pH-Dependent Release from Monoolein Cubic Phase Containing Hydrophobically Modified Chitosan

Monoolein (MO) cubic phase incorporating hydrophobically modified chosan (Hm chitosan) was prepared to obtain a pH-dependent release. Following calorimetric study, Hm chitosan had little effect on the crystal structure of MO cubic phase under acidic condition where Hm chitosan is readily soluble. At a higher pH (e.g., pH 9.0), however, the crystal structure of MO cubic phase was disturbed, possibly due to the insolubilization of Hm chitosan at the alkali condition. Whether the dye included in the cubic phase is anionic (amaranth) or cationic (methylene blue), the release from the cubic phase was suppressed as the pH of release medium increased. The structural change of cubic phase caused by the insolubilization of Hm chitosan, or the blockage of the water channel of the cubic phase by precipitated Hm chitosan would be responsible for the suppressed released.     

Glucose-Responsive Monoolein Cubic Phase Containing Glucose Oxidase

Glucose-responsive monoolein (MO) cubic phase was prepared by immobilizing proteinoid composed of Asp and Leu (PAL) and hydrophobically modified glucose oxidase (HmGOD) onto the MO bilayers. The hydrodynamic mean diameter of PAL aggregate in aqueous solution decreased with increasing the pH value. The number of pamitic acid residue per one molecule of HmGOD was determined to be 6.3 by a calorimetric method. HmGOD could acidify glucose solution in a few hours, possibly because it converted glucose to gluconic acid. PAL- and HmGOD-immobilized MO cubic phase was prepared by hydrating MO melt with the mixture aqueous solution of PAL and HmGOD. The cubic phase exhibited its phase transition around 62.5°C, determined by polarizing microscopy. The release of carboxylic fluorescein (CF) from the cubic phase was suppressed when the pH value of release medium decreased, possibly because PAL can aggregate more at a lower pH value. The release was suppressed when glucose concentration increased, possibly because the release medium can be more acidified and PAL will be more aggregated at a higher glucose concentration. The cubic phase could be used as a drug carrier which releases its content in a sustained manner when the glucose concentration is abnormally high.     

Monoolein cubic phase including in situ ionically gelled alginate and its salt-responsive release property

Salt-responsive monoolein (MO) cubic phase was prepared by in situ ionically gelling alginate contained in its water channels. On the TEM micrographs, bilayers, and water channels, characteristic of MO cubic phase were observed, and alginate and CaCl₂ had little effect on the structure. According to the differential scanning calorimetric thermogram, the cubic-to-hexagonal phase transition temperature of the cubic phase containing CaCl₂ solution was 46.8°C and it was much lower than that of the cubic phase containing distilled water, 60.5°C. The transition temperature was not significantly affected by alginate. The phase transition temperatures measured by the calorimetric analysis were in accordance with those determined by polarized optical microscopy. An initial burst release of dye (i.e., amaranth) was observed when the gelled alginate was not contained in the water channel of the cubic phase. A sustained release was obtained with the cubic phase containing the gelled alginate. The release of dye loaded in the cubic phase containing the gelled alginate was significantly promoted when the cubic phase came into contact with PBS (10?mM, pH 7.4), possibly because the multivalent cation (Ca²⁺) bound to alginate chains could be replaced by the monovalent cation (Na⁺).     

Monoolein cubic phase containing azobenzene and its UV/visible light irradiation-dependent release property

Monoolein (MO) cubic phase, whose MO/azobenzene mass ratios were 1:0, 1:0.0025, 1:0.005, and 1:0.025, was prepared by a melt-hydration method. According to the polarized optical micrographs and the differential thermograms, the phase transition temperature of the cubic phase was lower as the content of azobenzene was higher, and it decreased upon the subsequent irradiation of UV light for 1 hour and visible light for 1 hour. The photoirradiation significantly promoted the release of methylene blue (a water-soluble dye) loaded in the cubic phase only when the MO/azobenzene mass ratio was 1:0.025. The photoirradiation could promote the release of Nile red (an oil-soluble dye) even when the MO/azobenzene mass ratio was less than 1:0.025. The higher photo-susceptibility of Nile red release was possibly because the dye would be intercalated in the MO lipid matrix and the photoirradiation could affect the lipid matrix property.     

