CN115089995A - Guava leaf total flavone, extraction method and application - Google Patents
Guava leaf total flavone, extraction method and application Download PDFInfo
- Publication number
- CN115089995A CN115089995A CN202210710732.4A CN202210710732A CN115089995A CN 115089995 A CN115089995 A CN 115089995A CN 202210710732 A CN202210710732 A CN 202210710732A CN 115089995 A CN115089995 A CN 115089995A
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- CN
- China
- Prior art keywords
- guava
- leaves
- flavone
- total flavonoids
- specific adsorption
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D11/00—Solvent extraction
- B01D11/02—Solvent extraction of solids
- B01D11/0288—Applications, solvents
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D11/00—Solvent extraction
- B01D11/02—Solvent extraction of solids
- B01D11/0261—Solvent extraction of solids comprising vibrating mechanisms, e.g. mechanical, acoustical
- B01D11/0265—Applying ultrasound
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D15/00—Separating processes involving the treatment of liquids with solid sorbents; Apparatus therefor
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/223—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material containing metals, e.g. organo-metallic compounds, coordination complexes
- B01J20/226—Coordination polymers, e.g. metal-organic frameworks [MOF], zeolitic imidazolate frameworks [ZIF]
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28002—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
- B01J20/28009—Magnetic properties
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
- C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D311/04—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring
- C07D311/22—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 4
- C07D311/26—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 4 with aromatic rings attached in position 2 or 3
- C07D311/28—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 4 with aromatic rings attached in position 2 or 3 with aromatic rings attached in position 2 only
- C07D311/30—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 4 with aromatic rings attached in position 2 or 3 with aromatic rings attached in position 2 only not hydrogenated in the hetero ring, e.g. flavones
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- C—CHEMISTRY; METALLURGY
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- C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
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- C07H1/08—Separation; Purification from natural products
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- Chemical Kinetics & Catalysis (AREA)
- Analytical Chemistry (AREA)
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- Engineering & Computer Science (AREA)
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- General Health & Medical Sciences (AREA)
- Genetics & Genomics (AREA)
- Molecular Biology (AREA)
- Life Sciences & Earth Sciences (AREA)
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- Mechanical Engineering (AREA)
- Medicines Containing Plant Substances (AREA)
Abstract
The invention relates to the technical field of extraction and application of bioactive substances, in particular to total flavonoids in guava leaves, an extraction method and applicationAnd the influence of the mole ratio, solid-liquid ratio and extraction time of the donor on the extraction rate of the total flavonoids in the guava leaves, and a response surface test is designed by utilizing the Box-Behnken principle to optimize extraction process parameters. The invention also synthesizes Fe 3 O 4 The @ ZIF-8 magnetic MOFs material adopts a guava leaf total flavone specific adsorption material as a guava leaf flavone specific adsorption material, and the guava leaf total flavone specific adsorption material realizes specific adsorption and separation of flavone in natural guava leaves, so that the extraction and separation process of guava leaf flavone compounds is shortened.
Description
Technical Field
The invention relates to the technical field of extraction and application of bioactive substances, in particular to total flavonoids in guava leaves, an extraction method and application.
Background
The guava leaf is one of the traditional Chinese medicines, is the dry leaf of the plant guava of the guava genus, contains flavone, terpenes, phenolic acid and volatile oil components, is recorded by the literature as sweet and astringent in taste, mild in nature and non-toxic, has the effects of strengthening spleen, detoxifying, clearing heat and the like, and can be used for treating diabetes and diarrhea; the total flavonoids of the guava leaves belong to a class of compounds of dietary polyphenols, contain various bioactive components, have the effects of inhibiting bacteria, relieving diarrhea, resisting viruses, resisting oxidation, regulating immunity and the like, can be used as a preservative, an antidiarrheal agent, an immunomodulator and the like, and in recent years, pharmacological research also finds that the flavonoids extracted from the guava leaves also have the effects of dilating coronary arteries and reducing blood sugar, so that the total flavonoids of the guava leaves have wide pharmacological activity and good application prospect.
In addition to the biological effects of the total flavonoids in the guava leaves, the total flavonoids in the guava leaves can also chelate metal ions, and the chelated metal ions have high antioxidant activity and biological effect, so that the adsorption and extraction of the total flavonoids in the guava leaves are widely concerned and researched based on various applications of the total flavonoids in the guava leaves and metal complexes thereof in pharmacology and biology. In the research of the prior art, the flavonoid compounds are usually extracted by a traditional solvent extraction method, and the traditional solvent extraction method has the defects of large organic solvent consumption, environmental pollution and degradation of the flavonoid compounds caused by overlong extraction time, so that a new extraction method of the guava leaf flavonoid compounds is required to be provided to overcome the defects of the traditional solvent extraction method.
In addition, except for the traditional solvent extraction method for extracting the guava leaf flavonoid compounds, in the prior art, the flavonoid compounds are mainly enriched by materials such as macroporous adsorption resin, polyamide resin, silica nanoparticles, polytetrafluoroethylene films, halloysite and the like, but most of the materials cannot be effectively recycled, so that the application of the materials in the extraction of the total flavonoids in the guava leaves is limited, and therefore, a porous material which can be recycled and can efficiently adsorb and extract the total flavonoids in the guava leaves is required to be provided, so that the specific extraction and separation of the total flavonoids in the guava leaves are realized.
Disclosure of Invention
Aiming at the technical defects, the invention aims to provide guava leaf total flavonoids, an extraction method and application. The invention also synthesizes Fe 3 O 4 @ ZIF-8 magnetic MOFs material, and adopting guava leaf total flavone specific adsorption material Fe 3 O 4 The @ ZIF-8 magnetic MOFs material is used as a specific adsorption material of the guava leaf flavone, and the specific adsorption material of the total flavone of the guava leaves realizes specific adsorption and separation of the flavone in the natural guava leaves, so that the extraction and separation process of the guava leaf flavone compound is shortened.
