CN106832339A - 一种基于六面体低聚倍半硅氧烷和二茂铁的有机无机杂化纳米粒子及其制备方法 - Google Patents
一种基于六面体低聚倍半硅氧烷和二茂铁的有机无机杂化纳米粒子及其制备方法 Download PDFInfo
- Publication number
- CN106832339A CN106832339A CN201710104540.8A CN201710104540A CN106832339A CN 106832339 A CN106832339 A CN 106832339A CN 201710104540 A CN201710104540 A CN 201710104540A CN 106832339 A CN106832339 A CN 106832339A
- Authority
- CN
- China
- Prior art keywords
- organic
- inorganic hybrid
- oligomeric silsesquioxane
- hexahedral
- ferrocene
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000002245 particle Substances 0.000 title claims abstract description 29
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title abstract description 11
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 claims abstract description 20
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims abstract description 19
- JKNCOURZONDCGV-UHFFFAOYSA-N 2-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical compound CN(C)CCOC(=O)C(C)=C JKNCOURZONDCGV-UHFFFAOYSA-N 0.000 claims abstract description 18
- 230000033116 oxidation-reduction process Effects 0.000 claims abstract description 6
- 238000001338 self-assembly Methods 0.000 claims abstract description 4
- 239000002105 nanoparticle Substances 0.000 claims description 78
- 239000000243 solution Substances 0.000 claims description 26
- 238000006243 chemical reaction Methods 0.000 claims description 18
- 230000001105 regulatory effect Effects 0.000 claims description 16
- 239000007864 aqueous solution Substances 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 10
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 6
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 6
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 6
- 239000000178 monomer Substances 0.000 claims description 6
- 238000006116 polymerization reaction Methods 0.000 claims description 5
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 4
- 230000001590 oxidative effect Effects 0.000 claims description 4
- 230000004044 response Effects 0.000 claims description 4
- 229960005070 ascorbic acid Drugs 0.000 claims description 3
- 235000010323 ascorbic acid Nutrition 0.000 claims description 3
- 239000011668 ascorbic acid Substances 0.000 claims description 3
- 230000033228 biological regulation Effects 0.000 claims description 3
- 229910000667 (NH4)2Ce(NO3)6 Inorganic materials 0.000 claims description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 2
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 125000003118 aryl group Chemical class 0.000 claims description 2
- 238000010560 atom transfer radical polymerization reaction Methods 0.000 claims description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 claims description 2
