHO) for guiding countries around the world specify that the limit of the organic fluorine content should not be more than 1.5mg/L. The organic fluorine content of the domestic drinking water of the national standard GB5749-85 jointly formulated by the ministry of health and the ministry of construction of China is not more than 1.0mg/L.
Although more and more countries are beginning to ban the use of perfluorooctanoic acid, perfluorinated compounds such as us, japan, gana, turkish, australia and china are often detected in drinking water worldwide in recent years. In order to control and reduce the risk of exposure of perfluorinated compounds to humans, many countries have increasingly regulated the levels of perfluorinated compounds in drinking water. There is a great need to develop a simple and reliable method for detecting whether or not the water for daily use contains perfluorinated compounds, especially the more harmful perfluorooctanoic acid. The existing method for detecting the perfluorooctanoic acid comprises the following steps: nuclear magnetic resonance, gas chromatography, liquid chromatography/fluorescence detection, X-ray diffraction, etc., but these methods all require complicated preparation work and precise large-scale instruments, and thus the application of these methods is significantly limited.
Therefore, it is necessary to develop a detection method of perfluorooctanoic acid and its salt derivatives, which can eliminate large-scale equipment and complicated detection steps, and make it more advantageous for detection in daily life.
Disclosure of Invention
The invention aims to overcome the problems in the prior art and provide a membrane with a detection function, a preparation method and application thereof, wherein the membrane is simple to operate when used for detection, and gets rid of large instruments and complicated detection steps; and in the case that the content of the perfluorooctanoic acid and the salt thereof is 1 mu mol/L or more, whether the perfluorooctanoic acid and the salt thereof exist in the solution can be judged by naked eyes, so that the method is sensitive, and the preparation method of the membrane is simple and is beneficial to industrialization.
In order to achieve the above object, an aspect of the present invention provides a membrane having a detection function, the membrane comprising a membrane scaffold and a thiol-gold complex supported on the membrane scaffold;
wherein, relative to 1cm 2 The loading of thiol-gold complex is 0.05-0.5g;
wherein the average particle size of the thiol-gold complex is 1-100nm.
The second aspect of the present invention provides a method for producing a film having a detection function, the method comprising: loading thiol-gold complex on membrane skeleton relative to 1cm 2 The amount of thiol-gold complex used is 0.05-0.5g;
wherein the average particle size of the thiol-gold complex is 1-100nm.
A third aspect of the present invention provides a membrane with a detection function prepared by the method described above.
In a fourth aspect, the present invention provides the use of a membrane having a detection function as described in the first or third aspect for detecting perfluorooctanoic acid and/or perfluorooctanoic acid salts.
In a fifth aspect, the present invention provides a method for detecting perfluorooctanoic acid and/or perfluorooctanoic acid salt, the method comprising: the film having a detection function according to the first aspect or the third aspect is immersed in a solution containing perfluorooctanoic acid and/or perfluorooctanoic acid salt, and a color change of the film is observed.
The invention has the following beneficial effects:
1. the membrane provided by the invention is simple to operate when used for detection, and gets rid of large instruments and complicated detection steps.
2. The membrane provided by the invention has the advantages that the content of the perfluorooctanoic acid and the salt thereof is 1 mu mol/L or more (namely, the content of the perfluorooctanoic acid is about 0.414 mg/L), and whether the perfluorooctanoic acid and the salt thereof exist in the solution can be judged by observing the color change through naked eyes, so that the membrane is more sensitive.
3. The preparation method provided by the invention is simple to operate and is beneficial to industrialization.
Drawings
FIG. 1 is a surface topography of a product film prepared in example 1;
FIG. 2 is a surface topography of the film side of the product prepared in comparative example 3;
FIG. 3 is a graph of the surface topography of the membrane scaffold prepared in example 1.
Detailed Description
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
In a first aspect, the present invention provides a membrane having a detection function, the membrane comprising a membrane scaffold and a thiol-gold complex supported on the membrane scaffold;
wherein, relative to 1cm 2 The loading of thiol-gold complex is 0.05-0.5g;
wherein the average particle size of the thiol-gold complex is 1-100nm.
It is understood that thiol refers to a class of non-aromatic compounds containing thiol functional groups (-SH), and it is understood that in the above-described films, thiol-gold complexes are present on the film in the form of nanoparticles, at which time the film appears to be red (bright red, brownish red, wine red, mauve, etc.) to the naked eye due to the particular optical properties of the nanoparticles.
