CN105542083B - A kind of method for the bi-functional monomer polysaccharide molecule trace nano particle for preparing efficient absorption - Google Patents
A kind of method for the bi-functional monomer polysaccharide molecule trace nano particle for preparing efficient absorption Download PDFInfo
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Abstract
A kind of method for the bi-functional monomer polysaccharide molecule trace nano particle for preparing efficient absorption.The present invention relates to a kind of method for preparing polysaccharide molecule trace nano particle.The present invention in order to solve existing polysaccharide molecule trace nano particle to separation of polysaccharides purification steps troublesome, isolate and purify the problem of efficiency is low.Method：First, superparamagnetism Fe is prepared3O4Nano-particle；2nd, Fe3O4The silanization of magnetic nano-particle；3rd, epoxy radicals grafting Fe3O4@SiO2The preparation of particulate；4th, the preparation of bi-functional monomer polysaccharide molecule trace nano particle.The bi-functional monomer of the present invention can greatly improve selectivity and adsorbance of the magnetic nano molecular marking to template polysaccharide with the reversible covalent bonds of template molecule formation and the cooperative effect of hydrogen bond, bi-functional monomer polysaccharide molecule trace nano particle prepared by the present invention can efficiently, quick, specific adsorption desired polysaccharide, solve separation of polysaccharides purification steps troublesome, isolate and purify the problem of efficiency is low.
Description
Technical field
The present invention relates to a kind of method for preparing polysaccharide molecule trace nano particle.
Background technology
Polysaccharide is prevalent in plant, animal and microorganism, be sustain life activity normal operation base substance it
One.Show according to the study, the effects such as most plant polyoses has anti-oxidant, antitumor and antiviral, and plant polyose is originated
Extensively without cytotoxicity, toxic side effect is small, can be applied to field of medicaments, current people to the level of polysaccharide researches with level also
Far behind protein and nucleic acid, are primarily due to polysaccharide composition complexity, and some polysaccharide are combined with chromoprotein matter, are not readily separated
Purifying, so current polysaccharide preparation is generally not purified Thick many candies preparation, it is impossible to clear and definite dose relationship；Secondly, people couple
Water-soluble polysaccharide is paid attention to not enough, and the research to its primary structure and higher structure is deep not enough, it is impossible to taken off from molecular level
Show many still inexplicable polysaccharide biological mechanisms at present.The bioactivity of polysaccharide is mainly closely related with its structure, its
Structure change is frequently accompanied by the change of bioactivity.The monose composition of polysaccharide, glucosides key type, functional group and higher structure
Change may all influence its bioactivity.So the further investigation strengthened to polysaccharide structures is made to the bioactivity for illustrating polysaccharide
With promotion polysaccharose substance has great importance in the application of the world of medicine.
The content of the invention
The present invention in order to solve existing polysaccharide molecule trace nano particle to separation of polysaccharides purification steps troublesome, isolate and purify
The problem of efficiency is low, and a kind of method for the bi-functional monomer polysaccharide molecule trace nano particle for preparing efficient absorption is provided.
A kind of method of bi-functional monomer polysaccharide molecule trace nano particle for preparing efficient absorption of the present invention is by following
Step is carried out：
First, superparamagnetism Fe is prepared3O4Nano-particle：By FeCl3·6H2O is dissolved in ethylene glycol, and ultrasonically treated 10min~
15min, then adds anhydrous sodium acetate, low whipping speed be stirring 25min under conditions of 200r/min~400r/min~
35min, is transferred in stainless steel cauldron, and 5h~7h is reacted in the case where temperature is 180~220 DEG C, is stopped taking out after reaction and is reacted
Kettle naturally cools to room temperature, carries out carrying out washing treatment to obtained solid matter, described carrying out washing treatment is：First washed with absolute ethyl alcohol
Wash solid matter 3 times, then with distilled water washed solid 5 times, then temperature be dry under conditions of 40~70 DEG C 11h~
13h, obtains superparamagnetism Fe3O4Nano-particle；
FeCl described in step one3·6H2The ratio of O quality and the volume of ethylene glycol is 13.5g：(450~550) mL；
FeCl described in step one3·6H2The mass ratio of O and anhydrous sodium acetate is 13.5：(30~40)；
The volume and FeCl of absolute ethyl alcohol used in each carrying out washing treatment3·6H2The ratio of O quality is (14~30) mL：1g；
The volume and FeCl of distilled water used in each carrying out washing treatment3·6H2The ratio of O quality is (14~30) mL：1g；
2nd, Fe3O4The silanization of magnetic nano-particle：Low whipping speed be 200r/min~400r/min under conditions of to
The superparamagnetism Fe that step one is obtained3O4The mixture of isopropanol and distilled water is added in nano-particle, is mixed to being uniformly dispersed,
Then it is added dropwise after ammoniacal liquor, completion of dropping, then is added dropwise after tetraethyl orthosilicate, completion of dropping, at room temperature stirs speed
Spend and stir 10h~14h for 200r/min~400r/min, stop reaction, carrying out washing treatment is carried out to obtained solid matter, it is described
