CN101747512B - Electrostatic driving bionic super-molecule assembling body, preparation method thereof and purposes - Google Patents
Electrostatic driving bionic super-molecule assembling body, preparation method thereof and purposes Download PDFInfo
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Abstract
The invention discloses an electrostatic driving bionic super-molecule assembling body, a preparation method thereof and purposes. The bionic super-molecule assembling body is composed of a hydrophobic polymer containing carboxyl at the end and a hydrophilic polymer containing amino at the end, wherein the hydrophobic polymer and the hydrophilic polymer are combined together under the electrostatic function between the amino and the carboxyl. The bionic super-molecule assembling body preparation method includes the following steps: the hydrophilic polymer and the hydrophobic polymer are respectively dissolved into a solvent so as to prepare solution, and water is further added for self-assembling after the two polymer solution is mixed so as to obtain the bionic super-molecule assembling body. The bionic super-molecule assembling body which is obtained through electrostatic driving can be further used as a template to drive the template assembling of metal Nano particles. The preparation process is simple, the obtained bionic super-molecule assembling body has good biocompatibility, and the distribution of the Nano particles in the assembling body can be accurately controlled. The bionic super-molecule assembling body has wide application prospects in the fields of genes, drug delivery, a biological sensor and the like.
Description
Technical field
The present invention relates to polymer nano-particle mixture and preparation method, relate in particular to a kind of bionic super-molecule assembling body of static driven.
Background technology
Amphiphilic block copolymer has a wide range of applications in fields such as drug delivery, gene transmission, biosensors.Composition and assembling condition through the control multipolymer can access various structure assembling such as micella, vesica, vermiform.Recently, the application of polymer-metal particle nano-complex in fields such as drug delivery, gene transmission, biosensors more and more receives widely and paying close attention to.Hydrophobic part or in-situ reducing that polymer-metal particle nano-complex can combine through the metal nanoparticle that surface-treated is crossed to get into the polymkeric substance assembly generate metal nanoparticle.Yet this need carry out complicated modification to the surface of metal nanoparticle usually.And the performance of polymer-metal particle nano-complex depends on the distribution situation of nanoparticle in polymeric matrix greatly.Therefore prepare the polymer-metal particle nano-complex of accurately controlling that distributes through easy method and remain very big challenge.
Common polymkeric substance assembly is by the copolymer that connects through covalent linkage, yet the building-up process of multipolymer is loaded down with trivial details relatively, and operational condition requires than higher.The supramolecule multipolymer that couples together through reversible, non covalent bond provides a kind of method easily and effectively that makes up the polymkeric substance assembly.Electrostatic interaction is than other non covalent bond reactive force; Have many advantages like hydrogen bond, metal ligand chela and effect, Subjective and Objective effect etc.: at first, can the segmented copolymer that be difficult to prepare through common compound method be come true through static bonded method.Secondly, end has the polymkeric substance of positive electricity or negative electricity functional group can be through easier the making of the fashionable chain transfer reaction of radical polymerization, and do not need complicated loaded down with trivial details ion or controllable free-radical polymerisation thing operation.The 3rd, consider that electrostatic interaction is very general in living things system, so the toxicity of electrostatic interaction is lower.What is more important is compared with the assembly of the copolymer that is connected through covalent linkage, and the super-molecule assembling body for preparing through electrostatic interaction has the potentiality in the further functionalization in ionic bond interface.The nanoparticle that this super-molecule assembling body can control surface has an electric charge is distributed in the specific position of assembly.
Summary of the invention
The objective of the invention is to overcome the deficiency of prior art, the bionic super-molecule assembling body of one one kinds of static driven is provided.
The bionic super-molecule assembling body of static driven is that bionic super-molecule assembling body is made up of carboxylic hydrophobic polymer of end and the terminal hydrophilic polymer that contains amino; Wherein terminal carboxylic hydrophobic polymer and the terminal hydrophilic polymer that contains amino combine through the electrostatic interaction between amino and the carboxyl, and terminal carboxylic hydrophobic polymer is 1: 100～100: 1 with the terminal weight ratio that contains amino hydrophilic polymer.
The preparation method of the carboxylic hydrophobic polymer of described end is: in the 100ml tetrahydrofuran solvent; Add 0.001mg～20mg thiohydracrylic acid or Thiovanic acid, 0.001mg～10mg Diisopropyl azodicarboxylate and 0.1～100g hydrophobic monomer; Under 45～90 degrees centigrade, carry out free radical chain transfer polymerization 1～24hr,, obtain terminal carboxylic hydrophobic polymer with methanol extraction and vacuum-drying; Wherein, the carboxylic hydrophobic polymer molecular weight of described end is between 800～20000.
Said hydrophobic monomer is selected from vinylbenzene, TEB 3K, NSC 20956, stearyl methacrylate, methyl acrylate, Bing Xisuandingzhi or octadecyl acrylate.