- 239000003960 organic solvent Substances 0.000 claims description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- 230000020477 pH reduction Effects 0.000 abstract description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 18
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 12
- 239000000463 material Substances 0.000 description 10
- 229910052757 nitrogen Inorganic materials 0.000 description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 238000000502 dialysis Methods 0.000 description 8
- 239000002904 solvent Substances 0.000 description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 238000009826 distribution Methods 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 239000003638 chemical reducing agent Substances 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 230000003647 oxidation Effects 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- 229920002246 poly[2-(dimethylamino)ethyl methacrylate] polymer Polymers 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- QOSSAOTZNIDXMA-UHFFFAOYSA-N Dicylcohexylcarbodiimide Chemical compound C1CCCCC1N=C=NC1CCCCC1 QOSSAOTZNIDXMA-UHFFFAOYSA-N 0.000 description 4
- 238000007710 freezing Methods 0.000 description 4
- 230000008014 freezing Effects 0.000 description 4
- 238000003760 magnetic stirring Methods 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- 239000007800 oxidant agent Substances 0.000 description 4
- 239000003208 petroleum Substances 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 239000003814 drug Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 239000002861 polymer material Substances 0.000 description 3
- 230000004043 responsiveness Effects 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- YOCIJWAHRAJQFT-UHFFFAOYSA-N 2-bromo-2-methylpropanoyl bromide Chemical compound CC(C)(Br)C(Br)=O YOCIJWAHRAJQFT-UHFFFAOYSA-N 0.000 description 2
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 150000001879 copper Chemical class 0.000 description 2
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 239000003480 eluent Substances 0.000 description 2
- 238000010828 elution Methods 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 229920001002 functional polymer Polymers 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 239000000693 micelle Substances 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 230000001376 precipitating effect Effects 0.000 description 2
- 238000010791 quenching Methods 0.000 description 2
