CN117643800A - Ultraviolet light response type nano-channel membrane with adjustable permeability and preparation method and application thereof - Google Patents
Ultraviolet light response type nano-channel membrane with adjustable permeability and preparation method and application thereof Download PDFInfo
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Abstract
The invention provides an ultraviolet light response type nano channel membrane with adjustable permeability, which consists of a membrane substrate and an ultraviolet light response functional material grafted on the surface of the membrane substrate; the membrane substrate is provided with nano channels which are uniformly distributed and have uniform pore diameters, and the ultraviolet light response material consists of a coumarin mother nucleus, a carbon skeleton and a coupling group R; under the irradiation of ultraviolet light with different wavelengths and different irradiation doses, the ultraviolet light response functional material grafted on the surface of the film substrate can undergo photopolymerization reaction to form dimer or the photocleavage reaction of the dimer, so that the polymerization degree of the ultraviolet light response material is changed, the opening degree of the nanochannel of the ultraviolet light response nanochannel film is further changed, and the controllable adjustment of the permeability of the ultraviolet light response nanochannel film is realized. The invention also provides a preparation method of the ultraviolet light response type nano channel membrane and application of the ultraviolet light response type nano channel membrane as a controlled release material or a controllable substance separation material.
Description
Technical Field
The invention belongs to the field of intelligent membrane materials, and relates to an ultraviolet light response type nano channel membrane with adjustable permeability, a preparation method and application thereof.
Background
Increasingly serious chemical contamination of aquatic environments has become a global concern. The chemical pollutants not only can damage the balance of the aquatic ecological system and harm the diversity of aquatic organisms, but also can accumulate in human bodies through food chains, thereby causing great danger to the health of the human bodies. Currently, most research is focused on how to remove chemical contaminants in aquatic environments to reduce their concentration levels. In order to promote healthy growth of crops and aquatic products, various chemical drugs are actively applied to the environment. However, the residual medicine may cause direct pollution to the aquatic environment. Therefore, the method reduces the application amount of the medicine from the source and has important significance for controlling the chemical pollution of the water environment. Traditional methods of drug administration present a significant challenge in achieving accurate administration of the drug. Therefore, accurate and controllable drug release and safe drug release materials are particularly necessary for water environment management. However, the current drug controlled and sustained release materials still have some defects. On one hand, once the controlled and sustained release material is put into use, the dosage, the rate and the time of drug release are separated from manual control, which not only can lead to uncertainty of drug effect and environmental risk, but also prevents comprehensive intelligent management of future water environment; on the other hand, conventional controlled-release materials generally use microcapsules, particles or gels as carriers, which are difficult to recover after administration, and aggregated carriers and unreleased drugs pose new environmental hazards. Although imparting magnetism to the drug controlled-release material is one of effective strategies to solve the recovery problem, recovery rate by magnetism cannot be maintained at a high level when the application range of the drug controlled-release material is wide. Therefore, it is very significant and challenging to develop controlled release materials that are flexible to control, precisely controllable in release amount, and suitable for future administration of drugs in aquatic environments.
In recent years, nanochannel membranes have attracted considerable attention from researchers due to their excellent properties of highly ordered regular pore structure, adjustable pore size, high specific surface area, and the like. Meanwhile, the nano channel membrane has the characteristics of two-dimensional expansion, continuous macroscopic morphology and the like, and has good application potential in the fields of separation mass transfer, control/slow release, microminiaturization, device formation and the like. Although the nano-channel membrane has the functions of slow release, separation and the like, the nano-channel membrane has single function and has limitation in application in different scenes. Therefore, researchers have developed intelligent nanochannel membranes that can respond to external environmental stimuli by means of surface modification, etc. In many environmental stimuli, the light has the advantages of remote controllability, non-invasiveness, environmental friendliness and the like, and the fixed-point timing regulation of the performance of the light response material can be realized by adjusting parameters such as the wavelength, the intensity and the like of the light. These unique features make the light responsive controlled release system promising for future aquatic environment management. The light response film materials reported at present can realize mutual conversion between two states based on functional substances with light response characteristics, for example, realize conversion between hydrophilic state and hydrophobic state, conversion between film hole opening state and switching state, and the like. However, as the influence factors of photoreaction are more, the current controllable adjustability of the permeability of the photoreactive film is still lack of research, and the existing photoreactive film can only realize the switching between the two states of opening and closing of the film hole, but the intermediate state between the opening state and the closing state is difficult to realize the controllable adjustability. Thus, for the present stage, development of a light-responsive nanochannel membrane material with controllable and tunable permeability for better application in the field of controlled release and substance separation still faces a great challenge.
Disclosure of Invention
Aiming at the problem of lack of research on the controllable adjustability of the permeability of the existing light response membrane, the invention provides the ultraviolet light response type nano-channel membrane with adjustable permeability, and the preparation method and the application thereof, so that the membrane shows controllable and adjustable permeability under different ultraviolet light conditions, and provides a new thought for realizing controllable and accurate separation or release of substances in the fields of controllable separation and purification of the substances, controlled release of the substances and the like of the nano-channel membrane material.
In order to achieve the above purpose, the invention adopts the following technical scheme:
the ultraviolet light response type nano channel film with adjustable permeability consists of a film substrate and an ultraviolet light response functional material grafted on the surface of the film substrate; the membrane substrate is provided with nano channels with uniform distribution and uniform pore diameter, the ultraviolet light response material consists of a coumarin mother nucleus, a carbon skeleton and a coupling group R, and the structure of the ultraviolet light response material is shown as the formula (I):
in the formula (I), m and n are natural numbers, and the value of m+n ensures that the ultraviolet light response material grafted around the same nano channel of the film substrate can undergo photopolymerization reaction under the irradiation of ultraviolet light to form a dimer;
under the irradiation of ultraviolet light with different wavelengths and different irradiation doses, the ultraviolet light response functional material grafted on the surface of the film substrate can undergo photopolymerization reaction to form dimer or the photocleavage reaction of the dimer, so that the polymerization degree of the ultraviolet light response material is changed, the opening degree of the nanochannel of the ultraviolet light response nanochannel film is further changed, and the controllable adjustment of the permeability of the ultraviolet light response nanochannel film is realized.