The preparation method that described end contains amino hydrophilic polymer is: in the 100ml alcohol solvent; Add 0.001mg～20mg mercaptoethylamine, 0.001mg～10mg Diisopropyl azodicarboxylate and 0.1～100g hydrophilic monomer; Under 45～90 degrees centigrade, carry out free radical chain transfer polymerization 1～24hr,, obtain the terminal amino hydrophilic polymer that contains with THF deposition and vacuum-drying; Wherein, described end contains amino molecular weight hydrophilic polymer between 400～10000.
Described hydrophilic monomer is selected from methylacrylic acid phosphorylcholine ester, vinylformic acid phosphorylcholine ester, methylacrylic acid glucose ester, vinylformic acid glucose ester, methylacrylic acid polyoxyethylene ester or vinylformic acid polyoxyethylene ester.
The preparation method of the bionic super-molecule assembling body of static driven may further comprise the steps:
1) the carboxylic hydrophobic polymer of end being dissolved in tetrahydrofuran solvent, to be prepared into weight concentration be 0.01～20% solution A;
2) end being contained amino hydrophilic polymer is dissolved in ethanol preparation to become weight concentration is 0.005～10% solution B;
3) 1 parts by weight solution A is mixed with 1 parts by weight solution B carried out self-assembling reaction 1～100 minute, add 1～100 weight parts water, carry out dialysis treatment then, lyophilize removes and anhydrates, and obtains bionic super-molecule assembling body.
The bionic super-molecule assembling body of static driven is used for the embedded nano particle.
The method of the bionic super-molecule assembling body embedded nano particle of described static driven may further comprise the steps:
1) the carboxylic hydrophobic polymer of end is dissolved in to be prepared into weight concentration in the THF be 0.01～20% solution C;
2) end being contained amino hydrophilic polymer is dissolved in ethanol preparation to become weight concentration is 0.005～10% solution D;
3) nanoparticle that the surface is contained positive charge is dissolved in that to be prepared into weight concentration in the THF be 0.001～2% solution E;
4) 1 parts by weight solution C is mixed with 1 parts by weight solution D carried out self-assembling reaction 1～100 minute; Add 0.5 parts by weight solution E again and carried out self-assembling reaction 1～50 minute; Add 1～100 weight parts water; Carry out dialysis treatment then, lyophilize removes and anhydrates, and obtains being embedded with the nanoparticle bionic super-molecule assembling body.
The nano particle diameter that described surface contains positive charge is 1～20 nanometer.
The nanoparticle that described surface contains positive charge contains the golden nanometer particle of positive charge, the Nano silver grain that the surface contains positive charge, the nano platinum particle that the surface contains positive charge, the Cadmium telluride fine powder nanoparticle that the surface contains positive charge, cadmium sulfide nano-particles or the surperficial Nano particles of silicon dioxide that contains positive charge that the surface contains positive charge for the surface.
The beneficial effect that the present invention compared with prior art has is:
1, end have the polymkeric substance of positive electricity or negative electricity functional group can be through easier the making of the fashionable chain transfer reaction of radical polymerization, and do not need complicated loaded down with trivial details ion or controllable free-radical polymerisation thing operation;
2, to prepare process simple for the bionic super-molecule assembling body through static driven, and the gained assembly has good stability in the pure water environment;
3, gained super-molecule assembling body and can effectively regulate and control the specific region that nanoparticle is distributed in assembly need not carry out complicated modification to the surface of metal nanoparticle; The position of metal nanoparticle can accurately be controlled and the distribution of metal nanoparticle is vital for the mixture final properties
Description of drawings
Fig. 1 (a) is the nuclear-magnetism figure of end for the PS of carboxyl.
Fig. 1 (b) is the nuclear-magnetism figure of end for the polymethyl acrylic acid phosphorylcholine ester of amido.
Fig. 2 (a) is bowl-type assembly transmission electron microscope and the sem photograph that end is assembled out for the polymethyl acrylic acid phosphorylcholine ester of amido for the PS and the end of carboxyl.
Fig. 2 (b) is porous spherical assembly transmission electron microscope and the sem photograph that end is assembled out for the polymethyl acrylic acid phosphorylcholine ester of amido for the PS and the end of carboxyl.
Fig. 3 (a) is the bowl-type assembly embedding golden nanometer particle transmission electron microscope picture that end is assembled out for the polymethyl acrylic acid phosphorylcholine ester of amido for the PS and the end of carboxyl.
Fig. 3 (b) is the porous spherical assembly embedding golden nanometer particle transmission electron microscope picture that end is assembled out for the polymethyl acrylic acid phosphorylcholine ester of amido for the PS and the end of carboxyl.
Embodiment
The invention discloses a kind of bionic super-molecule assembling body and preparation and purposes of static driven.Bionic super-molecule assembling body is made up of carboxylic hydrophobic polymer of end and the terminal hydrophilic polymer that contains amino, and wherein hydrophilic polymer and hydrophobic polymer combine through the electrostatic interaction between amino and the carboxyl.The preparation method of bionic super-molecule assembling body comprises, hydrophilic polymer and hydrophobic polymer component is dissolved in solvent respectively is prepared into solution, two kinds of polymkeric substance further added entry after mixed carry out self-assembly, obtains bionic super-molecule assembling body.This through the resulting bionic super-molecule assembling body of static driven, can further assemble as the template of template-driven metal nanoparticle.
