一种新型聚酰亚胺-氨酯反渗透复合膜材料的合成及表征

采用关键功能单体N,N'-二甲基间苯二胺(DMMPD)和多元酰氯5-氯甲酰氧基-异肽酰氯(CFIC)聚合制备了一种耐氧化的聚酰亚胺-氨酯(DMMPD-CFIC)反渗透复合膜材料. 研究了水相溶剂、 多元胺浓度和组成及两相接触时间等因素对DMMPD聚合成膜的影响. 结果表明, 虽然DMMPD-CFIC膜的脱盐率不够理想, 但将4-甲基间苯二胺(MMPD)与DMMPD以2∶1(质量比)组合后制得的MMPD/DMMPD-CFIC膜的脱盐率得到显著提高, 并且对膜的耐氯性能影响不大. 采用傅里叶衰减全反射红外光谱(FTIR)和X射线光电子能谱(XPS)分析了2种膜的活性层的结构, 并利用扫描电镜(SEM)和原子力显微镜(AFM)对膜的表面形态进行了表征.     

Graphenes Prepared by Hummers,Staudenmaier and Hofmann Methods for Analysis of TNT‐Based Nitroaromatic Explosives in Seawater

The detection of TNT and related nitroaromatic compounds in seawater is of great interest. Electrochemical techniques can be applied for detection purposes since nitroaromatic compounds contain easily reducible nitro groups. In this study, we investigate the performance of thermally reduced graphenes prepared by three different oxidative methods: Hummers, Staudenmaier and Hofmann methods with consequent thermal exfoliation. The Hofmann method‐based graphene was found to exhibit the highest sensitivity in detecting TNT electrochemically. Extended study on the detection of TNT in seawater using the graphene material provided significant improvements in the detection sensitivity. These findings will have profound impacts on the detection of nitroaromatic explosives in seawater.     

Poly(acrylic acid)‐Modified Fe3O4 Microspheres for Magnetic‐Targeted and pH‐Triggered Anticancer Drug Delivery

Monodisperse poly(acrylic acid)‐modified Fe₃O₄ (PAA@Fe₃O₄) hybrid microspheres with dual responses (magnetic field and pH) were successfully fabricated. The PAA polymer was encapsulated into the inner cavity of Fe₃O₄ hollow spheres by a vacuum‐casting route and photo‐initiated polymerization. TEM images show that the samples consist of monodisperse porous spheres with a diameter around 200 nm. The Fe₃O₄ spheres, after modification with the PAA polymer, still possess enough space to hold guest molecules. We selected doxorubicin (DOX) as a model drug to investigate the drug loading and release behavior of as‐prepared composites. The release of DOX molecules was strongly dependent on the pH value due to the unique property of PAA. The HeLa cell‐uptake process of DOX‐loaded PAA@Fe₃O₄ was observed by confocal laser scanning microscopy (CLSM). After being incubated with HeLa cells under magnet magnetically guided conditions, the cytotoxtic effects of DOX‐loaded PAA@Fe₃O₄ increased. These results indicate that pH‐responsive magnetic PAA@Fe₃O₄ spheres have the potential to be used as anticancer drug carriers.     

Nucleophilic substitution of ferrocenyl alcohols catalyzed by bismuth(III) in aqueous medium at room temperature

A nucleophilic substitution reaction of an α‐ferrocenyl alcohol with various amines, indoles and thiols was successfully developed by using a catalytic amount of Bi(NO₃)₃.5H₂O at room temperature without the aid of phase transfer catalyst. The reactions proceeded in aqueous media, leading to the formation of new C=C, C=N and C=S bonds bearing ferrocenyl substituent with high efficiency. Copyright © 2012 John Wiley & Sons, Ltd.     

Rare‐Earth Nanoparticles with Enhanced Upconversion Emission and Suppressed Rare‐Earth‐Ion Leakage

Upconversion emissions from rare‐earth nanoparticles have attracted much interest as potential biolabels, for which small particle size and high emission intensity are both desired. Herein we report a facile way to achieve NaYF₄:Yb,Er@CaF₂ nanoparticles (NPs) with a small size (10–13 nm) and highly enhanced (ca. 300 times) upconversion emission compared with the pristine NPs. The CaF₂ shell protects the rare‐earth ions from leaking, when the nanoparticles are exposed to buffer solution, and ensures biological safety for the potential bioprobe applications. With the upconversion emission from NaYF₄:Yb,Er@CaF₂ NPs, HeLa cells were imaged with low background interference.     

Designs,Synthesis, Characterization and Direct Electrochemistry of Zinc‐Porphyrin Bearing Pyrene Noncovalent Functionalized Graphene Oxide Sheet

We have designed and synthesis a new compound of zinc‐porphyrin bearing four pyrene groups (ZnP‐t‐P(py)₄) and prepared a new hybrid materials of ZnP‐t‐P(py)₄ with graphene oxide (GO) via non‐covalent interactions. The ZnP‐t‐P(py)₄, along with four pendant pyrene entities ZnP‐t‐P(py)₄, stacking on the (GO) surface due to π‐ π interactions, has been revealed by AFM measurements. FTIR, UV‐vis absorption confirm the non‐covalent functionalization of the GO. Raman spectral measurements revealed the electronic structure of the GO to be intact upon hybrid formation. In this donor‐acceptor nanohybrid, the fluorescence of photoexcited ZnP‐t‐P(py)₄ is effectively quenched by a possible electron‐transfer process. The fluorescence and photoelectrical response measurements also showed that this hybrid may act as an efficient photoelectric conversion material for optoelectronic applications.     

Completely Green Synthesis of Colloid Adams’ Catalyst α‐PtO2 Nanocrystals and Derivative Pt Nanocrystals with High Activity and Stability for Oxygen Reduction

We report a first solution strategy for controlled synthesis of Adams’ catalyst (i.e., α‐PtO₂) by a facile and totally green approach using H₂PtCl₆ and water as reactants. The prepared α‐PtO₂ nanocrystals (NCs) are ultrasmall in size and have very “clean” surfaces, which can be reduced to Pt NCs easily in ethanol under ambient conditions. Such Adams’ catalysts have been applied as electrocatalysts beyond the field of heterogeneous catalysis. Noticeably, the water‐only synthesized α‐PtO₂ NCs and their derivative Pt NCs all exhibit much higher oxygen reduction reaction (ORR) activities and stabilities than that of the state‐of‐art Pt/C electrocatalysts. This study provides an example on the organics‐free synthesis of α‐PtO₂ and Pt NCs as promising cathode catalysts for fuel cell applications and, particularly, this simple, straightforward method may open a new way for the synthesis of other “clean” functional nanomaterials.     

免疫质谱法检测肝癌血清多肽标志物

建立免疫亲和富集分离与质谱分析相结合的免疫质谱法用于血清多肽标志物pep5的检测。多克隆抗体与蛋白A琼脂糖颗粒偶联用于捕获pep5,基质辅助激光解析电离飞行时间质谱检测标志物。本方法的线性范围为1～48 nmol/L,检出限0.2 nmol/L;回收率为93.0%～103.1%,相对标准偏差(RSD)为6.4%～11.8%;反复冻融3次pep5,检测结果稳定;检测临床肝癌/正常血清样本灵敏度为78.0%、特异度为90%。该方法方便、快速、准确,适用于临床样本中低浓度标志物的检测研究,对于癌症的早期诊断具有重要意义。