CN105903454A - Preparation method of surface molecularly-imprinted carbon microspheres and application of surface molecularly-imprinted carbon microspheres in solid-phase extraction device - Google Patents
Preparation method of surface molecularly-imprinted carbon microspheres and application of surface molecularly-imprinted carbon microspheres in solid-phase extraction device Download PDFInfo
- Publication number
- CN105903454A CN105903454A CN201610439908.1A CN201610439908A CN105903454A CN 105903454 A CN105903454 A CN 105903454A CN 201610439908 A CN201610439908 A CN 201610439908A CN 105903454 A CN105903454 A CN 105903454A
- Authority
- CN
- China
- Prior art keywords
- carbosphere
- silanization
- bisphenol
- solid
- present
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- 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
- B01J20/281—Sorbents specially adapted for preparative, analytical or investigative chromatography
-
- 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
- B01D15/08—Selective adsorption, e.g. chromatography
- B01D15/10—Selective adsorption, e.g. chromatography characterised by constructional or operational features
-
- 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
- B01J20/28014—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 form
- B01J20/28016—Particle form
- B01J20/28021—Hollow particles, e.g. hollow spheres, microspheres or cenospheres
-
- 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
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/80—Aspects related to sorbents specially adapted for preparative, analytical or investigative chromatography
Landscapes
- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention provides a preparation method of surface molecularly-imprinted carbon microspheres. The surface molecularly-imprinted carbon microspheres obtained through the preparation method have the good adsorption property on bisphenol A, are high in adsorption speed, large in adsorption capacity and good in adsorption stability and have the high adsorption selectivity in a low-concentration aqueous solution of bisphenol A; the maximum adsorption capacity of the surface molecularly-imprinted carbon microspheres on bisphenol A can reach 1,100 mg/kg in the low-concentration aqueous solution of bisphenol A. The invention further provides a solid-phase extraction device. The solid-phase extraction device comprises a solid-phase extraction column and a solid phase filled in the solid-phase extraction column, the solid phase is the surface molecularly-imprinted carbon microspheres, and the two ends of the solid phase are fixed with sieve plates; the ratio of the mass of the surface molecularly-imprinted carbon microspheres to the volume of a column pipe is (30-50) mg:(1-6) mL. The solid-phase extraction device has the good enrichment capacity on bisphenol A in a complex matrix water sample and the easy elution property, and the recycling rate can reach 90%-100%.
Description
Technical field
The present invention relates to molecular engram material technical field, particularly relate to a kind of surface molecule print carbosphere
Preparation method and application in solid-phase extraction device.
Background technology
Molecular imprinting, is a new branch of science, is by template molecule branding to certain matrix, makes
Matrix has special selectivity and a binding ability to template molecule, thus can be used for template molecule separation,
Enrichment and detection etc..So far, molecular imprinting chiral separation, SPE, enrichment,
The fields such as detection, enzyme simulation, chemobionics sensor show good application prospect.
The matrix of molecular engram material can be inorganic material, such as material with carbon element, silica gel, aluminum oxide etc., also
Can be polymeric material, but the recognition site of polymer microballoon is mostly inside polymer microballoon, identify
During bigger molecule, the existence of diffusional resistance can cause molecule to be identified to be combined difficulty with recognition site.
Molecularly imprinted material on surface is a kind of polymer at carrier surface synthesis specific molecular imprinted structures,
Template molecule is had to the material of specific adsorption performance after template removal.Surface molecule print carbon is micro-
Ball (sMIP-CMs) is a kind of well using material with carbon element as the molecularly imprinted material on surface of matrix,
SMIP-CMs surface have after modifying abundant bonding position, stable acid-base value, good heat endurance and
Mechanical performance.
In prior art, the synthesis of sMIP-CMs is typically all with dibenzothiophenes as template molecule, and it is adopted
Function monomer be 2-acrylamide-2-methyl propane sulfonic and methacrylic acid, synthesized material is only used
Remove the dibenzothiophenes in oil.The sMIP-CMs provided in prior art is generally individually for oil phase
In the middle of, there are no the relevant report about the sMIP-CMs that can be applicable to aqueous phase.
Summary of the invention
It is an object of the invention to provide the preparation method of a kind of surface molecule print carbosphere and extract in solid phase
Fetching put in application, obtain a kind of surface molecule print carbosphere that can be applicable to aqueous phase.
In order to realize foregoing invention purpose, the present invention provides techniques below scheme:
The invention provides the preparation method of a kind of surface molecule print carbosphere, comprise the following steps:
Carbosphere is carried out oxidation processes, obtains carbonoxide microballoon；
Using 3-(methyl propylene acyl-oxygen), propyl trimethoxy silicane is as silanization treating agent, by described carbonoxide
Microballoon carries out surface silanization process, obtains silanization carbosphere；
Under an inert atmosphere, by different to described silanization carbosphere, 4-vinylpridine, bisphenol-A, azo two
Butyronitrile and GDMA carry out thermal polymerization in organic solvent, after removing bisphenol-A,
To surface molecule print carbosphere.
Preferably, a diameter of the 240～300nm of described carbosphere.
Preferably, described silanization treatment particularly as follows:
Regulation includes that the pH value of the system of carbonoxide microballoon and ethanol solution, to 4～6, obtains acidic oxidation carbon
Microsphere system；
Described acidic oxidation carbosphere system and 3-(methyl propylene acyl-oxygen) propyl trimethoxy silicane are mixed
Carry out silanization treatment, obtain silanization carbosphere.
Preferably, the volumetric concentration of described ethanol solution is 70～80%；
The quality of described carbonoxide microballoon and the volume ratio of ethanol solution are (0.1～1) g:(100～150) mL；
The volume ratio of described ethanol solution and 3-(methyl propylene acyl-oxygen) propyl trimethoxy silicane is
(100～150): 1.
Preferably, the temperature of described silanization treatment is 50～80 DEG C；
The time of described silanization treatment is 2～5 hours.
Preferably, described silanization carbosphere mass concentration in organic solvent is 0.001～0.005g/mL；
Described organic solvent is (50～80) with the volume ratio of 4-vinylpridine: 1；
The mass ratio of described silanization carbosphere and bisphenol-A is 1:(100～1200)；
The mass ratio of described silanization carbosphere and azodiisobutyronitrile is 1:(100～300)；
Described organic solvent is (10～20) with the volume ratio of GDMA: 1.