Following embodiment further specifies of the present invention, rather than limits scope of the present invention.
Embodiment 1:
1) hydrophobic polymer is synthetic: in the 50mL round-bottomed flask, add vinylbenzene 5.75ml, and 3-thiohydracrylic acid 0.22mL, Diisopropyl azodicarboxylate 0.082 gram and 25mL THF vacuumizes three circulations and removes oxygen through freezing, then reacts 24 hours down at 75 ℃.Gained solution with cold anhydrous methanol precipitating three times, is removed unconjugated 3-thiohydracrylic acid after concentrating.With 50 ℃ of following dried overnight of solid collection, obtain the terminal PS of carboxyl that is then.Nuclear-magnetism and GPC result prove that product has expected structure, see Fig. 1 (a).
2) hydrophilic polymer is synthetic: in the 50mL round-bottomed flask, add methylacrylic acid phosphorylcholine ester 4.42 grams; Mercaptoethylamine hydrochloride 0.0852 gram; Diisopropyl azodicarboxylate 0.0246 gram and 25mL absolute ethyl alcohol; Vacuumize three circulations and remove oxygen through freezing, then 75 ℃ of reactions 24 hours down.Gained solution adds KOH 0.042 gram and Na through being concentrated to 5mL
2SO
41.5 gram stirred after 5 hours, and solution is removed by filter salinity, and the amido hydrochloride is converted into the amido form.With THF precipitating twice, use the anhydrous diethyl ether precipitating more once, to remove unconjugated mercaptoethylamine hydrochloride.With 50 ℃ of following dried overnight of solid collection, obtain the terminal polymethyl acrylic acid phosphorylcholine ester of amido that is then.Nuclear-magnetism and GPC result prove that product has expected structure, see Fig. 1 (b).
3) preparation of polymers soln: PS is dissolved in is prepared into the solution that weight concentration is 10mg/mL in the THF, use the aperture to filter as the teflon membrane filter of 220nm then, gained solution is preserved down in 4 ℃.Polymethyl acrylic acid phosphorylcholine ester is dissolved in the solution that is made into 5mg/mL in the anhydrous methanol, uses the teflon membrane filter filtration of aperture as 220nm then, gained solution is preserved down in 4 ℃.
4) preparation of static driven super-molecule assembling body: the 5mg/mL solution of the 10mg/mL solution of 10 μ L PS and 10 μ L polymethyl acrylic acid phosphorylcholine esters is added in the mixed solvent of 2mL THF and absolute ethyl alcohol (volume ratio is 1/1), stirred 30 minutes.Dropwise add deionized water 10mL, organic solvent is removed in dialysis then, obtains super-molecule assembling body.Transmission electron microscope and dynamic light scattering result prove and successfully obtain assembly, see Fig. 2 (a) and Fig. 2 (b).
5) preparation of golden nanometer particle: the aqueous solution of 30mL hydrochloro-auric acid 30mmol/L is joined in the toluene solution of 80mL four octyl group brometo de amonio 50mmol/L, and vigorous stirring is 1 hour then.Add 170 milligrams of Dodecyl Mercaptans again, and then add the aqueous solution of 25mL Peng Qinghuana 0.4mol/L under the vigorous stirring, under the lucifuge condition, stirred 3 hours then.Be concentrated to 10mL after organic phase is separated, pour the 400mL absolute ethyl alcohol then into and in-18 ℃ of held 4h the golden nanometer particle precipitating is come out, then the brown deposition is collected, with the absolute ethyl alcohol flushing for several times, vacuum-drying obtains hydrophobic golden nanometer particle.Then solid being dissolved in the solution that is made into 1mg/mL in the THF keeps in Dark Place under 4 ℃.TEM results proves and successfully gets golden nanometer particle.
6) preparation of nanoparticle polymer composite particle: the 5mg/mL solution of the 10mg/mL solution of 10 μ L PS and 10 μ L polymethyl acrylic acid phosphorylcholine esters is added in the mixed solvent of 2mL THF and absolute ethyl alcohol (volume ratio is 1/1), stirred 30 minutes.The solution that adds the THF 1mg/mL of 10 μ L golden nanometer particles then, restir 30 minutes dropwise adds deionized water 10mL, removes organic solvent through dialysis again, obtains the golden nanometer particle polymer composite particle.Transmission electron microscope and dynamic light scattering result prove and successfully obtain assembly, see Fig. 3 (a) and Fig. 3 (b).
