CN1559656A - Preparation method of nucleous-shell type nanometer composite particle of magnetic micro particle and quantum point - Google Patents
Preparation method of nucleous-shell type nanometer composite particle of magnetic micro particle and quantum point Download PDFInfo
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- CN1559656A CN1559656A CNA2004100164239A CN200410016423A CN1559656A CN 1559656 A CN1559656 A CN 1559656A CN A2004100164239 A CNA2004100164239 A CN A2004100164239A CN 200410016423 A CN200410016423 A CN 200410016423A CN 1559656 A CN1559656 A CN 1559656A
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Abstract
A process for preparing a core-shell type composite nanoparticles includes such steps as using high-molecular coupling agent to couple the quantum dots on the surface of magnetic nanoparticle as core to form a shell layer, and using the functional moleculae to decorate the surface of obtained composite nanoparticle.
Description
Technical field
What the present invention relates to is a kind of preparation method of compound particle, the preparation method of the core-shell type nano composite particle of especially a kind of magnetic particle and quantum dot.Belong to material and field of biomedicine technology.
Background technology
Magnetic particle, especially nano-scale magnetic particle, owing to have superparamagnetism, biocompatibility and a degradability, its preparation and be subjected to paying close attention to widely in the application of biomedical sector.In order more easily magnetic nano-particle to be used for fields such as cell separation, separate nucleic acid and purification, drug screening, targeted therapy, people have passed through several different methods magnetic nano-particle have been carried out surface coating processing, make its surface connect multiple reactivity functional group, comprise-OH ,-COOH ,-NH
2,-CN ,-SO
3H etc., the magnetic microsphere of preparation has the polystyrene magnetic microsphere, chitosan magnetic microsphere, albumin magnetic microsphere etc.
The magnetic microsphere that biopolymer coats, because the existence of reaction active groups, these magnetic microspheres can be connected with multiple bioactive molecule.If not only have and to be connected with biomolecule easily at the surface coated material of magnetic particle, and can also give more function, as functions such as labelling spike, photocatalysis, antibacterial, anticorrosion, sterilizations, then will make the application prospect of magnetic particle more wide, have important scientific research value and actual application value.
Semiconductor-quantum-point is the material that meets this requirement.Quantum dot is meant the semiconductor nano crystallite, and is main by II-VI bunch or IH-IV bunch of elementary composition nanoparticle.Because crystal grain is little, its electronics and hole are existed the highest discontinuous occupied molecular orbit and minimum vacant orbital energy level by quantum confinement, and energy gap broadens, under the exciting of light, can emitting fluorescence, and have the optical property of the incomparable uniqueness of conventional fluorescent material.The fluorescent characteristic that quantum dot is superior makes it become the focus of nanometer biotechnology research.More international famous publications such as Nature all constantly report the applied research of quantum dot at biomedical aspect, and application relates to cytobiology, molecular biology, immunology, medical diagnosis on disease etc.In addition, after quantum dot absorbed photon, the valence band electronics transitted to conduction band because of being stimulated, and formed conduction band electron, stayed the hole simultaneously on valence band, and the hole on conduction band electron and the valence band can react with quantum dot water and oxygen on every side respectively, generates O
2 -And OH, they are respectively strong Reducing agent and strong oxidizers, have strong photocatalytic activity, can divide the various compositions that are deconstructed into bacterial micro-organism, the breeding of microorganism can be killed or suppress to synthesizing of interferencing protein effectively.Because the quantum dot nano particle is small-sized, generally has only several nanometers, is tens nanometers to the maximum.This nanoparticle has high surface activity, and when granularity only was a few nanometer, it had very strong absorbability to object on every side.Therefore, when coating enough little quantum dot nano particle, can also make magnetic particle divide the period of the day from 11 p.m. to 1 a.m to be more prone at modified biological on the magnetic particle surface.
If magnetic particle and quantum dot can be carried out compoundly, then can make compound particle have magnetic particle concurrently and be easy to separate with the labelling spike of targeting location and quantum dot, antibacterial, anticorrosion, photocatalysis and surface and be easy to multiple advantages such as modification.
International " nature " (Nature) magazine reported quantum dot PbSe and magnetic particle Fe at 2003 the 423rd volumes
2O
3Be assembled into three-dimensional superlattice structure by the collochemistry method, this three-dimensional crystal lattice composite material has potential optical property and magnetic.The present invention then is to be nuclear with the magnetic particle, coats or intersperse the quantum dot nano particle on the nuclear surface, forms the compound particle of nuclear-hull shape, and this compound particle does not possess superlattice structure, but it can be applied to fields such as biomedicine and chemical industry better.
