CN113398781B - Microporous filter membrane material and preparation method and application thereof - Google Patents

Microporous filter membrane material and preparation method and application thereof Download PDF

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CN113398781B
CN113398781B CN202110678200.2A CN202110678200A CN113398781B CN 113398781 B CN113398781 B CN 113398781B CN 202110678200 A CN202110678200 A CN 202110678200A CN 113398781 B CN113398781 B CN 113398781B
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filter membrane
solution
ethanol
microporous filter
polyamide
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CN113398781A (en
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王瑞国
王培龙
李桐
王紫豪
谭天骄
崔娜
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Zhikong Shanghai Biotechnology Co ltd
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Institute of Agricultural Quality Standards and Testing Technology for Agro Products of CAAS
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/56—Polyamides, e.g. polyester-amides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
    • B01D61/14—Ultrafiltration; Microfiltration
    • B01D61/147—Microfiltration
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
    • B01D61/14—Ultrafiltration; Microfiltration
    • B01D61/18—Apparatus therefor
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
    • B01D67/0002—Organic membrane manufacture
    • B01D67/0006—Organic membrane manufacture by chemical reactions
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    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N1/00—Sampling; Preparing specimens for investigation
    • G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
    • G01N1/34—Purifying; Cleaning

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Abstract

The invention discloses a microporous filter membrane material and a preparation method and application thereof, belonging to the technical field of microporous filter membrane materials. The microporous filter membrane material is prepared by carrying out amidation reaction on a hydrolyzed polyamide filter membrane obtained by hydrolyzing a polyamide filter membrane to form benzoyl. The method can effectively retain particulate impurities in a sample solution, and simultaneously avoids the adsorption of a traditional polyamide microporous filter membrane on a target compound containing carboxyl or hydroxyl in a water-methanol or water-acetonitrile solution system, thereby expanding the application range of the traditional polyamide microporous filter membrane. It can be used for preparing microporous filter membrane, especially syringe type microporous filter membrane. The microporous filter membrane material and the corresponding microporous filter membrane can be used for filtering sample solution, especially sample solution in food safety detection, and can improve the accuracy of detection results.

Description

Microporous filter membrane material and preparation method and application thereof
Technical Field
The invention relates to the technical field of microporous filter membrane materials, in particular to a microporous filter membrane material and a preparation method and application thereof.
Background
In the detection of food safety samples, food samples are generally subjected to pretreatment steps such as extraction, purification, concentration, redissolution, filtration and the like, and then sample solutions for measurement by an analytical instrument are obtained.
The extraction of the target to be detected in the food sample generally adopts acetonitrile, methanol and other organic solvents, the sample extract is purified, the organic solvent is further volatilized through the concentration process, and the solid residue is dissolved by a solution containing a certain proportion of water phase (such as water-acetonitrile, water-methanol and the like). However, the presence of an aqueous phase in the solution often results in incomplete dissolution of the sample residue, resulting in insoluble solid particles, which can render the reconstituted sample solution a cloudy suspension.
Therefore, filtration of the sample solution is a critical step. The purpose of filtration is to remove particle impurities in a sample solution through the screen mesh interception function, so that the damage of the particle impurities to an analytical instrument (such as pipeline blockage, chromatographic column blockage, sample injection needle blockage, sprayer pollution and the like) is avoided, and the interference of the impurities to a detection signal of a subsequent instrument is reduced.
At present, the sample solution is filtered mainly by adopting a microporous filter membrane, and the material of the filter membrane comprises polyamide, vinylidene fluoride, polytetrafluoroethylene and the like. Among them, the polyamide (commonly called "nylon") filter membrane is most widely used in practice because of its advantages such as simple synthesis process, low cost, high mechanical strength, and organic solvent resistance. However, the polyamide membrane may also adsorb the target compound containing a carboxyl group or a hydroxyl group to be measured in the solution while retaining solid particle impurities. Thus, the detection result of such compounds is unstable, and the recovery rate is reduced.
In view of the above, the present invention is particularly proposed.
Disclosure of Invention
One of the purposes of the invention is to provide a microfiltration membrane material which can effectively retain particulate impurities in a sample solution and simultaneously avoid the adsorption of a target compound containing carboxyl or hydroxyl in a water-methanol or water-acetonitrile solution system by a traditional polyamide microfiltration membrane.
The second objective of the present invention is to provide a method for preparing the microporous membrane material.
The invention also aims to provide application of the microporous filter membrane material, such as filtration of a sample solution.
The fourth object of the present invention is to provide a microporous filtration membrane comprising the above microporous filtration membrane material.
The fifth purpose of the present invention is to provide an application of the microporous filter membrane, such as filtration of a sample solution.
The invention can be realized as follows:
in a first aspect, the present invention provides a microporous filter membrane material, which is prepared by subjecting a hydrolyzed polyamide filter membrane obtained by hydrolyzing a polyamide filter membrane to amidation reaction to form benzoyl.
In an alternative embodiment, the polyamide filter in the microporous filter material has a pore size of 0.2 to 0.5. mu.m.
In a second aspect, the present invention provides a method for preparing a microporous filtration membrane material according to the foregoing embodiment, comprising the following steps: and carrying out amidation reaction on the hydrolyzed polyamide filter membrane obtained by hydrolyzing the polyamide filter membrane to form benzoyl.
In an alternative embodiment, the hydrolyzed polyamide filter membrane is mixed with benzoic acid so that the amino groups in the hydrolyzed polyamide filter membrane react with the benzoic acid to form benzoyl groups, thereby obtaining the benzoyl group surface modified microporous filter membrane material.
In an alternative embodiment, the hydrolysis comprises: and (3) hydrolyzing the polyamide filter membrane in an alkaline solution to form a hydrolyzed polyamide filter membrane.
In alternative embodiments, the solute in the alkaline solution comprises sodium hydroxide or potassium hydroxide, and the solvent in the alkaline solution comprises water, an ethanol-water solution, a methanol-water solution, or an acetonitrile-water solution.
In a preferred embodiment, the alkaline solution is obtained by dissolving sodium hydroxide in an ethanol-water solution.