Embodiment 2:
1) hydrophobic polymer is synthetic: in the 50mL round-bottomed flask, add TEB 3K 5.33mL; 3-thiohydracrylic acid 0.22mL; Diisopropyl azodicarboxylate 0.082 gram and 25mL THF vacuumize three circulations and remove oxygen through freezing, then react 24 hours down at 75 ℃.Gained solution with cold anhydrous methanol precipitating three times, is removed unconjugated 3-thiohydracrylic acid after concentrating.With 50 ℃ of following dried overnight of solid collection, obtain the terminal polymethylmethacrylate of carboxyl that is then.Nuclear-magnetism and GPC result prove that product has expected structure.
2) hydrophilic polymer is synthetic: with embodiment 1.Nuclear-magnetism and GPC result prove that product has expected structure.
3) preparation of polymers soln: polymethylmethacrylate is dissolved in is prepared into the solution that weight concentration is 10mg/mL in the THF, use the aperture to filter as the teflon membrane filter of 220nm then, gained solution is preserved down in 4 ℃.Polymethyl acrylic acid phosphorylcholine ester is dissolved in the solution that is made into 5mg/mL in the anhydrous methanol, uses the teflon membrane filter filtration of aperture as 220nm then, gained solution is preserved down in 4 ℃.
4) preparation of static driven super-molecule assembling body: the 5mg/mL solution of the 10mg/mL solution of 10 μ L polymethylmethacrylates and 10 μ L polymethyl acrylic acid phosphorylcholine esters is added in the mixed solvent of 2mL THF and absolute ethyl alcohol (volume ratio is 1/1), stirred 30 minutes.Dropwise add deionized water 10mL then, organic solvent is removed in dialysis then, obtains super-molecule assembling body.Transmission electron microscope and dynamic light scattering result prove and successfully obtain assembly.
5) preparation of golden nanometer particle: with embodiment 1.TEM results proves and successfully gets golden nanometer particle.
6) preparation of nanoparticle polymer composite particle: the 5mg/mL solution of the 10mg/mL solution of 10 μ L polymethylmethacrylates and 10 μ L polymethyl acrylic acid phosphorylcholine esters is added in the mixed solvent of 2mL THF and absolute ethyl alcohol (volume ratio is 1/1), stirred 30 minutes.The solution that adds the THF 1mg/mL of 10 μ L golden nanometer particles then, restir 30 minutes dropwise adds deionized water 10mL, removes organic solvent through dialysis again, obtains the golden nanometer particle polymer composite particle.Transmission electron microscope and dynamic light scattering result prove and successfully obtain assembly
Embodiment 3:
1) hydrophobic polymer is synthetic: in the 50mL round-bottomed flask, add stearyl methacrylate 16.9 grams; 3-thiohydracrylic acid 0.22mL; Diisopropyl azodicarboxylate 0.082 gram and 25mL THF vacuumize three circulations and remove oxygen through freezing, then react 24 hours down at 75 ℃.Gained solution with cold anhydrous methanol precipitating three times, is removed unconjugated 3-thiohydracrylic acid after concentrating.With 50 ℃ of following dried overnight of solid collection, obtain the terminal stearyl methacrylate of carboxyl that is then.Nuclear-magnetism and GPC result prove that product has expected structure.
2) hydrophilic polymer is synthetic: with embodiment 1.Nuclear-magnetism and GPC result prove that product has expected structure.
3) preparation of polymers soln: the polymethyl acrylic acid octadecyl ester is dissolved in is prepared into the solution that weight concentration is 10mg/mL in the THF, use the aperture to filter as the teflon membrane filter of 220nm then, gained solution is preserved down in 4 ℃.Polymethyl acrylic acid phosphorylcholine ester is dissolved in the solution that is made into 5mg/mL in the anhydrous methanol, uses the teflon membrane filter filtration of aperture as 220nm then, gained solution is preserved down in 4 ℃.
4) preparation of static driven super-molecule assembling body: the 5mg/mL solution of the 10mg/mL solution of 10 μ L polymethyl acrylic acid octadecyl esters and 10 μ L polymethyl acrylic acid phosphorylcholine esters is added in the mixed solvent of 2mL THF and absolute ethyl alcohol (volume ratio is 1/1), stirred 30 minutes.Dropwise add deionized water 10mL then, organic solvent is removed in dialysis then, obtains super-molecule assembling body.Transmission electron microscope and dynamic light scattering result prove and successfully obtain assembly.
5) preparation of golden nanometer particle: with embodiment 1.TEM results proves and successfully gets golden nanometer particle.
6) preparation of nanoparticle polymer composite particle: the 5mg/mL solution of the 10mg/mL solution of 10 μ L polymethyl acrylic acid octadecyl esters and 10 μ L polymethyl acrylic acid phosphorylcholine esters is added in the mixed solvent of 2mL THF and absolute ethyl alcohol (volume ratio is 1/1), stirred 30 minutes.The solution that adds the THF 1mg/mL of 10 μ L golden nanometer particles then, restir 30 minutes dropwise adds deionized water 10mL, removes organic solvent through dialysis again, obtains the golden nanometer particle polymer composite particle.Transmission electron microscope and dynamic light scattering result prove and successfully obtain assembly.
