Bioprocess applications of model-based estimation techniques

The last decade has seen the development of a number of approaches for estimating those variables which are difficult to measure on-line in industrial process situations. Whilst a range of techniques is available, a common element is the use of process knowledge in the form of a system model. In the case of bioprocess systems, although a large range of models has been presented in the literature, their use in estimation schemes on an industrial scale has been limited. A number of reasons can be identified for their low level of utilisation. Of particular significance is the uncertainty which exists in quantifying system performance and the process-model mismatch which inevitably results. The level of ‘pre-defined model’ uncertainty, together with the knowledge gained during the course of the fermentation, serves to dictate estimator structure. The paper considers a range of estimation strategies and contrasts, through industrial applications, their performance characteristics and utility.     

浅析燕云十六州的战略价值

后晋天福三年(938年),"儿皇帝"石敬瑭"履约"向契丹割献燕云十六州.从此,中原王朝丧失了抵御北方游牧民族入侵的天然屏障,北方门户大开.宋代,燕云地区的争夺几乎贯穿了十至十二世纪北宋与辽金战争的整个过程.事实上,后人所指的"燕云十六州"与石敬瑭割辽的十六州在名称、时间和地域上有很大的差别;燕云地区内的险峻的山脉、横贯的河流与长城、五关一起构成了其巨大的军事价值;富庶的经济,众多的人口又构成了该地区巨大的经济价值;从历史上看,燕云十六州的归属于中原王朝和北方游牧民族政权双方而言,战略意义重大.     

N,N′-二(β-十八酰氧基)乙基乙二胺二乙酸钠的合成及性能研究

用 N,N′-二羟乙基乙二胺、氯乙酸钠合成了 N,N′-二羟乙基乙二胺二乙酸钠(中间体),中间体再与硬脂酰氯反应制备了一种新型 Gemini 两性表面活性剂 N,N′-二(β-十八酰氧基)乙基乙二胺二乙酸钠。对产物合成条件进行了考察,优化的反应条件为:n(硬脂酰氯):n(中间体)=2.5,溶剂 V(水):V(氯仿)=1:2,pH=9.0～10.0,反应温度15～20℃,反应时间5 h。通过红外光谱和质谱分析确定了产物结构,并测试了产物的表面性能。结果表明,在25℃时,该产物的临界胶束浓度为0.24 mmol/L,临界胶束浓度下的表面张力为35.7 mN/m;即时泡沫高度为250 mm,5 min 后泡沫高度为220 mm;乳化时间为22.48 min(甲苯-水物系)和4.65 min(正己烷-水物系),亲水-亲油平衡值为5.4,等电点为 pH 3.3～6.5。     

The effect of support morphology on the reaction of oxidative dehydrogenation of ethane to ethylene at short contact times

The oxidative dehydrogenation of ethane is carried out in short contact time reactors over Pt and LaMnO₃ based catalysts supported on a large number of different ceramic substrates (45, 60 and 80 ppi foam monoliths and 200, 400, 600, 900 and 1200 cpsi honeycomb monoliths). Experimental results, obtained under the same conditions at varying the C₂H₆/O₂ ratio, showed that the highest performance in terms of ethylene selectivity and yield is always attained on LaMnO₃ catalysts. Furthermore, the results are significantly influenced by the morphology and cell density of the support, with 45 and 60 ppi foams and 400 and 600 cpsi honeycombs giving the best performance. The experimental results are explained by means of geometrical and fluid dynamic considerations on the support, and by means of a 2D mathematical model, which clearly indicates an optimal intermediate cell density for maximising ethylene selectivity and yield.     

Development of calibration models for quality control in the production of ethylene/propylene copolymers by FTIR spectroscopy,multivariate statistical tools,and artificial neural networks

Principal component regression (PCR), partial least squares (PLS), StepWise ordinary least squares regression (OLS), and back‐propagation artificial neural network (BP‐ANN) are applied here for the determination of the propylene concentration of a set of 83 production samples of ethylene–propylene copolymers from their infrared spectra. The set of available samples was split into (a) a training set, for models calculation; (b) a test set, for selecting the correct number of latent variables in PCR and PLS and the end point of the training phase of BP‐ANN; (c) a production set, for evaluating the predictive ability of the models. The predictive ability of the models is thus evaluated by genuine predictions. The model obtained by StepWise OLS turned out to be the best one, both in fitting and prediction. The study of the breakdown number of samples to be included in the training set showed that at least 52 experiments are necessary to build a reliable and predictive calibration model. It can be concluded that FTIR spectroscopy and OLS can be properly employed for monitoring the synthesis or the final product of ethylene–propylene copolymers, by predicting the concentration of propylene directly along the process line. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Synthesis and characterization of a novel proton‐exchange membrane for fuel cells operating at high temperatures and low humidities

