CN113292595B - Hydrophobic vanadyl-organic molecular cage-based porous liquid for extracting L-tryptophan and preparation method and application thereof - Google Patents

Hydrophobic vanadyl-organic molecular cage-based porous liquid for extracting L-tryptophan and preparation method and application thereof Download PDF

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CN113292595B
CN113292595B CN202110486051.XA CN202110486051A CN113292595B CN 113292595 B CN113292595 B CN 113292595B CN 202110486051 A CN202110486051 A CN 202110486051A CN 113292595 B CN113292595 B CN 113292595B
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张竹修
乔旭
张冰洁
汤吉海
杨宝林
崔咪芬
陈献
费兆阳
刘清
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Nanjing Zihuan Engineering Technology Research Institute Co ltd
Nanjing Tech University
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Abstract

The invention discloses a hydrophobic vanadyl-organic molecular cage-based porous liquid for extracting L-tryptophan and a preparation method and application thereof. The hydrophobic vanadyl-organic molecular cage based porous liquid has the characteristics of pore channel diversity, adjustable pore diameter and the like, and the extraction of the L-tryptophan in the water is realized by adjusting the pore channel structure of the vanadyl-organic molecular cage. The method is environment-friendly, mild in operation condition and simple in process, and is an efficient and green method for separating L-tryptophan.

Description

Hydrophobic vanadyl-organic molecular cage-based porous liquid for extracting L-tryptophan and preparation method and application thereof
Technical Field
The invention belongs to the field of material preparation, and particularly relates to hydrophobic vanadyl-organic molecular cage-based porous liquid for extracting L-tryptophan, and a preparation method and application thereof.
Background
Amino acids have long been important as basic building blocks of life in human and animal nutrition and health maintenance, and aromatic amino acids (phenylalanine L-Phe, tyrosine L-Tyr, tryptophan L-Trp) have important effects on human body as essential amino acids for human body, especially L-tryptophan, play important roles in nutrition and pharmaceutical industry.
The industrial synthesis of amino acids is by fermentation or by chemoenzymatic processes, such as the enantioselective addition of L-Phe to trans-cinnamic acid by ammonia. Alternatively, the amino acids may be recovered by hydrolysis of non-feed protein waste. Such as poultry feather meal, sugarcane, sugar beet and the like obtained from chemical fertilizer manufacturing and biological ethanol preparation processes, the average mass fraction of aromatic amino acids in the protein-rich wastewater hydrolysate is between 5 and 10wt percent. Selective separation of amino acids from aqueous media is a critical step in these processes, but high performance separation techniques remain challenging.
The existing methods for separating amino acid include: technical crystallization, electrodialysis, reactive extraction, flotation complex extraction, polyelectrolyte membrane nanofiltration, ionic liquid adsorption and other recovery technologies. However, the above method consumes a large amount of energy and is difficult to operate practically. The adsorption of amino acids by using porous solid materials (such as MOF, ion exchange resins, zeolites) seems to be a promising research method, the MOF has a very low utilization rate although the pore channel structure is rich, the specific surface area is large, the pore volume is large, and the calculation shows that the unit pore volume can only absorb 0.46mmol/cm3Amino acids, for polyporeMaterial is a waste of voids. Therefore, it is urgently needed to develop a material with high pore utilization rate to realize high-efficiency extraction of amino acid.
The porous liquid is a novel liquid porous material (Nature 2015,527,216) with fluidity, the molecular cage is a main source of intrinsic pores of the porous liquid, the organic molecular cage is dissolved in the ionic liquid with larger site resistance, and the rapid preparation of the porous liquid is realized.
At present, most of the applications of porous liquids only reside in the storage and separation of gases, but only one example is that the porous liquids modified by cyclodextrin are used for chiral separation of nucleosides by xiadao et al (ACS appl. Considering the structural characteristics and the fluidity of the porous liquid, the extraction, the separation and the identification of the porous liquid in the biological field can be expected to have great prospect. So far, no report is found for the application of metal-organic molecular cages and ionic liquid as raw materials in the synthesis of porous liquid in the extraction of amino acid.
Disclosure of Invention
Aiming at the defects of the prior art, the first object of the invention is to provide a preparation method of hydrophobic vanadyl-organic molecular cage-based porous liquid for extracting L-tryptophan; the second purpose is to provide the hydrophobic vanadyl-organic molecular cage-based porous liquid prepared by the preparation method; the third purpose is to provide the application of the hydrophobic vanadyl-organic molecular cage-based porous liquid in extracting water for L-tryptophan. The method utilizes the negative charges of the vanadium-based cluster-based metal organic molecular cage to fully fuse the vanadium-oxygen cluster-based metal organic cage with the ionic liquid through electrostatic interaction, realizes the liquefaction of VMOPs intrinsic pores, utilizes the intrinsic pores of the VMOPs to extract L-tryptophan, and can realize the absorption of 15.92mmol/cm per unit pore volume of the VMOPs through calculation3An amino acid.
