CN102008924A - Method for preparing single polyelectrolyte microcapsule based on ferrocene hydrophobic interaction - Google Patents

Method for preparing single polyelectrolyte microcapsule based on ferrocene hydrophobic interaction Download PDF

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CN102008924A
CN102008924A CN 201010298911 CN201010298911A CN102008924A CN 102008924 A CN102008924 A CN 102008924A CN 201010298911 CN201010298911 CN 201010298911 CN 201010298911 A CN201010298911 A CN 201010298911A CN 102008924 A CN102008924 A CN 102008924A
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ferrocene
microcapsule
polyelectrolyte
amino
aqueous solution
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CN102008924B (en
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高长有
王志鹏
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Zhejiang University ZJU
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Abstract

The invention discloses a method for preparing a single polyelectrolyte microcapsule based on ferrocene hydrophobic interaction. The method is characterized by taking a polyelectrolyte doped colloid particle as a template, utilizing amido in polyelectrolyte to react with ferrocene carboxaldehyde, deacidizing a formed shiff's base chemical bond to an iumine bond by utilizing sodium borohydride to obtain the polyelectrolyte modified by ferrocene, and removing the colloid particle to obtain the single polyelectrolyte microcapsule with the microcapsule wall modified by the ferrocene. A large number of the polyelectrolyte doped in the colloid particle can be remained in the microcapsule so that the microcapsule has a thick microcapsule wall and a stable structure. Meanwhile, because the ferrocene has good redox properties, the microcapsule has sensitive redox responsiveness. By utilizing the characteristic, the microcapsule can realize molecular encapsulation and release controlled by redox. The microcapsule prepared by adopting the method of the invention has broad potential application value on aspects of nanometer materials, medicament release, biosensors, and the like.

Description

A kind of method for preparing single polyelectrolyte multiplayer microcapsule based on the ferrocene hydrophobic interaction
Technical field
The present invention relates to a kind of method for preparing hollow microcapsule.Especially utilize the ferrocene hydrophobic interaction to prepare the method for single polyelectrolyte multiplayer microcapsule.
Background technology
Microcapsules are by film forming matter the space in the capsule and the capsule external space to be kept apart to form the material of particular geometric configuration.The shape of microcapsules also can be oval, square or rectangular, polygonal and various irregularly shaped based on spherical structure.Tradition microcapsules size usually at micron to the millimeter level, wall thickness in sub-micron to the hundreds of micron.Microcapsules all have crucial application in food, medicine, cosmetics, bioengineering and organizational project.The preparation method of microcapsules has a lot.According to the principle that cyst wall forms, the traditional preparation process technology of microcapsules cardinal principle can be divided three classes: the physical method of the chemical method of utilization reaction generation cyst wall, the physico-chemical process that utilizes the formation cyst wall that is separated and utilization machinery or other physical action formation cyst wall.Cyst wall is made up of natural or synthetic macromolecular material usually, also inorganic compound.
In recent years, developed the preparation method of many new microcapsules again, as template assembling, matrix polymerization, surface grafting polymerization, dispersin polymerization etc.Wherein, be template with colloidal particles, utilize layer-by-layer on the template particulate, to assemble polymer ultra-thin film, remove that the microcapsules that prepare after the template have structure and performance is controlled, easily give characteristics such as various unique functions.The driving force of self assembly layer by layer mainly contains electrostatic force, hydrogen bond, hydrophobic force etc.Wherein, by the microcapsules that electrostatic interaction forms, its preparation process can be carried out in water, can avoid the pollution to environment.The size of gained microcapsules is controlled in advance by template, and its wall thickness can be controlled in the nanoscale.The permeability of microcapsules and the release performance of embedding substance can be controlled by environmental condition such as temperature, ionic species and ionic strength, pH value, SOLUTION PROPERTIES, light, electricity, sound etc.Therefore discharge in medicine control, fields such as the embedding of enzyme and catalytic reaction, organizational project have shown crucial application prospect.But, the shortcoming that there are many, the consuming time length of step in this preparation method, waste raw material, these drawbacks limit its promotion and application, especially be difficult to adapt to the extensive requirement of preparation fast.Simultaneously, the size of microcapsules and permeability obtain regulation and control by redox reaction, do not appear in the newspapers.