Preferably, the temperature of described thermal polymerization is 50～80 DEG C；
The time of described thermal polymerization is 20～30 hours.
The invention provides the surface molecule print carbosphere that a kind of above-mentioned preparation method obtains, its feature
Being, described surface molecule print carbosphere is in the aqueous solution that bisphenol A concentration is relatively low, for bisphenol-A
Having good absorption property, maximal absorptive capacity can reach 1100mg/kg.
The invention provides the application as fixing phase of the above-mentioned surface molecule print carbosphere.
Present invention also offers a kind of solid-phase extraction device, including solid-phase extraction column be filled in described solid phase
Fixing phase in extraction column, it is characterised in that described fixing is above-mentioned surface molecule print carbosphere mutually,
Described fixing phase two ends sieve plate is fixed；The quality of described surface molecule print carbosphere and described column jecket
The ratio of volume is (30～500) mg:(1～6) mL.
The invention provides the preparation method of a kind of surface molecule print carbosphere, comprise the following steps: right
Carbosphere carries out oxidation processes, obtains carbonoxide microballoon；With 3-(methyl propylene acyl-oxygen) propyl trimethoxy silicon
Described carbonoxide microballoon, as silanization treating agent, is carried out surface silanization process, obtains silanization by alkane
Carbosphere；Under an inert atmosphere, by described silanization carbosphere, 4-vinylpridine, bisphenol-A, azo
Bis-isobutyronitrile and GDMA carry out thermal polymerization in organic solvent, after removing bisphenol-A,
Obtain surface molecule print carbosphere.The surface imprinted carbosphere that the present invention prepares is at bisphenol A concentration
In the relatively low aqueous solution, having good absorption property for bisphenol-A, adsorption rate is fast, adsorbance is big
And absorption stability is good.Test result indicate that of embodiment, the surface molecule print carbon that the application obtains is micro-
Ball, in the aqueous solution that bisphenol A concentration is relatively low, the maximal absorptive capacity for bisphenol-A can reach 1100
mg/kg。
Present invention also offers a kind of solid-phase extraction device, including solid-phase extraction column be filled in described solid phase
Fixing phase in extraction column, described fixing is above-mentioned surface molecule print carbosphere mutually, described fixing phase
Two ends sieve plate is fixed；The quality of described surface molecule print carbosphere with the ratio of the volume of described column jecket is
(30～500) mg:(1～6) mL.Test result indicate that of embodiment, the solid-phase extraction device pair that the application provides
Bisphenol-A in aqueous phase has good accumulation ability, easy elution property, and effectively suppression water sample base
The performance of matter interference, bisphenol-A recovery of extraction can reach 90～100%.
Accompanying drawing explanation
Fig. 1 is the synthesis flow schematic diagram that the embodiment of the present invention 1 uses；
Fig. 2 is the curve of adsorption kinetics of the sMIP-CMs that the embodiment of the present invention 1 obtains；
Fig. 3 is the adsorption isotherm of the sMIP-CMs that the embodiment of the present invention 1 obtains；
The structural representation of the solid-phase extraction device that Fig. 4 provides for the embodiment of the present invention 4；
Fig. 5 is the embodiment of the present invention 5 device and comparative example device to be compared for the recovery of extraction of BPA.
Detailed description of the invention
The invention provides the preparation method of a kind of surface molecule print carbosphere, comprise the following steps:
Carbosphere is carried out oxidation processes, obtains carbonoxide microballoon；
Using 3-(methyl propylene acyl-oxygen), propyl trimethoxy silicane is as silanization treating agent, by described carbonoxide
Microballoon carries out surface silanization process, obtains silanization carbosphere；
Under an inert atmosphere, by different to described silanization carbosphere, 4-vinylpridine, bisphenol-A, azo two
Butyronitrile and GDMA carry out thermal polymerization in organic solvent, after removing bisphenol-A,
To surface molecule print carbosphere.
The present invention carries out oxidation processes to carbosphere, obtains carbonoxide microballoon.In the present invention, described carbon
The diameter of microballoon is preferably 240～300nm, more preferably 250～290nm, most preferably 260～280nm.
The present invention does not has particular/special requirement to the source of described carbosphere, uses carbon well-known to those skilled in the art
Microballoon, concrete can be the commercially available prod of carbosphere.
The present invention does not has particular/special requirement to the concrete mode of described oxidation processes, uses those skilled in the art
The mode of oxidizing of known carbosphere carries out aoxidizing.Present invention preferably employs mixed acid to carbosphere
Carry out oxidation processes, obtain carbonoxide microballoon.In the present invention, described mixed acid is preferably sulfuric acid and nitre
The mixed liquor of acid.In the present invention, the volume ratio of described sulfuric acid and nitric acid is preferably 1:(2～5), concrete
Can be 1:2,1:3,1:4 or 1:5.The present invention does not has particular/special requirement to the source of described sulfuric acid and nitric acid,
Using sulfuric acid well-known to those skilled in the art and nitric acid, concrete can be sulfuric acid and nitric acid
Commercially available prod.In the specific embodiment of the invention, the mass concentration of described nitric acid is 65～68%, described sulphur
The mass concentration of acid is 98%.
In the present invention, the quality of described carbosphere and the volume ratio of mixed acid are preferably
(0.1～3) g:(100～150) mL, more preferably (0.5～2.5) g:(110～140) mL, most preferably
2g:(120～130) mL.The present invention does not has particular/special requirement to the order by merging of described carbosphere and mixed acid, this
Carbosphere is preferably joined in mixed acid by invention.
In the present invention, the temperature of described oxidation processes is preferably 50～100 DEG C, more preferably 60～90 DEG C,
Most preferably 70～80 DEG C；The time of described oxidation processes is preferably 30～60 minutes, more preferably 35～50
Minute, most preferably 40～50 minutes.In the present invention, described oxidation processes is preferably in ultrasonic vibration
Under the conditions of carry out.In the present invention, the frequency of described ultrasonic vibration is preferably 60～80W, more preferably
62～68W, most preferably 64～66W.
