CN114019054A - Method for calculating concentration of traditional Chinese medicine components in interface layer of nanofiltration membrane - Google Patents

Method for calculating concentration of traditional Chinese medicine components in interface layer of nanofiltration membrane Download PDF

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CN114019054A
CN114019054A CN202111316854.7A CN202111316854A CN114019054A CN 114019054 A CN114019054 A CN 114019054A CN 202111316854 A CN202111316854 A CN 202111316854A CN 114019054 A CN114019054 A CN 114019054A
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李存玉
支兴蕾
彭国平
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    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
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    • G01N30/02Column chromatography
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    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
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    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02Column chromatography
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Abstract

The invention relates to a method for calculating the concentration of traditional Chinese medicine components in an interface layer of a nanofiltration membrane, which establishes a calculation method based on the interface mass transfer basic theory of nanofiltration separation aiming at the technical bottleneck that a liquid-solid interface layer cannot be directly obtained and solute component concentration analysis is difficult to carry out. The invention innovatively provides a technical means for clarifying the solute distribution behavior of the liquid-solid two-phase interface layer, and visually analyzes the affinity of the components and the membrane material and the root cause of the pollution generated by the membrane according to the concentration distribution condition of the components of the interface layer; is helpful for researching and developing new membrane material, adjusting the concentration difference of different traditional Chinese medicine components distributed on the interface layer, amplifying the separation difference and carrying out targeted separation.