In the technical scheme of the ultraviolet light response type nano channel film with adjustable permeability, the ultraviolet light response functional material grafted on the surface of the film substrate can undergo photopolymerization reaction to form a dimer under the irradiation of ultraviolet light with the wavelength of more than 350nm (for example, the wavelength is 350-370 nm); the ultraviolet light response functional material grafted on the surface of the film substrate can simultaneously generate photopolymerization reaction for forming dimer and photocleavage reaction for cracking the formed dimer under the irradiation of ultraviolet light with the wavelength of less than 260nm (for example, the wavelength is 250-260 nm), but the photocleavage reaction is mainly adopted, and the photopolymerization reaction and the photocleavage reaction can finally reach dynamic balance.
In the technical scheme of the ultraviolet light response type nano-channel membrane with adjustable permeability, the aperture of the nano-channel of the membrane substrate is in the range of 1.5-10 nm.
Further, in the technical scheme of the ultraviolet light response type nano-channel membrane with adjustable permeability, when the aperture of the nano-channel of the membrane substrate is in the range of 1.5-10 nm, in the ultraviolet light response material with the structure shown as the formula (I), the specific value of m+n=0-53, the specific value of m+n is related to the aperture of the nano-channel of the membrane substrate, and the value of m+n is increased along with the increase of the aperture of the nano-channel of the membrane substrate; after the value of m+n is determined, the specific values of m and n in practical application can be comprehensively considered according to the raw material market, the availability and the synthesis difficulty.
In the technical scheme of the ultraviolet light response type nano channel membrane with adjustable permeability, the material of the membrane base material is required to meet the requirement that the ultraviolet light response functional material can be grafted on the membrane base material; in the ultraviolet light response material with the structure shown in the formula (I), the coupling group R is determined according to the material of the membrane base material, and the structure of the coupling group R is required to be satisfied that the coupling group R can be subjected to grafting reaction with the membrane base material. For example, when the film substrate has hydroxyl groups and the coupling group R is a functional group such as ethoxysilyl group or methoxysilyl group, covalent coupling can occur between the two functional groups to graft the ultraviolet light responsive material with the structure shown as formula (I) on the surface of the film substrate.
In the technical scheme of the ultraviolet light response type nano channel film with adjustable permeability, the basic requirements which the film base material should meet are as follows: the nano channels are uniformly distributed and have uniform pore diameters, stable physical properties and chemical properties, and the ultraviolet light response functional material can be grafted on the membrane substrate. On the basis of meeting these basic requirements, there are no other particular requirements on the choice of film substrate. Possible film substrates include silicon-based film substrates (for example, the film substrate is made of silicon-containing materials such as silicon dioxide and silicon oxide), metal oxide-based film substrates (for example, the film substrate is made of metal oxide materials such as titanium dioxide and titanium oxide), carbon-based film substrates (for example, the film substrate is made of carbon material), and the like, and may be selected according to specific application requirements in practical applications.
Further, in the technical scheme of the ultraviolet light response type nano-channel membrane with adjustable permeability, the coupling group R comprises ethoxysilane group or methoxysilane group.
In the technical scheme of the ultraviolet light response type nano-channel membrane with adjustable permeability, the grafting amount of the ultraviolet light response material with the structure shown as the formula (I) on the membrane substrate is required to meet the requirement that the permeability of the ultraviolet light response type nano-channel membrane has ultraviolet response characteristics. The specific grafting amount of the ultraviolet light response material with the structure shown as the formula (I) on the membrane substrate is related to the nano-channel structure of the membrane substrate, such as the structural parameters of nano-channel pore diameter and the like. For example, when the membrane substrate is made of silicon dioxide and the aperture of the nano-channel of the membrane substrate is in the range of 1.5-3 nm, when the grafting amount of the ultraviolet light response material with the structure shown as the formula (II) on the membrane substrate is such that the atomic ratio of N to Si in the ultraviolet light response nano-channel membrane is between 15-25, the permeability of the ultraviolet light response nano-channel membrane with adjustable permeability can be ensured to have excellent ultraviolet light responsiveness and adjustability.
In the technical scheme of the ultraviolet light response type nano-channel film with adjustable permeability, the permeability of the ultraviolet light response type nano-channel film has a correlation with ultraviolet irradiation dose (within a specific ultraviolet light wavelength range and an ultraviolet irradiation dose range), and the ultraviolet response dynamics characteristic of the ultraviolet light response type nano-channel film accords with a double-exponential function model.
For example, when the above-mentioned permeation-adjustable uv-responsive nano-channel film is irradiated with uv light having a wavelength of more than 350nm (for example, a wavelength of 350 to 370 nm), the permeation of the permeation-adjustable uv-responsive nano-channel film is reduced with an increase in irradiation dose in a certain uv irradiation dose range, and there is a correlation between the permeation of the permeation-adjustable uv-responsive nano-channel film and the uv irradiation dose, and uv-responsive dynamic characteristics of the uv-responsive nano-channel film conform to a double-exponential function model.
For another example, when the above-mentioned permeation-adjustable uv-responsive nano-channel film is irradiated with uv light having a wavelength of less than 260nm (for example, having a wavelength of 250 to 260 nm), the permeation of the permeation-adjustable uv-responsive nano-channel film increases with an increase in irradiation dose within a certain uv irradiation dose range, and there is a correlation between the permeation of the permeation-adjustable uv-responsive nano-channel film and the uv irradiation dose, and uv-responsive dynamic characteristics of the uv-responsive nano-channel film conform to a double-exponential function model.
