负载纳米银复合微球制备及其催化性能

以具有温度和pH双重敏感性能的N-异丙基丙烯酰胺(NIPAM)共聚丙烯酸(AA) P(NIPAM-co-AA)高分子微凝胶为模板, 以乙醇为还原剂, 原位还原得到负载纳米银的微米尺度Ag/P(NIPAM-co-AA)复合微凝胶材料. 通过扫描电子显微镜(SEM)、X射线衍射(XRD)仪和紫外-可见(UV-Vis)分光光度计等对复合材料的形貌、组成和催化性能进行表征. 研究结果表明, Ag/P(NIPAM-co-AA)复合微球具有均一的表面结构, 微凝胶的限域作用显著提高了纳米银的分散性和稳定性. 另外, Ag/P(NIPAM-co-AA)复合微球对对硝基苯酚(4-NP)的还原具有较好的催化活性, 且其催化活性与微凝胶网络结构的溶胀、收缩行为有一定关系, 即模板微凝胶的温敏特性可以实现对对硝基苯酚催化反应活性的调控作用.     

快速响应的温敏性聚(N-异丙基丙烯酰胺)水凝胶的制备及表征

以不同浓度的β-环糊精水溶液为反应介质制备了一系列快速响应的温度敏感性聚(N-异丙基丙烯酰胺)水凝胶。利用SEM观察其表面形态,并测定了不同温度下达到平衡时水凝胶的溶胀比,研究了水凝胶的去溶胀动力学。结果表明,与传统水凝胶相比,该水凝胶的溶胀性能略有提高,并且对温度的变化具有非常快的响应速率。以0·25(wt)%的β-环糊精水溶液中制备的水凝胶为例,该水凝胶仅1min内就失去约94%的水,而传统水凝胶在15min内仅失去66%左右的水。     

含自由氨基酸侧链的温敏性微凝胶的制备及性能

采用无皂乳液聚合法使N-异丙基丙烯酰胺(NIPAM)、ε-丙烯酰基-L-赖氨酸(εACRLLY)和N,N-亚甲基双丙烯酰胺(BA)交联共聚,制备了含有自由氨基酸侧链的温敏性微凝胶.利用透射电子显微技术(TEM)、动态光散射技术(DLS)及浊度法对所制备的微凝胶的形态及相转变进行了表征.TEM结果表明,所得的微凝胶具有规则的球型形态,微凝胶的粒径随εACRLLY含量的增加而减小.DLS及浊度结果表明,微凝胶粒径呈单分散的窄分布,随着温度的升高,微凝胶粒径减小,有着明显的体积相转变温度(VPTT);亲水单体εACRLLY的引入能够有效地调节共聚物微凝胶的VPTT,并且VPTT随εACRLLY含量的增加几乎呈线性上升.微凝胶在对盐酸阿霉素的药物释放研究表明,所制备的微凝胶在20℃,12 h内释放了56%,37℃下释放了73%;37℃,pH=7.4下13 h内释放73%,pH=4.5下基本释放完毕,该微凝胶表现出良好的药物缓释性能.     

双敏性微凝胶的絮凝及聚沉行为

用沉降聚合法制备了聚(N-异丙基丙烯酰胺-co-甲基丙烯酸)微凝胶, 并用NMR, DLS分析测定了微凝胶结构及凝胶颗粒在不同离子强度下粒径和表面电势的变化. 25 ℃时在pH＝7的溶液中Zeta电位为－18 mV, 随离子强度增加, 逐渐减小. 当NaCl浓度达0.2 mol/L时基本不变, 表明微凝胶表面电荷受到屏蔽, 浓度继续增加主要使凝胶颗粒收缩. 加热引起微凝胶收缩, 颗粒表面电荷密度增大, Zeta电位增大. 在0.2 mol/L NaCl溶液中, 41 ℃时微凝胶的Zeta电位可达－12.4 mV, 使微凝胶稳定. 较高离子强度时, Zeta电位随温度升高发生突变, 微凝胶表面几乎为中性, 其突变温度与临界絮凝温度(CFT)相当. CFT随离子强度增加向低温迁移, 微凝胶聚集速率在高温时比低温时快.     