After described oxidation processes terminates, the cooling of product that described oxidation processes is preferably obtained by the present invention,
Wash and be dried, obtain aoxidizing microballoon.In the present invention, described cooling is preferably cooled to room temperature.
After described cooling, the oxidation product after described cooling is preferably washed to neutral by the present invention with water.
The present invention does not has particular/special requirement to the kind of described water, deionized water that concrete can be, pure water or
Distilled water.
After described washing, the oxidation product after described washing is preferably dried by the present invention, obtains
Carbonoxide microballoon.In the present invention, described dry temperature is preferably 50～70 DEG C, more preferably 52～68 DEG C,
Most preferably 55～65 DEG C；The described dry time is preferably 20～30 hours, more preferably 22～26 hours,
Most preferably 24～25 hours.The present invention does not has particular/special requirement to described dry detailed description of the invention, adopts
It is dried by dry means well-known to those skilled in the art.In the present invention, described dry
Preferably carry out in vacuum drying chamber.
After obtaining described carbonoxide microballoon, the present invention is with 3-(methyl propylene acyl-oxygen) propyl trimethoxy silicane
As silanization treating agent, described carbonoxide microballoon is carried out surface silanization process, obtains silanization carbon
Microballoon.In the present invention, described silanization treatment is preferably particularly as follows: regulate carbonoxide microballoon and ethanol
The pH value of solution is 4～6, obtains acidic oxidation carbosphere system；By described acidic oxidation carbosphere system
Carry out silanization treatment with 3-(methyl propylene acyl-oxygen) propyl trimethoxy silicane, obtain silanization carbosphere.
The present invention preferably regulates the pH value of the system including carbonoxide microballoon and ethanol solution to 4～6, obtains
Acidic oxidation carbosphere system.In the present invention, described ethanol solution is preferably ethanol water；Described
The volumetric concentration of ethanol solution is preferably 70～80%, concrete can be 70%, 71%, 73%, 75%,
77%, 79% or 80%.In the present invention, the quality of described carbonoxide microballoon and the volume ratio of ethanol solution
It is preferably (0.1～1) g:(100～150) mL, more preferably (0.3～0.8) g:(110～140) mL, most preferably
(0.4～0.6) g:(120～130) mL.
Present invention regulation include the pH value of system of carbonoxide microballoon and ethanol solution to 4～6, more specifically
Can regulate pH value is 4,5 or 6.Present invention preferably uses glacial acetic acid molten to carbonoxide microballoon and ethanol
The pH value of liquid is adjusted.
After obtaining described acidic oxidation carbosphere system, the present invention is by described acidic oxidation carbosphere system
Carry out silanization treatment with 3-(methyl propylene acyl-oxygen) propyl trimethoxy silicane, obtain silanization carbosphere.
In the present invention, the volume ratio of described ethanol solution and 3-(methyl propylene acyl-oxygen) propyl trimethoxy silicane is excellent
Elect as (100～150): 1, more preferably (110～140): 1, most preferably (120～130): 1.The present invention is to institute
The source stating 3-(methyl propylene acyl-oxygen) propyl trimethoxy silicane (KH-570) does not has particular/special requirement, adopts
With 3-well-known to those skilled in the art (methyl propylene acyl-oxygen) propyl trimethoxy silicane, concrete
It can be the commercially available prod of 3-(methyl propylene acyl-oxygen) propyl trimethoxy silicane.In the specific embodiment of the invention
In, the purity of described 3-(methyl propylene acyl-oxygen) propyl trimethoxy silicane is 97%.
In the present invention, the temperature of described silanization treatment is preferably 50～80 DEG C, more preferably 60～70 DEG C,
Most preferably 65～68 DEG C；The time of described silanization treatment is 2～5 hours, concrete can be 2 hours,
3 hours, 4 hours or 5 hours.
The present invention does not has particular/special requirement to the device that described silanization treatment is used, and uses art technology
Can the reaction unit of heated for controlling temperature carry out known to personnel, concrete can be that constant temperature magnetic force stirs
Mix water-bath.In the present invention, the stir speed (S.S.) of described temperature constant magnetic stirring water-bath is preferably
90～110r/min, more preferably 95～105r/min, most preferably 100r/min.
After described silanization treatment terminates, the silanization treatment that obtains preferably is produced by the present invention with ethanol
Thing washs, to remove the unreacted material in surface.After described washing, the present invention preferably will with water
The silanization treatment product washing of ethanol washing is to neutral.The present invention does not has special wanting to the kind of described water
Asking, concrete can be deionized water, pure water or distilled water.
After described washing, the silanization treatment product after washing is preferably dried by the present invention,
To silanization carbosphere.In the present invention, described dry temperature is preferably 50～70 DEG C, more preferably
52～68 DEG C, most preferably 55～65 DEG C；The described dry time is preferably 20～30 hours, more preferably
22～26 hours, most preferably 24～25 hours.The present invention does not has spy to described dry detailed description of the invention
Different requirement, uses dry means well-known to those skilled in the art to be dried.In the present invention,
Described being dried preferably is carried out in drying box.
After obtaining described silanization carbosphere, the present invention under an inert atmosphere, by micro-for described silanization carbon
Ball, 4-vinylpridine, bisphenol-A, azodiisobutyronitrile and GDMA are organic molten
Agent carries out thermal polymerization, after removing bisphenol-A, obtains surface molecule print carbosphere.The present invention is with 4-second
Thiazolinyl pyridine be function monomer, bisphenol-A be template molecule, azodiisobutyronitrile be initiator, dimethyl
Acrylic acid glycol ester is that crosslinking agent carries out thermal polymerization on described silanization carbosphere surface.
In the present invention, described organic solvent is preferably acetonitrile or toluene.In the present invention, described silicon
Alkanisation carbosphere mass concentration in organic solvent is preferably 0.001～0.005g/mL, and concrete can be
0.001g/mL, 0.002g/mL, 0.003g/mL, 0.0033g/mL, 0.004g/mL or 0.005g/mL.
In the present invention, described organic solvent is preferably (50～80) with the volume ratio of 4-vinylpridine: 1,
More preferably (55～75): 1, most preferably (60～70): 1.In the present invention, described silanization carbosphere and
The mass ratio of bisphenol-A is preferably 1:(100～1200), more preferably 1:(500～1150), most preferably
1:(1000～1140).
