CN109942828A - A kind of amino-acid functional Zn-MOFs functional material and the preparation method and application thereof - Google Patents
A kind of amino-acid functional Zn-MOFs functional material and the preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a kind of amino-acid functional Zn-MOFs functional materials and the preparation method and application thereof.Triethylamine (TEA) is added in 2-methylimidazole solution, then zinc nitrate solution is added dropwise to dropwise in above-mentioned solution, is then centrifuged for, activates, obtain the MOFs material with defective hole.Defect MOFs material ultrasonic disperse is added dropwise in drawbacks described above MOFs dispersion liquid in methanol solution, then by 3- amino-1,2,4-triazole solution, is then centrifuged for, activates, obtains the Zn-MOFs material Zn-MOFs-A with defective hole and amino.In aqueous solution by the dispersion of Zn-MOFs-A material, sequentially add amino acid solution, 1- (3- dimethylamino-propyl) -3- ethyl-carbodiimide hydrochloride (EDC) solution, n-hydroxysuccinimide (NHS) solution, and a small amount of TEA is added and adjusts pH, it is then centrifuged for, activates, obtain the Zn-MOFs functional material of amino-acid functional.The material can be applied to absorption ACE and inhibit polypeptide.
Description
Technical field
The invention belongs to new function material fields, and in particular to the preparation of amino-acid functional Zn-MOFs functional material
Method and application.
Background technique
ACE inhibits polypeptide to have been a concern as the natural drug for the treatment of hypertension, and exploitation orienting enriching ACE inhibits more
The functional material of peptide also becomes the hot spot studied at present.Metal-organic framework (Metal-Organic Frameworks), referred to as
MOFs, be by metal ion and organic ligand or cluster by coordinate bond be self-assembly of with molecule inner pore it is organic-
Inorganic hybrid material.Metal organic frame (MOFs) material is a kind of emerging nano-porous materials, the ratio table with superelevation
Area (1000-4000m2/ g), regulatable nano pore and high density surface activated adoption position, peptide molecule can be carried out high
Effect absorption.
Summary of the invention
The purpose of the present invention is inhibiting polypeptide that can generate hydrogen bond with the key amino acid in ACE active site based on ACE, together
When can provide a kind of amino-acid functional Zn- with the ACE polypeptide suppression mechanism of the Zn-O tetrahedron competitive coordination in ACE again
MOFs functional material and the preparation method and application thereof.
The purpose of the present invention is achieved through the following technical solutions:
A kind of amino-acid functional Zn-MOFs functional material is three-dimensional porous reticular structure, Langmuir specific surface area
For 700~1000m2/ g, crystalline size size are 40~50nm, and crystal structure is positive 12 face of the uniform rule of form
Body structure contains amino, carboxyl and imidazole radicals functional group in crystalline framework.The material inhibits polypeptide to have preferable inhale ACE
Attached effect.
The preparation method of amino-acid functional Zn-MOFs functional material of the invention, includes the following steps:
(1) it the preparation of zinc nitrate solution: is added in the aqueous solvent of 12~16L by the zinc nitrate of 1mol, mechanical stirring makes nitre
Sour zinc sufficiently dissolves, and zinc nitrate solution can be obtained；It is denoted as solution A；
(2) preparation of 2-methylimidazole solution: 2-methylimidazole Hmin is added in the container equipped with water, according to every 1mol
2-methylimidazole Hmin be added 1.5~3L aqueous solvent configuration, mechanical stirring dissolves it sufficiently, adds 2~6mL's
Triethylamine TEA solution, obtains methylimidazole solution, is denoted as solution B；
(3) preparation of 2- amino 1,2,4- triazole solution: by 2- amino 1,2,4- triazole Atz according to the 2- of every 1mol
Amino 1,2, the proportion that the methanol solvate of 1~2L is added in 4- triazole Atz are added in the container equipped with methanol, and mechanical stirring makes it
Sufficiently dissolution, can be obtained 1,2,4- triazole solution of 2- amino, is denoted as solution C.
(4) preparation of amino acid solution: matching mixing by the aqueous solvent that 12~16L is added in the amino acid of every 1mol, mechanical
Stirring dissolves it sufficiently, and amino acid solution can be obtained, be denoted as solution D.
(5) preparation of 1- (3- dimethylamino-propyl) -3- ethyl-carbodiimide hydrochloride solution: by the 1- (3- of every 1mol
Dimethylamino-propyl) -3- ethyl-carbodiimide hydrochloride (EDC) is added the aqueous solvent of 6~8L and matches mixing, and mechanical stirring makes it
Sufficiently dissolution, can be obtained 1- (3- dimethylamino-propyl) -3- ethyl-carbodiimide hydrochloride solution；It is denoted as solution E.
(6) preparation of n-hydroxysuccinimide solution: by every 1mol n-hydroxysuccinimide (NHS) be added 6~
In the aqueous solvent of 8L, mechanical stirring dissolves it sufficiently, and n-hydroxysuccinimide solution can be obtained, and is denoted as solution F.
(7) with the preparation of defective hole MOFs material: B solution being transferred to thermostat temperature control, solution A is slowly added to dropwise
Mechanical stirring in solution B is centrifuged after reaction, activates, the MOFs material with defective hole can be obtained.
(8) step (7) material the preparation of the Zn-MOFs material with defective hole and amino: is added to the appearance that methanol is housed
In device, ultrasound is dispersed in it in methanol solution, is slowly added to solution C dropwise, and mechanical stirring is centrifuged after reaction, is living
Change, the Zn-MOFs material with defective hole and amino can be obtained, be denoted as Zn-MOFs-A.
(9) preparation of amino-acid functional Zn-MOFs functional material: Zn-MOFs-A is added in the container equipped with water, is surpassed
Sound keeps its evenly dispersed in aqueous solution, is successively slowly added to D, E, F solution, adds a certain amount of triethylamine TEA solution tune
Whole pH=8, mechanical stirring are centrifuged after reaction, activate, the Zn-MOFs functional material with amino-acid functional can be obtained.
As the further preferred of scheme, zinc nitrate in the step (7), methylimidazole Hmin, triethylamine TEA rub
You are than being 1:8:4-8, and reaction temperature is 30 DEG C, and the reaction time is for 24 hours.Further preferably, zinc nitrate, methylimidazole Hmin,
The molar ratio of triethylamine TEA is 1:8:8.