含功能性羟基的温敏性聚(N-异丙基丙烯酰胺)微凝胶的制备及性能研究

采用两步合成路线合成了二缩三乙二醇单甲基丙烯酸酯 (TREGMA) ,并对其结构进行了表征 ;利用无皂乳液聚合法使N 异丙基丙烯酰胺 (NIPAM)、TREGMA和N ,N 亚甲基双丙烯酰胺 (BA)交联共聚 ,制备了含有功能性羟基的温敏性微凝胶 .微凝胶的去溶胀性能研究表明 ,TREGMA的引入使得微凝胶的体积相转变温度得到提高 ,同时所制得微凝胶具有较好的温敏性 .该类微凝胶有望成为良好的生物医用材料 .     

聚丙烯酰胺/聚异丙基丙烯酰胺互穿网络水凝胶的制备与性能

采用分步法用电子加速器辐射合成了聚丙烯酰胺(PAAm)/聚异丙基丙烯酰胺(PNIPAAm)互穿网络水凝胶,并考察了温度、pH值、离子强度对其溶胀性能的影响.研究表明:互穿水凝胶具有温度敏感性,且其体积相变与互穿网络中PAAm和PNIPAAm含量有关,随着网络中PAAm含量的增加水凝胶的体积相变趋于平缓,可以通过改变PAAm和PNIPAAm的组成比来控制水凝胶的体积相变行为.此外,互穿水凝胶还具有pH敏感性和一定的抗盐性.     

温度、pH敏感性核壳结构微凝胶的制备及性质

以无皂乳液分步聚合的方法, 将N-异丙基丙烯酰胺(NIPAM)与N,N-亚甲基双丙烯酰胺(MBA)交联反应3 h, 制得种子乳液, 再向种子乳液中加入甲基丙烯酸(MAA)功能性单体继续反应2 h, 制备了具有温度、pH敏感性的核壳结构微凝胶. 通过透射电子显微镜(TEM)、红外光谱(IR)等表征了微凝胶外貌形态及结构组成, 动态光散射(DLS)测定了微凝胶粒径响应热、pH的变化及微凝胶Zeta电位的变化. 结果表明凝胶形貌为异型核壳结构; Zeta电位与微凝胶粒径随温度、pH变化相关.     

体积相转变温度可调的温敏性N-异丙基丙烯酰胺共聚物微凝胶的制备与性能研究

选用甲基丙烯酸异丙酯(iPMA)与N-异丙基丙烯酰胺(NIPAM)共聚,制备了一系列疏水改性、相转变温度可调的温敏性P(NIPAM-co-iPMA)微凝胶.利用透射电子显微技术(TEM)、浊度法、动态光散射(DLS)技术及示差扫描量热(DSC)技术对所得微凝胶的形态及去溶胀行为进行了表征.TEM与DLS结果表明,所制备的微凝胶具有规则的球型形态.浊度、DLS及DSC结果表明,疏水性单体iPMA的引入能有效调节共聚物微凝胶的相转变温度;在所考察的范围内,微凝胶的相转变温度随iPMA投料比的增加几乎呈线性降低.     

PNI PAM/CS微凝胶的性质测定

以N-异丙基丙烯酰胺(NIPAM)、壳聚糖(CS)为单体,N,N-亚甲基双丙烯酰胺(MBA)为交联剂,制备了PNIPAM/CS微凝胶.测定了不同单体配比对微凝胶体积相转变温度(VPTT)的影响和25℃不同pH条件下微凝胶液浊度及粒径的变化.研究表明,PNIPAM/CS微凝胶具有温敏性;并且随着pH的增大,微凝胶粒径先变小后变大,显示pH敏感性;浊度法测定结果与粒径测定一致.     

相转变温度范围窄的聚(N-异丙基丙烯酰胺)温敏性微凝胶

采用间歇式、半间歇式和连续式无皂乳液聚合(SFEP)法合成温敏性聚(N-异丙基丙烯酰胺)(PNIPAM)微凝胶。连续式或半间歇式SFEP法合成的PNIPAM微凝胶相转变温度范围明显地比间歇式SFEP法合成的窄,其中又以连续式SFEP法的效果最明显。相同交联剂用量的情况下,连续式SFEP法合成的PNIPAM微凝胶的粒径和溶胀比最大,而间歇式SFEP法合成的最小。通过研究微凝胶合成过程中溶胀比随反应时间的变化关系,证明了连续式或半间歇式SFEP法合成的PNIPAM微凝胶具有比较均匀的内部交联结构。     

