On the interpretation of metastable zone width in anti‐solvent crystallization

Considering nonlinear dependence of solute concentration on anti‐solvent–solvent composition a modified Nývlt‐like equation based on traditional power‐law relation between nucleation rate and developing supersaturation and a new equation based on the classical theory of three‐dimension nucleation are proposed to explain the dependence of anti‐solvent addition rate on metastable zone width defined as excessive anti‐solvent composition in anti‐solvent crystallization. The experimental data on the metastable zone width in anti‐solvent crystallization of benzoic acid are analyzed and discussed from the standpoint of these equations. It is found that the new approach based on the classical nucleation theory provides better insight into the processes involved in anti‐solvent crystallization. Analysis of the experimental results on anti‐solvent crystallization of benzoic acid [D. O'Grady, M. Barret, E. Casey, and B. Glennon, Trans. IChemE A 85 , 945, (2007)] revealed that: (1) the value of metastable zone width for a solvent–anti‐solvent system is determined by the solute–solvent and solute–anti‐solvent interactions, (2) the dependence of the metastable zone width on stirring is associated with the enthalpy of mixing, and (3) the new approach predicts a threshold anti‐solvent addition rate associated with the setting up of an equilibrium between solvent and anti‐solvent and a maximum anti‐solvent addition rate connected with the induction period t_ind for the onset of crystallization. (© 2010 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Determination of nucleation kinetics of lovastatin in acetone solution

The metastable zone widths of lovastatin in acetone solution were determined at different temperatures, cooling rates and initial concentrations by polythermal method. It decreases with the increase of temperature and initial concentration, increases with the increase of cooling rate. The induction periods of lovastatin in acetone solution were also investigated as a function of supersaturation ratios. The crystal‐liquid interfacial tension, thus the fundermental nucleation parameters including Gibbs free energy change for the formation of critical nucleus, radius of critical nucleus and number of molecules in the critical nucleus have been gotten based on the classical homogeneous nucleation theory. (© 2010 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Damage of semicrystalline polyamide 6 assessed by 3D X-ray tomography: From microstructural evolution to constitutive modeling

In this study an attempt is made to link the damage and microstructural evolution of semicrystalline polymers, in particular polyamide 6, to the macroscopic material behavior during tensile and creep tests. Tensile specimens, removed before failure were seen to have undergone striction. They were examined using synchrotron radiation tomography. These samples showed elongated axisymmetric columns of voids separated by thin ligaments of material. These observations were confirmed and refined through a cryofractography experiment of a different tensile sample, stopped before failure. An attempt was made to obtain quantitative data about void volume fraction and morphology through image analysis. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 48: 1516–1525, 2010     

Two-step stacking in capillary zone electrophoresis featuring sweeping and micelle to solvent stacking: I. Organic cations

Two-step stacking of organic cations by sweeping and micelle to solvent stacking (MSS) in capillary zone electrophoresis (CZE) is presented. The simple procedure involves hydrodynamic injection of a micellar sodium dodecyl sulfate solution before the sample that is prepared without the micelles. The micelles sweep and transport the cations to the boundary zone between the sample and CZE buffer. The presence of organic solvent in the CZE buffer induces the second stacking step of MSS. The LODs obtained for the four beta blocker and two tricyclic antidepressant test drugs were 20-50 times better compared to typical injection.     

Simultaneous determination of substrate and product in the process of preparation of valienamine by capillary zone electrophoresis

A simple and rapid CZE method was established for the simultaneous determination of valienamine, acarbose and validamycin A, using a 20‐kV CZE with the detection wavelength of 193 nm and 50 mM phosphoric acid–20 mM Tris (pH 5.3) as a running buffer. The calibration curves of valienamine, acarbose, and validamycin A showed a good linear relationship at a concentration range of 5–1000 μg/mL. The detection limits of valienamine, acarbose, and validamycin A were 0.3, 0.6, and 0.6 μg/mL, respectively, and the average recoveries of each of the above were 99.9, 99.5, and 100.3%. The method has been successfully applied for simultaneous determination of substrate and product in the process of preparation of valienamine.     