Carrying out washing treatment be：First with distilled water washed solid 5 times, then with absolute ethyl alcohol washed solid 3 times, then use neodymium iron
Boron magnets carry out magnetic separation sedimentation, pour out after supernatant liquid, and solid matter is placed in temperature to do under conditions of 40~70 DEG C
Dry 11h~13h, obtains Fe3O4@SiO2Particulate；
The superparamagnetism Fe that the step of described in step 2 one obtains3O4The quality of nano-particle and isopropanol and distilled water
Mixture volume ratio be 1.0g：(150~1000) mL；Isopropyl in wherein described isopropanol and the mixture of distilled water
The volume ratio of alcohol and distilled water is 4：1；The superparamagnetism Fe that the step of described in step 2 one obtains3O4The quality of nano-particle
Ratio with the volume of ammoniacal liquor is 1.0g：(5~25) mL；The superparamagnetism Fe that the step of described in step 2 one obtains3O4Nanoparticle
The ratio of the quality of son and the volume of tetraethyl orthosilicate is 1.0g：(5~10) mL；
The superparamagnetism Fe that the volume of absolute ethyl alcohol used in each carrying out washing treatment is obtained with step one3O4The matter of nano-particle
The ratio of amount is (200~700) mL：1g；The superparamagnetism that the volume of distilled water used in each carrying out washing treatment is obtained with step one
Fe3O4The mass ratio of nano-particle is (200~700) mL：1g；
3rd, epoxy radicals grafting Fe3O4@SiO2The preparation of particulate：The Fe that step 2 is obtained3O4@SiO2First is dissolved in particulate
In benzene, ultrasonically treated 5~15min is then heated to temperature for 20~60 DEG C, adds 3- glycidyloxypropyl front threes
TMOS, under nitrogen atmosphere protection, is stirred under conditions of mixing speed is 100r/min~300r/min and condensing reflux
6h~14h is mixed, stops reaction, carrying out washing treatment is carried out to obtained solid matter, described carrying out washing treatment is：First washed with toluene
Solid matter 2 times, then with ethanol washed solid 5 times, then carry out magnetic separation sedimentation with ndfeb magnet, pour out upper strata
After liquid, solid matter is placed in temperature to dry 11h~13h under conditions of 40~70 DEG C, Fe is obtained3O4@SiO2@COC are micro-
Grain；
The Fe that the step of described in step 3 two obtains3O4@SiO2The ratio of the quality of particulate and the volume of toluene is 1.0g：
(150~1000) mL；The Fe that the step of described in step 3 two obtains3O4@SiO2The quality of particulate and 3- glycidyl epoxides
The ratio of the volume of propyl trimethoxy silicane is 1.0g：(5~15) mL；
The Fe that the volume of toluene used in each carrying out washing treatment is obtained with step 23O4@SiO2The ratio of the quality of particulate is (200
~700) mL：1g；The Fe that the volume of absolute ethyl alcohol used in each carrying out washing treatment is obtained with step 23O4@SiO2The quality of particulate
Than for (200~700) mL：1g；
4th, the preparation of bi-functional monomer polysaccharide molecule trace nano particle：By starch, Resocinol-phenol formaldehyde resin and 2- propyl group acyls
Amido -2- methyl propane sulfonic acids are dissolved in the phosphate buffer solution that 0.02mol/L pH value is 9.0, and ultrasonically treated 5min~
10min, is then aged 1h~3h at room temperature, then adds the Fe that step 3 is obtained3O4@SiO2@COC particulates, low whipping speed is
Under conditions of 100r/min~300r/min and nitrogen atmosphere are protected, over cure is added by 1mL/min~5mL/min of rate of addition
The phosphate buffer solution of sour ammonium, oil bath reaction 24h~36h, then uses neodymium-iron-boron under conditions of temperature is 40~80 DEG C
Iron carries out magnetic separation sedimentation, pours out after supernatant liquid, and remove template molecule with elution detects to without polysaccharide, obtains
Bi-MMIPs nano particles, i.e. bi-functional monomer polysaccharide molecule trace nano particle；
The molal weight ratio of starch and Resocinol-phenol formaldehyde resin described in step 4 is 1：(100~1000)；In step 4
The molal weight ratio of described Resocinol-phenol formaldehyde resin and 2- propyl amides base -2- methyl propane sulfonic acids is 1：(0.2~1.0)；Step
Fe described in four3O4@SiO2The quality of@COC particulates and 0.02mol/L pH value for 9.0 phosphate buffer solution volume
Ratio be 1mg：(0.3~1) mL；The Fe that starch described in step 4 is obtained with step 33O4@SiO2The quality of@COC particulates
Than for 1：(35~45)；Starch described in step 4 and in the phosphate buffer solution of ammonium persulfate ammonium persulfate mass ratio
For 1：(15~20).
Beneficial effect of the present invention
The present invention is by function monomer Resocinol-phenol formaldehyde resin (APBA), miscellaneous function monomer 2- propyl amides base -2- methyl-props
Sulfonic acid (AMPS) carries out prepolymerization under certain condition with template molecule (starch), bi-functional monomer is can be good at and template
Molecule is combined, and then adds initiator and polymer reaction formation copolymer occurs under certain condition for carrier, then will be this
Copolymer is eluted, and the cavity with template molecule specific recognition will be formed on imprinted polymer surface, this cavity can
With the selectivity recognition template molecule (starch) in mixed solution.It is reversible common that bi-functional monomer and template molecule (starch) are formed
The cooperative effect of valence link and hydrogen bond can greatly improve selectivity and adsorbance of the magnetic nano molecular marking to template polysaccharide, this hair
The bi-functional monomer polysaccharide molecule trace nano particle of bright preparation can efficiently, quick, specific adsorption desired polysaccharide, solve
Separation of polysaccharides purification steps troublesome, isolate and purify the low problem of efficiency.