Described silanization carbosphere is preferably scattered in organic solvent by the present invention, then carries out with other materials
Thermal polymerization, preferred organic solution, 4-vinylpridine and bisphenol-A by described silanization carbosphere
Carry out mixing with azodiisobutyronitrile and GDMA again after mixing and carry out thermal polymerization.
Organic solution, 4-vinylpridine and the bisphenol-A of described silanization carbosphere is preferably mixed by the present invention
To mixture be stirred.In the present invention, described stirring is preferably magnetic agitation；Described stirring
Time is preferably 20～40 minutes, more preferably 22～35 minutes, most preferably 25～32 minutes.This
The bright speed to described stirring does not has particular/special requirement, it is possible to by the organic solution of described silanization carbosphere,
4-vinylpridine and bisphenol-A mix.
In the present invention, the mass ratio of described silanization carbosphere and azodiisobutyronitrile is preferably
1:(100～300), more preferably 1:(150～250), most preferably 1:(200～220).In the present invention, institute
The volume ratio stating organic solvent and GDMA is preferably (10～20): 1, more preferably
(12～18): 1, most preferably (14～16): 1.
The present invention is to described 4-vinylpridine, bisphenol-A, azodiisobutyronitrile and dimethacrylate second
The source of diol ester does not has particular/special requirement, use 4-vinylpridine well-known to those skilled in the art,
Bisphenol-A, azodiisobutyronitrile and GDMA, concrete can be 4-ethene
The commercially available prod of yl pyridines, bisphenol-A, azodiisobutyronitrile and GDMA.
In the present invention, the temperature of described thermal polymerization is preferably 50～80 DEG C, more preferably 55～70 DEG C,
It is preferably 60～65 DEG C；The time of described thermal polymerization is 20～30 hours, more preferably 22～28 hours,
It is preferably 24～26 hours.
In the present invention, described inert atmosphere is preferably argon gas or nitrogen.The present invention is preferably in described heat
Inert gas first it is passed through, with the air in eliminating system before polymerization.In the present invention, described eliminating body
The time of the air in system is preferably 20～60 minutes, more preferably 30～50 minutes, most preferably 40～45
Minute.
The present invention does not has particular/special requirement to the device that described heat polymerization is used, and uses art technology
Can the reaction unit of heated for controlling temperature carry out known to personnel, concrete can be that constant temperature magnetic force stirs
Mix water-bath.In the present invention, the stir speed (S.S.) of described temperature constant magnetic stirring water-bath is preferably
0～110r/min, more preferably 95～105r/min, most preferably 100r/min.
After described heat polymerization terminates, the product system of heat polymerization is preferably carried out by the present invention
Filter, obtain solid product.The present invention does not has particular/special requirement to the detailed description of the invention of described filtration, adopts
Carry out with filter type well-known to those skilled in the art.In the specific embodiment of the invention, institute
State and filter concrete use filter, cross organic filter membrane of 0.45 μm.
After described filtration terminates, the solid product obtained preferably is washed by the present invention with methyl alcohol, with
Remove the unreacted material in surface.In the present invention, the number of times of described washing is preferably 1～5 time, specifically
Can be 1 time, 2 times, 3 times, 4 times or 5 times.
In the present invention, described removing bisphenol-A is preferably the mixed solution with acetic acid and methyl alcohol to solid product
Thing is carried out, until not having bisphenol-A to detect.In the present invention, described acetic acid and the volume ratio of methyl alcohol
Be preferably (1～3): (7～10), concrete can be 1:7,1:8,1:9,1:10,2:7,2:8,2:9,2:10,
3:7,3:8,3:9 or 1:10.
After removing bisphenol-A, the solid product obtained preferably is dried by the present invention, obtains surface and divides
Sub-imprinted carbon microspheres.In the present invention, described dry temperature is preferably 50～70 DEG C, more preferably
52～68 DEG C, most preferably 55～65 DEG C；The described dry time is preferably 20～30 hours, more preferably
22～26 hours, most preferably 24～25 hours.The present invention does not has spy to described dry detailed description of the invention
Different requirement, uses dry means well-known to those skilled in the art to be dried.In the present invention,
Described being dried preferably is carried out in drying box, more preferably carries out in vacuumizing drying box.
The invention provides the surface molecule print carbosphere that a kind of above-mentioned preparation method obtains, described table
Face molecular engram carbosphere, in the aqueous solution that bisphenol A concentration is relatively low, has good suction for bisphenol-A
Attached performance, maximal absorptive capacity can reach 1100mg/kg.
The invention provides above-mentioned surface molecule print carbosphere and fix answering of phase as solid-phase extraction device
With.
Present invention also offers a kind of solid-phase extraction device, including solid-phase extraction column be filled in described solid phase
Fixing phase in extraction column, described fixing is above-mentioned surface molecule print carbosphere mutually, described fixing phase
Two ends sieve plate is fixed；The quality of described surface molecule print carbosphere with the ratio of the volume of described column jecket is
(30～500) mg:(1～6) mL.
In the present invention, the quality of described surface molecule print carbosphere and the ratio of the volume of described column jecket are excellent
Elect (30～500) mg:(1～6 as) mL, more preferably (50～400) mg:(2～5) mL, most preferably
(100～200) mg:(3～4) mL.
In the present invention, the material of described column jecket is preferably polypropylene or glass；The volume of described column jecket
Being preferably 1-6mL, that concrete can be 1mL, 2mL, 3mL, 4mL, 5mL or 6mL.At this
In invention, described sieve plate is the supporting sieve plate of column jecket, and the material of described sieve plate is preferably mineral wool or quartz
Cotton.