聚乙二醇单甲醚(MPEG)/聚乙烯醇(PVA)高分子固-固相变材料的合成与性能

高分子固-固相转变材料是近年来新兴的课题,其主要优点是体积变化小,发生相转变时不出现液态,可以减少对容器的要求,甚至不需要容器即可把相变材料作为结构材料,可简化工艺和降低成本,我们相继合成了系列聚乙二醇／聚乙烯醇高分子固-固相变材料,由于形成交联网络结构,难溶于一般有机溶剂。     

聚甲基丙烯酸甲酯/聚甲基丙烯酸-2-羟乙酯复合微球的合成及药物吸放性能

采用在甲基丙烯酸甲酯（MMA）悬浮聚合过程中滴加甲基丙烯酸-2-羟乙酯（HEMA）乳液聚合组分的悬浮-乳液耦合聚合方法,制备了大粒径聚甲基丙烯酸甲酯／聚甲基丙烯酸-2-羟乙酯（PMMA／PHEMA）复合微球。PMMA／PHEMA复合微球表面以HEMA乳液聚合物为主,且具有微孔结构。PMMA／PHEMA复合微球在水和苄醇中的平衡溶胀率大于PMMA微球。PMMA／PHEMA复合微球48h异丁苯丙酸负载百分比为35．6％,PMMA为27．6％。在磷酸盐缓冲液中释放时间达到360h,释放量占负载总量的82％;而PMMA微球的释放时间为216h,释放量仅占负载总量的60％。     

聚苯乙烯-丙烯酸丁酯新型固相微萃取吸附质的研究与应用

合成了苯乙烯-丙烯酸丁酯共聚物,研究了此聚合物作为固相微萃取吸附质的性能。用顶空萃取法对水中低级芳烃化合物进行了萃取实验,考察了此高聚物涂层的热稳定性及单体比例与萃取率的关系。将自制涂层与商品聚二甲基硅氧烷(PDMS)涂层对低级芳烃化合物的萃取效果进行了比较。     

PEG‐Modified Macroporous Poly(Glycidyl Methacrylate) and Poly(2‐Hydroxyethyl Methacrylate) Microspheres to Reduce Non‐Specific Protein Adsorption

To minimize non‐specific protein adsorption on macroporous poly(glycidyl methacrylate) and poly(2‐hydroxyethyl methacrylate) microspheres containing amino and/or carboxyl groups, the microspheres are coated with α,ω‐bis‐carboxy poly(ethylene glycol) and amino‐terminated poly(ethylene glycol‐co‐propylene glycol) or α‐methoxy‐ω‐amino poly(ethylene glycol). Adsorption of bovine serum albumin (BSA), γ‐globulin, ¹²⁵I‐BSA, pepsin, and chymotrypsin on neat and PEGylated microspheres is determined by UV–VIS spectroscopy of supernatants and eluates or by measurement of radioactivity in an ionization chamber. Neat and PEGylated microspheres adsorb 0.8–70% and 0.02–44% of protein, respectively.

     

Novel Dual-Grafted Copolymer Bearing Glassy Polystyrene and Crystalline Poly(Ethylene Oxide) as Side Chains

A novel grafted copolymer with two different types of side chains was synthesized via a combination of grafting-onto and grafting-from strategy. Graft copolymer with one side chains polybutadiene-graft-polystyrene (PB-g-PS) was first synthesized though the grafting-onto method. Following the subsequent grafting-from method, the second kind of side chain was introduced to the copolymer with anionic ring open polymerization of ethylene oxide, obtaining dual-grafted copolymer polybutadiene-graft-(polystyrene; poly(ethylene oxide)) (PB-g-(PS;PEO)). By this combined strategy, linear and star-shaped dual-grafted copolymer were synthesized. The resulting dual-grafted copolymers had controlled molecular weights and narrow molecular weight distributions (Mw/Mn < 1.20). The thermal behavior of this dual-grafted copolymer bearing glassy and crystalline side chains was determined by differential scanning calorimetry (DSC), revealing that poly(ethylene oxide) grafts underwent confined crystallization, and the star-shaped copolymer had more confinement effects than did the linear ones.     