As the further preferred of scheme, the methanol of 0.2~0.6L of Zn-MOFs addition of every 1g is molten in above-mentioned steps (8)
Agent, the mass ratio of Zn-MOFs and 1,2,4- triazole (Atz) of 2- amino are 1:2-6, and reaction temperature is 50 DEG C, and the reaction time is
12~for 24 hours.Further preferably, the mass ratio of Zn-MOFs and 1,2,4- triazole (Atz) of 2- amino is 1:3.
As the further preferred of scheme, the water-soluble of 0.05-0.15L is added in the Zn-MOFs-A of every 1g in the step (9)
Agent, Zn-MOFs-A and amino acid, 1- (3- dimethylamino-propyl) -3- ethyl-carbodiimide hydrochloride (EDC), N- hydroxysuccinimidyl
The mass ratio of acid imide (NHS) be 6:1~2:5:3, reaction temperature be 30 DEG C, the reaction time be 12~for 24 hours.Further preferably,
Zn-MOFs-A and amino acid, 1- (3- dimethylamino-propyl) -3- ethyl-carbodiimide hydrochloride (EDC), N- hydroxysuccinimidyl acyl are sub-
The mass ratio of amine (NHS) is 6:2:5:3.
Mechanical stirring speed is 300~500rmp/min in the present invention.
The principle of the present invention: synthesizing defect Zn-MOFs skeleton under room temperature state, recycles mode modified after synthesizing by ammonia
Into defect Zn-MOFs skeleton, obtained material not only has high-ratio surface, and contains a large amount of ammonia for base and amino acid modification
Base and amino acid functional group's (including amino, carboxyl, phenyl ring, imidazole ring etc.), can form multidigit point synergistic sorption with peptide molecule
(hydrogen bond and Zn-O coordination), realizes the bionical identification function for inhibiting polypeptide to ACE.
After amino-acid functional Zn-MOFs functional material of the invention synthesizes at normal temperature, inhibit the spy of polypeptide to ACE
Different adsorption capacity is apparently higher than other materials, reaches 350g/L, and optimal to the adsorption capacity of WW dipeptides, is higher than 500g/L.
The present invention is, as skeleton, to utilize ammonia with superelevation specific surface and varying surface property and the regulatable MOFs of pore structure
Base acid constructs the pore structure with " class ACE active pocket " feature on Zn-MOFs skeleton.On the one hand, constructed " class ACE
The structure feature of the bionical ACE active site of active pocket " energy forms multidigit point with the peptide molecule for inhibiting function with ACE and cooperates with
Absorption (hydrogen bond and Zn-O coordination), realizes the bionical identification for inhibiting polypeptide to ACE；On the other hand, the distinctive high-ratio surface of MOFs
Polypeptide can be inhibited to generate high-adsorption-capacity ACE with the Modulatory character of high density active adsorption potential and pore structure, improve material
Orienting enriching efficiency.
Compared with prior art, the present invention is advantageous in that:
(1) method used in the present invention is normal temperature method, and reaction condition is mild, strong operability.
(2) present invention is adjustable passes through triethylamine TEA additional amount, thus it is possible to vary material pore structure size makes its micropore
Increase, improves the selection adsorption capacity that material inhibits polypeptide to different molecular weight ACE.
(3) pass through 3- amino -1,2, the change of 4- triazole Atz additional amount, thus it is possible to vary the amino amount of material surface
And then change the hydrophily of material, improve the selection adsorption capacity that material inhibits peptide molecule to different hydrophilic ACE.
(4) pass through the type and quantity of regulation amino acid amide reaction, thus it is possible to vary amino, carboxyl and the miaow of material surface
Azoles number of rings amount and then the polarity for changing material surface improve the selective absorption that material inhibits peptide molecule to opposed polarity ACE
Ability.
(5) material prepared by the present invention is applied to absorption ACE inhibition polypeptide, and adsorbance can reach 350g/L, pass through
Amino acid amide reaction, adjusts the surface nature of material, and the different types of ACE of material selective absorption is enable to inhibit polypeptide.
(6) the invention firstly uses pore structure of the TEA to Zn-MOFs to carry out adjusting in situ, recycles 3- amino -1,2,4-
Triazole ligand exchange, it is amido modified to Zn-MOFs progress, it is finally reacted using amino acid amide, ammonia is carried out to Zn-MOFs
The modification of base acid, the R base group of obtained Zn-MOFs material specific surface area and amino, amino acid with higher press down ACE
Polypeptide adsorbance with higher processed and preferable suction-operated.
Detailed description of the invention
Fig. 1 is the Zn-MOFs functional material of Zn-MOFs material and histidine, glutamic acid modification without amino acid modification
XRD diagram；
Fig. 2 is the SEM figure of the Zn-MOFs material without amino acid modification；
Fig. 3 is the SEM figure of the Zn-MOFs functional material of histidine modification；
Fig. 4 is the Zn-MOFs functional material of Zn-MOFs material and histidine, glutamic acid modification without amino acid modification
Nitrogen adsorption desorption curve；
Fig. 5 is the Zn-MOFs functional material of Zn-MOFs material and histidine, glutamic acid modification without amino acid modification
Pore size distribution curve；
The different Zn-MOFs function of the pore size that Fig. 6, which is Zn-MOFs material without amino acid modification, to be modified with histidine
It can material absorption ACE inhibition polypeptide adsorbance histogram；
Fig. 7 is Zn-MOFs material and the absorption of different degrees of amination Zn-MOFs functional material without amino acid modification
ACE inhibits polypeptide adsorbance histogram；
Fig. 8 is that the Zn-MOFs material and histidine modification without amino acid modification measure different Zn-MOFs functional material suctions
Attached ACE inhibits polypeptide adsorbance histogram；
Fig. 9 is the Zn-MOFs functional material of Zn-MOFs material and histidine, glutamic acid modification without amino acid modification
It adsorbs ACE and inhibits polypeptide adsorbance histogram.
Specific embodiment
The present invention will be further described with reference to the accompanying drawings and examples, but the scope of protection of present invention is not
It is confined to the range of embodiment statement.