- 230000000171 quenching effect Effects 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000013270 controlled release Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- GPRSOIDYHMXAGW-UHFFFAOYSA-N cyclopenta-1,3-diene cyclopentanecarboxylic acid iron Chemical compound [CH-]1[CH-][CH-][C-]([CH-]1)C(=O)O.[CH-]1C=CC=C1.[Fe] GPRSOIDYHMXAGW-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000001415 gene therapy Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 229920000592 inorganic polymer Polymers 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- VMGSQCIDWAUGLQ-UHFFFAOYSA-N n',n'-bis[2-(dimethylamino)ethyl]-n,n-dimethylethane-1,2-diamine Chemical compound CN(C)CCN(CCN(C)C)CCN(C)C VMGSQCIDWAUGLQ-UHFFFAOYSA-N 0.000 description 1
- OKDQKPLMQBXTNH-UHFFFAOYSA-N n,n-dimethyl-2h-pyridin-1-amine Chemical compound CN(C)N1CC=CC=C1 OKDQKPLMQBXTNH-UHFFFAOYSA-N 0.000 description 1
- PSHKMPUSSFXUIA-UHFFFAOYSA-N n,n-dimethylpyridin-2-amine Chemical compound CN(C)C1=CC=CC=N1 PSHKMPUSSFXUIA-UHFFFAOYSA-N 0.000 description 1
- 239000002539 nanocarrier Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- UKODFQOELJFMII-UHFFFAOYSA-N pentamethyldiethylenetriamine Chemical compound CN(C)CCN(C)CCN(C)C UKODFQOELJFMII-UHFFFAOYSA-N 0.000 description 1
- 230000001766 physiological effect Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000035440 response to pH Effects 0.000 description 1
- 230000006903 response to temperature Effects 0.000 description 1
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 1
- 229940043267 rhodamine b Drugs 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 150000003623 transition metal compounds Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
- C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
- C08J3/07—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media from polymer solutions
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/34—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F230/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
- C08F230/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F293/00—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule
- C08F293/005—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule using free radical "living" or "controlled" polymerisation, e.g. using a complexing agent
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/38—Polysiloxanes modified by chemical after-treatment
- C08G77/382—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon
- C08G77/385—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon containing halogens
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2438/00—Living radical polymerisation
- C08F2438/01—Atom Transfer Radical Polymerization [ATRP] or reverse ATRP
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2353/00—Characterised by the use of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Dispersion Chemistry (AREA)
