Packed-microtubes model for flowthrough chromatography of protein

A mathematical model for flowthrough (perfusion) chromatography, namely packed-microtubes (PMT) model, has been proposed for a column packed with biporous (BiP) anion exchanger in which the mesopores and flowthrough pores are created with liquid and solid porogens, respectively. The model is established based on the assumption that the BiP particle is made up of packed microtubes. Bovine serum albumin (BSA) is used as a model protein and three kinds of anion exchangers (i.e., mesoporous, macroporous and BiP resins) are used as adsorbents to determine the model parameters and to evaluate the model. Adsorption equilibrium and finite bath experiments are performed to determine the adsorption isotherms and kinetics parameters. Both the bound amounts of the protein on the surface of the mesopores and macropores are experimentally determined and taken into account in the mathematical model. With all the model parameters determined by independent experiments or calculated from available correlations, model simulations are performed and compared with the experimentally determined breakthrough profiles of the BiP column. It is found that the model predictions agree reasonably well with the experimental data obtained under various conditions and the PMT model fit experimental data better than the modified double linear driving force (LLDF) model proposed by Leitão and Rodriogues (1999. Biochemical Engineering Journal 3, 131) in which the adsorbent particle is considered to be made up of packed microparticles. The results indicate that the PMT model is more reasonable for this kind of BiP adsorbent.     

用循环伏安法研究醌亚胺的脱氨反应

用循环伏安法研究了N,N-二乙基对苯二胺,N,N,N′,N′-四乙基对苯二胺,N,N-二乙基氨基酚三类化合物的电化学氧化及其氧化产物的后继化学反应,求算了脱氨反应速率常数,揭示了苯环上甲基取代基和氮原子上不同取代基对脱氨反应的影响。 脱氨反应为OH~-或水进攻醌亚胺的亲核反应。由于甲基的斥电子效应,当苯环上引进甲基取代基时,环上负电荷增大,带正电荷的醌亚胺趋于稳定,水解反应速度减慢。 苯环上引进二个甲基取代基,其相应的苯胺化合物的半波电位下降大约120mV。二乙基对苯二胺的苯环上每引进一个甲基取代基,其氧化产物与彩色成色剂偶合生成的染料的吸收峰向长波方向移动20—30nm。     

充油S-SBR加工行为的研究

在中试装置上合成相对分子质量分布较宽的充油S-SBR，考察不同环烷油和芳烃油填充量的充油S-SBR的流变性能和混炼行为。结果表明，增大油的填充量能提高充油S-SBR的流动性能，充芳烃油S-SBR相对于充环烷油的S-SBR对温度更敏感，宽相对分子质量分布的充环烷油S-SBR的混炼性能优于S-SBR1204及E-SBRl778，竟相对分子质量分布的充芳烃油S-SBR的混炼性能优于S-SBR1204，Solprene380和E-SBR1712。     

Security concepts for the dynamics of autonomous vehicle networks

The secure operation of autonomous vehicle networks in the presence of adversarial observation is examined, in the context of a canonical double-integrator-network (DIN) model. Specifically, we study the ability of a sentient adversary to estimate the full network’s state, from noisy local measurements of vehicle motions. Algebraic, spectral, and graphical characterizations are provided, which indicate the critical role of the inter-vehicle communication topology and control scheme in achieving security.     

合成氢化松香乙酯的新工艺研究

以DRC为催化剂,在无溶剂条件下,通过氢化松香与乙醇的直接酯化反应合成氢化松香乙酯。探索了反应温度、催化剂用量、反应时间、物料配比等因素对反应酯化率的影响,确定最佳反应条件为:反应温度180℃,催化剂用量为原料氢化松香质量的6%,反应时间6h,醇与酸的摩尔比为3∶1。在最佳条件下酯化率达92.2%。还探讨了用阴离子交换树脂柱层析分离纯化氢化松香乙酯粗产物的方法。此外,利用红外光谱对氢化松香乙酯精制产物进行了表征;用GC-MS分别对氢化松香乙酯粗产物及其精制产物进行了定性和定量分析,比较了柱层析前后化学组成的变化。     