In order to solve the technical problems, the invention provides the following technical scheme:
a preparation method of hydrophobic vanadyl-organic molecular cage-based porous liquid for extracting L-tryptophan comprises the steps of dispersing vanadyl-based metal organic cages in ionic liquid through electrostatic interaction, combining anion vanadyl-based metal organic cages with cations of the ionic liquid through ion exchange, and purifying to obtain pure vanadyl-organic molecular cage-based porous liquid.
Wherein the ionic liquid is trihexyltetradecylphosphine chloride, 1-hexyl-3-methylimidazole chloride, 1-octyl-3-methylimidazole chloride or 1-decyl-3-methylimidazole chloride, and preferably trihexyltetradecylphosphine chloride.
Specifically, adding vanadium oxygen cluster-based metal organic cage powder into hydrophobic ionic liquid, performing ion exchange to enable counter cations of vanadium oxygen-organic molecular cages and anions in the ionic liquid to form ammonium chloride salts, and removing the counter cations by reducing the solubility of the ammonium chloride salts and performing crystallization separation; and (3) removing the solvent from the crystallized liquid through reduced pressure distillation to obtain pure vanadyl-organic molecular cage-based porous liquid.
As the preferable technical scheme, the size of the window of the vanadium-oxygen cluster-based metal organic cage is 0.30-2.00 nm, preferably 0.65-1.2 nm.
As a preferred technical scheme of the application, the organic cage is a regular octahedral vanadium-oxygen cluster-based coordination molecular cage (VMOP-1), an ammonia-substituted regular octahedral vanadium-oxygen cluster-based coordination molecular cage (VMOP-2), a bromine-substituted regular octahedral vanadium-oxygen cluster-based coordination molecular cage (VMOP-3), a triangular prism vanadium-oxygen cluster-based coordination molecular cage (VMOP-4), a quadrangular vanadium-oxygen cluster-based coordination molecular cage (VMOP-5), an octahedral vanadium-oxygen cluster-based coordination molecular cage (VMOP-6), a tetrahedral vanadium-oxygen cluster-based coordination molecular cage (VMOP-11), an ammonia-substituted tetrahedral vanadium-oxygen cluster-based coordination molecular cage (VMOP-12), a bromine-substituted tetrahedral vanadium-oxygen cluster-based coordination molecular cage (VMOP-13), a tetrahedral vanadium-oxygen cluster-coordination molecular cage of trimesic acid (VMOP-14), a 1,3, 5-tris (4-carboxyphenyl) benzene-type vanadium-oxygen cluster-based coordination molecular cage (VMOP-15 OP-15) ) A truncated tetrahedral V-O cluster based coordination molecular cage (VMOP-16), an ammonia-substituted truncated tetrahedral V-O cluster based coordination molecular cage (VMOP-17), a vanadium-substituted octahedral V-O cluster based coordination molecular cage (VMOP-17)-18), a thiooctahedral vanadyl coordination molecular cage (VMOP-19), 2,4, 6-tris [ (p-carboxyphenyl) amino group]-a 1,3, 5-triazine regular octahedral vanadyl coordination molecular cage (VMOP-20), a trimesic acid octahedral vanadyl coordination molecular cage (VMOP-21), a thirty octahedral vanadyl coordination molecular cage (VMOP-22), a forty tetrahedral vanadyl coordination molecular cage (VMOP-23), a fifty facial vanadyl coordination molecular cage (VMOP-24), a twenty facial vanadyl coordination molecular cage (VMOP-25), a 1, 4-naphthalenedicarboxylic acid octahedral vanadyl oxygen cluster coordination molecular cage (VMOP-26), a 2,4, 6-tris (4-carboxyphenyl) -1,3, 5-triazine octahedral vanadyl coordination molecular cage (VMOP-31), a 4,4' - (1, 2-acetylenediyl) dibenzoic acid truncated tetrahedral vanadyl coordination molecular cage (VMOP- α), bromine substituted cyclic vanadium oxygen cluster base coordination molecule cage (hydoghnut-2), methoxy substituted cyclic vanadium oxygen cluster base coordination molecule cage (hydoghnut-3), cyclic vanadium oxygen cluster base coordination molecule cage (hydoghnut-1) and homologous series of ammonia substituted cyclic vanadium oxygen cluster base coordination molecule cage (hydogughnout-NH)2) Hydroxyl-substituted vanadyl coordination molecules (hydoughughmut-OH) and the like; preferably, the compound is Hydoughut-2, Hydoughut-3, Hydoughut-OH or VMOP-16, and more preferably, Hydoughut-OH.
Wherein, the synthesis methods of hydoughughmut-NH 2 and hydoughughmut-OH are the same as those of hydoughughmut-2, hydoughmut-3 and hydoughughmut-1, only the ligands are different, and the synthesis methods are not innovated.
