Turbulent flow technique for the estimation of oxygen diffusive permeability of membranes for the oxygenation of blood and other cell suspensions

When transport-efficient membrane modules (such as those where the liquid flows outside hollow fibre membranes) or membranes with prolonged resistance to wetting are used for the oxygenation of blood or other cell suspensions, membrane contribution to the overall oxygen transfer resistance into the liquid may become significant. Thus, estimation of membrane diffusive permeability towards relevant gases (e.g., oxygen) is important to develop new membranes and to ensure reproducible commercial membrane performance.

In this paper, we report on a turbulent flow technique for the estimation of the oxygen diffusive permeability of membranes used in outside-flow oxygenators. Water is re-circulated under turbulent flow conditions in a closed-loop from a reservoir to the shell of lab-scale membrane modules. The overall oxygen transfer to water coefficient is estimated at increasing water flow rates from the time the change of dissolved oxygen tension in the stream leaving the water reservoir occurs. Oxygen diffusive permeability is estimated as the reciprocal overall transfer resistance at infinitely high water flow rates, for negligible gas-side oxygen transport resistance. The technique was used to estimate oxygen diffusive permeability of commercial Oxyphan^® polypropylene membranes for blood oxygenation and of two laboratory polypropylene membranes, the one featuring a microporous wall structure with smaller-than-standard pore size, the other featuring an outer thin, dense layer supported by a thick spongy layer. The turbulent flow technique yields oxygen diffusive permeability estimates consistent both with membrane hydraulic permeability towards gaseous nitrogen, membrane wall structure, and with values in literature obtained using a liquid reactive with oxygen, but without the complications associated with reaction and physical transport kinetic characterisation. We conclude that the turbulent flow technique is a useful tool in the development and quality control of membranes for the oxygenation of blood and other cell suspensions.     

化学探头法与荧光光谱法测定水中溶解氧量

探讨了化学探头法和荧光光谱法测定水中溶解氧的关系。分别用F检验和t检验对两组数据进行了比较,结果表明两组数据的精密度和系统误差都没有显著差异,两种方法测定溶解氧的相对标准偏差(RSD,n=9)分别为0.35%,0.33%。进而又探讨了溶解氧与NaCl含量、温度之间的关系,结果表明溶解氧含量随NaCl含量的增加、温度的升高而逐渐降低。     

水中溶解氧的微量滴定

将微量滴定技术应用于常规的碘量法测定水中溶解氧。在实验中采用了WD-CO3型微量滴定装置,并使用自行设计制成的高精度微量移液管（移液的体积可准确至0．001mL）,作为转移标准溶液及试样溶液的工具。对微量滴定及微量移液与常量滴定和常量移液作了对比试验,结果表明两者的分析结果完全吻合,微量滴定（其中包括微量移液）所得结果的精密度也在定量分析允许范围之内。由此,微量滴定技术应用于水中溶解氧的日常分析的可行性得到了验证。     

Oxygen permeability and the state of water in Nafion® membranes with alkali metal and amino sugar counterions

The mobility of hydration water and the dissolved oxygen permeability through different cation forms of the Nafion^® membranes were determined. Two alkali metals (Na and K) and two amino sugars (an equivalent molar mixture of d-glucopyranosyl-α(1′ → 6)-2-amino-2-deoxy-d-mannitol and its sorbitol (GPA)and d-glucosamine (GLU)) were used as counterions. Based on the two-state model, the content and mobility of hydration water were determined using DSC and ¹⁷O NMR. The dissolved oxygen permeability through the Nafion^® membrane containing GPA was the lowest value in this study because, for the membrane, the fraction of hydration water was the greatest and the mobility of hydration water was the lowest. The amount and location of the hydrophilic group contained in substances as well as the kind of hydrophilic group affected the fraction and mobility of hydration water and dissolved oxygen permeability through the membranes.     

