基于离子交换和表面引发接枝聚合制备阴离子表面印迹材料及其识别特性研究

建立了一种新的离子表面印迹(IIP)方法. 使用偶联剂γ-氨丙基三甲氧基硅烷(AMPS)对微米级硅胶微粒进行表面改性, 制得表面含有氨基的改性硅胶AMPS-SiO₂. 凭借离子交换作用, 阳离子单体甲基丙烯酰氧乙基三甲基氯化铵(DMC)结合在模板离子磷酸根周围; 改性硅胶AMPS-SiO₂表面的氨基与溶液中的过硫酸盐构成氧化还原引发体系, 使DMC及交联剂N,N'-亚甲基双丙烯酰胺(MBA)在硅胶微粒表面发生接枝交联聚合, 从而实现了磷酸根离子的表面印迹, 制得了阴离子表面印迹材料IIP-PDMC/SiO₂. 采用静态与动态两种方法, 考察研究了IIP-PDMC/SiO₂对PO₄^3-离子的识别特性与结合性能. 研究结果表明, 离子表面印迹材料IIP-PDMC/SiO₂对PO₄^3-离子具有特异的识别选择性与优良的结合亲和性, 相对于对比离子高锰酸根离子, IIP-PDMC/SiO₂对PO₄^3-离子的识别选择性系数为9.58.     

含羧基交联型质子交换膜的制备及其性能

合成了一种含酯基的磺化聚合物,利用后水解的方法得到了含有羧基侧基的聚合物;将磺化聚合物与聚乙烯醇通过溶液共混,热处理后得到交联型的共混膜材料。 研究结果表明,膜材料的玻璃化转变温度(Tg)有明显的上升,证明了交联反应的发生;同时,膜的吸水率和溶胀率有一定的下降,力学性能和热稳定性也有一定的提升。 通过共价交联的方法,制备了综合性能优异的磺化聚芳醚质子交换膜材料。 在100 ℃,交联膜的质子传导率为0.072~0.065 S/cm,吸水率为51%~89%,溶胀率为19%~30%。     

The synthesis and exchange bias effect of monodisperse NiO nanocrystals

Monodisperse NiO nanocrystals with an average particle size of 3 ± 0.4 nm are successfully synthesized by the thermal decomposition of Ni-oleylamine complex in an organic solvent under a continuous O2 flux. The crystalline structure and the morphology of the product are investigated by X-ray diffraction, X-ray photoelectron spectroscopy, and transmission electron microscopy. Magnetization and alternating-current (ac) susceptibility measurements indicate that the structure of the particles can be considered as consisting of an antiferromagnetically ordered core and a spin-glass-like surface shell. In addition, both the exchange bias field and the vertical magnetization shift can be observed in this system at 10 K after field cooling. This observed exchange bias effect is explained in terms of the exchange interaction between the antiferromagnetic core and the spin-glass-like shell.     

KCaA型分子筛制备及其对CO2吸附性能的研究

采用离子交换法,在CaA型分子筛中加入氯化钾水溶液,并搅拌一定时间,将功能K+引入到CaA型分子筛结构中,以调控CaA型分子筛的孔径和增加它的吸附活性位点.考察了离子交换时间和气体吸附压力等条件对制备的KCaA型分子筛的结构、形貌和CO2吸附性能的影响.通过X射线衍射、扫描电子显微镜和CO2吸附等温线等表征手段,结果发现:获得的KCaA型分子筛具有与CaA型分子筛相同的结构与形貌;增大气体吸附压力,分子筛对CO2的吸附量增大;但随着离子交换时间的增长,分子筛对CO2的吸附能力先增大后减小;在室温及1bar气压下对CO2气体的吸附性能比原CaA型分子筛提高了26.7%.     

超大孔离子交换制备色谱分离纯化高活性凝血因子VIII

建立了一条从人血浆中分离高活性凝血因子VIII(FVIII)的纯化工艺。基于FVIII和介质孔径的尺度比及其对蛋白质活性影响的分析,设计了以超大孔离子交换制备色谱为核心步骤的新型分离纯化工艺。分别进行超大孔离子交换色谱与传统离子交换色谱的条件优化,并对优化工艺所得产品进行了活性检测(底物显色法)和纯度检测(高效凝胶过滤和凝胶电泳)。结果表明,超大孔介质结构不但可以有效地保护蛋白质大分子结构,而且能够大幅度地提高制备色谱的传质速率,从而得到具有高凝血活性的FVIII产品。FVIII在超大孔制备色谱过程中的回收率(85%)比传统离子交换制备色谱高4～5倍,产品比活高达154 IU/mg。此外,还研究了超大孔介质的再生程序,采用5个柱体积的1 mol/L NaOH低流速清洗色谱柱,保证了色谱工艺的稳定性。本纯化工艺步骤简单,重现性好,易于放大生产。     