Description

Method for calculating concentration of traditional Chinese medicine components in interface layer of nanofiltration membrane
Technical Field
The invention relates to a method for calculating the concentration of a traditional Chinese medicine component in a nanofiltration membrane interface layer, in particular to a method for calculating the concentration of the component in the nanofiltration membrane interface layer based on a mode of realizing separation of the traditional Chinese medicine component by interface mass transfer, and belongs to the field of medicines.
Background
The existence of the interface is the root of all interface phenomena, so that the discussion of the equilibrium condition of the interface layer to the heterogeneous phase substances is carried out from Gibbs in the 19 th century, and the extensive attention of an analysis method and a theoretical model of a two-phase interface and the interface layer (interface region) is also attracted. At present, in the field of interface chemistry, three main recognitions are mainly provided for component concentration distribution of a two-phase interface layer, namely a Gibbs divided surface type interface layer model: it is believed that the energy, entropy, density, concentration, etc. of the two intersecting phases are uniform within each phase up to the physical interface when the two phases are brought into contact. Guggenheim transition layer type interface layer model: an interfacial layer is considered to be a thermodynamic entity having a certain volume and a certain content. And the distribution of material in the interfacial layer is not uniform. Double interface layer model: the two intersecting phases each have their own interface layer and the respective thermodynamic parameters are different, the concentration of the component in phase 1 changes as it transitions from the interior of phase 2 to the interface layer, but the concentration levels off as it approaches phase 2.
When different phases are contacted, a molecular heterogeneous distribution layer which is formed by two-phase molecular interpenetration exists at the contact position, wherein the evaluation of the physical and chemical properties of two-phase interface layers represented by alloys is relatively easy because the interface layers of the alloys are relatively fixed. The interface layer generated by the liquid-solid two phases is a thin layer of fluid formed around or on the solid relative to the flowing fluid, is a transition layer generated after the solution contacts with the solid, has physical and chemical properties different from those of the solution and the solid, has a thickness of between a few nanometers and a few micrometers, and cannot realize quantitative analysis of the component composition of the interface layer because the fluid of the interface layer is difficult to obtain directly.
In the nanofiltration separation process of traditional Chinese medicine components, the pore diameter of the nanofiltration membrane is distributed within the range of 100-1000 Da, the diameter is within the nanometer range, and the thickness of an interface layer generated after the nanofiltration membrane is contacted with the two phases is close to that of the interface layer, so that enough transmembrane pressure difference needs to be provided during nanofiltration separation to push the interface layer to enter the pore diameter of the membrane so as to realize separation. Therefore, the nanofiltration separation is a separation process realized on the basis of interface mass transfer, and theoretical support is provided for the calculation of the solute concentration of the liquid-solid two-phase interface layer on the basis of the separation process.
Based on the background, the invention provides a method for calculating the concentration of the traditional Chinese medicine components in the interface layer of the nanofiltration membrane, innovatively provides a technical means for clarifying the solute distribution behavior of the liquid-solid two-phase interface layer, and is beneficial to analyzing the tropism of the solute distribution after the two phases are contacted, so that the pollution mechanism of the nanofiltration membrane is clarified. The method is also helpful to the oriented separation of components in a complex solution environment by means of the distribution trend and the development of novel membrane materials.
Disclosure of Invention
The purpose of the invention is as follows: the invention aims to provide a method for calculating the concentration of traditional Chinese medicine components in an interface layer of a nanofiltration membrane, which can be used for analyzing the solute distribution characteristics of a liquid-solid two-phase interface layer.
The invention also aims to provide the application of the method for calculating the concentration of the traditional Chinese medicine components in the interface layer of the nanofiltration membrane in the aspects of analyzing the membrane pollution mechanism and the affinity of the components and the membrane material.
The technical scheme is as follows: a method for calculating the concentration of traditional Chinese medicine components in an interface layer of a nanofiltration membrane comprises the following steps: a. placing the nanofiltration membrane and Chinese medicinal components to be evaluated in a separation system, and detecting the concentration C of the Chinese medicinal components to be analyzed in the solution0(ii) a b. B, performing membrane separation on the traditional Chinese medicine solution in the step a, adjusting transmembrane pressure difference to be within the range of 0.05-2.0 MPa, and respectively collecting membrane flux (J) and component retention rate (R) data under corresponding transmembrane pressure difference; c. calculating the membrane separation coefficient k according to formula (1) from J and R under the series of transmembrane pressure differences in step b by pairing ln [ (1-R). J/R]And J linear regression, wherein
Figure BSA0000257095960000021
Is the intercept of a linear equation with a slope of 1/k
Figure BSA0000257095960000022
d. According to the separation coefficient k obtained by calculation in the step C, the concentration C of the traditional Chinese medicine component to be analyzed of the membrane interface layer is calculated according to the formula (2)m
Figure BSA0000257095960000023
The trans-membrane pressure difference in the step b needs to be selected from more than 3 trans-membrane pressure difference values.
And (c) calculating the component rejection rate (R) in the step (b) by using the method of R ═ trapped liquid solute concentration/raw liquid solute concentration.
And c, the regression coefficient of the linear equation in the step c is more than or equal to 0.99.
A method for calculating concentration of Chinese medicinal components in interface layer of nanofiltration membrane can be used for analyzing membrane pollution characteristics of Chinese medicinal components and affinity of Chinese medicinal components and membrane material.
A method for calculating concentration of Chinese medicinal components in interface layer of nanofiltration membrane is suitable for aqueous solution and organic solution.
Has the advantages that: (1) the technical bottleneck that the solute component concentration analysis is difficult to carry out due to the fact that the liquid-solid two-phase interface layer cannot be directly obtained is solved. (2) According to the concentration distribution of the interface layer components, the affinity of the components and the membrane material is visually analyzed, and the root cause of the pollution of the membrane is analyzed. (3) Is helpful for researching and developing new membrane material, adjusting the concentration difference of different traditional Chinese medicine components distributed on the interface layer, amplifying the separation difference and carrying out targeted separation.
Detailed Description
The foregoing aspects of the present invention are described in further detail below by way of examples, but it should not be construed that the scope of the above-described subject matter of the present invention is limited to the following examples, and that all the technologies implemented based on the above-described aspects of the present invention are within the scope of the present invention.