In order to solve the technical problems, the invention adopts the following technical scheme:
a method for extracting total flavonoids from guava leaves comprises the following steps:
(1) preparation of eutectic solvent: mixing choline chloride and ethylene glycol until the choline chloride and the ethylene glycol are completely dissolved and are clear and transparent to obtain a eutectic solvent;
wherein the mol ratio of choline chloride to glycol is 1: 5-25;
(2) adding the crushed guava leaves into the eutectic solvent, and performing ultrasonic treatment and centrifugation to obtain the total flavonoids in the guava leaves;
wherein the volume ratio of the mass of the guava leaves to the eutectic solvent is 1 g: 5-25 mL.
Preferably, the molar ratio of choline chloride to ethylene glycol in the step (1) is 1: 15-25.
Preferably, the ultrasonic treatment conditions are as follows: ultrasonic treating at 30-90 deg.c for 20-100min under the condition of 200-350W.
Preferably, the ultrasonic time in the step (2) is 60-100min, and the volume ratio of the mass of the guava leaves to the eutectic solvent in the step (2) is 1 g: 10-20 mL.
The invention also protects the guava leaf total flavone extracted by the extraction method of the guava leaf total flavone.
The invention also protects the application of the guava leaf total flavonoids in preparing the specific adsorption material of the guava leaf total flavonoids.
Preferably, the guava leaf total flavone specific adsorption material is prepared according to the following steps:
(1)Fe 3 O 4 the preparation method of the @ ZIF-8 magnetic MOFs material comprises the following steps:
to Fe 3 O 4 Adding anhydrous sodium acetate solution, ultrasonically dispersing uniformly, and washing with deionized water to obtain Fe 3 O 4 A solution;
zn (NO) 3 ) 2 ·6H 2 Adding O, 2-methylimidazole into methanol, and then adding Fe 3 O 4 Stirring the solution at 30-70 deg.C for 0.5-12h, washing with anhydrous ethanol, and vacuum drying to obtain Fe 3 O 4 @ ZIF-8 magnetic MOFs materials;
(2) mixing Fe 3 O 4 And adding the @ ZIF-8 magnetic MOFs material into the total flavone solution of the guava leaves, stirring, adsorbing and drying to obtain the specific adsorption material for the total flavone of the guava leaves.
Preferably, said Fe 3 O 4 The preparation method comprises the following steps:
FeCl is added 3 ·6H 2 Adding O into ethylene glycol, stirring to obtain a clear solution, adding anhydrous sodium acetate into the clear solution, stirring to obtain a mixed solution, reacting the mixed solution at the temperature of 180 ℃ and 220 ℃ for 8 hours, washing with anhydrous ethanol, and drying in vacuum to obtain Fe 3 O 4 。
Preferably, the adsorption method of the guava leaf total flavone specific adsorption material comprises the following steps:
mixing the specific adsorption material with the total flavone solution, adjusting pH to 5-8, and reacting at 25 deg.C for 20-60 min;
the mass ratio of the guava leaf total flavone solution to the guava leaf total flavone specific adsorption material is 1: 6-22.
Compared with the prior art, the invention has the beneficial effects that:
1. the deep eutectic solvent method is a new system formed by mixing a hydrogen bond acceptor and a hydrogen bond donor and interacting through hydrogen bonds, is a green mixed solvent, has the characteristics of environmental protection, no toxicity, biodegradability, good biocompatibility, low cost, easy synthesis and the like, is applied to analysis of food, biology and environmental samples, and is used for flavone extraction of plants such as rhizoma polygonati, flos Trollii, moringa leaves and the like, so that the application adopts the green deep eutectic solvent to extract the total flavonoids in the guava leaves, and provides reference for development of the total flavonoids in the guava leaves feed additive.
2. In the modern research progress, MOFs materials have been successfully modified, such as Cu-MOF-199 chelated by metal copper, Ni-MOF-74 taking metal nickel as a core, NH2-MIL-101(Cr) taking metal chromium as a center, and the like, and proper metals, ligands and internal structure changes are selected to change the properties of the MOFs materials, so that high-efficiency medicine loading and proper medicine release rate can be realized; based on the research, the invention prepares Fe 3 O 4 @ ZIF-8 magnetic MOFs material, using Fe 3 O 4 The @ ZIF-8 adsorbs the total flavonoids in the leaves of the guava which is a magnetic MOFs material, and is prepared into a specific adsorption material of the total flavonoids in the leaves of the guava, a memory site is formed on the specific adsorption material of the total flavonoids in the leaves of the guava, and then the specific adsorption material of the total flavonoids in the leaves of the guava is adopted to separate the total flavonoids in the leaves of the guava and the analogues of the total flavonoids in the leaves of the guava.