The inventor of the present invention found in the study that, when the film described above is immersed in a solution containing perfluorooctanoic acid or its salt, gold moves toward a place where the concentration of perfluorooctanoic acid is high, so that aggregation occurs, the color at the aggregation place can be changed from original reddish-white to bluish-violet or purplish-red, and the change in color can be observed with naked eyes, the more obvious the difference between the front and rear of the color is, the better the effect of the film is, so that the film can be used for simply and quickly identifying whether the solution contains perfluorooctanoic acid or its salt, and large-scale instruments and complicated detection steps can be eliminated. When the content of the perfluorooctanoic acid and the salt thereof is 1 mu mol/L or more, the membrane provided by the invention can confirm the existence of the perfluorooctanoic acid and the salt thereof and is more sensitive.
According to the invention, it is preferable that the distance relative to 1cm 2 The loading of the thiol-gold complex is 0.05 to 0.25g (e.g., may be a value within a range formed by 0.05g, 0.07g, 0.08g, 0.1g, 0.11g, 0.12g, 0.13g, 0.14g, 0.15g, 0.16g, 0.17g, 0.18g, 0.19g, 0.2g, 0.25g, and any two of the above).
According to the present invention, it is preferable that the thiol-gold complex has an average particle size of 1 to 40nm.
When the above range is satisfied, it is further ensured that when perfluorooctanoic acid or a salt thereof is contained in the solution, significant aggregation occurs on the film, and thus a change in color is more easily observed.
According to the present invention, the substance for providing the thiol structural unit in the thiol-gold complex is preferably selected from the group consisting of thiols having 2 to 15 carbon atoms, preferably at least one selected from the group consisting of 2-aminoethanethiolate, 2, 3-dimercaptopropanol, mercaptoethane, butanethiol, dimercaptopropionic acid, cysteine, cystine, ethanedithiol, 2, 3-dimercaptobenzimidazole, 1-propanethiol, hexanedithiol, 1, 3-propanedithiol and dodecanethiol.
According to the present invention, the porosity of the film is preferably 50 to 80% (for example, may be 50%, 55%, 60%, 65%, 70%, 75%,80% and any two or more values within the range formed).
According to the present invention, it is preferable that the average pore diameter of the membrane is 0.1 to 10 μm (for example, may be a value in a range formed of 0.1 μm, 0.5 μm, 1 μm, 2 μm, 3 μm, 4 μm, 5 μm, 6 μm, 7 μm, 8 μm, 9 μm, 10 μm, and any two values thereof).
According to the present invention, it is preferable that the thickness of the film is 100 to 180 μm (for example, a value in a range formed of any two values of 100 μm, 110 μm, 120 μm, 130 μm, 140 μm, 150 μm, 160 μm, 170 μm, 180 μm and above), and the thickness of the film skeleton is 60 to 100 μm (for example, a value in a range formed of any two values of 60 μm, 70 μm, 80 μm, 90 μm, 100 μm and above).
According to the present invention, preferably, the membrane scaffold is composed of a film-forming polymer.
Wherein the film-forming polymer is not particularly limited and may be selected conventionally in the art. Preferably, the film-forming polymer is at least one selected from polyethersulfone, acetate, polyacrylamide, polyacrylonitrile, polyethersulfone, chitin, chitosan, polyacrylic acid, dopamine, polylactic acid, polysulfone, polyethersulfone, polyvinylidene fluoride, polyvinyl chloride and polystyrene.
According to the invention, it is preferred that the film-forming polymer has a weight average molecular weight of 10000-400000g/mol.
According to the invention, preferably, the membrane further comprises a support layer. It will be appreciated that the support layer serves to support the membrane scaffold.
According to the invention, the thickness of the support layer is preferably 50-110mm.
According to the present invention, preferably, the material of the supporting layer is selected from non-woven fabrics. Wherein the nonwoven fabric may be a polyester nonwoven fabric, a polypropylene nonwoven fabric, a polyethylene terephthalate (PET) nonwoven fabric, or the like.
In a second aspect, the present invention provides a method for producing a membrane having a detection function, the method comprising: loading thiol-gold complex on membrane skeleton relative to 1cm 2 The amount of thiol-gold complex used is 0.05-0.5g;
wherein the average particle size of the thiol-gold complex is 1-100nm.