Summary of the invention
The purpose of this invention is to provide a kind of easy, prepare the method for single polyelectrolyte multiplayer microcapsule based on the ferrocene hydrophobic interaction fast.
1. one kind prepares the method for single amino-contained polyelectrolyte multiplayer microcapsule based on the ferrocene hydrophobic interaction, and this method may further comprise the steps:
1) with Ca (NO 3) 2And Na 2CO 3Be made into the 0.33M aqueous solution respectively, to Ca (NO 3) 2Add the amino-contained polyelectrolyte in the aqueous solution, the amino-contained polyelectrolyte is at Ca (NO 3) 2Concentration in the aqueous solution is 1-10mg/mL, stirs it is mixed; Under magnetic agitation to wherein adding Na 2CO 3The aqueous solution, Na 2CO 3The aqueous solution and Ca (NO 3) 2The volume ratio of the aqueous solution is 1: 1, continue to stir, and leaves standstill reaction then, collects the gained particulate, washing, the CaCO of the amino-contained polyelectrolyte that obtains mixing 3Particulate;
2) the step 1) gained is doped with the CaCO of amino-contained polyelectrolyte 3Particulate is put into the methanol solution that concentration is the ferrocene formaldehyde of 5-40mg/mL, and vibration forms suspension, and persistent oscillation 1-5 hour, centrifugal then, with ethanol washing and dispersion colloid particle; In the alcohol suspension of colloidal particle, add excessive NaBH 4Solution, and vibrated 30-60 minute, centrifugal then, wash with water and the dispersion colloid particle;
3) to step 2) to add concentration in the suspension of resulting colloidal particle be the edta solution of 0.02-0.2mol/L, obtains cyst wall and be the hollow microcapsule of the single amino-contained polyelectrolyte that ferrocene modifies.
2. according to claim 1ly prepare the method for single amino-contained polyelectrolyte multiplayer microcapsule, it is characterized in that said amino-contained polyelectrolyte is PAH (PAH) or polylysine (PLL) based on the ferrocene hydrophobic interaction.
Principle of the present invention is: at first amino-contained polyelectrolyte PAH or PLL are entrained in CaCO 3In the colloidal particle.Utilize amino among polyelectrolyte PAH or the PLL and the aldehyde radical in the ferrocene formaldehyde (Fc-CHO) by the west not alkali reaction prepare the PLL (PLL-Fc) that PAH (PAH-Fc) that ferrocene formaldehyde modifies or ferrocene formaldehyde are modified.With not alkali reduction of west, make its steady chemical structure on this basis.Because ferrocene is a kind of hydrophobic organic molecule; therefore after in the aqueous solution, removing the colloidal particle template; ferrocene can spontaneously be assembled the hydrophobic microcell of formation; under the protection of hydrophilic polyelectrolyte PAH or PLL, PAH-Fc or PLL-Fc can form complete microcapsules by molecular chain movement simultaneously.
Beneficial effect of the present invention is: technical process of the present invention is simple, and controllability is good, and material source is extensive, is suitable for a large amount of fast preparations of hollow microcapsule.Because ferrocene is the organic molecule with good oxidation reducing property, so contains the single polyelectrolyte multiplayer microcapsule that ferrocene modifies among the present invention and also have good redox response.For example, when adding the oxidant of low concentration in the suspension of microcapsules, ferrocene is because oxidized and positively charged, thereby hydrophobic interaction power is reduced, and the microcapsules size expands.The diameter difference can reach one times before and after expanding.When adding the reducing agent of low concentration, the ferrocene of oxidation is reduced again, hydrophobicly firmly strengthens in mutually, thereby makes the dimensional contraction of microcapsules.The permeance property of while microcapsules is the accuracy controlling along with the process of redox reaction also.When the microcapsules oxidation was expanded, the permeance property of microcapsules strengthened, and large biological molecule or drug molecule can easily pass in and out microcapsules; When the microcapsules reduction was shunk, the microcapsules permeance property weakened, and large biological molecule or drug molecule are embedded in the microcapsules or completely cut off outside the microcapsules cyst wall.By changing the concentration of oxidant, the rate of release behind microcapsule embedded large biological molecule or the drug molecule can be accurately controlled.
