CN105153367A - Preparation method of dicyandiamide mesoporous surface molecularly imprinted polymer microspheres - Google Patents
Preparation method of dicyandiamide mesoporous surface molecularly imprinted polymer microspheres Download PDFInfo
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Abstract
The invention relates to a preparation method of dicyandiamide mesoporous surface molecularly imprinted polymer microspheres. The method comprises the following steps: carrying out ultrasonic dispersion on a mesoporous SBA-15 powder in a toluene solution, and adding 3-(trimethoxysilyl)propyl acrylate to obtain modified mesoporous SBA-15; dissolving dicyandiamide in acetonitrile under the ultrasonic action, adding a functional monomer methacrylic acid and the modified mesoporous SBA-15, and carrying out ultrasonic preassembly; adding a crosslinking agent ethylene glycol dimethyl acrylate and an initiator azoethyl butyronitrile, carrying out ultrasonic treatment for 10 minutes, introducing nitrogen into the solution for 10 minutes, and stirring at 60 DEG C for 24 hours; and after the reaction finishes, centrifuging to remove the supernatant, carrying out repeated ultrasonic washing with a methanol-acetic acid mixed solution, and washing with methanol to neutrality, thereby obtaining the dicyandiamide mesoporous surface molecularly imprinted polymer. The preparation method can obtain the spherical molecularly imprinted polymer with the advantages of high selectivity, high adsorption capacity and uniform particle size, and can be widely used for enrichment and analysis on dicyandiamide in the milk powder and aquatic environment sample.
Description
Technical field
The invention belongs to molecularly imprinted polymer technical field, particularly relate to the preparation method of mesopore surfaces molecularly imprinted polymer Dyhard RU 100 to specific recognition.
Background technology
Dyhard RU 100 (dicyandiamide, DCD) is the dimer of cyanamide, white crystalline powder, stable time dry.It is active that Dyhard RU 100 has suppression nitrobacteria, is used as nitrification inhibitor and is widely used in agriculture production to reduce nitrification speeds, the minimizing nitrogen loss of soil.But use can cause gathering of DCD frequently, detects Dyhard RU 100 from infant formula powder.Dyhard RU 100 nitrogen content is higher in addition, is likely added in milk source to improve N content.There is not the examination criteria of milk powder and milk preparation Dyhard RU 100 in current China, the Dyhard RU 100 of high dosage has stronger toxicity to human body especially infant, therefore the detection method of Dyhard RU 100 in a kind of quick, accurate, sensitive milk powder and milk preparation is set up, for the contents level accurately understanding Dyhard RU 100 in milk powder on market, science formulates the limitation level of Dyhard RU 100 in milk powder, all significant.
Because in milk powder or environmental sample, the content of DCD is extremely low, add that sample matrices is complicated, be difficult to direct mensuration, usually need just can analyze after sample pre-treatments.Therefore, the Sample Processes New Method developing efficient highly selective is significant.
Molecular imprinting (MolecularImprintingTechnique, MIT) is the technology of preparing for obtaining the polymkeric substance mated completely with certain a part (template molecule) on space structure and binding site.And surface molecule print technology sets up at material surface the method being obtained molecular recognition system by molecular imprinting.Compared with traditional molecular imprinting, utilize the obtained surface imprinted polymer of the method effectively to overcome the shortcomings such as trace hole embedded deeply, template molecule elution is not thorough, there is the advantages such as loading capacity is high, selectivity good, binding site is not easily destroyed.What require along with sample detection improves constantly the widespread use with modern detecting, and the application development of surface molecule print technology in compartment analysis science is very active.
SBA-15 is the highly ordered mesosize pores silicon-dioxide of the linear symmetric of the arrangement in hexagonal, has large aperture (7-9nm), large specific surface area (550-600m
2/ g), thick hole wall (about 3.1-6.4nm) and high pore volume (~ 1.3cm
3/ g), there is better chemical machinery stability.The character of SBA-15 makes it be applicable to doing parcel and the upholder on surface.At separation field, be generally by carrying out inorganic group (-NH to SBA-15
2,-SH) and finishing or organically-modified its selectivity that makes is higher, loading capacity is larger, thus makes its adsorption separation performance of raising.And select SBA-15 as substrate material utilize surface imprinted technology synthesize imprinted polymer carry out Dyhard RU 100 absorption rarely have report with the research be separated.