According to the present invention, preferably, the method for preparing a membrane scaffold comprises: in the presence of the support layer, a casting solution containing a film-forming polymer is used for film formation and immersed in a coagulation bath.
Wherein the film-forming polymer in the casting solution and its concentration may be selected as is conventional in the art. However, it is preferable that the concentration of the film-forming polymer in the casting solution is 5 to 30wt%, more preferably 6 to 20wt%.
Preferably, the film-forming polymer is at least one selected from polyethersulfone, acetate, polyacrylamide, polyacrylonitrile, polyethersulfone, chitin, chitosan, polyacrylic acid, dopamine, polylactic acid, polysulfone, polyethersulfone, polyvinylidene fluoride, polyvinyl chloride and polystyrene. It can be appreciated that dopamine can undergo self-polymerization to yield polydopamine, and that if the film-forming polymer is polydopamine, then adding dopamine to the solvent can yield a polydopamine solution.
Preferably, the film-forming polymer has a weight average molecular weight of 10000-400000g/mol.
The solvent of the casting solution is not particularly limited as long as it has a strong dissolving ability for the polymer solute. Generally, the interaction parameter χ (also known as Huggins parameter) of the solvent and the film-forming polymer should be less than 0.5, such a solvent having greater solubility for the polymer solute and less variation in interaction energy during mixing with the polymer solute. Preferably, the solvent in the casting solution is at least one selected from chloroform, dimethyl sulfoxide, tetrahydrofuran, toluene, benzene, hexane, octane, acetone, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone and dioxane.
According to the present invention, the temperature of the coagulation bath is preferably 10 to 40 ℃ (for example, it may be a value in a range of any two values of 10 ℃, 15 ℃, 20 ℃, 25 ℃, 30 ℃, 35 ℃, 40 ℃ and above), and the time of the coagulation bath is preferably 15 to 200s (for example, it may be a value in a range of any two values of 15s, 20s, 40s, 60s, 80s, 100s, 120s, 140s, 160s, 180s, 200s and above). The casting solution contains solvent, the solvent in the formed film is not removed, at this time, the film is placed in a reagent (or called an extractant, which may be water) with stronger mutual solubility with the solvent in the casting solution, the solvent is extracted, the solvent remained on the film is removed, and the film is solidified, and the operation is a coagulation bath. The temperature of the coagulation bath is also the temperature of the extractant used.
According to the present invention, it is preferable that the film is formed such that the thickness of the film skeleton is 60 to 100 μm and the thickness of the film is 100 to 180 μm.
The specific mode of film formation is not particularly limited, and for example, film scraping can be performed by a doctor blade.
Among them, the specific method for supporting the thiol-gold complex on the membrane scaffold is not particularly limited as long as the thiol-gold complex can be supported on the membrane. Preferably, however, the method for supporting the thiol-gold complex on the membrane scaffold comprises: the membrane scaffold is immersed in a dispersion containing thiol-gold complexes. Thiol-gold complexes self-assemble onto the membrane scaffold.
In order to sufficiently and stably load the thiol-gold complex onto the membrane scaffold according to the present invention, it is preferable to keep the membrane scaffold for 0.5 to 24 hours, more preferably 5 to 10 hours after immersing the membrane scaffold in the dispersion containing the thiol-gold complex.
According to the invention, it is preferred that the concentration of thiol-gold complexes in the dispersion containing thiol-gold complexes is 0.5-10wt%.
According to the invention, a method for preparing a dispersion containing thiol-gold complexes comprises: reducing chloroauric acid in the presence of a reducing agent to obtain a solution containing gold nanoparticles; the solution containing gold nanoparticles and thiol are mixed and compounded to obtain a dispersion of thiol-gold complexes having a concentration of thiol-gold complexes of 0.5 to 10wt% (for example, values in the range of 0.5wt%, 1wt%, 2wt%, 3wt%, 4wt%, 5wt%, 6wt%, 7wt%, 8wt%, 9wt%, 10wt% and any two of the above values).
Wherein in the thiol-gold complex prepared as above, there is a certain interaction between thiol and gold, which may be a coordination bond, electrostatic interaction or other type. Can realize the detection of the perfluorooctanoic acid and the salt thereof as long as the two have certain interaction,
among these, the reducing agent may be a conventional one such as sodium citrate. The chloroauric acid can be reduced with a reducing agent in a state where the solution is boiling. The amounts of the reducing agent and chloroauric acid (or the concentrations in the solution) are adjusted based on the desired concentration of gold nanoparticles in the gold nanoparticle-containing solution.