Embodiment 1
A kind of preparation method of the Zn-MOFs material without amino acid modification, includes the following steps:
(4) preparation of zinc nitrate solution: 1.5000g (5mmol) zinc nitrate Zn (NO is weighed3)2·6H2O is in 100ml beaker
In, it is slowly added to 70ml water, being placed on magnetic stirring apparatus dissolves zinc nitrate sufficiently with the revolving speed mechanical stirring of 400rmp/min,
It is denoted as solution A；
(5) it the preparation of 2-methylimidazole solution: takes and claims 3.3000g (40mmol) 2-methylimidazole Hmin in 100ml beaker
In, it is slowly added to 70ml water, be placed on magnetic stirring apparatus keeps 2-methylimidazole abundant with the revolving speed mechanical stirring of 400rmp/min
Dissolution, adds 5.56ml (40mmol) triethylamine TEA solution, is denoted as solution B；
(6) with defective hole Zn-MOFs material preparation: by B solution in thermostat 30 DEG C of temperature controls, be stabilized to temperature
After 30 DEG C, solution A is added dropwise in solution B, is persistently stirred for 24 hours with the revolving speed of 400rmp/min, is centrifuged after reaction, is used
Methanol is washed three times, every minor tick 12h, and the Zn-MOFs material with defective hole can be obtained, also referred to as in 120 DEG C of vacuum drying
Zn-MOFs material without amino acid modification.
Embodiment 2
A kind of preparation method of amino-acid functional Zn-MOFs functional material, includes the following steps:
(1) preparation of zinc nitrate solution: 1.5000g (5mmol) zinc nitrate Zn (NO is weighed3)2·6H2O is in 100ml beaker
In, it is slowly added to 70ml water, being placed on magnetic stirring apparatus dissolves zinc nitrate sufficiently with the revolving speed mechanical stirring of 400rmp/min,
It is denoted as solution A；
(2) it the preparation of 2-methylimidazole solution: takes and claims 3.3000g (40mmol) 2-methylimidazole Hmin in 100ml beaker
In, it is slowly added to 70ml water, be placed on magnetic stirring apparatus keeps 2-methylimidazole abundant with the revolving speed mechanical stirring of 400rmp/min
Dissolution, adds 5.56ml (40mmol) triethylamine TEA solution, is denoted as solution B；
(3) preparation of 2- amino 1,2,4- triazole solution: 2.3400g (27.84mmol) 2- amino 1,2,4- tri- is weighed
Nitrogen azoles (Atz) is slowly added to 40ml methanol in 50ml beaker, is placed in mechanical with the revolving speed of 400rmp/min on magnetic stirring apparatus
Stirring dissolves 1,2,4- triazole of 2- amino sufficiently, is denoted as solution C.
(4) preparation of histidine solution: 0.2040g (1.32mmol) histidine is weighed in 50ml beaker, is slowly added to
20ml water, being placed on magnetic stirring apparatus dissolves histidine sufficiently with the revolving speed mechanical stirring of 400rmp/min, is denoted as solution D.
(5) preparation of 1- (3- dimethylamino-propyl) -3- ethyl-carbodiimide hydrochloride solution: 1- (3- diformazan ammonia is weighed
Base propyl) -3- ethyl-carbodiimide hydrochloride (EDC) 0.5040g (2.64mmol) in 50ml beaker, is slowly added to 20ml
Water, being placed on magnetic stirring apparatus dissolves histidine sufficiently with the revolving speed mechanical stirring of 400rmp/min, is denoted as solution E.
(6) preparation of n-hydroxysuccinimide solution: n-hydroxysuccinimide (NHS) 0.3000g is weighed
(2.64mmol) is slowly added to 20ml water in 50ml beaker, is placed in mechanical with the revolving speed of 400rmp/min on magnetic stirring apparatus
Stirring dissolves histidine sufficiently, is denoted as solution F.
(7) with defective hole Zn-MOFs material preparation: by B solution in thermostat 30 DEG C of temperature controls, be stabilized to temperature
After 30 DEG C, solution A is added dropwise in solution B, is persistently stirred for 24 hours with the revolving speed of 400rmp/min, is centrifuged after reaction, is used
Methanol is washed three times, every minor tick 12h, and the Zn-MOFs material with defective hole can be obtained in 120 DEG C of vacuum drying.
(8) preparation of the Zn-MOFs material with defective hole and amino: 0.8000g step (7) material is weighed in 500ml
In round-bottomed flask, 240ml methanol solution is added, ultrasonic 30min is dispersed in it in methanol solution, then burns round bottom
Bottle in 50 DEG C of thermostats temperature control, solution C is added dropwise, is persistently stirred for 24 hours with the revolving speed of 400rmp/min, after reaction from
The heart is washed three times with methanol, every minor tick 12h, and the Zn-MOFs material with defective hole and amino can be obtained in 70 DEG C of vacuum drying
Material, is denoted as Zn-MOFs-A.
(9) preparation of amino-acid functional Zn-MOFs functional material: Zn-MOFs-A 0.6000g is weighed in 250ml round bottom
In flask, 60ml aqueous solution is added, ultrasonic 30min keeps Zn-MOFs-A evenly dispersed in aqueous solution, then by round-bottomed flask
The temperature control in 30 DEG C of thermostats is successively slowly added to D, E, F solution, and the triethylamine TEA solution that 360 μ L are added adjusts pH=8,
It is persistently stirred for 24 hours with the revolving speed of 400rmp/min, is centrifuged after reaction, is washed with water three times, every minor tick 12h, 70 DEG C of vacuum
It is dry, the Zn-MOFs functional material with amino-acid functional can be obtained.
Embodiment 3
A kind of preparation method of amino-acid functional Zn-MOFs functional material, includes the following steps:
(1) preparation of zinc nitrate solution: 1.5000g (5mmol) zinc nitrate Zn (NO is weighed3)2·6H2O is in 100ml beaker
In, it is slowly added to 70ml water, being placed on magnetic stirring apparatus dissolves zinc nitrate sufficiently with the revolving speed mechanical stirring of 400rmp/min,
It is denoted as solution A；
(2) it the preparation of 2-methylimidazole solution: takes and claims 3.3000g (40mmol) 2-methylimidazole Hmin in 100ml beaker
In, it is slowly added to 70ml water, be placed on magnetic stirring apparatus keeps 2-methylimidazole abundant with the revolving speed mechanical stirring of 400rmp/min
Dissolution, adds 5.56ml (40mmol) triethylamine TEA solution, is denoted as solution B；
(3) preparation of 2- amino 1,2,4- triazole solution: 2.3400g (27.84mmol) 2- amino 1,2,4- tri- is weighed
Nitrogen azoles (Atz) is slowly added to 40ml methanol in 50ml beaker, is placed in mechanical with the revolving speed of 400rmp/min on magnetic stirring apparatus
Stirring dissolves 1,2,4- triazole of 2- amino sufficiently, is denoted as solution C.