As a preferred technical scheme of the application, the ionic liquid is trihexyltetradecylphosphine chloride, 1-hexyl-3-methylimidazole chloride, 1-octyl-3-methylimidazole chloride or 1-decyl-3-methylimidazole chloride, and trihexyltetradecylphosphine chloride is preferred.
Preferably, the molar ratio of the ionic liquid to the organic cage is 1: 100.
Preferably, the preparation of the vanadyl-organic molecular cage-based porous liquid comprises the following specific steps: respectively weighing ionic liquid and an organic cage, adding the ionic liquid into a glass bottle, heating and stirring, and heating to 60 ℃; slowly adding the weighed organic cage into the ionic liquid, continuously stirring until the organic cage is uniformly mixed, and cooling to room temperature; and adding acetonitrile into the porous liquid, stirring, centrifuging, removing ammonium chloride salt, and performing rotary evaporation on the residual liquid at 50 ℃ for 30min to finally obtain the porous liquid.
The invention also protects the hydrophobic vanadyl-organic molecular cage-based porous liquid prepared by the preparation method.
The invention also protects the application of the hydrophobic vanadyl-organic molecular cage-based porous liquid in the extraction of L-tryptophan.
Specifically, the method comprises the following steps: adding the porous liquid into an amino acid aqueous solution at the temperature of 25-60 ℃ and the stirring speed of 100-1200 rpm, adjusting the pH, stirring for 0.5-48 h at the temperature of 25-80 ℃, and fully mixing; and centrifuging, layering and filtering the mixed solution to obtain an extracted L-tryptophan aqueous solution, and analyzing the amino acid concentration in the aqueous phase before and after extraction by HPLC.
As a preferable technical scheme, when the dosage of the hydrophobic vanadyl-organic molecular cage-based porous liquid used as an extracting agent is 0.00001-5 g, the dosage of an L-tryptophan aqueous solution is 1-5 ml.
More preferably, when the dosage of the hydrophobic vanadyl-organic molecular cage-based porous liquid used as an extracting agent is 0.01-5 g, the dosage of the L-tryptophan aqueous solution is 2-3 mL.
Wherein the concentration of the extracted L-tryptophan is 0.00001-0.05M, preferably 0.01-0.05M.
As a preferred technical scheme of the application, the pH of the extracted L-tryptophan aqueous solution is 2-10, preferably 3-9, and more preferably 6-7.
As the preferable technical scheme, the extraction temperature is 25-80 ℃, preferably 25-40 ℃, and more preferably 30-40 ℃.
As a preferred technical scheme of the application, the extraction time is 0.5-48 h, preferably 0.5-12 h, and more preferably 8-12 h.
The preparation mechanism of the hydrophobic vanadyl-organic molecular cage-based porous liquid is as follows: the pore diameter of the vanadium-based metal organic cage is 0.65-1.20 nm, and the vanadium-based metal organic cage is dispersed in ionic liquid with the molecular diameter of 1.9-2.5 nm to ensure the retention of intrinsic pores of the vanadium-based metal organic cage; the retention of the intrinsic hole provides conditions for the extraction of amino acid, and the amino acid enters the cavity of the cage, so that the extraction of L-tryptophan is realized.
Advantageous effects
The invention provides hydrophobic vanadyl-organic molecular cage-based porous liquid, a preparation method thereof and application thereof in extraction of L-tryptophan, wherein the hydrophobic vanadyl-organic molecular cage-based porous liquid has the characteristics of cage pore channel diversification, pore diameter controllability and the like, the extraction of the L-tryptophan in water can be realized by adjusting the pore channel structure of a vanadyl-organic molecular cage, and the unit pore volume absorption of VMOPs (VMOPs) can be realized by calculation at 15.92mmol/cm3An amino acid.
The method has mild operation conditions and simple flow, and is an efficient and green L-tryptophan separation method.
Drawings
FIG. 1 is a FT-IR spectrum of example 1;
FIG. 2 is a standard curve for L-tryptophan;
FIG. 3 is an HPLC chromatogram of an L-tryptophan solution;
the device name: agilent high performance liquid chromatography 1260; the chromatographic conditions are as follows: chromatography column C18(5 μm, 250 mm. times.4.6 mm); the column temperature is 30 ℃; the sample volume is 20 mu L; the flow rate is 1 mL/min; a DAD detector with a detection wavelength of 280 nm; the mobile phase is 8mmol/L potassium dihydrogen phosphate solution methanol (9: 1). Taking peak area (mAU) as ordinate, R is good in linear relation within the range of 0-1.5 mg/mL20.9985, and 31122X +655.25, and can be effectively used for the quantitative analysis of L-tryptophan in water.
Detailed Description
The present invention is further illustrated by the following examples, in which experimental procedures not specifically identified are generally performed by means well known in the art.