According to the present invention, it is preferable that in the solution containing gold nanoparticles, the gold nanoparticles have an average particle diameter of 1 to 40nm. The gold nanoparticles meeting the above range can be obtained by further controlling the reaction rate by controlling the reaction temperature, the dropping speed and the dosage of the reducing agent, and the like. It can be appreciated that after mixing with the thiol, the average particle size of the thiol-gold complex formed is substantially the same as the average particle size of the gold nanoparticles in the gold nanoparticle-containing solution.
According to the present invention, it is preferable that the concentration of gold nanoparticles in the solution containing gold nanoparticles is 0.01 to 0.1g/ml. The concentration of gold nanoparticles can be adjusted by controlling the concentration of chloroauric acid and the amount of thiol in the solution.
According to the present invention, it is preferable that the thiol is used in the form of a thiol solution in which the concentration of the thiol is 0.1 to 10wt%, more preferably 0.5 to 8wt% (for example, may be a value ranging from 0.5wt%, 0.7wt%, 1wt%, 1.2wt%, 1.5wt%, 2wt%, 3wt%, 4wt%, 5wt%, 6wt%, 7wt%, 8wt% and any two of the above).
According to the invention, the preferred weight ratio of chloroauric acid to thiol is (10-25): 1.
According to the invention, the compounding time is preferably 1 to 30 minutes. Within the above range, the recombination of thiol and gold can be sufficiently ensured, and a thiol-gold complex can be formed.
According to the present invention, it is preferable that the thiol is selected from thiols having 1 to 15 carbon atoms, preferably at least one selected from 2-aminoethanethiolate, 2, 3-dimercaptopropanol, mercaptoethane, butanethiol, dimercaptopropionic acid, cysteine, cystine, ethanedithiol, 2, 3-dimercaptobenzimidazole, 1-propanethiol, hexanedithiol, 1, 3-propanedithiol, and dodecanethiol.
In a third aspect, the present invention provides a membrane with a detection function prepared by the method described above.
In a fourth aspect, the present invention provides the use of a membrane having a detection function as described in the first or third aspect for detecting perfluorooctanoic acid and/or perfluorooctanoic acid salts.
In a fifth aspect, the present invention provides a method for detecting perfluorooctanoic acid and/or perfluorooctanoic acid salts, the method comprising: the film having a detection function according to the first aspect or the third aspect is immersed in a solution containing perfluorooctanoic acid and/or perfluorooctanoic acid salt, and a color change of the film is observed.
According to a preferred embodiment of the invention, the membrane is immersed vertically in a solution containing perfluorooctanoic acid and/or perfluorooctanoic acid salts. It will be appreciated that the membrane carrying the thiol-gold complex will appear red before immersion and that if the solution contains perfluorooctanoic acid and/or perfluorooctanoate (at a concentration of 1. Mu. Mol/L or more) the membrane will change colour to blue-violet after gold agglomeration.
According to a particularly preferred embodiment of the invention, the membrane with the detection function is prepared according to the following method:
1) DMF is taken as a solvent, polyacrylonitrile is added, stirring is carried out to prepare casting solution with the concentration of 8-10wt% of polyacrylonitrile, a doctor blade is controlled to knife-coat the casting solution on a supporting layer with the thickness of 90-100 mu m, then the supporting layer is put into deionized water with the temperature of 25-28 ℃ to be immersed into a coagulating bath, the temperature is kept for 60-75s, and a film skeleton is obtained on the supporting layer (the film forming condition is that the thickness of the film is 170-180 mu m).
2) Sodium citrate is used as a reducing agent, and chloroauric acid solution is reduced in a boiling solution state, so that gold nanoparticle-containing solution with the particle size of about 5-9nm and the gold nanoparticle concentration of 0.045-0.05g/ml is obtained.
After cooling, 2-2.5wt% of 2, 3-dimercaptopropanol solution (the dosage of the solution is such that the weight ratio of chloroauric acid to mercaptan is 15-18:1) is added, and the mixture is compounded for 10-14min to obtain a dispersion liquid containing mercaptan-gold complex.