近岸缓流区河道动能修正系数的研究

动能修正系数值是工程一维数学模型计算中应考虑的主要因素,其通常取值为1,但动能修正系数常规取值对边侧存在近岸缓流区的天然河道并不适用。从动能修正系数的定义出发,对近岸缓流区河道动能修正系数作理论推导,同时结合水槽概化模型试验对公式进行验证。得到了近岸缓流区河道动能修正系数的计算方法和沿程变化的一些规律。相关成果可为工程中涉及近岸缓流区河道一维数学模型计算提供参考。     

气浮池接触区微气泡粒径及气含率分布实验研究

气浮技术作为高效清洁的除油工艺,常用于密度相近的液-液两相流或水中悬浮颗粒的分离。作为微气泡的产生及微气泡与油滴等悬浮物质黏附的场所,气浮池接触区水利流动状态下的微气泡粒径及气含率分布对除油效率有着重要影响。实验表明,溶气压力0.34 MPa时微气泡尺寸更小;双释放头能显著提高气含率;接触区宽度较小时,湍动作用加强微气泡聚并严重;表面活性剂浓度能降低表面张力,有效抑制微气泡聚并;最佳浓度为0.5 mg/L时,平均尺寸维持在65~70μm。     

Two-dimensional electrophoresis on a microfluidic chip for quantitative amino acid analysis

Analysis of complex biological samples requires the use of high-throughput analytical tools. In this work, a microfluidic two-dimensional electrophoresis system was developed with mercury-lamp-induced fluorescence detection. Mixtures of 20 standard amino acids were used to evaluate the separation performance of the system. After fluorescent labeling with fluorescein isothiocyanate, mixtures of amino acids were separated by micellar electrokinetic chromatography in the first dimension and by capillary zone electrophoresis in the second. A double electrokinetic valve system was employed for the sample injection and the switching between separation channels. Under the optimized conditions, 20 standard amino acids were effectively separated within 20 min with high resolution and repeatability. Quantitative analysis revealed linear dynamic ranges of over three orders of magnitudes with detection limits at micromolar range. To further evaluate the reliability of the system, quantitative analysis of a commercial nutrition supplement liquid was successfully demonstrated. Figure       

南盘江地区紫云变形带分段特征

利用实测南盘江地区紫云变形带(镇宁-桑郎一段)的几条构造剖面及前人资料,分析了沿紫云变形带不同段落的几何学特征、变形样式及运动学特征.紫云变形带上的分段运动特点十分显著.北段(大花哨段)变形卷入地层主要为二叠系-三叠系,变形样式以一系列倾角较缓的逆冲断层和箱状、尖棱褶皱为主,表现出卷入地层相对较新、主滑脱面相对较浅(下三叠统)的表皮逆冲构造的特点.南段(紫云段)变形卷入地层为中泥盆统-三叠系,变形样式以一系列高角度逆冲断层、构造直立带和尖棱状褶皱、揉皱为主,表现为卷入地层相对较早、主滑脱面相对较深(中泥盆统)的薄皮大型倒转背斜.这种差异是由北段位于威宁断陷带和广西裂谷带的交接部位,裂陷较浅,沉积以刚性较强的浅水碳酸盐沉积为主;而南段位于广西裂谷带内,沉积以较软的盆地相泥岩、硅质岩为主造成的.解剖变形带不同段落的沉积、变形特征可更好地研究变形带不同部位的构造特征.     

Aspects of ionic diffusion through thick matrices of charged particles

A review of the literature on ionic diffusion through matrices of charged particles shows that many workers have reported higher diffusivity of co-ions than of counterions. If these observations are correct then the requirement of electroneutrality of bulk solutions is violated. In those experiments other, not looked for, ions must have been taking part. It therefore appears that complete chemical analyses of solutions of both up- and downstream sides should be carried out, otherwise misleading inferences may be drawn, with practical consequences. Some researchers have studied transport of water under osmotic pressure differentials across clay membranes. However, a diffusing ion, during its transport from higher concentration to lower concentration, always carries its water of hydration. This second water transport process has not received attention. This suggests that at a critical concentration two transport processes will cancel each other. Attention has been drawn to this second type of water flow and its consequences. In ionic diffusion, each side of the membrane-outside solution interface is subject to the effects of the Nernst layer and Donnan zone. However, these layers and zones are seldom treated quantitatively. This has been carried out in this paper by two different methods. Both methods give identical thicknesses of the Nernst layer and Donnan zone. Finally, the effects of the presence of soluble bivalent salts on the diffusivity of different types of ions have been commented up on. In these cases some of the co-ions diffuse to the upstream side.