In an alternative embodiment, the concentration of sodium hydroxide in the ethanol-water solution is 0.01 to 0.1mol/L, preferably 0.05 mol/L.
In an alternative embodiment, the concentration of ethanol in the ethanol-water solution is 80 to 95 vt%, preferably 95 vt%.
In an alternative embodiment, the hydrolysis temperature is 20-80 ℃, preferably 60 ℃.
In an alternative embodiment, the hydrolysis time is 10-30min, preferably 20 min.
In an alternative embodiment, the hydrolysis is carried out under shaking conditions.
In an alternative embodiment, the method of making further comprises: removing residual sodium hydroxide on the surface of the polyamide filter membrane by water depolymerization.
In alternative embodiments, removing the sodium hydroxide comprises: and (3) soaking the hydrolyzed polyamide filter membrane in a first washing solution, and performing ultrasonic treatment.
In an alternative embodiment, the first wash solution is water or an ethanol-water solution, preferably a 45-55 vt% ethanol-water solution, more preferably a 50 vt% ethanol-water solution.
In an alternative embodiment, the washing comprises: the hydrolyzed polyamide filter membrane is soaked in 50 vt% ethanol-water solution, and after ultrasonic treatment, the ethanol-water solution is removed.
In an alternative embodiment, the amidation reaction is to react the washed hydrolyzed polyamide filter membrane with a solution containing benzoic acid.
In alternative embodiments, the benzoic acid containing solution is a benzoic acid-ethanol solution or a benzoic acid-methanol solution.
In a preferred embodiment, the benzoic acid containing solution is a benzoic acid-ethanol solution.
In an alternative embodiment, the concentration of benzoic acid in the benzoic acid-ethanol solution is 1-5 vt%, preferably 5 vt%.
In an alternative embodiment, the amidation reaction temperature is 50-90 deg.C, preferably 80 deg.C.
In an alternative embodiment, the amidation reaction time is from 20 to 60min, preferably 40 min.
In an alternative embodiment, the method of preparation further comprises washing the benzoyl-surface modified microfiltration membrane material to neutrality.
In an alternative embodiment, the washing comprises: and soaking the microporous filter membrane material with the benzoyl surface modified in a second washing solution, and performing ultrasonic treatment.
In an alternative embodiment, the second wash liquor comprises water or an ethanol-water solution, preferably a 45-55 vt% ethanol-water solution, more preferably a 50 vt% ethanol-water solution.
In an alternative embodiment, the benzoyl surface modified microfiltration membrane material is soaked in 50 vt% ethanol-water solution, and after ultrasonic treatment, the ethanol-water solution is removed.
In an alternative embodiment, the method of making further comprises: and drying the microporous filter membrane material which is washed to be neutral and is modified by the benzoyl surface.
In an alternative embodiment, the drying is carried out at 45-55 deg.C for 50-70min, preferably at 50 deg.C for 60 min.
In a third aspect, the present invention provides the use of a microfiltration membrane material according to the preceding embodiment, for example for filtering a sample solution.
In an alternative embodiment, the sample solution is a sample solution for food safety testing.
In a fourth aspect, the present invention provides a microfiltration membrane comprising the microfiltration membrane material of the preceding embodiment.
In an alternative embodiment, the microfiltration membrane is a syringe-type microfiltration membrane.
In an optional embodiment, the syringe type microporous filter membrane comprises an upper shell and a lower shell which are mutually matched and buckled, and the microporous filter membrane material is clamped between the upper shell and the lower shell.
In an alternative embodiment, the syringe-style microfiltration membrane further comprises a syringe port connected to the upper housing, the syringe port being non-parallel and non-collinear with the microfiltration membrane material.
In an alternative embodiment, the syringe-type microporous filtration membrane further comprises a pintle interface connected to the lower housing, the pintle interface being non-parallel and non-collinear with the microporous filtration membrane material.
In a fifth aspect, the present invention provides the use of a microfiltration membrane according to the preceding embodiment, for example for filtering a sample solution.
In an alternative embodiment, the sample solution is a sample solution for food safety testing.
The beneficial effects of the invention include:
the hydrolytic polyamide filter membrane obtained by hydrolyzing the polyamide filter membrane is subjected to amidation reaction to form benzoyl, so that the benzoyl surface modified microporous filter membrane material is prepared, the residual amino on the surface of the membrane can be sealed, particulate impurities in a sample solution can be effectively intercepted, the adsorption of a traditional polyamide microporous filter membrane on a carboxyl or hydroxyl-containing target compound in a water-methanol or water-acetonitrile solution system is avoided, and the application range of the polyamide microporous filter membrane is expanded. It can be used for preparing microporous filter membrane, especially syringe type microporous filter membrane. The microporous filter membrane material and the corresponding microporous filter membrane can be used for filtering sample solution, especially sample solution in food safety detection, and can improve the accuracy of detection results.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the embodiments will be briefly described below, it should be understood that the following drawings only illustrate some embodiments of the present invention and therefore should not be considered as limiting the scope, and for those skilled in the art, other related drawings can be obtained according to the drawings without inventive efforts.
FIG. 1 is a schematic diagram of the structure of a syringe-type microporous filtration membrane provided in example 5 of the present application.
An icon: 1-an upper shell; 2-a lower shell; 3-microporous membrane material; 4-an injector interface; 5-pintle interface.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
The microporous filter membrane material provided by the present application, and the preparation method and application thereof are specifically described below.
The application provides a microporous filter membrane material which is prepared by carrying out amidation reaction on a hydrolyzed polyamide filter membrane obtained by hydrolyzing a polyamide filter membrane to form benzoyl.
It is worth emphasizing that a certain amount of amino groups exist on the surface of the untreated polyamide membrane, and can be combined and reacted with a compound containing carboxyl or hydroxyl in a solution system containing an aqueous phase, so that the compound can retain solid particle impurities and can adsorb a target compound containing carboxyl or hydroxyl to be detected in the solution, the detection result of the compound is unstable, and the recovery rate is reduced. According to the method, the polyamide microporous filter membrane is subjected to benzoyl modification, and residual amino on the surface of the membrane is sealed, so that the adsorption of the polyamide microporous filter membrane on target compounds containing carboxyl or hydroxyl in a water-methanol or water-acetonitrile solution system can be effectively reduced, the polyamide microporous filter membrane is used for filtering a sample solution in food safety detection, and the accuracy of the measurement result of the target compounds is improved.