Example 1
Preparing vanadium oxide-organic molecular cage-based porous liquid: 1g of trihexyltetradecylphosphine chloride and 59.6mg of hydaughnut-OH (hydaughnut-OH: trihexyltetradecylphosphine chloride in a molar ratio of 1:100) were weighed, respectively, and trihexyltetradecylphosphine chloride was added to a glass bottle, heated with stirring, and heated to 60 ℃. Slowly adding the weighed hydaughnut-OH into trihexyltetradecylphosphine chloride, continuously stirring until the mixture is uniformly mixed, and cooling to room temperature. And adding 20ml of acetonitrile into the porous liquid, stirring, centrifuging, removing ammonium chloride salt, and performing rotary evaporation on the residual liquid at 50 ℃ for 30min to finally obtain the porous liquid, namely hydoughughcut-OH-IL.
Adding 0.1g of hydoghnut-OH-IL into a 20ml glass bottle, adding 2ml of L-tryptophan aqueous solution (pH is 6) with different concentrations, keeping the temperature at 40 ℃, stirring for 12h, centrifuging, separating and filtering to obtain an amino acid aqueous solution with a clarified lower layer, analyzing by HPLC, measuring the concentration change by an external standard method, and calculating the extraction efficiency of hydoghnut-OH-IL, wherein the specific data are shown in Table 1.
TABLE 1
Figure GDA0003464186810000061
FIG. 1 is an infrared test conducted after extraction of hydoughhnut-OH-IL, found at 3400cm-1A vibration peak of N-H on indole appears, which indicates that PL-HD-OH successfully extracts L-tryptophan.
Example 2
Preparing vanadium oxide-organic molecular cage-based porous liquid: 1g of trihexyltetradecylphosphine chloride and 59.6mg of hydaughnut-OH (hydaughnut-OH: trihexyltetradecylphosphine chloride in a molar ratio of 1:100) were weighed, respectively, and trihexyltetradecylphosphine chloride was added to a glass bottle, heated with stirring, and heated to 60 ℃. Slowly adding the weighed hydaughnut-OH into trihexyltetradecylphosphine chloride, continuously stirring until the mixture is uniformly mixed, and cooling to room temperature. And adding 20ml of acetonitrile into the porous liquid, stirring, centrifuging, removing ammonium chloride salt, and performing rotary evaporation on the residual liquid at 50 ℃ for 30min to finally obtain the porous liquid, namely hydoughughcut-OH-IL.
Adding 0.1g of hydoghnut-OH-IL into a 20ml glass bottle, adding 2ml of L-tryptophan aqueous solution with different concentrations (pH is adjusted to be 9), keeping the temperature at 40 ℃, stirring for 12h, centrifuging, separating and filtering to obtain an amino acid aqueous solution with a clarified lower layer, analyzing by HPLC, measuring the concentration change by an external standard method, and calculating the extraction efficiency of hydoghnut-OH-IL, wherein the specific data are shown in Table 2.
TABLE 2
Figure GDA0003464186810000062
Example 3
Preparing vanadium oxide-organic molecular cage-based porous liquid: 1g of trihexyltetradecylphosphine chloride and 59.6mg of hydaughnut-OH (hydaughnut-OH: trihexyltetradecylphosphine chloride in a molar ratio of 1:100) were weighed, respectively, and trihexyltetradecylphosphine chloride was added to a glass bottle, heated with stirring, and heated to 60 ℃. Slowly adding the weighed hydaughnut-OH into trihexyltetradecylphosphine chloride, continuously stirring until the mixture is uniformly mixed, and cooling to room temperature. And adding 20ml of acetonitrile into the porous liquid, stirring, centrifuging, removing ammonium chloride salt, and performing rotary evaporation on the residual liquid at 50 ℃ for 30min to finally obtain the porous liquid, namely hydoughughcut-OH-IL.
Adding 0.1g of hydoghnut-OH-IL into a 20ml glass bottle, adding 2ml of L-tryptophan aqueous solution with different concentrations (pH is adjusted to be 3), keeping the temperature at 40 ℃, stirring for 12h, centrifuging, separating and filtering to obtain an amino acid aqueous solution with a clarified lower layer, analyzing by HPLC, measuring the concentration change by an external standard method, and calculating the extraction efficiency of hydoghnut-OH-IL, wherein the specific data are shown in Table 3.
TABLE 3
Figure GDA0003464186810000071
Example 4
Preparing vanadium oxide-organic molecular cage-based porous liquid: 1g of trihexyltetradecylphosphine chloride and 87.1mg of VMOP-16 (VMOP-16: trihexyltetradecylphosphine chloride molar ratio 1:100) were weighed, respectively, and trihexyltetradecylphosphine chloride was added to a glass bottle, heated with stirring, and heated to 60 ℃. And slowly adding the weighed VMOP-16 into the trihexyltetradecyl phosphine chloride, continuously stirring until the mixture is uniformly mixed, and cooling to room temperature. Adding 20ml acetonitrile into the porous liquid, stirring, centrifuging, removing ammonium chloride salt, and rotary evaporating the residual liquid at 50 ℃ for 30min to obtain the porous liquid named VMOP-16-IL.