The invention provides the preparation method of a kind of surface molecule print carbosphere, comprise the following steps: right
Carbosphere carries out oxidation processes, obtains carbonoxide microballoon；With 3-(methyl propylene acyl-oxygen) propyl trimethoxy silicon
Described carbonoxide microballoon, as silanization treating agent, is carried out surface silanization process, obtains silanization by alkane
Carbosphere；Under an inert atmosphere, by described silanization carbosphere, 4-vinylpridine, bisphenol-A, azo
Bis-isobutyronitrile and GDMA carry out thermal polymerization in organic solvent, after removing bisphenol-A,
Obtain surface molecule print carbosphere.The surface imprinted carbosphere that the present invention prepares is at bisphenol A concentration
In the relatively low aqueous solution, having good absorption property for bisphenol-A, adsorption rate is fast, adsorbance is big
And absorption stability is good.Test result indicate that of embodiment, the surface molecule print carbon that the application obtains is micro-
Ball, in the aqueous solution that bisphenol A concentration is relatively low, the maximal absorptive capacity for bisphenol-A can reach 1100
mg/kg。
Present invention also offers a kind of solid-phase extraction device, including solid-phase extraction column be filled in described solid phase
Fixing phase in extraction column, described fixing is above-mentioned surface molecule print carbosphere mutually, described fixing phase
Two ends sieve plate is fixed；The quality of described surface molecule print carbosphere with the ratio of the volume of described column jecket is
(30～500) mg:(1～6) mL.Test result indicate that of embodiment, the solid-phase extraction device pair that the application provides
Bisphenol-A in aqueous phase has good accumulation ability and easy elution property, and the rate of recovery can reach
90～100%.
The preparation method of a kind of surface molecule print carbosphere present invention provided below in conjunction with embodiment and
Application in solid-phase extraction device is described in detail, but they can not be interpreted as the present invention
The restriction of protection domain.
Embodiment 1
The carbosphere taking a diameter of 250nm of 2g commercial particulate joins the sulphur that 120mL volume ratio is 1:3
In the mixed solution of acid and nitric acid, ultrasonic 40min under the conditions of 70 DEG C.After end, liquid to be mixed is cooled to
Room temperature, filters, and using distilled water to carry out washing to pH value is 7, is placed in drying box, under the conditions of 60 DEG C
It is dried 24h, obtains the carbosphere of oxidation.
Take 0.6g carbonoxide microballoon and be placed in the pure water and the mixed solution of ethanol that 120mL volume ratio is 1:3
And use glacial acetic acid regulation pH value to 5.Add the KH-570 of 1mL, be subsequently placed in temperature constant magnetic stirring
In water-bath, reflux under the conditions of 65 DEG C 3h, removes surface first by ethanol washing unreacted after terminating
Material, then makes to be washed with distilled water to neutrality, is placed in vacuum drying chamber, is dried 24h under the conditions of 60 DEG C,
Obtain the carbosphere of silanization.
Take the silanization ball of 0.2g, be placed in the acetonitrile of 60mL, be subsequently adding 4-vinylpridine
4-VPY, 1mL, bisphenol-A 228mg, magnetic agitation 30min under room temperature condition, make various material fill
Divide mixing, be subsequently adding the AIBN of 40mg as azodiisobutyronitrile, the EGDMA conduct of 4mL
GDMA.Nitrogen blows 30min with the air in eliminating system.It is placed in constant temperature magnetic force to stir
Mix in water-bath, thermal polymerization 24h under the conditions of 60 DEG C, after terminating after thing to be mixed cooling, use solvent
Filter filters, and obtains product.First by methyl alcohol, product is washed 3 times to remove surface
Unreacted material, the acetic acid then using volume ratio to be 1:9 and the mixed solution cyclic washing of methyl alcohol are to nothing
Bisphenol-A detects, and is placed in drying box, under the conditions of 60 DEG C, vacuumizes dry 24h, obtain product
sMIP-CMs。
The synthesis flow schematic diagram of the present embodiment is as it is shown in figure 1, Fig. 1 is the embodiment of the present invention 1 resultant current
Journey schematic diagram.
The absorption property of the sMIP-CMs that the present embodiment is obtained by the present invention is tested, testing scheme
As follows:
Adsorption dynamics adsorption kinetics: in adsorption dynamics adsorption kinetics test process, sets solid water ratio for 1g:500mL, and concentration is
1mg/L, wherein sMIP-CMs consumption is 10mg, and mark-on aqueous solution volume is 5mL.Object
Concentration is 1mg/L.Sample time is set as 0,5,10,15,20,30,60,120,180,240,
1440min, is centrifuged making its separation of solid and liquid immediately after taking-up, Aspirate supernatant 1mL 15000
High speed centrifugation 5min under conditions of r/min, is transferred to sample introduction bottle, uses HPLC to carry out quantitative test.
Adsorption isotherm: adsorption isotherm sets solid water ratio for 1g:500mL, and adsorbent amount is 10mg,
Setting target concentration, 0,0.01,0.05,0.1,0.2,0.5,1,2,4,8mg/L, mark-on water
Liquor capacity is 5mL.Adsorption temp is 25 DEG C, and adsorption time is 2h, centrifugation after sampling, and
Take 1mL supernatant under the conditions of 15000r/min, high speed centrifugation 5min, it is then transferred to sample injection bottle,
HPLC is used to measure target concentration in supernatant.
Stability: for test sMIP-CMs for the absorption stability of BPA, test 5 Duplicate Samples
Product, solid water is than for 1g:500mL, and the concentration of object is 1mg/L, and adsorption time is 2h, after sampling
Centrifugation, after using HPLC quantitative analysis, calculates its adsorbance, calculates relative standard deviation value
(RSD)。
Curve of adsorption kinetics is as in figure 2 it is shown, Fig. 2 is the sMIP-CMs that the embodiment of the present invention 1 obtains
Curve of adsorption kinetics.SMIP-CMs material synthesized by the present invention is for water as seen from Figure 2
In solution, BPA adsorption rate is very fast, this shows that its effective adsorption site is concentrated mainly on material
Surface.
Adsorption isotherm is as it is shown on figure 3, suction that Fig. 3 is the sMIP-CMs that the embodiment of the present invention 1 obtains
Attached thermoisopleth.SMIP-CMs material synthesized by the present invention is relatively low in BPA concentration as seen from Figure 3
The aqueous solution in, for BPA, there is good absorption property, maximal absorptive capacity can reach 1000mg/kg.
Absorption stability about material: repeat experiment by 5 times and can obtain the relative of its adsorption capacity
Standard deviation RSD is 10.4%, and the absorption stability of material is good.