The invention also provides a preparation method of the ultraviolet light response type nano channel film with adjustable permeability, which comprises the following steps:
(1) Dissolving an ultraviolet light response functional material with a structure shown as a formula (I) in a solvent to obtain a grafting solution, wherein the concentration of the ultraviolet light response functional material in the grafting solution is 1-15 mg/mL;
(2) Immersing the membrane substrate in the grafting liquid, incubating for 10 min-3 d to graft the ultraviolet light response functional material with the structure shown as the formula (I) on the membrane substrate, then cleaning to remove the ultraviolet light response functional material which is combined with the membrane substrate unstably, and drying to obtain the ultraviolet light response nano-channel membrane with adjustable permeability.
In the technical scheme of the preparation method, the concentration of the ultraviolet light functional response material in the grafting liquid in the step (1), the reaction temperature and the incubation time in the step (2) can jointly influence the grafting amount of the ultraviolet light functional response material on the surface of the membrane substrate, the grafting amount can influence the permeability of the ultraviolet light response nano channel membrane, and the concentration of the ultraviolet light response material in the grafting liquid, the reaction temperature and the incubation time can be determined according to specific application requirements in practical application.
Further, in the technical scheme of the preparation method, the concentration of the ultraviolet light response functional material in the grafting liquid is preferably 2-8 mg/mL.
Further, in the technical scheme of the preparation method, the reaction temperature is controlled to be 20-60 ℃ in the step (2), and the reaction temperature is preferably controlled to be 20-30 ℃ in the step (2).
Further, in the technical scheme of the preparation method, the incubation time is preferably 10-60 min.
The principle that the permeability of the ultraviolet light response type nano channel film with adjustable permeability has controllable ultraviolet light response characteristics is as follows:
the membrane substrate adopted by the application is a nano-channel membrane, and the nano-channels of the membrane substrate are uniformly distributed and have highly uniform pore diameters; the ultraviolet light response functional material with the structure shown as the formula (I) is a coumarin derivative which can respond to different ultraviolet light irradiation conditions to generate photodimerization reaction and photocleavage reaction of dimer. The ultraviolet light response functional material with the structure shown as the formula (I) is grafted on the surface of the film substrate.
When the ultraviolet light response type nano channel film is irradiated by ultraviolet light with the wavelength of more than 350nm, the ultraviolet light response functional material grafted on the surface of the film substrate can generate photopolymerization reaction, and the ultraviolet light response functional material grafted on the surface of the film substrate can generate photopolymerization reaction to form a dimer, namely, a cyclobutane ring is formed through [2+2] cycloaddition; after forming a cyclobutane ring, when the ultraviolet light response type nano channel film is irradiated by ultraviolet light with the ultraviolet light wavelength smaller than 260nm, the cyclobutane ring formed by the photopolymerization reaction can be converted into two ultraviolet light response functional material monomers grafted on the film base material, but the ultraviolet light response functional material grafted on the surface of the film base material can also undergo the photopolymerization reaction to form a dimer, and the photopolymerization and the photocleavage reaction can finally reach dynamic balance. When the ultraviolet light response functional material grafted on the surface of the membrane substrate is subjected to photodimerization reaction, the nano-channel permeability of the ultraviolet light response nano-channel membrane is reduced to different degrees along with different photodimerization reaction degrees, and when the dimer formed by the ultraviolet light response functional material grafted on the surface of the membrane substrate in the photopolymerization reaction is subjected to photocleavage reaction, the nano-channel permeability of the ultraviolet light response nano-channel membrane is increased to different degrees, so that the change of the permeability of the ultraviolet light response nano-channel membrane is realized.
Experiments show that the ultraviolet irradiation dose absorbed by the ultraviolet light response type nano channel film is a key factor influencing the light response behavior of the ultraviolet light response functional material grafted on the surface of the film substrate, and the photopolymerization degree of the ultraviolet light response functional material grafted on the surface of the film substrate and the photocomposition degree of a dimer formed by photopolymerization are different under different ultraviolet light irradiation conditions. In addition, in a certain ultraviolet irradiation dose range, the ultraviolet light response type nano channel film has a correlation between the permeability and the ultraviolet irradiation dose, and on the basis of determining the correlation between the permeability and the ultraviolet irradiation dose of the ultraviolet light response type nano channel film, the controllable regulation and control of the permeability of the ultraviolet light response type nano channel film can be realized on the basis of the correlation.
The invention is proved by experiments that: when a silica nano-channel membrane with the aperture of 1.9nm is used as a membrane substrate and coumarin derivatives with the structural formula shown in the formula (II) are used as ultraviolet light response materials, the prepared ultraviolet light response nano-channel membrane with adjustable permeability has the following characteristics:
the permeability-adjustable ultraviolet light response type nano-channel film can reduce the permeability of the ultraviolet light response type nano-channel film under the irradiation of ultraviolet light with the wavelength of 365nm, and then the permeability-adjustable ultraviolet light response type nano-channel film is irradiated under the ultraviolet light with the wavelength of 254nm, so that the permeability of the ultraviolet light response type nano-channel film can be improved, and the controllable adjustment of the permeability of the ultraviolet light response type nano-channel film can be realized. And the maximum degree of photopolymerization of the ultraviolet light responsive material grafted on the film substrate is 0-82.2 mJ cm -2 ·min -1 The actual degree of photopolymerization reaction is 0-1644 mJ.cm, which is irrelevant to the ultraviolet irradiation intensity in the ultraviolet irradiation intensity range -2 Has the adjustability in the ultraviolet irradiation dose range of the unit area; after photopolymerization, the ultraviolet light response material grafted on the film substrate has the maximum photocleavage reaction of dimer of 0-1.2 mJ.cm -2 ·min -1 The ultraviolet light irradiation intensity is inversely related to the ultraviolet light irradiation intensity, and the actual degree of the photo-cracking reaction is 0-24 mJ.cm -2 Has the adjustability in the ultraviolet irradiation dosage range of the unit area. In practical application, the controllable adjustment of the permeability of the ultraviolet light response type nano channel membrane can be realized according to the ultraviolet irradiation dose range.