- Silicon Polymers (AREA)
Abstract
本发明公开了一种基于六面体低聚倍半硅氧烷和二茂铁的有机无机杂化纳米粒子及其制备方法,有机无机杂化纳米粒子由六面体低聚倍半硅氧烷封端的聚(甲基丙烯酸二甲氨基乙酯)‑b‑聚(二茂铁基甲基丙烯酸羟乙酯)在水溶液中自组装得到;该制备方法简单,条件温和,制备的有机无机杂化纳米粒子同时具有温度、pH和氧化还原性响应的特点,易于通过调节环境中的温度、pH和氧化还原性等调控粒径大小,其在功能高分子领域具有潜在的应用价值。
Description
技术领域
本发明涉及一种有机无机杂化纳米粒子,特别涉及一种基于六面体低聚倍半硅氧烷和二茂铁的有机无机杂化纳米粒子及其制备方法,属于高分子材料领域。
背景技术
多面体低聚倍半硅氧烷(Polyhedral Oligomeric Silsesquioxanes,POSS)是最小的笼型的纳米二氧化硅,它具有非常稳定的结构,包含有一个无机的硅氧核,八个顶角连接着可以变换的基团,因此POSS是一种具有良好反应性的有机-无机杂化分子。由于POSS无毒,有良好的生物相容性,化学惰性,机械稳定性并且具有纳米级尺寸,所以POSS可用于生物医学材料。POSS在各种杂化材料中,能够均匀分布,从而可以提高杂化材料的热学性能和机械性能。
二茂铁是一种具有芳香族性质的有机过渡金属化合物,由于二茂铁具有夹心型结构和芳香性的高度富电子特性,热稳定性好,电化学活性和生理活性高,广泛应用于高灵敏生物传感器的构建。极化的二茂铁衍生物具有独特的电化学及光学特性,其在工业、农业、医药、航天、节能、环保等行业具有广泛地应用。
Hu等人合成了POSS-P(SPMA-co-DMAEMA)无规杂化材料,POSS将无机组分的热学特性引入光敏性杂化材料中,可以改善杂化纳米粒子应用于可控释放领域时形态稳定性差、光敏性杂化材料耐热稳定性差等问题。然而,该无规杂化材料是由两种单体毫无规律地共聚形成的,各组分的聚合度不易调控,同时,螺吡喃类单体制备步骤繁琐,价格昂贵。Zhang等人合成了对pH敏感的POSS-PAA杂化材料,该杂化材料并没有形成一种简单的以POSS为核以PAA为壳的纳米粒子,而是POSS组分分散在胶束中形成了一种更稳定的聚集体。但是,该纳米粒子只是具有较单一的pH响应性。Liu等人制备了一种具有氧化还原响应的PEG-PMAEFc嵌段杂化材料,该杂化材料作为纳米载体应用于药物(罗丹明B)的负载,具有负载量高、负载量可控、缓释效果好的特点。然而,同样的,该纳米粒子只是具有较单一的氧化还原响应性。目前,还未见基于POSS和二茂铁的有机无机杂化纳米粒子相关报道。
发明内容
针对现有技术存在的缺陷,本发明的一个目的是在于提供一种同时具有温度、pH及氧化还原性响应,易于通过温度、pH和氧化剂及还原剂调控粒径大小的基于六面体低聚倍半硅氧烷(POSS)和二茂铁的有机无机杂化纳米粒子,其在功能高分子材料领域具有潜在应用价值。
本发明的另一个目的在于提供一种操作简单、条件温和,低成本的制备所述基于六面体低聚倍半硅氧烷和二茂铁的有机无机杂化纳米粒子的方法。
为了实现上述技术目的,本发明提供了一种基于六面体低聚倍半硅氧烷和二茂铁的有机无机杂化纳米粒子,其由六面体低聚倍半硅氧烷封端的聚(甲基丙烯酸二甲氨基乙酯)-b-聚(二茂铁基甲基丙烯酸羟乙酯)通过自组装得到:
所述六面体低聚倍半硅氧烷封端的聚(甲基丙烯酸二甲氨基乙酯)-b-聚(二茂铁基甲基丙烯酸羟乙酯)具有式1结构:
其中,
R为烷基;
m为聚甲基丙烯酸二甲氨基乙酯嵌段的聚合度,大小为10~200;
n为聚二茂铁基甲基丙烯酸羟乙酯嵌段的聚合度,大小为5~50。
本发明的六面体低聚倍半硅氧烷(POSS)封端的聚(甲基丙烯酸二甲氨基乙酯)-b-聚(二茂铁基甲基丙烯酸羟乙酯)包含聚甲基丙烯酸二甲氨基乙酯(PDMAEMA)嵌段和聚二茂铁基甲基丙烯酸羟乙酯嵌段(PMAEFc),PDMAEMA嵌段对温度和pH具有响应性,而PMAEFc嵌段具有氧化还原响应性。通过六面体低聚倍半硅氧烷封端的聚(甲基丙烯酸二甲氨基乙酯)-b-聚(二茂铁基甲基丙烯酸羟乙酯)在水溶液中自组装形成的有机无机杂化纳米粒子是以憎水性POSS和PMAEFc为核,以亲水性PDMAEMA为壳的胶束,可以利用环境的温度和pH及氧化还原性来调节有机无机杂化纳米粒子的粒径。
本发明的有机无机杂化纳米粒子结构如式2所示:
其中,憎水性的POSS和PMAEFc为核,亲水性的PDMAEMA为壳。
优选的方案,R为异丁基。
优选的方案,所述有机无机杂化纳米粒子具有pH、温度及氧化还原响应,通过调节有机无机杂化纳米粒子所处环境的pH和/或温度和/或氧化还原性实现其粒径大小的调控。
较优选的方案,通过调节有机无机杂化纳米粒子所处环境的pH在3~11范围内实现其粒径在100纳米~500纳米调控。pH越小,有机无机杂化纳米粒子相应的半径越大,呈现规律变化。
较优选的方案,通过调节有机无机杂化纳米粒子所处环境的温度在5~75℃范围内实现其粒径在100纳米~500纳米调控。温度越小,有机无机杂化纳米粒子相应的半径越大,呈现规律变化。
较优选的方案,通过调节有机无机杂化纳米粒子所处环境的氧化还原性实现其粒径在100纳米~500纳米调控,其中,氧化性通过H2O2、Fe2(SO4)3、(NH4)2Ce(NO3)6、FeCl3中至少一种调节,还原性通过抗坏血酸、NaHSO3、Na2S2O3、KI中至少一种调节,通过采用不同的氧化剂或还原剂,以及调节它们的浓度,可以实现有机无机杂化纳米粒子粒径大小的调控。
本发明还提供了一种所述的基于六面体低聚倍半硅氧烷和二茂铁的有机无机杂化纳米粒子的制备方法,该方法是往含六面体低聚倍半硅氧烷封端的聚(甲基丙烯酸二甲氨基乙酯)-b-聚(二茂铁基甲基丙烯酸羟乙酯)的有机溶液中滴加水溶液,即得。
优选的方案,含六面体低聚倍半硅氧烷封端的聚(甲基丙烯酸二甲氨基乙酯)-b-聚(二茂铁基甲基丙烯酸羟乙酯)的有机溶液中有机溶剂为四氢呋喃和/或吡啶。
优选的方案,所述水溶液为纯水溶液、1.0wt%~10.0wt%的双氧水或1.0wt%~10.0%wt的Fe2(SO4)3溶液。
较优选的方案,所述六面体低聚倍半硅氧烷封端的聚(甲基丙烯酸二甲氨基乙酯)-b-聚(二茂铁基甲基丙烯酸羟乙酯)是以溴代异丁酰胺化的六面体低聚倍半硅氧烷作为大分子引发剂,以甲基丙烯酸二甲氨基乙酯和二茂铁基甲基丙烯酸羟乙酯为聚合单体,通过两步原子转移自由基聚合法制备得到。