3) Taking the product prepared in step 1), and placing into the above dispersion (such that the relative distance is 1cm 2 The amount of the thiol-gold complex is 0.08-0.1 g), and standing for 9-10h to obtain the product film.
The present invention will be described in detail by examples. In the following examples of the present invention,
polyacrylonitrile (PAN) purchased from Shaoxing Trojan composite materials Co., ltd., china, with the brand name of P60C and the weight average molecular weight of 58000g/mol;
polystyrene, available from the chemical company of Sjog, the weight average molecular weight of which is 100000g/mol;
polysulfone, available from Innock technologies, inc., has a weight average molecular weight of 22000g/mol;
dopamine, purchased from the suwei group; the dopamine can be self-polymerized in the solution to obtain polydopamine, and the weight average molecular weight of the polydopamine can be measured by gel chromatography;
cellulose acetate, purchased from the suwei group, with a weight average molecular weight of 55000g/mol;
polyvinylidene fluoride (PVDF), available from the Suwei group, having a weight average molecular weight of 300000g/mol; .
Chitosan, available from enokawa ltd, having a weight average molecular weight of 60000g/mol;
sodium citrate, chloroauric acid, available from enokava limited.
Nitrogen Methyl Pyrrolidone (NMP), N-Dimethylformamide (DMF), and N, N-Dimethylacetamide (DMAC), all available from ridge chemistry inc.
Example 1
1) DMF was used as a solvent, polyacrylonitrile was added, and a casting solution having a polyacrylonitrile concentration of 8wt% was prepared by stirring, the casting solution was blade-coated on a support layer (PET nonwoven fabric) having a thickness of 100 μm by controlling a doctor blade, and then placed in deionized water having a temperature of 25 ℃ (i.e., immersed in a coagulation bath), and kept for 60 seconds, to obtain a film skeleton on the support layer.
2) And (3) reducing chloroauric acid solution in a boiling solution state by taking sodium citrate as a reducing agent to obtain gold nanoparticle-containing solution with the gold nanoparticle particle size of about 8nm and the gold nanoparticle concentration of 0.05 g/ml.
After cooling, a 2wt% solution of 2, 3-dimercaptopropanol (in such an amount that the weight ratio of chloroauric acid to thiol is 15:1) was added and compounded for 10 minutes to give 217ml of a dispersion containing thiol-gold complex, wherein the concentration of thiol-gold complex was 4.6wt%.
3) 100cm is taken 2 The product prepared in the step 1) is put into 217ml of the dispersion liquid and is kept stand for 10 hours, thus obtaining the product film.
Example 2
1) DMAc is used as a solvent, polyacrylonitrile and dopamine are added, and stirring is carried out to prepare casting solution with the concentration of polyacrylonitrile being 8wt% and the concentration of polydopamine being 62000g/mol being 8wt%, a scraper is controlled to carry out film formation on clean PET non-woven fabrics with a supporting layer thickness being 85 mu m, then the casting solution is put into deionized water with the temperature being 20 ℃ (i.e. immersed into a coagulating bath) and kept for 100s, and a film skeleton is obtained on the supporting layer.
2) And (3) reducing chloroauric acid solution in a boiling solution state by taking sodium citrate as a reducing agent to obtain gold nanoparticle-containing solution with the gold nanoparticle particle size of about 10nm and the gold nanoparticle concentration of 0.1g/ml.
After cooling, 1wt% cysteine-cystine (the amount of the solution is such that the weight ratio of chloroauric acid to thiol is 10:1) was added and compounded for 15min to give 220ml of a dispersion containing thiol-gold complex, wherein the concentration of thiol-gold complex was 9wt%.
3) 100cm is taken 2 And (3) putting the product prepared in the step (1) into 220ml of the dispersion liquid, and standing for 5 hours to obtain a product film.
Example 3
1) DMF is used as a solvent, acetate fibers and chitosan are added, a casting solution with the acetate fibers concentration of 10wt% and the chitosan concentration of 4wt% is prepared by stirring, a scraper is controlled to form a film on a clean PET non-woven fabric of a supporting layer, the thickness of the supporting layer is 65 mu m, and finally the film is put into deionized water with the temperature of 25 ℃ (i.e. immersed into a coagulating bath) and kept for 180 seconds, so that a film skeleton is obtained on the supporting layer.
2) And (3) reducing chloroauric acid solution in a boiling solution state by taking sodium citrate as a reducing agent to obtain gold nanoparticle-containing solution with the gold nanoparticle particle size of about 30nm and the gold nanoparticle concentration of 0.1g/ml.