Drawings
FIG. 1 is a graph showing the effect of eutectic solvents of different compositions on the extraction rate of total flavonoids according to the present invention;
FIG. 2 is a graph showing the effect of different molar ratios of choline chloride-ethylene glycol on the extraction rate of total flavonoids from guava leaves;
FIG. 3 is a graph showing the effect of solid-liquid ratio on the extraction rate of total flavonoids from guava leaves;
FIG. 4 is a graph showing the effect of extraction time on the extraction rate of total flavonoids from guava leaves;
FIG. 5 is a graph of analysis of the response surface of interaction AB on the extraction rate of total flavonoids in guava leaves, wherein the left graph is the degree of a curved surface, and the right graph is the contour ellipticity of interaction AB;
FIG. 6 is a graph of analysis of the response surface of interaction AC to the extraction rate of total flavonoids in guava leaves, wherein the left graph is the degree of the curved surface and the right graph is the ellipse ratio of the interaction AC contour line;
FIG. 7 is a graph of analysis of the response surface of interaction BC to the extraction rate of total flavonoids in guava leaves, wherein the left graph is the degree of the curved surface and the right graph is the ellipse ratio of the contour line of interaction BC;
FIG. 8 is a comparison graph of the adsorption amounts of the total flavonoids in guava leaves at different concentrations and adsorbed by a specific adsorption material for the total flavonoids in the guava leaves for different times;
FIG. 9 is a graph showing the adsorption capacity of the specific adsorption material for total flavonoids in guava leaves at different pH values;
FIG. 10 is a graph showing the relationship between the amount of the total flavonoid-specific adsorbent and the amount of the adsorbent;
FIG. 11 shows first order kinetic fitting parameters and second order kinetic fitting parameters of the total flavonoid-specific adsorption material of guava leaves, wherein the left graph shows the first order kinetic fitting parameters, and the right graph shows the second order kinetic fitting parameters;
FIG. 12 shows Langmuir model fitting and Freundich model fitting of the total flavonoid-specific adsorption material of guava leaves, wherein the left graph is Langmuir model fitting, and the right graph is Freundich model fitting;
FIG. 13 shows the desorption amounts of the total flavonoids from the specific adsorption material of guava leaves at different reaction times;
FIG. 14 is a graph showing the recycling performance of the specific adsorption material of guava leaf total flavonoids;
FIG. 15 shows Fe 3 O 4 Different amplifications of @ ZIF-8 magnetic MOFs materialsMultiple electron microscope images, wherein the left image is an electron microscope image under the multiple of 10 μm, and the right image is an electron microscope image under the multiple of 2 μm;
FIG. 16 is Fe 3 O 4 The XRD pattern of @ ZIF-8 magnetic MOFs;
FIG. 17 is Fe 3 O 4 @ ZIF-8 magnetic MOFs material infrared spectrum.
Detailed Description
The following detailed description of specific embodiments of the invention is provided, but it should be understood that the scope of the invention is not limited to the specific embodiments. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention. The experimental methods described in the examples of the present invention are all conventional methods unless otherwise specified.
In the experiments of the invention, all Fe 3 O 4 The @ ZIF-8 magnetic MOFs material is prepared by the following steps:
Fe 3 O 4 the preparation of (1):
weighing FeCl 3 ·6H 2 O1.345 g, 1.345g of FeCl was added to a 100mL beaker 3 ·6H 2 O, adding 75mL of glycol, and stirring for about 30min until the solution is not turbid; then 3.605g of anhydrous sodium acetate is added into a beaker, stirred at 500r/min at 25 ℃ until the mixture is clear, and subjected to ultrasonic treatment for 30 min; pouring the solution into a reaction kettle made of polytetrafluoroethylene material, reacting for 8h at the temperature of 200 ℃, washing the product for several times by using absolute ethyl alcohol, eliminating the interference of other factors of the material, putting the product into a vacuum drying oven, and drying at the temperature of 60 ℃ to obtain Fe 3 O 4 ；
Fe 3 O 4 The preparation method of the @ ZIF-8 magnetic MOFs material comprises the following steps:
weigh 0.25g of Fe prepared above 3 O 4 Placing into a beaker, adding 0.3% anhydrous sodium acetate solution with volume of 30mL, ultrasonically dispersing for 20min, washing with deionized water, and weighing 0.152g Zn (NO) 3 ) 2 ·6H 2 O and 0.247g of 2-methylimidazole are placed together in a three-necked flask, 30mL of methanol are added thereto and the mixture is stirred well, and thenThe prepared Fe 3 O 4 Adding the solution into the flask, mixing, reacting at 50 deg.C for 3h under magnetic stirring at 500r/min, washing with anhydrous ethanol to obtain solvent-free material, soaking in ethanol for 24h, and oven drying in vacuum drying oven to constant weight to obtain Fe 3 O 4 @ ZIF-8 magnetic MOFs materials;
example 1
The extraction method of the guava leaf total flavonoids comprises the following steps:
(1) preparation of eutectic solvent: mixing choline chloride and ethylene glycol until the choline chloride and the ethylene glycol are completely dissolved and are clear and transparent to obtain a eutectic solvent;
wherein the mol ratio of choline chloride to glycol is 1: 15;
(2) adding pulverized guava leaves into the eutectic solvent, performing ultrasonic treatment at 45 deg.C and 300W for 40min, and centrifuging to obtain guava leaf total flavonoids;
wherein the volume ratio of the mass of the guava leaves to the eutectic solvent is 1 g: 15 mL.
Comparative example 1
The same procedure as in example 1 was followed except that the eutectic solvent was replaced with choline chloride/lactic acid in an equimolar ratio by choline chloride and ethylene glycol in a molar ratio of 1: 20.
Comparative example 2
The same procedure as in example 1 was followed except that the eutectic solvent was replaced with choline chloride/1, 4-butanediol at an equimolar ratio by choline chloride and ethylene glycol at a molar ratio of 1: 20.
Comparative example 3
The same procedure as in example 1 was followed except that the eutectic solvent was replaced with choline chloride and ethylene glycol at a molar ratio of 1:20 in place of choline chloride/1, 3-butanediol at an equimolar ratio.
Comparative example 4
The same procedure as in example 1 was followed except that the eutectic solvent was replaced with choline chloride/1, 2-propanediol in an equimolar ratio by choline chloride and ethylene glycol in a molar ratio of 1: 20.
Comparative example 5
The same procedure as in example 1 was followed except that the eutectic solvent was replaced with choline chloride and ethylene glycol at a molar ratio of 1:20 in place of choline chloride/methanol at an equimolar ratio.