相对现有技术,本发明的技术方案带来的有益效果:
1、本发明的有机无机杂化纳米粒子兼具有机聚合物的柔性及无机聚合物的强度等特性,且同时对环境中的温度、pH及氧化还原性具有响应,易于通过温度、pH和氧化还原调控粒径大小,在功能高分子材料领域具有潜在应用价值,如利用刺激响应性大分子的自组装可以制备出具有环境刺激响应性、催化、药物控释、基因治疗作用等功能材料与器件。
2、本发明的有机无机杂化纳米粒子直接在水溶液中自组装生成,方法简单,条件温和,且易于通过环境中的温度、pH及氧化还原性实现有机无机杂化纳米粒子粒径的调控,以实现不同粒径有机无机杂化纳米粒子的合成。
附图说明
【图1】为本发明实施例4中合成的POSS-PDMAEMA108-PMAEFc30的核磁共振氢谱图。
【图2】为本发明实施例5中杂化纳米粒子的粒径分布图(DLS)。
【图3】为本发明实施例5中杂化纳米粒子的透射电镜(TEM)图。
【图4】为本发明实施例6中杂化纳米粒子在不同温度下的粒径分布图(DLS)。
【图5】为本发明实施例7中杂化纳米粒子在不同pH值下的粒径分布图(DLS)。
【图6】为本发明实施例8中杂化纳米粒子在加入氧化剂和还原剂时的粒径变化图。
具体实施方式
以下实施例旨在说明本发明内容,而不是对本发明权利要求保护范围的进一步限定。
实施例1
二茂铁基甲基丙烯酸羟乙酯(MAEFc)的合成:
将10.0g(43.47mmol)二茂铁甲酸(Fc-COOH),8.49g(65.21mmol)甲基丙烯酸羟乙酯(HEMA)和0.64g(5.22mmol)N,N-二甲氨基吡啶(DMAP)加入到含300mL超干二氯甲烷溶剂的圆底烧瓶中,磁力搅拌,将反应体系放置低温反应釜中冷却至0℃。氮气保护下,从恒压滴液漏斗慢慢滴入10.75g(52.16mmol)N,N’-二环己基碳酰亚胺(DCC)和50mL超干二氯甲烷溶剂的混合溶液,滴加完后0℃继续反应2小时,随后室温反应24h。将反应液抽滤,滤液加入硅胶粉拌样,干法过柱,洗脱剂为石油醚:乙酸乙酯=19:1,洗脱分离出第一个点,用旋转蒸发仪旋干溶剂,得到的黄色固体放置40℃真空干燥箱中干燥24h。
实施例2
溴代异丁酰胺化的六面体低聚倍半硅氧烷(POSS-Br)的合成:
向250mL的单口圆底烧瓶中加入8g(9.15mmol)POSS-NH2、3.71g(36.59mmol)三乙胺(NEt3)、150mL超干二氯甲烷溶剂并在磁力搅拌下溶解,将反应体系放置低温反应釜中冷却至0℃,从恒压滴液漏斗慢慢滴入4.21g(18.30mmol)α-溴代异丁酰溴(BIBB)和20mL超干二氯甲烷溶剂的混合溶液,滴加完后0℃再反应2小时,随后室温反应24h。将反应液抽滤除去白色沉淀,旋转蒸发仪浓缩至40mL,依次用1mol/L的稀HCl溶液、1mol/L的NaOH溶液、去离子水反复洗涤至溶液pH=7~8,无水MgSO4干燥,过滤,旋蒸除去大部分溶剂。再湿法过硅胶柱,洗脱剂为乙酸乙酯:石油醚=10:1,洗脱分离出第一个点,旋干溶剂,得到的白色固体放置于40℃真空干燥箱中干燥24h。
实施例3
POSS-PDMAEMA108-Br的合成:
将0.326g(0.318mmol)POSS-Br、5.0g(31.8mmol)DMAEMA、0.1102g(0.636mmol)PMDETA、5mLTHF加入到带支口的聚合物反应瓶中,液氮冷冻抽真空,乙醇解冻通氮气,如此反复3次,最后加入0.0472g(0.477mmol)CuCl,同样液氮冷冻抽真空,乙醇解冻通氮气,反复3次,以排除反应体系内的氧气。60℃反应3h,反应完后,淬冷,将体系暴露在空气中,并加入20mLTHF终止反应,以THE为流动相,过200~300目的中性氧化铝柱除去铜盐,旋转蒸发仪浓缩至5mL,逐滴滴加到40mL冰冻石油醚中沉淀,得到白色粘稠固体,倒掉上层液体,如此反复沉淀3~4次,以完全除掉未反应的单体,得到的固体放置于40℃真空干燥箱中干燥24h。
实施例4
POSS-PDMAEMA108-PMAEFc30的合成
将0.6g(0.033mmol)POSS-PDMAEMA108-Br、1.1292g(3.3mmol)MAEFc、0.0176g(18μL)Me6TREN、3mL甲苯加入到带支口的聚合物反应瓶中,液氮冷冻抽真空,乙醇解冻通氮气,如此反复3次,最后加入0.0033g(0.033mmol)CuCl,同样液氮冷冻抽真空,乙醇解冻通氮气,反复3次,以排除反应体系内的氧气。90℃反应48h,反应完后,淬冷,将体系暴露在空气中,并加入20mLTHF终止反应,以THE为流动相,过200~300目的中性氧化铝柱除去铜盐,旋转蒸发仪浓缩至2mL,逐滴滴加到16mL冰冻石油醚中沉淀,得到黄色粘稠固体,倒掉上层液体,如此反复沉淀3~4次,以完全除掉未反应的单体,得到的固体放置于45℃真空干燥箱中干燥24h。
实施例5
基于六面体低聚倍半硅氧烷和二茂铁的有机无机杂化纳米粒子的制备:
取45mg聚合物POSS-PDMAEMA108-PMAEFc30,使其充分溶解在1mLTHF中,在磁力搅拌下,往其中缓慢滴加5mL去离子水,滴加完毕后,继续搅拌3h,然后将溶液转移到截留分子量为3500的透析袋中,去离子透析1天,每隔3h换一次水,得到浓度为5mg/mL的杂化纳米粒子水溶液。图3为列举实例,平均粒径为221.7纳米。
所制得杂化纳米粒子透射电镜(TEM)测试方法:用注射器吸取0.1mg/mL的组装体,滴在透射电镜专用铜网薄膜上,室温干燥24h。粒径结果见图2,杂化纳米粒子的平均粒径为168.0纳米。
实施例6
在温度为5℃和75℃时基于六面体低聚倍半硅氧烷和二茂铁的有机无机杂化纳米粒子的制备
取45mg聚合物POSS-PDMAEMA200-PMAEFc31,使其充分溶解在1mLTHF中,在磁力搅拌下,往其中缓慢滴加5mL去离子水,滴加完毕后,继续搅拌3h,然后将溶液转移到截留分子量为3500的透析袋中,去离子透析1天,每隔3h换一次水,得到浓度为5mg/mL杂化纳米粒子水溶液。将杂化纳米粒子水溶液分别降温至5℃和升温至75℃,即得。图4为列举实例:温度为5℃和75℃,杂化纳米粒子的平均粒径分别是304.9纳米和157.4纳米。
实施例7
在pH值为5.01和10.97时基于六面体低聚倍半硅氧烷和二茂铁的有机无机杂化纳米粒子的制备