After cooling, a 1wt% solution of 1, 3-propanedithiol (in such an amount that the weight ratio of chloroauric acid to thiol is 20:1) was added and compounded for 30 minutes to give 210ml of a dispersion containing thiol-gold complex, the concentration of which was 9.5wt%.
3) 100cm is taken 2 The product prepared in the step 1) is placed into 210ml of the dispersion liquid, and is kept stand for 8 hours, so that a sample film is obtained.
Example 4
1) DMF was used as solvent, polystyrene was added, the casting solution was stirred to prepare a polystyrene concentration of 8wt%, the doctor blade was controlled to form a film on a clean supporting layer PET nonwoven fabric, the supporting layer thickness was 65 μm, and then placed in deionized water at 36℃for 60 seconds (i.e., immersed in a coagulation bath), and a film frame was obtained on the supporting layer.
2) Sodium citrate is used as a reducing agent, chloroauric acid solution is reduced in a boiling solution state, and a solution containing gold nanoparticles, wherein the particle size of the gold nanoparticles is about 20nm, and the concentration of the gold nanoparticles is 0.06 g/ml.
After cooling, a 1wt% solution of ethanedithiol (the amount of the solution being such that the weight ratio of chloroauric acid to thiol is 25:1) was added and compounded for 30 minutes to obtain 300ml of a dispersion containing thiol-gold complex, wherein the concentration of the thiol-gold complex was 5.8wt%.
3) 100cm is taken 2 And (3) placing the membrane skeleton prepared in the step (1) into 208ml of the dispersion liquid, and standing for 8 hours to obtain a product membrane.
Example 5
1) NMP is used as a solvent, chitosan and acetate fibers are added, casting film liquid with the concentration of chitosan being 6wt% and the concentration of acetate fibers being 8wt% is prepared by stirring, a scraper is controlled to form a film on a clean supporting layer PET non-woven fabric, the thickness of the supporting layer is 100 mu m, then the film is put into deionized water with the temperature of 35 ℃ (i.e. immersed in a coagulating bath), the film is kept for 150 seconds, and a film skeleton is obtained on the supporting layer.
2) And (3) reducing chloroauric acid solution in a boiling solution state by taking sodium citrate as a reducing agent to obtain gold nanoparticle-containing solution with the gold nanoparticle particle size of about 40nm and the gold nanoparticle concentration of 0.04 g/ml.
After cooling, a 1wt% solution of 1, 3-propanedithiol (in such an amount that the weight ratio of chloroauric acid to thiol is 20:1) was added and compounded for 30 minutes to give 210ml of a dispersion containing thiol-gold complex, wherein the concentration of the thiol-gold complex was 3.8wt%.
3) 100cm is taken 2 The product prepared in the step 1) is put into 210ml of the dispersion liquid and is kept stand for 8 hours, thus obtaining a product film.
Example 6
1) DMF was used as solvent, polysulfone was added, casting solution with polysulfone concentration of 6wt% was prepared by stirring, film formation was performed on clean supporting layer PET nonwoven fabric with a doctor blade under a supporting layer thickness of 65 μm, and then put into deionized water with a temperature of 30 ℃ (i.e. immersed in coagulation bath) and held for 80s, to obtain a membrane skeleton on the supporting layer.
2) Sodium citrate is used as a reducing agent, chloroauric acid solution is reduced in a boiling solution state, and a solution containing gold nanoparticles, wherein the particle size of the gold nanoparticles is about 40nm, and the concentration of the gold nanoparticles is 0.03 g/ml.
After cooling, 1wt% of a 1, 3-propanedithiol solution (the amount of the solution is such that the weight ratio of chloroauric acid to thiol is 15:1) was added and compounded for 30 minutes to give 213ml of a dispersion containing thiol-gold complex, the concentration of which was 2.8wt%.
3, taking 100cm 2 The product prepared in the step 1) is put into 213ml of the dispersion liquid and is kept stand for 8 hours, thus obtaining a product film.
Example 7
Prepared as in example 4 except that the gold nanoparticles were about 100nm in particle size in the solution containing gold nanoparticles by controlling the reaction temperature.
Example 8
Prepared as in example 4 except that the amounts of chloroauric acid and ethanedithiol solution were varied so that the concentration of thiol-gold complex in the dispersion containing thiol-gold complex was 1wt%.