Description of drawings
Fig. 1 is the CaCO that is doped with PAH 3The stereoscan photograph of particulate.
Fig. 2 is the dried stereoscan photographs of PAH-Fc microcapsules.
Fig. 3 is the dried stereoscan photographs of PAH-Fc microcapsules.
Fig. 4 is the laser confocal microscope photo of PAH-Fc microcapsules.Microcapsules are dispersed in the water, and add a small amount of fluorescein and carry out mark.
Fig. 5 is the laser confocal microscope photo of PAH-Fc microcapsules.Microcapsules are dispersed in the water, and add a small amount of fluorescein and carry out mark.
Fig. 6 is the laser confocal microscope photo of PLL-Fc microcapsules.Microcapsules are dispersed in the water, and add a small amount of fluorescein and carry out mark.
Fig. 7 is the dried stereoscan photographs of PLL-Fc microcapsules.
Fig. 8 is the laser confocal microscope photo of PLL-Fc microcapsules.Microcapsules are dispersed in the water, and add a small amount of fluorescein and carry out mark.
Fig. 9 is the dried stereoscan photographs of PLL-Fc microcapsules.
The specific embodiment
Further specify the present invention below in conjunction with example, but these examples are not used for limiting the present invention.
Embodiment 1
1) with Ca (NO 3) 2And Na 2CO 3Be made into the 0.33M aqueous solution respectively, get 100mL Ca (NO 3) 2Add PAH in the solution, PAH is at Ca (NO 3) 2Concentration in the solution is 2mg/mL, stirs it is mixed; Under magnetic agitation rapidly to wherein adding 100mL Na 2CO 3The aqueous solution continues to stir 40 seconds, allows it leave standstill reaction then, precipitates fully until all particulates that generate; With the centrifugal collection of gained particulate, wash 3 times, obtain the CaCO that diameter is about 5.5 microns 3Particulate, its stereoscan photograph is seen Fig. 1; This CaCO 3Particulate is the template of the colloidal particle that mixes with PAH.
2) the step 1) gained is doped with the CaCO of PAH 3Particulate is put into the methanol solution that 20mL concentration is the ferrocene formaldehyde of 20mg/mL, and vibration forms suspension, and the persistent oscillation west alkali reaction not that carried out the amino of PAH and ferrocene formaldehyde in 3 hours.Centrifugal then, with ethanol washing and dispersion colloid particle; In the alcohol suspension of colloidal particle, add excessive NaBH 4Solution, and vibrated 40 minutes, centrifugal then, wash with water and the dispersion colloid particle;
3) to step 2) to add concentration in the suspension of resulting colloidal particle be the edta solution of 0.1mol/L, obtains cyst wall and be the hollow microcapsule of the PAH that ferrocene modifies, its stereoscan photograph is seen Fig. 2.
Embodiment 2
1) with Ca (NO 3) 2And Na 2CO 3Be made into the 0.33M aqueous solution respectively, get 70mL Ca (NO 3) 2Add PAH in the solution, PAH is at Ca (NO 3) 2Concentration in the solution is 5mg/mL, stirs it is mixed; Under magnetic agitation rapidly to wherein adding 70mL Na 2CO 3The aqueous solution continues to stir 50 seconds, allows it leave standstill reaction then, precipitates fully until all particulates that generate; With the centrifugal collection of gained particulate, wash 3 times, obtain the colloid CaCO that mixes with PAH 3Particulate.
