交联度对原位聚合法制备聚合物胶束性质的影响及相应的空心球制备

用原位聚合法成功地制备出不同响应温度的温敏性聚乳酸/聚(异丙基丙烯酰胺-co-丙烯酰胺)[P(D,L-LA)/P(NIPAM-co-AM)]核壳胶束. 实验中发现, 壳层的交联剂含量对粒子的尺寸有很大的影响, 当交联剂的摩尔分数从5%提高到15%时, 粒子在25 ℃时的流体力学直径从170.2 nm增加到886.5 nm. 通过对胶束粒子的核进行生物降解, 方便地得到了相应的空心球. 用FTIR监测核的降解过程, 用SEM和AFM检测核降解完全后粒子的外在形貌和内在结构变化. DLS结果表明, 空心球粒子同样具有良好的温度响应性, 其响应温度可通过改变原位聚合时单体AM的含量加以调节.     

聚（异丙基丙烯酰胺）-b-聚（4-乙烯基吡啶）胶束负载铂纳米粒子的温度响应性催化

嵌段共聚物聚(N-异丙基丙烯酰胺)-b-聚(4-乙烯基吡啶)(PNPIAM-b-P4VP)在pH6.5的水溶液中自组装成,以聚(4-乙烯基吡啶)为胶束的核,以热响应聚(N-异丙基丙烯酰胺)为胶束壳的球形胶束.通过与4VP基络合作用,将氯铂酸(H2PtCl6)导入胶束的核中,原位还原获得胶束负载2~4nm的铂纳米粒子的温度敏感型催化体系.结果显示,最低临界溶解温度(LCST)为33℃,在LCST以下,催化反应速率会随着温度的升高而提高;在LCST以上,PNPIAM嵌段变成疏水而塌缩在催化剂表面,阻碍了反应物的扩散,因此胶束负载的铂纳米粒子的催化活性会随着温度的上升而下降.     

基于星型杂臂环糊精聚合物的纳米胶束: 构筑及包合特性

通过胺化反应和原子转移自由基聚合(ATRP),合成了以β-环糊精为“核”,以1条聚乙二醇和2~4条聚N-异丙基丙烯酰胺为“臂”的双亲水性星型杂臂聚合物(MPEG-CD-PNIPAMx)。通过1H NMR,13C NMR和凝胶渗透色谱/多角度激光光散射联用(SEC/MALLS)对其结构进行了表征。对1H NMR峰面积积分计算得聚N-异丙基丙烯酰胺“臂”数为2~4。通过紫外-可见分光光度计测得该星型大分子的较低溶液临界温度(LCST)为37℃。MPEG-CD-PNIPAMx在其水溶液温度达到LCST以上时呈现两亲性,并通过疏水相互作用自组装成以聚N-异丙基丙烯酰胺为“核”,以β-环糊精及聚乙二醇为“壳”的纳米级胶束粒子。通过MPEG-CD-PNIPAMx及其胶束粒子在芘溶液中的荧光光谱,发现胶束粒子对疏水性客体小分子的包合可发生在处于壳层的β-环糊精的疏水性空腔和胶束粒子的疏水性内核。     

碳酸钙在聚合物胶束控制下的仿生合成

合成了温敏性的聚(N-异丙基丙烯酰胺)-b-聚(L-谷氨酸)(PNIPAM-b-PLGA)嵌段共聚物,在较高温度下制备了以PNIPAM为核、以PLGA为壳的自组装胶束,研究了胶束对碳酸钙晶体生长的控制作用.使用扫描电镜和X射线衍射表征了碳酸钙晶体的形貌和晶型.当聚合物胶束浓度较高时,得到纤维状的文石;当胶束浓度较低时,...     

