Free-solvent model shows osmotic pressure is the dominant factor in limiting flux during protein ultrafiltration

In protein ultrafiltration (UF), the limiting flux phenomenon has been generally considered a consequence of the presence of membrane fouling or the perceived formation of a cake/gel layer that develops at high operating pressures. Subsequently, numerous theoretical models on gel/cake physics have been made to address how these factors can result in limiting flux. In a paradigm shift, the present article reestablishes the significance of osmotic pressure by examining its contribution to limiting flux in the framework of the recently developed free solvent osmotic pressure model. The resulting free-solvent-based flux model (FSB) uses the Kedem–Katchalsky model, film theory and the free solvent representation for osmotic pressure in its development. Single protein tangential-flow diafiltration experiments (30 kDa MWCO CRC membranes) were also conducted using ovalbumin (OVA, 45 kDa), bovine serum albumin (BSA, 69 kDa), and immuno-gamma globulin (IgG, 155 kDa) in moderate NaCl buffered solutions at pH 4.5, 5.4, 7 and 7.4. The membrane was preconditioned to minimize membrane fouling development during the experimental procedure. The pressure was randomly selected and flux and sieving were determined. The experimental results clearly demonstrated that the limiting flux phenomenon is not dominated by membrane fouling and the FSB model theoretically illustrates that osmotic pressure is the primary factor in limiting flux during UF. The FSB model provides excellent agreement with the experimental results while producing realistic protein wall concentrations. In addition, the pH dependence of the limiting flux is shown to correlate to the pH dependency of the specific protein diffusion coefficient.     

Novel membrane-based sensor for online membrane integrity monitoring

A novel membrane-based sensor device for upstream membrane integrity monitoring has been developed and evaluated in this study. The sensor is based on relative trans-membrane pressures created by two membranes in series inside the sensor device that detects deposition from the sample stream onto the first of the sensor membranes. The sensor pressure signals can distinguish between intact or damaged membranes in the upstream membrane filtration process. Studies were conducted to evaluate both stabilities and sensitivities of the relative trans-membrane pressure monitoring technique. Sensitivity, based on the response times of the membrane sensor for particle detection, was determined for a range of operating conditions, membrane sandwich configurations, and particle concentrations in both simulated membrane failures and for actual pin-hole defects on a submerged MF membrane. The results showed that both sensitivities and stability strongly depended on membrane sandwich configurations (membrane characteristics) in the sensor, and mode of operation (pressurized or vacuum). The membrane sensor detected bentonite particles with a concentration of 0.3 mg/L (turbidity ∼0.3 NTU) in approximately 35 min in the vacuum mode. The sensor is reliable, sensitive and low cost. It has potential applications in decentralized systems or in multichannel monitoring of local conditions in a large plant. Possible applications of the membrane sensor for fouling monitoring are also discussed.     

Methane formation from CaCO3 reduction catalyzed by high pressure

Under high pressures of several giga-pascals using hydrothermal diamond anvil cell,methane generated directly from CaCO3 reduction in gold-lined chamber is in situ measured by Raman spectroscopy at the temperature of 550℃ Fhe reducing agents include FeO,SiO and natural fayalite（Fe2SiO4）,and the resource of hydrogen are water and natural serpentine（Mg3Si2O5（OH）4）. The study demonstrates the existence of abiogenic formation of methane under high pressures in the Earth＇s interior and that the application of high pressure to catalyze multicomponent reactions is a very promising method.     

Economic aspects of critical flux operability in star shaped microfiltration membranes: Influence of some operating conditions

The economic feasibility of operating at the achievable critical flux under different operating parameters (feed concentration, crossflow velocities and pH) using non-circular channelled membranes has been investigated. The increase in critical fluxes with increasing crossflow velocities is accompanied by increasing axial pressure loss. This leads to substantial increase in the specific energy consumption, reducing the energy-saving potential. Minimum specific energy consumption occurs at the crossflow velocity of 0.9 m s⁻¹ where the trade-off between axial pressure loss and the achievable critical flux occurs. Increasing the feed concentrations and pH led to declining and increasing critical fluxes, respectively. Axial pressure loss remains consistent at feed concentrations <10 g l⁻¹ and increases at feed concentrations >10 g l⁻¹. This is attributed to the change in the viscosity of the suspension which affects the specific energy consumption. The influence of pH on critical flux is attributed to the changes in the titanium dioxide particle charges and coincides with the changes in the viscosity of the suspension. The optimum energy-saving potential was found at pH 9.0. Solution chemistry (particle charges and rheology) and hydrodynamics influence the achievable critical flux and axial pressure loss within these channels which ultimately determine the economics of operation.     