(4) preparation of glutamic acid solution: 0.1940g (1.32mmol) histidine is weighed in 50ml beaker, is slowly added to
20ml water, being placed on magnetic stirring apparatus dissolves histidine sufficiently with the revolving speed mechanical stirring of 400rmp/min, is denoted as solution D.
(5) preparation of 1- (3- dimethylamino-propyl) -3- ethyl-carbodiimide hydrochloride solution: 1- (3- diformazan ammonia is weighed
Base propyl) -3- ethyl-carbodiimide hydrochloride (EDC) 0.5040g (2.64mmol) in 50ml beaker, is slowly added to 20ml
Water, being placed on magnetic stirring apparatus dissolves histidine sufficiently with the revolving speed mechanical stirring of 400rmp/min, is denoted as solution E.
(6) preparation of n-hydroxysuccinimide solution: n-hydroxysuccinimide (NHS) 0.3000g is weighed
(2.64mmol) is slowly added to 20ml water in 50ml beaker, is placed in mechanical with the revolving speed of 400rmp/min on magnetic stirring apparatus
Stirring dissolves histidine sufficiently, is denoted as solution F.
(7) with defective hole Zn-MOFs material preparation: by B solution in thermostat 30 DEG C of temperature controls, be stabilized to temperature
After 30 DEG C, solution A is added dropwise in solution B, is persistently stirred for 24 hours with the revolving speed of 400rmp/min, is centrifuged after reaction, is used
Methanol is washed three times, every minor tick 12h, and the Zn-MOFs material with defective hole can be obtained in 120 DEG C of vacuum drying.
(8) preparation of the Zn-MOFs material with defective hole and amino: 0.8000g step (7) material is weighed in 500ml
In round-bottomed flask, 240ml methanol solution is added, ultrasonic 30min is dispersed in it in methanol solution, then burns round bottom
Bottle in 50 DEG C of thermostats temperature control, solution C is added dropwise, is persistently stirred for 24 hours with the revolving speed of 400rmp/min, after reaction from
The heart is washed three times with methanol, every minor tick 12h, and MOFs (Zn) material with defective hole and amino can be obtained in 70 DEG C of vacuum drying
Material, is denoted as Zn-MOFs-A.
(9) preparation of amino-acid functional Zn-MOFs functional material: Zn-MOFs-A 0.6000g is weighed in 250ml round bottom
In flask, 60ml aqueous solution is added, ultrasonic 30min keeps Zn-MOFs-A evenly dispersed in aqueous solution, then by round-bottomed flask
The temperature control in 30 DEG C of thermostats is successively slowly added to D, E, F solution, and the triethylamine TEA solution that 450 μ L are added adjusts pH=8,
It is persistently stirred for 24 hours with the revolving speed of 400rmp/min, is centrifuged after reaction, is washed with water three times, every minor tick 12h, 70 DEG C of vacuum
It is dry, the Zn-MOFs functional material with amino-acid functional can be obtained.
Embodiment 4
A kind of preparation method of amino-acid functional Zn-MOFs functional material, includes the following steps:
(1) preparation of zinc nitrate solution: 1.5000g (5mmol) zinc nitrate Zn (NO is weighed3)2·6H2O is in 100ml beaker
In, it is slowly added to 70ml water, being placed on magnetic stirring apparatus dissolves zinc nitrate sufficiently with the revolving speed mechanical stirring of 400rmp/min,
It is denoted as solution A；
(2) it the preparation of 2-methylimidazole solution: takes and claims 3.3000g (40mmol) 2-methylimidazole Hmin in 100ml beaker
In, it is slowly added to 70ml water, be placed on magnetic stirring apparatus keeps 2-methylimidazole abundant with the revolving speed mechanical stirring of 400rmp/min
Dissolution, adds 2.78ml (20mmol) triethylamine TEA solution, is denoted as solution B；
(3) preparation of 2- amino 1,2,4- triazole solution: 2.3400g (27.84mmol) 2- amino 1,2,4- tri- is weighed
Nitrogen azoles (Atz) is slowly added to 40ml methanol in 50ml beaker, is placed in mechanical with the revolving speed of 400rmp/min on magnetic stirring apparatus
Stirring dissolves 1,2,4- triazole of 2- amino sufficiently, is denoted as solution C.
(4) preparation of histidine solution: 0.2040g (1.32mmol) histidine is weighed in 50ml beaker, is slowly added to
20ml water, being placed on magnetic stirring apparatus dissolves histidine sufficiently with the revolving speed mechanical stirring of 400rmp/min, is denoted as solution D.
(5) preparation of 1- (3- dimethylamino-propyl) -3- ethyl-carbodiimide hydrochloride solution: 1- (3- diformazan ammonia is weighed
Base propyl) -3- ethyl-carbodiimide hydrochloride (EDC) 0.5040g (2.64mmol) in 50ml beaker, is slowly added to 20ml
Water, being placed on magnetic stirring apparatus dissolves histidine sufficiently with the revolving speed mechanical stirring of 400rmp/min, is denoted as solution E.
(6) preparation of n-hydroxysuccinimide solution: n-hydroxysuccinimide (NHS) 0.3000g is weighed
(2.64mmol) is slowly added to 20ml water in 50ml beaker, is placed in mechanical with the revolving speed of 400rmp/min on magnetic stirring apparatus
Stirring dissolves histidine sufficiently, is denoted as solution F.
(7) with defective hole Zn-MOFs material preparation: by B solution in thermostat 30 DEG C of temperature controls, be stabilized to temperature
After 30 DEG C, solution A is added dropwise in solution B, is persistently stirred for 24 hours with the revolving speed of 400rmp/min, is centrifuged after reaction, is used
Methanol is washed three times, every minor tick 12h, and the Zn-MOFs material with defective hole can be obtained in 120 DEG C of vacuum drying.