Summary of the invention
The objective of the invention is to overcome deficiency of the prior art, the preparation method of the core-shell type nano composite particle of a kind of magnetic particle and quantum dot is provided.Make described this nano-complex particle have magnetic particle concurrently and be easy to separate and the labelling spike of targeting location and quantum dot, antibacterial, anticorrosion, photocatalysis and the surperficial multiple advantage that is easy to modify, make magnetic particle and quantum dot more wide in the range of application of biomedical sector.
The present invention is achieved by the following technical solutions, and the present invention is nuclear with the magnetic particle, by macromolecule or micromolecular coupled effect, quantum dot is connected the magnetic particle surface, forms the core-shell type nano composite particle of magnetic particle and quantum dot.When adopting macromolecule to make coupling agent, can also form the mutual alternative shell of layer high molecule and quantum dot.Can further modify the functional molecular that one or more have effects such as strengthening particle stability or specific recognition on this core-shell type nano composite particle surface, make it can be used for fields such as medical diagnosis on disease and treatment, drug screening, drug conveying and antibiotic, photocatalysis.
With the magnetic particle is nuclear, coats one or more layers quanta point material on its surface, forms the core-shell type nano composite particle of cladded type; Intersperse one or more layers quanta point material on its surface, form the core-shell type nano composite particle of interspersing; Be connected with the quantum dot nano particle by micromolecular coupled effect, form cladded type or intersperse the core-shell type nano composite particle of type with coupling characteristic.
The core-shell type nano composite particle of magnetic particle of the present invention and quantum dot is to be nuclear with the magnetic particle, can adopt 3 kinds of methods that quantum dot is connected the magnetic particle surface respectively, and these 3 kinds of methods are:
Method 1
(1) with the magnetic particle is nuclear, attraction force acts on its surface by chemical reaction or dissimilar charges connects one deck macromolecule, attraction force acts by chemical reaction or dissimilar charges is connected quantum dot on the macromolecule then, forms that quantum dot coats or the magnetic particle that quantum dot is interspersed and the core-shell type nano composite particle of quantum dot;
(2) on quantum dot coats or quantum dot is interspersed the magnetic particle and the core-shell type nano composite particle surface of quantum dot, can further connect one deck macromolecule by the attraction force acts of chemical reaction or dissimilar charges;
(3) and then the attraction force acts by chemical reaction or dissimilar charges quantum dot is connected on the macromolecule, form that twice quantum dot coats or the magnetic particle that twice quantum dot interspersed and the core-shell type nano composite particle of quantum dot;
(4), can form the magnetic particle that three times, four times, five times, six times quantum dot coatings or quantum dot intersperse and the core-shell type nano composite particle of quantum dot so by alternately being connected mutually of macromolecule layer and quantum dot layer.
Method 2
With the magnetic particle is nuclear, is connected with the quantum dot nano particle by the micromolecular coupled effect with coupling characteristic, forms cladded type or intersperses the core-shell type nano composite particle of type.
Method 3
With the magnetic particle is nuclear, and the micromolecule that connects one deck macromolecule or have the coupling characteristic by the attraction force acts of chemical reaction or dissimilar charges on its surface carries out chemosynthesis reaction then and generates the quantum dot nanoparticle around it.Synthetic method is: add cation such as Zn earlier
2+, Cd
2+, Hg
2+, Pb
2+, Mg
2+, Ca
2+, Sr
2+, In
3+, Cu
2+In a kind ofly carry out Electrostatic Absorption or complexation with the macromolecule or the micromolecule that are connected magnetic particle, then add anion S
2-, Se
2-, Te
2-, P
3-, As
3-In a kind of, perhaps alternately add cation and anion, reaction generates the quantum dot nanoparticle and also is connected on the magnetic particle.
The preparation method of the core-shell type nano composite particle of described magnetic particle and quantum dot, be meant the core-shell type nano composite particle for preparing magnetic particle and quantum dot earlier, one or more have the functional molecular of effects such as strengthening particle stability or specific recognition in its finishing then.When the nano-complex particle finishing has the molecule that strengthens particle stability, also can in the process of this nano-complex particle of preparation, carry out.