Comparative example 1
Prepared as in example 4 except that the film backbone was not placed into the dispersion.
Comparative example 2
Prepared according to the method of example 4, except that 100cm of the one prepared in step 1) is taken 2 The membrane skeleton is put into 20ml of dispersion liquid and is kept stand for 8 hours, thus obtaining the product.
Comparative example 3
Prepared as in example 4 except that the particle size of the gold nanoparticles prepared was 800nm by controlling the reaction temperature.
Test example 1
Taking films prepared in each example and comparative example:
determining the loading amount of the thiol-gold complex loaded on the membrane by electron spectroscopy;
the thickness of the membrane and the membrane skeleton were measured by a micrometer bench type film thickness gauge (available from Shanghai precision instruments and meters, inc., model Q/ILBN 2-2006);
the average pore size of the membrane was determined by a PSMA-30 instrument purchased from south kyo high-power materials science, inc;
the porosity measurement method comprises the following steps: the method comprises the steps of weighing a film with a certain volume size, wherein the weight is dry weight, soaking the film in water completely, weighing, wherein the weight is the wet weight of a wet film, the difference between the wet weight and the dry weight is the weight of water reserved in a hole, converting the weight into the volume of water, namely the volume of the hole, and dividing the volume of the hole by the volume of a film sample to obtain the porosity.
Wherein the average particle size of the thiol-gold complex is substantially the same as the particle size of gold nanoparticles in the gold nanoparticle-containing solution during the film preparation process.
The results are shown in Table 1.
TABLE 1
In Table 1, the loading amounts refer to relative to 1cm 2 Is a membrane having a thiol-gold complex loading.
In addition, taking example 1 as an example, in the preparation process, a scanning electron microscope is adopted for observation, the surface topography of a film skeleton of the gold nanoparticle which is not loaded is shown in fig. 3, and after the preparation is completed, the surface topography of the film loaded with the gold nanoparticle is shown in fig. 3. It can be seen that the gold nanoparticles were uniformly supported on the film of example 1 after the completion of the preparation. The surface morphology of the film prepared in comparative example 3 is shown in fig. 2, and it can be seen that aggregation occurs between supported gold nanoparticles on the film of comparative example 3, which is not better than the dispersion of the film prepared in example 1.
Test example 2
Taking films prepared in each example and comparative example: the membrane was immersed vertically into a solution containing 1. Mu. Mol/L perfluorooctanoic acid. And observing the time required by the color change to bluish violet through a timer, namely the color change speed. The results are shown in Table 2.
TABLE 2
Wherein the color change speed is within 2 min. The larger the difference in color front and back, the better the film effect. Compared with the brownish red, the three colors of the reddish wine, the reddish purple and the final bluish purple are more obvious, which indicates that the film has better effect and is more suitable for practical use. It can be seen that the membrane provided by the invention is simple to operate when used for detection, and gets rid of large instruments and complicated detection steps.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.
Claims (13)
1. A membrane with a detection function, characterized in that the membrane comprises a membrane skeleton and a thiol-gold complex supported on the membrane skeleton;
wherein, relative to 1cm 2 The loading of thiol-gold complex is 0.05-0.5g;
wherein the average particle size of the thiol-gold complex is 1-100nm.
2. The film of claim 1, wherein the film is positioned relative to 1cm 2 The loading of thiol-gold complex is 0.05-0.25g;
and/or the thiol-gold complex has an average particle size of 1-40nm;
and/or the substance for providing the thiol structural unit in the thiol-gold complex is selected from thiols having 1 to 15 carbon atoms, preferably at least one selected from 2-aminoethanethiolate, 2, 3-dimercaptopropanol, mercaptoethane, butanethiol, dimercaptopropionic acid, cysteine, cystine, ethanedithiol, 2, 3-dimercaptobenzimidazole, 1-propanethiol, hexanedithiol, 1, 3-propanedithiol and dodecanethiol.
3. The membrane of claim 1, wherein the porosity of the membrane is 50-80%;
and/or the membrane has an average pore size of 0.1 to 10 μm;
and/or the thickness of the film is 100-180 μm, and the thickness of the film skeleton is 60-100 μm.