(8) preparation of the Zn-MOFs material with defective hole and amino: 0.8000g step (7) material is weighed in 500ml
In round-bottomed flask, 240ml methanol solution is added, ultrasonic 30min is dispersed in it in methanol solution, then burns round bottom
Bottle in 50 DEG C of thermostats temperature control, solution C is added dropwise, is persistently stirred for 24 hours with the revolving speed of 400rmp/min, after reaction from
The heart is washed three times with methanol, every minor tick 12h, and the Zn-MOFs material with defective hole and amino can be obtained in 70 DEG C of vacuum drying
Material, is denoted as Zn-MOFs-A.
(9) preparation of amino-acid functional Zn-MOFs functional material: Zn-MOFs-A 0.6000g is weighed in 250ml round bottom
In flask, 60ml aqueous solution is added, ultrasonic 30min keeps Zn-MOFs-A evenly dispersed in aqueous solution, then by round-bottomed flask
The temperature control in 30 DEG C of thermostats is successively slowly added to D, E, F solution, and the triethylamine TEA solution that 360 μ L are added adjusts pH=8,
It is persistently stirred for 24 hours with the revolving speed of 400rmp/min, is centrifuged after reaction, is washed with water three times, every minor tick 12h, 70 DEG C of vacuum
It is dry, the Zn-MOFs functional material with amino-acid functional can be obtained.
Embodiment 5
A kind of preparation method of amino-acid functional Zn-MOFs functional material, includes the following steps:
(1) preparation of zinc nitrate solution: 1.5000g (5mmol) zinc nitrate Zn (NO is weighed3)2·6H2O is in 100ml beaker
In, it is slowly added to 70ml water, being placed on magnetic stirring apparatus dissolves zinc nitrate sufficiently with the revolving speed mechanical stirring of 400rmp/min,
It is denoted as solution A；
(2) it the preparation of 2-methylimidazole solution: takes and claims 3.3000g (40mmol) 2-methylimidazole Hmin in 100ml beaker
In, it is slowly added to 70ml water, be placed on magnetic stirring apparatus keeps 2-methylimidazole abundant with the revolving speed mechanical stirring of 400rmp/min
Dissolution, adds 5.56ml (40mmol) triethylamine TEA solution, is denoted as solution B；
(3) preparation of 2- amino 1,2,4- triazole solution: 4.6800g (55.68mmol) 2- amino 1,2,4- tri- is weighed
Nitrogen azoles (Atz) is slowly added to 40ml methanol in 50ml beaker, is placed in mechanical with the revolving speed of 400rmp/min on magnetic stirring apparatus
Stirring dissolves 1,2,4- triazole of 2- amino sufficiently, is denoted as solution C.
(4) preparation of histidine solution: 0.2040g (1.32mmol) histidine is weighed in 50ml beaker, is slowly added to
20ml water, being placed on magnetic stirring apparatus dissolves histidine sufficiently with the revolving speed mechanical stirring of 400rmp/min, is denoted as solution D.
(5) preparation of 1- (3- dimethylamino-propyl) -3- ethyl-carbodiimide hydrochloride solution: 1- (3- diformazan ammonia is weighed
Base propyl) -3- ethyl-carbodiimide hydrochloride (EDC) 0.5040g (2.64mmol) in 50ml beaker, is slowly added to 20ml
Water, being placed on magnetic stirring apparatus dissolves histidine sufficiently with the revolving speed mechanical stirring of 400rmp/min, is denoted as solution E.
(6) preparation of n-hydroxysuccinimide solution: n-hydroxysuccinimide (NHS) 0.3000g is weighed
(2.64mmol) is slowly added to 20ml water in 50ml beaker, is placed in mechanical with the revolving speed of 400rmp/min on magnetic stirring apparatus
Stirring dissolves histidine sufficiently, is denoted as solution F.
(7) with defective hole Zn-MOFs material preparation: by B solution in thermostat 30 DEG C of temperature controls, be stabilized to temperature
After 30 DEG C, solution A is added dropwise in solution B, is persistently stirred for 24 hours with the revolving speed of 400rmp/min, is centrifuged after reaction, is used
Methanol is washed three times, every minor tick 12h, and the Zn-MOFs material with defective hole can be obtained in 120 DEG C of vacuum drying.
(8) preparation of the Zn-MOFs material with defective hole and amino: 0.8000g step (7) material is weighed in 500ml
In round-bottomed flask, 240ml methanol solution is added, ultrasonic 30min is dispersed in it in methanol solution, then burns round bottom
Bottle in 50 DEG C of thermostats temperature control, solution C is added dropwise, is persistently stirred for 24 hours with the revolving speed of 400rmp/min, after reaction from
The heart is washed three times with methanol, every minor tick 12h, and the Zn-MOFs material with defective hole and amino can be obtained in 70 DEG C of vacuum drying
Material, is denoted as Zn-MOFs-A.
(9) preparation of amino-acid functional Zn-MOFs functional material: Zn-MOFs-A 0.6000g is weighed in 250ml round bottom
In flask, 60ml aqueous solution is added, ultrasonic 30min keeps Zn-MOFs-A evenly dispersed in aqueous solution, then by round-bottomed flask
The temperature control in 30 DEG C of thermostats is successively slowly added to D, E, F solution, and the triethylamine TEA solution that 360 μ L are added adjusts pH=8,
It is persistently stirred for 24 hours with the revolving speed of 400rmp/min, is centrifuged after reaction, is washed with water three times, every minor tick 12h, 70 DEG C of vacuum
It is dry, the Zn-MOFs functional material with amino-acid functional can be obtained.
Embodiment 6
A kind of preparation method of amino-acid functional Zn-MOFs functional material, includes the following steps:
(1) preparation of zinc nitrate solution: 1.5000g (5mmol) zinc nitrate Zn (NO is weighed3)2·6H2O is in 100ml beaker
In, it is slowly added to 70ml water, being placed on magnetic stirring apparatus dissolves zinc nitrate sufficiently with the revolving speed mechanical stirring of 400rmp/min,
It is denoted as solution A；
(2) it the preparation of 2-methylimidazole solution: takes and claims 3.3000g (40mmol) 2-methylimidazole Hmin in 100ml beaker
In, it is slowly added to 70ml water, be placed on magnetic stirring apparatus keeps 2-methylimidazole abundant with the revolving speed mechanical stirring of 400rmp/min
Dissolution, adds 5.56ml (40mmol) triethylamine TEA solution, is denoted as solution B；
(3) preparation of 2- amino 1,2,4- triazole solution: 2.3400g (27.84mmol) 2- amino 1,2,4- tri- is weighed
Nitrogen azoles (Atz) is slowly added to 40ml methanol in 50ml beaker, is placed in mechanical with the revolving speed of 400rmp/min on magnetic stirring apparatus
Stirring dissolves 1,2,4- triazole of 2- amino sufficiently, is denoted as solution C.