Brief description of the drawings
The SEM photograph for the Bi-MMIPs nano particles that Fig. 1 obtains for experiment one；
The infrared spectrum spectrogram for the Bi-MMIPs nano particles that Fig. 2 obtains for experiment one；
The Bi-MMIPs nano particles and Bi-MNIPs that Fig. 3 obtains for experiment one are bent to adsorbance-time of starch-polysaccharides
Line chart；Wherein a represents Bi-MMIPs, and b represents Bi-MNIPs；
Fig. 4 is the canonical plotting for determining starch-polysaccharides absorbance.
Embodiment
Technical scheme is not limited to any between detailed description below, in addition to each embodiment
Combination.
Embodiment one：A kind of bi-functional monomer polysaccharide molecule trace for preparing efficient absorption of present embodiment is received
The method of rice grain is carried out according to the following steps：
First, superparamagnetism Fe is prepared3O4Nano-particle：By FeCl3·6H2O is dissolved in ethylene glycol, and ultrasonically treated 10min~
15min, then adds anhydrous sodium acetate, low whipping speed be stirring 25min under conditions of 200r/min~400r/min~
35min, is transferred in stainless steel cauldron, and 5h~7h is reacted in the case where temperature is 180~220 DEG C, is stopped taking out after reaction and is reacted
Kettle naturally cools to room temperature, carries out carrying out washing treatment to obtained solid matter, described carrying out washing treatment is：First washed with absolute ethyl alcohol
Wash solid matter 3 times, then with distilled water washed solid 5 times, then temperature be dry under conditions of 40~70 DEG C 11h~
13h, obtains superparamagnetism Fe3O4Nano-particle；
FeCl described in step one3·6H2The ratio of O quality and the volume of ethylene glycol is 13.5g：(450~550) mL；
FeCl described in step one3·6H2The mass ratio of O and anhydrous sodium acetate is 13.5：(30~40)；
The volume and FeCl of absolute ethyl alcohol used in each carrying out washing treatment3·6H2The ratio of O quality is (14~30) mL：1g；
The volume and FeCl of distilled water used in each carrying out washing treatment3·6H2The ratio of O quality is (14~30) mL：1g；
2nd, Fe3O4The silanization of magnetic nano-particle：Low whipping speed be 200r/min~400r/min under conditions of to
The superparamagnetism Fe that step one is obtained3O4The mixture of isopropanol and distilled water is added in nano-particle, is mixed to being uniformly dispersed,
Then it is added dropwise after ammoniacal liquor, completion of dropping, then is added dropwise after tetraethyl orthosilicate, completion of dropping, at room temperature stirs speed
Spend and stir 10h~14h for 200r/min~400r/min, stop reaction, carrying out washing treatment is carried out to obtained solid matter, it is described
Carrying out washing treatment be：First with distilled water washed solid 5 times, then with absolute ethyl alcohol washed solid 3 times, then use neodymium iron
Boron magnets carry out magnetic separation sedimentation, pour out after supernatant liquid, and solid matter is placed in temperature to do under conditions of 40~70 DEG C
Dry 11h~13h, obtains Fe3O4@SiO2Particulate；
The superparamagnetism Fe that the step of described in step 2 one obtains3O4The quality of nano-particle and isopropanol and distilled water
Mixture volume ratio be 1.0g：(150~1000) mL；Isopropyl in wherein described isopropanol and the mixture of distilled water
The volume ratio of alcohol and distilled water is 4：1；The superparamagnetism Fe that the step of described in step 2 one obtains3O4The quality of nano-particle
Ratio with the volume of ammoniacal liquor is 1.0g：(5~25) mL；The superparamagnetism Fe that the step of described in step 2 one obtains3O4Nanoparticle
The ratio of the quality of son and the volume of tetraethyl orthosilicate is 1.0g：(5~10) mL；
The superparamagnetism Fe that the volume of absolute ethyl alcohol used in each carrying out washing treatment is obtained with step one3O4The matter of nano-particle
The ratio of amount is (200~700) mL：1g；The superparamagnetism that the volume of distilled water used in each carrying out washing treatment is obtained with step one
Fe3O4The mass ratio of nano-particle is (200~700) mL：1g；
3rd, epoxy radicals grafting Fe3O4@SiO2The preparation of particulate：The Fe that step 2 is obtained3O4@SiO2First is dissolved in particulate
In benzene, ultrasonically treated 5~15min is then heated to temperature for 20~60 DEG C, adds 3- glycidyloxypropyl front threes
TMOS, under nitrogen atmosphere protection, is stirred under conditions of mixing speed is 100r/min~300r/min and condensing reflux
6h~14h is mixed, stops reaction, carrying out washing treatment is carried out to obtained solid matter, described carrying out washing treatment is：First washed with toluene
Solid matter 2 times, then with ethanol washed solid 5 times, then carry out magnetic separation sedimentation with ndfeb magnet, pour out upper strata
After liquid, solid matter is placed in temperature to dry 11h~13h under conditions of 40~70 DEG C DEG C, Fe is obtained3O4@SiO2@COC are micro-
Grain；
The Fe that the step of described in step 3 two obtains3O4@SiO2The ratio of the quality of particulate and the volume of toluene is 1.0g：
(150~1000) mL；The Fe that the step of described in step 3 two obtains3O4@SiO2The quality of particulate and 3- glycidyl epoxides
The ratio of the volume of propyl trimethoxy silicane is 1.0g：(5~15) mL；
The Fe that the volume of toluene used in each carrying out washing treatment is obtained with step 23O4@SiO2The ratio of the quality of particulate is (200
~700) mL：1g；The Fe that the volume of absolute ethyl alcohol used in each carrying out washing treatment is obtained with step 23O4@SiO2The quality of particulate
Than for (200~700) mL：1g；
4th, the preparation of bi-functional monomer polysaccharide molecule trace nano particle：By starch, Resocinol-phenol formaldehyde resin and 2- propyl group acyls
Amido -2- methyl propane sulfonic acids are dissolved in the phosphate buffer solution that 0.02mol/L pH value is 9.0, and ultrasonically treated 5min~
10min, is then aged 1h~3h at room temperature, then adds the Fe that step 3 is obtained3O4@SiO2@COC particulates, low whipping speed is
Under conditions of 100r/min~300r/min and nitrogen atmosphere are protected, over cure is added by 1mL/min~5mL/min of rate of addition
The phosphate buffer solution of sour ammonium, oil bath reaction 24h~36h, then uses neodymium-iron-boron under conditions of temperature is 40~80 DEG C
Iron carries out magnetic separation sedimentation, pours out after supernatant liquid, and remove template molecule with elution detects to without polysaccharide, obtains
Bi-MMIPs nano particles, i.e. bi-functional monomer polysaccharide molecule trace nano particle；
Non- trace nano particle is in addition to without using template molecule (starch), preparation method and molecular engram nano particle phase
Together.