聚(N-异丙基丙烯酰胺)类材料的应用

聚(N-异丙基丙烯酰胺)(PNIPAAm)及其共聚物,在水溶液中表现出最低临界溶液温度(LCST),在LCST附近会发生可逆相转变。利用这种特性,可将热敏性高分子材料应用于生物医学工程、免疫分析、催化、分离提纯等领域。主要综述了热敏性PNIPAAm类高分子材料,在这些领域中的应用情况。     

聚丙烯酸(钾)/凹凸棒吸水剂的制备及性能研究

在凹凸棒存在的情况下,以丙烯酸为单体,以N,N-亚甲基双丙烯酰胺(MBA)为交联剂,过硫酸钾(KPS)为引发剂,采用水溶液聚合法合成了聚丙烯酸(钾)／凹凸棒吸水剂。用TGA和SEM对产物进行了表征。IR分析证实了凹凸棒与丙烯酸发生了接枝共聚反应。研究了引发剂的用量、交联剂的用量和粘土的用量等反应条件对复合吸水剂吸水性的影响。当凹凸棒w=0．10时,复合吸水材料在蒸馏水和生理盐水中的吸水倍数分别大于1200和100。     

Interaction of Ionic Surfactants with a Hydrophobic Modified Thermosensitive Polymer

The interactions of a hydrophobic modified thermosensitive polymer poly(N-isopropylacrylamide)-ran-poly(methacrylic acid)-ran-poly(octadecyl acrylate) with five ionic surfactants, namely, sodium dodecyl sulfate (SDS), dodecayltrimethylaminium bromide (DTAB), 1,2-bis(dodecyldimethylammonio)- hexane dibromide (12-6-12), 1-dodecanaminium, N,N′-[(1,4-dioxo-1,4-butanediyl) bis(oxy-2,1-ethanediyl)] bis[N,N-dimethyl-, bromide] (12-su-12), and dodecanaminium, N, N′-[[(2E)-1,4-dioxo-2-butene-1, 4-diyl]bis(o-xy-2,1ethanediy-l)] bis[N,N-dimethyl-, bromide] (12-fo-12) were investigated by the static-steady fluorescence methods using crystal violet and pyrene as the probes. It was found that the SDS interacted with the polymer driven by the hydrophobic interaction, while the cationic surfactants first entered the core of the polymer micelle through the hydrophobic interaction then the corona area of the polymer micelle through the hydrophobic and static electrical interactions. Measurements of the transmittances of the polymer/surfactants/PBS mixtures at different temperatures showed that the SDS suppressed the phase transition of the system, while additions of the cationic surfactants into the polymer induced the phase transitions of the polymer complex systems first, then suppressed them after the minimum values of the lower critical phase transition temperatures (LPTT) was reached. It was also found that increase of the MAA content in the polymer could broaden the LPTT range adjusted by the cationic surfactants.      

丝素蛋白纤维/聚N-异丙基丙烯酰胺复合水凝胶的性能

以丝素蛋白纤维为填充材料,采用自由基聚合的方法制备复合聚N-异丙基丙烯酰胺(PNIPPAm)水凝胶,研究复合水凝胶的黏弹性能、溶胀性能和反复溶胀-收缩性能。结果表明:丝素蛋白纤维的加入改善了复合水凝胶的力学性能,其平衡溶胀率不仅与温度有关,而且与丝素蛋白纤维的含量有关。此外,处在表面的丝素蛋白纤维与水凝胶之间存在间隙,在反复溶胀-收缩过程中可以作为输水通道,有利于水分子进出,提高了PNIPPAm水凝胶对温度的响应速率并使其溶胀-收缩重复性更好。     

Behavior of PNIPAM Microgels in Different Organic Solvents

In this research, we studied, in detail, the behavior of common PNIPAM microgels, obtained through surfactant-free precipitation polymerization, in a number of organic solvents. We showed that many of the selected solvents serve as good solvents for the PNIPAM microgels and that the size and architecture of the microgels depend on the solvent chosen. Expanding the range of solvents used for PNIPAM microgel incubation greatly enhances the possible routes for microparticle functionalization and modification, as well as the encapsulation of water-insoluble species. In this demonstration, we successfully encapsulated water-insoluble Sudan III dye in PNIPAM microgels and prepared the aqueous dispersions of such composite-colored microparticles.     