Embodiment 2
The carbosphere taking a diameter of 300nm of 2g commercial particulate joins the sulphur that 120mL volume ratio is 1:4
In the mixed solution of acid and nitric acid, ultrasonic 35min under the conditions of 70 DEG C.After end, liquid to be mixed is cooled to room
Temperature, filters, and using distilled water to carry out washing to pH value is 7, is placed in drying box, dry under the conditions of 65 DEG C
Dry 24h, obtains the carbosphere of oxidation.
Take 0.6g carbonoxide microballoon and be placed in the pure water and the mixed solution of ethanol that 100mL volume ratio is 1:3
And use glacial acetic acid regulation pH value to 5.Add the KH-570 of 1mL, be subsequently placed in temperature constant magnetic stirring
In water-bath, reflux under the conditions of 60 DEG C 3.5h, removes surface unreacted first by ethanol washing after terminating
Material, then make to be washed with distilled water to neutrality, be placed in vacuum drying chamber, under the conditions of 60 DEG C be dried
25h, obtains the carbosphere of silanization.
Take the silanization ball of 0.22g, be placed in the toluene of 60mL, be subsequently adding 4-vinylpridine
4-VPY, 1mL, bisphenol-A 230mg, magnetic agitation 30min under room temperature condition, make various material fill
Divide mixing, be subsequently adding the AIBN of 40mg as azodiisobutyronitrile, the EGDMA conduct of 4mL
GDMA.Nitrogen blows 30min with the air in eliminating system.It is placed in constant temperature magnetic force to stir
Mix in water-bath, thermal polymerization 24h under the conditions of 60 DEG C, after terminating after thing to be mixed cooling, use solvent
Filter filters, and obtains product.First by methyl alcohol, product is washed 3 times to remove surface
Unreacted material, the acetic acid then using volume ratio to be 1:9 and the mixed solution cyclic washing of methyl alcohol are to nothing
Bisphenol-A detects, and is placed in drying box, under the conditions of 60 DEG C, vacuumizes dry 24h, obtain product
sMIP-CMs。
The sMIP-CMs that the present embodiment is obtained by the present invention is examined according to the detection mode of embodiment 1
Survey.Testing result shows, the maximal absorptive capacity of the sMIP-CMs that the present embodiment obtains can reach
1100mg/kg, adsorption dynamics adsorption kinetics and stability result are consistent with embodiment 1 result, no longer go to live in the household of one's in-laws on getting married at this
State.
Embodiment 3
Taking the carbosphere of a diameter of 280nm of 2.5g commercial particulate and joining 120mL volume ratio is 1:3's
In the mixed solution of sulfuric acid and nitric acid, ultrasonic 45min under the conditions of 75 DEG C.After end, liquid to be mixed cools down
To room temperature, filtering, using distilled water to carry out washing to pH value is 7, is placed in drying box, 60 DEG C of conditions
Under be dried 25h, obtain oxidation carbosphere.
Take 0.6g carbonoxide microballoon and be placed in the pure water and the mixed solution of ethanol that 150mL volume ratio is 1:3
And use glacial acetic acid regulation pH value to 5.Add the KH-570 of 1mL, be subsequently placed in temperature constant magnetic stirring
In water-bath, reflux under the conditions of 70 DEG C 3.5h, removes surface unreacted first by ethanol washing after terminating
Material, then make to be washed with distilled water to neutrality, be placed in vacuum drying chamber, under the conditions of 65 DEG C be dried
24h, obtains the carbosphere of silanization.
Take the silanization ball of 0.2g, be placed in the acetonitrile of 60mL, be subsequently adding 4-vinylpridine
4-VPY, 1mL, bisphenol-A 225mg, magnetic agitation 35min under room temperature condition, make various material fill
Divide mixing, be subsequently adding the AIBN of 40mg as azodiisobutyronitrile, the EGDMA conduct of 4mL
GDMA.Nitrogen blows 30min with the air in eliminating system.It is placed in constant temperature magnetic force to stir
Mix in water-bath, thermal polymerization 22h under the conditions of 65 DEG C, after terminating after thing to be mixed cooling, use solvent
Filter filters, and obtains product.First by methyl alcohol, product is washed 3 times to remove surface
Unreacted material, the acetic acid then using volume ratio to be 1:9 and the mixed solution cyclic washing of methyl alcohol are to nothing
Bisphenol-A detects, and is placed in drying box, under the conditions of 65 DEG C, vacuumizes dry 22h, obtain product
sMIP-CMs。
The sMIP-CMs that the present embodiment is obtained by the present invention is examined according to the detection mode of embodiment 1
Survey.Testing result shows, the maximal absorptive capacity of the sMIP-CMs that the present embodiment obtains can reach
1050mg/kg, adsorption dynamics adsorption kinetics and stability result are consistent with embodiment 1 result, no longer go to live in the household of one's in-laws on getting married at this
State.
Embodiment 4
The sMIP-CMs filler taking 30mg embodiment 1 synthesis loads the empty solid phase extraction that volume is 1mL
Taking (SPE) column jecket, two ends are compacted with supporting sieve plate, stand-by.Simultaneously with the SPE column jecket of same model
Load non-surface molecule print carbosphere (NIP-CMs) as comparison.
As shown in Figure 4, Fig. 4 is this to the structural representation of the solid-phase extraction device that the present embodiment 1 obtains
The structural representation of the solid-phase extraction device that bright embodiment 4 provides.
The present invention the BPA in the aqueous solution is enriched with to the solid-phase extraction device that the present embodiment provides
Being detected with the effect purified, detection method is as follows:
Pillar is carried out and balances by the acetonitrile and the pure water that use 3mL respectively, take the most respectively 20mL,
Pure water matrix and the DOM matrix sample of 10 μ g/L cross pillar, drain 30min, then make after terminating
Eluting with the acetic acid methanol solution of 4mL, 10%, wash-out takes the above-mentioned eluent of 1mL after terminating to be carried out
Nitrogen is blown to dip dry, and the methanol aqueous solution constant volume then using volume fraction to be 70%, to 1mL, uses HPLC
Test.
Accumulation ability: finding to add in aqueous at BPA to be designated as 10 μ g/L, applied sample amount is 20mL, adopts
When washing for object with the acetic acid methanol solution that volume ratio is 1:9, its rate of recovery can reach
90～100%.The solid-phase extraction device that surface the present embodiment provides has well for the BPA in the aqueous solution
Accumulation ability, simultaneously the most also explanation absorption is easily washed away at the BPA molecule of material surface.