取45mg聚合物POSS-PDMAEMA200-PMAEFc31,使其充分溶解在1mLTHF中,在磁力搅拌下,往其中逐滴缓慢滴加5mL去离子水,滴加完毕后,继续搅拌3h,然后将溶液转移到截留分子量为3500的透析袋中,去离子透析1天,每隔3h换一次水,得到浓度为5mg/mL的杂化纳米粒子水溶液。分别通过NaOH(1mol/mL)溶液和HCl(1mol/mL)溶液调节杂化纳米粒子水溶液的pH值至10.97和5.01,即得。图5为列举实例:pH值为5.01和10.97,杂化纳米粒子的平均粒径分别为457.5纳米和198.0纳米。
实施例8
在Fe2(SO4)3和抗坏血酸存在下有机无机杂化纳米粒子的粒径变化:
取45mg聚合物POSS-PDMAEMA108-PMAEFc30,使其充分溶解在1mLTHF中,在磁力搅拌下,往其中逐滴缓慢滴加5mL去离子水,滴加完毕后,继续搅拌3h,然后将溶液转移到截留分子量为3500的透析袋中,去离子透析1天,每隔3h换一次水,得到浓度为5mg/mL的杂化纳米粒子水溶液。取2mL 5mg/mL的纳米粒子水溶液,加入2.2mg的Fe2(SO4)3,搅拌1h,即得到处于氧化态的杂化纳米粒子水溶液。然后加入50μL 20.56mg/mL的还原剂Vc水溶液,搅拌12h,此时溶液中的杂化纳米粒子水溶液重新变回还原态,如此循环三次。图6为列举实例:原始态、第一次氧化、第一次还原、第二次氧化、第二次还原、第三次氧化和第三次还原后杂化纳米粒子的平均粒径分别是289.4纳米、369.0纳米、288.5纳米、366.4纳米、286.7纳米、370.0纳米和279.7纳米。
Claims (10)
1.一种基于六面体低聚倍半硅氧烷和二茂铁的有机无机杂化纳米粒子,其特征在于:由六面体低聚倍半硅氧烷封端的聚(甲基丙烯酸二甲氨基乙酯)-b-聚(二茂铁基甲基丙烯酸羟乙酯)通过自组装得到:
所述六面体低聚倍半硅氧烷封端的聚(甲基丙烯酸二甲氨基乙酯)-b-聚(二茂铁基甲基丙烯酸羟乙酯)具有式1结构:
其中,
R为烷基;
m为10~200;
n为5~50。
2.根据权利要求1所述的基于六面体低聚倍半硅氧烷和二茂铁的有机无机杂化纳米粒子,其特征在于:R为异丁基。
3.根据权利要求1或2所述的基于六面体低聚倍半硅氧烷和二茂铁的有机无机杂化纳米粒子,其特征在于:所述有机无机杂化纳米粒子具有pH、温度及氧化还原响应,通过调节有机无机杂化纳米粒子所处环境的pH和/或温度和/或氧化还原性实现其粒径大小的调控。
4.根据权利要求3所述的基于六面体低聚倍半硅氧烷和二茂铁的有机无机杂化纳米粒子,其特征在于:通过调节有机无机杂化纳米粒子所处环境的pH在3~11范围内实现其粒径在100纳米~500纳米调控。
5.根据权利要求3所述的基于六面体低聚倍半硅氧烷和二茂铁的有机无机杂化纳米粒子,其特征在于:通过调节有机无机杂化纳米粒子所处环境的温度在5~75℃范围内实现其粒径在100纳米~500纳米调控。
6.根据权利要求3所述的基于六面体低聚倍半硅氧烷和二茂铁的有机无机杂化纳米粒子,其特征在于:通过调节有机无机杂化纳米粒子所处环境的氧化还原性实现其粒径在100纳米~500纳米调控,其中,氧化性通过H2O2、Fe2(SO4)3、(NH4)2Ce(NO3)6、FeCl3中至少一种调节,还原性通过抗坏血酸、NaHSO3、Na2S2O3、KI中至少一种调节。
7.权利要求1~6任一项所述的基于六面体低聚倍半硅氧烷和二茂铁的有机无机杂化纳米粒子的制备方法,其特征在于:往含六面体低聚倍半硅氧烷封端的聚(甲基丙烯酸二甲氨基乙酯)-b-聚(二茂铁基甲基丙烯酸羟乙酯)的有机溶液中滴加水溶液,即得。
8.根据权利要求7所述的基于六面体低聚倍半硅氧烷和二茂铁的有机无机杂化纳米粒子的制备方法,其特征在于:含六面体低聚倍半硅氧烷封端的聚(甲基丙烯酸二甲氨基乙酯)-b-聚(二茂铁基甲基丙烯酸羟乙酯)的有机溶液中有机溶剂为四氢呋喃和/或吡啶。
9.根据权利要求7所述的基于六面体低聚倍半硅氧烷和二茂铁的有机无机杂化纳米粒子的制备方法,其特征在于:所述水溶液为纯水溶液、1.0wt%~10.0wt%的双氧水或1.0wt%~10.0wt%的Fe2(SO4)3溶液。
10.根据权利要求7所述的基于六面体低聚倍半硅氧烷和二茂铁的有机无机杂化纳米粒子的制备方法,其特征在于:所述六面体低聚倍半硅氧烷封端的聚(甲基丙烯酸二甲氨基乙酯)-b-聚(二茂铁基甲基丙烯酸羟乙酯)是以溴代异丁酰胺化的六面体低聚倍半硅氧烷作为大分子引发剂,以甲基丙烯酸二甲氨基乙酯和二茂铁基甲基丙烯酸羟乙酯为聚合单体,通过两步原子转移自由基聚合法制备得到。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201710104540.8A CN106832339B (zh) | 2017-02-24 | 2017-02-24 | 一种基于六面体低聚倍半硅氧烷和二茂铁的有机无机杂化纳米粒子及其制备方法 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201710104540.8A CN106832339B (zh) | 2017-02-24 | 2017-02-24 | 一种基于六面体低聚倍半硅氧烷和二茂铁的有机无机杂化纳米粒子及其制备方法 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN106832339A true CN106832339A (zh) | 2017-06-13 |
CN106832339B CN106832339B (zh) | 2018-10-26 |
Family
ID=59133621
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201710104540.8A Expired - Fee Related CN106832339B (zh) | 2017-02-24 | 2017-02-24 | 一种基于六面体低聚倍半硅氧烷和二茂铁的有机无机杂化纳米粒子及其制备方法 |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN106832339B (zh) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN107936203A (zh) * | 2017-11-29 | 2018-04-20 | 中南大学 | 一种含多面体低聚倍半硅氧烷和二茂铁的两亲性嵌段共聚物及其制备方法和应用 |
