原子转移自由基聚合技术制备新型手性配体交换色谱固定相及对手性化合物的拆分

采用原子转移自由基聚合(ATRP)技术, 以溴代硅胶为引发剂, CuCl/2,2'-联吡啶(Bpy)为催化体系, 水为溶剂, N-丙烯酰基-L-脯氨酸为单体, 室温下在硅胶表面进行聚合反应, 制得硅胶接枝聚N-丙烯酰基-L-脯氨酸分子刷. 通过改变ATRP反应体系中单体的量, 制备了3种不同键合量且键合量可控的手性配体交换色谱固定相, 利用元素分析和热重分析对其进行表征. 考察了配体接枝率、 流动相Cu²⁺浓度、 pH值和柱温等对DL-氨基酸和α-羟基酸拆分的影响, 优化了色谱分离条件, 探讨了拆分过程的热力学. 结果表明, 所合成的手性配体交换色谱固定相能够分离9种DL-氨基酸和α-羟基酸, 其中DL-酪氨酸、 DL-色氨酸和DL-苏氨酸3种氨基酸可同时进行拆分, 且拆分过程由熵控制.     

Preparation and Characterization of Nanostructured Ni-TiN Composite Films

Ni-TiN nanocomposite films were produced from a Ni plating bath containing TiN nanopar-ticles by using dc electroplating method. The structure and surface morphology of Ni-TiN composite coatings were analyzed by atom force microscope, X-ray diffraction, and trans-mission electron microscopy. Meanwhile, the anti-corrosion properties, hardness and ther-mostability of Ni-TiN nanocomposite films were also investigated and compared with the traditional polycrystalline Ni coatings. The results show that, compared with the tradi-tional polycrystalline Ni film, Ni-TiN nanocomposite coatings display much better corrosion resistance, higher film hardness, and thermal stability. In addition, the hardness of Ni-TiN nanocomposite coatings decreases slightly with the increase of electroplating current density,which may be due to the synergism of hydrogen evolution and faster nucleation/growth rate of nickel crystallites.     

First-order gradient damage theory

Taking the strain tensor, the scalar damage variable, and the damage gradient as the state variables of the Helmholtz free energy, the general expressions of the firstorder gradient damage constitutive equations are derived directly from the basic law of irreversible thermodynamics with the constitutive functional expansion method at the natural state. When the damage variable is equal to zero, the expressions can be simplified to the linear elastic constitutive equations. When the damage gradient vanishes, the expressions can be simplified to the classical damage constitutive equations based on the strain equivalence hypothesis. A one-dimensional problem is presented to indicate that the damage field changes from the non-periodic solutions to the spatial periodic-like solutions with stress increment. The peak value region develops a localization band. The onset mechanism of strain localization is proposed. Damage localization emerges after damage occurs for a short time. The width of the localization band is proportional to the internal characteristic length.     

A partially insulated interface crack between a graded orthotropic coating and a homogeneous orthotropic substrate under heat flux supply

In this paper, thermal response of an orthotropic functionally graded coating-substrate structure with a partially insulated interface crack under heat flux supply is considered. It is assumed that there exists thermal resistance to heat conduction through the crack region. The mixed boundary value problems are reduced to a system of singular integral equations and solved numerically. Higher order asymptotic terms for the singular integral kernels are considered to improve the accuracy and the convergence efficiency of the numerical integrals. Numerical results are presented to show the effects of the orthotropy parameters, thermo-elastic nonhomogeneity parameters, and dimensionless thermal resistance on the temperature distribution and the thermal stress intensity factors (SIFs).     

CS-MCM-48复合载体固定化脂肪酶催化苯乙酮一锅法还原转酯化拆分反应

将天然聚合物壳聚糖(CS)涂覆在介孔分子筛MCM-48表面制得CS-MCM-48复合载体,控制CS与介孔分子筛MCM-48质量比为1∶10时,CS-MCM-48的比表面积、平均孔径和孔容分别为408m2/g、2.14nm和0.38cm3/g。在磷酸盐缓冲溶液-异辛烷混合溶剂中制备了固定化假单胞菌脂肪酶(Pseudomonas Cepacia Lipase,PSL)PSL/CS-MCM-48,并用于潜手性苯乙酮一锅法还原转酯化手性拆分反应。结果表明,PSL/CS-MCM-48的催化活性和对映选择性均明显优于纯介孔分子筛MCM-48和壳聚糖制备的固定化酶PSL/MCM-48和PSL/CS。甲苯作溶剂,反应温度为40℃时,底物1-苯乙醇转化率达15.3%,产物(R)-乙酸苯乙酯和(S)-1-苯乙醇的对映体过量值分别为99%和18.0%,对映选择性参数E值达237,固定化酶PSL/CS-MCM-48显示出良好的手性拆分性能。     