Adding 0.1g of VMOP-16-IL into a 20ml glass bottle, adding 2ml of L-tryptophan aqueous solution (pH is 6) with different concentrations, stirring for 12h at the constant temperature of 40 ℃, centrifuging, separating and filtering to obtain an amino acid aqueous solution with a clarified lower layer, analyzing by HPLC, measuring the concentration change by an external standard method, and calculating the extraction efficiency of VMOP-16-IL, wherein the specific data are shown in Table 4.
TABLE 4
Figure GDA0003464186810000081
Example 5
Preparing vanadium oxide-organic molecular cage-based porous liquid: 1g of trihexyltetradecylphosphine chloride and 87.1mg of VMOP-16 (VMOP-16: trihexyltetradecylphosphine chloride molar ratio 1:100) were weighed, respectively, and trihexyltetradecylphosphine chloride was added to a glass bottle, heated with stirring, and heated to 60 ℃. And slowly adding the weighed VMOP-16 into the trihexyltetradecyl phosphine chloride, continuously stirring until the mixture is uniformly mixed, and cooling to room temperature. Adding 20ml acetonitrile into the porous liquid, stirring, centrifuging, removing ammonium chloride salt, and rotary evaporating the residual liquid at 50 ℃ for 30min to obtain the porous liquid named VMOP-16-IL.
Adding 0.1g of VMOP-16-IL into a 20ml glass bottle, adding 2ml of L-tryptophan aqueous solution with different concentrations (pH is adjusted to 9), keeping the temperature at 40 ℃, stirring for 12h, centrifuging, separating and filtering to obtain an amino acid aqueous solution with a clarified lower layer, analyzing by HPLC, measuring the concentration change by an external standard method, and calculating the extraction efficiency of VMOP-16-IL, wherein the specific data are shown in Table 5.
TABLE 5
Figure GDA0003464186810000082
Example 6
Preparing vanadium oxide-organic molecular cage-based porous liquid: 1g of trihexyltetradecylphosphine chloride and 87.1mg of VMOP-16 (VMOP-16: trihexyltetradecylphosphine chloride molar ratio 1:100) were weighed, respectively, and trihexyltetradecylphosphine chloride was added to a glass bottle, heated with stirring, and heated to 60 ℃. And slowly adding the weighed VMOP-16 into the trihexyltetradecyl phosphine chloride, continuously stirring until the mixture is uniformly mixed, and cooling to room temperature. Adding 20ml acetonitrile into the porous liquid, stirring, centrifuging, removing ammonium chloride salt, and rotary evaporating the residual liquid at 50 ℃ for 30min to obtain the porous liquid named VMOP-16-IL.
Adding 0.1g of VMOP-16-IL into a 20ml glass bottle, adding 2ml of L-tryptophan aqueous solution with different concentrations (pH is adjusted to be 3), keeping the temperature at 40 ℃, stirring for 12h, centrifuging, separating and filtering to obtain an amino acid aqueous solution with a clarified lower layer, analyzing by HPLC, measuring the concentration change by an external standard method, and calculating the extraction efficiency of the VMOP-16-IL, wherein the specific data are shown in Table 6.
TABLE 6
Figure GDA0003464186810000091
Example 7
Preparing vanadium oxide-organic molecular cage-based porous liquid: 1g of trihexyltetradecylphosphine chloride and 94.9mg of VMOP-12 (VMOP-12: trihexyltetradecylphosphine molar ratio 1:100) were weighed, respectively, and trihexyltetradecylphosphine chloride was added to a glass bottle, heated with stirring, and heated to 60 ℃. And slowly adding the weighed VMOP-12 into trihexyltetradecyl phosphine chloride, continuously stirring until the mixture is uniformly mixed, and cooling to room temperature. Adding 20ml acetonitrile into the porous liquid, stirring, centrifuging, removing ammonium chloride salt, and rotary evaporating the residual liquid at 50 ℃ for 30min to obtain the porous liquid named VMOP-12-IL.
0.1g of VMOP-12-IL is added into a 20ml glass bottle, 2ml of L-tryptophan aqueous solution (pH is 6) with different concentrations is added, the temperature is controlled at 40 ℃, the mixture is stirred for 12 hours, and the amino acid aqueous solution with a clear lower layer is obtained through centrifugation, separation and filtration, the amino acid aqueous solution is analyzed through HPLC, the concentration change is measured through an external standard method, and the extraction efficiency of the VMOP-12-IL is calculated, and the specific data are shown in Table 6.