Example 1 concentration of chlorogenic acid in aqueous extract of honeysuckle in interfacial layer of composite polyamide nanofiltration membrane
Weighing the honeysuckle water extract, and detecting by adopting a high performance liquid chromatography, wherein the chromatographic conditions are as follows: waters e2695 HPLC, full-wavelength UV detector, Welch ultmate C18The method comprises the steps of carrying out chromatographic column chromatography, using acetonitrile-0.5% phosphoric acid (v/v 30: 70), carrying out volume flow rate of 1.0mL/min, carrying out column temperature of 30 ℃, carrying out detection wavelength of 340m, calculating the concentration of chlorogenic acid in a honeysuckle medicinal material water extract to be 112.02 mu g/mL by adopting an external standard point method, placing a 300Da composite polyamide nanofiltration membrane and the honeysuckle water extract in a separation system, adjusting transmembrane pressure differences to be 0.2, 0.5, 0.8, 1.0, 1.5 and 2.0MPa, and respectively collecting membrane flux (J) and component retention rate (R) data under the corresponding transmembrane pressure differences.
The membrane separation coefficient k was calculated according to equation (1) from J and R at a series of transmembrane pressure differences.
Figure BSA0000257095960000031
By the pair ln [ (1-R). J/R]And J linear regression, wherein
Figure BSA0000257095960000032
The slope is 1/k, the intercept of the linear equation. Fitting ln [ (1-R). J/R]And the linear equation for J is:
Figure BSA0000257095960000033
the regression coefficient was 0.9920.
Calculating the concentration C of chlorogenic acid in the film interface layer according to the formula (2) based on the calculated separation coefficient km
Figure BSA0000257095960000034
CmAnd 115.02 mu g/mL indicates that the concentration of the chlorogenic acid in the interface layer is higher than the bulk concentration of the solution, and the chlorogenic acid is easy to approach the composite polyamide nanofiltration membrane.
Example 2 concentration of chlorogenic acid monomer compound in interfacial layer of composite polyamide nanofiltration membrane
Chlorogenic acid aqueous solution with the concentration of 112.0 mug/mL is prepared and is separated by a composite polyamide nanofiltration membrane of 300Da, transmembrane pressure differences are adjusted to be 0.2, 0.5, 0.8, 1.0, 1.5 and 2.0MPa, membrane fluxes (J) under the corresponding transmembrane pressure differences are respectively collected, and component rejection rate (R) data are measured and calculated by the liquid phase detection method in the embodiment 1.
The membrane separation coefficient k was calculated according to equation (1) from J and R at a series of transmembrane pressure differences.
Figure BSA0000257095960000035
By the pair ln [ (1-R). J/R]And J linear regression, wherein
Figure BSA0000257095960000036
The slope is 1/k, the intercept of the linear equation. Fitting ln [ (1-R). J/R]And the linear equation for J is:
Figure BSA0000257095960000037
the regression coefficient was 0.9908.
Calculating the concentration C of chlorogenic acid in the film interface layer according to the formula (2) based on the calculated separation coefficient km
Figure BSA0000257095960000038
CmWhen the concentration of chlorogenic acid in the interface layer is higher than the bulk concentration of the solution in 143.02 μ g/mL, it can be seen that the concentration of chlorogenic acid of a single compound in the interface layer is higher than that of the honeysuckle extract in comparative example 1, which indicates that the other components in the honeysuckle extract are lower than that of chlorogenic acid and enter the interface layer to have a competitive effect.
Example 3 matrine and oxymatrine concentration in Sophora flavescens in nanofiltration Membrane interface layer
Weighing 1.0kg of radix Sophorae Flavescentis, extracting with 10 times of water for 2 times, each for 1 hr, mixing extractive solutions, filtering with microporous membrane to obtain radix Sophorae Flavescentis extractive solution, detecting by high performance liquid chromatography with the following chromatographic conditions: waters e2695 HPLC, full-wavelength UV detector, Agilent NH2Chromatographic column, acetonitrile-absolute ethyl alcohol-3% phosphoric acid (v/v/v 80: 10), volume flow rate of 1.0mL/min, column temperature of 25 deg.C, detection wavelength of 220nm, and external standard one-point method to calculate matrine concentration of 0.46 μ g/mL and oxymatrine concentration of 0.53 μ g/mL in water extract of radix Sophorae Flavescentis.
Separating with 500Da polyacrylonitrile nanofiltration membrane, adjusting transmembrane pressure difference to 0.2, 0.5, 0.8, 1.0, 1.5, and 2.0MPa, respectively collecting membrane flux (J) under corresponding transmembrane pressure difference, and calculating retention rate (R) data of matrine and oxymatrine.
The membrane separation coefficient k was calculated according to equation (1) from J and R at a series of transmembrane pressure differences.
Figure BSA0000257095960000041
By the pair ln [ (1-R). J/R]And J linear regression, wherein
Figure BSA0000257095960000042
The slope is 1/k, the intercept of the linear equation. Fitting ln [ (1-R). J/R]And the linear equation for J is:
matrine:
Figure BSA0000257095960000043
the regression coefficient was 0.9910.
Oxymatrine:
Figure BSA0000257095960000044
the regression coefficient was 0.9906.
Calculating the concentration C of matrine and oxymatrine at the membrane interface layer according to formula (2) based on the calculated separation coefficient km
Figure BSA0000257095960000045
Matrine Cm0.41 mug/mL oxymatrine CmAnd in the aqueous extract of the radix sophorae flavescentis, the concentration of the matrine in the polyacrylonitrile nanofiltration membrane interface layer is higher than that of the oxymatrine, so that the matrine can easily enter the interface layer and permeate the nanofiltration membrane.
Example 4 concentration of matrine and oxymatrine in Sophora flavescens in nanofiltration membrane interface layer under ethanol solution environment
Weighing 1.0kg of radix Sophorae Flavescentis, extracting with 10 times of ethanol for 2 times, each for 1 hr, mixing extractive solutions, filtering with microporous membrane to obtain radix Sophorae Flavescentis ethanol extractive solution, detecting by high performance liquid chromatography with the following chromatographic conditions: waters e2695 HPLC, full-wavelength UV detector, Agilent NH2Chromatographic column, acetonitrile-absolute ethyl alcohol-3% phosphoric acid (v/v/v 80: 10), volume flow rate of 1.0mL/min, column temperature of 25 deg.C, detection wavelength of 220nm, and external standard one-point method for calculating matrine concentration of 0.54 μ g/mL in water extractive solution of radix Sophorae Flavescentis, and oxymatrineThe concentration of the base was 0.61. mu.g/mL.
Separating with 500Da polyacrylonitrile nanofiltration membrane, adjusting transmembrane pressure difference to 0.2, 0.5, 0.8, 1.0, 1.5, and 2.0MPa, respectively collecting membrane flux (J) under corresponding transmembrane pressure difference, and calculating retention rate (R) data of matrine and oxymatrine.
The membrane separation coefficient k was calculated according to equation (1) from J and R at a series of transmembrane pressure differences.
Figure BSA0000257095960000046
By the pair ln [ (1-R). J/R]And J linear regression, wherein
Figure BSA0000257095960000047
The slope is 1/k, the intercept of the linear equation. Fitting ln [ (1-R). J/R]And the linear equation for J is:
matrine:
Figure BSA0000257095960000048
the regression coefficient was 0.9908.
Oxymatrine:
Figure BSA0000257095960000049
the regression coefficient was 0.9924.
Calculating the concentration C of matrine and oxymatrine at the membrane interface layer according to formula (2) based on the calculated separation coefficient km
Figure BSA0000257095960000051
Matrine Cm0.47 mug/mL oxymatrine Cm0.72 mu g/mL, compared with the aqueous solution environment, the k values of matrine and oxymatrine in the sophora flavescens ethanol extract are relatively reduced, the concentration of oxymatrine in the homopolymerization acrylonitrile nanofiltration membrane interface layer is obviously higher than that of matrine, which indicates that the oxymatrine can enter the interface layer formed by the ethanol solution environment and polyacrylonitrile more easilyAnd (4) a nanofiltration membrane is used.