In an alternative embodiment, the polyamide filter membrane of the microfiltration membrane material has a pore size of 0.2 to 0.5 μm.
The pore size of the microporous filter membrane has a great influence on the filtration of the sample solution: if the pore diameter of the microporous filter membrane is too large, the microporous filter membrane can not effectively intercept solid particle impurities, and the effective filtration effect can not be achieved; if the aperture of the microporous filter membrane is too small, solid particle impurities are easy to block the filter membrane, so that the filtrate cannot smoothly pass through the filter membrane. The polyamide filter membrane with the aperture of 0.2-0.5 mu m is adopted, so that particles in a sample solution can be effectively intercepted, and the sample solution can be ensured to smoothly pass through the filter membrane.
Correspondingly, the invention also provides a preparation method of the microporous filter membrane material, which comprises the following steps: and carrying out amidation reaction on the hydrolyzed polyamide filter membrane obtained by hydrolyzing the polyamide filter membrane to form benzoyl.
Specifically, the hydrolyzed polyamide filter membrane is mixed with benzoic acid so that amino in the hydrolyzed polyamide filter membrane reacts with the benzoic acid to form benzoyl, and the benzoyl surface modified microporous filter membrane material is obtained.
The polyamide filter membrane is hydrolyzed in an alkaline solution, so that amino groups on the surface of the membrane can be exposed and activated (namely, amide bonds on the surface of the polyamide filter membrane are converted into active amino groups), and the subsequent reaction with benzoic acid is facilitated. And then mixing the membrane with a benzoic acid solution to enable the activated amino on the surface of the membrane to react with benzoic acid to form benzoyl, and blocking the residual amino on the surface of the membrane.
In an alternative embodiment, the hydrolysis may be performed by subjecting the polyamide filter membrane to hydrolysis in an alkaline solution to form a hydrolyzed polyamide filter membrane.
The solute in the alkaline solution can comprise sodium hydroxide or potassium hydroxide, and the solvent in the alkaline solution can comprise water, ethanol-water solution, methanol-water solution or acetonitrile-water solution.
In some preferred embodiments, the alkaline solution is obtained by dissolving sodium hydroxide in an ethanol-water solution.
The concentration of sodium hydroxide in the ethanol-water solution may, by reference, be 0.01-0.1mol/L, such as 0.01mol/L, 0.05mol/L, 0.08mol/L or 0.1mol/L, etc., preferably 0.05 mol/L.
It is worth to mention that too low a concentration of the alkaline solution is detrimental to the hydrolysis reaction, and too high a concentration may cause excessive hydrolysis and damage the surface structure of the filter membrane. The concentration of sodium hydroxide in the ethanol-water solution is preferably controlled to be 0.05mol/L, so that residual amino on the surface of the polyamide filter membrane can be effectively activated, and excessive hydrolysis is not carried out to form more active amino.
The concentration of ethanol in the ethanol-water solution may, by reference, be 80-95 vt%, such as 80 vt%, 85 vt%, 90 vt% or 95 vt%, etc., preferably 95 vt%.
The ethanol-water solution with the concentration of 95vt percent can fully contain hydroxide ions and inorganic salt ions, has lower surface tension, can fully contact with the surface of the polyamide membrane, and is beneficial to the hydrolysis reaction.
The hydrolysis temperature may, for example, be 20-80 deg.C, such as 20 deg.C, 40 deg.C, 50 deg.C, 60 deg.C or 80 deg.C, preferably 60 deg.C.
The increase of the temperature is helpful for the hydrolysis reaction, and the optimal 60 ℃ can ensure the smooth operation of the hydrolysis reaction and is convenient for the safety protection of operators.
The hydrolysis time may be, for example, 10-30min, such as 10min, 15min, 20min, 25min or 30min, preferably 20 min.
Preferably, the hydrolysis is carried out under shaking conditions.
It is worth to be noted that residual hydroxyl on the surface of the polyamide filter membrane can be fully activated without excessive hydrolysis and damaging the original structure and properties of the filter membrane by oscillating and hydrolyzing the polyamide filter membrane in 95 vt% ethanol-water solution containing 0.05mol/L sodium hydroxide for 20min at the temperature of 60 ℃.
Further, the preparation method also comprises the following steps: removing residual sodium hydroxide on the surface of the polyamide filter membrane.
Referring to, removing sodium hydroxide may include: and (3) soaking the hydrolyzed polyamide filter membrane in a first washing solution, and performing ultrasonic treatment.
The first washing solution may be water or an ethanol-water solution, that is, pure water, or an ethanol-water solution containing ethanol at any concentration. In some preferred embodiments, the first wash solution is a 45-55 vt% ethanol-water solution, more preferably a 50 vt% ethanol-water solution.
In an alternative embodiment, the washing comprises: soaking the hydrolyzed polyamide filter membrane in 50 vt% ethanol-water solution, performing ultrasonic treatment (such as 5-15min), and removing ethanol-water solution. The aqueous solution may then be rinsed with purified water until the pH of the rinsed aqueous solution is 6.5-7.5.
In this application, the amidation reaction is carried out by reacting the washed hydrolyzed polyamide filter membrane with a solution containing benzoic acid.
The benzoic acid-containing solution may be a benzoic acid-ethanol solution or a benzoic acid-methanol solution, and may be a solution formed by combining benzoic acid with another solvent capable of dissolving benzoic acid. In a preferred embodiment, the benzoic acid containing solution is a benzoic acid-ethanol solution.
In alternative embodiments, the concentration of benzoic acid in the benzoic acid-ethanol solution may be 1-5 vt%, such as 1 vt%, 2 vt%, 3 vt%, 4 vt%, or 5 vt%, etc., preferably 5 vt%.
It is worth mentioning that increasing the concentration of benzoic acid helps to increase the speed of amidation reaction, but ethanol has limited solubility to benzoic acid, and adding excessive benzoic acid to ethanol would result in saturation of the solution and waste of reagents.