CN108241011A (zh) * | 2018-01-31 | 2018-07-03 | 陕西师范大学 | 一种镶金的碳纳米管接枝二茂铁聚合物纳米复合电化学传感材料及其制备方法和应用 |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102443113A (zh) * | 2011-11-01 | 2012-05-09 | 同济大学 | 一种poss为核的可调温度响应性星形杂化材料的制备方法 |
CN104497226A (zh) * | 2014-12-11 | 2015-04-08 | 同济大学 | 一种poss为核具有ucst和uv响应性的星形杂化材料的制备方法 |
CN104829793A (zh) * | 2015-04-16 | 2015-08-12 | 同济大学 | 具有温度和pH敏感性的有机/无机杂化材料POSS/PDMAEMA-b-PNIPAM的制备方法 |
CN104829763A (zh) * | 2015-04-16 | 2015-08-12 | 同济大学 | 具有温度和pH敏感性的有机/无机杂化材料POSS-PDMAEMA的制备方法 |
-
2017
- 2017-02-24 CN CN201710104540.8A patent/CN106832339B/zh not_active Expired - Fee Related
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102443113A (zh) * | 2011-11-01 | 2012-05-09 | 同济大学 | 一种poss为核的可调温度响应性星形杂化材料的制备方法 |
CN104497226A (zh) * | 2014-12-11 | 2015-04-08 | 同济大学 | 一种poss为核具有ucst和uv响应性的星形杂化材料的制备方法 |
CN104829793A (zh) * | 2015-04-16 | 2015-08-12 | 同济大学 | 具有温度和pH敏感性的有机/无机杂化材料POSS/PDMAEMA-b-PNIPAM的制备方法 |
CN104829763A (zh) * | 2015-04-16 | 2015-08-12 | 同济大学 | 具有温度和pH敏感性的有机/无机杂化材料POSS-PDMAEMA的制备方法 |
Non-Patent Citations (3)
Title |
---|
FUKE WANG等: ""Some recent developments of polyhedral oligomeric silsesquioxane (POSS)-based polymeric materials"", 《JOURNAL OF MATERIALS CHEMISTRY》 * |
潘其维等: ""六面体倍半硅氧烷(POSS)杂化材料"", 《化学进展》 * |
许一婷等: ""聚合物纳米杂化材料的控制合成、自组装及功能化"", 《中国科学:化学》 * |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN107936203A (zh) * | 2017-11-29 | 2018-04-20 | 中南大学 | 一种含多面体低聚倍半硅氧烷和二茂铁的两亲性嵌段共聚物及其制备方法和应用 |
CN108241011A (zh) * | 2018-01-31 | 2018-07-03 | 陕西师范大学 | 一种镶金的碳纳米管接枝二茂铁聚合物纳米复合电化学传感材料及其制备方法和应用 |
CN108241011B (zh) * | 2018-01-31 | 2019-10-25 | 陕西师范大学 | 一种镶金的碳纳米管接枝二茂铁聚合物纳米复合电化学传感材料及其制备方法和应用 |
Also Published As
Publication number | Publication date |
---|---|
CN106832339B (zh) | 2018-10-26 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
Pourjavadi et al. | pH and thermal dual-responsive poly (NIPAM-co-GMA)-coated magnetic nanoparticles via surface-initiated RAFT polymerization for controlled drug delivery | |
Soppimath et al. | pH‐triggered thermally responsive polymer core–shell nanoparticles for drug delivery | |
Shan et al. | Recent advances in polymer protected gold nanoparticles: synthesis, properties and applications | |
Lei et al. | A facile two-step modifying process for preparation of poly (SStNa)-grafted Fe3O4/SiO2 particles | |
Zhu et al. | Magnetic SBA-15/poly (N-isopropylacrylamide) composite: Preparation, characterization and temperature-responsive drug release property | |
Ghorbani et al. | Preparation of thermo and pH-responsive polymer@ Au/Fe 3 O 4 core/shell nanoparticles as a carrier for delivery of anticancer agent | |