Based on the ultraviolet light response characteristic of the ultraviolet light response type nano-channel film with adjustable permeability, the invention also provides application of the ultraviolet light response type nano-channel film with adjustable permeability as a controlled release material or a controllable substance separation material.
Further, when the ultraviolet light response type nano-channel membrane with adjustable permeability is used as a controlled release material or a controllable substance separation material, the change relation of the permeation rate of the target substance to be released or separated on the ultraviolet light response type nano-channel membrane with adjustable permeability along with the ultraviolet irradiation dose accords with a double-exponential function model, firstly, the correlation relation of the permeation rate of the target substance to be released or separated on the ultraviolet light response type nano-channel membrane with adjustable permeability along with the change of the ultraviolet irradiation dose is determined, and then, based on the determined correlation relation, the quantitative regulation and control of the permeation rate of the target substance to be released or separated on the ultraviolet light response type nano-channel membrane with adjustable permeability can be realized by adjusting the ultraviolet irradiation dose.
Compared with the prior art, the technical scheme provided by the invention has the following beneficial technical effects:
1. the invention provides an ultraviolet light response type nano-channel membrane with adjustable permeability, which consists of a membrane substrate and an ultraviolet light response functional material grafted on the surface of the membrane substrate; the ultraviolet light response material consists of a coumarin mother nucleus, a carbon skeleton and a coupling group R, and the ultraviolet light response material grafted around the same nanometer channel of the membrane substrate can undergo photopolymerization reaction under ultraviolet irradiation to form a dimer or the photocleavage reaction is converted into a monomer; under the irradiation of ultraviolet light with different wavelengths and different irradiation doses, the ultraviolet light response functional material grafted on the surface of the film substrate can undergo photopolymerization reaction to form dimer and photocleavage reaction of the dimer, so that the polymerization degree of the ultraviolet light response material is changed, and the opening degree of the nanochannel of the ultraviolet light response nanochannel film is further changed, and the controllable adjustment of the permeability of the ultraviolet light response nanochannel film is realized. The permeability of the ultraviolet light response type nano-channel membrane can be regulated and controlled by regulating and controlling the ultraviolet irradiation dose, so that the ultraviolet light response type nano-channel membrane can be utilized to realize the controllable release or controllable separation of substances. Fills the research blank that the controllability of the permeability of the existing light response film is still lacking.
2. The invention also provides a preparation method of the ultraviolet light response type nano-channel membrane with adjustable permeability, which has the advantages of simple operation, mild process conditions, flexibility, controllability and easy realization, and can realize the high-efficiency and low-cost preparation of the ultraviolet light response type nano-channel membrane with adjustable permeability, thereby being beneficial to popularization and application of the ultraviolet light response type nano-channel membrane with adjustable permeability.
3. The invention also provides application of the ultraviolet light response type nano-channel membrane with adjustable permeability as a controlled release material or a controllable substance separation material, when the ultraviolet light response type nano-channel membrane with adjustable permeability is applied, the change relation of the permeation rate of a target substance to be released or separated on the ultraviolet light response type nano-channel membrane with adjustable permeability along with the irradiation dose accords with a double-exponential function model, firstly, the correlation relation of the permeation rate of the target substance to be released or separated on the ultraviolet light response type nano-channel membrane with adjustable permeability along with the change of the irradiation dose is determined, and then, based on the determined correlation relation, quantitative regulation and control of the permeation rate of the target substance to be released or separated on the ultraviolet light response type nano-channel membrane with adjustable permeability can be realized by adjusting the ultraviolet irradiation dose. For example, when the ultraviolet light response type nano channel film with adjustable permeability provided by the invention is used as a controlled release material, the accurate regulation and control of the release rate of a substance to be released can be realized, and the problems that the substance release process of the existing controlled release material is uncontrollable, the substance remains or the release is excessive, and the environment is damaged can be solved.
Drawings
FIG. 1 is a schematic diagram of the synthetic route and nuclear magnetic resonance hydrogen spectrum of CTC in example 1.
FIG. 2 is an elemental distribution map of CTC@SNM-20 prepared in example 3.
FIG. 3 a is the results of X-ray photoelectron spectroscopy tests of CTC@SNM-10, CTC@SNM-20, CTC@SNM-60 and SNM, and FIG. 3 b is the variation of the ratio (N/Si) of the N element signal to the Si element signal in CTC@SNM-10, CTC@SNM-20, CTC@SNM-60 and SNM with the grafting time.
The Water Contact Angles (WCA) of CTC@SNM-10, CTC@SNM-20, CTC@SNM-60 and SNM are plotted as a function of time, and water contact angles after equilibration, respectively, for both graphs a, b of FIG. 4.
Fig. 5 is a uv response characteristic test result of CTCs.
FIG. 6 is a graph showing the results of ultraviolet response characteristics of CTC@SNM-10, CTC@SNM-20, and CTC@SNM-60 and SNM.
FIG. 7 is a graph showing the results of the permeability and UV response kinetics test of CTC@SNM-10, CTC@SNM-20, CTC@SNM-60 and SNM.