加盐导致的全氟辛酸盐表面活性的反常行为

通过测定全氟辛酸铵(APFO)、全氟辛酸三甲铵(TMHPFO)、全氟辛酸三乙铵(TEHPFO)在不同浓度NaCl (0.1, 0.3, 0.5 mol•L^－1)存在时水溶液的表面张力曲线, 考察不同反离子的氟表面活性剂其表面活性随无机盐浓度的变化. 结果表明, NaCl对APFO的胶束化有明显的促进作用|对于TMHPFO和TEHPFO则在NaCl浓度较低时有很小的促进作用, NaCl浓度较高时由于Na^＋和N(CH₃) (或N(CH₂CH₃) )之间的离子交换作用反而临界胶束浓度(cmc)增大. APFO, TMHPFO的最低表面张力(γ_cmc)随着NaCl浓度的增大而增大. 而对于TEHPFO, 少量NaCl的加入有利于降低γ_cmc、然后随着NaCl浓度的增大TEHPFO的γ_cmc增大. 这说明, 加盐溶液中始终存在着屏蔽效应和离子交换作用的竞争, 随着NaCl浓度增大离子交换趋势增大|对于疏水性较高的三乙铵离子在NaCl存在的情况下离子交换作用导致的γ_cmc升高需要更高的NaCl浓度才能显现. 通常认为外加无机盐是增强表面活性剂的表面活性的方法之一, 本工作表明, 对于有些反离子为有机阳离子的氟表面活性剂, 外加无机盐, 如NaCl, 不仅不能起到显著的增效作用, 浓度大时甚至会降低表面活性剂的效能. 所以这类表面活性剂在实际使用时应尽量避免高盐环境.     

Fluctuation relations for heat exchange in the generalized Gibbs ensemble

In this work, we investigate the heat exchange between two quantum systems whose initial equilibrium states are described by the generalized Gibbs ensemble. First, we generalize the fluctuation relations for heat exchange discovered by Jarzynski and Wójcik to quantum systems prepared in the equilibrium states described by the generalized Gibbs ensemble at various generalized temperatures. Secondly, we extend the connections between heat exchange and the Rényi divergences to quantum systems under generic initial conditions. These relations are applicable for quantum systems with conserved quantities and universally valid for quantum systems in the integrable and chaotic regimes.     

Determination of Water and Solute Transport in Polyacrylamide Gels

Summary: Water exchange between five polyacrylamide gels (Bulkamid®, Aquamid®, Rectamid®, HV-PAAG, Acuvue) with a physiological salt solution was determined by means of tritium-labeled water. Urea and chloride exchange was also determined in Acuvue. The method was a modified version to measure rapid transport processes in red blood cells. The study shows that water and solutes easily exchange between the hydrogel under study and the surrounding medium, independent of the solid polymer content (2.5–40 wt%) and an over ten-fold variation of the cross-linking density.     

Adsorption Behavior of Metal Ions by Amidoxime Chelating Resins

In this work, the acrylonitrile (AN) – divinylbenzene (DVB) –methylacrylate (MA) resin was synthesized via suspension polymerization in the presence of toluene as diluent, and benzoylperoxide (BPO) as initiator. The effect of MA, toluene and alkaline treatment on the exchange capacity of the resin were investigated. The results showed that the anion exchange capacity decreased with an increase in the amount of MA, while alkaline treatment had no significant effect. Also, the cation exchange capacity increased with an increase in the amount of hydrophilic agent and reached a maximum point. The sorption equilibrium was achieved relatively fast within 40 mins, and the resin exhibited affinity towards lead (II), copper (II) and in particular uranium (VI). The adsorption of uranium was directly depended up on the pH value. Furthermore, the macroreticular chelating resin, containing amidoxime group had higher adsorption of uranium (VI) in comparison to other metal ions studied. Finally, the alkaline treatment enhanced the potential for much faster adsorption characteristics and the highly porous chelating resin provided a more favorable pore structure for the rapid rate of diffusion of metal ions.     

人民币汇率波动对我国出口价格的传递效应研究——区分持久性与暂时性汇率变动的不同影响

实体经济的变化和货币政策与金融市场的扰动,分别造成汇率的持久性变动与暂时性变动。为了研究这两种不同的汇率变动对出口价格产生的影响,本文通过研究不完全竞争市场中出口企业的定价行为,建立理论分析框架,并使用Blanchard-Quah方法对汇率变动进行分解,得出两种不同的汇率变动。基于VEC模型,采用1997年1月至2012年12月我国的出口价格数据进行实证分析,结果表明:人民币实际有效汇率的持久性变动和暂时性变动对我国出口价格的传递系数分别为0.84和0.67。因此,加快出口行业的转型与升级以及维持好货币政策与金融市场的稳定,对降低汇率波动对我国出口企业的影响具有重要的意义。