TABLE 7
Figure GDA0003464186810000092
Figure GDA0003464186810000101
Example 8
Preparing vanadium oxide-organic molecular cage-based porous liquid: 1g of trihexyltetradecylphosphine chloride and 94.9mg of VMOP-12 (VMOP-12: trihexyltetradecylphosphine chloride molar ratio 1:100) were weighed, respectively, and trihexyltetradecylphosphine chloride was added to a glass bottle, heated with stirring, and heated to 60 ℃. And slowly adding the weighed VMOP-12 into trihexyltetradecyl phosphine chloride, continuously stirring until the mixture is uniformly mixed, and cooling to room temperature. Adding 20ml acetonitrile into the porous liquid, stirring, centrifuging, removing ammonium chloride salt, and rotary evaporating the residual liquid at 50 ℃ for 30min to obtain the porous liquid named VMOP-12-IL.
Adding 0.1g of VMOP-12-IL into a 20ml glass bottle, adding 2ml of L-tryptophan aqueous solution with different concentrations (pH is adjusted to 9), keeping the temperature at 40 ℃, stirring for 12h, centrifuging, separating and filtering to obtain an amino acid aqueous solution with a clarified lower layer, analyzing by HPLC, measuring the concentration change by an external standard method, and calculating the extraction efficiency of VMOP-12-IL, wherein the specific data are shown in Table 8.
TABLE 8
Figure GDA0003464186810000102
Example 9
Preparing vanadium oxide-organic molecular cage-based porous liquid: 1g of trihexyltetradecylphosphine chloride and 94.9mg of VMOP-12 (molar ratio 1:100) were weighed out, respectively, and trihexyltetradecylphosphine chloride was added to a glass bottle, heated with stirring, and heated to 60 ℃. And slowly adding the weighed VMOP-12 into trihexyltetradecyl phosphine chloride, continuously stirring until the mixture is uniformly mixed, and cooling to room temperature. Adding 20ml acetonitrile into the porous liquid, stirring, centrifuging, removing ammonium chloride salt, and rotary evaporating the residual liquid at 50 ℃ for 30min to obtain the porous liquid named VMOP-12-IL.
0.1g VMOP-12-IL (VMOP-12: trihexyltetradecylphosphorus chloride molar ratio 1:100) is added into a 20ml glass bottle, 2ml L-tryptophan aqueous solutions with different concentrations are added (pH is adjusted to 3), stirring is carried out for 12h at constant temperature controlled at 40 ℃, centrifugation, separation and filtration are carried out to obtain an amino acid aqueous solution with a clear lower layer, the amino acid aqueous solution is analyzed by HPLC, the concentration change is measured by an external standard method, and the extraction efficiency of the VMOP-12-IL is calculated, and the specific data are shown in Table 9.
TABLE 9
Figure GDA0003464186810000111
Comparative example 1
Adding 0.1g of IL (trihexyltetradecylphosphonium chloride) into a 20ml glass bottle, adding 2ml of L-tryptophan aqueous solution (pH is 6) with different concentrations, stirring at the constant temperature of 40 ℃ for 12 hours, centrifuging, separating and filtering to obtain an amino acid aqueous solution with a clarified lower layer, analyzing by HPLC, measuring the concentration change by an external standard method, and calculating the extraction efficiency of the IL, wherein the specific data are shown in Table 10.
Watch 10
Figure GDA0003464186810000112
Comparative example 2
Adding 0.1g of IL (trihexyltetradecylphosphonium chloride) into a 20ml glass bottle, adding 2ml of L-tryptophan aqueous solution with different concentrations (pH is adjusted to 9), keeping the temperature at 40 ℃, stirring for 12 hours, centrifuging, separating and filtering to obtain an amino acid aqueous solution with a clarified lower layer, analyzing by HPLC, measuring the concentration change by an external standard method, and calculating the extraction efficiency of the IL, wherein the specific data are shown in Table 11.
TABLE 11
Figure GDA0003464186810000121
Comparative example 3
Adding 0.1g of IL (trihexyltetradecylphosphonium chloride) into a 20ml glass bottle, adding 2ml of L-tryptophan aqueous solution with different concentrations (pH is adjusted to 3), keeping the temperature at 40 ℃, stirring for 12h, centrifuging, separating and filtering to obtain an amino acid aqueous solution with a clarified lower layer, analyzing by HPLC, measuring the concentration change by an external standard method, and calculating the extraction efficiency of the IL, wherein the specific data are shown in Table 12.