2) the step 1) gained is doped with the CaCO of PAH 3Particulate is put into the methanol solution that 30mL concentration is the ferrocene formaldehyde of 10mg/mL, and vibration forms suspension, and the persistent oscillation west alkali reaction not that carried out the amino of PAH and ferrocene formaldehyde in 4 hours.Centrifugal then, with ethanol washing and dispersion colloid particle; In the alcohol suspension of colloidal particle, add excessive NaBH 4Solution, and vibrated 30 minutes, centrifugal then, wash with water and the dispersion colloid particle;
3) to step 2) to add concentration in the suspension of resulting colloidal particle be the edta solution of 0.2mol/L, obtains cyst wall and be the hollow microcapsule of the PAH that ferrocene modifies, its stereoscan photograph is seen Fig. 3.
Embodiment 3
1) with Ca (NO 3) 2And Na 2CO 3Be made into the 0.33M aqueous solution respectively, get 50mL Ca (NO 3) 2Add PAH in the solution, PAH is at Ca (NO 3) 2Concentration in the solution is 10mg/mL, stirs it is mixed; Under magnetic agitation rapidly to wherein adding 50mL Na 2CO 3The aqueous solution continues to stir 60 seconds, allows it leave standstill reaction then, precipitates fully until all particulates that generate; With the centrifugal collection of gained particulate, wash 3 times, obtain the colloid CaCO that mixes with PAH 3Particulate.
2) the step 1) gained is doped with the CaCO of PAH 3Particulate is put into the methanol solution that 20mL concentration is the ferrocene formaldehyde of 30mg/mL, and vibration forms suspension, and the persistent oscillation west alkali reaction not that carried out the amino of PAH and ferrocene formaldehyde in 4 hours.Centrifugal then, with ethanol washing and dispersion colloid particle; In the alcohol suspension of colloidal particle, add excessive NaBH 4Solution, and vibrated 30 minutes, centrifugal then, wash with water and the dispersion colloid particle;
3) to step 2) to add concentration in the suspension of resulting colloidal particle be the edta solution of 0.2mol/L, obtains cyst wall and be the hollow microcapsule of the PAH that ferrocene modifies, its laser confocal microscope photo is seen Fig. 4.
Embodiment 4
1) with Ca (NO 3) 2And Na 2CO 3Be made into the 0.33M aqueous solution respectively, get 150mL Ca (NO 3) 2Add PAH in the solution, PAH is at Ca (NO 3) 2Concentration in the solution is 10mg/mL, stirs it is mixed; Under magnetic agitation rapidly to wherein adding 150mL Na 2CO 3The aqueous solution continues to stir 60 seconds, allows it leave standstill reaction then, precipitates fully until all particulates that generate; With the centrifugal collection of gained particulate, wash 3 times, obtain the colloid CaCO that mixes with PAH 3Particulate.
2) the step 1) gained is doped with the CaCO of PAH 3Particulate is put into the methanol solution that 40mL concentration is the ferrocene formaldehyde of 30mg/mL, and vibration forms suspension, and the persistent oscillation west alkali reaction not that carried out the amino of PAH and ferrocene formaldehyde in 6 hours.Centrifugal then, with ethanol washing and dispersion colloid particle; In the alcohol suspension of colloidal particle, add excessive NaBH 4Solution, and vibrated 60 minutes, centrifugal then, wash with water and the dispersion colloid particle;
3) to step 2) to add concentration in the suspension of resulting colloidal particle be the edta solution of 0.2mol/L, obtains cyst wall and be the hollow microcapsule of the PAH that ferrocene modifies, its laser confocal microscope photo is seen Fig. 5.
Embodiment 5
1) with Ca (NO 3) 2And Na 2CO 3Be made into the 0.33M aqueous solution respectively, get 100mL Ca (NO 3) 2Add PLL in the solution, PLL is at Ca (NO 3) 2Concentration in the solution is 2mg/mL, stirs it is mixed; Under magnetic agitation rapidly to wherein adding 100mL Na 2CO 3The aqueous solution continues to stir 40 seconds, allows it leave standstill reaction then, precipitates fully until all particulates that generate; With the centrifugal collection of gained particulate, wash 3 times, obtain the colloid CaCO that mixes with PLL 3Particulate.