Effect of pumping methods on transmembrane pressure, fluid balance and relative recovery in microdialysis

There is a growing interest in using large pore size probes for microdialysis of macromolecular markers to monitor cell and tissue functions. Fluid balance could be an important issue when using large pore size microdialysis probes, which are affected by the mode of operation. In this study, the effect of pumping systems, push, pull, push-and-pull, and the resulting transmembrane pressure on the fluid balance, as well as, the relative recovery of small molecular nutrients and metabolites and macromolecules (proteins) were examined. The validity of the internal reference in situ calibration was examined in detail. It is concluded that a push-and-pull system is the only effective method of eliminating fluid loss or gain. The relative recovery of small solutes is not affected much by the applied pumping methods; however, the relative recovery of macromolecules is significantly influenced by them. The in situ calibration technique using Phenol Red can provide reliable results for small molecules including glucose and lactic acid. Using 10 and 70-kDa fluorescent dextrans as the internal standard for large molecules in situ calibration of similar size does not work for the pull pump system, but does work well when using a push-and-pull pumping method.     

Ionic and pH effects on the osmotic properties and structure of polyelectrolyte gels

We investigate the effects of salt concentration and pH on neutralized poly(acrylic acid) (PAA) gels in near physiological salt solutions. Either adding calcium ions or decreasing the pH is found to induce reversible volume transitions but the nature of these transitions seems to be different. For example, the osmotic pressure exhibits a simple power law dependence on the concentration as the transition is approached in both systems, but the power law exponent n is substantially different in the two cases. On decreasing the pH the value of n gradually increases from 2.1 (at pH = 7) to 3.2 (at pH = 1). By contrast, n decreases with increasing calcium ion concentration from 2.1 (in 100 mM NaCl solution) to 1.6 (0.8 mM CaCl₂ in 100 mM NaCl solution). In both systems, a strong increase of the small-angle neutron scattering intensity (SANS) is observed near the volume transition. The SANS results reveal that calcium ions favor the formation of linearly aligned regions in PAA gels. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 2803–2810, 2008     

Di-hydroxybenzenes: Catechol, resorcinol, and hydroquinone: Enthalpies of phase transitions revisited

Molar enthalpies of sublimation of 1,2-di-hydroxybenzene, 1,3-di-hydroxybenzene, and 1,4-di-hydroxybenzene were obtained from the temperature dependence of the vapor pressure measured by the transpiration method. The molar enthalpies of fusion of 1,2- and 1,4-isomers were measured by differential scanning calorimetry (DSC). A large number of the primary experimental results on the temperature dependences of vapor pressure and phase transitions have been collected from the literature and have been treated in a uniform manner in order to derive sublimation, vaporization and fusion enthalpies of di-hydroxybenzenes at the reference temperature 298.15 K. The data sets on phase transitions were checked for internal consistency. This collection together with the new experimental results reported here has helped to resolve contradictions in the available thermochemical data and to recommend consistent and reliable sublimation, vaporization and fusion enthalpies for all three isomers under study.     

在线气体分析的电晕放电大气压电离质谱

研制了适合在线气体分析的电晕放电大气压电离源(corona discharge atmospheric pressure ionization source)及其与商品质谱仪(LTQ-MS)的接口,对其试剂离子的产生机理进行了研究,以H2O. (H2O)为试剂离子,对乙醇气体进行检测,并分析了该离子的产生机制。实验结果表明:在潮湿氮气中电晕放电产生的主要试剂离子是m/z36、37和55;而在含丙酮的潮湿氮气中则产生m/z59和76等离子。利用静态顶空-电晕放电大气压电离质谱对不同浓度的乙醇水溶液进行分析,结果表明:以m/z64为检测对象,乙醇气体浓度的最低检出限可达2.4×10-7g/L;而以m/z47为检测对象,检出限为5.9×10-6g/L。同时还利用动态顶空-电晕放电大气压电离质谱对栀子花香气成分进行了检测,为生物挥发性物质的在线检测提供了一种新方法。     

基于增量式PID控制的全静压测试系统设计

针对现阶段全静压测试设备结构复杂、价格昂贵,并且自动化程度低、测试效率低等问题,提出一种基于增量式PID控制的全静压测试系统的设计方法。系统通过STM32单片机完成核心控制任务,实现对密闭容器及管路中压力的精确控制,并完成压力的自动测量和相关飞行参数的显示。实验证明该系统具有响应速度快,超调量小等优点,并且能达到全静压系统测试精度的要求。该全静压测试系统成本低廉,通用性强,使用方便,测试周期短,适合于多种机型,具有较好有应用前景。