A flow system for calibration of dissolved oxygen sensors

Well-defined oxygen standard solutions were obtained by the electrolysis of water in a coulometric oxygen generator. The generator was integrated into a flow system that includes the degassing of the carrier electrolyte, the generation of dissolved oxygen and the temperature control of the carrier electrolyte. The current efficiency of oxygen generation was found to be 100% by the Winkler titration method. Calibrations of a home made laboratory sensor and a WTW CellOx dissolved oxygen sensor have been made in a concentration range of 0.02 to 8 mg/L at temperatures from 5°C to 30°C. The calibration of the WTW sensor on water vapour saturated air was compared with the electrochemical calibration method. Both methods gave reliable results provided that the temperature equilibration between the sensor and the ambient air was successful. Received: 24 March 1997 / Revised: 15 May 1997 / Accepted: 15 May 1997     

How the structural and physicochemical properties of polyacrylamide/alginate hydrogel influence its oxygen permeability

Interpenetrating hydrogels based on sodium-alginate and crosslinked poly(acrylamide) were studied in term of their oxygen permeability. Such properties as the equilibrium water content, the free water content and the porosity are known to be preponderant for the oxygen transport through hydrated polymeric materials but are also strongly affected by the crosslinking density of the network. In the present work, these relations were studied and described. The amount of non-bound adsorbed water was determined thanks to DSC analysis. The thermoporosity method allowed the evaluation of the apparent hydrogel porosity and the electrochemical polarographic method was applied for determining the oxygen permeability level. Relations between oxygen transport properties, “free water” content and structural parameters of polymer networks were discussed.     

Thin layer gas electrode and its application to measurement of dissolved oxygen

A novel thin layer cell equipped with thin layer gas electrode (TLGE) was studied as electrochemical gas sensor for the measurement of dissolved oxygen in water or aqueous solutions. The working electrode (TLGE) is a hydrophobic gas diffusing electrode placed between the cell electrolyte and the solution to be tested. The hydrophobic pores in TLGE serve as a gas chamber. After the sampling period, in which the partial pressure of dissolved oxygen in test solution becomes in equilibrium with that in the gas chamber, the TLGE is polarized with square wave or linear potential signal. Then the Faradaic charge (Q) consumed in depletion of the oxygen contained in pores of TLGE is measured. The main merits of this system are good linearity between the partial pressure of dissolved oxygen in test solution and Q, low zero-reading, negligible liquid-gas difference, convenient calibration and very low temperature coefficient (ca. 0.5%/°C). This technique can also be applied to the measurement of oxygen partial pressure in gas phases.     

Influence of Mg^2＋ on Initial Stages of CaCO3 Scale Formed on Metal Surface

Magnesium ions, which exist in formation water and injection water under downhole conditions in the oil and gas production industry, are a key determinant in the CaCO3 scale formation. Many studies have focused their attention on the effect of magnesium on the kinetics, the morphology and the content of Mg in the Ca-CO3 scale. Little attention has been paid to the effect of Mg^2 on the initial stages of CaCO3 formation on a metal surface. In this study, an electrochemical technique was used to study the influence of Mg^2 on the ini-tial stages of CaCO3 scale formed on a metal surface. With this electrochemical technique, the reduction of the dissolved oxygen in an analysis solution is considered on the surface of a rotating disk electrode (RDE) un-der potentiostatic control. The rate of oxygen reduction on the surface of the RDE enables the extent of sur-face coverage of scale to be assessed. With this electrochemical technique, a new insight into the effect of Mg^2 on CaCO3 scale formed on a metal surface is given.     

Ta/BDD薄膜电极电化学催化氧化硝基酚

研究了热丝化学气相沉积法(HFCVD)制备得到钽衬底掺硼金刚石膜电极(Ta/BDD)的物理性质和电势窗口, 并考察了其用于电化学催化氧化硝基酚过程中的性能及各种影响因素. 扫描电镜和拉曼光谱表明, Ta/BDD电极具有良好的物理性能, 通过测试Ta/BDD电势窗口发现, 该电极具有较高的析氧过电位. 在Ta/BDD电化学催化氧化硝基酚过程中, 化学需氧量(COD)和高效液相色谱测试表明, 硝基酚能够有效降解, 电流密度、支持电解液及浓度对降解过程影响较大, 温度影响不明显. 强化寿命实验表明, Ta/BDD电极具有较好的稳定性. 实验结果表明, Ta/BDD电极是一种适于硝基酚降解和COD去除的优良电极.     

The repassivation kinetics study of Alloy 800 in high-temperature pressurized water

The repassivation kinetics of Alloy 800 is studied in high-temperature pressurized water with different dissolved hydrogen (DH) and dissolved oxygen (DO) at 300 °C. The results demonstrate that under DO conditions, the cBV value increases with the rise of DO concentration; and under DH conditions, the cBV value passes through a local maximum at DH = 1.0 ppm. In addition, the repassivation results in the present work confirm the applicability of the slip-dissolution model for explaining stress corrosion cracking in high-temperature pressurized water by means of electrochemical measurement. Compared with other methods of evaluating stress corrosion cracking susceptibility of engineering materials, studying the repassivation kinetics by rapid scratch technique is a more economical and time-efficient evaluation method for nuclear materials in high-temperature pressurized water.     