N-异丙基丙烯酰胺/丙烯酸胆甾醇酯共聚物研究

合成和表征了N 异丙基丙烯酰胺 (NIPAM)与丙烯酸胆甾醇酯 (CHA)的共聚物 .利用表面张力和荧光探针法研究了共聚物水溶液的表面活性性能 ,确定了其临界胶束浓度 (CMC) .利用浊度法和荧光探针法测定了共聚物的最低临界溶液温度 (LCST) .研究发现 ,在聚N 异丙基丙烯酰胺 (PNIPAM)分子链中引入疏水结构单元CHA会使其LCST下降 ;且随着共聚物中CHA含量的增加 ,LCST下降幅度增加 .在PNIPAM链段中引入少量的CHA就会使其表现出明显的两亲性 ,共聚物在水中能形成有壳核结构的稳定胶束 .通过将疏水化合物胆甾醇作为模拟药物包埋在胶束的疏水核中的研究 ,证实所得的胶束能包埋疏水药物 ,且随着包埋胆甾醇含量的增加 ,胶束平均粒径增大 .     

基于葡萄糖和苯硼酸基元之间的可逆共价键构筑多重响应性高分子复合物胶束

通过可逆加成-断裂链转移(RAFT)的聚合方法,合成了分别含有苯硼酸基元和葡萄糖基元的聚(N-异丙基丙烯酰胺)-b-聚(丙烯酰胺基苯硼酸)(PNIPAM-b-PAPBA)和聚(N-异丙基丙烯酰胺)-b-聚(丙烯酰葡萄糖胺)(PNIPAM-b-PAGA)二嵌段聚合物.由于苯硼酸和葡萄糖基元之间在弱碱性条件下(pH9.3)形成硼酸酯共价键,两种二嵌段聚合物的水溶液混合后能自发形成以PAPBA/PAGA络合物为核,PNIPAM为壳层的高分子复合物胶束.由于硼酸酯共价键在pH值和葡萄糖浓度改变时能可逆形成和断裂,以及胶束PNIPAM壳层的温敏性,所制备的基于苯硼酸/葡萄糖可逆共价键的高分子复合物胶束对pH、葡萄糖和温度具有多重响应性.     

温敏性含氟两亲接枝共聚物的制备及胶束化行为

以聚乙二醇单甲醚甲基丙烯酸酯(MPEGMA)为大分子单体, 甲基丙烯酸六氟丁酯(HFMA)为含氟单体, N-异丙基丙烯酰胺(NIPAAm)为功能性单体, 采用大分子单体接枝共聚法, 制备了一种温敏性含氟两亲接枝共聚物P(NIPAAm-co-HFMA)-g-PEG. 利用FTIR, ¹H NMR, ¹⁹F NMR和GPC对共聚物的结构进行表征; 采用紫外-可见分光光度计测定了共聚物的低临界溶解温度(LCST)约为38.9 ℃, 高于人体正常的生理温度; 利用荧光探针技术测定了共聚物的临界胶束浓度(cmc), 结果表明, 当共聚物溶液温度高于LCST时, 其cmc明显变小; 利用激光光散射粒度仪(LLS)测定了共聚物胶束的水合粒径及其分布, 当温度达到LCST时, 胶束粒径明显变小, 温度过高时, 粒径又有所增大; 利用透射电子显微镜(TEM)研究了共聚物胶束的形貌, 结果表明, P(NIPAAm-co-HFMA)-g-PEG在水溶液中可自组装成球状胶束粒子, 随着温度的升高, 共聚物胶束由松散的核壳结构转变成更加紧凑的球状结构, 且粒径明显变小.     

无皂种子分散聚合法制备单分散双重响应性微凝胶

以N-异丙基丙烯酰胺及2-乙烯基吡啶为主要单体, 采用无皂种子分散聚合法制备了单分散的、具有温度及pH双重响应性能的核-壳结构微凝胶, 并以扫描电镜及动态激光光散射等手段对微凝胶粒子的结构和性能进行了研究. 溶胀行为研究表明, 微凝胶粒子具有独立的互不干扰的温度及pH敏感性能, 其体积相变温度与纯聚N-异丙基丙烯酰胺(PNIPAM)凝胶基本一致, 说明局部分布的弱电离单体不会对PNIPAM凝胶的体积相变温度造成影响.     

