Solvent effects on the S0(1(1)Ag-) --> S2(1(1)Bu+) transition of beta-carotene, echinenone, canthaxanthin, and astaxanthin in supercritical CO2 and CF3H

Solvent-induced spectral shifts of the four C40 carotenoids, beta-carotene, echinenone, canthaxantin, and astaxanthin, have been studied in supercritical CO2 and CF3H. In situ absorption spectroscopic analysis was used to determine the maximum peak position of the electronic transitions from the ground state (1(1)Ag-) to the S2 state (1(1)Bu+) of the carotenoids. The medium polarizability function, R(n) = (n2 - 1)/(n2 + 2) of the refractive index of the solvent was varied over the range R(n) = 0.08-0.14, by changing the pressure of CO2 or CF3H between 90 and 300 bar at the temperature 308 K. For all the carotenoids studied here, a significant hypsochromic shift of ca. 20-30 nm was observed in supercritical fluids as compared to that in nonpolar liquids. The spectral shifts in supercritical fluids were compared with those in liquids and showed a clear linear dependence on the medium polarizability. The temperature-dependent shift of the absorption maxima was less significant. Interestingly, there was almost no difference in the energetic position of the absorption maxima in supercritical CO2 and CF3H at a given R(n) value. This is in contrast to previous extrapolations from studies in liquids at larger R(n) values, which yielded different slopes of the R(n)-dependent spectral shifts for polar and nonpolar solvents toward the gas-phase limit of R(n) = 0. The current experimental results in the gas-to-liquid range show that the polarity of the solvent has only a minor influence on the 1(1)Ag- --> 1(1)Bu+ transition energy in the region of low R(n). We also obtain more reliable extrapolations of this 0-0 transition energy to the gas-phase limit nu(0-0)(gas-phase) approximately (23,000 +/- 120) cm(-1) for beta-carotene.     

模拟树脂移动床实验装置的建立及其在果葡糖分离中的应用

采用13根色谱柱制作安装了简易的模拟移动床实验装置,配合强酸阳离子色谱分离树脂,用于果葡糖浆的分离实验,证实达到了连续分离的效果,可用于树脂的测试评价。     

聚乙二醇、聚丙二醇和环氧乙烷-环氧丙烷嵌段共聚物在固液界面上的吸附——Ⅱ.硅胶/水界面

测定了25℃时硅胶自水溶液中吸附五种聚乙二醇(PEG)、一种聚丙二醇(PPG)和三种环氧乙烷(EO)-环氧丙烷(PO)嵌段共聚物的吸附等温线。除PPG的等温线为S型外,其余的均为Langmuir型的。计算结果表明,对于PEG系列和EO-PO嵌段共聚物系列都可得到极限吸附时的分子面积(A)与分子中所含EO数(n_(EO))的关系为不通过原点的曲线。当PEG分子量大到一定程度后,此A-n_(EO)关系即成近似于通过原点的直线。根据所得结果的分析,以及考虑了吸附水的影响,初步可得出分子是以平躺的方式被吸附的结论。文中还计算了吸附直由能,并对计算结果作了初步的解释。     

Study of enzymatic degradation of microbial copolyesters consisting of 3-hydroxybutyrate and medium-chain-length 3-hydroxyalkanoates

Enzymatic degradation of poly(3-hydroxybutyrate-co-3-hydroxyalkanoates) (PHBA) biopolyester consisting of 3-hydroxybutyrate (HB) and 15 mol% medium-chain-length 3-hydroxyalkanoates (HA) was studied using a polyhydroxyalkanoates (PHA) depolymerase produced by Ralstonia pickettii T1. It was found that PHBA films did not lose their weight after 25 h of depolymerase treatment. In contrast, three commercially available PHAs including poly-3-hydroxybutyrate (PHB), poly(3-hydroxybutyrate-19 mol% 3-hydroxyvalerate) (PHBV) and poly(3-hydroxybutyrate-19 mol% 3-hydroxyhexanoate) (PHBHHx) lost 75%, 94% and 39% of their original weights. Slow degradation of PHBA was also confirmed by the absence of HA monomers, dimers or trimers as degradation products in their depolymerase solution compared with abundance of degradation products released by the other three PHAs under the same condition. Surface erosion of PHBA was only observed after 48 h of enzymatic treatment compared with those of PHB, PHBV and PHBHHx which already had obvious surface changes after 7.5 h of same treatment. Although the crystallinities of PHB, PHBV, PHBHHx and PHBA were in the order PHB > PHBV > PHBHHx > PHBA valued at 55.8%, 47.8%, 45.9% and 40.9%, respectively, the order of degradability was PHBV > PHB > PHBHHx > PHBA. It can be proposed that PHA enzymatic degradation using this depolymerase was structure related: longer side-chain PHA including PHBHHx and PHBA was less favorable for the depolymerase degradation, longer the side chain, less the biodegradation.     