Comparative example 6
The same procedure as in example 1 was followed except that the eutectic solvent was replaced with choline chloride and ethylene glycol at a molar ratio of 1:20 in place of choline chloride/ethanol at an equimolar ratio.
The method for preparing the guava leaf total flavone specific adsorption material by adopting the guava leaf total flavone comprises the following steps:
mixing Fe 3 O 4 And adding the @ ZIF-8 magnetic MOFs material into the total flavone solution of the guava leaves, stirring, adsorbing and drying to obtain the specific adsorption material for the total flavone of the guava leaves.
Results and discussion
Firstly, extracting conditions and analyzing extracts of guava leaf total flavonoids:
(1) measuring the total flavone content of the guava leaves:
s1, drawing a standard curve:
determining total flavonoids by using a sodium nitrite-aluminum nitrate color development method; taking rutin, accurately preparing 0.3mg/mL mother solution by using ethanol with the volume fraction of 70%, respectively taking 0mL, 1mL, 2mL, 3mL, 4mL, 5mL, 6mL and 7mL mother solutions in an isocratic manner to 8 numbered 25mL volumetric flasks, sequentially adding 0.75mL, 5% sodium nitrite, 0.75mL, 10% aluminum nitrate nonahydrate and 10mL and 4% sodium hydroxide, fixing the volume to scale by using 70% ethanol, measuring the absorbance value at 510nm, drawing a concentration-absorbance standard curve, and fitting a linear equation: y 11.206x-0.0035, R 2 ＝0.9997；
S2, determination of total flavone content:
and (3) measuring the absorbance value by using a sodium nitrite-aluminum nitrate color development method, and calculating the content of the total flavone according to a linear equation.
(2) Single factor experiments:
(a) selection of eutectic solvent (DES):
placing a hydrogen bond receptor choline chloride and different hydrogen bond donors in a conical flask according to a molar ratio (1:20), sealing the flask opening with a preservative film, magnetically stirring at 80 ℃ until the choline chloride and the different hydrogen bond donors are completely dissolved to be clear and transparent, and placing at room temperature for later use; weighing 0.5g of crushed guava leaves in a conical flask, adding 10mL of DES (DES standard deviations) with different compositions, performing ultrasonic extraction, centrifuging, measuring an absorbance value by adopting a sodium nitrite-aluminum nitrate color development method, calculating the extraction rate of flavonoids, and inspecting the influence of DES composition on the extraction rate;
substances shown in Table 1 DES
The results in figure 1 show that under the conditions of different DES compositions, the extraction rate of guava leaf flavone is greatly different, wherein two DES (choline chloride/ethylene glycol) and choline chloride/lactic acid are used for achieving a good effect, and the extraction rate of flavone under the current experimental conditions reaches about 16%, so that the choline chloride/ethylene glycol system with the best extraction effect is selected in subsequent experiments for further investigation.
(b) Influence of choline chloride/ethylene glycol molar ratio on flavonoid extraction yield:
dissolving choline chloride (ChCl) and Ethylene Glycol (EG) according to different molar ratios of 1:5, 1:10, 1:15, 1:20 and 1:25 to prepare DES (data encryption standard) with different concentrations, weighing 0.5g of crushed guava leaves into a conical flask, adding 10mL of ChCl-EG with different concentrations, performing ultrasonic extraction, centrifuging, measuring an absorbance value by using a sodium nitrite-aluminum nitrate chromogenic method, calculating the extraction rate of flavonoids compounds, and inspecting the influence of the ChCl-EG molar ratio on the extraction rate;
the results in FIG. 2 show that the extraction rate of the flavonoid compounds gradually increases along with the increase of the molar ratio of ChCl-EG, the whole extraction rate shows an increasing trend, when the molar ratio is 1:15, an inflection point appears, and based on the comprehensive consideration of factors such as economy, environmental protection, safety and the like, the molar ratio of ChCl-EG is 1:15, which is the optimal extraction solvent molar ratio.
(c) Influence of solid-liquid ratio on extraction rate of flavonoids:
weighing 0.5g of crushed guava leaves in a conical flask, respectively adding 2.5mL, 5mL, 7.5mL, 10mL and 12.5mL of DES (the molar ratio of ChCl-EG is 1:25), performing ultrasonic extraction, centrifuging, measuring the absorbance value by using a sodium nitrite-aluminum nitrate chromogenic method, calculating the extraction rate of flavonoids compounds, and investigating the influence of solid-liquid ratio on the extraction rate;
the results in figure 3 show that the extraction rate of the flavonoids compounds is increased along with the increase of the DES solvent amount, the solid-liquid ratio is in a stable increasing trend between 1:5 and 20, the solid-liquid ratio is slightly reduced compared with 1:20 at 1:25, the flavonoids compounds in the guava leaves are certain, the extraction amount of the flavonoids compounds reaches the maximum at 1:20, the solid-liquid ratio and the production benefit are closely related in the actual production process, and the difference of 0.4% between the extraction rates of 1:15 and 1:20 can be regarded as approximate, so in order to reduce the cost, the optimal extraction solid-liquid ratio of 1:20 is selected.
(d) Influence of ultrasound extraction time on extraction yield:
weighing 0.5g of crushed guava leaves into a conical flask, adding 7.5mL of DES (the molar ratio of ChCl-EG is 1:25), performing ultrasonic treatment at 45 ℃ and 300W for 20min, 40min, 60min, 80min and 100min respectively, centrifuging, measuring the absorbance value by adopting a sodium nitrite-aluminum nitrate color development method, calculating the extraction rate of flavonoids compounds, and examining the influence of time on the extraction rate;
the results in fig. 4 show that the extraction rate gradually increases in the period of 20-60min, a gentle trend appears in 60-80min, and other substance components may be dissolved along with the increase of the extraction time after 60min, so that the dissolution amount of the flavonoids is inhibited, and the extraction rate of the flavonoids becomes gentle. The rising trend appears within 80-100min, which may be that the temperature is not constant due to overlong use time of the ultrasonic instrument, and the rising fluctuation of the temperature has influence on the extraction rate of the flavonoid compound; therefore, in order to ensure effective and stable extraction process, 40min is selected as the optimal extraction time.