FIG. 8 is a graph showing the results of a controlled release performance test of a controlled release system constructed based on CTC@SNM-20 and SNM.
Detailed Description
The ultraviolet light response type nano-channel membrane with adjustable permeability, and the preparation method and application thereof provided by the invention are further described below through examples. It is noted that the following examples are given solely for the purpose of illustration and are not to be construed as limitations of the present invention, as many insubstantial modifications and variations of the present invention will be apparent to those skilled in the art in light of the foregoing disclosure, and are still within the scope of the invention.
In each of the following examples and comparative examples, a silica nanochannel membrane (membrane substrate) was synthesized by the method described in Nano Lett 2014,14,923-32,Angew Chem Int Ed Engl 2012,51,2173-7, and the nanochannels denoted as SNM had uniform pore diameters and an average pore diameter of 1.9nm.
Example 1
In this embodiment, the synthetic structure of the ultraviolet light response functional material (CTC) is shown in formula (II), and the synthetic route is shown in a graph a of fig. 1, and the specific steps are as follows:
(1) 7-Hydroxycoumarin (HC) (30 mmol) and anhydrous potassium carbonate (150 mmol) were dissolved in N, N-dimethylformamide (150 mL) at room temperature, and stirred under reflux at 80deg.C for 60min to give a reaction solution; 4-bromobutyl acetate (60 mmol) was dissolved in dichloromethane (20 mL) and added dropwise to the aforementioned reaction solution; the reaction progress was monitored by TLC (developer: dichloromethane/methanol=95/5, v/v), after the reaction was completed, the obtained reaction product was suction-filtered, the obtained cake was washed with a small amount of dichloromethane, the obtained filtrate was spin-distilled to remove the solvent to obtain a crude product, and the crude product was separated by silica gel column chromatography to obtain pale yellow solid compound 1.
(2) Compound 1 (1.6 mmol) was added to sodium methoxide/methanol solution (0.25 mol/L,20 mL) and reacted under reflux at 50 ℃; the reaction process was monitored by TLC (developing solvent: dichloromethane/methanol=95/5, v/v), after the reaction was completed, an appropriate amount of diluted acetic acid was added to neutralize the obtained reaction solution, the solvent was removed by rotary evaporation to obtain a crude product, and the crude product was separated by column chromatography on silica gel (dichloromethane/methanol=100/1, v/v) to obtain compound 2 as a white solid.
(3) Compound 2 (3.6 mmol) was dissolved in tetrahydrofuran (20 mL) at room temperature, and (3-isocyanopropyl) triethoxysilane (3-ICPTES, 1.8 mL) and dibutyltin dilaurate (DBTDL, 2 mL) were added and reacted under reflux at 70℃with stirring; the reaction process (developing agent: dichloromethane/methanol=95/5, v/v) is monitored by TLC, after the reaction is finished, the solvent of the obtained reaction product is removed by rotary evaporation to obtain a crude product, the crude product is subjected to column chromatography of silica gel (dichloromethane/methanol=100/2, v/v) to quickly separate to obtain a compound 3, wherein the compound 3 is CTC, and the compound is refrigerated and stored.
The nuclear magnetic resonance hydrogen spectrum of the CTCs prepared in this example is shown in fig. 1 b, and as can be seen from fig. 1 b, CTCs having the structure shown in formula (II) were successfully synthesized in this example.
Example 2
In this embodiment, an ultraviolet light response type nanochannel membrane with adjustable permeability is prepared, and the steps are as follows:
(1) The CTC prepared in example 1 was added to anhydrous toluene and stirred well until the CTC dissolved to give a grafting solution in which the concentration of CTC was 5mg/mL.
(2) And immersing SNM in a grafting solution, standing at room temperature for incubation for 10min, then washing the CTC combined with the SNM unstably by using absolute ethyl alcohol, and drying to obtain the ultraviolet light response type nano channel membrane with adjustable permeability, which is named CTC@SNM-10.
Example 3
The operation of this example was essentially the same as that of example 2, except that the prepared ultraviolet light-responsive nanochannel membrane with adjustable permeability was designated ctc@snm-20 by standing at room temperature for 20min of incubation.
Example 4
The operation of this example was essentially the same as that of example 2, except that the prepared ultraviolet light-responsive nanochannel membrane with adjustable permeability was designated ctc@snm-60 by standing at room temperature for 60min.
Comparative example 1
In this example, nanochannel silica membranes (SNMs) were prepared, specifically with reference to the method in Nano Lett 2014,14,923-32,Angew Chem Int Ed Engl 2012,51,2173-7 to synthesize SNMs.
Example 5
In this example, the chemical compositions of CTC@SNM-10, CTC@SNM-20, CTC@SNM-60 prepared in examples 2 to 4, and comparative example 1 were tested.
FIG. 2 is a distribution of elements of CTC@SNM-20 prepared in example 3, wherein C, N, O and Si contained in CTC@SNM-20 in FIG. 2 are uniformly distributed, indicating that CTC is uniformly grafted on SNM.
FIG. 3 a shows the results of X-ray photoelectron spectroscopy of CTC@SNM-10, CTC@SNM-20, CTC@SNM-60 and SNM, and FIG. 3 b shows the variation of the ratio of N element signal to Si element signal (i.e., N/Si atomic ratio) in CTC@SNM-10, CTC@SNM-20, CTC@SNM-60 and SNM with the time of grafting. In the ultraviolet light response type nano channel film with adjustable permeability, an N element signal is provided by CTC, an Si element signal is provided by SNM, and N/Si in a b diagram of FIG. 3 is calculated based on an X-ray photoelectron spectroscopy test result. As can be seen from fig. 3, the CTC content gradually increases with the increase of the grafting time on the surface of the uv-responsive nanochannel membrane with adjustable permeability.