连续小波在医学图像处理中的一种应用

本文构造了一类具有紧支撑的无限次可导的对称小波，提出了适应医学图像处理的边缘检测算法，并给出了计算实例。     

Pb－Ti复合醇盐的水解聚结过程

采用浊度法研究了Ｐｂ－Ｔｉ复合醇盐的水解聚结过程。发现该过程随水量和醇盐浓度的增大而加快，碱（ＮＨ＿４ＯＨ）能够大大促进水解聚结反应，酸（ＨＯＡｃ）则在低浓度时起促进作用高浓度时起抑制作用。根据醇盐水解聚结的反应机理对以上结果作了解释。     

Investigation on RF styrene plasma by emission spectroscopy

In order to gain an insight into the processes in an RF styrene plasma, gas phase plasmas were investigated by emission spectroscopy. The plasma reactor was a bell-jar-type chamber with two parallel plate electrodes. The measurement of plasma emission spectra was made with axial resolution. The correlations among the emission intensities of CH and C₄H₂⁺ species, the polymer deposition rate and the polymeric structure of the deposited films were studied. The proposed analysis showed that the gas flow pattern in the plasma reactor, and the difference in collisions between styrene monomer molecules and energetic free electrons occurring in the plasma region and RF sheath, made the fragments and ions produced change in the different regions, resulting in a change in polymeric structure and deposition rate of the polymer films. With increasing distance between the substrate position and the lower electrode, the deposition rate and the concentration of phenyl groups both at the polymer surface and in the bulk decreased     

Temperature‐dependent polymorphic crystalline structure and melting behavior of poly(butylene adipate) investigated by time‐resolved FTIR spectroscopy

The polymorphic crystalline structure and melting behavior of biodegradable poly(butylene adipate) (PBA) samples melt‐crystallized at different crystallization temperatures were studied by differential scanning calorimetry (DSC) and fourier transform infrared (FTIR) spectroscopy. The crystalline structure and melting behavior of PBA were found to be greatly dependent on the crystallization temperature. By comparison of the FTIR spectra and the corresponding second derivatives between the α‐ and β‐crystal of PBA, the spectral differences were identified for the IR bands appeared at 1485, 1271, 1183, and 930 cm^?1 and the possible reasons were presented. Especially, the 930 cm^?1 band was found to be a characteristic band for the β‐crystal. Combining the DSC data with the analysis of normalized intensity changes of several main IR bands during the melting process, the melting behaviors of the α‐ and β‐crystal were clarified in detail. It is demonstrated by the in situ IR measurement that the β‐crystalline phase would transform into the α‐crystalline phase during the melting process, and the solid–solid phase transition from the β‐ to α‐crystal was well elucidated by comparing the intensity changes of the 1170 and 930 cm^?1 bands. The dependence of the β‐ to α‐crystal phase transition on the heating rate was revealed by monitoring the intensity ratio of the 909 and 930 cm^?1 band. It was suggested that at the heating rate of 0.5 or 1 °C/min, the percent amount of the transformed α‐crystal from the β‐crystal was much higher than that at the higher heating rate. The β‐crystal transforms into the α‐crystal incompletely at the higher heating rate because of the less time available for the phase transition. In addition, the β‐ to α‐crystal phase transition was further confirmed by the IR band shifts during the melting process. © 2009 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 47: 1997–2007, 2009     

Classification of nonoscillatory solutions of second order self-adjoint neutral difference equations

This paper deals with existence of positive solutions of nonlinear elliptic singular boundary value problems in a ball. It is shown that results of Grandall et al. [1] and [2] follow as special cases of our results proved in this article.     

超燃火焰稳定凹腔自激振荡特性的数值研究

对超声速冷流条件下用于超燃冲压发动机的凹腔火焰稳定器的自激振荡特性进行研究.采用混合RANS/LES方法对非定常流场进行数值模拟,考虑了凹腔的长深比和后缘角度两个关键参数.混合RANS/LES方法很好的捕捉到流场非定常大尺度结构并揭示了凹腔自由剪切层的演化过程.对凹腔压力振荡历程进行幅频分析,所得到的频率和理论分析结果与文献计算结果符合的很好.结果表明,凹腔的长深比和后缘角度对凹腔自激振荡特性都有很大的影响.随着凹腔长深比的减小,振荡能量趋于集中到某些频率对应的振荡模式上.随着凹腔后缘倾角的减小,大部分频率对应的振荡很快的被削弱;相对于陡后缘凹腔,小角度后缘凹腔只有较高频率对应的振荡模式存在.