Summary of the invention
In order to solve the deficiencies in the prior art, the object of the present invention is to provide a kind of preparation method of Dyhard RU 100 mesopore surfaces molecular blotting polymer microsphere, the global molecular imprinted polymer that the method can prepare a kind of selectivity and loading capacity is high, particle diameter is more homogeneous, can be widely used in the enrichment of Dyhard RU 100 in milk powder, environmental water sample, analysis, recovery of extraction reaches more than 95%.
The preparation method of Dyhard RU 100 mesopore surfaces molecular blotting polymer microsphere of the present invention comprises the following steps: mesoporous molecular sieve SBA-15 powder ultrasonic is scattered in toluene solution by A., then adds 3-(trimethoxy is silica-based) propyl acrylate, N
2in 60 DEG C of stirring in water bath 3 hours under protection, obtained modify after mesoporous SBA-15; Mesoporous SBA-15 after above-mentioned modification is used successively toluene, methyl alcohol supersound washing, centrifugal, last 60 DEG C of vacuum-dryings 12 hours, for subsequent use; B. Dyhard RU 100 is used acetonitrile ultrasonic dissolution, add the mesoporous SBA-15 after function monomer methacrylic acid, modification, ultrasonic pre-assembled; Add linking agent ethylene glycol dimethacrylate and initiator azo second butyronitrile again, ultrasonic 10 minutes, nitrogen is passed into after 10 minutes to solution, 60 DEG C are stirred after 24 hours, reaction terminates rear centrifugal removing supernatant liquor, the supersound washing repeatedly of product with methylalcohol-acetic acid mixed solution, then with methanol wash column to neutral, obtain Dyhard RU 100 mesopore surfaces molecularly imprinted polymer.
According to the further feature of the preparation method of Dyhard RU 100 mesopore surfaces molecular blotting polymer microsphere of the present invention, described mesoporous molecular sieve SBA-15 powder is prepared by following steps: 4g polyoxyethylene-poly-oxypropylene polyoxyethylene triblock copolymer and 6 grams of Repone K are placed in Erlenmeyer flask, add 120ml water, 19.8ml concentrated hydrochloric acid, be stirred to transparent, add 3 grams of sym-trimethylbenzene and stir 2 hours again; 9.5 grams of tetraethyl orthosilicates are added gradually, vigorous stirring 10 minutes under stirring; 40 DEG C of ageings 24 hours, 80 DEG C of ageings 24 hours; Suction filtration, cleans to filtrate clarification with water, 70 DEG C of vacuum-drying 6 hours repeatedly; Products therefrom in retort furnace with 5 DEG C/min of temperature programmings to 550 DEG C, then in 550 DEG C of roastings 6 hours, obtained SBA-15 powder.
According to the further feature of the preparation method of Dyhard RU 100 mesopore surfaces molecular blotting polymer microsphere of the present invention, in step B, by 0.25mmol Dyhard RU 100 20mL acetonitrile ultrasonic dissolution, add the mesoporous SBA-15 after 1mmol function monomer methacrylic acid, 1.0g modification, ultrasonic pre-assembled.Add 5mmol linking agent ethylene glycol dimethacrylate and 30g initiator azo second butyronitrile again, ultrasonic 10 minutes, nitrogen is passed into after 10 minutes to solution, 60 DEG C are stirred after 24 hours, reaction terminates rear centrifugal removing supernatant liquor, the supersound washing repeatedly of product with methylalcohol-acetic acid mixed solution, then with methanol wash column to neutral, obtain Dyhard RU 100 mesopore surfaces molecular blotting polymer microsphere.
Dyhard RU 100 mesopore surfaces molecular blotting polymer microsphere of the present invention and preparation method thereof, has the following advantages:
(1) the present invention adopts the Dyhard RU 100 mesopore surfaces molecularly imprinted polymer that the surface imprinted polymerization method of the simple and effective of improvement obtains having spherical morphology, particle diameter is more homogeneous, selectivity is high, loading capacity is high, recovery of extraction is high.
(2) the preparation-obtained imprinted polymer of the present invention has spherical morphology (as shown in Figure 2), particle diameter more homogeneous (aperture is about 2.94-3.53 μm), selectivity is high, loading capacity is high (to be measured through Staticadsorption experiment, 2.5mg/g is respectively to the maximal absorptive capacity of Dyhard RU 100), recovery of extraction is high (with the mesoporous imprinted polymer microballoon prepared for solid phase extraction filler, load at methyl alcohol, 2mL acetonitrile and water mixed solution drip washing, 8mL acetate-methanol (9:1, V/V) under elution requirement, through Solid-Phase Extraction measuring, 85.2-105.3% is reached to the Dyhard RU 100 rate of recovery).