Preparation and Chiral Recognition of Thermosensitive Poly(N-isopropylacrylamide) Microgels Containing Modified L-Phenylalanine Groups

Thermosensitive poly[N-isopropylacrylamide(NIPAM)-co-N-acryloyl-L-phenylalanine ethyl ester (NALPE)] microgels were prepared by the free radical polymerization of NIPAM and chiral monomer, NALPE. Such microgels exhibited spherical shape and favorable monodispersity. Increasing the content of NALPE units would enhance the average diameter, but decrease the thermosensitivity and volume-phase transition temperatures of the microgels. Compared with PNIPAM microgels, the microgels containing NALPE units performed chiral recognozable capacities for D-phenylalanine and D-tartaric acid, and the enantioselectivity and adsorption capacity of the microgels improved with increasing the temperature and/or the content of NALPE units.     

Graft copolymers having hydrophobic backbone and hydrophilic branches. XI. Preparation and thermosensitive properties of polystyrene microspheres having poly (N-isopropylacrylamide) branches on their surfaces

Thermosensitive microspheres with 0.4–1.2 μm diameter consisting of a polystyrene core and poly(N-isopropylacrylamide) (polyNIPAAm) branches on their surfaces were prepared by the free radical polymerization of a polyNIPAAm macromonomer and styrene in ethanol. Electron spectroscopy for chemical analysis (ESCA) of the microsphere surface suggested that polyNIPAAm chains were favorably located on the surface of the microspheres. The morphology of the microspheres was observed by transmission electron micrograph (TEM) and the particle size of was estimated by submicron particle analyzer. The molecular weight of the polyNIPAAm macromonomer, the ratio of the macromonomer and styrene, and the polymerization temperature affected the particle size. Thermosensitive properties of polyNIPAAm-coated polystyrene microspheres were evaluated by the turbidity of their dispersion solutions and the hydrodynamic size of the miocrospheres. The transmittance in dispersion solutions changed clearly, similar to oligoNIPAAm and polyNIPAAm macromonomers. In addition, the particle size of microspheres decreased with rising temperature. These results were explained by the thermosensitivity of polyNIPAAm branches on the microsphere surface. © 1996 John Wiley & Sons, Inc.     

Thermosensitive Poly(N-isopropylacrylamide)-g -Polyamidoamine Dendrimer Derivatives: Preparation and the Drug Release Behaviors

Summary: A series of thermally responsive dendritic core-shell polymers were prepared based upon dendritic polyamidoamine (PAMAM), modified with carboxyl end-capped linear poly(N-isopropylacrylamide) (PNIPAAm-COOH) in different ratios via an esterification process to obtain PNIPAAm-g-PAMAM. The graft ratio of PNIPAAm could be adjusted by changing the feed ratio of PAMAM-OH to PNIPAAm-COOH and was verified by ¹H NMR and gel penetration chromatography (GPC). The lower critical solution temperature (LCST) of PNIPAAm-g-PAMAM evaluated by UV-vis spectrophotometer was about 32 °C. Indomethacin (IMC) as a model drug was loaded in the thermosensitive polymer-grafted dendrimer derivative and its release behavior was studied below and above its LCST (27 °C vs 37 °C). Results showed that the LCST of PNIPAAm-g-PAMAM was around 32 °C compared with that of the pure PNIPAAm. The release behavior of the indomethacin entrapped in the internal cavities of the PNIPAAm-g-PAMAM showed that almost 77% of the drug was cumulatively released at 27 °C after 10 hours, whereas only 20% was released at 37 °C. The release rate of IMC from the IMC/PNIPAAm-g-PAMAM complex at 37 °C is significantly slower than that at 27 °C, which indicates that the PNIPAAm chains grafted on the surface of PAMAM dendrimer could act as a channel switching on-off button through expending or contracting in response to the temperature variation and could control the drug release by varying the surrounding temperature.     

静电纺丝法制备聚乳酸/纳米磷酸钙复合纳米纤维及其表征

首先合成了纳米磷酸钙(NCP),用扫描电镜(SEM)和X射线衍射(XRD)进行了表征.再利用静电纺丝法制备了PLA/NCP复合纳米纤维,对纤维进行了TEM,SEM,XRD以及单轴拉力测试的表征.TEM和XRD测试表明,NCP已成功掺杂到聚乳酸纤维中,获得的纤维为复合纤维.SEM测试表明,NCP在溶液中浓度较小时,复合纳米纤维的形貌变化不大;NCP浓度超过PLA质量的7%后,纤维表面出现粒状物;随着浓度继续增大,粒状物逐渐增多,最后很难成纤.拉伸实验结果表明,复合纤维拉伸强度先随着NCP浓度的增加而增大,但NCP浓度超过7%后拉伸强度随着浓度的增加反而减小.