4. A membrane according to claim 1 or 3, wherein the membrane scaffold is composed of a film-forming polymer;
preferably, the film-forming polymer is at least one selected from polyethersulfone, acetate fiber, polyacrylamide, polyacrylonitrile, polyethersulfone, chitin, chitosan, polyacrylic acid, polydopamine, polylactic acid, polysulfone, polyethersulfone, polyvinylidene fluoride, polyvinyl chloride and polystyrene;
preferably, the film-forming polymer has a weight average molecular weight of 10000-400000g/mol.
5. A film according to claim 1 or 3, wherein the film further comprises a support layer;
preferably, the thickness of the supporting layer is 50-110 μm;
preferably, the material of the supporting layer is selected from non-woven fabrics.
6. A method for preparing a membrane with a detection function, the method comprising: loading thiol-gold complex on membrane skeleton relative to 1cm 2 The amount of thiol-gold complex used is 0.05-0.5g;
wherein the average particle size of the thiol-gold complex is 1-100nm.
7. The method of claim 6, wherein the method of preparing the membrane scaffold comprises: in the presence of the support layer, using a casting solution containing a film-forming polymer for film formation and immersing in a coagulation bath;
preferably, the concentration of the film-forming polymer in the casting solution is 5 to 30wt%, more preferably 6 to 20wt%;
preferably, the film-forming polymer is at least one selected from polyethersulfone, acetate fiber, polyacrylamide, polyacrylonitrile, polyethersulfone, chitin, chitosan, polyacrylic acid, polydopamine, polylactic acid, polysulfone, polyethersulfone, polyvinylidene fluoride, polyvinyl chloride and polystyrene;
preferably, the film-forming polymer has a weight average molecular weight of 10000-400000g/mol;
preferably, the solvent in the casting solution is at least one selected from chloroform, dimethyl sulfoxide, tetrahydrofuran, toluene, benzene, hexane, octane, acetone, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone and dioxane;
preferably, the temperature of the coagulating bath is 10-40 ℃, and the time of the coagulating bath is 15-200s;
preferably, the film is formed such that the thickness of the film skeleton is 60 to 100 μm and the thickness of the film is 100 to 180 μm.
8. The method of claim 6, wherein the loading of the thiol-gold complex on the membrane scaffold comprises: immersing the membrane scaffold in a dispersion comprising thiol-gold complexes;
preferably, the membrane scaffold is maintained for 0.5 to 24 hours, more preferably 5 to 10 hours after immersing in the dispersion containing the thiol-gold complex.
9. The method of claim 8, wherein the concentration of thiol-gold complex in the dispersion containing thiol-gold complex is 0.5-10wt%;
preferably, the preparation method of the dispersion liquid containing the thiol-gold complex comprises the following steps: reducing chloroauric acid in the presence of a reducing agent to obtain a solution containing gold nanoparticles; mixing the solution containing gold nanoparticles with mercaptan, and compounding to obtain a mercaptan-gold complex dispersion with a mercaptan-gold complex concentration of 0.5-10wt%;
preferably, in the solution containing gold nanoparticles, the average particle size of the gold nanoparticles is 1-40nm;
preferably, the concentration of the gold nanoparticles in the solution containing the gold nanoparticles is 0.01-0.1g/ml;
preferably, the mercaptan is used in the form of a mercaptan solution having a concentration of 0.1 to 10wt%, more preferably 0.5 to 8wt%;
preferably, the weight ratio of chloroauric acid to mercaptan is (10-25): 1;
preferably, the compounding time is 1-30min.
10. The process according to claim 9, wherein the thiol is selected from thiols having a carbon number of 1-15, preferably from at least one of 2-aminoethanethiolate, 2, 3-dimercaptopropanol, mercaptoethane, butanethiol, dimercaptopropionic acid, cysteine, cystine, ethanedithiol, 2, 3-dimercaptobenzimidazole, 1-propanethiol, hexanedithiol, 1, 3-propanedithiol and dodecanethiol.
11. A membrane with a detection function prepared by the method of any one of claims 6 to 10.
12. Use of a membrane with a detection function according to any one of claims 1-5 and 11 for detecting perfluorooctanoic acid and/or perfluorooctanoic acid salts.
13. A method for detecting perfluorooctanoic acid and/or perfluorooctanoic acid salt, characterized in that the method comprises: immersing the film having a detection function according to any one of claims 1 to 5 and claim 11 in a solution containing perfluorooctanoic acid and/or perfluorooctanoic acid salt, and observing a color change of the film.
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