乙基纤维素接枝聚N-异丙基丙烯酰胺共聚物合成及其胶束化研究

通过单电子转移“活性”/可控自由基聚合的方法制备了具有双亲性及温度响应性的乙基纤维素接枝聚N-异丙基丙烯酰胺共聚物(EC-g-PNIPAm). 通过凝胶渗透色谱、核磁氢谱和红外光谱等对合成的接枝共聚物进行了表征. 我们发现此反应在混合溶剂四氢呋喃/甲醇的混合溶剂中是活性可控的. EC-g-PNIPAm接枝共聚物能够在选择性溶剂水中发生自组装现象, 形成稳定的以乙基纤维素为核、聚N-异丙基丙烯酰胺为壳的球形胶束. 并且随着温度的升高, 支链聚N-异丙基丙烯酰胺发生塌缩使得球形胶束发生收缩.     

具有疏水核/亲水壳的双亲胶体粒子的制备

制备了具有疏水性聚苯乙烯核/亲水性聚丙烯酰胺壳的双亲粒子.疏水核通过超浓乳液聚合制备,亲水壳层通过过氧化羟基异丙苯和硫酸亚铁的界面引发制备.控制条件可得到网孔(半包覆)、褶皱(全包覆)两种形态的壳层.壳层孔的存在使得核层聚合物能够与外界接触.粒子的双亲性通过吸水吸油率进行表征.     

Camptothecin-incorporating N-phthaloylchitosan-g-mPEG self-assembly micellar system: effect of degree of deacetylation

Amphiphilic grafted copolymers, N-phthaloylchitosan-grafted poly (ethylene glycol) methyl ether (PLC-g-mPEG), were synthesized from chitosan with different degree of deacetylation (DD=80%, 85%, 90% and 95%). Due to their amphiphilic characteristic, these copolymers could form micelle-like nanoparticles. The critical micelle concentration (CMC) of these nanoparticles with different DD in water was similar (28microg/ml). Under transmission electron microscope (TEM), the nanoparticles exhibited a regular spherical shape with core-shell structure. The particle sizes determined by dynamic light scattering were in the range of 100-250nm, and increased as the %DD of chitosan increased. The cytotoxicity of phthaloylchitosans (PLC) and PLC-g-mPEG in Hela cells line were evaluated. The results showed that cytotoxicity of PLC and PLC-g-mPEG increased with increasing %DD of chitosan. The cytotoxicity of PLC-g-mPEG was significantly lower than that of PLC. Camptothecin as a model drug was loaded into the inner core of the micelles by dialysis method. It was found that %DD of chitosan, corresponding to the N-phthaloyl groups in the inner core of the nanoparticle obtained, was a key factor in controlling %yield, stability of the drug-loaded micelles, and drug release behavior. As the %DD increased, the CPT-loaded micelles stability increased. Release of CPT from the micelles was dependent on the %DD and a sustained release was obtained in high %DD.     

Formation of gold@polymer core-shell particles and gold particle clusters on a template of thermoresponsive and pH-responsive coordination triblock copolymer

Template synthesis of various morphological gold colloidal nanoparticles using a thermoresponsive and pH-responsive coordination triblock copolymer of poly(ethylene glycol)-b-poly(4-vinylpyridine)-b-poly(N-isopropylacrylamide) is studied. The template morphology of the thermoresponsive and pH-responsive coordination triblock copolymer, which can be tuned by simply changing the pH or temperature of the triblock copolymer aqueous solution, ranges from single chains to core-corona micelles and further to micellar clusters. Various morphological gold colloidal nanoparticles such as discrete gold nanoparticles, gold@polymer core-shell nanoparticles, and gold nanoparticle clusters are synthesized on the corresponding template of the triblock copolymer by first coordination with gold ions and then reduction by NaBH4. All three resultant gold colloidal nanoparticles are stable in aqueous solution, and their sizes are 2, 10, and 7 nm, respectively. The gold@polymer core-shell nanoparticles are thermoresponsive. The gold nanoparticle cluster has a novel structure, and each one holds about 40 single gold nanoparticles.     