TABLE 12
Figure GDA0003464186810000122
Comparative example 4
Preparing vanadium oxide-organic molecular cage-based porous liquid: separately, 1g of 1-hexyl-3-methylimidazolium chloride and 152.6mg of hydoughughmut-OH (hydoughughmut-OH: 1-hexyl-3-methylimidazolium chloride in a molar ratio of 1:100) were weighed, trihexyltetradecylphosphine chloride was added to a glass bottle, heated with stirring and heated to 60 ℃. Slowly adding the weighed hydaughnut-OH into 1-hexyl-3-methylimidazolium chloride, continuously stirring until the mixture is uniformly mixed, and cooling to room temperature. Adding 20ml acetonitrile into the porous liquid, stirring, centrifuging, removing ammonium chloride salt, and rotary evaporating the residual liquid at 50 deg.C for 30min to obtain porous liquid named as hydoughughcut-OH-C10H19ClN2。
0.1g of hydoughughcut-OH-C10H19ClN2Adding into a 20ml glass bottle, adding 2ml L-tryptophan water solution with different concentrations (pH is adjusted to 6), stirring at constant temperature of 40 deg.C for 12h, centrifuging, separating, filtering to obtain lower clear amino acid water solution, analyzing by HPLC, measuring concentration change by external standard method, and calculating to obtain hyoughcut-OH-C10H19ClN2The specific data of the extraction efficiency of (A) are shown in Table 13.
Watch 13
Figure GDA0003464186810000131
Comparative example 5
Preparing vanadium oxide-organic molecular cage-based porous liquid: 1g of trihexyltetradecylphosphine chloride and 59.6mg of hydaughnut-OH (hydaughnut-OH: trihexyltetradecylphosphine chloride in a molar ratio of 1:100) were weighed, respectively, and trihexyltetradecylphosphine chloride was added to a glass bottle, heated with stirring, and heated to 60 ℃. Slowly adding the weighed hydaughnut-OH into trihexyltetradecylphosphine chloride, continuously stirring until the mixture is uniformly mixed, and cooling to room temperature. And adding 20ml of acetonitrile into the porous liquid, stirring, centrifuging, removing ammonium chloride salt, and performing rotary evaporation on the residual liquid at 50 ℃ for 30min to finally obtain the porous liquid, namely hydoughughcut-OH-IL.
Adding 5g of hydoghnut-OH-IL into a 20ml glass bottle, adding 5ml of 0.05M L-tryptophan aqueous solution (pH is adjusted to be 10), keeping the temperature at 80 ℃, stirring for 0.5h, centrifuging, separating and filtering to obtain a lower-layer clarified amino acid aqueous solution, analyzing by HPLC (high performance liquid chromatography), measuring the concentration change by an external standard method, and calculating the extraction efficiency of hydoghnut-OH-IL to be 5.98%.
Comparative example 6
Preparing vanadium oxide-organic molecular cage-based porous liquid: 1g of trihexyltetradecylphosphine chloride and 94.9mg of VMOP-12 (VMOP-12: trihexyltetradecylphosphine chloride molar ratio 1:100) were weighed, respectively, and trihexyltetradecylphosphine chloride was added to a glass bottle, heated with stirring, and heated to 60 ℃. And slowly adding the weighed VMOP-12 into trihexyltetradecyl phosphine chloride, continuously stirring until the mixture is uniformly mixed, and cooling to room temperature. Adding 20ml acetonitrile into the porous liquid, stirring, centrifuging, removing ammonium chloride salt, and rotary evaporating the residual liquid at 50 ℃ for 30min to obtain the porous liquid named VMOP-12-IL.
0.01g VMOP-12-IL is added into a 20ml glass bottle, 1ml L-tryptophan aqueous solution with the concentration of 0.00001M (the pH value is adjusted to 2) is added, the mixture is stirred for 0.5h at the constant temperature of 25 ℃, the lower layer clarified amino acid aqueous solution is obtained by centrifugation, separation and filtration, the amino acid aqueous solution is analyzed by HPLC, the concentration change is measured by an external standard method, and the extraction efficiency of the VMOP-12-IL is calculated to be 0.05 percent.
The protection of the present invention is not limited to the above embodiments. Variations and advantages that may occur to those skilled in the art may be incorporated into the invention without departing from the spirit and scope of the inventive concept and the scope of the appended claims is intended to be protected.

Claims (18)

1. A preparation method of hydrophobic vanadyl-organic molecular cage-based porous liquid for extracting L-tryptophan is characterized in that vanadyl metallo-organic cage powder is added into hydrophobic ionic liquid, counter cations in a cage and anions in the ionic liquid form ammonium chloride salt through ion exchange, and the ammonium chloride salt enters a crystallization area through reducing the solubility of the ammonium chloride salt to remove the counter cations; obtaining pure vanadyl-organic molecular cage-based porous liquid; wherein the ionic liquid is trihexyltetradecyl phosphine chloride or 1-hexyl-3-methylimidazolium chloride; the vanadium-oxygen cluster-based metal organic cage is Hydoughmut-OH, VMOP-16 or VMOP-12.
2. The method for preparing the hydrophobic vanadyl-organic molecular cage-based porous liquid according to claim 1, wherein the ionic liquid is trihexyltetradecylphosphine chloride.
3. The method for preparing the hydrophobic vanadyl-organic molecular cage-based porous liquid as claimed in claim 1, wherein the size of the window of the vanadyl metal-organic cage is 0.30-2.00 nm.