The molal weight ratio of starch and Resocinol-phenol formaldehyde resin described in step 4 is 1：(100~1000)；In step 4
The molal weight ratio of described Resocinol-phenol formaldehyde resin and 2- propyl amides base -2- methyl propane sulfonic acids is 1：(0.2~1.0)；Step
Fe described in four3O4@SiO2The quality of@COC particulates and 0.02mol/L pH value for 9.0 phosphate buffer solution volume
Ratio be 1mg：(0.3~1) mL；The Fe that starch described in step 4 is obtained with step 33O4@SiO2The quality of@COC particulates
Than for 1：(35~45)；Starch described in step 4 and in the phosphate buffer solution of ammonium persulfate ammonium persulfate mass ratio
For 1：(15~20).
Embodiment two：Present embodiment from unlike embodiment one：Described in step one
FeCl3·6H2The ratio of O quality and the volume of ethylene glycol is 13.5g：500mL；FeCl described in step one3·6H2O and nothing
The mass ratio of water sodium acetate is 13.5：36.Other steps are identical with embodiment one with parameter.
Embodiment three：Present embodiment from unlike embodiment one or two：It is transferred in step one
In stainless steel cauldron, 6h is reacted in the case where temperature is 200 DEG C.Other steps are identical with parameter with embodiment one or two.
Embodiment four：Unlike one of present embodiment and embodiment one to three：Institute in step 2
The superparamagnetism Fe that the step of stating one obtains3O4The quality of nano-particle and isopropanol and the ratio of the volume of the mixture of distilled water
For 1.0g：1000mL；The superparamagnetism Fe that the step of described in step 2 one obtains3O4The quality of nano-particle and the body of ammoniacal liquor
Long-pending ratio is 1.0g：25mL；The superparamagnetism Fe that the step of described in step 2 one obtains3O4The quality of nano-particle and positive silicon
The ratio of the volume of acetoacetic ester is 1.0g：10mL.Other steps are identical with one of embodiment one to three with parameter.
Embodiment five：Unlike one of present embodiment and embodiment one to four：Institute in step 3
The Fe that the step of stating two obtains3O4@SiO2The ratio of the quality of particulate and the volume of toluene is 1g：1000mL；Described in step 3
The Fe that step 2 is obtained3O4@SiO2The ratio of the quality of particulate and the volume of 3- glycidyloxypropyl trimethoxy silanes is
1g：10mL.Other steps are identical with one of embodiment one to four with parameter.
Embodiment six：Unlike one of present embodiment and embodiment one to five：Will in step 3
The Fe that step 2 is obtained3O4@SiO2It is dissolved in particulate in toluene, ultrasonically treated 10min, is then heated to temperature for 40 DEG C.It is other
Step is identical with one of embodiment one to five with parameter.
Embodiment seven：Unlike one of present embodiment and embodiment one to six：Institute in step 4
The starch and the molal weight ratio of Resocinol-phenol formaldehyde resin stated are 3：1000；Resocinol-phenol formaldehyde resin and 2- propyl group described in step 4
The molal weight ratio of amide groups -2- methyl propane sulfonic acids is 1：0.8；The quality Fe of starch described in step 43O4@SiO2@COC
The ratio of the volume for the phosphate buffer solution that the quality of particulate and 0.02mol/L pH value are 9.0 is 30mg：20mL；Step
The Fe that starch described in four is obtained with step 33O4@SiO2The mass ratio of@COC particulates is 1：40；Shallow lake described in step 4
The mass ratio of ammonium persulfate is 1 in the phosphate buffer solution of powder and ammonium persulfate：16.2.Other steps are real with parameter and specifically
Apply one of mode one to six identical.