Example 6
In this example, CTC@SNM-10, CTC@SNM-20, CTC@SNM-60 prepared in examples 2 to 4, and comparative example 1 were tested for hydrophilicity and hydrophobicity of the prepared SNM.
The Water Contact Angles (WCA) of CTC@SNM-10, CTC@SNM-20, CTC@SNM-60 and SNM were measured respectively with time, the results are shown in a graph of FIG. 4, the water contact angles after balancing are shown in a graph b of FIG. 4, and CTC@SNM in the graph b of FIG. 4 is a generic name of CTC@SNM-10, CTC@SNM-20 and CTC@SNM-60. The hydrophilicity and hydrophobicity of the membrane are important for the wettability of the membrane and mass transfer in the pores, and can directly influence the permeability of the membrane. As can be seen from fig. 4, the water contact angle of SNM was 29.6 ° before CTC grafting; after grafting CTCs on the surface of SNM, the water contact angle of the membrane increased with the extension of the grafting time, the water contact angles of ctc@snm-10, ctc@snm-20 and ctc@snm-60 were 45.0 °, 57.6 ° and 68.5 °, respectively, the increase in water contact angle being due to the decrease in the silicon hydroxyl groups on the membrane surface and the increase in hydrophobic CTCs, which is consistent with the conclusion of example 5.
Example 7
In this example, the ultraviolet light response characteristics of CTC, CTC@SNM-10, CTC@SNM-20, CTC@SNM-60 prepared in examples 2 to 4, and SNM prepared in comparative example 1 were examined.
For CTCs, 3mL of CTC aqueous solution was added to the cuvette, sealed, and temperature controlled using a 25 ℃ hot bench; ultraviolet light with the wavelength of 365nm or 254nm is used for irradiating for a certain time (0-20 min) at different distances (0, 2.5, 5, 10, 20 and 30 cm), and an ultraviolet-visible spectrophotometer is used for testing the absorbance change condition of the CTC aqueous solution caused by photodimerization reaction and the photocleavage reaction of the dimer of CTC.
Under alternating irradiation of ultraviolet light with the wavelength of 365nm and 254nm, the photodimerization reaction of the CTC and the photocleavage reaction of the dimer of the CTC have certain reversibility, and the photodimerization degree (PDD) and the photocleavage degree (PCD) are calculated:
PDD＝100％×(A 0 -A T )/A 0
in the above two formulas, A 0 ,A T ,A t Respectively, in the initial state, T min was irradiated with ultraviolet light having a wavelength of 365nm, and T was irradiated with ultraviolet light having a wavelength of 365nm 0 min, t min was irradiated with ultraviolet light of wavelength 254nm, absorbance value of CTC aqueous solution at wavelength 323 nm.
Fig. 5 is a uv response characteristic test result of CTCs. Each curve in the graph a of fig. 5 sequentially increases from top to bottom (irradiation with ultraviolet light at 365 nm); the curves in the d plot of FIG. 5 increase in sequence from bottom to top (irradiation with 254nm UV light). In both graphs a, d of fig. 5, the uv spectrum has two characteristic absorption bands, including a characteristic absorption band of n-pi transition belonging to carbonyl functions between 310 and 340nm, and a characteristic absorption band of pi-pi transition belonging to conjugated pi system between 250 and 300 nm. As can be seen from FIG. 5 a, with irradiation of ultraviolet light with a wavelength of 365nm, CTC undergoes photopolymerization to form a dimer, CTC forms a cyclobutane ring, the length of the conjugated pi system is reduced, and the intensity of an absorption peak at 323nm is reduced. From the d-plot of FIG. 5, irradiation with ultraviolet light at 254nm triggers a photo-cleavage reaction of the CTC dimer, resulting in restoration of a portion of the CTC dimer to the monomer state and an increase in the intensity of the absorption peak at 323 nm. As can be seen from the b-chart of fig. 5, as the irradiation time of ultraviolet light with a wavelength of 365nm increases, the photodimerization degree (PDD) of CTCs increases and reaches a constant value at the time of irradiation for 20min, for example, when the irradiation distance is 0cm, the PDD is finally constant at 78%. As can be seen from the e-chart of fig. 5, as the irradiation time of ultraviolet light with a wavelength of 254nm increases, the photo-cracking degree (PCD) of CTC dimer increases and reaches a constant value at 20min of irradiation, for example, when the irradiation distance is 0cm, the PCD is finally constant at 52%. Since the photo-cleavage reaction of CTC dimers and the photo-dimerization reaction of CTCs are in dynamic equilibrium under irradiation of ultraviolet light with a wavelength of 254nm, PCD does not increase to a higher level with the increase of irradiation time. The relationship between the ultraviolet response characteristic and the light irradiation intensity of the CTCs is shown in the two graphs c and f of fig. 5, and the light response behavior of the CTCs accords with a double-exponential function model.
Example 8
In this example, the ultraviolet light response characteristics of CTC@SNM-10, CTC@SNM-20, CTC@SNM-60 prepared in examples 2 to 4, and SNM prepared in comparative example 1 were examined.