2) the step 1) gained is doped with the CaCO of PLL 3Particulate is put into the methanol solution that 20mL concentration is the ferrocene formaldehyde of 20mg/mL, and vibration forms suspension, and the persistent oscillation west alkali reaction not that carried out the amino of PLL and ferrocene formaldehyde in 3 hours.Centrifugal then, with ethanol washing and dispersion colloid particle; In the alcohol suspension of colloidal particle, add excessive NaBH 4Solution, and vibrated 40 minutes, centrifugal then, wash with water and the dispersion colloid particle;
3) to step 2) to add concentration in the suspension of resulting colloidal particle be the edta solution of 0.1mol/L, obtains cyst wall and be the hollow microcapsule of the PLL that ferrocene modifies, its laser confocal microscope photo is seen Fig. 6.
Embodiment 6
1) with Ca (NO 3) 2And Na 2CO 3Be made into the 0.33M aqueous solution respectively, get 70mL Ca (NO 3) 2Add PLL in the solution, PLL is at Ca (NO 3) 2Concentration in the solution is 5mg/mL, stirs it is mixed; Under magnetic agitation rapidly to wherein adding 70mL Na 2CO 3The aqueous solution continues to stir 50 seconds, allows it leave standstill reaction then, precipitates fully until all particulates that generate; With the centrifugal collection of gained particulate, wash 3 times, obtain the colloid CaCO that mixes with PLL 3Particulate.
2) the step 1) gained is doped with the CaCO of PLL 3Particulate is put into the methanol solution that 30mL concentration is the ferrocene formaldehyde of 10mg/mL, and vibration forms suspension, and the persistent oscillation west alkali reaction not that carried out the amino of PLL and ferrocene formaldehyde in 4 hours.Centrifugal then, with ethanol washing and dispersion colloid particle; In the alcohol suspension of colloidal particle, add excessive NaBH 4Solution, and vibrated 30 minutes, centrifugal then, wash with water and the dispersion colloid particle;
3) to step 2) to add concentration in the suspension of resulting colloidal particle be the edta solution of 0.2mol/L, obtains cyst wall and be the hollow microcapsule of the PLL that ferrocene modifies, its stereoscan photograph is seen Fig. 7.
Embodiment 7
1) with Ca (NO 3) 2And Na 2CO 3Be made into the 0.33M aqueous solution respectively, get 50mL Ca (NO 3) 2Add PLL in the solution, PLL is at Ca (NO 3) 2Concentration in the solution is 10mg/mL, stirs it is mixed; Under magnetic agitation rapidly to wherein adding 50mL Na 2CO 3The aqueous solution continues to stir 60 seconds, allows it leave standstill reaction then, precipitates fully until all particulates that generate; With the centrifugal collection of gained particulate, wash 3 times, obtain the colloid CaCO that mixes with PLL 3Particulate.
2) the step 1) gained is doped with the CaCO of PLL 3Particulate is put into the methanol solution that 20mL concentration is the ferrocene formaldehyde of 30mg/mL, and vibration forms suspension, and the persistent oscillation west alkali reaction not that carried out the amino of PLL and ferrocene formaldehyde in 4 hours.Centrifugal then, with ethanol washing and dispersion colloid particle; In the alcohol suspension of colloidal particle, add excessive NaBH 4Solution, and vibrated 30 minutes, centrifugal then, wash with water and the dispersion colloid particle;
3) to step 2) to add concentration in the suspension of resulting colloidal particle be the edta solution of 0.2mol/L, obtains cyst wall and be the hollow microcapsule of the PLL that ferrocene modifies, its laser confocal microscope photo is seen Fig. 8.
Embodiment 8
1) with Ca (NO 3) 2And Na 2CO 3Be made into the 0.33M aqueous solution respectively, get 150mL Ca (NO 3) 2Add PLL in the solution, PLL is at Ca (NO 3) 2Concentration in the solution is 10mg/mL, stirs it is mixed; Under magnetic agitation rapidly to wherein adding 150mL Na 2CO 3The aqueous solution continues to stir 60 seconds, allows it leave standstill reaction then, precipitates fully until all particulates that generate; With the centrifugal collection of gained particulate, wash 3 times, obtain the colloid CaCO that mixes with PLL 3Particulate.