(3) with under the chaff interference concurrent conditions of target compound structural similitude, mesoporous trace microballoon provided by the present invention can preference identification target compound Dyhard RU 100, there is good application prospect for Dyhard RU 100 aspect in monitoring food and environmental water sample, be highly suitable for the concentration and analysis of trace Dyhard RU 100 in milk powder and environmental water sample.
(4) the mesoporous trace method for preparing microsphere of high-specific surface area provided by the present invention can be applied to the monitoring of other organic pollutant, has a wide range of applications in food safety etc.
Accompanying drawing explanation
Fig. 1 is the action principle figure that the present invention prepares mesopore surfaces molecularly imprinted polymer.
Fig. 2 is the scanning electron microscope (SEM) photograph that the present invention prepares mesopore surfaces imprinted polymer.
Fig. 3 is the curve of adsorption kinetics figure of the mesopore surfaces imprinted polymer that embodiment 1 obtains, and in figure, ■ represents MIP; ● represent NIP.
Fig. 4 is the Static Adsorption isothermal map of the mesopore surfaces imprinted polymer that embodiment 1 obtains, and in figure, ■ represents MIP; ● represent NIP.
Embodiment
Embodiment one: Dyhard RU 100 mesopore surfaces molecularly imprinted polymer of the present invention
As shown in Figure 1, preparation method comprises the following steps the schematic diagram of the preparation of the Dyhard RU 100 mesopore surfaces molecularly imprinted polymer described in the present embodiment:
1. Dyhard RU 100 mesopore surfaces molecular blotting polymer microsphere, its preparation process is:
Mesoporous SBA-15 powder ultrasonic is scattered in toluene solution, then adds 3-(trimethoxy is silica-based) propyl acrylate, N
2in 60 DEG C of stirring in water bath 3 hours under protection, obtained modify after mesoporous SBA-15, then use toluene, methyl alcohol supersound washing, centrifugal successively, last 60 DEG C of vacuum-dryings 12 hours, for subsequent use; Dyhard RU 100 is used acetonitrile ultrasonic dissolution, add the mesoporous SBA-15 after function monomer methacrylic acid, modification, ultrasonic pre-assembled.Add linking agent ethylene glycol dimethacrylate and initiator azo second butyronitrile again, ultrasonic 10 minutes, nitrogen is passed into after 10 minutes to solution, 60 DEG C are stirred after 24 hours, reaction terminates rear centrifugal removing supernatant liquor, the supersound washing repeatedly of product with methylalcohol-acetic acid mixed solution, then with methanol wash column to neutral, obtain Dyhard RU 100 mesopore surfaces molecularly imprinted polymer.
2. the preparation method of Dyhard RU 100 mesopore surfaces molecular blotting polymer microsphere, its preparation process is:
Mesoporous SBA-15 powder ultrasonic is scattered in toluene solution, then adds 3-(trimethoxy is silica-based) propyl acrylate, N
2in 60 DEG C of stirring in water bath 3 hours under protection, obtained modify after mesoporous SBA-15, then use toluene, methyl alcohol supersound washing, centrifugal successively, last 60 DEG C of vacuum-dryings 12 hours, for subsequent use;
Dyhard RU 100 is used acetonitrile ultrasonic dissolution, add the mesoporous SBA-15 after function monomer methacrylic acid, modification, ultrasonic pre-assembled.Add linking agent ethylene glycol dimethacrylate and initiator azo second butyronitrile again, ultrasonic 10 minutes, nitrogen is passed into after 10 minutes to solution, 60 DEG C are stirred after 24 hours, reaction terminates rear centrifugal removing supernatant liquor, the supersound washing repeatedly of product with methylalcohol-acetic acid mixed solution, then with methanol wash column to neutral, obtain Dyhard RU 100 mesopore surfaces molecularly imprinted polymer.
Embodiment two: adsorptive capacity is tested
The dicyandiamide solution one group of 10mL concentration being 0.01mg/mL adds the imprinted polymer and non-imprinted polymer that quality is the Dyhard RU 100 of 20mg respectively, Static Adsorption 5,10,20,30,60,180min.Be transferred to centrifuge tube after having adsorbed, in the centrifugal 5min of 3000r/min, get supernatant liquor after centrifugal, by UV spectrophotometer measuring, when trying to achieve adsorption equilibrium, MIP is to the adsorption concentration of target molecule Dyhard RU 100.The maximal absorptive capacity Qmax of this polymkeric substance to Dyhard RU 100 is calculated again by the change in concentration before and after absorption.Result shows, and saturated extent of adsorption is about 2.5mg/g.