嵌段共聚物聚(异丙基丙烯酰胺)-b-聚(双丙酮丙烯酰胺)制备及其对叶酸的载负和释放

以N-异丙基丙烯酰胺(NIPAm)和双丙酮丙烯酰胺(DAAM)为原料,采用可逆加成 断裂链转移(RAFT)可控聚合反应法合成了两亲性两嵌段共聚物 聚(异丙基丙烯酰胺)-b-聚(双丙酮丙烯酰胺)(PNIPAm-b-PDAAM),用红外光谱(FT-IR)、核磁共振(1H NMR)和凝胶渗透色谱(GPC)对其结构和组成进行了表征。 这种共聚物在水溶液中能够自组装成稳定的聚合物胶束,通过荧光探针测得其低临界胶束浓度(CMC)约为7.0 mg/L。 采用扫描电子显微镜(SEM)和动态激光光散射(DLS)测得,PNIPAm-b-PDAAM在水溶液中自组装成核壳结构的球形胶束,SEM测得其直径约150 nm,且分散性良好。 以其聚合物胶束为载体、叶酸(FA)为模型药物,模拟人体生理环境进行药物体外释放。 结果表明,叶酸的负载量及负载率分别为25%和74%。 在人体温度37℃、pH值分别为4.0、6.86、9.18磷酸缓冲溶液(PBS)中,FA在20 h内的释放均比25 ℃快,释放速率随pH值增加而增大,最大累积释放率分别为31%、67%和72%。     

Self-assembled micellar nanoparticles of a novel star copolymer for thermo and pH dual-responsive drug release

An amphiphilic star block copolymer comprised of a hydrophobic PMMA block and a hydrophilic tri-arm poly(NIPAAm-co-DMAEMA) block was synthesized by copolymerization of NIPAAm and DMAEMA, with Ce(4+) ions and tris(hydroxymethyl)methylamine as a redox initiatory system. The star copolymer undergoes self-assembly to the micellar nanoparticles with a core-shell structure and the thermo/pH dual-response, originated from the thermo-sensitivity of PNIPAAm and the pH-sensitivity of PDMAEMA. A fluorescence probe study showed the pH-dependent low CMCs (7.5 to 11.2 mg/L) of the micelles, confirming the formation of stable micelles. Morphological investigations showed that the blank and drug-loaded micelles both had spherical and uniform shapes. The sizes of the blank and drug-loaded nanoparticles were between 80 and 120 nm, depending on the given pH. The LCSTs of the star copolymer were determined to be 32 degrees C, 36.6 degrees C and 39.5 degrees C, corresponding to pH 5, pH 7.4 and pH 9, respectively, demonstrating a pH-dependent thermo-response. As a drug delivery, the micellar nanoparticles showed the dual-responsive release profiles in vitro, which were confirmed by the drug release studies. The obtained results showed the thermo-triggered accelerated release at pH 7.4, and the pH-triggered accelerated release at 37 degrees C, indicating the micelles nanoparticles would be a promising site-specific drug delivery for enhancing the accumulation of drug in targeting pathological areas.     

具有温敏性的混合胶束的制备与表征及药物体外释放

通过原子转移自由基聚合(ATRP)合成了以胆固醇为端基的两亲性聚(N-异丙基丙烯酰胺)(Chol-PNIPAAm),利用FTIR、1H-NMR和GPC等方法表征了聚合物的结构.将该两亲性温敏聚合物与聚乙二醇单甲醚硬脂酸酯(mPEG-SA)通过简单混合,即可得到稳定的Chol-PNIPAAm/mPEG-SA混合胶束体系....     

Preparation of stimuli-responsive nanogels based on poly(N,N-diethylaminoethyl methacrylate) by a simple “surfactant-free” methodology

The synthesis of poly(N,N-diethylaminoethyl methacrylate)-core-polyethyleneglycol-shell (PDEAEM-core-PEG-shell) nanogels was achieved by using a “surfactant-free” emulsion polymerization with the aid of commercially available polyethyleneglycol methyl ether methacrylates (PEGMAs) as polymerizable stabilizers. By adjusting the synthetic parameters like the choice of initiator, cross-linker, PEGMA:DEAEM ratio, and molecular weight of PEGMA, a series of core-shell nanogels varying in size (50–350 nm), PDEAEM content, and pH/temperature responsive behavior were obtained in reactions taking only 60 min. The nanogels were used as nanoreactors for the preparation of gold nanoparticles. The PEGylated nanogels have a great potential to be used for diagnosis and therapy.     