Embodiment 4:
1) hydrophobic polymer is synthetic: with embodiment 1.Nuclear-magnetism and GPC result prove that product has expected structure.
2) hydrophilic polymer is synthetic: in the 50mL round-bottomed flask, add methylacrylic acid polyoxyethylene ester (molecular weight 360) 5.36 grams; Mercaptoethylamine hydrochloride 0.0852 gram; Diisopropyl azodicarboxylate 0.0246 gram and 25mL absolute ethyl alcohol; Vacuumize three circulations and remove oxygen through freezing, then 75 ℃ of reactions 24 hours down.Gained solution adds KOH 0.042 gram and Na through being concentrated to 5mL
2SO
41.5 gram stirred after 5 hours, and solution is removed by filter salinity, and the amido hydrochloride is converted into the amido form.Use ether precipitating twice again, to remove unconjugated mercaptoethylamine hydrochloride.With 50 ℃ of following dried overnight of solid collection, obtain the terminal polymethyl acrylic acid polyoxyethylene ester of amido that is then.Nuclear-magnetism and GPC result prove that product has expected structure.
3) preparation of polymers soln: PS is dissolved in is prepared into the solution that weight concentration is 10mg/mL in the THF, use the aperture to filter as the teflon membrane filter of 220nm then, gained solution is preserved down in 4 ℃.Polymethyl acrylic acid polyoxyethylene ester is dissolved in the solution that is made into 5mg/mL in the anhydrous methanol, uses the teflon membrane filter filtration of aperture as 220nm then, gained solution is preserved down in 4 ℃.
4) preparation of static driven super-molecule assembling body: the 5mg/mL solution of the 10mg/mL solution of 10 μ L PS and 10 μ L polymethyl acrylic acid polyoxyethylene esters is added in the mixed solvent of 2mL THF and absolute ethyl alcohol (volume ratio is 1/1), stirred 30 minutes.Dropwise add deionized water 10mL then, organic solvent is removed in dialysis then, obtains super-molecule assembling body.Transmission electron microscope and dynamic light scattering result prove and successfully obtain assembly.
5) preparation of golden nanometer particle: with embodiment 1.TEM results proves and successfully gets golden nanometer particle.
6) preparation of nanoparticle polymer composite particle: the 5mg/mL solution of the 10mg/mL solution of 10 μ L PS and 10 μ L polymethyl acrylic acid polyoxyethylene esters is added in the mixed solvent of 2mL THF and absolute ethyl alcohol (volume ratio is 1/1), stirred 30 minutes.The solution that adds the THF 1mg/mL of 10 μ L golden nanometer particles then, restir 30 minutes dropwise adds deionized water 10mL, removes organic solvent through dialysis again, obtains the golden nanometer particle polymer composite particle.Transmission electron microscope and dynamic light scattering result prove and successfully obtain assembly.
Embodiment 5:
1) hydrophobic polymer is synthetic: with embodiment 1.Nuclear-magnetism and GPC result prove that product has expected structure.
2) hydrophilic polymer is synthetic: in the 50mL round-bottomed flask, add methylacrylic acid glucose ester (molecular weight 292) 4.35 grams; Mercaptoethylamine hydrochloride 0.0852 gram; Diisopropyl azodicarboxylate 0.0246 gram and 25mL absolute ethyl alcohol; Vacuumize three circulations and remove oxygen through freezing, then 75 ℃ of reactions 24 hours down.Gained solution adds KOH 0.042 gram and Na through being concentrated to 5mL
2SO
41.5 gram stirred after 5 hours, and solution is removed by filter salinity, and the amido hydrochloride is converted into the amido form.Use ether precipitating twice again, to remove unconjugated mercaptoethylamine hydrochloride.With 50 ℃ of following dried overnight of solid collection, obtain the terminal polymethyl acrylic acid glucose ester of amido that is then.Nuclear-magnetism and GPC result prove that product has expected structure.
3) preparation of polymers soln: PS is dissolved in is prepared into the solution that weight concentration is 10mg/mL in the THF, use the aperture to filter as the teflon membrane filter of 220nm then, gained solution is preserved down in 4 ℃.The polymethyl acrylic acid glucose ester is dissolved in the solution that is made into 5mg/mL in the mixed solvent (volume ratio 2/3) of anhydrous methanol and water, uses the aperture to filter as the teflon membrane filter of 220nm then, gained solution is preserved down in 4 ℃.
4) preparation of static driven super-molecule assembling body: the 5mg/mL solution of the 10mg/mL solution of 10 μ L PS and 10 μ L polymethyl acrylic acid glucose esters is added in the mixed solvent of 2mL THF and absolute ethyl alcohol (volume ratio is 1/1), stirred 30 minutes.Dropwise add deionized water 10mL then, organic solvent is removed in dialysis then, obtains super-molecule assembling body.Transmission electron microscope and dynamic light scattering result prove and successfully obtain assembly.