The main material that the present invention uses is magnetic particle, quantum dot, macromolecule and micromolecule.
Described functional molecular is a macromolecule, micromolecule part, and combination; Described magnetic particle is meant: ferroso-ferric oxide (Fe
3O
4) and iron sesquioxide (Fe
2O
3) in a kind of, granularity is between 1nm-1000nm.Described quantum dot is meant CdS, ZnS, HgS, GdSe, ZnSe, HgSe, GdTe, ZnTe, ZnO, PbSe, HgTe, CaAs, InP, InAs, InCaAs, CdS/ZnS, CdS/Ag2S, CdS/PbS, CdS/Cd (OH) 2, CdS/HgS, CdS/HgS/CdS, ZnS/CdS, ZnS/CdS/ZnS, ZnS/HgS/ZnS/CdS, CdSe/CdS, CdSe/ZnS, CdSe/ZnSe, CdSe/CuSe, CdSe/HgTe, CdSe/HgSe, CdSe/HgSe/CdSe, CdTe/HgS, InAs/InP, InAs/CdSe, InAs/ZnSe, MgS, MgSe, MgTe, CaS, CaSe, CaTe, SrS, SrSe, SeTe, BaS, BaSe, BaTe, CdS:Mn, ZnS:Mn, CdS:Cu, ZnS:Cu, CdS:Tb, a kind of or several combinations arbitrarily among the ZnS:Tb with nanoparticle of different fluorescent characteristicss.
Described macromolecule is meant the macromolecule of chemosynthesis, a kind of or several combination arbitrarily in synthetic macromolecule of biotechnology and the natural polymer, as: polyglycolic acid, polylactic acid, lactic acid-ethanol copolymer, Merlon, polycaprolactone, poe, paracyanogen base alkyl acrylate, Polyurethane, poly butyric ester, polyvinylpyrrolidone, Polyethylene Glycol, polyvinyl alcohol, polystyrene, polyethylene, polypropylene, polrvinyl chloride, politef, polyacrylonitrile, polyacrylic acid, polyacrylamide, diallyl dimethyl ammoniumchloride, polyformaldehyde, metacetaldehyde, polymethyl methacrylate, polyethyl methacrylate, polyamide, polyamino acid, polydextrose acid, methylcellulose, ethyl cellulose, hydroxypropyl cellulose, natural rubber, chitosan, glucosan, albumin, collagen, starch, sodium alginate, gelatin, arabic gum, agar, part, antibody, cytokine, polypeptide, nucleic acid.
Described micromolecule is meant: have one or more polar groups, as :-NH2 ,-COOH ,-SO
3H ,-micromolecule of SH, as: ethylenediamine, ethylenediaminetetraacetic acid, thioacetamide, mercaptan acid, dodecyl sodium sulfate; And the silane coupling agent, as CH
2=CHSi (OC
2H
5)
3, CH
2=CHSi (OCH
3)
2, CH
2=CHSi (OC
2H
4OCH
3)
3, CH
2=C (CH
3) COOC
3H
6Si (OCH
3)
3, HSC
3H
6Si (OCH
3)
3, H
2NC
3H
6Si (OC
2H
5)
3, H
2NC
2H
4NHC
3H
6Si (OCH
3)
3, H
2NCONHC
3H
6Si (OC
2H
5)
3, CH
3Si (OC
2H
5)
3, (CH
3)
3SiNHSi (CH
3)
3
The present invention has substantive distinguishing features and marked improvement, and the prepared magnetic particle and the core-shell type nano composite particle of quantum dot can connect the functional molecular that one or more have effects such as strengthening particle stability or specific recognition separately on its surface.Make it can be used for fields such as medical diagnosis on disease and treatment, drug screening, drug conveying and antibiotic, photocatalysis.