(3) Response surface optimal design:
taking the extraction rate of total flavonoids in guava leaves as a response value, selecting a ChCl-EG molar ratio, a solid-liquid ratio and time as variable response surface factors for investigation, and as shown in Table 2:
TABLE 2 response surface optimization test factor horizon
(a) Designing a response surface optimization scheme:
based on the single-factor test result, a scheme that the molar ratio (A), the solid-liquid ratio (B) and the time (C) are used as variable factors, the flavonoid extraction rate (Y) is used as a response surface value is formulated, extraction optimization is carried out by the aid of software Design-Expert 10.0.7, 17 groups of data are given for carrying out experiments, and 17 groups of optimized data and results are shown in Table 3.
TABLE 3 response surface optimization scheme and results table
(b) Regression model analysis of variance
According to 17 groups of experimental results in table 3, data are input into software Design-Expert 10.0.7 for analysis, the influence of three independent process variables of ChCl-EG molar ratio (A), solid-liquid ratio (B) and time (C) on the extraction rate (%) of flavonoids compounds in response values is evaluated, the established regression model is fitted, the statistical significance evaluation is carried out on the established regression equation, and the fitted second-order polynomial equation of the regression analysis of the response values is obtained as follows: the extraction rate of flavonoids is 21.5-0.14A +0.92B +1.42C-0.27AB +0.07AC-0.15BC-0.91A 2 -1.56B 2 -1.37C 2 。
Table 4 analysis of variance table of regression model
| Sources of differences | Sum of squares | Degree of freedom | Mean square | F value | P value | Significance of |
| Model (model) | 47.31 | 9 | 5.26 | 20.55 | 0.0003 | ** |
| A | 0.15 | 1 | 0.15 | 0.59 | 0.4671 | |
| B | 6.70 | 1 | 6.70 | 26.18 | 0.0014 | ** |
| C | 16.19 | 1 | 16.19 | 63.28 | <0.0001 | ** |
| AB | 0.28 | 1 | 0.28 | 1.10 | 0.3295 | |
| AC | 0.020 | 1 | 0.020 | 0.077 | 0.7899 | |
| BC | 0.096 | 1 | 0.096 | 0.38 | 0.5593 | |
| A 2 | 3.46 | 1 | 3.46 | 13.51 | 0.0079 | * |
| B 2 | 10.19 | 1 | 10.19 | 39.85 | 0.0004 | ** |
| C 2 | 7.86 | 1 | 7.86 | 30.71 | 0.0009 | ** |
| Residual error | 1.79 | 7 | 0.26 | |||
| Missimilitude term | 0.19 | 3 | 0.062 | 0.15 | 0.9218 | |
| Pure error | 1.61 | 4 | 0.40 | |||
| Sum of | 49.1 | 16 |
Note: "x" indicates that the difference was extremely significant (P < 0.01); ") indicates significant difference (0.01< P < 0.05).
As shown in Table 4, the test values (F values), degrees of freedom (df), probabilities (P values), and determination coefficients (R values) were examined for the analysis of variance table of the regression model 2 ) The influence of the isoparametric on the response values; the regression model was found to be statistically significant from the analysis of variance table, F20.55 and P0.0003<The 0.01 model is extremely significant; mismatch term P0.9218>The 0.05 model mismatch term was not significant, indicating model feasibility. Coefficient of determination R of this test 2 0.9635, the coefficient R is adjusted 2 adj The result shows that the model has higher fitting degree with the actual extraction process and small experimental error, and can be used for analyzing the ChCl-EG molar ratio (A)And (4) predicting the trend of the solid-liquid ratio (B) and the time (C) of the extraction rate (%) of the flavonoid compounds along with the factor change and the extraction rate.
According to the influence of each single factor on the extraction rate effect in the table 4, the F value and the P value show that the C is greater than B and greater than A, the solid-liquid ratio (B) and the time (C) factors have obvious influence on the extraction rate (%) of the flavonoid compound, and the ChCl-EG molar ratio (A) has no obvious influence; the interaction exists among the factors, the interaction AB, AC and AB shows no significance (P >0.05), the bending degree of the response surface and the significance of the interaction are in a direct proportion relation, and the interaction is more significant when the curve degree of the three-dimensional model is more bent, and the interaction is not significant when the curve degree is more gentle. As shown in fig. 5-7, the response surfaces of the interactions AB, AC and BC are not significant, the ellipticity of the contour lines of the interactions AB and AC is high, but the curved surface of the response surface is gentle, which indicates that the interaction is not significant, while the steeply sloping surface of the response surface BC of fig. 6 is curved compared with the contours AB and AC, but the contour lines tend to be circular, which indicates that the interaction is not significant, and the results of table 4 are consistent.
(3) Stability test:
a. and (3) precision experiment:
taking 0.1mL of guava extract, sequentially adding reagents according to the sodium nitrite-aluminum nitrate color development method, after the color development is finished, measuring the absorbance value once every 10 minutes, making 3 groups of parallel, and calculating the RSD according to a formula RSD ═ 100% of the standard deviation of the absorbance/the average absorbance;
b. reproducibility test:
taking 5 parts of 0.1mL of guava extract, sequentially adding reagents according to the sodium nitrite-aluminum nitrate color development method, after the color development is finished, measuring an absorbance value, and calculating RSD according to a formula RSD ═ 100% of (standard deviation of absorbance/average absorbance);
the result shows that the experiment precision of extracting the guava leaf total flavonoids by the eutectic solvent method is good, the RSD is 1.63%, the color reproduction is good, the RSD is 1.70%, the recovery rate value of flavonoids in the sample recovery experiment is 101.35%, and the RSD is 0.65%. The method is stable and feasible.