And (3) performing permeability investigation on CTC@SNM-10, CTC@SNM-20, CTC@SNM-60 and SNM by adopting a vertical diffusion cell, and testing by combining a fluorescence spectrophotometer to obtain model molecules (sodium fluorescein), wherein the permeation quantity of the membrane changes with time after ultraviolet light irradiation of 365nm in wavelength and ultraviolet light irradiation of 254nm for 6min before ultraviolet light irradiation so as to study the light response performance of the membrane. The supply side was 3mL containing 0.5mmol/L sodium fluoresceinAnd 1mol/L of an aqueous potassium chloride solution, 15mL of the aqueous 1mol/L potassium chloride solution was used as a receiving solution. Before the permeation experiment, the membrane was soaked in ethanol for 10min, naturally dried, then soaked in a receiving solution for 2h to be completely wetted, and then the permeation experiment was performed. After starting permeation, the concentration of model molecules in the receiving solution was measured with a fluorescence spectrophotometer every 20min and calculated from the standard curve of model molecules. FIG. 6 is a graph showing the results of ultraviolet response characteristics of CTC@SNM-10, CTC@SNM-20, and CTC@SNM-60, and SNM. The graphs a-d of FIG. 6 are plots of molecular permeation of model molecules in the pristine (i.e., without ultraviolet light irradiation) and in response to ultraviolet light irradiation at 365nm and 254nm, respectively, for SNM, CTC@SNM-10, CTC@SNM-20, and CTC@SNM-60, over time. In the graphs a to d of fig. 6, the slope of the straight line indicates the permeation rate of the model molecule. As is clear from the graphs a to d of FIG. 6, the molecular permeation weights of SNM do not have UV response characteristics, and the molecular permeation weights of CTC@SNM-10 and CTC@SNM-20 have UV response characteristics. FIG. 6 e is a graph showing the calculated permeability of model molecules in the original state for SNM, CTC@SNM-10, CTC@SNM-20 and CTC@SNM-60, as it can be seen that the membrane permeability decreases with increasing grafting time, since CTCs grafted around nanochannels of the membrane substrate act as gating impeding the entry of model molecules into nanochannels. FIG. 6 is a graph f showing the rate of change of permeation rates of SNM, CTC@SNM-10, CTC@SNM-20 and CTC@SNM-60 before and after optical response (R P )。
R P ＝100％×P light /P 0
In the above, P 0 And P light The permeation rate of the model molecule through the membrane in the initial state and after uv irradiation, respectively.
Compared with the CTC@SNM-20, the ultraviolet light response characteristic of molecular permeability is better, and the CTC grafting amount in the CTC@SNM-20 is the most reasonable, and of course, the CTC@SNM-10 can also meet the requirements of practical application.
Example 9
In this example, the permeability controllability of CTC@SNM-10, CTC@SNM-20, CTC@SNM-60 prepared in examples 2 to 4, and the prepared SNM of comparative example 1 was examined. The same test method as in example 7 was used to examine the transmembrane permeation rate of model molecules, except that the tested films were irradiated with ultraviolet light having a wavelength of 365nm or 254nm for a specific time at an illumination distance of 5 cm.
FIG. 7 is a graph showing the results of the permeation and UV response kinetics test of CTC@SNM-10, CTC@SNM-20, CTC@SNM-60, and SNM. FIG. 7 a is a graph showing the permeation rate of model molecules released from a membrane after the model molecules are irradiated with ultraviolet light having a wavelength of 365/254nm for a specific period of time. As can be seen from graph a of FIG. 7, as the irradiation time of ultraviolet light with a wavelength of 365nm increases, the permeation rates of model molecules in CTC@SNM-10, CTC@SNM-20 and CTC@SNM-60 tend to gradually decrease and then tend to stabilize; with the increase of the ultraviolet irradiation time with the wavelength of 254nm, the permeation rate of model molecules in CTC@SNM-10, CTC@SNM-20 and CTC@SNM-60 is gradually increased and then tends to be stable; the permeation rate of the model molecules in the SNM does not change along with the irradiation of ultraviolet light, and the permeation rate is always in a constant state. CTC@SNM-10, CTC@SNM-20 and CTC@SNM-60 show similar ultraviolet response trends, except that the permeation rate of model molecules in CTC@SNM-60 and the change rate thereof are relatively smaller. FIG. 7 b is a graph showing the relationship between Photodimerization (PDD) and photo response speed with irradiation dose of CTC@SNM-20 under irradiation of ultraviolet light having a wavelength of 365 nm. FIG. 7 c is a graph showing the relationship between the photo-cracking degree (PCD) and the photo-response speed of CTC@SNM-20 under irradiation of ultraviolet light having a wavelength of 254 nm. From the graphs b-c of FIG. 7, it can be seen that the photo-response behavior of CTC@SNM-20 also conforms to a double exponential function model. Either photodimerization of CTCs grafted onto SNM or photocleavage of dimers of CTCs, at low uv radiation doses, exhibit rapid photoreactive behavior. As the uv irradiation dose is gradually increased, the photo response rate gradually decreases and the photo response becomes saturated. In the practical application of the ultraviolet light response type nano channel film, the permeation performance of the film can be regulated and controlled by adjusting the irradiation dose by taking the change relation curve of the light response rate and the permeation rate along with the irradiation dose as a reference.
Example 10
In this example, ctc@snm-20 prepared in example 3 and SNM prepared in comparative example 1 were used for drug controlled release, and the difference in performance was compared.