Detergent power: Fig. 5 is the embodiment of the present invention 5 device and comparative example device to return for the extraction of BPA
Yield compares, although using the solid phase extraction procedure of sMIP-CMs filler to eliminate as seen from Figure 5
Drip washing dedoping step, but when matrix complexity, sMIP-CMs filler is unaffected for the extraction of BPA,
NIP-CMs filler then can significantly decline for the extraction quantity of BPA, and the surface that the present invention provides is described
Molecular engram carbosphere has preferable selectivity for the BPA in the aqueous solution.
Extraction eluent respectively for bi-material makes using pure water matrix extraction eluent as reference solution
Under 254nm wavelength condition, test its absorbance with ultraviolet-uisible spectrophotometer, find sMIP-CMs
Solid-phase extraction column eluent value as filler is 0.684, and NIP-CMs is as the pillar eluent of filler
Value is 1.0285, shows that sMIP-CMs can preferably suppress the complex matrices in water environment to disturb.
As seen from the above embodiment, the invention provides the preparation method of a kind of surface molecule print carbosphere,
Comprise the following steps: carbosphere is carried out oxidation processes, obtain carbonoxide microballoon；With 3-(methyl propylene acyl
Oxygen) propyl trimethoxy silicane as silanization treating agent, described carbonoxide microballoon is carried out surface silanization
Process, obtain silanization carbosphere；Under an inert atmosphere, by described silanization carbosphere, 4-vinylpyridine
Pyridine, bisphenol-A, azodiisobutyronitrile and GDMA carry out hot polymerization in organic solvent
Close, after removing bisphenol-A, obtain surface molecule print carbosphere.It is surface imprinted that the present invention prepares
Carbosphere, in the aqueous solution that bisphenol A concentration is relatively low, has good absorption property for bisphenol-A, inhales
Attached speed is fast, adsorbance is big, good stability and have high selectivity.Test result indicate that of embodiment,
The surface molecule print carbosphere that the application obtains, in the aqueous solution that bisphenol A concentration is relatively low, for double
The maximal absorptive capacity of phenol A can reach 1100mg/kg.
Present invention also offers a kind of solid-phase extraction device, including solid-phase extraction column be filled in described solid phase
Fixing phase in extraction column, described fixing is above-mentioned surface molecule print carbosphere mutually, described fixing phase
Two ends sieve plate is fixed；The quality of described surface molecule print carbosphere with the ratio of the volume of described column jecket is
(30～500) mg:(1～6) mL.Test result indicate that of embodiment, the solid-phase extraction device pair that the application provides
Bisphenol-A in aqueous phase has good accumulation ability and easy elution property, and can effectively suppress water sample
The interference of middle complex matrices, recovery of extraction can reach 90～100%.
The above is only the preferred embodiment of the present invention, it is noted that general for the art
For logical technical staff, under the premise without departing from the principles of the invention, it is also possible to make some improvement and profit
Decorations, these improvements and modifications also should be regarded as protection scope of the present invention.
Claims (10)
1. a preparation method for surface molecule print carbosphere, comprises the following steps:
Carbosphere is carried out oxidation processes, obtains carbonoxide microballoon；
Using 3-(methyl propylene acyl-oxygen), propyl trimethoxy silicane is as silanization treating agent, by described carbonoxide
Microballoon carries out surface silanization process, obtains silanization carbosphere；
Under an inert atmosphere, by different to described silanization carbosphere, 4-vinylpridine, bisphenol-A, azo two
Butyronitrile and GDMA carry out thermal polymerization in organic solvent, after removing bisphenol-A,
To surface molecule print carbosphere.
Preparation method the most according to claim 1, it is characterised in that described carbosphere a diameter of
240～300nm.
Preparation method the most according to claim 1, it is characterised in that described silanization treatment is concrete
For:
Regulation includes that the pH value of the system of carbonoxide microballoon and ethanol solution, to 4～6, obtains acidic oxidation carbon
Microsphere system；
Described acidic oxidation carbosphere system and 3-(methyl propylene acyl-oxygen) propyl trimethoxy silicane are mixed
Carry out silanization treatment, obtain silanization carbosphere.
Preparation method the most according to claim 3, it is characterised in that the volume of described ethanol solution
Concentration is 70～80%；
The quality of described carbonoxide microballoon and the volume ratio of ethanol solution are (0.1～1) g:(100～150) mL；
The volume ratio of described ethanol solution and 3-(methyl propylene acyl-oxygen) propyl trimethoxy silicane is
(100～150): 1.
5. according to the preparation method described in claim 1,3 or 4, it is characterised in that described silanization
The temperature processed is 50～80 DEG C；
The time of described silanization treatment is 2～5 hours.
Preparation method the most according to claim 1, it is characterised in that described silanization carbosphere exists
Mass concentration in organic solvent is 0.001～0.005g/mL；
Described organic solvent is (50～80) with the volume ratio of 4-vinylpridine: 1；
The mass ratio of described silanization carbosphere and bisphenol-A is 1:(100～1200)；
The mass ratio of described silanization carbosphere and azodiisobutyronitrile is 1:(100～300)；
Described organic solvent is (10～20) with the volume ratio of GDMA: 1.
7. according to the preparation method described in claim 1 or 6, it is characterised in that the temperature of described thermal polymerization
Degree is 50～80 DEG C；
The time of described thermal polymerization is 20～30 hours.
8. the surface molecule print carbosphere that the preparation method described in claim 1～7 any one obtains,
It is characterized in that, described surface molecule print carbosphere in the aqueous solution that bisphenol A concentration is relatively low, for
Bisphenol-A has good absorption property, and maximal absorptive capacity can reach 1100mg/kg.
9. surface molecule print carbosphere described in claim 8 is as the application of fixing phase.