The specific embodiment
Embodiment 1
Adopting chemical coprecipitation method to prepare particle mean size earlier is the Fe of 150nm
3O
4Nanoparticle is behind ethanol and deionized water wash, with Fe
3O
4Be dispersed in the diallyl dimethyl ammoniumchloride aqueous solution of positively charged.Mechanical agitation 30min makes the diallyl dimethyl ammoniumchloride Molecular Adsorption at Fe
3O
4Nanoparticle surface forms the macromolecule shell.Separate the diallyl dimethyl ammoniumchloride molecule that flush away does not adsorb by magnetic.Under nitrogen protection, the surface is coated the Fe of diallyl dimethyl ammoniumchloride molecule
3O
4Nanoparticle is scattered in the electronegative quantum dot CdSe/ZnS solution, mechanical agitation 30min, the CdSe/ZnS nanoparticle is adsorbed on the diallyl dimethyl ammoniumchloride molecular layer, form the shell of quantum dot CdSe/ZnS, separate by magnetic, the CdSe/ZnS nanoparticle that flush away does not adsorb just obtains the Fe that quantum dot CdSe/ZnS coats
3O
4/ CdSe/ZnS nano-complex particle.
Fe with a quantum dot CdSe/ZnS coating
3O
4/ CdSe/ZnS nano-complex particle is distributed in the diallyl dimethyl ammoniumchloride aqueous solution, adsorb one deck diallyl dimethyl ammoniumchloride molecule again on the nano-complex particle surface by same method, after washing, this nano-complex particle is distributed in the CdSe/ZnS solution, the CdSe/ZnS nanoparticle is adsorbed on the diallyl dimethyl ammoniumchloride molecular layer, separating, washing just obtains the Fe that twice CdSe/ZnS coats
3O
4/ CdSe/ZnS nano-complex particle.
The result shows, under transmission electron microscope, and Fe
3O
4Nanoparticle is a nano spherical particle, and after itself and quantum dot were compound, there was an obvious shell on the surface, and rough.X-ray diffraction shows that compound quantum dot is many more, and the characteristic diffraction peak of quantum dot is just strong more.
Embodiment 2
Adopting chemical coprecipitation method to prepare particle mean size earlier is the Fe of 20nm
3O
4Nanoparticle is behind ethanol and deionized water wash, with Fe
3O
4Be dispersed in dehydrated alcohol and the silane coupling agent KH550 solution,, separate, use deionized water wash, obtain the Fe that the surface connects micromolecule KH550 by magnetic in 60 ℃ of reaction 2h
3O
4Nanoparticle.To this Fe
3O
4Add an amount of glutaraldehyde in the nanoparticle aqueous solution, and under room temperature stirring reaction 3h, and then with the isolating method of magnetic to this Fe
3O
4Nanoparticle washs.Under nitrogen protection, in quantum dot CdSe/ZnS nano-particle solution, add an amount of mercaptoethylmaine, react 3h under the room temperature, then unreacted mercaptoethylmaine dialysis is removed.The CdSe/ZnS that the surface is connected mercaptoethylmaine is connected the Fe of KH550 with the surface
3O
4Nanoparticle carries out the mixed at room temperature reaction in aqueous solution, make CdSe/ZnS be connected Fe
3O
4The surface is separated the CdSe/ZnS that will not connect by magnetic and is removed.
Under fluorescence microscope, excite visible Fe with the exciting light of 488nm nano-complex particle to preparation
3O
4There is very strong yellow quantum dot fluorescence on the surface, and independent Fe
3O
4Then there is not any fluorescence.This compound particle has very strong magnetic, because this nano-complex particle can be attracted with common Magnet.
Embodiment 3
Adopting chemical coprecipitation method to prepare particle mean size earlier is the Fe of 150nm
3O
4Nanoparticle is behind ethanol and deionized water wash, with Fe
3O
4Be dispersed in the polyacrylic acid aqueous solution, react 3h under the room temperature, separate deionized water wash then by magnetic.Surface behind separating, washing coats the Fe of polyacrylic acid molecule
3O
4Drip CdCl in the aqueous solution
2Solution, and the pH of solution is transferred to 9 with NaOH, stir 3h under the room temperature.Under nitrogen protection, in this mixed solution, slowly drip Na
2S solution is mixed with mechanical agitation, and reaction is spent the night.Separate by magnetic then, residual ion in the reactant liquor is removed, promptly obtain Fe
3O
4The nano-complex particle of/CdS.This nano-complex particle is scattered in the gelatin solution, and the result has stability preferably.
With synthetic preceding black Fe
3O
4Compare, this nano-complex particle presents faint yellow, shows at Fe
3O
4The surface has coated CdS, observes under transmission electron microscope and finds that nano-complex particle is rough, and the X-ray has further proved the CdS thing phase that has the cubic zinc blende structure in the compound particle.Can attract by faint yellow particle with common Magnet, show that the compound particle of preparation has very strong magnetic.