(4) preparation of histidine solution: 0.1020g (0.66mmol) histidine is weighed in 50ml beaker, is slowly added to
1ml water, being placed on magnetic stirring apparatus dissolves histidine sufficiently with the revolving speed mechanical stirring of 400rmp/min, is denoted as solution D.
(5) preparation of 1- (3- dimethylamino-propyl) -3- ethyl-carbodiimide hydrochloride solution: 1- (3- diformazan ammonia is weighed
Base propyl) -3- ethyl-carbodiimide hydrochloride (EDC) 0.5040g (2.64mmol) in 50ml beaker, is slowly added to 20ml
Water, being placed on magnetic stirring apparatus dissolves histidine sufficiently with the revolving speed mechanical stirring of 400rmp/min, is denoted as solution E.
(6) preparation of n-hydroxysuccinimide solution: n-hydroxysuccinimide (NHS) 0.3000g is weighed
(2.64mmol) is slowly added to 20ml water in 50ml beaker, is placed in mechanical with the revolving speed of 400rmp/min on magnetic stirring apparatus
Stirring dissolves histidine sufficiently, is denoted as solution F.
(7) with defective hole Zn-MOFs material preparation: by B solution in thermostat 30 DEG C of temperature controls, be stabilized to temperature
After 30 DEG C, solution A is added dropwise in solution B, is persistently stirred for 24 hours with the revolving speed of 400rmp/min, is centrifuged after reaction, is used
Methanol is washed three times, every minor tick 12h, and the Zn-MOFs material with defective hole can be obtained in 120 DEG C of vacuum drying.
(8) preparation of the Zn-MOFs material with defective hole and amino: 0.8000g step (7) material is weighed in 500ml
In round-bottomed flask, 240ml methanol solution is added, ultrasonic 30min is dispersed in it in methanol solution, then burns round bottom
Bottle in 50 DEG C of thermostats temperature control, solution C is added dropwise, is persistently stirred for 24 hours with the revolving speed of 400rmp/min, after reaction from
The heart is washed three times with methanol, every minor tick 12h, and the Zn-MOFs material with defective hole and amino can be obtained in 70 DEG C of vacuum drying
Material, is denoted as Zn-MOFs-A.
(9) preparation of amino-acid functional Zn-MOFs functional material: Zn-MOFs-A 0.6000g is weighed in 250ml round bottom
In flask, 60ml aqueous solution is added, ultrasonic 30min keeps Zn-MOFs-A evenly dispersed in aqueous solution, then by round-bottomed flask
The temperature control in 30 DEG C of thermostats is successively slowly added to D, E, F solution, and the triethylamine TEA solution that 200 μ L are added adjusts pH=8,
It is persistently stirred for 24 hours with the revolving speed of 400rmp/min, is centrifuged after reaction, is washed with water three times, every minor tick 12h, 70 DEG C of vacuum
It is dry, the Zn-MOFs functional material with amino-acid functional can be obtained.
Embodiment 7
A kind of preparation method of amino-acid functional Zn-MOFs functional material, includes the following steps:
(1) preparation of zinc nitrate solution: 1.5000g (5mmol) zinc nitrate Zn (NO is weighed3)2·6H2O is in 100ml beaker
In, it is slowly added to 60ml water, being placed on magnetic stirring apparatus dissolves zinc nitrate sufficiently with the revolving speed mechanical stirring of 400rmp/min,
It is denoted as solution A；
(2) it the preparation of 2-methylimidazole solution: takes and claims 3.3000g (40mmol) 2-methylimidazole Hmin in 100ml beaker
In, it is slowly added to 60ml water, be placed on magnetic stirring apparatus keeps 2-methylimidazole abundant with the revolving speed mechanical stirring of 400rmp/min
Dissolution, adds 11.12ml (80mmol) triethylamine TEA solution, is denoted as solution B；
(3) preparation of 2- amino 1,2,4- triazole solution: 2.3400g (27.84mmol) 2- amino 1,2,4- tri- is weighed
Nitrogen azoles (Atz) is slowly added to 30ml methanol in 50ml beaker, is placed in mechanical with the revolving speed of 400rmp/min on magnetic stirring apparatus
Stirring dissolves 1,2,4- triazole of 2- amino sufficiently, is denoted as solution C.
(4) preparation of histidine solution: 0.2040g (1.32mmol) 0.408g (2.64mmol) histidine is weighed in 50ml
In beaker, it is slowly added to 16ml water, be placed on magnetic stirring apparatus keeps histidine abundant with the revolving speed mechanical stirring of 400rmp/min
Dissolution, is denoted as solution D.
(5) preparation of 1- (3- dimethylamino-propyl) -3- ethyl-carbodiimide hydrochloride solution: 1- (3- diformazan ammonia is weighed
Base propyl) -3- ethyl-carbodiimide hydrochloride (EDC) 0.5040g (2.64mmol) in 50ml beaker, is slowly added to 20ml
Water, being placed on magnetic stirring apparatus dissolves histidine sufficiently with the revolving speed mechanical stirring of 400rmp/min, is denoted as solution E.
(6) preparation of n-hydroxysuccinimide solution: n-hydroxysuccinimide (NHS) 0.3000g is weighed
(2.64mmol) is slowly added to 20ml water in 50ml beaker, is placed in mechanical with the revolving speed of 400rmp/min on magnetic stirring apparatus
Stirring dissolves histidine sufficiently, is denoted as solution F.
(7) with defective hole Zn-MOFs material preparation: by B solution in thermostat 30 DEG C of temperature controls, be stabilized to temperature
After 30 DEG C, solution A is added dropwise in solution B, is persistently stirred for 24 hours with the revolving speed of 400rmp/min, is centrifuged after reaction, is used
Methanol is washed three times, every minor tick 12h, and the Zn-MOFs material with defective hole can be obtained in 120 DEG C of vacuum drying.