The amidation reaction temperature may be, for example, 50 to 90 ℃ such as 50 ℃, 60 ℃, 70 ℃, 80 ℃ or 90 ℃, preferably 80 ℃.
The temperature of 80 ℃ as the amidation reaction temperature is more favorable for the amidation reaction than other temperature conditions, and is favorable for volatilizing moisture generated by the amidation reaction as soon as possible.
The amidation reaction time may be, for example, 20 to 60min, such as 20min, 30min, 40min, 50min or 60min, etc., preferably 40 min.
By controlling the amidation reaction time within the above range, on the one hand, insufficient reaction due to too short reaction time can be avoided, and on the other hand, efficiency reduction due to too long reaction time can be avoided. 40min is taken as amidation reaction time to ensure that the surface active amino of the polyamide filter membrane is fully amidated to form the benzoyl modified polyamide filter membrane.
Further, the benzoyl surface modified microfiltration membrane material was washed to neutrality.
By reference, the washing of the benzoyl-based surface-modified microfiltration membrane material can be: and soaking the microporous filter membrane material with the benzoyl surface modified in a second washing solution, and performing ultrasonic treatment.
The second washing solution may also include water or an ethanol-water solution, specifically, pure water, or an ethanol-water solution containing ethanol at any concentration. In some preferred embodiments, the second wash solution is a 45-55 vt% ethanol-water solution, more preferably a 50 vt% ethanol-water solution.
In an alternative embodiment, the washing of the benzoyl surface modified microporous filter membrane material may be performed by soaking the benzoyl surface modified microporous filter membrane material in 50 vt% ethanol-water solution, and removing the ethanol-water solution after ultrasonic treatment (e.g., 5-15 min). The subsequent washing with 50 vt% ethanol-water solution was repeated once under the above conditions, and the washed solution was washed with pure water until the pH of the solution was 6.5 to 7.5, indicating that the residual free benzoic acid on the membrane surface was effectively removed.
Further, the benzoyl-based surface-modified microporous filter membrane material which is washed to be neutral is dried.
For reference, the drying may be performed at 45 to 55 ℃ for 50 to 70min, preferably at 50 ℃ for 60 min.
It is worth emphasizing that the degree of hydrolysis of activated surface amino groups by the polyamide filter membrane depends on the concentration of the alkaline solution, the hydrolysis conditions and the nature of the solvent, the degree of benzoyl modification depends on the concentration of the benzoic acid solution, the reaction temperature, the reaction time and the nature of the solvent, and the effect of different conditions is different. The inventor obtains the above preparation conditions of the application after long-term research and numerous tests and verifications, and under the cooperation of the above conditions, the prepared microporous filter membrane material can effectively retain particulate impurities in a sample solution, and simultaneously, the polyamide filter membrane is prevented from adsorbing target compounds containing carboxyl or hydroxyl in a water-methanol or water-acetonitrile solution system.
In addition, the application also provides the application of the microporous filter membrane material, such as can be used for filtering sample solution. The sample solution is preferably used for food safety detection, and the accuracy of the measured data of the target compound containing carboxyl or hydroxyl can be effectively improved.
In addition, the application also provides a microporous filter membrane, which comprises the microporous filter membrane material.
In some alternative embodiments, the microfiltration membrane is a syringe-type microfiltration membrane.
According to the syringe type microfiltration membrane, the needle cylinder type microfiltration membrane comprises an upper shell and a lower shell which are mutually matched and buckled, and the microfiltration membrane material is clamped between the upper shell and the lower shell. The size of the microporous filter membrane material is consistent with that of the contact surface of the upper shell and the lower shell. The periphery of the microporous filter membrane material is used for being abutted against the inner wall of the buckling part of the upper shell and the lower shell.
Further, the syringe type microporous filter membrane also comprises a syringe interface connected with the upper shell, and the syringe interface and the microporous filter membrane material are not parallel and collinear.
Specifically, the setting direction of the syringe interface and the microporous membrane material clamped between the upper shell and the lower shell form a certain included angle, preferably 90 degrees, so that the sample solution injected from the syringe interface can be sufficiently filtered through the microporous membrane material.
Furthermore, the syringe type microporous filter membrane also comprises a pintle interface connected with the lower shell, and the pintle interface and the microporous filter membrane material are not parallel and not collinear.
Specifically, the setting direction of the pintle interface and the microporous filter membrane material clamped between the upper shell and the lower shell form a certain included angle, preferably 90 degrees.
Correspondingly, the invention also provides application of the microporous filter membrane, the microporous filter membrane can also be used for filtering a sample solution, particulate impurities in the sample solution are trapped through physical action, and the filtrate can be used for subsequent instrument analysis. Similarly, the sample solution is preferably used for food safety detection, and can effectively improve the accuracy of the measured data of the target compound containing carboxyl or hydroxyl.
The features and properties of the present invention are described in further detail below with reference to examples.