Claims (6)

1. A method for calculating the concentration of traditional Chinese medicine components in an interface layer of a nanofiltration membrane is characterized by comprising the following steps:
a. placing the nanofiltration membrane and Chinese medicinal components to be evaluated in a separation system, and detecting the concentration C of the Chinese medicinal components to be analyzed in the solution0
b. B, performing membrane separation on the traditional Chinese medicine solution in the step a, adjusting transmembrane pressure difference to be within the range of 0.05-2.0 MPa, and respectively collecting membrane flux (J) and component retention rate (R) data under corresponding transmembrane pressure difference;
c. calculating the membrane separation coefficient k according to formula (1) from J and R under the series of transmembrane pressure differences in step b by pairing ln [ (1-R). J/R]And J linear regression, wherein
Figure FSA0000257095950000011
Is the intercept of a linear equation with a slope of 1/k
Figure FSA0000257095950000012
d. According to the separation coefficient k obtained by calculation in the step C, the concentration C of the traditional Chinese medicine component to be analyzed of the membrane interface layer is calculated according to the formula (2)m
Figure FSA0000257095950000013
2. The method of claim 1, wherein more than 3 transmembrane pressure difference values are selected for the transmembrane pressure difference in step b.
3. The method of claim 1, wherein the component rejection rate (R) in step b is calculated as R-solute concentration of the retentate/solute concentration of the concentrate.
4. The method for calculating the concentration of the traditional Chinese medicine components in the nanofiltration membrane interface layer according to claim 1, wherein the regression coefficient of the linear equation in the step c is not less than 0.99.
5. The method of claim 1, wherein the method can be used to analyze the membrane contamination characteristics of herbal constituents and the affinity of herbal constituents with membrane materials.
6. The method of claim 1, wherein the method is suitable for aqueous solutions and organic solutions.
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