Secondly, experimental study on the adsorption performance of the guava leaf total flavone specific adsorption material is carried out, and the specific method comprises the following steps:
(1) single factor experiments:
(a) influence of initial concentration and contact time:
adding 20mL of guava leaf total flavone solutions with the concentrations of 20mg/L, 25mg/L and 30mg/L respectively into three 50mL conical flasks, adding 5mg of a guava leaf total flavone specific adsorption material, adsorbing for a period of time at room temperature at 500r/min, measuring absorbance by using a magnet adsorption material, taking supernate, and then calculating the adsorption capacity of the guava leaf total flavone specific adsorption material on the guava leaf total flavone;
TABLE 5 adsorption amounts calculated at different concentrations and times
As shown in fig. 8 and table 5, the adsorption amount of the adsorbent increased with time at the same concentration, and half of the adsorption amount was reached in the first 10min compared to the equilibrium, indicating a rapid adsorption phase in the first 10 min; when the reaction lasts for 60min, the specific adsorption material of the guava leaf total flavonoids reaches the adsorption balance. Under the 3 different concentrations, the higher the concentration is, the larger the adsorption amount of the specific adsorption material of the total flavonoids in the guava leaves is, but the unit adsorption amount of the total flavonoids in the guava leaves with the concentration of 25mg/L is the highest.
(b) Influence of the pH value
Taking 20mL of 25mg/L guava leaf total flavone solution, adjusting the pH value with 0.05mol/L NaOH solution and HCl solution or ammonia water, adjusting the pH value to be 3-10, adding 5mg of guava leaf total flavone specific adsorption material into the solution, reacting for 60min at the temperature of 25 ℃ at 300r/min, measuring the absorbance of the solution by using a spectrophotometer, and calculating the adsorption amount of the guava leaf total flavone specific adsorption material on the guava leaf total flavone;
TABLE 6 adsorption at different pH values
As shown in fig. 9 and table 6, when the pH is 6, the adsorption amount of the total flavone specific adsorption material of guava leaves is the largest, which can reach 79.40mg/g, and when the pH is less than 6, the unit adsorption amount and the pH value of the total flavone specific adsorption material of guava leaves are in a positive proportion, and the adsorption amount changes obviously from 63.66mg/g to 79.60 mg/g; when the pH is more than 6, the unit adsorption amount is inversely proportional to the pH, and the adsorption tendency is less changed than that in the case of adsorption less than 6.
(c) Influence of dosage of total flavone specific adsorption material of guava leaves
Transferring 20mL of 25mg/L guava leaf total flavone solution into an erlenmeyer flask, adding 3mg, 5mg, 7mg, 9mg and 11mg of the guava leaf total flavone specific adsorption material, reacting for 60min, measuring the absorbance of the solution by using a spectrophotometer, and calculating the adsorption amount of the guava leaf total flavone specific adsorption material on the guava leaf total flavone;
TABLE 7 adsorption and removal rates at different dosages
| Dosage (mg) | Removal rate% | Adsorption Capacity (mg/g) |
| 3 | 35.15 | 58.58 |
| 5 | 42.52 | 42.52 |
| 7 | 57.84 | 41.32 |
| 9 | 71.04 | 39.47 |
| 11 | 81.8 | 37.18 |
As shown in fig. 10 and table 7, when the total flavonoids of guava leaves were added in an amount of 3mg, the adsorption removal rate was only 35.15%, when the addition amount was increased to 5mg, the adsorption removal rate was 42.52%, and when the addition amount was increased to 11mg, the removal rate reached a maximum of 81.82%; experiments show that the unit adsorption amount of the adsorbent is reduced along with the increase of the dosage of the specific adsorption material of the guava leaf total flavonoids, because the adsorption amount of the adsorbent in unit mass is not in direct proportion to the dosage when the concentration and the volume of the guava leaf total flavonoids are fixed, but waste is caused by too much adsorbent, and the optimal dosage of the specific adsorption material of the guava leaf total flavonoids is 5 mg.
(2) Quadrature test
Selecting 4 factors of initial concentration, contact time, pH value and adding amount to carry out orthogonal experiment, and designing the orthogonal experiment by taking absorbance after adsorption balance as an index, wherein the adsorption conditions are as follows: the initial concentration is 25mg/L of total flavonoids of guava leaf, the contact time is 60min, the pH is 6, and the dosage is 5 mg.
TABLE 8 level table of orthogonal experimental factors
| Level of | Initial concentration (mg/L) | Contact time (min) | pH value | Dosage (mg) |
| 1 | 20 | 30 | 5 | 3 |
| 2 | 25 | 60 | 6 | 5 |
| 3 | 30 | 90 | 7 | 7 |
TABLE 9 orthogonal experimental factors and levels
| Factors of the fact | Initial concentration | pH value | Contact time | Amount of addition | Adsorption |
| Experiment | |||||
| 1 | 1 | 1 | 1 | 1 | 71.6 |
| |
1 | 2 | 2 | 2 | 37.4 |
| |
1 | 3 | 3 | 3 | 57.75 |
| |
2 | 1 | 2 | 3 | 33.88 |
| |
2 | 2 | 3 | 1 | 41.24 |
| |
2 | 3 | 1 | 2 | 80.52 |
| |
3 | 1 | 3 | 2 | 38.5 |
| |
3 | 2 | 1 | 3 | 37.67 |
| |
3 | 3 | 2 | 1 | 38.27 |
| |
55.583 | 47.993 | 62.263 | 50.370 | — |
| |
51.880 | 38.770 | 36.517 | 51.140 | — |
| |
38.147 | 58.847 | 45.830 | 43.100 | — |
| Extreme difference | 17.436 | 20.077 | 26.746 | 9.040 | — |
TABLE 10 ANOVA TABLE
As can be seen from the results of the orthogonal experiment table, the order of the range difference values is as follows: contact time, pH value, initial concentration and adding amount; through range analysis and comprehensive consideration of production cost and feasibility analysis, the optimal adsorption process is preferably as follows: the initial concentration of total flavonoids in folium Psidii Guajavae is 20mg/L, pH is 7, contact time is 30min, and dosage is 5 mg.