聚(乙烯基对苯二甲酸二烷基酯)的非寻常相转变

以聚(乙烯基对苯二甲酸二烷基酯)(PDAVT)为对象,用热分析、X射线衍射、流变及固体核磁共振等方法考察了甲壳型液晶高分子中存在的"低温无序、高温有序"的非寻常相行为.实验证明,在升温过程中,烷基基团为丁基、己基和辛基的PDAVT(P4、P6和P8)可从无定形态发育出柱状(Col)液晶相,导致在高温区体系模量升高.降温时P6和P8可完全回到无定形态,表现出典型的"各向同性相重入"行为.PDAVT液晶相畴的生长具有一维生长的特点,是成核控制的,升高温度可加快Col相的形成.固体核磁共振实验表明,样品从无定形态转变为Col相的过程与侧链运动性的不断加强有密切关系.我们也初步探索了剪切场或拉伸场对液晶转变的影响,发现当温度不高时,剪切或拉伸既不改变液晶转变温度,也没有提高液晶态样品的液晶化程度.综合分析多方面的实验结果可以看出,PDAVT的非寻常相行为是熵主导的.侧链的加速运动会增强"甲壳效应",Col相是侧链熵最大化的结果.     

Phase Transitions and Structures of Poly(ethylene-co-chlorotrifluoroethylene)

Poly( ethylene-co-chlorotrifluoroethylene) having 1∶ 1 molar ratio of ethylene andchlorotrifluoroethylene components( PECTFE) is widely used in cable coating industryand lining for dry boxes and chemical tanks[1 ,2 ] .This polymer has been commonlycharacterized as a semicrystalline polymer,and its structures and properties have beenwidely reported.It was originally described as a two-phase( crystalline-amorphous)material consisting of distinct amorphous and hexagonal crystal domains at room…     

苯丙共聚物-聚硅氧烷复合固相微萃取涂层的制备及性能研究

合成了苯乙烯-丙烯酸乙酯共聚物,以此聚合物与甲基聚硅氧烷色谱固定液混合作为固相微萃取头涂层。通过热分析手段考察了该涂层的热稳定性,涂层使用温度可达280℃。使用微量进样器和不锈钢毛细管,自制了SPME装置。使用该涂层萃取分析了水中氯苯系化合物,各标准样品质量浓度在0—20μg／L内与色谱峰面积呈良好线性关系（r=0．9674—0．9934）,检出限为0．28—0．64ng／L,相对标准偏差为5．4％-7．7％,加标回收率为91％-99％。将自制涂层与商品涂层（PDMS、PA）进行了比较,结果表明苯丙聚合物-甲基聚硅氧烷复合涂层对氯苯系化合物具有优良的吸附特性。在固相微萃取研究和应用中,提供了新的吸附物质和色谱固定液与石英纤维结合的新途径。     

Phase Behavior of Poly(n-butyl acrylate) and Poly(2-ethylhexyl acrylate) in Nematic Liquid Crystal E7

Summary: This paper reports on the phase behavior of photochemically crosslinked poly(n-butyl acrylate) (PABu) and poly(2-ethylhexyl acrylate) (PEHA) networks in a nematic liquid crystal (LC) solvent. The swelling properties of these networks were studied as a function of temperature using a low molecular weight LC (LMWLC), which is an eutectic mixture of cyanoparaphenylenes named E7. To obtain different polymer network densities, the ratio of the reactive monomers ABu (or EHA) to the crosslinking agent hexanedioldiacrylate (HDDA) was varied prior to polymerization/crosslinking reactions. Immersion of these networks in an excess of LC solvent allowed for the measurement of size increase by polarizing optical microscopy in terms of temperature. Diameter ratios were calculated considering swollen to dry network states of the samples. The uptake of LMWLC inside the network preferentially takes place around the nematic to isotropic transition temperature of the solvent. Phase diagrams in the concentration-temperature framework were given and discussed as a function of crosslinking degree of the polymer network and temperature and phase behavior of the solvent.     

Effects of Surfactants on Phase Transition of Poly(N-isopropylacrylamide) and Poly(N-isopropylacrylamide-co-dimethylaminoethylmethacrylate)

The effect of surfactants on the phase transition of poly(N-isopropylacrylamide) (PNIPAM) and poly(N-isopropylacrylamide-co-dimethylaminoethylmethacrylate) (P(NIPAM-co-DMAEMA)) was extensively investigated by a turbidometry. When the concentration of cetyltrimethyl ammoniumchloride (CTAC) increased from 0.01 to 0.32%, the cloud point of PNIPAM increased from 32 to 38.5°C. When the concentration of sodium dodecyl sulfate (SDS) increased from 0.01 to 0.08%, the cloud point increased from 32.5 to 38°C. The cloud points with SDS were higher than the values obtained with CTAC. In addition, SDS suppressed the temperature sensitivity much more effectively than CTAC did. The adsorption of the ionic surfactants (CTAC, SDS) on the polymer chains may account for the increase in the cloud point. On the other hand, Tween 20 had little effect on the cloud point and the temperature sensitivity of the homopolymer, possible because it is nonionic. The effect of surfactants on the phase transition of P(NIPAM-co-DMAEMA) exhibited a trend similar to the effect on the phase transition of PNIPAM.     