Embodiment 4
Be equipped with Fe by embodiment 1-2 either party legal system
3O
4/ CdSe/ZnS; this nano-complex particle is scattered in aqueous solution; under nitrogen protection; add an amount of TGA; behind the room temperature reaction 2h; magnetic separates; remove unreacted TGA, then this nano-complex particle is scattered in the phosphate buffer of pH7.4, add [1-Ethyl-3-(3-dimethyl-aminopropyl) carbodiimide] solution of 200mM; behind the mix homogeneously; add epidermal growth factor (EGF),, use the Tris cessation reaction in 25 ℃ of reaction 2h; then under 4 ℃ of conditions, dialyse in the phosphate buffer with pH7.4, just obtain at Fe
3O
4The nano-complex particle of/CdSe/ZnS surface-binding matter EGF.The quantum dot fluorescence spectrum of connection EGF is blue shift slightly.
Claims (8)
1, the preparation method of the core-shell type nano composite particle of a kind of magnetic particle and quantum dot, it is characterized in that, with the magnetic particle is nuclear, by macromolecule or micromolecular coupled effect, quantum dot is connected the magnetic particle surface, form the core-shell type nano composite particle of magnetic particle and quantum dot, when adopting macromolecule to make coupling agent, form layer high molecule and the mutual alternative shell of quantum dot, further modify the functional molecular that one or more have effects such as strengthening particle stability or specific recognition on this core-shell type nano composite particle surface.
2, the preparation method of the core-shell type nano composite particle of magnetic particle according to claim 1 and quantum dot, it is characterized in that, described is nuclear with the magnetic particle, coats one or more layers quanta point material on its surface, forms the core-shell type nano composite particle of cladded type; Intersperse one or more layers quanta point material on its surface, form the core-shell type nano composite particle of interspersing; Be connected with the quantum dot nano particle by micromolecular coupled effect, form cladded type or intersperse the core-shell type nano composite particle of type with coupling characteristic.
3, the preparation method of the core-shell type nano composite particle of magnetic particle according to claim 1 and quantum dot is characterized in that, described quantum dot is connected the magnetic particle surface can be respectively with following a kind of method:
Method one:
(1) with the magnetic particle is nuclear, attraction force acts on its surface by chemical reaction or dissimilar charges connects one deck macromolecule, attraction force acts by chemical reaction or dissimilar charges is connected quantum dot on the macromolecule then, forms that quantum dot coats or the magnetic particle that quantum dot is interspersed and the core-shell type nano composite particle of quantum dot;
(2) on quantum dot coats or quantum dot is interspersed the magnetic particle and the core-shell type nano composite particle surface of quantum dot, can further connect one deck macromolecule by the attraction force acts of chemical reaction or dissimilar charges;
(3) and then the attraction force acts by chemical reaction or dissimilar charges quantum dot is connected on the macromolecule, form that twice quantum dot coats or the magnetic particle that twice quantum dot interspersed and the core-shell type nano composite particle of quantum dot;
(4), can form the magnetic particle that three times, four times, five times, six times quantum dot coatings or quantum dot intersperse and the core-shell type nano composite particle of quantum dot so by alternately being connected mutually of macromolecule layer and quantum dot layer;
Method two:
With the magnetic particle is nuclear, is connected with the quantum dot nano particle by the micromolecular coupled effect with coupling characteristic, forms cladded type or intersperses the core-shell type nano composite particle of type;
Method three:
With the magnetic particle is nuclear, the micromolecule that connects one deck macromolecule or have the coupling characteristic by the attraction force acts of chemical reaction or dissimilar charges on its surface, carry out chemosynthesis reaction then and generate the quantum dot nanoparticle around it, synthetic method is: add cation such as Zn earlier
2+, Cd
2+, Hg
2+, Pb
2+, Mg
2+, Ca
2+, Sr
2+, In
3+, Cu
2+In a kind ofly carry out Electrostatic Absorption or complexation with the macromolecule or the micromolecule that are connected magnetic particle, then add anion S
2-, Se
2-, Te
2-, P
3-, As
3-In a kind of, make anion and cationoid reaction, perhaps alternately add cation and anion, reaction generates the quantum dot nanoparticle and also is connected on the magnetic particle.