(a) And (3) dynamic data fitting:
TABLE 11 kinetic fitting parameters
As can be understood from FIG. 11 and Table 11, the linear effect of the second order kinetics is better than the first order kinetics as a result of fitting the adsorption data, where R is the fitted R of the second order kinetic model 2 The values are 0.9996, 0.9993 and 0.9987 respectively, and the experimentally measured value and the fitted value are not very different; the conclusion is that the second-order kinetic model is suitable for the process that the specific adsorption material of the total flavonoids in the guava leaves adsorbs the total flavonoids in the guava leaves, and belongs to chemical adsorption.
(b) Adsorption isotherm:
the experimentally measured data can be fitted using the Langmuir adsorption isotherm equation and Freundlich adsorption isotherm.
TABLE 12 isotherm fitting parameters
As shown in FIG. 12 and Table 12, the Langmuir model has a higher linear correlation, and the fitted R 2 When 0.9939 is greater than 0.9828, the adsorption belongs to monolayer adsorption, and the result shows that the adsorption of the guava leaf total flavone specific adsorption material to the guava leaf total flavone is applicable to Langmuir adsorption isotherms.
(3) Desorption experiments:
(a)Fe 3 O 4 @ ZIF-8 desorption experiment of guava leaf total flavone solution:
separating the guava leaf total flavone specific adsorption material which finishes adsorption balance from the solution by using a magnet, repeatedly cleaning by using deionized water, drying, adding 20mL of ethanol as a desorbent, desorbing within 60min of a specified time, measuring absorbance, calculating corresponding desorption amount, and researching the influence on the adsorption performance of the guava leaf total flavone specific adsorption material under different contact time;
TABLE 13 desorption amounts at different reaction times
As can be seen from fig. 13 and table 13, the desorption amount of the absolute ethanol solution to the guava leaf total flavone specific adsorption material is continuously increased when the time is increased in a period of time before the desorption, but the desorption amount tends to be gentle when the time is 30 min; the reason is that in the process of just beginning desorption of the desorbent, the concentration of the guava leaf total flavone solution is higher, the desorption power is very high, the desorption speed is naturally accelerated, the desorption reaches an equilibrium state along with the increase of time, the reaction time is prolonged, the desorption result does not obviously change, and the time is wasted, so that the optimum time for desorption is selected to be 30 min.
(b) Experiment on influence of different desorbents on desorption effect
As the optimum desorption time is 30min, the reaction time is 30min, wherein 5 different desorbents, namely absolute ethyl alcohol, 30% ethyl alcohol, water, n-butyl alcohol and ethyl acetate are adopted to be consistent with the treatment method, the desorption amount is calculated, and the desorption effect of the guava leaf total flavone specific adsorption material at 30min is considered;
TABLE 14 Desorption Effect of different Desorptors
| Desorption liquid | Desorption amount (mg/g) | Desorption ratio (%) |
| Anhydrous ethanol | 45.70 | 84.16 |
| 30% ethanol | 41.59 | 71.20 |
| Water (I) | 39.04 | 64.04 |
| N-butanol | 42.87 | 75.21 |
| Ethyl acetate | 44.84 | 81.32 |
As can be seen from table 14, in the organic solvent with higher concentration, the desorption amount and desorption rate of the specific adsorption material of guava leaf total flavonoids are higher than those of water, and the total flavonoids can be eluted during desorption due to the principle of similar compatibility of the total flavonoids and the organic solvent; of these 5 desorbents, the desorption effect was: absolute ethyl alcohol > ethyl acetate > n-butyl alcohol > 30% ethyl alcohol > water, wherein the absolute ethyl alcohol has the best desorption effect, and the absolute ethyl alcohol is ethyl acetate, but the absolute ethyl alcohol is selected as the desorption solvent due to the fact that the ethyl acetate is slightly toxic and has higher price compared with the absolute ethyl alcohol.
(4) Recyclability of the material
Adding 5mg of a guava leaf total flavone specific adsorption material into a guava leaf total flavone solution with the concentration of 25mg/L, reacting for 60min, repeatedly washing with deionized water after adsorption balance is completed each time, collecting a solid adsorbent, drying, adding the solid adsorbent into a new guava leaf total flavone solution with the same concentration, repeating the process for several times, measuring absorbance according to an ultraviolet spectrophotometer, and calculating the adsorption rate;
as can be seen from fig. 14, the adsorption rate of the adsorbent, namely the total flavonoids in guava leaves, is decreased with the increase of the utilization times of the adsorbent, but in the 5-cycle experiment, the decrease of the adsorption rate of the total flavonoids in guava leaves is not obvious, and is decreased from 80.84% to 76.74%, and is only decreased by 4.1%, so that the total flavonoids in guava leaves as the adsorbent has high adsorption efficiency, can be effectively recycled, and is an excellent adsorbent.