5) preparation of golden nanometer particle: with embodiment 1.TEM results proves and successfully gets golden nanometer particle.
6) preparation of nanoparticle polymer composite particle: the 5mg/mL solution of the 10mg/mL solution of 10 μ L PS and 10 μ L polymethyl acrylic acid glucose esters is added in the mixed solvent of 2mL THF and absolute ethyl alcohol (volume ratio is 1/1), stirred 30 minutes.The solution that adds the THF 1mg/mL of 10 μ L golden nanometer particles then, restir 30 minutes dropwise adds deionized water 10mL, removes organic solvent through dialysis again, obtains the golden nanometer particle polymer composite particle.Transmission electron microscope and dynamic light scattering result prove and successfully obtain assembly.
Embodiment 6:
1) hydrophobic polymer is synthetic: with embodiment 1.Nuclear-magnetism and GPC result prove that product has expected structure.
2) hydrophilic polymer is synthetic: with embodiment 1.Nuclear-magnetism and GPC result prove that product has expected structure.
3) preparation of polymers soln: with embodiment 1.Gained solution is preserved down in 4 ℃.
4) preparation of static driven super-molecule assembling body: with embodiment 1.Transmission electron microscope and dynamic light scattering result prove and successfully obtain assembly.
5) preparation of Nano silver grain: the aqueous solution of 30mL Silver Nitrate 30mmol/L is joined in the toluene solution of 80mL four octyl group brometo de amonio 50mmol/L, and vigorous stirring is 1 hour then.Add 170 milligrams of Dodecyl Mercaptans again, and then add the aqueous solution of 25mL Peng Qinghuana 0.4mol/L under the vigorous stirring, under the lucifuge condition, stirred 3 hours then.Be concentrated to 10mL after organic phase is separated, pour the 400mL absolute ethyl alcohol then into and in-18 ℃ of held 4h the golden nanometer particle precipitating is come out, then the brown deposition is collected, with the absolute ethyl alcohol flushing for several times, vacuum-drying obtains hydrophobic golden nanometer particle.Then solid being dissolved in the solution that is made into 1mg/mL in the THF keeps in Dark Place under 4 ℃.TEM results proves and successfully gets Nano silver grain.
6) preparation of nanoparticle polymer composite particle: the 5mg/mL solution of the 10mg/mL solution of 10 μ L PS and 10 μ L polymethyl acrylic acid phosphorylcholine esters is added in the mixed solvent of 2mL THF and absolute ethyl alcohol (volume ratio is 1/1), stirred 30 minutes.The solution that adds the THF 1mg/mL of 10 μ L Nano silver grains then, restir 30 minutes dropwise adds deionized water 10mL, removes organic solvent through dialysis again, obtains the Nano silver grain polymer composite particle.Transmission electron microscope and dynamic light scattering result prove and successfully obtain assembly.
Embodiment 7:
1) hydrophobic polymer is synthetic: with embodiment 1.Nuclear-magnetism and GPC result prove that product has expected structure.
2) hydrophilic polymer is synthetic: with embodiment 1.Nuclear-magnetism and GPC result prove that product has expected structure.
3) preparation of polymers soln: with embodiment 1.Gained solution is preserved down in 4 ℃.
4) preparation of static driven super-molecule assembling body: with embodiment 1.Transmission electron microscope and dynamic light scattering result prove and successfully obtain assembly.
5) preparation of nano platinum particle: the aqueous solution of 30mL Platinic chloride 30mmol/L is joined in the toluene solution of 80mL four octyl group brometo de amonio 50mmol/L, and vigorous stirring is 1 hour then.Add 170 milligrams of Dodecyl Mercaptans again, and then add the aqueous solution of 25mL Peng Qinghuana 0.4mol/L under the vigorous stirring, under the lucifuge condition, stirred 3 hours then.Be concentrated to 10mL after organic phase is separated, pour the 400mL absolute ethyl alcohol then into and in-18 ℃ of held 4h the golden nanometer particle precipitating is come out, then the brown deposition is collected, with the absolute ethyl alcohol flushing for several times, vacuum-drying obtains hydrophobic golden nanometer particle.Then solid being dissolved in the solution that is made into 1mg/mL in the THF keeps in Dark Place under 4 ℃.TEM results proves and successfully gets nano platinum particle.
6) preparation of nanoparticle polymer composite particle: the 5mg/mL solution of the 10mg/mL solution of 10 μ L PS and 10 μ L polymethyl acrylic acid phosphorylcholine esters is added in the mixed solvent of 2mL THF and absolute ethyl alcohol (volume ratio is 1/1), stirred 30 minutes.The solution that adds the THF 1mg/mL of 10 μ L nano platinum particles then, restir 30 minutes dropwise adds deionized water 10mL, removes organic solvent through dialysis again, obtains the nano platinum particle polymer composite particle.Transmission electron microscope and dynamic light scattering result prove and successfully obtain assembly.
Embodiment 8:
1) hydrophobic polymer is synthetic: with embodiment 1.Nuclear-magnetism and GPC result prove that product has expected structure.