Example 1
The embodiment provides a preparation method of a benzoyl surface modified polyamide microporous filter membrane material, which specifically comprises the following steps:
step (1): weighing 2.00g of sodium hydroxide, firstly dissolving the sodium hydroxide by using about 200mL of 95 vt% ethanol-water solution, standing until the sodium hydroxide solution is cooled to room temperature, transferring all the cooled sodium hydroxide solution into a 1000mL volumetric flask, washing the beaker by using 100mL of 95 vt% ethanol-water solution for 2 times, transferring the solution into the volumetric flask, and then fixing the volume of the solution to 1000mL by using the 95 vt% ethanol-water solution to obtain 0.05mol/L sodium hydroxide-95 vt% ethanol-water solution;
Step (2): taking 400mL of 0.1mol/L sodium hydroxide-95 vt% ethanol-water solution in a 500mL wide-mouth bottle, completely immersing a polyamide membrane with the aperture of 0.2-0.5 mu m in the solution, and placing the polyamide membrane in a constant temperature oscillator to hydrolyze for 20min at the temperature of 60 ℃ and under the condition of 200 r/min to obtain a hydrolyzed polyamide filter membrane;
and (3): after the hydrolysis is finished, taking out the hydrolyzed polyamide filter membrane, adding 400mL of 50% ethanol-water solution (first washing solution), performing ultrasonic treatment for 10min, discarding the solution, and washing the filter membrane by pure water until the pH value of the water solution is 7.0 +/-0.5;
and (4): weighing 50g of benzoic acid, placing the benzoic acid in a reagent bottle, adding 1000mL of absolute ethyl alcohol into the reagent bottle, and carrying out ultrasonic treatment for 30min to dissolve the benzoic acid so as to obtain a 5 vt% benzoic acid-ethyl alcohol solution;
and (5): putting 400mL of 5 vt% benzoic acid-ethanol solution into a 500mL wide-mouth bottle, completely immersing the hydrolyzed polyamide membrane washed in the step (4) into the benzoic acid-ethanol solution, and placing the hydrolyzed polyamide membrane into a constant-temperature oscillator to react for 40min under the conditions of 80 ℃ and 200 r/min to obtain a benzoyl surface modified microporous filter membrane material;
and (6): immersing the benzoyl surface modified microporous filter membrane material into 50 vt% ethanol-water solution (second washing solution), performing ultrasonic treatment for 10min, discarding the 50 vt% ethanol-water solution, and repeating the operation for 1 time; washing with pure water until the pH value of the water solution is 7.0 +/-0.5;
And (7): and (3) placing the cleaned microporous filter membrane material with the formyl surface modified in a blast air dryer, and drying for 1h at 50 ℃.
Wherein the specification of the used materials and reagents is as follows:
sodium hydroxide: CAS number 1310-73-2, analytically pure.
Benzoic acid: CAS number 65-85-0, analytically pure.
Formic acid: CAS number 64-18-6, chromatographically pure.
Ethanol: CAS number 64-17-5, chromatographically pure.
Acetonitrile: CAS number 75-05-8, chromatographically pure.
Methanol: CAS number 67-56-1, chromatographically pure.
Anhydrous ethanol: CAS number 64-17-5, analytically pure.
Polyamide microporous filter membrane: the aperture is 0.2-0.5 μm.
Fusaric acid: CAS number 303-47-9, purity more than or equal to 99%.
Fumonisins B1: CAS number 116355-83-0, purity is more than or equal to 99%.
Penicillic acid: CAS number 90-65-3, purity more than or equal to 99%.
Mycophenolic acid: CAS No. 24280-93-1, the purity is more than or equal to 99 percent.
The experimental water was Milli-Q ultrapure water.
Example 2
This example differs from example 1 in that (the remaining operating steps and conditions are the same):
the alkaline solution used for hydrolysis was 0.01mol/L sodium hydroxide-80 vt% ethanol aqueous solution.
The hydrolysis temperature is 20 deg.C, and the hydrolysis time is 30 min.
The first wash was a 45 vt% ethanol-water solution.
The benzoic acid containing solution was a 1 vt% benzoic acid-ethanol solution.
The temperature of the amidation reaction is 50 ℃, and the time of the amidation reaction is 60 min.
The second wash was a 45 vt% ethanol-water solution.
The drying is carried out at 45 ℃ for 70 min.
Example 3
This example differs from example 1 in that (the remaining operating steps and conditions are the same):
the alkaline solution used for hydrolysis was 0.1mol/L sodium hydroxide-90 vt% ethanol aqueous solution.
The hydrolysis temperature is 80 deg.C, and the hydrolysis time is 10 min.
The first wash was a 55 vt% ethanol-water solution.
The benzoic acid containing solution was a 3 vt% benzoic acid-ethanol solution.
The temperature of the amidation reaction is 90 ℃, and the time of the amidation reaction is 20 min.
The second wash was 55 vt% ethanol-water solution.
The drying is carried out at 55 deg.C for 50 min.
Example 4
This example differs from example 1 in that (the remaining operating steps and conditions are the same):
the alkaline solution used for the hydrolysis was 0.05mol/L potassium hydroxide-95 vt% aqueous methanol.
The first washing liquid is pure water.
The benzoic acid containing solution was a 5 vt% benzoic acid-methanol solution.
The second washing solution is pure water.
Example 5
Referring to fig. 1, the syringe type microporous filter membrane includes an upper housing 1, a lower housing 2, a microporous filter membrane material 3, a syringe port 4, and a pintle port 5.
Wherein, the upper shell 1 and the lower shell 2 are mutually matched and buckled, and the microporous filter membrane material 3 is clamped between the upper shell 1 and the lower shell 2. The size of the microporous filter membrane material 3 is consistent with the size of the contact surface of the upper shell 1 and the lower shell 2. The periphery of the microporous filter membrane material 3 is used for abutting against the inner wall of the buckling part of the upper shell 1 and the lower shell 2.
The injector interface 4 is connected with the upper shell 1 and forms 90 degrees with the microporous filter membrane material 3 clamped between the upper shell and the lower shell, and the pintle interface 5 is connected with the lower shell 2 and forms 90 degrees with the microporous filter membrane material 3 clamped between the upper shell and the lower shell.
It can be prepared by the following steps: taking an empty syringe type microporous filter membrane shell (the structure of which comprises the upper shell 1, the lower shell 2, the syringe interface 4 and the pintle interface 5), cutting the benzoyl surface modified polyamide microporous filter membrane material prepared in the embodiment 1 into a circle with the same inner diameter as the empty syringe type microporous filter membrane shell, and placing the round hollow syringe type microporous filter membrane shell into the empty syringe type microporous filter membrane shell.
Test example 1
The adsorption performance was examined by taking the benzoyl group surface-modified polyamide microporous filter membrane material prepared in example 1 as an example.
The benzoyl-surface modified polyamide microfiltration membrane material prepared in example 1 was used for filtering 3 carboxyl-containing compounds in a 20 vt% acetonitrile-water solution, and compared with a conventional polyamide microfiltration membrane (i.e., the original polyamide microfiltration membrane in example 1, which had not undergone hydrolysis and amidation reactions).