Firstly, a controlled release system formed by assembling an amber glass bottle, two gaskets, a film to be tested and a screw cap type open bottle cap is constructed. Wherein the film to be measured is sandwiched between two gaskets, and 3mL of 0.5mmol/L methylene blue aqueous solution is contained in a glass bottle. The activity of the hydromyces is inhibited by taking the hydromyces as an antibacterial object and taking the methylene blue as an antibacterial drug. Drug (methylene blue) is released into the aqueous solution of the aqueous mould hypha blocks at the receiving side through CTC@SNM-20 and SNM respectively, after the drug is released for 8 hours, the drug reaches effective antibacterial concentration, 365nm ultraviolet light is adopted to irradiate for 10 minutes so as to reduce the opening degree of the nano channel and reduce the drug release speed. The concentration of the drug and the residual quantity of the pesticide in the mycelium pellet after the release for different times were tested by an ultraviolet spectrophotometer. The effect of the drug on hyphal activity was examined quantitatively by plating. FIG. 8, panel a, is a graph of UV controlled drug release, from which it is seen that upon UV irradiation at 365nm, the rate of drug release from CTC@SNM-20 is significantly reduced relative to SNM, due to a decrease in membrane permeability. FIG. 8 b is an electron microscopic image of hyphae of CTC@SNM-20 before drug release (b 1-b 2 images) and after 8h of drug release (b 3-b 4 images), and the image shows that the hyphae have obvious collapse and shrinkage, which indicates that the drug released by a controlled release system constructed based on CTC@SNM-20 reaches an effective antibacterial concentration. FIG. 8 c is a graph showing the change of the inhibition rate of the controlled release system constructed based on SNM and CTC@SNM-20 to the water mold with the release time, wherein the antibacterial effect is consistent and has no obvious difference. The d plot of FIG. 8 shows the drug residue of the mycelium pellet. From the graphs c to d in FIG. 8, it is shown that the permeability of CTC@SNM-20 is regulated in time during the drug release for 8 hours, so that the drug residue is lower than that of SNM, but the inhibition effect on the hydromycete is not affected. This example illustrates that the permeability-adjustable ultraviolet light-responsive nanochannel membrane provided by the invention can be used for flexibly adjusting the controlled release behavior of a drug.
Claims (10)
1. The ultraviolet light response type nano-channel membrane with adjustable permeability is characterized by comprising a membrane substrate and an ultraviolet light response functional material grafted on the surface of the membrane substrate; the membrane substrate is provided with nano channels with uniform distribution and uniform pore diameter, the ultraviolet light response material consists of a coumarin mother nucleus, a carbon skeleton and a coupling group R, and the structure of the ultraviolet light response material is shown as the formula (I):
in the formula (I), m and n are natural numbers, and the value of m+n ensures that the ultraviolet light response material grafted around the same nano channel of the film substrate can undergo photopolymerization reaction under the irradiation of ultraviolet light to form a dimer;
under the irradiation of ultraviolet light with different wavelengths and different irradiation doses, the ultraviolet light response functional material grafted on the surface of the film substrate can undergo photopolymerization reaction to form dimer or the photocleavage reaction of the dimer, so that the polymerization degree of the ultraviolet light response material is changed, the opening degree of the nanochannel of the ultraviolet light response nanochannel film is further changed, and the controllable adjustment of the permeability of the ultraviolet light response nanochannel film is realized.
2. The ultra-violet light responsive nano-channel membrane of adjustable permeability in accordance with claim 1, wherein the nano-channel of the membrane substrate has a pore size in a range of 1.5-10 nm.
3. The ultraviolet light-responsive nanochannel membrane with adjustable permeability according to claim 2, wherein in the ultraviolet light-responsive material with the structure shown in formula (i), the specific value of m+n=0 to 53 is related to the pore diameter of the nanochannel of the membrane substrate, and the value of m+n increases with the increase of the pore diameter of the nanochannel of the membrane substrate.
4. The ultraviolet light-responsive nanochannel membrane of claim 1, wherein the membrane substrate is of a material such that the ultraviolet light-responsive functional material can be grafted onto the membrane substrate; in the ultraviolet light response material with the structure shown in the formula (I), the coupling group R is determined according to the material of the membrane base material, and the structure of the coupling group R is required to be satisfied that the coupling group R can be subjected to grafting reaction with the membrane base material.
5. The tunable ultraviolet light responsive nanochannel membrane of claim 4 wherein coupling group R comprises an ethoxysilyl or methoxysilyl group.
6. The tunable permeability uv responsive nanochannel membrane of any one of claims 1 to 5 wherein the uv responsive nanochannel membrane has a correlation in permeability with uv irradiation dose and the uv responsive kinetics of the uv responsive nanochannel membrane conforms to a bi-exponential function model.
7. A method for preparing the ultraviolet light responsive nanochannel membrane with adjustable permeability as claimed in any one of claims 1 to 6, comprising the steps of:
(1) Dissolving an ultraviolet light response functional material with a structure shown as a formula (I) in a solvent to obtain a grafting solution, wherein the concentration of the ultraviolet light response functional material in the grafting solution is 1-15 mg/mL;
(2) Immersing the membrane substrate in the grafting liquid, incubating for 10 min-3 d to graft the ultraviolet light response functional material with the structure shown as the formula (I) on the membrane substrate, then cleaning to remove the ultraviolet light response functional material which is combined with the membrane substrate unstably, and drying to obtain the ultraviolet light response nano-channel membrane with adjustable permeability.
8. The method for preparing a permeation-adjustable ultraviolet light response type nano-channel membrane according to claim 7, wherein the reaction temperature is controlled to be 20-60 ℃ in the step (2).
9. Use of a permeation-tunable ultraviolet light-responsive nanochannel membrane as claimed in any one of claims 1 to 6 as a controlled release material or a controlled substance separation material.
10. The use according to claim 9, wherein when the permeable tunable uv-responsive nanochannel membrane is used as a controlled release material or a controllable substance separation material, the relation of the change of the permeation rate uv of the target substance to be released or separated on the permeable tunable uv-responsive nanochannel membrane with the irradiation dose conforms to a double-exponential function model, the relation of the change of the permeation rate uv of the target substance to be released or separated on the permeable tunable uv-responsive nanochannel membrane with the irradiation dose is determined first, and then based on the determined relation, quantitative regulation of the permeation rate uv of the target substance to be released or separated on the permeable tunable uv-responsive nanochannel membrane can be achieved by adjusting the uv irradiation dose.
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| CN202311637843.8A CN117643800A (en) | 2023-12-01 | 2023-12-01 | Ultraviolet light response type nano-channel membrane with adjustable permeability and preparation method and application thereof |
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