4, according to the preparation method of the core-shell type nano composite particle of claim 1 or 2 described magnetic particles and quantum dot; It is characterized in that; The core-shell type nano composite particle for preparing earlier magnetic particle and quantum dot; One or more have the functional molecular of effects such as strengthening particle stability or specific recognition in its finishing then; When the nano-complex particle finishing has the molecule that strengthens particle stability; Method of modifying is included in the process for preparing this nano-complex particle and carries out; After this nano-complex particle of preparation, carry out
The core-shell type nano composite particle of described magnetic particle and quantum dot is meant: one or more have the magnetic particle of functional molecular of effects such as strengthening particle stability or specific recognition and the core-shell type nano composite particle of quantum dot in its finishing;
Described functional molecular is an organic polymer, comprises protein, antibody, part, and combination.
5, according to the preparation method of the core-shell type nano composite particle of claim 1 or 2 or 3 described magnetic particles and quantum dot, it is characterized in that, described magnetic particle is meant: a kind of in ferroso-ferric oxide and the iron sesquioxide, granularity is between 1nm-1000nm.
6, preparation method according to the core-shell type nano composite particle of claim 1 or 2 or 3 described magnetic particles and quantum dot is characterized in that described quantum dot is meant CdS, ZnS, HgS, GdSe, ZnSe, HgSe, GdTe, ZnTe, ZnO, PbSe, HgTe, CaAs, InP, InAs, InCaAs, CdS/ZnS, CdS/Ag2S, CdS/PbS, CdS/Cd (OH) 2, CdS/HgS, CdS/HgS/CdS, ZnS/CdS, ZnS/CdS/ZnS, ZnS/HgS/ZnS/CdS, CdSe/CdS, CdSe/ZnS, CdSe/ZnSe, CdSe/CuSe, CdSe/HgTe, CdSe/HgSe, CdSe/HgSe/CdSe, CdTe/HgS, InAs/InP, InAs/CdSe, InAs/ZnSe, MgS, MgSe, MgTe, CaS, CaSe, CaTe, SrS, SrSe, SeTe, BaS, BaSe, BaTe, CdS:Mn, ZnS:Mn, CdS:Cu, ZnS:Cu, CdS:Tb, a kind of or several combinations arbitrarily among the ZnS:Tb with nanoparticle of different fluorescent characteristicss.
7, preparation method according to the core-shell type nano composite particle of claim 1 or 3 described magnetic particles and quantum dot is characterized in that described macromolecule, be meant the macromolecule of chemosynthesis, a kind of or several combination arbitrarily in synthetic macromolecule of biotechnology and the natural polymer, as: polyglycolic acid, polylactic acid, lactic acid-ethanol copolymer, Merlon, polycaprolactone, poe, paracyanogen base alkyl acrylate, Polyurethane, poly butyric ester, polyvinylpyrrolidone, Polyethylene Glycol, polyvinyl alcohol, polystyrene, polyethylene, polypropylene, polrvinyl chloride, politef, polyacrylonitrile, polyacrylic acid, polyacrylamide, diallyl dimethyl ammoniumchloride, polyformaldehyde, metacetaldehyde, polymethyl methacrylate, polyethyl methacrylate, polyamide, polyamino acid, polydextrose acid, methylcellulose, ethyl cellulose, hydroxypropyl cellulose, natural rubber, chitosan, glucosan, albumin, collagen, starch, sodium alginate, gelatin, arabic gum, agar, part, antibody, cytokine, polypeptide, nucleic acid.
8, according to the preparation method of the core-shell type nano composite particle of claim 1 or 2 or 3 described magnetic particles and quantum dot, it is characterized in that, described micromolecule is meant: have one or more polar groups, as :-NH2 ,-COOH ,-SO3H ,-micromolecule of SH, as: mercaptan acid, ethylenediamine, ethylenediaminetetraacetic acid, thioacetamide, dodecyl sodium sulfate; And the silane coupling agent, as CH
2=CHSi (OC
2H
5)
3, CH
2=CHSi (OCH
3)
2, CH
2=CHSi (OC
2H
4OCH
3)
3, CH
2=C (CH
3) COOC
3H
6Si (OCH
3)
3, HSC
3H
6Si (OCH
3)
3, H
2NC
3H
6Si (OC
2H
5)
3, H
2NC
2H
4NHC
3H
6Si (OCH
3)
3, H
2NCONHC
3H
6Si (OC
2H
5)
3, CH
3Si (OC
2H
5)
3, (CH
3)
3SiNHSi (CH
3)
3
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