Synthesis of sharply thermo and PH responsive PMA-b-PNIPAM-b-PEG-b-PNIPAM-b-PMA by RAFT radical polymerization and its schizophrenic micellization in aqueous solutions

Sharply thermo- and pH-responsive pentablock terpolymer with a core-shell-corona structure was prepared by RAFT polymerization of N-isopropylacrylamide and methacrylic acid monomers using PEG-based benzoate-type of RAFT agent. The PEG-based RAFT agent could be easily synthesized by dihydroxyl-capped PEG with 4-cyano-4-(thiobenzoyl) sulfanylpentanoic acids, using esterification reaction. This pentablock terpolymer was characterized by ¹H NMR, FT-IR, and GPC. The PDI was obtained by GPC, indicating that the molecular weight distribution was narrow and the polymerization was well controlled. The thermo- and pH-responsive micellization of the pentablock terpolymer in aqueous solution was investigated using ?uorescence spectroscopy technique, UV–vis transmittance, and TEM. The LCST of pentablock terpolymer increased (over 50 °C) compared to the NIPAM homopolymer (~32 °C), due to the incorporation of the hydrophilic PEG and PMA blocks in pentablock terpolymer (PNIPAM block as the core, PEG the block and the hydrophilic PMA block as the shell and the corona). Also, pH-dependent phase transition behavior shows at a pH value of about ~5.8, according to pKa of MAA. Thus, in acidic solution at room temperature, the pentablock terpolymer self-assembled to form core–shell–corona micelles, with the hydrophobic PMA block as the core, the PNIPAM block and the hydrophilic PEG block as the shell and the corona, respectively.     

Hierarchically Ordered Supramolecular Protein-Polymer Composites with Thermoresponsive Properties

Synthetic macromolecules that can bind and co-assemble with proteins are important for the future development of biohybrid materials. Active systems are further required to create materials that can respond and change their behavior in response to external stimuli. Here we report that stimuli-responsive linear-branched diblock copolymers consisting of a cationic multivalent dendron with a linear thermoresponsive polymer tail at the focal point, can bind and complex Pyrococcus furiosus ferritin protein cages into crystalline arrays. The multivalent dendron structure utilizes cationic spermine units to bind electrostatically on the surface of the negatively charged ferritin cage and the in situ polymerized poly(di(ethylene glycol) methyl ether methacrylate) linear block enables control with temperature. Cloud point of the final product was determined with dynamic light scattering (DLS), and it was shown to be approximately 31 °C at a concentration of 150 mg/L. Complexation of the polymer binder and apoferritin was studied with DLS, small-angle X-ray scattering, and transmission electron microscopy, which showed the presence of crystalline arrays of ferritin cages with a face-centered cubic (fcc Fm3¯m) Bravais lattice where lattice parameter a = 18.6 nm. The complexation process was not temperature dependent but the final complexes had thermoresponsive characteristics with negative thermal expansion.     

复合型乳液拓扑结构调控及其应用研究进展

复合型乳液由于内相拥有多种不相溶的组分且可作为模板制备各向异性材料而备受关注,其特殊的结构和性能已成为科学研究热点,如何实现复合型乳液相行为及拓扑结构进行简单可控和批量化制备是该研究方向中的重点和难点。该文着重阐述了近期国内外对复合型乳液拓扑结构的调控方法,主要有微流体法、相分离法、一步高速剪切法及刺激响应调控等方法,并说明了不同调控方法的优势及弊端,目前关于该方面的综述侧重于阐述单个方法的研究进展并没有对不同方法的对比。利用简单、无污染、智能且能大批量制备的方法来调控复合型乳液是今后发展趋势。介绍了复合型乳液拓扑结构的调控在光学透镜、传感器、材料及生物医药等方面的应用     

Morphological Change of Cell Membrane by Interaction with Domain‐Swapped Cytochrome c Oligomers

Monomeric cyt c has been reported to bind to the mitochondrial membrane by electrostatic and hydrophobic interactions with anionic phospholipids. We have previously shown that domain‐swapped oligomeric cyt c retains the secondary structure of the monomer, and its surface possesses a larger area and more charges compared to the monomer. However, the effect of oligomerization of cyt c on cells has yet to be revealed. Herein, we investigated the interaction of oligomeric cyt c with anionic phospholipid‐containing vesicles and the outer membrane of HeLa cells. Oligomeric cyt c interacted more strongly than monomeric cyt c with anionic phospholipid‐containing vesicles and the outer membrane of HeLa cells. Oligomeric cyt c induced lateral phase separation of lipids in LUVs and GUVs, thereby leading to membrane disruption, whereas monomeric cyt c did not. Morphological changes in HeLa cells resulted from interaction with oligomeric cyt c, but little from interaction with the monomer. These results show that domain‐swapped oligomeric proteins might exhibit properties different to those of monomer in cell systems.     

弱相互作用调控表面活性剂自组装(Ⅲ)——响应性表面活性剂

天然的或合成的两亲分子(表面活性剂)可以自组装形成多尺度的聚集体结构,比如胶束、囊泡、液晶和纤维等。在表面活性剂中引入功能性基团,借助外界环境(比如光、温度、pH、CO2、磁等)的改变可以实现对表面活性剂的聚集方式的调控。本文主要介绍响应性表面活性剂的种类、结构以及环境刺激与响应性能之间的关系。     

Double stimuli-responsive behavior of linear and star-shaped poly(N,N-diethylaminoethyl methacrylate) in aqueous solution

We report on the synthesis and characterization of linear and star-shaped poly(N,N-diethylaminoethyl methacrylate) (PDEA). The synthesis was accomplished by Atom Transfer Radical Polymerization (ATRP) via a core-first approach using sugar-based multifunctional initiators. The investigation of the solution properties in water shows that PDEA is both pH- and temperature-responsive, analogous to the behavior of poly(N,N-dimethylaminoethyl methacrylate) (PDMA). In literature, PDEA is frequently referred to as being only pH-sensitive. The critical pH values for the aggregation are close to the apparent pK_a values in all cases, i.e. a high charge density is necessary to keep the polymers soluble. The cloud points show a strong dependence on the pH value of the solution but no dependence on either molecular weight or architecture. Thus, the two polymers differ only quantitatively, as PDEA has cloud points about 40 K lower than PDMA and critical pH values which are 1.5-2 units lower than PDMA.     

磷苯妥英的合成

以抗囊痫药物苯妥英为原料,通过合成3-羟甲基-苯妥英、3-氯甲基-苯妥英、3-羟甲基-苯妥英磷酸二苄酯、3-羟甲基-苯妥英磷酸酯等4种中间产物,最终得到目标产物磷苯妥英,总收率35.9%.     

智能聚合物在生物化学领域的应用进展

简要介绍了智能水凝胶的制备,概述了近年来智能聚合物在酶固定、蛋白质分离与重折叠、基因载体、细胞培养等生物化学领域中的应用进展.