10. a solid-phase extraction device, including solid-phase extraction column and being filled in described solid-phase extraction column
Fixing phase, it is characterised in that described fixing mutually for the surface molecule print carbosphere described in claim 8,
Described fixing phase two ends sieve plate is fixed；The quality of described surface molecule print carbosphere and described column jecket
The ratio of volume is (30～500) mg:(1～6) mL.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610439908.1A CN105903454A (en) | 2016-06-15 | 2016-06-15 | Preparation method of surface molecularly-imprinted carbon microspheres and application of surface molecularly-imprinted carbon microspheres in solid-phase extraction device |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610439908.1A CN105903454A (en) | 2016-06-15 | 2016-06-15 | Preparation method of surface molecularly-imprinted carbon microspheres and application of surface molecularly-imprinted carbon microspheres in solid-phase extraction device |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN105903454A true CN105903454A (en) | 2016-08-31 |
Family
ID=56750437
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610439908.1A Pending CN105903454A (en) | 2016-06-15 | 2016-06-15 | Preparation method of surface molecularly-imprinted carbon microspheres and application of surface molecularly-imprinted carbon microspheres in solid-phase extraction device |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105903454A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110711568A (en) * | 2019-11-25 | 2020-01-21 | 太原理工大学 | Hydrophilic bifunctional monomer imprinting adsorption material and preparation method thereof |
| CN110734571A (en) * | 2019-10-24 | 2020-01-31 | 河南师范大学 | Preparation method and application of bisphenol A molecularly imprinted polymers |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104772127A (en) * | 2015-03-25 | 2015-07-15 | 南开大学 | Production method of carbon fiber cloth surface molecular imprinting passive sampling membrane for organic pollutants in water environment |
-
2016
- 2016-06-15 CN CN201610439908.1A patent/CN105903454A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104772127A (en) * | 2015-03-25 | 2015-07-15 | 南开大学 | Production method of carbon fiber cloth surface molecular imprinting passive sampling membrane for organic pollutants in water environment |
Non-Patent Citations (1)
| Title |
|---|
| CAO FENGMEI ET AL.: "Synthesis of a perfluorooctanoic acid molecularly imprinted polymer for the selective removal of perfluorooctanoic acid in an aqueous environment", 《JOURNAL OF APPLIED POLYMER SCIENCE》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110734571A (en) * | 2019-10-24 | 2020-01-31 | 河南师范大学 | Preparation method and application of bisphenol A molecularly imprinted polymers |
| CN110734571B (en) * | 2019-10-24 | 2021-12-07 | 河南师范大学 | Preparation method and application of bisphenol A molecularly imprinted polymer |
| CN110711568A (en) * | 2019-11-25 | 2020-01-21 | 太原理工大学 | Hydrophilic bifunctional monomer imprinting adsorption material and preparation method thereof |
| CN110711568B (en) * | 2019-11-25 | 2022-04-08 | 太原理工大学 | Hydrophilic bifunctional monomer imprinting adsorption material and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Rui et al. | Selective extraction and enrichment of aflatoxins from food samples by mesoporous silica FDU-12 supported aflatoxins imprinted polymers based on surface molecularly imprinting technique | |
| Ma et al. | Development of magnetic molecularly imprinted polymers based on carbon nanotubes–Application for trace analysis of pyrethroids in fruit matrices | |
| Li et al. | Preparation of a hollow porous molecularly imprinted polymer using tetrabromobisphenol A as a dummy template and its application as SPE sorbent for determination of bisphenol A in tap water | |
| Jiang et al. | Molecularly imprinted solid-phase extraction for the selective determination of 17β-estradiol in fishery samples with high performance liquid chromatography | |
| Dong et al. | Thermosensitive molecularly imprinted polymers on porous carriers: preparation, characterization and properties as novel adsorbents for bisphenol A | |
| You et al. | High-capacity thermo-responsive magnetic molecularly imprinted polymers for selective extraction of curcuminoids | |
| Xia et al. | Selective separation of quercetin by molecular imprinting using chitosan beads as functional matrix | |
| Ge et al. | Combined magnetic porous molecularly imprinted polymers and deep eutectic solvents for efficient and selective extraction of aristolochic acid I and II from rat urine | |
| CN102898566B (en) | Preparation method of metal organic framework molecularly imprinted polymer used for enriching trace amounts of Metolcarb | |
| Wan et al. | Novel dual functional monomers based molecularly imprinted polymers for selective extraction of myricetin from herbal medicines | |
| Liu et al. | Synthesis of core-shell molecularly imprinted polymers (MIP) for spiramycin I and their application in MIP chromatography | |
| CN104148030A (en) | Organic phenylboronic acid-rich polyethyleneimine modified silicon dioxide microsphere, preparation method and application of organic phenylboronic acid-rich polyethyleneimine modified silicon dioxide microsphere | |
| Wang et al. | Surface molecularly imprinted polymers based on yeast prepared by atom transfer radical emulsion polymerization for selective recognition of ciprofloxacin from aqueous medium | |
| WO2015192387A1 (en) | Aqueous phase metal organic framework molecular imprinting material of enriched trace metolcarb | |
| Yu et al. | Preparation of molecularly imprinted polymers coupled with high-performance liquid chromatography for the selective extraction of salidroside from Rhodiola crenulata | |
| Fan et al. | Study of molecularly imprinted solid-phase extraction of diphenylguanidine and its structural analogs | |
| Qiu et al. | Fabrication of novel stir bar sorptive extraction coating based on magnetic molecularly imprinted polymer through atom transfer radical polymerization for trace analysis of estrogens in milk | |
| Pataer et al. | Preparation of a stoichiometric molecularly imprinted polymer for auramine O and application in solid‐phase extraction | |
| Yang et al. | A photoresponsive surface molecularly imprinted polymer shell for determination of trace griseofulvin in milk | |
| CN105903454A (en) | Preparation method of surface molecularly-imprinted carbon microspheres and application of surface molecularly-imprinted carbon microspheres in solid-phase extraction device | |
| CN111171212B (en) | Metal organic framework surface molecularly imprinted polymer and preparation method and application thereof | |
| CN105921129A (en) | Preparation method of magnetic molecularly imprinted microspheres and application in separation and enrichment of cucurbitane triterpenoid | |
| Luo et al. | Preparation and application of molecularly imprinted polymers for the selective extraction of naringin and genistein from herbal medicines | |
| CN108579696A (en) | A kind of theophylline molecular engram material and its preparation method and application of silver nano-grain doping | |
| Yang et al. | Synthesis of the artemisinin‐imprinting polymers on silica surface and its adsorption behavior in supercritical CO2 fluid |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20160831 |