Embodiment eight：Unlike one of one of present embodiment and embodiment one to seven：Step 4
Described in ammonium persulfate phosphate buffer solution in the concentration of ammonium persulfate be 4.564mg/mL, described ammonium persulfate
The concentration of phosphate buffer solution is 0.02mol/L in phosphate buffer solution, and pH value is 9.0.Other steps and parameter and tool
One of body embodiment one to seven is identical.
Embodiment nine：Unlike one of present embodiment and embodiment one to eight：Institute in step 4
The phosphate buffer solution that the pH value that the eluent stated is 0.02mol/L is 5.0.Other steps and parameter and embodiment
One of one to eight is identical.
Embodiment ten：Unlike one of present embodiment and embodiment one to nine：In step 4
Temperature is oil bath reaction 24h under conditions of 60 DEG C.Other steps are identical with one of embodiment one to nine with parameter.
With following verification experimental verification beneficial effects of the present invention：
Experiment one, a kind of method for the bi-functional monomer polysaccharide molecule trace nano particle for preparing efficient absorption are by following step
It is rapid to carry out：
First, superparamagnetism Fe is prepared3O4Nano-particle：By 13.5gFeCl3·6H2O is dissolved in 500mL ethylene glycol, ultrasound
10min is handled, 36g anhydrous sodium acetates are then added, low whipping speed is transferred to stir 30min under conditions of 300r/min
In stainless steel cauldron, 6h is reacted in the case where temperature is 200 DEG C, stops taking-up reactor after reaction and naturally cools to room temperature, to
The solid matter arrived carries out carrying out washing treatment, and described carrying out washing treatment is：First with absolute ethyl alcohol washed solid 3 times, then with double
Steam water washing solid matter 5 times, then dry 12h under conditions of temperature is 45 DEG C, obtain superparamagnetism Fe3O4Nano-particle；
The volume and FeCl of absolute ethyl alcohol used in each carrying out washing treatment3·6H2The ratio of O quality is 25mL：1g；Wash every time
Wash the volume and FeCl of processing distilled water used3·6H2The ratio of O quality is 25mL：1g；
2nd, Fe3O4The silanization of magnetic nano-particle：Low whipping speed is to 0.2g steps one under conditions of 300r/min
Obtained superparamagnetism Fe3O4The mixture of 200mL isopropanols and distilled water is added in nano-particle, is mixed to being uniformly dispersed, so
After be added dropwise after 5mL ammoniacal liquor, completion of dropping, then be added dropwise after 2mL tetraethyl orthosilicates, completion of dropping, at room temperature to stir
Mix speed and stir 12h for 300r/min, stop reaction, carrying out washing treatment, described carrying out washing treatment are carried out to obtained solid matter
For：First with distilled water washed solid 5 times, then with absolute ethyl alcohol washed solid 3 times, then carried out with ndfeb magnet
Magnetic separation is settled, and is poured out after supernatant liquid, and solid matter is placed in into temperature to dry 12h under conditions of 45 DEG C, Fe is obtained3O4@
SiO2Particulate；
Isopropanol described in the step 2 and volume ratio of isopropanol and distilled water is 4 in the mixture of distilled water：1；
The superparamagnetism Fe that the volume of absolute ethyl alcohol used in each carrying out washing treatment is obtained with step one3O4The matter of nano-particle
The ratio of amount is 100mL：0.2g；The volume and superparamagnetism Fe of distilled water used in each carrying out washing treatment3O4The mass ratio of nano-particle
For 100mL：0.2g；
3rd, epoxy radicals grafting Fe3O4@SiO2The preparation of particulate：The Fe that 0.2g step 2 is obtained3O4@SiO2It is molten in particulate
In 200mL toluene, ultrasonically treated 10min is then heated to temperature for 40 DEG C, adds 2.0mL 3- glycidyl oxygen
Base propyl trimethoxy silicane, under nitrogen atmosphere protection, is stirred under conditions of mixing speed is 200r/min and condensing reflux
12h is mixed, stops reaction, carrying out washing treatment is carried out to obtained solid matter, described carrying out washing treatment is：First solid is washed with toluene
Material 2 times, then with ethanol washed solid 5 times, then carry out magnetic separation sedimentation with ndfeb magnet, pour out supernatant liquid
Afterwards, solid matter is placed in temperature to dry 12h under conditions of 45 DEG C, obtains Fe3O4@SiO2@COC particulates；
The Fe that the volume of toluene used in each carrying out washing treatment is obtained with step 23O4@SiO2The ratio of the quality of particulate is
100mL：0.2g；The Fe that the volume of absolute ethyl alcohol used in each carrying out washing treatment is obtained with step 23O4@SiO2The quality of particulate
Than for 100mL：0.2g；
4th, the preparation of bi-functional monomer polysaccharide molecule trace nano particle：By 0.768mg starch, 3.099mg m-aminophenyls
The phosphoric acid that the pH value that boric acid and 3.316mg 2- propyl amides base -2- methyl propane sulfonic acids are dissolved in 17mL 0.02mol/L is 9.0
In salt buffer solution, then ultrasonically treated 5min is aged 1h at room temperature, then adds the Fe that 30mg step 3 is obtained3O4@SiO2@
COC particulates, under conditions of low whipping speed is 200r/min and nitrogen atmosphere protection, 3mL is added by 3mL/min of rate of addition
The phosphate buffer solution of ammonium persulfate, oil bath reaction 24h, is then carried out with ndfeb magnet under conditions of temperature is 60 DEG C
Magnetic separation is settled, and is poured out after supernatant liquid, and remove template molecule with elution detects to without polysaccharide, obtains Bi-MMIPs
Nano particle, i.e. bi-functional monomer polysaccharide molecule trace nano particle；
The concentration of ammonium persulfate is 4.564mg/mL, institute in the phosphate buffer solution of ammonium persulfate described in step 4
The concentration of phosphate buffer solution is 0.02mol/L in the phosphate buffer solution for the ammonium persulfate stated, and pH value is 9.0；
The phosphate buffer solution that the pH value that eluent described in step 4 is 0.02mol/L is 5.0.