(III) Fe 3 O 4 Characterization of the @ ZIF-8 material:
(1) scanning Electron microscope analysis (SEM)
FIG. 15 is an electron micrograph of Fe at a magnification of 2 μm to 10 μm 3 O 4 The @ ZIF-8 nano particle is in a spherical structure, the particle size is about 498nm, the sizes are different, the interaction between a ligand and a central ion possibly exists, the action between the ligand and a solvent possibly is related, and a 10 mu m diagram is wrapped by a block which is Fe modified by ZIF 3 O 4 。
(2) XRD analysis
As can be seen from FIG. 16, Fe 3 O 4 The characteristic peaks appear at the 2 theta of 30.13 degrees, 35.26 degrees, 43.17 degrees, 57.25 degrees and 63.12 degrees of the @ ZIF-8 material, which indicates that Fe 3 O 4 The @ ZIF-8 material has been synthesized successfully, and via Fe 3 O 4 The comparison shows that the crystal form structure synthesized in the experiment is not changed, so that the Fe3O4@ ZIF-8 obtained by the method also has better magnetic separation performance.
(3) FTIR analysis:
fe in FIG. 17 3 O 4 In the infrared spectrum of @ ZIF-8, the characteristic peak of N-H absorption is 3412cm -1 At 1616cm -1 The peak is the telescopic vibration peak of C ═ N, 1637cm -1 Is the absorption characteristic peak of C-N. Furthermore, 617cm -1 The characteristic absorption peak of Fe-O-Fe appears. Comprehensive analysis, Fe 3 O 4 @ ZIF-8 has been successfully synthesized.
It will be apparent to those skilled in the art that various changes and modifications may be made in the invention without departing from the spirit and scope of the invention. Thus, if such modifications and variations of the present invention fall within the scope of the claims of the present invention and their equivalents, the present invention is also intended to include such modifications and variations.
Claims (9)
1. The extraction method of the total flavonoids in the guava leaves is characterized by comprising the following steps:
(1) preparation of eutectic solvent: mixing choline chloride and ethylene glycol until the choline chloride and the ethylene glycol are completely dissolved and are clear and transparent to obtain a eutectic solvent;
wherein the mol ratio of choline chloride to glycol is 1: 5-25;
(2) adding the crushed guava leaves into the eutectic solvent, and performing ultrasonic treatment and centrifugation to obtain total flavonoids in the guava leaves;
wherein the volume ratio of the mass of the guava leaves to the eutectic solvent is 1 g: 5-25 mL.
2. The method for extracting total flavonoids from guava leaves according to claim 1, wherein the molar ratio of choline chloride to ethylene glycol in the step (1) is 1: 15-25.
3. The method for extracting total flavonoids from guava leaves according to claim 1, wherein the ultrasonic treatment conditions are as follows: ultrasonic treating at 30-90 deg.c for 15-100min under the condition of 200-350W.
4. The method for extracting total flavonoids from guava leaves according to claim 3, wherein the ultrasound time in the step (2) is 60-100min, and the volume ratio of the mass of the guava leaves to the eutectic solvent in the step (2) is 1 g: 10-20 mL.
5. The guava leaf total flavonoids extracted by the method for extracting guava leaf total flavonoids according to any one of claims 1 to 4.
6. An application of the guava leaf total flavonoids of claim 5 in preparing a specific adsorption material of the guava leaf total flavonoids.
7. The use of claim 6, wherein the guava leaf total flavone specific adsorbent material is prepared by the following steps:
(1)Fe 3 O 4 the preparation method of the @ ZIF-8 magnetic MOFs material comprises the following steps:
to Fe 3 O 4 Adding anhydrous sodium acetate solution, ultrasonically dispersing uniformly, and washing with deionized water to obtain Fe 3 O 4 A solution;
adding Zn (NO) 3 ) 2 ·6H 2 Adding O, 2-methylimidazole into methanol, and then adding Fe 3 O 4 Stirring the solution at 30-70 deg.C for 0.5-12h, washing with anhydrous ethanol, and vacuum drying to obtain Fe 3 O 4 @ ZIF-8 magnetic MOFs materials;
(2) mixing Fe 3 O 4 And adding the @ ZIF-8 magnetic MOFs material into the total flavone solution of the guava leaves, stirring, adsorbing and drying to obtain the specific adsorption material for the total flavone of the guava leaves.
8. Use according to claim 7, wherein the Fe is 3 O 4 The preparation method comprises the following steps:
FeCl is added 3 ·6H 2 Adding O into ethylene glycol, stirring to obtain a clear solution, adding anhydrous sodium acetate into the clear solution, stirring to obtain a mixed solution, reacting the mixed solution at the temperature of 180 ℃ and 220 ℃ for 8 hours, washing with anhydrous ethanol, and drying in vacuum to obtain Fe 3 O 4 。
9. The use of claim 8, wherein the guava leaf total flavone specific adsorption material is adsorbed by the following method:
mixing the specific adsorption material with the total flavone solution, adjusting pH to 5-8, and reacting at 25 deg.C for 20-60 min;
the mass ratio of the guava leaf total flavone solution to the guava leaf total flavone specific adsorption material is 1: 6-22.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115672278A (en) * | 2022-11-16 | 2023-02-03 | 西南政法大学 | Methacarbone adsorbent and application thereof |
| CN116920007A (en) * | 2023-08-04 | 2023-10-24 | 上海应用技术大学 | Method for extracting lettuce leaf flavone by eutectic solvent |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115672278A (en) * | 2022-11-16 | 2023-02-03 | 西南政法大学 | Methacarbone adsorbent and application thereof |
| CN115672278B (en) * | 2022-11-16 | 2024-05-24 | 西南政法大学 | Mecalcidone adsorbent and application thereof |
| CN116920007A (en) * | 2023-08-04 | 2023-10-24 | 上海应用技术大学 | Method for extracting lettuce leaf flavone by eutectic solvent |
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