Synthesis of Poly(2‐Hydroxyethyl Methacrylate)‐based Hybrid Nanoparticles via Visible‐Light‐Initiated Radical Polymerization

We report a new, unique process for the design of poly(2‐hydroxyethyl methacrylate) (PHEMA )‐based hybrid materials, which involves the coating of PHEMA on TiO₂ and TiO₂ /Ag nanoparticle surface under visible light. New hybrid materials initiated under different conditions were prepared under visible light, which could be used for the theoretical design of nanohybrid materials. The hybrid materials thus prepared were characterized by Fourier transform infrared spectroscopy (FTIR ), transmission electron microscopy (TEM ), and thermogravimetric analysis (TGA ). The experimental results confirmed the successful synthesis of TiO₂–PHEMA hybrid materials. Compared to other methods, the method reported here involving the direct combination of PHEMA on the TiO₂ surface was simply catalyzed by visible light without the addition of initiators.     

Poly(p‐phenylene) with Poly(ethylene glycol) Chains and Amino Groups as a Functional Platform for Controlled Drug Release and Radiotherapy

Conventional cancer treatments such as chemotherapy, radiotherapy, or combination of these two result in side effects, which lower the quality of life of the patients. To overcome problems with these methods, altering the drug properties by conjugating them to carrier polymers has emerged. Such polymeric carriers also hold the potential to make tumor cells more sensitive to radiation therapy. Herein, poly(p‐phenylene) (PPP) polymer with poly(ethylene glycol) (PEG) chains and primary amino groups (PPP‐NH₂‐g‐PEG) is synthesized and conjugated with anticancer drug Doxorubicin (DOX). pH dependent drug release experiments are performed at pH 5.3 and pH 7.4, respectively. Cell viability studies on human cervix adenocarcinoma cells show that lower doses of DOX inhibit cell proliferation when conjugated with nontoxic doses of PPP‐NH₂‐g‐PEG polymer. Additionally, PPP‐NH₂‐g‐PEG/Cys/DOX bioconjugate significantly increases radiosensitive properties of DOX. It is possible to use lower doses of DOX when conjugated to PPP‐NH₂‐g‐PEG in combination with radiotherapy.

     

壳聚糖-g-聚甲基丙烯酸凝胶粒的制备及其药物释放行为

以壳聚糖和甲基丙烯酸为原料,硝酸铈铵为引发剂,合成了不同接枝率的壳聚糖-g-聚甲基丙烯酸(CS-g-PMAA),用FTIR、1H NMR和元素分析表征了产物的结构,以柠檬酸三钠和戊二醛为交联剂制备了具有核壳结构的CS-g-PMAA载药体系。 用UV/Vis检测了CS-g-PMAA粒子对模型药物的释放行为。 结果表明,CS-g-PMAA接枝率为12.21%时药物释放速率最慢,其在pH=1.8介质中药物累积释放量(11 h)为44.18%,而壳聚糖粒子的累积释放量高达65.24%,即接枝改性壳聚糖粒子对药物的缓慢控制释放性能较好; CS-g-PMAA粒子的释药行为还依赖于介质的pH值和盐浓度,在低pH值和低盐浓度下,药物释放速率较快;酶环境下由于载体材料的降解使药物释放速率加快。 分析了不同条件下CS-g-PMAA载药粒子中药物的释放机理。     

聚羟乙谷氨酰胺-5-氟尿嘧啶-1-乙酸的合成、表征与缓释性

聚羟乙谷氨酰胺-5-氟尿嘧啶-1-乙酸的合成、表征与缓释性;高分子前药     

聚乙二醇共聚对苯二甲酸丁二醇酯的合成及在生物材料中的应用

综述了聚醚酯热塑性弹性体聚忆二醇／聚对苯二甲酸丁二醇酯（PEG／PBT）的合成、组成与性能关系及其在组织工程和药物缓释体系等方面的应用研究进展。PEG／PBT是一类力学性能优良、可降解和生物相容性良好、极具应用潜力的生物材料。     

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%。