Catalytic deoxygenation of high-purity water using membrane electrode units

A new method for water deoxygenation using membrane technologies was suggested. The method is based on electrochemical reduction of dissolved oxygen on the surface of membrane electrode units in combination with its chemical reduction with hydrogen on a catalytically active sorbent. A pilot setup for deoxygenation of high-purity water with the output of up to 200 L h^–1 was developed on the basis of the results obtained.     

Pulsed Deposited Manganese and Vanadium Oxide Film Modified with Carbon Nanotube and Gold Nanoparticle: Chitosan and Ionic Liquid‐based Biosensor

Present study describes the synthesis of mixed oxide films of manganese and vanadium by electrochemical pulsed deposition technique on a glassy carbon electrode (GCE) modified with multiwall carbon nanotubes (MWCNT). The film was further decorated with gold nanoparticles to enhance the reduction signal of dissolved oxygen in pH 5.17 acetate buffer solution. All of the electrochemical synthesized modified electrodes have been characterized with Scanning electron microscopy(SEM), High‐resolution transmission electron microscopy (HRTEM), X‐Ray photoelectron spectroscopy (XPS), X‐Ray diffraction (XRD) techniques. The electrode obtained (AuNPs/MnOx?VOx/CNT/GCE) was utilized as a platform for glucose biosensor where the glucose oxidase enzyme was immobilized on the composite film with the aid of chitosan and an ionic liquid. The electrochemical performance of the biosensor was investigated by cyclic voltammetry and the relative parameters have been optimized by amperometric measurements in pH 5.17 acetate buffer solution. The developed biosensor exhibited a linear range for glucose between 0.1–1.0 mM and the limit of detection was calculated as 0.02 mM.     

A Novel Cell Design for the Improved Stripping Voltammetric Detection of Zn(II), Cd(II), and Pb(II) on Commercial Screen‐Printed Strips by Bismuth Codeposition in Stirred Solutions

A novel electrochemical cell design is proposed to allow fast, reproducible and highly efficient convective transport of dissolved substances to screen‐printed electrochemical three‐electrode strips mounted on miniaturized plastic vessels, with the goal of improving detection limits in disposable electrochemical stripping field sensors. The experimental configuration has been tested for accumulation of the selected heavy metals ions Zn(II), Cd(II), and Pb(II), codeposited with bismuth ions on a carbon disk screen‐printed working electrode before detection by square wave anodic stripping voltammetry. Chemical and instrumental variables of the proposed device and associate electrochemical method were optimized. Selected parameters gave detection limits in the low ng mL^?1 range with moderate deposition time (120 s). Practical applicability was tested on certified water and real samples (tap water and waste water), with acceptable results, suggesting potential usefulness for field environmental monitoring of heavy metals.     

含活泼质子水溶性化合物的核磁共振结构解析

利用核磁共振对在水溶剂易溶且含活泼质子的化合物的结构进行解析.实验中将待测样品直接溶解于二次去离子水中,并利用外标进行锁场.这样既保证了核磁共振实验的正常进行,同时避免了实验中氘代试剂对活泼质子的置换效应,为化合物中活泼质子的定位提供了直接的依据.为了保证外标锁场实验核磁共振谱图的质量,本工作采用了溶剂峰压制的核磁共振实验技术,获取了一组高质量的1D、2D谱图,并在此基础上顺利完成了对头孢米诺盐的结构确定.     

Determination of nickel,cobalt, copper and uranium in water by cathodic stripping chronopotentiometry with continuous flow

The potential of cathodic stripping chronopotentiometry for the determination of trace metals in a continuous-flow system is investigated. An automated analyzer with a fast rate of data acquisition (250 kHz) is described. The cathodic scans are preceded by adsorptive collection of surface-active metal complexes on the hanging mercury drop electrode. The scans are done by passing a constant current of between 0.8 (in deaerated solution) and 60 μA (in solutions saturated with air) through the working electrode. Copper, uranium, and nickel can be determined in the presence of dissolved oxygen, but the sensitivity for nickel is then much reduced. The sensitivity of stripping chronopotentiometry in the presence of dissolved oxygen is similar to that of fast linear-sweep voltammetry in the absence of dissolved oxygen. The limits of detection were 0.1 nM Ni, 0.1 nM Co, 1.8 nM Cu and 1.6 nM U, when the measurements were preceded by 60-s stirred adsorption; in the presence of dissolved oxygen the limit of detection for nickel was higher at 0.6 nM, and cobalt could not be determined, as its peak was located on top of the oxygen peak. The determinations of copper and uranium were not adversely affected by dissolved oxygen. The limits of detection can be lowered further by using a prolonged collection period (up to 300 s). The technique was successfully tested by measuring nickel with continuous flow in water pumped on board of a small vessel in the Tamar estuary.     