Embodiment three: the rate of recovery is tested
Successively with 4mL water, 4mL methyl alcohol activation SBA-15 mesoporous molecular imprinted material post, the loading volume of 5mL, the leacheate drip washing of 4mL acetonitrile/water=1/1 (V/V), the elution of 8mL methyl alcohol/acetic acid=9/1 (V/V), sample size 30 μ L, moving phase is acetic acid solution (pH=3.5)/acetonitrile=85/15 (V/V), flow velocity 0.3mL/min, and determined wavelength is 220nm.Carry out powdered milk sample and sample to add target and detect.Be 85.2 ~ 105.3% by calculating the recovery of standard addition of gained milk powder, relative standard deviation (RSD) is 2.3 ~ 3.3%.
testing example:
Mesoporous molecular sieve SBA-15 composite nano surface imprinted polymer and the non-imprinted polymer of getting synthesis in above-described embodiment 1 carry out following test experiments.
Testing example 1: scanning electron microscope characterizes
Fig. 2 is the mesoporous molecular sieve SBA-15 scanning electron microscope (SEM) photograph that the present invention synthesizes, visible, the duct queueing discipline of mesoporous molecular sieve SBA-15, aperture comparatively large (about 2.94-3.53 μm).
Testing example 2: kinetics of adsorption is tested
Precision takes each 6 parts of MIP and NIP (20.0mg), be placed in 15mL triangular flask, add the dicyandiamide solution 5mL of 0.01mg/mL respectively, ultrasonic disperse, rocked at room temperature, got supernatant liquor respectively 20,40,60,80,100 and 120 minutes time, with 0.22 μm of filtering with microporous membrane, quantitative dilution, ultraviolet spectrophotometer measures dicyandiamide solution concentration before and after absorption in 220nm place, calculates and calculates equilibrium adsorption capacity Q according to formula (1)
e, replicate(determination) three times.
Q
e＝(C
0-C
e)V/W(1)
In formula: C
0and C
ebe respectively initial concentration and the equilibrium concentration (mg/mL) of template molecule; V is the volume (mL) of adsorbent solution; W is the quality (g) of imprinted polymer.
As seen from Figure 3, mesoporous imprinted material has adsorption rate faster, can reach adsorption equilibrium rapidly, and the adsorption rate of MIP and adsorptive capacity is greater than NIP in 80 minutes.Tracing it to its cause is that its recognition site of MIP prepared by surface molecule print is positioned at material surface, and accessibility is strong, and mass transfer velocity is fast, can reach adsorption equilibrium fast.
Testing example 3: Static Adsorption is tested
Precision takes each 7 parts of MIP and NIP (20.0mg), be placed in 15mL triangular flask, add the dicyandiamide solution 5mL of 3,4,5,6,7,8 and 9mg/mL respectively, ultrasonic disperse, rocked at room temperature 2h, gets supernatant liquor, with 0.22 μm of filtering with microporous membrane, quantitative dilution, ultraviolet spectrophotometer measures dicyandiamide solution concentration before and after absorption in 220nm place, calculates and calculates equilibrium adsorption capacity Q according to formula (1)
e, replicate(determination) three times.
As shown in Figure 4, the adsorptive capacity of MIP to Dyhard RU 100 is obviously greater than NIP, show that the absorption of MIP to Dyhard RU 100 is different from physical adsorption, but a kind of selective adsorption having specific recognition site, to illustrate in printing process template molecule in mip selectivity bonding create the active binding site on imprinted cavity and hole, have specific recognition to template molecule.
Claims (3)
1. a preparation method for Dyhard RU 100 mesopore surfaces molecular blotting polymer microsphere, is characterized in that, comprises the following steps:
A. mesoporous molecular sieve SBA-15 powder ultrasonic is scattered in toluene solution, then adds 3-(trimethoxy is silica-based) propyl acrylate, N
2in 60 DEG C of stirring in water bath 3 hours under protection, obtained modify after mesoporous SBA-15; Mesoporous SBA-15 after above-mentioned modification is used successively toluene, methyl alcohol supersound washing, centrifugal, last 60 DEG C of vacuum-dryings 12 hours, for subsequent use;
B. Dyhard RU 100 is used acetonitrile ultrasonic dissolution, add the mesoporous SBA-15 after function monomer methacrylic acid, modification, ultrasonic pre-assembled; Add linking agent ethylene glycol dimethacrylate and initiator azo second butyronitrile again, ultrasonic 10 minutes, nitrogen is passed into after 10 minutes to solution, 60 DEG C are stirred after 24 hours, reaction terminates rear centrifugal removing supernatant liquor, the supersound washing repeatedly of product with methylalcohol-acetic acid mixed solution, then with methanol wash column to neutral, obtain Dyhard RU 100 mesopore surfaces molecularly imprinted polymer.