2) hydrophilic polymer is synthetic: with embodiment 1.Nuclear-magnetism and GPC result prove that product has expected structure.
3) preparation of polymers soln: with embodiment 1.Gained solution is preserved down in 4 ℃.
4) preparation of static driven super-molecule assembling body: with embodiment 1.Transmission electron microscope and dynamic light scattering result prove and successfully obtain assembly.
5) Preparation of Nano-particles of CdS: in Erlenmeyer flask, add CdSO
48/3H
2O (0.01mol) uses the 25mL dissolved in distilled water, and (0.02mol) slowly splashes under stirring state with Dodecyl Mercaptan, generates one deck white floss; After continuing to stir 10min, add the 25mL distilled water solution of cetyl trimethylammonium bromide (0.005mol), solution becomes white casse, and there is one deck foam on the surface; After stirring 5h, add the saturated H2S solution of different amounts, solution becomes faint yellow, stirring reaction 12h.The CdS nano colloidal particles solution that generates is extracted with toluene and acetone mixed solution; Then CdS nano colloidal particles solution rotating is evaporated to 10mL; Use 200mL ethanol precipitating 3 times again, deposition is removed in spinning, and supernatant liquid spontaneous evaporation at room temperature is dry; Use the 20mL washing with alcohol again 3 times, the gained solid is dry under vacuum.The gained cadmium sulfide nano-particles is dissolved in the solution that is made into 1mg/mL in the THF and under 4 ℃, keeps in Dark Place.TEM results proves and successfully gets cadmium sulfide nano-particles.
6) preparation of nanoparticle polymer composite particle: the 5mg/mL solution of the 10mg/mL solution of 10 μ L PS and 10 μ L polymethyl acrylic acid phosphorylcholine esters is added in the mixed solvent of 2mL THF and absolute ethyl alcohol (volume ratio is 1/1), stirred 30 minutes.The solution that adds the THF 1mg/mL of 10 μ L cadmium sulfide nano-particles then, restir 30 minutes dropwise adds deionized water 10mL, removes organic solvent through dialysis again, obtains the cadmium sulfide nano-particles polymer composite particle.Transmission electron microscope and dynamic light scattering result prove and successfully obtain assembly.
Embodiment 9: with embodiment 1; The preparation of static driven super-molecule assembling body: the 5mg/mL solution of the 10mg/mL solution of 60 μ L PS and 60 μ L polymethyl acrylic acid phosphorylcholine esters is added in the mixed solvent of 2mL THF and absolute ethyl alcohol (volume ratio is 1/1), stirred 30 minutes.Dropwise add deionized water 10mL, organic solvent is removed in dialysis then, obtains super-molecule assembling body.Transmission electron microscope and dynamic light scattering result prove and successfully obtain assembly.
The preparation of nanoparticle polymer composite particle: the 5mg/mL solution of the 10mg/mL solution of 60 μ L PS and 60 μ L polymethyl acrylic acid phosphorylcholine esters is added in the mixed solvent of 2mL THF and absolute ethyl alcohol (volume ratio is 1/1), stirred 30 minutes.The solution that adds the THF 1mg/mL of 60 μ L golden nanometer particles then, restir 30 minutes dropwise adds deionized water 10mL, removes organic solvent through dialysis again, obtains the golden nanometer particle polymer composite particle.Transmission electron microscope and dynamic light scattering result prove and successfully obtain assembly.
Embodiment 10: with embodiment 5; The preparation of static driven super-molecule assembling body: the 5mg/mL solution of the 10mg/mL solution of 30 μ L PS and 30 μ L polymethyl acrylic acid glucose esters is added in the mixed solvent of 2mL THF and absolute ethyl alcohol (volume ratio is 1/1), stirred 30 minutes.Dropwise add deionized water 10mL then, organic solvent is removed in dialysis then, obtains super-molecule assembling body.Transmission electron microscope and dynamic light scattering result prove and successfully obtain assembly.
The preparation of nanoparticle polymer composite particle: the 5mg/mL solution of the 10mg/mL solution of 30 μ L PS and 30 μ L polymethyl acrylic acid glucose esters is added in the mixed solvent of 2mL THF and absolute ethyl alcohol (volume ratio is 1/1), stirred 30 minutes.The solution that adds the THF 1mg/mL of 30 μ L golden nanometer particles then, restir 30 minutes dropwise adds deionized water 10mL, removes organic solvent through dialysis again, obtains the golden nanometer particle polymer composite particle.Transmission electron microscope and dynamic light scattering result prove and successfully obtain assembly.