血红素LB膜的电化学行为

采用循环伏安法研究了血红素与脑磷脂混合Y型LB（Langmuir-Blodgett）膜在玻碳电极上的电化学行为，结果表明血红素LB膜有良好的电化学活性，在0．1mol/L KCl溶液中有一对氧化还原峰（－0．42V／－0．30V）；将血红素LB膜转移到玻碳电极表面得到的血红素LB膜修饰电极（heme LB-GC）对溶液中溶解氧的电化学还原有良好的催化作用，其催化还原过程具有不可逆电荷传递特性。     

A solid composite electrode for the determination of the electrochemical oxygen demand of aqueous samples

A composite electrode containing graphite, paraffin, AgO and CuO is described for the determination of the electrochemical oxygen demand (EOD) of waste waters. The oxidation of dissolved organic compounds at the electrode is based on a heterogeneous chemical reaction of AgO/CuO with the organic constituents of the waste water. This chemical reaction can be followed by a solid state electrochemical oxidation of the formed Ag₂O/Cu₂O. The method has been tested with various organic compounds and applied to real samples of sewage water. The EOD values correlate well to BOD and COD values.     

Screen-printed dissolved oxygen sensor based on cerium oxide-supported silver catalyst and polydimethylsiloxane film

A screen-printed dissolved oxygen sensor was fabricated using cerium oxide-supported silver catalyst and polydimethylsiloxane (PDMS) film. A PDMS film of 3 μm thickness showed good permeability for oxygen and impermeability for hydrogen peroxide. The calibration curve has shown a linear relationship with a correlation coefficient of 0.996 for the dissolved oxygen concentration. The sensitivity and detection limit of the present sensor were calculated at -158 μA mM(-1) and 8.4 μM, respectively.     

基于电化学方法测定饮用水源水中的痕量铜离子

本文建立了一种饮用水源水中痕量溶解态铜离子（Cu²⁺）的定性和定量电化学检测方法. 该方法首先通过电化学循环伏安法于玻碳电极表面制备粒径约为70 nm的金纳米粒子（Au NPs）,然后采用方波阳极溶出伏安法进行待测水样中Cu²⁺的定性定量分析. 研究结果表明,对于标准溶液,方法的检出限为1.3μg·L^-1,线性范围在2 ~ 50μg·L^-1之间,常见重金属离子对其定性定量分析几无影响. 在此基础上,将该方法应用于福建省重要的饮用水源水--闽江中游水样中Cu²⁺的含量分析,所得测试结果与国家标准方法（石墨炉原子吸收光谱法）无显著性差异,标准偏差在20%以内. 本方法具有电极制备简单、测定成本低以及分析快速等优点,进一步优化电极制备方法以提高方法的重现性和定量准确度,将可望用于现场测定各种饮用水源水中的痕量溶解态Cu²⁺.     

Hybride process,microfiltration-electroperoxidation,for water treatment

Cross-flow microfiltration through a 0.8 μm inorganic tubular membrane was enhanced by coupling with a two electrode electrolysis cell producing hydrogen peroxide at high rate, without adding any chemical, by use of carbon felt cathode and dimensional stabilised anode (titanium coated with RuO₂). Anodic oxygen and transfer from atmosphere supplied the required oxygen. The current should be maintained under a maximum value to avoid peroxide reduction. This electrochemical process, called electroperoxidation, upgraded the water quality by removing contaminants that limit mass transport through the membrane, i.e. turbidity, dissolved organic carbon (DOC) and microorganisms. Transient filtration was adjusted to an internal clogging model whose coefficient decreased at the same rate as DOC. The microfiltration steady state flux was multiplied by a factor proportional to the peroxide concentration introduced in the filtration loop. The induced resistance decreased simultaneously with chemical oxygen demand and 254 nm absorbance. Steady state fluxes 2.5 times higher than without treatment were experimentally obtained.