The specific treatment process is as follows:
(1) preparation of mycotoxin solution
Taking 0.1mL of each of fusaric acid, fumonisin B1 and mycophenolic acid standard solution (the solvent is acetonitrile) with the concentration of 100 mu g/mL into a 50mL volumetric flask, and using 5 vt% acetonitrile-water solution to perform constant volume to 50mL to obtain 3 mycotoxin mixed standard working solutions with the concentrations of 0.2 mu g/mL, such as fusaric acid, fumonisin B1, mycophenolic acid and the like.
(2) Filtering with microporous filter membrane
Taking a syringe type microporous filter membrane provided in the embodiment 5, connecting a 2mL plastic syringe at an upper end syringe interface, and receiving filtrate by using a glass sample injection vial at a lower end pintle interface; sucking 1mL of 3 mycotoxin mixed standard working solutions into a syringe, applying pressure by using a syringe piston, and enabling the solutions to flow into a glass sample injection vial through a filter membrane; a total of 5 were parallel.
A common syringe type polyamide microporous filter membrane (namely, the polyamide microporous filter membrane material in the example 5 is replaced by the original polyamide filter membrane which is not subjected to hydrolysis and amidation reaction) is taken, and 3 mycotoxin mixed standard working solutions are filtered in 5 parallel according to the above operation steps.
(3) UPLC-MS/MS assay
A. Chromatographic conditions
An Acquity UPLC BEH RP18 chromatography column (100mm × 2.1mm, 1.7 μm, Waters corporation, usa); mobile phase A: 0.1mM ammonium acetate solution (containing 0.1 vt% formic acid); mobile phase B: methanol solution (containing 0.1 vt% formic acid); the column temperature is 40 ℃; the flow rate is 0.3 mL/min; the injection volume was 0.5. mu.L. Gradient elution procedure: 0-2 min, 95% A; 2-4 min, 95% -80% A; 4-12 min, 80-5% A; 12-12.1 min, 5% -1% A; 12.1-13 min, 1% A; 13-13.5 min, 1% -95% A; 13.5-15 min, 95% A.
B. Conditions of Mass Spectrometry
Electrospray ion source positive ion scanning (ESI +), multiple reaction monitoring mode (MRM), capillary voltage 0.6kV, ion source temperature 150 deg.C, desolvation temperature 450 deg.C, desolvation gas and cone gas are both N2The desolventizing air flow rate is 800L/h, and the taper hole air flow rate is 150L/h. The parameters of parent ion, daughter ion, collision energy, and cone voltage of the target compound are shown in Table 1.
TABLE 1 Retention time, parent ion, daughter ion, Cone hole Voltage and Collision energy of the target Compound
Figure BDA0003121686670000151
aTo quantify the ions.
(4) Analysis of results
Respectively measuring the chromatographic peak areas of 3 mycotoxins such as fusaric acid, fumonisin B1, mycophenolic acid and the like by using LC-MS/MS on 3 mycotoxin mixed standard working solutions (A) which are not filtered by the filter membrane, 3 mycotoxin mixed standard working solutions (B) which are filtered by the benzoyl surface modified polyamide microporous filter membrane and 3 mycotoxin mixed standard working solutions (C) which are filtered by the common polyamide microporous filter membrane.
And respectively dividing the peak areas of the 3 mycotoxins in the solution after the filtration by the peak areas of the 3 mycotoxins which are not filtered by the filtration membrane, and multiplying by 100 percent to obtain the recovery rate of the mycotoxin filtration by the filtration membrane. The higher the recovery rate is, the weaker the adsorption of the filter membrane on the mycotoxin target is; conversely, lower recovery yields indicate greater adsorption of mycotoxin target by the filter, and the results are shown in Table 2.
TABLE 25 vt% acetonitrile-water solution 3 mycotoxin targets filtered through different microporous filter membranes
Target object Benzoyl surface modified polyamide microporous filter membrane Ordinary polyamide microporous filter membrane
Fusarium acid 92.3±2.1％ 63.4±12.3％
Fumonisins B1 91.4±3.3％ 51.5±7.1％
Mycophenolic acid 100.3±2.8％ 64.6±4.3％
Note: recovery is expressed as mean ± standard deviation.
As shown in table 2, the average recovery rate of 3 mycotoxins, such as fusaric acid, fumonisin B1 and mycophenolic acid, in a 5 vt% acetonitrile-water solution filtered by the benzoyl-based surface-modified polyamide microporous filter membrane material prepared in example 1 of the present application is 94.7%, which indicates that the average 94.7% of the 3 carboxyl-containing acidic mycotoxins in the solution pass through the filter membrane, and only the average 5.3% of the acidic mycotoxins are adsorbed on the filter membrane.
Correspondingly, the average recovery rate of 3 mycotoxins such as fusaric acid, fumonisin B1 and mycophenolic acid in 5 vt% acetonitrile-water solution is 59.8% by adopting a common polyamide microporous filter membrane for filtration, which shows that only the average 59.8% of the 3 carboxyl-containing acidic mycotoxins in the solution pass through the filter membrane, and about 40.2% of the acidic mycotoxins are adsorbed on the filter membrane.
In comparison, the adsorption rate of the benzoyl-based surface-modified polyamide microporous filter membrane material provided in example 1 of the present application to acidic compounds containing carboxyl groups in a solution is less than 10%, while the adsorption rate of a common polyamide microporous filter membrane is about 40%, and the adsorption rate of the benzoyl-based surface-modified polyamide microporous filter membrane provided in the present application to acidic compounds containing carboxyl groups in a 5 vt% acetonitrile-water solution is much lower than that of a common polyamide microporous filter membrane.
Therefore, the benzoyl surface modified polyamide microporous filter membrane prepared by the method can overcome the strong adsorption property of the common polyamide microporous filter membrane to the acidic compound in the solution, so that the recovery rate of filtering the acidic compound is improved, and the application range of the common polyamide microporous filter membrane is expanded.
Test example 2
The test example provides an application of a syringe type benzoyl surface modified polyamide microporous filter membrane.
Using the syringe-type benzoyl surface-modified polyamide microporous membrane provided in the present application (the structure is the same as example 5, and the membrane material is the benzoyl surface-modified polyamide microporous membrane material prepared in example 1), the sample solution obtained when 3 mycotoxins in a corn sample were measured simultaneously was filtered, and the filtering effect was compared with that of an ordinary polyamide microporous membrane (i.e., the original polyamide microporous membrane in example 1, which had not undergone hydrolysis and amidation reactions).