(1) the Bi-MMIPs nano particles obtained by field emission scanning electron microscope to experiment one have carried out pattern
Analysis, obtains the SEM figures for the Bi-MMIPs nano particles that experiment one as shown in Figure 1 is obtained, it will be noted from fig. 1 that Bi-
MMIPs nano grain surfaces are coarse rough, and adhesion phenomenon occur in part Bi-MMIPs surfaces, and at Bi-MMIPs nanometers
Grain surface occurs in that the cavity that form differs.
(2) infrared spectrum detection is carried out to the Bi-MMIPs nano particles that experiment one is obtained, obtains examination as shown in Figure 2
The infrared spectrum spectrogram of an obtained Bi-MMIPs nano particles is tested, it can be seen in fig. 2 that organic sulfonic acid group-CH2-SO3 -Spy
Levy absworption peak：620cm-1It is the characteristic absorption peak of C-S keys：1040cm-1It is the characteristic absorption peak of S-O keys；1200cm-1It is-S=O
The characteristic absorption peak of key, also 1640cm-1 are the characteristic absorption peaks of c h bond in-C=C groups；1710cm-1 is-C=O keys
Characteristic absorption peak, these characteristic absorption peaks demonstrate compound AMPS and combined on molecular engram.In 3308cm-1Nearby occur
N-H stretches peak, 1565cm-1,1511cm-1Nearby there is N-H vibration peaks, 1343cm-1Nearby there are C-N vibration peaks, these peaks are all
For the characteristic absorption peak of secondary amine group, illustrate APBA success graftings on Bi-MMIPs surfaces.
(3) adsorbance detection is carried out to the Bi-MMIPs nano particles that experiment one is obtained, process is as follows：Accurately weigh
Bi-MMIPs nano particles (MMIPs) and 40mg non-molecularly imprinted polymers (MNIPs) that 40mg experiment one is obtained, add respectively
Enter 20mL concentration and be individually positioned in progress concussion mixing on Clothoid type oscillator, earthquake mixing for 40mg/L starch solution
Neodymium iron boron when 5min, 10min, 15min, 20min, 30min, 40min, 60min, 80min, 120min, 150min, 180min
Magnet is adsorbed, and takes 1mL supernatants, with glucose solution in supernatant after the different adsorption times of phend-sulphuric acid measure
Concentration, calculates the adsorbance of Bi-MMIPs and Bi-MNIPs to glucose in different time according to formula (1), draws out
To adsorbance-time graph of glucose when Bi-MMIPs and Bi-MNIPs are changed over time, as shown in Figure 3.
Wherein Q is the adsorbance (mg/g) to starch；C0For the initial concentration (mg/L) of starch before absorption；CtFor it is different when
Between be spaced when starch concentration (mg/L)；V is the volume (mL) of solution；W is Bi-MMIPs (Bi-MNIPs) quality (g).
Without starch template when wherein prepared by non-molecularly imprinted polymer (Bi-MNIPs), other steps are with preparing Bi-
MMIPs method is identical.
Can be drawn from Fig. 3, the adsorption efficiency of Bi-MMIPs trace nano particles apparently higher than Bi-MNIPs nanoparticles,
Bi-MMIPs traces nano particle adsorbs in 20min and basically reaches saturation, and adsorbance during 20min is 13.55mg/g, and
The adsorbance of Bi-MNIPs nano particles is 5.28mg/g, and the adsorbance of molecular engram is 2.6 times of non-molecular engram adsorbance.
The assay method of wherein starch-polysaccharides concentration is as follows：
Phenol sulfuric acid procedure surveys starch-polysaccharides content：Herein from phend-sulphuric acid come the content of starch in determining.Starch is more
Sugar can hydrolyze generation monose, and rapid dehydration generation furfural derivatives under concentrated sulfuric acid effect, and furfural derivatives can contract with phenol
Conjunction forms orange-yellow compound, and the compound colors are stable, and UV detector detects absorption maximum at wavelength 490nm,
The absorbance measured and total sugar content linear correlation, therefore, it can utilize ultraviolet determination prepare liquid absorbance, are converted into prepare liquid
Middle sugared concentration.
(1) standard curve is made：Accurately weighing standard starch polysaccharide 10mg is dissolved in 250mL (sugared concentration 40mg/L) volumetric flask
In, scale is added water to, 0.4mL, 0.6mL, 0.8mL, 1.0mL, 1.2mL, 1.4mL, 1.6mL and 1.8mL, each constant volume are drawn respectively
To 2.0mL, then add 6% phenol 1.0mL and the concentrated sulfuric acid 5.0mL, static 10min, shake up, room temperature place 20min with after
490nm surveys light absorption value, using distilled water as blank, obtains standard curve (n=3) and regression equation, canonical plotting such as Fig. 4 institutes
Show, regression equation is Y=-0.00422+0.00909X；Wherein abscissa is starch-polysaccharides content (μ g), and ordinate is light absorption value
(Abs), standard error R2=0.99937.
