用共轭亚油酸构筑层状液晶的药物传递系统

在水相中用共轭亚油酸(CLA)及其钠盐(SCL)构筑层状液晶相, 并考察了其药物缓释行为. 借助偏光显微镜并辅以目测确定CLA/SCL/H₂O三元相图中的层状液晶相区, 然后用偏光显微镜、 小角X射线散射仪和旋转流变仪获得层状液晶的偏光织构、 相参数和流变参数等, 证实其适用于药物传递系统(DDS). 采用透析法研究了负载亲水性药物5-氟尿嘧啶或亲油性药物姜黄素的层状液晶的释药曲线, 结果表明, 该类层状液晶对2种药物均有良好的缓释能力.     

阳离子纤维素-十二烷基苯磺酸钠的拟聚阴离子研究

采用浊度法、 表面张力法、 zeta电位法和毛细管电泳法(CE)研究了典型的阳离子纤维素(JR400)与典型的阴离子表面活性剂十二烷基苯磺酸钠(SDBS)之间的缔合作用. 浊度法和zeta电位法实验结果表明, 在等电区附近产生的沉淀区随JR400浓度减小而变窄, 加入过量SDBS后沉淀消失, 而且发现阳离子纤维素同系物的分子量和取代度对结果的影响较小. 表面张力法实验结果显示, 该类复合体系的表面张力曲线表观上与典型“中性聚合物-阴离子表面活性剂”体系相似, 具有3个拐点(但第二拐点易被沉淀区覆盖)且SDBS与阳离子纤维素间形成缔合物. zeta电位法实验结果表明, 沉淀区前少量SDBS存在时该缔合物具有正电位, 因而维持聚阳离子特性; 沉淀区后过量SDBS存在时该缔合物具有负电位, CE分析进一步证明其为拟聚阴离子. 上述实验结果和结论对研究该类复合体系具有较大理论意义和实用价值.     

一种家蚕茧衍生具有蜂窝状结构的钴-锰共掺杂碳材料双功能电解水催化剂

通过一步碳化石墨化过程,由家蚕茧制得了一种具有蜂窝状结构的氮钴锰共掺杂碳材料。该材料具有蜂窝状结构和高比表面积,同时由于暴露的钴-锰活性位点以及富含的吡啶氮和石墨氮,3%钴-锰/蚕茧的碳材料(3%Co-Mn/SCC)显示了高析氢反应活性,其初始电位和10 m A·cm~(-2)过电位分别只有121和155 m V,Tafel斜率为130 m V·dec~(-1),并且在酸性条件下具有很好的稳定性。与此同时,2%Co-Mn/SCC在碱性条件下表现出优异的析氧反应催化性能,具有较低的初始电位,Tafel斜率为143 m V·dec~(-1)。     

Preparation of modified alginate nanoflocculant and adsorbing properties for Pb2+ in wastewater

A novel nano flocculant was prepared through the modification of sodium alginate. In the preparation partially oxidised sodium alginate reacted with triethylenetetramine (TETA) and then reacted with carbon disulfide. The structure of the flocculants was confirmed by elemental analysis, Fourier transform infrared and UV spectrophotometry. The flocculant showed nanoparticle sizes with diameters of 300–350 nm in aqueous solution, and became precipitates after flocculation with Pb²⁺ ions. The flocculant was employed to adsorb Pb²⁺ in wastewater, and the influence of flocculant concentration, flocculation temperature, pH, and time on the adsorption properties were investigated. The results showed that adsorption capacity of the flocculant for Pb²⁺ could reach up to 3.43 mmol g^–1, and the removal rate for Pb²⁺ was over 97%. The adsorption processes corresponded to pseudo second order kinetics and Langmuir isotherm model. The adsorption mechanism involved electrostatic attraction, chemical chelation, netting and sweeping actions.

     

基于离子液体和二芳基乙烯的离子凝胶的光致变色、导电、自修复及柔性传感性能

在丙烯酸聚合中原位引入4,4''-(全氟环戊烯-1,2-二基)双(5-甲基噻吩-2-甲醛)(DEA)和离子液体1-丁基-3-甲基咪唑四氟硼酸盐((BMIm) BF₄),制备了一种同时具有光致变色、导电、自黏附且具有宽温度工作区间等性能的新型离子自修复凝胶DPZI。由于(BMIm) BF₄的高热稳定性和低蒸气压,所获得的DPZI凝胶在-20~40℃较宽的温度下表现出高度稳定的机械和离子导电性能。DPZI系统中引入的Zn²⁺与—COO^-形成动态配位键,使得凝胶具有快速的自修复能力,0.06 s即可超快恢复电阻响应;离子液体的引入同时赋予了凝胶优异的抗冻性。DPZI因光致变色单元DEA的异构化可在10 s内快速发生黄-蓝颜色可逆转变,且光致变色单元的开环/闭环异构化能够实现对凝胶导电性的调节。此外,DPZI凝胶应变/压力式传感器可迅速、精准感知人体不同部位的运动并做出相应的响应;也可对呼吸、心率、声音做出精准识别,应变灵敏度为0.2%。     