Claims (2)
1. the preparation method of the bionic super-molecule assembling body of a static driven is characterized in that being made up of following steps:
1) hydrophobic polymer is synthetic: in the 50mL round-bottomed flask, add vinylbenzene 5.75ml, 3-thiohydracrylic acid 0.22mL, Diisopropyl azodicarboxylate 0.082 gram and 25mL THF; Vacuumize three circulations and remove oxygen through freezing, then 75 ℃ of reactions 24 hours down, gained solution is after concentrated; With cold anhydrous methanol precipitating three times; Remove unconjugated 3-thiohydracrylic acid,, obtain the terminal PS of carboxyl that is then with 50 ℃ of following dried overnight of solid collection;
2) hydrophilic polymer is synthetic: in the 50mL round-bottomed flask, add methylacrylic acid phosphorylcholine ester 4.42 grams; Mercaptoethylamine hydrochloride 0.0852 gram; Diisopropyl azodicarboxylate 0.0246 gram and 25mL absolute ethyl alcohol vacuumize three circulations and remove oxygen through freezing, then react 24 hours down at 75 ℃; Gained solution adds KOH 0.042 gram and Na through being concentrated to 5mL
2SO
41.5 gram stirred after 5 hours, and solution is removed by filter salinity; The amido hydrochloride is converted into the amido form; With THF precipitating twice, use the anhydrous diethyl ether precipitating more once, to remove unconjugated mercaptoethylamine hydrochloride; With 50 ℃ of following dried overnight of solid collection, obtain the terminal polymethyl acrylic acid phosphorylcholine ester of amido that is then;
3) preparation of polymers soln: PS is dissolved in is prepared into the solution that weight concentration is 10mg/mL in the THF; Use the teflon membrane filter filtration of aperture then as 220nm; The gained polystyrene solution is preserved down in 4 ℃; Polymethyl acrylic acid phosphorylcholine ester is dissolved in the solution that is made into 5mg/mL in the anhydrous methanol, uses the teflon membrane filter filtration of aperture as 220nm then, gained polymethyl acrylic acid phosphorylcholine ester solution is preserved down in 4 ℃;
4) preparation of static driven super-molecule assembling body: with 10 μ L concentration is that the polystyrene solution of 10mg/mL and polymethyl acrylic acid phosphorylcholine ester solution that 10 μ L concentration are 5mg/mL add in the mixed solvent of 2mL THF and absolute ethyl alcohol; The volume ratio of THF and absolute ethyl alcohol is 1/1; Stirred 30 minutes; Dropwise add deionized water 10mL, organic solvent is removed in dialysis then, obtains the bionic super-molecule assembling body of static driven.
2. the preparation method of the bionic super-molecule assembling body of a static driven is characterized in that being made up of following steps:
1) hydrophobic polymer is synthetic: in the 50mL round-bottomed flask, add TEB 3K 5.33mL, 3-thiohydracrylic acid 0.22mL, Diisopropyl azodicarboxylate 0.082 gram and 25mL THF; Vacuumize three circulations and remove oxygen through freezing, then 75 ℃ of reactions 24 hours down, gained solution is after concentrated; With cold anhydrous methanol precipitating three times; Remove unconjugated 3-thiohydracrylic acid,, obtain the terminal polymethylmethacrylate of carboxyl that is then with 50 ℃ of following dried overnight of solid collection;
2) hydrophilic polymer is synthetic: in the 50mL round-bottomed flask, add methylacrylic acid phosphorylcholine ester 4.42 grams; Mercaptoethylamine hydrochloride 0.0852 gram; Diisopropyl azodicarboxylate 0.0246 gram and 25mL absolute ethyl alcohol vacuumize three circulations and remove oxygen through freezing, then react 24 hours down at 75 ℃; Gained solution adds KOH 0.042 gram and Na through being concentrated to 5mL
2SO
41.5 gram stirred after 5 hours, and solution is removed by filter salinity; The amido hydrochloride is converted into the amido form; With THF precipitating twice, use the anhydrous diethyl ether precipitating more once, to remove unconjugated mercaptoethylamine hydrochloride; With 50 ℃ of following dried overnight of solid collection, obtain the terminal polymethyl acrylic acid phosphorylcholine ester of amido that is then;
3) preparation of polymers soln: polymethylmethacrylate is dissolved in is prepared into the solution that weight concentration is 10mg/mL in the THF; Use the teflon membrane filter filtration of aperture then as 220nm; The gained polymethyl methacrylate solution is preserved down in 4 ℃; Polymethyl acrylic acid phosphorylcholine ester is dissolved in the solution that is made into 5mg/mL in the anhydrous methanol, uses the teflon membrane filter filtration of aperture as 220nm then, gained polymethyl acrylic acid phosphorylcholine ester solution is preserved down in 4 ℃;
4) preparation of static driven super-molecule assembling body: with 10 μ L concentration is that the polymethyl methacrylate solution of 10mg/mL and polymethyl acrylic acid phosphorylcholine ester solution that 10 μ L concentration are 5mg/mL add in the mixed solvent of 2mL THF and absolute ethyl alcohol; The volume ratio of THF and absolute ethyl alcohol is 1/1; Stirred 30 minutes; Dropwise add deionized water 10mL then, organic solvent is removed in dialysis then, obtains the bionic super-molecule assembling body of static driven.
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