含环糊精的聚乙烯亚胺-g-聚(N-异丙基丙烯酰胺)的合成与表征

以支化聚乙烯亚胺(BPEI)为骨架,将β-环糊精(β-CD)和聚(N-异丙基丙烯酰胺)(PNIPAm)引入到BPEI上,合成出了接枝共聚物(BPEI-CD)-g-PNIPAm。用FTIR、SEC/MALLS和1H NMR进行了表征。结果表明,聚合物具有温度敏感性和超分子包合性能。     

Immobilization of invertase onto crosslinked poly(p‐chloromethylstyrene) beads

Invertase was immobilized onto poly(p‐chloromethylstyrene) (PCMS) beads that were produced by a suspension polymerization with an average size of 186 μm. The beads had a nonporous but reasonably rough surface. Because of this, a reasonably large external surface area (i.e., 14.1 m²/g) could be achieved with the proposed carrier. A two‐step functionalization protocol was followed for the covalent attachment of invertase onto the bead surface. For this purpose, a polymeric ligand that carried amine groups, polyethylenimine (PEI), was covalently attached onto the bead surface by a direct chemical reaction. Next, the free amine groups of PEI were activated by glutaraldehyde. Invertase was covalently attached onto the bead surface via the direct chemical reaction between aldehyde and amine groups. The appropriate enzyme binding conditions and the batch‐reactor performance of the immobilized enzyme system were investigated. Under optimum immobilization conditions, 19 mg of invertase was immobilized onto each gram of beads with 80% retained activity after immobilization. The effects of pH and temperature on the immobilized invertase activity were determined and compared with the free enzyme. The kinetic parameters K_M and V_M were determined with the Michealis–Menten model. K_M of immobilized invertase was 1.75 folds higher than that of the free invertase. The immobilization caused a significant improvement in the thermal stability of invertase, especially in the range of 55–65°C. No significant internal diffusion limitation was detected in the immobilized enzyme system, probably due to the surface morphology of the selected carrier. This result was confirmed by the determination of the activation energies of both free and immobilized invertases. The activity half‐life of the immobilized invertase was approximately 5 times longer than that of the free enzyme. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 1268–1279, 2002     

Proton-resistant quantum dots: Stability in gastrointestinal fluids and implications for oral delivery of nanoparticle agents

Semiconductor quantum dots (QDs) have shown great promise as fluorescent probes for molecular, cellular and in vivo imaging. However, the fluorescence of traditional polymer-encapsulated QDs is often quenched by proton-induced etching in acidic environments. This is a major problem for applications of QDs in the gastrointestinal tract because the gastric (stomach) environment is strongly acidic (pH 1–2). Here we report the use of proton-resistant surface coatings to stabilize QD fluorescence under acidic conditions. Using both hyperbranched polyethylenimine (PEI) and its polyethylene glycol derivative (PEG-grafted PEI), we show that the fluorescence of core shell CdSe /CdS/ ZnS QDs is effectively protected from quenching in simulated gastric fluids. In comparison, amphiphilic lipid or polymer coatings provide no protection under similarly acidic conditions. The proton-resistant QDs are found to cause moderate membrane damage to cultured epithelial cells, but PEGylation (PEG grafting) can be used to reduce cellular toxicity and to improve nanoparticle stability.      

COS-g-PEI修饰纳米银粒子的制备及其抗菌性研究

首先以离子液体1-丁基-3-甲基咪唑氯盐（[BMIM]Cl）为反应介质和催化剂,羰基二咪唑为偶联剂,均相合成了壳寡糖接枝聚乙烯亚胺共聚物 (COS-g-PEI);其次,以COS-g-PEI为稳定剂,硝酸银为前驱体,硼氢化钠为还原剂,采用原位还原法制备了COS-g-PEI修饰纳米银复合粒子（Ag NPs@-COS-g-PEI）。采用IR、1H-NMR对聚合物结构进行表征,结果证实成功合成了COS-g-PEI 接枝共聚物;UV-Vis、TEM结果表明,成功制备了稳定的Ag NPs@-COS-g-PEI 复合粒子。通过滤纸片法和抑菌圈法测试了COS-g-PEI 及Ag NPs@-COS-g-PEI对金黄色葡萄球菌和大肠杆菌的抗菌性能,Ag NPs@-COS-g-PEI的抑菌圈直径均比COS-g-PEI大,结果表明,Ag NPs与COS-g-PEI有机结合大大提高了抗菌性能。     

Efficiency enhancement of InP‐based inverted QD‐LEDs by incorporation of a polyethylenimine modified Al:ZnO layer

We report efficiency enhancement of indium phosphide (InP) quantum dot‐based light‐emitting diodes (QD‐LEDs) by using an polyethylenimine (PEI) surface modifier. By adapting a solution processed PEI layer on top of a aluminum doped zinc oxide (Al:ZnO) nanoparticle (NP) film, the leakage current of the inverted device was substantially suppressed. In addition, the electron injection into the conduction band edge (CBE) of InP/ZnSe/ZnS QDs was also facilitated by the low work function (WF) of the Al:ZnO film which was realized by the strong interfacial dipoles of the thin film of PEI. As a result, the charge balance in the inverted devices was controlled by the change of surface roughness, the WF and the thickness of neighboring layers via spin‐coating the PEI dissolved in alcohol mixture on the Al:ZnO layer such that the current efficiency was dramatically increased from 0.07 cd/A to 3.17 cd/A. The performance of our device is not comparable to Cd‐based devices; however, it shows the great potential for using an interfacial dipole layer to develop highly efficient InP‐based inverted QD‐LEDs.     

一种新型体修饰酶生物燃料电池研究

介绍了多壁碳纳米管体修饰石墨电极和天青A膜电聚合的制备方法,研究了电聚合膜时的影响因素。实验结果表明,当硝酸钠加入量为3.400 g(0.4 mol/L),引发电位范围为-1.0~2.0 V,电聚合pH=6.5,聚合圈数为10时制得的导电聚合物膜导电性能最佳。Graphit-MWNTs/PAA/GOD/PEI阳极在含0.1 mmol/L葡萄糖(pH=7.4)的PBS中,-0.375 V(vs.SCE)处电流密度为0.021 mA/cm2,实验表明该电极可使用寿命较长,应用前景广。     

季铵化聚乙烯亚胺/SiO_2微粒的制备及其抗菌性能

通过4-溴丁酰氯的媒介,将水溶性聚乙烯亚胺(PEI)接枝在纳米SiO2表面,分别用1-溴己烷和碘甲烷对接枝的PEI进行N-烷基化修饰,使PEI中的部分氨基转变成季铵盐,得到水不溶性季铵化聚乙烯亚胺(QPEI)/SiO2微粒,其中PEI接枝量质量分数为14.8%,季铵化的氨基质量分数22.8%。红外光谱分析证实PEI接枝在纳米SiO2表面,随后成功地被卤代烷N-烷基化修饰。透射电镜观察发现QPEI/SiO2的形态不规则,大多数颗粒团聚成200—300 nm的微粒。抗菌检测结果表明,QPEI/SiO2微粒对金黄色葡萄球菌(S.aureu)和大肠杆菌(E.coli)的最小抑菌质量浓度(MIC)分别为80μg/mL和1 200μg/mL。QPEI/SiO2微粒破坏了细胞的完整性,最终将整个细胞分解成碎片。