(8) preparation of the Zn-MOFs material with defective hole and amino: 0.8000g step (7) material is weighed in 500ml
In round-bottomed flask, 240ml methanol solution is added, ultrasonic 30min is dispersed in it in methanol solution, then burns round bottom
Bottle in 50 DEG C of thermostats temperature control, solution C is added dropwise, is persistently stirred for 24 hours with the revolving speed of 400rmp/min, after reaction from
The heart is washed three times with methanol, every minor tick 12h, and the Zn-MOFs material with defective hole and amino can be obtained in 70 DEG C of vacuum drying
Material, is denoted as Zn-MOFs-A.
(9) preparation of amino-acid functional Zn-MOFs functional material: Zn-MOFs-A 0.6000g is weighed in 250ml round bottom
In flask, 60ml aqueous solution is added, ultrasonic 30min keeps Zn-MOFs-A evenly dispersed in aqueous solution, then by round-bottomed flask
The temperature control in 30 DEG C of thermostats is successively slowly added to D, E, F solution, and the triethylamine TEA solution that 360 μ L are added adjusts pH=8,
It is persistently stirred for 24 hours with the revolving speed of 400rmp/min, is centrifuged after reaction, is washed with water three times, every minor tick 12h, 70 DEG C of vacuum
It is dry, the Zn-MOFs functional material with amino-acid functional can be obtained.
Material properties test:
(1) XRD characterization of material
Fig. 1 is the Zn-MOFs material without amino acid modification, the Zn-MOFs functional material that histidine, glutamic acid are modified
The XRD peak type difference of XRD characterization figure, case study on implementation 1,2,3 is little, illustrates the Zn-MOFs function of modifying through histidine, glutamic acid
The Zn-MOFs functional material that material synthesizes on crystal structure with without amino acid modification is almost the same.
(2) surface topography of material
Zn-MOFs material by embodiment 1 without amino acid modification, the Zn-MOFs function material of 2 histidine of embodiment modification
Material carries out electron-microscope scanning, obtains the SEM figure of Fig. 2~3, case study on implementation 2 is larger compared with the crystal grain of 1 synthetic material of embodiment, says
The modification of bright histidine affects the structure of crystal grain.
(3) adsorption capacity of material
Fig. 4 is the Zn-MOFs material without amino acid modification, the Zn-MOFs functional material nitrogen that histidine, glutamic acid are modified
Gas adsorption/desorption curve (embodiment 1,2,3 and 5)；
Fig. 5 is the Zn-MOFs material without amino acid modification, the Zn-MOFs functional material hole that histidine, glutamic acid are modified
Diameter distribution curve (embodiment 1,2,3 and 5)；
Table 1 is the Zn-MOFs material without amino acid modification, the Zn-MOFs functional material that histidine, glutamic acid are modified
Specific surface area and distribution of pores data.
The specific surface area and parameter of pore structure of 1 material of table
As can be seen from the data in table 1, the Langmuir specific surface area of three kinds of embodiment materials is in 700~1000m2/ g, total hole
Hold about in 0.4~0.6cm3/ g, micropore specific area and micro pore volume increase after amino acid modification, illustrate amino acid modification meeting
There are some effects to the pore structure of Zn-MOFs functional material.Wherein, after histidine is modified Zn-MOFs functional material compared with paddy
The Zn-MOFs functional material micropore area increase of propylhomoserin modification is more, and aperture is also smaller (Fig. 4,5).This is because histidine point
Son is big compared with glutamate molecule, therefore the material aperture after synthesis is also corresponding smaller.
(4) ACE inhibits polypeptide adsorption experiment
In order to verify the material to ACE inhibit polypeptide selective absorption effect, select WW, RR, FSSA, GAMVVH and
Five kinds of molecular weight of SSNSNV polypeptide solution (800mg/L) different with ACE inhibitory activity, respectively by 50mg Examples 1 to 6 material
It is put into 100mL polypeptide solution, obtains Zn-MOFs material without amino acid modification, histidine and glutamic acid under different ratio
The Zn-MOFs functional material of modification inhibits polypeptide adsorbance to ACE, as a result such as attached drawing 6~9.(W- tryptophan；R- arginine；F-
Phenylalanine；S- serine；A- alanine；G- glycine；M- methionine；V- valine；H- histidine；N- aspartic acid)
The molecular weight and 503nhibiting concentration table of the inhibition polypeptide of ACE selected by table 2
The different Zn-MOFs function of the pore size that Fig. 6, which is Zn-MOFs material without amino acid modification, to be modified with histidine
The adsorbance result (embodiment 1,2 and 4) of energy material.It can be seen from the figure that ACE inhibits the molecular weight of polypeptide smaller, material
Adsorbance it is bigger, and the adsorbance of the Zn-MOFs functional material of amino acid modification is compared with the Zn-MOFs material without amino acid modification
Material significantly increases.It is also seen that the bigger adsorbance in aperture is bigger (embodiment 2 and 4), this is because biggish aperture material from figure
Material is that ACE inhibition polypeptide provides the more broad channel into skeleton, so adsorbance also relative increase.
Fig. 7 is the adsorbance of different degrees of amination Zn-MOFs material as a result, since excessive amination makes Zn-MOFs
Material pore volume and specific surface area significantly reduce (Fig. 4), so the adsorbance of case study on implementation 5 is remarkably decreased.Meanwhile adsorbance
It is not only related with the aperture of material, specific surface area, also inhibit the activity of polypeptide to have with the type of modified amino acid, quantity and ACE
It closes.Amino acid modification amount is higher, and the active site provided by material in conjunction with ACE inhibition polypeptide is also more, corresponding to adsorb
Amount also improves.The histidine modification amount of 2 material of embodiment is twice of 6 material of embodiment, and corresponding adsorbance is also substantially real
Apply twice (Fig. 8) of 6 material of example.For WW and RR, GAMVVH and SSNSNV, since the polarity of RR and SSNSNV are relatively large,
So material is smaller to their adsorbance (Fig. 9).As can be seen from Figure 9, the material polypeptide absorption higher to ACE inhibitory activity
Amount is bigger, cooperate with this is because the zinc ion and amino acid in Zn-MOFs material can form multidigit point with the higher polypeptide of activity
Absorption (hydrogen bond and Zn-O coordination), enhances the suction-operated that ACE inhibits polypeptide and material, so that adsorbance increases.For more
The adsorbance (446.3mg/g) of peptide GAMVVH, 3 material of embodiment are apparently higher than 2 material of embodiment (371.5mg/g), this be because
For the carboxyl slant acidity that 3 material Glutamic Acid of embodiment contains, the imidazole radicals meta-alkalescence that histidine contains in 2 material of embodiment,
So 3 material of embodiment is higher to polypeptide (GAMVVH) adsorbance containing basic amino acid, thus illustrate the adsorbance of polypeptide
It is related with amino acid modification type, that is, property of material.