The synthesis of a p‐toluidine/formaldehyde (PTF) resin was performed, and the effects of the molar ratio of the individual monomers and the polymerization conditions on the structure of the PTF resin were studied. Fourier transform infrared and ¹³C‐NMR spectra were used to characterize the PTF. Wide‐angle X‐ray diffraction patterns revealed the crystalline structures of various PTFs. Polarized optical microscopy revealed that the molar ratio of the monomers had a strong effect on the crystalline morphologies. A longer polymerization time turned out a polymer with a higher intrinsic viscosity and molecular weight, which led to differences in the proton conductivity. All of the PTFs showed a higher proton conductivity than a commercial Nafion membrane at 90–100°C and 0% relative humidity. The proton conductivity of the PTF series could be improved by sulfonation with sulfuric acid and could be maintained after blending with polyurethane. Pure methanol could be used as a fuel source because of the insolubility and nonwetting properties of PTF in methanol to increase the output current density for a PTF membrane electrode assembly. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2008     

Preparation and adsorption behavior of a cellulose‐based,mixed‐mode adsorbent with a benzylamine ligand for expanded bed applications

A novel mixed‐mode expanded bed adsorbent with anion‐exchange properties was explored with benzylamine as the functional ligand. The cellulose composite matrix, densified with stainless steel powder, was prepared with the method of water‐in‐oil suspension thermal regeneration. High activation levels of the cellulose matrix were obtained with allyl bromide because of the relative inertness of the allyl group under the conditions of the activation reaction. After the formation of the bromohydrin with N‐bromosuccinimide and coupling with benzylamine, the activated matrix was derived to function as a mixed‐mode adsorbent containing both hydrophobic and ionic groups. The protein adsorption capacity was investigated with bovine serum albumin as a model protein. The results indicated that the prepared adsorbent could bind bovine serum albumin with a high adsorption capacity, and it showed salt tolerance. Effective desorption was achieved by a pH adjustment across the isoelectric point of the protein. The interactions between the cell and adsorbent were studied, and the bioadhesion was shielded by the adjustment of the salt concentration above 0.1M. Stable fluidization in the expanded bed was obtained even in a 2% (dry weight) yeast suspension. The direct capture of target proteins from a biomass‐containing feedstock without extra dilution steps could be expected with the mixed‐mode adsorbent prepared in this work, and this would be especially appropriate for expanded bed adsorption applications. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Synthesis and characterization of novel copolymer containing pyridylazo-2-naphthoxyl group via reversible addition–fragmentation chain transfer (RAFT) polymerization

A novel monomer containing pyridylazo-2-naphthoxyl group, 1-(1-(4-vinylbenzyloxy)naphthalen-2-yl)-2-(pyridin-2-yl)diazene (VBNPA), was successfully synthesized and copolymerized with styrene (St) in N,N-dimethyl formamide (DMF) via reversible addition–fragmentation chain transfer (RAFT) polymerization using 2-cyanoprop-2-yl-1-dithionaphthalate (CPDN) as RAFT agent. The polymerization behavior exhibited “living”/controlled characters. The obtained copolymer, poly(St-co-VBNPA), with pre-determinable molecular weight and narrow molecular weight distribution can be used as a carrier in metal ion detection and analysis via pre-concentration technique. The copolymer–metal ion (copper (Cu) and europium (Eu)) complexes were prepared and characterized.     

Red Wine Polyphenols for Cancer Prevention

Conventional cancer therapies, the second leading cause of death worldwide, result in serious side effects and, at best, merely extend the patient''s lifespan by a few years. Searching for effective prevention is of high priority in both basic and clinical sciences. In recent decades natural products have been considered to be an important source of cancer chemopreventive agents. Red wine polyphenols, which consisted of various powerful antioxidants such as flavonoids and stilbenes, have been implicated in cancer prevention and that promote human health without recognizable side effects. Since resveratrol, a major component of red wine polyphenols, has been studied and reviewed extensively for its chemopreventive activity to interfere with the multi-stage carcinogenesis, this review focuses on recent progress in studies on cancer chemopreventive activities of red wine polyphenol extracts and fractions as well as other red wine polyphenols, like procyanidin B5 analogues and myricetin.