4. The method for preparing the hydrophobic vanadyl-organic molecular cage-based porous liquid as claimed in claim 3, wherein the size of the window of the vanadyl metal-organic cage is 0.65-1.2 nm.
5. The method for preparing the hydrophobic vanadyl-organic molecular caged porous liquid of claim 1, wherein the vanadyl-based metal-organic cage is a hydroxyl-substituted vanadyl coordination molecular cage.
6. A hydrophobic vanadyl-organic molecular cage-based porous liquid prepared by the preparation method of any one of claims 1 to 5.
7. Use of the hydrophobic vanadyl-organic molecule cage-based porous liquid of claim 6 for the extraction of L-tryptophan.
8. The application of claim 7, comprising the following specific steps: adding the porous liquid into an L-tryptophan aqueous solution at the temperature of 25-60 ℃ and the stirring speed of 100-1200 rpm, adjusting the pH, stirring for 0.5-48 h at the temperature of 25-80 ℃, and fully mixing; and centrifuging, layering and filtering the mixed solution to obtain the extracted L-tryptophan aqueous solution.
9. Use according to claim 8, wherein the extraction temperature is 25-80 ℃.
10. Use according to claim 9, wherein the extraction temperature is 25-40 ℃.
11. Use according to claim 10, wherein the extraction temperature is 30-40 ℃.
12. The use according to claim 8, wherein the extraction time is 0.5 to 48 hours.
13. The use according to claim 12, wherein the extraction time is 0.5 to 12 hours.
14. Use according to claim 13, wherein the extraction time is 8 to 12 hours.
15. Use according to any one of claims 8 to 14, wherein the pH is 2 to 10.
16. Use according to claim 15, wherein the pH is 6 to 7.
17. The use of claim 8, wherein the amount of the hydrophobic vanadyl-organic molecular cage-based porous liquid used as an extractant is 0.00001-5 g, and the amount of the aqueous solution of L-tryptophan used before extraction is 1-5 ml.
18. The use of claim 17, wherein the amount of the hydrophobic vanadyl-organic molecular cage-based porous liquid used as an extractant is 0.01-5 g, and the amount of the aqueous solution of L-tryptophan used before extraction is 2-3 ml.
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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109647343A (en) * 2018-12-28 2019-04-19 南京工业大学 More activated adoption site metal-organic framework composite materials and its preparation and application
CN107754855B (en) * 2017-11-12 2020-06-12 闽江学院 Preparation and application of functionalized vanadium-doped heteropoly acid ionic liquid
CN107626201B (en) * 2017-09-19 2020-09-04 北京理工大学 Chemical warfare agent simulant catalytically degraded by amphiphilic multi-niobium oxygen cluster emulsion

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102267933B (en) * 2011-05-03 2013-06-05 大连大学 Tryptophan extraction process with aqueous two-phase system based on amide functional ionic liquid
WO2016045754A1 (en) * 2014-09-26 2016-03-31 Mebius D.O.O Polyoxometalate salts, proton exchange membranes and precursors, membrane-electrode assemblies, fuel cells and methods
CN108192109A (en) * 2018-02-12 2018-06-22 华中科技大学 A kind of method of ionic liquid enhancing metal-organic framework materials stability
CN111097527A (en) * 2018-10-25 2020-05-05 中国石油化工股份有限公司 Supported heteropolyacid catalyst, preparation method and application
KR102203784B1 (en) * 2019-02-08 2021-01-14 숙명여자대학교산학협력단 Porous liquids composition using metal-organic polyhedra and method of preparation of the same
CN110256355A (en) * 2019-06-06 2019-09-20 大连理工大学 1- butyl -3- methylimidazole three (hexafluoroacetylacetone) closes cobalt (II) magnetic ionic liquids, preparation method and application
CN111589422B (en) * 2020-05-26 2023-02-28 南京工业大学 Preparation method and application of metal organic framework-ionic liquid composite material
AU2020101523A4 (en) * 2020-07-28 2020-09-03 Ningbo Center For Disease Control And Prevention The Preparation Method of an Ionic Liquid-MOFs-based Aldehyde and Ketone Adsorption Tube and its Application
CN112138506A (en) * 2020-09-19 2020-12-29 西北工业大学 Low-viscosity III-type porous liquid and preparation method thereof
CN112624904B (en) * 2020-12-21 2022-09-23 山东科技大学 Method for separating difluoroethanol and water by taking porous liquid as extracting agent

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107626201B (en) * 2017-09-19 2020-09-04 北京理工大学 Chemical warfare agent simulant catalytically degraded by amphiphilic multi-niobium oxygen cluster emulsion
CN107754855B (en) * 2017-11-12 2020-06-12 闽江学院 Preparation and application of functionalized vanadium-doped heteropoly acid ionic liquid
CN109647343A (en) * 2018-12-28 2019-04-19 南京工业大学 More activated adoption site metal-organic framework composite materials and its preparation and application

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