The specific treatment process is as follows:
1. pretreatment of corn samples
(1) Sample preparation: putting 5g of a blank corn sample without mycotoxin into a 50mL plastic centrifuge tube, adding 0.01mL each of 100 mu g/mL fusaric acid, fumonisin B1 and a mycophenolic acid standard solution (the solvent is acetonitrile), and uniformly mixing in a vortex manner to prepare a labeled sample with fusaric acid, fumonisin B1 and mycophenolic acid concentrations of 0.2 mu g/g respectively;
(2) Extraction: adding 10mL of pure water and 20mL of acetonitrile into the standard adding sample, performing vortex extraction for 1min, adding 3g of sodium chloride, performing vortex extraction for 1min, performing centrifugation for 5min at speed of 5000 r/min, and taking out an upper acetonitrile solution for later use (at the moment, extracting mycotoxin in the sample into the acetonitrile solution);
(3) purification: taking 5mL of the upper acetonitrile solution, adding 500mg of anhydrous magnesium sulfate and 500mg of C18 purification material into a 10mL plastic centrifuge tube, swirling for 1min, centrifuging for 5min in a centrifuge at 5000rpm, and taking out 2mL of supernatant to another 10mL plastic centrifuge tube; drying with nitrogen at 60 ℃;
(4) and (3) concentrating: placing the plastic centrifuge tube containing the 2mL of supernatant on a nitrogen blowing instrument, drying the centrifuge tube at 60 ℃ by using nitrogen, then adding 1mL of 5 vt% acetonitrile-water solution into the centrifuge tube, and vortexing for 1min to fully dissolve residues in the solution;
(5) and (3) filtering: the concentrated solution of the sample is filtered by the benzoyl surface modified polyamide microporous filter membrane and the common polyamide microporous filter membrane respectively, and the filtrate is placed in a sample injection vial for UPLC-MS/M determination.
UPLC-MS/MS assay
(1) Chromatographic conditions
An Acquity UPLC BEH RP18 chromatography column (100mm × 2.1mm, 1.7 μm, Waters corporation, usa); mobile phase A: 0.1mM ammonium acetate solution (containing 0.1 vt% formic acid); mobile phase B: methanol solution (containing 0.1 vt% formic acid); the column temperature is 40 ℃; the flow rate is 0.3 mL/min; the injection volume was 0.5. mu.L. Gradient elution procedure: 0-2 min, 95% A; 2-4 min, 95% -80% A; 4 min-12 min, 80% -5% A; 12-12.1 min, 5% -1% of A; 12.1-13 min, 1% of A; 13-13.5 min, 1% -95% A; 13.5-15 min, 95% A.
(2) Conditions of Mass Spectrometry
Electrospray ion source positive ion scanning (ESI +), multiple reaction monitoring mode (MRM), capillary voltage 0.6kV, ion source temperature 150 deg.C, desolvation temperature 450 deg.C, desolvation gas and cone hole gas are both N2The flow rate of the desolventizing agent is 800L/h, and the flow rate of the taper hole is 150L/h. The parameters of the target compound, such as parent ion, daughter ion, collision energy, cone hole voltage, etc., are as shown in Table 1.
3. Analysis of results
The measured values of the concentrations of the 3 mycotoxins in the spiked samples were calculated from the areas of the chromatographic peaks of the 3 mycotoxin target substances, and the measured values of the concentrations were divided by the theoretical value of the spiked concentration of the sample (0.2 μ g/g) to determine the recovery rates of the mycotoxin target substances, and the results are shown in table 3.
TABLE 3 recovery rate of 3 mycotoxin targets in corn sample concentrate by filtration through different microporous filter membranes
Object of interest Benzoyl surface modified polyamide microporous filter membrane Ordinary polyamide microporous filter membrane
Fusarium acid 90.6±4.7％ 57.1±9.4％
Fumonisins B1 94.7±3.1％ 44.7±6.2％
Mycophenolic acid 92.1±3.4％ 60.1±3.5％
Note: recovery is expressed as mean ± standard deviation.
As shown in table 3, the average recovery rate of 3 mycotoxins, such as fusaric acid, fumonisin B1, mycophenolic acid, etc., in the corn sample concentrated solution filtered by using the syringe type benzoyl-based surface modified polyamide microporous filter membrane provided by the present application is 92.5%, which indicates that the average 92.5% of the 3 carboxyl-containing acidic mycotoxins in the solution pass through the filter membrane, and only the average 7.5% is adsorbed on the filter membrane.
Correspondingly, the average recovery rate of the 3 mycotoxins such as fusaric acid, fumonisin B1 and mycophenolic acid in the corn sample concentrated solution is 54.0% by adopting a common polyamide microporous filter membrane, which shows that only 54.0% of the 3 acidic mycotoxins containing carboxyl in the solution passes through the filter membrane on average, and about 46.0% of the acidic mycotoxins are adsorbed on the filter membrane.
The comparison of the two shows that the adsorption rate of the needle cylinder type benzoyl surface modified polyamide microporous filter membrane provided by the application to the acidic compounds containing carboxyl in the corn sample concentrated solution is less than 10%, while the adsorption rate of the common polyamide microporous filter membrane reaches about 46%, and the adsorption rate of the needle cylinder type benzoyl surface modified polyamide microporous filter membrane provided by the application to the acidic compounds containing carboxyl in the corn sample concentrated solution is far lower than that of the common polyamide microporous filter membrane.
Comparative example
In summary, the hydrolyzed polyamide filter membrane obtained by hydrolyzing the polyamide filter membrane is subjected to amidation reaction to form benzoyl, so that the benzoyl-based surface-modified microporous filter membrane material is prepared, the residual amino on the surface of the membrane can be sealed, the adsorption of the traditional polyamide microporous filter membrane on target compounds containing carboxyl or hydroxyl in a water-methanol or water-acetonitrile solution system can be avoided while the particulate impurities in the sample solution can be effectively intercepted, and the application range of the polyamide microporous filter membrane is expanded. It can be used for preparing microporous filter membrane, especially syringe type microporous filter membrane. The microporous filter membrane material and the corresponding microporous filter membrane can be used for filtering sample solution, especially sample solution in food safety detection, and can improve the accuracy of detection results.