2) the step 1) gained is doped with the CaCO of PLL 3Particulate is put into the methanol solution that 40mL concentration is the ferrocene formaldehyde of 30mg/mL, and vibration forms suspension, and the persistent oscillation west alkali reaction not that carried out the amino of PLL and ferrocene formaldehyde in 6 hours.Centrifugal then, with ethanol washing and dispersion colloid particle; In the alcohol suspension of colloidal particle, add excessive NaBH 4Solution, and vibrated 60 minutes, centrifugal then, wash with water and the dispersion colloid particle;
3) to step 2) to add concentration in the suspension of resulting colloidal particle be the edta solution of 0.2mol/L, obtains cyst wall and be the hollow microcapsule of the PLL that ferrocene modifies, its stereoscan photograph is seen Fig. 9.

Claims (2)

1. one kind prepares the method for single amino-contained polyelectrolyte multiplayer microcapsule based on the ferrocene hydrophobic interaction, and this method may further comprise the steps:
1) with Ca (NO 3) 2And Na 2CO 3Be made into the 0.33M aqueous solution respectively, to Ca (NO 3) 2Add the amino-contained polyelectrolyte in the aqueous solution, the amino-contained polyelectrolyte is at Ca (NO 3) 2Concentration in the aqueous solution is 1-10mg/mL, stirs it is mixed; Under magnetic agitation to wherein adding Na 2CO 3The aqueous solution, Na 2CO 3The aqueous solution and Ca (NO 3) 2The volume ratio of the aqueous solution is 1: 1, continue to stir, and leaves standstill reaction then, collects the gained particulate, washing, the CaCO of the amino-contained polyelectrolyte that obtains mixing 3Particulate;
2) the step 1) gained is doped with the CaCO of amino-contained polyelectrolyte 3Particulate is put into the methanol solution that concentration is the ferrocene formaldehyde of 5-40mg/mL, and vibration forms suspension, and persistent oscillation 1-5 hour, centrifugal then, with ethanol washing and dispersion colloid particle.In the alcohol suspension of colloidal particle, add excessive NaBH 4Solution, and vibrated 30-60 minute, centrifugal then, wash with water and the dispersion colloid particle;
3) to step 2) to add concentration in the suspension of resulting colloidal particle be the edta solution of 0.02-0.2mol/L, obtains cyst wall and be the hollow microcapsule of the single amino-contained polyelectrolyte that ferrocene modifies.
2. according to claim 1ly prepare the method for single amino-contained polyelectrolyte multiplayer microcapsule, it is characterized in that said amino-contained polyelectrolyte is PAH or polylysine based on the ferrocene hydrophobic interaction.
CN2010102989119A 2010-09-30 2010-09-30 Method for preparing single polyelectrolyte microcapsule based on ferrocene hydrophobic interaction Expired - Fee Related CN102008924B (en)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1919445A (en) * 2006-08-15 2007-02-28 浙江大学 Method for preparing microcapsule by using doping porous calcium carbonate mould plates
CN101053813A (en) * 2007-04-28 2007-10-17 浙江大学 Method for preparing layer-layer assembled microcapsule based on host-guest interactions
CN101172223A (en) * 2007-08-10 2008-05-07 浙江大学 Method for producing microcapsule by using surface controllable deposition and crosslinke

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1919445A (en) * 2006-08-15 2007-02-28 浙江大学 Method for preparing microcapsule by using doping porous calcium carbonate mould plates
CN101053813A (en) * 2007-04-28 2007-10-17 浙江大学 Method for preparing layer-layer assembled microcapsule based on host-guest interactions
CN101172223A (en) * 2007-08-10 2008-05-07 浙江大学 Method for producing microcapsule by using surface controllable deposition and crosslinke

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