(2) sample size is determined：Pipette samples liquid 1.0mL is operated by above-mentioned steps, densitometric absorbance, with standard
Curve calculates the content of starch.(n=3).
Claims (10)
1. a kind of method for the bi-functional monomer polysaccharide molecule trace nano particle for preparing efficient absorption, it is characterised in that this method
Carry out according to the following steps：
First, superparamagnetism Fe is prepared3O4Nano-particle：By FeCl3·6H2O is dissolved in ethylene glycol, and ultrasonically treated 10min~
15min, then adds anhydrous sodium acetate, low whipping speed be stirring 25min under conditions of 200r/min~400r/min~
35min, is transferred in stainless steel cauldron, and 5h~7h is reacted in the case where temperature is 180~220 DEG C, is stopped taking out after reaction and is reacted
Kettle naturally cools to room temperature, carries out carrying out washing treatment to obtained solid matter, described carrying out washing treatment is：First washed with absolute ethyl alcohol
Wash solid matter 3 times, then with distilled water washed solid 5 times, then temperature be dry under conditions of 40~70 DEG C 11h~
13h, obtains superparamagnetism Fe3O4Nano-particle；
FeCl described in step one3·6H2The ratio of O quality and the volume of ethylene glycol is 13.5g：(450~550) mL；Step
FeCl described in one3·6H2The mass ratio of O and anhydrous sodium acetate is 13.5：(30~40)；
The volume and FeCl of absolute ethyl alcohol used in each carrying out washing treatment3·6H2The ratio of O quality is (14~30) mL：1g；Every time
The volume and FeCl of distilled water used in carrying out washing treatment3·6H2The ratio of O quality is (14~30) mL：1g；
2nd, Fe3O4The silanization of magnetic nano-particle：Low whipping speed is to step under conditions of 200r/min~400r/min
One obtained superparamagnetism Fe3O4The mixture of isopropanol and distilled water is added in nano-particle, is mixed to being uniformly dispersed, then
Be added dropwise after ammoniacal liquor, completion of dropping, then be added dropwise after tetraethyl orthosilicate, completion of dropping, at room temperature using mixing speed as
200r/min~400r/min stirs 10h~14h, stops reaction, carries out carrying out washing treatment to obtained solid matter, described washes
Wash and be processed as：First with distilled water washed solid 5 times, then with absolute ethyl alcohol washed solid 3 times, then use neodymium-iron-boron
Iron carries out magnetic separation sedimentation, pours out after supernatant liquid, and solid matter is placed in temperature to dry 11h under conditions of 40~70 DEG C
~13h, obtains Fe3O4@SiO2Particulate；
The superparamagnetism Fe that the step of described in step 2 one obtains3O4The quality and isopropanol of nano-particle and mixing for distilled water
The ratio of the volume of compound is 1.0g：(150~1000) mL；In wherein described isopropanol and the mixture of distilled water isopropanol with
The volume ratio of distilled water is 4：1；The superparamagnetism Fe that the step of described in step 2 one obtains3O4The quality and ammonia of nano-particle
The ratio of the volume of water is 1.0g：(5~25) mL；The superparamagnetism Fe that the step of described in step 2 one obtains3O4Nano-particle
The ratio of quality and the volume of tetraethyl orthosilicate is 1.0g：(5~10) mL；
The superparamagnetism Fe that the volume of absolute ethyl alcohol used in each carrying out washing treatment is obtained with step one3O4The quality of nano-particle
Than for (200~700) mL：1g；The superparamagnetism Fe that the volume of distilled water used in each carrying out washing treatment is obtained with step one3O4Receive
The mass ratio of rice corpuscles is (200~700) mL：1g；
3rd, epoxy radicals grafting Fe3O4@SiO2The preparation of particulate：The Fe that step 2 is obtained3O4@SiO2Particulate is dissolved in toluene, is surpassed
5~15min of sonication, is then heated to temperature for 20~60 DEG C, adds 3- glycidyloxypropyl trimethoxy silicon
Alkane, under nitrogen atmosphere protection, under conditions of mixing speed is 100r/min~300r/min and condensing reflux stirring 6h~
14h, stops reaction, carries out carrying out washing treatment to obtained solid matter, described carrying out washing treatment is：First solids is washed with toluene
Matter 2 times, then with ethanol washed solid 5 times, then carry out magnetic separation sedimentation with ndfeb magnet, pour out supernatant liquid
Afterwards, solid matter is placed in temperature to dry 11h~13h under conditions of 40~70 DEG C, obtains Fe3O4@SiO2@COC particulates；
The Fe that the step of described in step 3 two obtains3O4@SiO2The ratio of the quality of particulate and the volume of toluene is 1.0g：(150
~1000) mL；The Fe that the step of described in step 3 two obtains3O4@SiO2The quality of particulate and 3- glycidyloxypropyls
The ratio of the volume of trimethoxy silane is 1.0g：(5~15) mL；
The Fe that the volume of toluene used in each carrying out washing treatment is obtained with step 23O4@SiO2The ratio of the quality of particulate for (200~
700)mL：1g；The Fe that the volume of absolute ethyl alcohol used in each carrying out washing treatment is obtained with step 23O4@SiO2The ratio of the quality of particulate
For (200~700) mL：1g；
4th, the preparation of bi-functional monomer polysaccharide molecule trace nano particle：By starch, Resocinol-phenol formaldehyde resin and 2- acrylamides