聚多巴胺在强负电型微球表面的形貌调控

多巴胺(DA)已被证实可在多种材料的表面进行氧化自聚而形成聚多巴胺(PDA),但其在带强负电荷的表面上的聚合机理和所形成的形貌却还不太明确。 为考察材料表面的电负性、氧化条件等对DA氧化自聚速度和聚多巴胺层形貌的影响,本文通过无皂乳液聚合制备了以聚苯乙烯(PS)为核、聚丙烯酸(PAA)为壳的纳米粒子(PS/PAA NPs),探究其表面的阴离子在不同pH缓冲液、反应时间下与DA的加入量对聚合过程及其形貌的影响。 通过扫描电子显微镜(SEM)、透射电子显微镜(TEM)和Zeta电势对所得纳米粒子的结构、形貌与尺寸等进行分析。 结果发现,在pH值为8.5的三羟甲基氨基甲烷(Tris)缓冲溶液中,当DA与PS/PAA NPs的质量比为1∶1时,在反应24 h后,PDA以纳米颗粒的形式存在于PS/PAA NPs的表面,即所形成的PS/PAA/PDA NPs为明显的树莓状结构。 随着DA含量的增加和反应时间的延长,所形成的树莓状粒子粒径增大;当DA远远过量时,PDA最终在微球表面形成致密、均匀的壳层。 Zeta电势结果表明树莓状结构是由于DA在PAA表面聚合过程中受到静电相互作用和电荷排斥作用间的竞争而形成的,随着DA量的增大和反应时间的延长,形成的静电作用增大,使较多的PDA粘附至PAA表面而形成较致密的均匀壳层。 同时,DA在电负性较小的PS/SDS微球和非离子的PS微球表面聚合时,均形成致密的PDA壳层。 因而,材料表面的电负性大小可以调控DA在其表面的沉积,以制备不同形貌的PDA复合材料。     

Single and Binary Dye Adsorption of Methylene Blue and Methyl Orange in Alcohol Aqueous Solution via Rice Husk Based Activated Carbon: Kinetics and Equilibrium Studies

The present work was mainly focused on the single and binary adsorption of methylene blue(MB) and methyl orange(MO) from alcohol aqueous solution over rice husk based activated carbon(RHAC). The study of single dye adsorption equilibrium experiments found that the Langmuir adsorption model was consistent with the adsorption behavior of RHAC on MB and MO, indicating that it was a single layer adsorption. The adsorption behavior conformed to the pseudo-second-order kinetic model. The binary dye adsorption experiments showed that the Langmuir-Freundlich model could be applied to describe the adsorption behavior of RHAC on MB and MO. Comparation with the single dye system, the adsorption capacity on the binary dye system was larger, and there was "competitive adsorption" and "synergistic adsorption" effects existed. Meanwhile, the pseudo-second-order kinetic model also fit for the binary dye adsorption behavior.     

High-efficient liquid exfoliation of 2D metal-organic framework using deep-eutectic solvents

The exfoliation of bulk two-dimensional metal–organic framework (MOF) into few-layered nanosheets has attracted much attention recently. In this work, an environmental-friendly route has been developed for layered-MOF (MAMS-1) delamination using deep eutectic solvent (DES), which is more sustainable and efficient alternative than conventional organic solvents for MOF nanosheet preparation. Under sonication condition, DES as solvents, the highest exfoliation rate of MAMS-1 is up to 70% with two host layers via poly(vinylpyrrolidone) (PVP) surfactant-assisted method. The presence of tert-butyl exteriors and the atomically thickness endow the MOF nanosheets stable suspension for at least one month. Due to the 2D structure and excellent stability, MAMS-1 nanosheet (MAMS-1-NS) was chosen as a good candidate to encapsulate Eu³⁺ cations. The obtained Eu³⁺@MAMS-1-NS acts as a multi-responsive luminescent sensor through fluorescence quenching, and can specifically recognize Fe³⁺ (LOD = 0.40 μM, K_SV = 1.05 × 10⁵ M^−l), Hg²⁺ (LOD = 0.038 μM, K_SV = 5.78 × 10⁶ M^−l), Cr₂O₇²⁻ (LOD = 0.33 μM, K_SV = 1.55 × 10⁵ M^−l) and MnO₄⁻ (LOD = 0.088 μM, K_SV = 4.49 × 10⁵ M^−l). Compared with bulk Eu³⁺@MAMS-1, the sensitivity of Eu³⁺@MAMS-1-NS is greatly improved owing to its ultrathin nanosheet morphology and highly accessible active sites on the surface.     

Surfactant‐Dependent Charge Transfer between Polyoxometalates and Single‐Walled Carbon Nanotubes: A Fluorescence Spectroscopic Study

Hybridizations of redox‐active polyoxometalates (POMs) with single‐walled carbon nanotubes (SWNTs) have been widely investigated for their diverse applications. For the purpose of constructing high‐quality electronic devices, controlling charge transfer within POM/SWNT hybrids is an inevitable issue. As determined by means of fluorescence spectroscopy, electron transfer between SWNTs and a common POM dopant, phosphomolybdic acid (PMo₁₂), can be tuned simply by an alteration of nanotube surfactant type from anionic to nonionic. The mechanism is attributed to the influence of surfactant type on the stabilization of the electron donor–acceptor hybrid and effect of surfactant–nanotube interactions. These results will be important to control charge‐transport behavior in nanohybrids consisting of carbon nanotubes.     

卤素离子触发亚铁四面体笼的自旋状态转换

合理构筑了3个具有固态自旋交叉特性的亚铁四面体笼状化合物1~3。单晶X射线衍射分析证实了化合物是由6个咪唑席夫碱配体和4个亚铁离子组装形成的边导向封顶胶囊结构。金属中心占据四面体的顶点,而配体组成了四面体的边。这些笼状化合物的内部空腔被咪唑基团环绕,而外部则被取代苯环包围。一个阴离子客体被限域在笼状化合物空腔内,并与笼状化合物主体产生较强的相互作用。当在笼状化合物的乙腈溶液中加入卤素离子（Cl^-和Br^-）时,溶液的颜色和MLCT峰强度会发生明显变化,表明亚铁四面体笼状化合物的自旋状态由低自旋向髙自旋发生了转换。