Deng et al. | Preparation and characterization of hollow Fe3O4/SiO2@ PEG–PLA nanoparticles for drug delivery | |
Liu | Facile preparation of monodispersed core/shell zinc oxide@ polystyrene (ZnO@ PS) nanoparticles via soapless seeded microemulsion polymerization | |
Li et al. | Reduction-responsive drug delivery based on mesoporous silica nanoparticle core with crosslinked poly (acrylic acid) shell | |
Haldorai et al. | Supercritical fluid mediated synthesis of poly (2-hydroxyethyl methacrylate)/Fe3O4 hybrid nanocomposite | |
Chen et al. | In situ self-assembly of gold nanorods with thermal-responsive microgel for multi-synergistic remote drug delivery | |
Wang et al. | Targeted delivery and pH-responsive release of stereoisomeric anti-cancer drugs using β-cyclodextrin assemblied Fe3O4 nanoparticles | |
WO2009038544A1 (en) | Amphiphilic polymer and processes of forming the same | |
CN107828032B (zh) | 一种超支化星状聚离子液体及其制备方法和应用 | |
CN106832339B (zh) | 一种基于六面体低聚倍半硅氧烷和二茂铁的有机无机杂化纳米粒子及其制备方法 | |
Dong et al. | Fabrication of redox and pH dual-responsive magnetic graphene oxide microcapsules via sonochemical method | |
Wang et al. | Dual stimuli-responsive Fe 3 O 4 graft poly (acrylic acid)-block-poly (2-methacryloyloxyethyl ferrocenecarboxylate) copolymer micromicelles: surface RAFT synthesis, self-assembly and drug release applications | |
Hao et al. | Controllable fabrication and characterization of biocompatible core-shell particles and hollow capsules as drug carrier | |
US9842679B2 (en) | POSS-containing in-situ composite nanogel with magnetic responsiveness and method for preparing the same | |
Bhosale et al. | Flower‐Like Superstructures: Structural Features, Applications and Future Perspectives | |
Kohestanian et al. | Facile and tunable method for polymeric surface modification of magnetic nanoparticles via RAFT polymerization: preparation, characterization, and drug release properties | |
Wu et al. | Poly (N-isopropylacrylamide) modified Fe3O4@ Au nanoparticles with magnetic and temperature responsive properties | |
Zhang et al. | Large-scale synthesis and characterization of magnetic poly (acrylic acid) nanogels via miniemulsion polymerization | |
Mi et al. | Modified reduced graphene oxide as stabilizer for Pickering w/o emulsions | |
Safiullah et al. | Poly (glycidyl methacrylate)—A soft template for the facile preparation of poly (glycidyl methacrylate) core-copper nanoparticle shell nanocomposite |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant | ||
CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20181026 Termination date: 20200224 |
|
CF01 | Termination of patent right due to non-payment of annual fee |