Base -2- methyl propane sulfonic acids are dissolved in the phosphate buffer solution that 0.02mol/L pH value is 9.0, and ultrasonically treated 5min~
10min, is then aged 1h~3h at room temperature, then adds the Fe that step 3 is obtained3O4@SiO2@COC particulates, low whipping speed is
Under conditions of 100r/min~300r/min and nitrogen atmosphere are protected, over cure is added by 1mL/min~5mL/min of rate of addition
The phosphate buffer solution of sour ammonium, oil bath reaction 24h~36h, then uses neodymium-iron-boron under conditions of temperature is 40~80 DEG C
Iron carries out magnetic separation sedimentation, pours out after supernatant liquid, and remove template molecule with elution detects to without polysaccharide, obtains
Bi-MMIPs nano particles, i.e. bi-functional monomer polysaccharide molecule trace nano particle；
The mass ratio of starch and Resocinol-phenol formaldehyde resin described in step 4 is 0.768：3.099；Ammonia between described in step 4
The mol ratio of base phenyl boric acid and 2- acrylamide-2-methylpro panesulfonic acids is 1：(0.2~1.0)；Fe described in step 43O4@
SiO2The ratio of the volume for the phosphate buffer solution that the quality of@COC particulates and 0.02mol/L pH value are 9.0 is 1mg：(0.3
~1) mL；The Fe that starch described in step 4 is obtained with step 33O4@SiO2The mass ratio of@COC particulates is 1：(35~45)；
Starch described in the step 4 and mass ratio of ammonium persulfate is 1 in the phosphate buffer solution of ammonium persulfate：(15~20).
2. a kind of side of bi-functional monomer polysaccharide molecule trace nano particle for preparing efficient absorption according to claim 1
Method, it is characterised in that the FeCl described in step one3·6H2The ratio of O quality and the volume of ethylene glycol is 13.5g：500mL；Step
FeCl described in rapid one3·6H2The mass ratio of O and anhydrous sodium acetate is 13.5：36.
3. a kind of side of bi-functional monomer polysaccharide molecule trace nano particle for preparing efficient absorption according to claim 1
Method, it is characterised in that be transferred in step one in stainless steel cauldron, 6h is reacted in the case where temperature is 200 DEG C.
4. a kind of side of bi-functional monomer polysaccharide molecule trace nano particle for preparing efficient absorption according to claim 1
Method, it is characterised in that one obtained superparamagnetism Fe the step of described in step 23O4The quality of nano-particle and isopropanol and steaming
The ratio of the volume of the mixture of distilled water is 1.0g：1000mL；The superparamagnetism Fe that the step of described in step 2 one obtains3O4Receive
The ratio of the quality of rice corpuscles and the volume of ammoniacal liquor is 1.0g：25mL；The superparamagnetism that the step of described in step 2 one obtains
Fe3O4The ratio of the quality of nano-particle and the volume of tetraethyl orthosilicate is 1.0g：10mL.
5. a kind of side of bi-functional monomer polysaccharide molecule trace nano particle for preparing efficient absorption according to claim 1
Method, it is characterised in that two obtained Fe the step of described in step 33O4@SiO2The ratio of the quality of particulate and the volume of toluene is
1g：1000mL；The Fe that the step of described in step 3 two obtains3O4@SiO2The quality of particulate and 3- glycidyloxypropyls
The ratio of the volume of trimethoxy silane is 1g：10mL.
6. a kind of side of bi-functional monomer polysaccharide molecule trace nano particle for preparing efficient absorption according to claim 1
Method, it is characterised in that the Fe for obtaining step 2 in step 33O4@SiO2Particulate is dissolved in toluene, ultrasonically treated 10min, then
Temperature is heated to for 40 DEG C.
7. a kind of side of bi-functional monomer polysaccharide molecule trace nano particle for preparing efficient absorption according to claim 1
Method, it is characterised in that the mol ratio of Resocinol-phenol formaldehyde resin and 2- acrylamide-2-methylpro panesulfonic acids described in step 4 is
1：0.8；Fe described in step 43O4@SiO2The quality of@COC particulates and the phosphate-buffered that 0.02mol/L pH value is 9.0
The ratio of the volume of solution is 30mg：20mL；The Fe that starch described in step 4 is obtained with step 33O4@SiO2@COC particulates
Mass ratio is 1：40；Starch described in the step 4 and mass ratio of ammonium persulfate is in the phosphate buffer solution of ammonium persulfate
1：16.2.
8. a kind of side of bi-functional monomer polysaccharide molecule trace nano particle for preparing efficient absorption according to claim 1
Method, it is characterised in that the concentration of ammonium persulfate is 4.564mg/ in the phosphate buffer solution of the ammonium persulfate described in step 4
The concentration of phosphate buffer solution is 0.02mol/L in mL, the phosphate buffer solution of described ammonium persulfate, and pH value is 9.0.
9. a kind of side of bi-functional monomer polysaccharide molecule trace nano particle for preparing efficient absorption according to claim 1
Method, it is characterised in that the phosphate buffer solution that the pH value that the eluent described in step 4 is 0.02mol/L is 5.0.
10. a kind of bi-functional monomer polysaccharide molecule trace nano particle for preparing efficient absorption according to claim 1
Method, it is characterised in that 24h is reacted in oil bath under conditions of temperature is 60 DEG C in step 4.
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