近红外光谱技术在天然草地植被管理中的应用

植被是监测草地健康和生产力的主要依据,其变化是草地生态系统退化和恢复状况的最直接体现。及时掌握草地植被的变化信息是防止草地退化、实现草地生态系统可持续发展的首要条件。近红外光谱技术以其简便、快捷等优越性广泛应用于不同领域,在草地资源管理中有巨大的应用潜力和前景。文章介绍了近红外光谱技术的原理、特点及其在草地植被物种组成、草地植物茎叶比、凋落物及牧草品质测定等方面的应用特点,综合阐述了近红外光谱技术在草地植被管理中的应用现状,并对其应用前景进行了展望。     

单分散大孔亲水弱阳离子交换填料的制备及其对鱼精蛋白的分离纯化

以自制的5.0 μm单分散大孔亲水交联聚甲基丙烯酸环氧丙酯(PGMA/EDMA)微球为基质,对其表面进行化学改性,合成弱阳离子交换色谱填料(WCX)。详细考察了该填料对标准蛋白质的分离性能、表面亲水性能、稳定性和重现性以及流速对蛋白保留的影响。实验结果表明,该色谱填料对蛋白的分离性能、重现性及稳定性良好;在流速为3 mL/min时,采用线性梯度洗脱,6 min内可分离4种标准碱性蛋白质,以溶菌酶测定的该填料的动力学吸附容量为29.86 mg/g。将其用于鱼精蛋白的分离纯化,经反相高效液相色谱测定纯化后鱼精蛋白的纯度为99.2%;与商品Shodex IEC SP-825强阳离子交换色谱柱比较,纯化结果几乎一样。     

The Preparation of Ionic Liquid Catalysts and Their Catalytic Performance

Ionic liquid, a new type catalyst, was developed in recent years, on which some good catalytic performance appeared in some reactions such as olefins' oligomerization, hydrogenation and Freidel-Crafts reaction just for their strong electrophilic catalysis^[1]. However, it was reported that only in vacuum and seal condition ionic liquid could be prepared with the halogerated hydrocarbon and heterocyclic compounds or their homologues^[2]. So it was necessary to develop a new method to synthesize ionic liquid. Therefore, inert gases (such as N₂) protection instead of vacuum was employed in this experimental, and the rules of preparation parameters on the products' type and yield were investigated, based on which the catalytic performance of these ionic liquid was studied in a model reaction of new compound synthesis from methane and carbon dioxide.     

活性蓝F3GA固载的无孔单分散亲水性交联聚甲基丙烯酸环氧丙酯亲和色谱填料的制备与应用

以3.0 μm无孔单分散亲水性交联聚甲基丙烯酸环氧丙酯树脂为基质,与三嗪染料活性蓝F3GA(Cibacron Blue F3GA)反应,制备出 一种固定化染料聚合物高效亲和色谱填料。考察了应用该填料时流动相中的盐离子浓度、有机溶剂及流速等对牛血清白蛋白(BSA)和 溶菌酶(Lys)保留行为的影响。实验结果表明,该染料亲和填料具有良好的色谱性能。利用前沿色谱法测定了染料与溶菌酶之间的表观 解离常数为5.26×10-5 mol/L。使用该填料成功地从鸡蛋清和小牛血清中分别分离纯化了Lys和BSA,十二烷基硫酸钠-聚丙烯酰胺凝胶 电泳(SDS-PAGE)分析显示Lys和BSA的纯度分别为95%和92%。     

基于高光谱成像技术的土壤水分机理研究及模型建立

为了研究宁夏地区土壤的水分迁移机理以及对土壤水分快速无损检测,利用高光谱成像(光谱范围900~1 700 nm)技术对土壤的含水率进行了研究。通过高光谱成像系统采集了208个土样,比较了不同天数下土壤含水率与光谱的变化、不同质量含水量光谱的差异。对采集到的土样进行PLSR模型建立,对比分析不同光谱预处理方法、不同方法提取特征波长(UVE、CARS、β系数、SPA)、不同建模方法(MLR、PCR、PLSR)建立的模型,优选出最佳模型。结果表明:在一定的土壤含水量范围内,光谱曲线的反射率与土壤含水率成反比;当增大到超过田间持水率时,光谱曲线的反射率与土壤含水率成正比。对比分析了不同预处理方法,优选出单位向量归一化预处理方法。对比不同的模型,优选出SPA提取的特征波长的MLR模型。最优的特征波长为987,1 386,1 466,1 568,1 636,1 645 nm,最优模型的预测相关系数Rp=0.984,预测均方根误差RMSEP为0.631。因此,今后可采用不同波段对土壤含水率进行定量分析。