Core-shell magnetite nanoparticles surface encapsulated with smart stimuli-responsive polymer: synthesis, characterization, and LCST of viable drug-targeting delivery system

We describe here the synthesis of a novel magnetic drug-targeting carrier characterized by a core-shell structure. The core-shell carrier combines the advantages of a magnetic core and the stimuli-responsive property of the thermosensitive biodegradable polymer shell (e.g., an on-off mechanism responsive to external temperature change). The composite nanoparticles are approximately 8 nm in diameter with approximately 3 nm shell. The lower critical solution temperature (LCST) is approximately 38 degrees C as determined by UV-vis absorption spectroscopy. The carrier is composed of cross-linked dextran grafted with a poly(N-isopropylacrylamide-co-N,N-dimethylacrylamide) [dextran-g-poly(NIPAAm-co-DMAAm)] shell and superparamagnetic Fe3O4 core. Fourier transform infrared spectroscopy (FTIR) confirmed the composition of the carrier. The synthesized magnetic carrier system has potential applications in magnetic drug-targeting delivery and magnetic resonance imaging.     

聚甲基丙烯酸甲酯/聚(异戊二烯-co-苯乙烯)核壳纳米乳液的合成与直接氢化方法的研究

利用可控微乳液法合成粒径19~200 nm,且呈球状分布均匀的聚甲基丙烯酸甲酯/聚(异戊二烯-co-苯乙烯)(PMMA/PIS)核壳纳米粒子,通过水合肼产生原位氢的技术,对合成的PMMA/PIS乳液体系进行直接常压氢化,对影响氢化度的因素、聚合物氢化前后结构、热性能进行了研究.结果显示,聚合物粒径、水合肼及双氧水用量等都是影响聚合物的氢化度的因素.研究发现,氢化以PMMA为核,PIS为壳的核壳结构乳液可以显著提高PIS氢化程度,减少氢化过程中凝胶产生.利用FTIR、~1H-NMR、Na_2S_2O_3滴定法测定了乳液的氢化度.结果表明,当聚合物粒径小于200 nm时,乳液氢化度可达到95%以上,且无凝胶现象产生.GPC结果证明了反应是氢化而非凝胶过程.利用TEM、DLS测试了氢化后乳液的核壳结构和粒径.实验结果显示,PMMA/HPIS为核壳纳米结构.TGA结果显示,当氢化度为98%时,聚合物耐热性提高41°C.     

Ag Nanocomposite Particles: Preparation,Characterization and Application

Summary Herein, we report that different core-shell particles could be successfully used as the carrier systems for the deposition of silver nanoparticles. Firstly, thermosensitive core-shell microgel particles have been used as the carrier system for the deposition of Ag nanoparticles, in which the core consists of poly (styrene) (PS) whereas the shell consists of poly (N-isopropylacrylamide) (PNIPA) network cross-linked by N, N′-methylenebisacrylamide (BIS). Immersed in water the shell of these particles is swollen. Heating the suspension above 32 °C leads to a volume transition within the shell, which is followed by a marked shrinking of the network of the shell. Secondly, “nano-tree” type polymer brush can be used as “nanoreactor” for the generation of silver nanoparticles also. This kind of carrier particles consists of a solid core of PS onto which bottlebrush chains synthesized by the macromonomer poly (ethylene glycol) methacrylate (PEGMA) are affixed by “grafting from” technique. Thirdly, silver nanoparticles can be in-situ immobilized onto polystyrene (PS) core-polyacrylic acid (PAA) polyelectrolyte brush particles by UV irradiation. Monodisperse Ag nanoparticles with diameter of 8.5 nm, 7.5 nm and 3 nm can be deposited into thermosensitive microgels, “nano-tree” type polymer brushes and polyelectrolyte brush particles, respectively. Moreover, obtained silver nano-composites show different catalytic activity for the catalytic reduction of p-nitrophenol depending on the carrier system used for preparation.