The present invention has been described in terms of the preferred embodiment, and it is not intended to be limited to the embodiment. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (36)

1. A microporous filter membrane material is characterized in that the microporous filter membrane material is prepared by carrying out amidation reaction on a hydrolyzed polyamide filter membrane obtained by hydrolyzing a polyamide filter membrane to form benzoyl;
the hydrolysis comprises the following steps: hydrolyzing the polyamide filter membrane in an alkaline solution to form a hydrolyzed polyamide filter membrane; the solute in the alkaline solution is sodium hydroxide, and the solvent in the alkaline solution is ethanol-water solution; the concentration of the sodium hydroxide in the ethanol-water solution is 0.01-0.1mol/L, and the concentration of the ethanol in the ethanol-water solution is 80-95 vt%; the hydrolysis temperature is 20-80 ℃; the hydrolysis time is 10-30 min;
the amidation reaction is to react the hydrolyzed polyamide filter membrane with a solution containing benzoic acid; the solution containing the benzoic acid is a benzoic acid-ethanol solution; the concentration of benzoic acid in the benzoic acid-ethanol solution is 1-5 vt%; the temperature of amidation reaction is 50-90 ℃; the amidation reaction time is 20-60 min;
The aperture of the polyamide filter membrane in the microporous filter membrane material is 0.2-0.5 μm.
2. The method for preparing a microfiltration membrane material according to claim 1 comprising the steps of: and carrying out amidation reaction on the hydrolyzed polyamide filter membrane obtained by hydrolyzing the polyamide filter membrane to form benzoyl.
3. The method for preparing a microporous filter membrane according to claim 2, wherein the hydrolyzed polyamide filter membrane is mixed with benzoic acid to react the amino groups in the hydrolyzed polyamide filter membrane with benzoic acid to form benzoyl groups, thereby obtaining a benzoyl group surface-modified microporous filter membrane material.
4. The method according to claim 3, wherein the concentration of the sodium hydroxide in the ethanol-water solution is 0.05 mol/L.
5. The method according to claim 3, wherein the concentration of ethanol in the ethanol-water solution is 95 vt%.
6. The method of claim 3, wherein the hydrolysis temperature is 60 ℃.
7. The method of claim 3, wherein the hydrolysis time is 20 min.
8. The method of claim 3, wherein the hydrolysis is performed under shaking conditions.
9. The method of manufacturing according to claim 3, further comprising: and removing residual sodium hydroxide on the surface of the hydrolyzed polyamide filter membrane.
10. The method of claim 9, wherein removing the sodium hydroxide comprises: and soaking the hydrolyzed polyamide filter membrane in a first washing solution, and performing ultrasonic treatment.
11. The method according to claim 10, wherein the first washing solution is water or an ethanol-water solution.
12. The method of claim 11, wherein the first washing solution is a 45-55 vt% ethanol-water solution.
13. The method according to claim 12, wherein the first washing solution is a 50 vt% ethanol-water solution.
14. The method of claim 13, wherein the first wash solution washing comprises: soaking the hydrolyzed polyamide filter membrane in 50 vt% ethanol-water solution, and removing the ethanol-water solution after ultrasonic treatment.
15. The method according to claim 9, wherein the amidation reaction is carried out by reacting the washed hydrolyzed polyamide filter membrane with a solution containing benzoic acid.
16. The production method according to claim 15, wherein the concentration of benzoic acid in the benzoic acid-ethanol solution is 5 vt%.
17. The process according to claim 9, wherein the amidation reaction temperature is 80 ℃.
18. The process according to claim 9, wherein the amidation reaction time is 40 min.
19. The method of claim 15, further comprising washing the benzoyl-surface modified microfiltration membrane material to neutrality.
20. The method of claim 19, wherein washing comprises: and (3) soaking the benzoyl surface modified microporous filter membrane material in a second washing solution, and performing ultrasonic treatment.
21. The method of claim 20, wherein the second washing solution comprises water or an ethanol-water solution.
22. A method of preparation according to claim 21 wherein the second wash solution is a 45-55 vt% ethanol-water solution.
23. The method according to claim 22, wherein the second washing solution is a 50 vt% ethanol-water solution.
24. The method according to claim 23, wherein the benzoyl-based surface-modified microfiltration membrane material is immersed in a 50 vt% ethanol-water solution, and the ethanol-water solution is removed after the ultrasonic treatment.
25. The method of manufacturing of claim 20, further comprising: and drying the benzoyl surface modified microporous filter membrane material which is washed to be neutral.
26. The method of claim 25, wherein the drying is performed at 45-55 ℃ for 50-70 min.
27. The method of claim 26, wherein the drying is performed at 50 ℃ for 60 min.
28. Use of a microfiltration membrane material according to claim 1 for filtering a sample solution.
29. The use according to claim 28, wherein the sample solution is a sample solution for food safety testing.
30. A microfiltration membrane comprising the microfiltration membrane material of claim 1.
31. The microfiltration membrane according to claim 30 wherein the microfiltration membrane is a syringe type microfiltration membrane.
32. The microfiltration membrane according to claim 31 wherein the syringe type microfiltration membrane comprises an upper casing and a lower casing which are fitted and fastened with each other, and the microfiltration membrane material is sandwiched between the upper casing and the lower casing.
33. The microfiltration membrane of claim 32 wherein the syringe-style microfiltration membrane further comprises a syringe port connected to the upper housing, the syringe port being non-parallel and non-collinear with the microfiltration membrane material.
34. The microporous filtration membrane of claim 33, wherein the syringe-style microporous filtration membrane further comprises a pintle interface connected to the lower housing, the pintle interface being non-parallel and non-collinear with the microporous filtration membrane material.
35. Use of a microfiltration membrane according to any one of claims 30-34 for filtering a sample solution.
36. The use according to claim 35, wherein the sample solution is a sample solution for food safety testing.
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