COMPUTER SIMULATION OF HYDRODEMETALLATION IN FIXED-BED REACTORS

An isothermal model for hydrodemetallation (HDM) of crude oils in catalytic fixed-bed reactors is proposed. This model involves a consecutive reaction mechanism, which is capable of accounting for particle deposit profiles with interior maxima. Consistent with the fact that HDM catalysts are conglomerates formed by precipitation, the porous catalyst itself is modeled as randomly overlapping spheres of equal size. The metal is deposited as growing metal sulfide crystallites on the inner surface of the catalyst. These crystallites originate from a certain number of randomly scattered nuclei and increase in size as the deposition proceeds. The random sphere model for the catalyst and the deposit provides the changes in the catalyst pore structure—local porosity and surface area.

The mass transport within the domain of the particle is due to restricted liquid diffusion, since the diameter of the metal bearing compound (porphyrin) and the intermediate are comparable to the pore size. The diffusion restrictions taken into account are the enhanced drag imposed on a molecule by adjacent pore walls and steric partitioning.

Since the deposition process is much slower than diffusion and reaction, the pseudo-steady-state assumption can be justified. The equations of conservation for mass are solved by orthogonal collocation on finite elements. Based on this solution technique a computer simulation program of HDM is designed that allows two modes of operation: constant temperature and constant conversion. The simulation program “SIMULA” is highly flexible with regard to reaction kinetics, catalyst structure, reactor design, and operating conditions. In comparison to a base case with uniform activity, the effect of intraparticle (radial) and bed (axial) activity profiles on the conversion rate is discussed. For the case investigated, a radial distribution of activity higher at the center of the particle than at the edge can increase catalyst life by 25%, but axial distribution was less successful.     

熔融缩聚法制备聚乳酸

通过熔融缩聚法制备了聚乳酸。探讨了反应温度、催化剂类型及用量、反应时间对聚乳酸的影响，并用红外光谱和1↑H NMR对聚合物进行了表征。结果表明，最佳的反应条件为：聚合时间30h左右、聚合温度160℃、以O．2％的对甲苯磺酸作为酸催化剂、O．5％的氯化亚锡为催化剂、真空度为O—1333Pa；而提高乳酸纯度是制备高摩尔质量聚乳酸的关键条件之一。     

荧光染料用于涤纶织物染色的荧光性能研究

在实验条件下，染色织物的荧光反射率随荧光染料的浓度增加而增加，超过一定浓度后，有下降趋势；在pH=5左右，荧光反射率最高；荧光增白剂会提高染色织物的荧光反射率，在荧光黄2GFL中，当荧光增白剂的浓度由0.1％增加到5％时，荧光反射率由8．43增加至18．59，而对非荧光染料只有增艳的作用，不产生荧光。荧光染料染色织物的荧光反射率随着加入非荧光染料量的增加而减弱。     

Propylene epoxidation in a microreactor with electric heating

Gas phase propylene epoxidation on gold catalysts has attracted wide attention from industry and academia due to its high selectivity. However, it suffers from low propylene conversion and rapid catalyst deactivation. Experiments showed that propylene conversion could be increased by raising H₂, O₂, or C₃H₆ concentration in the feed, but the feed compositions were within the explosion limit. It was also shown that the activity of the used catalyst could be fully recovered, but the regeneration temperature was 280 °C, much higher than that for reaction. Therefore a microchannel reactor was devised to suppress explosion and was constructed with Fecralloy, to raise the temperature rapidly for catalyst regeneration by electric heating. In two minutes the temperature of the reactor could be raised from 50 to 300 °C. Catalysts were coated on the alloy belt by dip coating, and the performance of the reactor was evaluated under different operating conditions. Results showed that in the microreactor the overall reaction rate was controlled mainly by the intrinsic reaction rate, and also influenced by film diffusion to a certain extent. The deactivated catalyst was regenerated in the microchannel reactor and the activity was fully recovered.