Claims (10)
1. a kind of amino-acid functional Zn-MOFs functional material, which is characterized in that the material is three-dimensional porous reticular structure,
Langmuir specific surface area is 700~1000m2/ g, crystalline size size are 40~50nm, and crystal structure is that form size is equal
One regular regular dodecahedron structure；Contain amino, carboxyl and imidazole radicals functional group in crystalline framework.
2. the preparation method of amino-acid functional Zn-MOFs functional material as described in claim 1, which is characterized in that including
Following steps:
(1) with the preparation of defective hole MOFs material: 2-methylimidazole is soluble in water, and mechanical stirring makes it dissolve, and adds
A certain amount of TEA solution, obtains methylimidazole solution, is transferred in thermostat, temperature control, and zinc nitrate solution is slowly added to simultaneously machine
Tool stirring is centrifuged after reaction, activates, the MOFs material with defective hole can be obtained, be denoted as Zn-MOFs；
(2) preparation of the Zn-MOFs material with defective hole and amino: Zn-MOFs is added in the container equipped with methanol, is surpassed
Sound is dispersed in it in methanol solution, is slowly added to 1,2,4- triazole solution of 2- amino, mechanical stirring, centrifugation after reaction,
Activation, can be obtained the Zn-MOFs material with defective hole and amino, is denoted as Zn-MOFs-A；
(3) preparation of amino-acid functional Zn-MOFs functional material: Zn-MOFs-A being added in the container equipped with water, ultrasound,
Keep its evenly dispersed in aqueous solution, it is sub- to be successively slowly added to amino acid solution, 1- (3- dimethylamino-propyl) -3- ethyl carbon two
Amide hydrochloride, n-hydroxysuccinimide Solutions Solution add a certain amount of triethylamine TEA solution adjustment pH=8, machine
Tool stirring is centrifuged after reaction, activates, the Zn-MOFs functional material with amino-acid functional can be obtained.
3. the preparation method of amino-acid functional Zn-MOFs functional material according to claim 2, it is characterised in that: institute
State zinc nitrate solution in step (1), methylimidazole, triethylamine TEA molar ratio be 1:8:4-16, reaction temperature be 30 DEG C,
Reaction time is for 24 hours.
4. the preparation method of amino-acid functional Zn-MOFs functional material according to claim 2, it is characterised in that: institute
The mass ratio for stating Zn-MOFs and 1,2,4- triazole of 2- amino in step (2) is 1:2-6, and reaction temperature is 50 DEG C, and the reaction time is
12-24h。
5. the preparation method of amino-acid functional Zn-MOFs functional material according to claim 2, it is characterised in that: institute
State Zn-MOFs-A and amino acid, 1- (3- dimethylamino-propyl) -3- ethyl-carbodiimide hydrochloride (EDC), N- in step (3)
The mass ratio of HOSu NHS (NHS) is 6:1-4:5:3, and reaction temperature is 30 DEG C, reaction time 12-24h.
6. the preparation method of amino-acid functional Zn-MOFs functional material according to claim 2, it is characterised in that: institute
The methanol solvate of 0.2~0.6L is added in the Zn-MOFs for stating every 1g in step (2), the Zn-MOFs-A of every 1g in the step (3)
The aqueous solvent of 0.05-0.15L is added, the mechanical stirring speed in step (1)~(3) is 300~500rmp/min.
7. the preparation method of amino-acid functional Zn-MOFs functional material according to claim 2, it is characterised in that: institute
It states and is added in step (1) by the zinc nitrate of 1mol in the aqueous solvent of 12~16L, mechanical stirring dissolves zinc nitrate sufficiently
Obtain zinc nitrate solution；
The preparation of the 2-methylimidazole solution: 2-methylimidazole Hmin is added in the container equipped with water, according to every 1mol's
The configuration of the aqueous solvent of 1.5~3L is added in 2-methylimidazole Hmin, and mechanical stirring dissolves it sufficiently, adds the three of 2~8mL
Ethamine TEA solution, obtains methylimidazole solution.
8. the preparation method of amino-acid functional Zn-MOFs functional material according to claim 2, it is characterised in that: institute
State the preparation of 2- amino 1,2,4- triazole solution: the 2- amino 1,2,4- by 2- amino 1,2,4-triazole Atz according to every 1mol
The proportion that the methanol solvate of 1~2L is added in triazole Atz is added in the container equipped with methanol, and mechanical stirring dissolves it sufficiently,
2- amino 1,2,4-triazole solution can be obtained.
9. the preparation method of amino-acid functional Zn-MOFs functional material according to claim 2, it is characterised in that: institute
It states the preparation of amino acid solution: the aqueous solvent proportion mixing of 12~16L being added by the amino acid of every 1mol, mechanical stirring fills it
Divide dissolution, amino acid solution can be obtained；
The preparation of 1- (3- the dimethylamino-propyl) -3- ethyl-carbodiimide hydrochloride solution: by 1- (the 3- diformazan of every 1mol
Aminopropyl) -3- ethyl-carbodiimide hydrochloride (EDC) be added 6~8L aqueous solvent match mixing, mechanical stirring make its sufficiently
Dissolution, can be obtained 1- (3- dimethylamino-propyl) -3- ethyl-carbodiimide hydrochloride solution；
The preparation of the n-hydroxysuccinimide solution: it is added 6~8L's by the n-hydroxysuccinimide (NHS) of every 1mol
In aqueous solvent, mechanical stirring dissolves it sufficiently, and n-hydroxysuccinimide solution can be obtained.
10. the application of amino-acid functional Zn-MOFs functional material as described in claim 1, it is characterised in that: it is being adsorbed
ACE inhibits the utilization in terms of polypeptide.
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