2. the preparation method of Dyhard RU 100 mesopore surfaces molecular blotting polymer microsphere according to claim 1, it is characterized in that, described mesoporous molecular sieve SBA-15 powder is prepared by following steps: 4g polyoxyethylene-poly-oxypropylene polyoxyethylene triblock copolymer and 6 grams of Repone K are placed in Erlenmeyer flask, add 120ml water, 19.8ml concentrated hydrochloric acid, be stirred to transparent, add 3 grams of sym-trimethylbenzene and stir 2 hours again; 9.5 grams of tetraethyl orthosilicates are added gradually, vigorous stirring 10 minutes under stirring; 40 DEG C of ageings 24 hours, 80 DEG C of ageings 24 hours; Suction filtration, cleans to filtrate clarification with water, 70 DEG C of vacuum-drying 6 hours repeatedly; Products therefrom in retort furnace with 5 DEG C/min of temperature programmings to 550 DEG C, then in 550 DEG C of roastings 6 hours, obtained SBA-15 powder.
3. the preparation method of Dyhard RU 100 mesopore surfaces molecular blotting polymer microsphere according to claim 1, it is characterized in that: in step B, by 0.25mmol Dyhard RU 100 20mL acetonitrile ultrasonic dissolution, add the mesoporous SBA-15 after 1mmol function monomer methacrylic acid, 1.0g modification, ultrasonic pre-assembled.Add 5mmol linking agent ethylene glycol dimethacrylate and 30g initiator azo second butyronitrile again, ultrasonic 10 minutes, nitrogen is passed into after 10 minutes to solution, 60 DEG C are stirred after 24 hours, reaction terminates rear centrifugal removing supernatant liquor, the supersound washing repeatedly of product with methylalcohol-acetic acid mixed solution, then with methanol wash column to neutral, obtain Dyhard RU 100 mesopore surfaces molecular blotting polymer microsphere.
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| CN106753329A (en) * | 2016-11-01 | 2017-05-31 | 北京工商大学 | Fluorescence trace sensing material and response element and preparation method thereof and the application in dicyandiamide is detected |
| WO2017198693A1 (en) * | 2016-05-17 | 2017-11-23 | Basf Se | A composition comprising mesoporous silicon dioxide particles and a nitrification inhibitor |
| CN110183594A (en) * | 2019-06-12 | 2019-08-30 | 河南工业大学 | Aflatoxin surface imprinted polymer and its application based on SBA-15 |
| CN112138635A (en) * | 2020-08-03 | 2020-12-29 | 江苏理工学院 | Preparation method and application of modified polymer adsorption material |
| CN112619435A (en) * | 2020-12-02 | 2021-04-09 | 石河子大学 | Preparation method of molecularly imprinted hybrid membrane for separating phenylethanoid glycosides |
| CN113072659A (en) * | 2021-03-30 | 2021-07-06 | 华南农业大学 | Sulfadimidine mesoporous molecularly imprinted polymer and preparation method and application thereof |
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Cited By (8)
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| WO2017198693A1 (en) * | 2016-05-17 | 2017-11-23 | Basf Se | A composition comprising mesoporous silicon dioxide particles and a nitrification inhibitor |
| CN106753329A (en) * | 2016-11-01 | 2017-05-31 | 北京工商大学 | Fluorescence trace sensing material and response element and preparation method thereof and the application in dicyandiamide is detected |
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| CN112619435A (en) * | 2020-12-02 | 2021-04-09 | 石河子大学 | Preparation method of molecularly imprinted hybrid membrane for separating phenylethanoid glycosides |
| CN113072659A (en) * | 2021-03-30 | 2021-07-06 | 华南农业大学 | Sulfadimidine mesoporous molecularly imprinted polymer and preparation method and application thereof |
| CN113072659B (en) * | 2021-03-30 | 2022-05-10 | 华南农业大学 | Sulfadimidine mesoporous molecularly imprinted polymer and preparation method and application thereof |
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