• Bulletin of the Korean Chemical Society
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• v.32 no.3
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• pp.768-778
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• 2011

Calixpyrroles and related macrocycles are non-planer synthetic anion receptors that have attracted considerable attentions in recent years. Although the synthesis of calix[4]pyrrole (known as meso-octamethylporphyrinogen) was reported more than 100 years ago, the anion binding properties were first discovered in 1996. The simple calix[4]pyrroles can be synthesized in single step in high yield by condensation of pyrrole with acetone. The compounds showed preferential binding for halide anions including fluoride, phosphate, carboxylate, and chloride in organic media. Efforts to improve the anion affinity of calix[4]pyrrole and to enhance its selectivity have led to the synthesis of a variety of new calixpyrrole derivatives. Among the various modifications, introduction of straps on one side of the calix[4]pyrroles are the most effective. Incorporation of aromatic rings other than pyrroles also exhibited interesting binding behaviour. Introduction of signalling units as part of the strapping element enable to detect the anions on chromogenic or fluorogenic fashion. Finding of the anion transport properties across the membrane and cytotoxic effects of the calix[4]pyrroles open new window for calixpyrrole-related research. The polymer-incorporated systems have also been employed as anion complexants in solvent-solvent extraction. These old, yet easy-to-make macrocycles have well advanced more recently with the discovery of the ion-pair complexation properties. In this review, the synthetic developments and anion binding properties of calixpyrroles for the last decades will be discussed and will cover the advances in calixpyrrole chemistry.

• Membrane Journal
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• v.26 no.6
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• pp.432-448
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• 2016

In the last decade, various types of energy harvesting and conversion systems based on ion exchange membranes (IEMs) have been developed for eco-friendly power generation and energy-grid systems. In these membrane-based energy systems, high ion selectivity and conductivity properties of IEMs are critical parameters to improve efficiency of the systems such as proton exchange membrane fuel cells, anion exchange membrane fuel cells, redox flow batteries, water electrodialysis for hydrogen production, and reverse electrodialysis. This article suggests variable approaches to overcome trade-off limitation of polymeric membrane ion transport properties by reviewing various types of composite ion-exchange membranes including novel inorganic-organic nanocomposite membrane, surface modified membranes, cross-linked and pore-filled membranes.

• Membrane Journal
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• v.32 no.6
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• pp.486-495
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• 2022

This study presents the improved recovery efficiency of rare metal ions through the modified separation membrane wettability and hydrogen ion permeation in the anion exchange membrane (AEM) under the recovery process of combined electrodialysis and solvent extraction. Specifically, the wettability of the separator was enhanced by hydrophilic modification on one separator surface through polydopamine (PDA) and lipophilic modification on the other surface through SiO₂ or graphene oxide (GO). In addition, the modified surface of AEM with polyethyleneimine (PEI), PDA, poly(vinylidene fluoride) (PVDF), etc. reduces the water uptake and modify the pore structure for proton ions generation. The suppressed transport resulted in the reduced hydrogen ion permeation. In the characterization, the surface morphology, chemical properties and composition of membrane or AEM were analyzed with Scanning Electron Microscopy (SEM) and Fourier Transform-Infrared Spectroscopy (FT-IR). Based on the analyses, improved extraction and stripping and hydrogen ion transport inhibition were demonstrated for the copper ion recovery system.

• Proceedings of the Korean Vacuum Society Conference
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• 2013.02a
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• pp.263-263
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• 2013

This work examines the dynamic properties of ice surfaces in vacuum for the temperature range of 140~180 K, which extends over the onset temperatures for ice sublimation and the phase transition from amorphous to crystallization ice. In particular, the study focuses on the transport processes of excess protons and chloride ions in ice and their segregative behavior to the ice surface. These phenomena were studied by conducting experiments with a relatively thick (~100 BL) ice film constructed with a bottom $H_2O$ layer and an upper $D_2O$ layer, with excess hydronium and chloride ions trapped at the $H_2O$/$D_2O$ interface as they were generated by the ionization of hydrogen chloride. The migration of protons, chloride ions, and water molecules to the ice film surface and their H/D exchange reactions were measured as a function of temperature using the methods of low energy sputtering (LES) and Cs+ reactive ion scattering (RIS). Temperature programmed desorption (TPD) experiments monitored the desorption of water and hydrogen chloride from the surface. Our observations indicated that both hydronium and chloride ions migrated from the interfacial layer to segregate to the surface at high temperature. Hydrogen chloride gas desorbs via recombination reaction of hydronium and chloride ions floating on the surface. Surface segregation of these species is driven by thermodynamic potential gradient present near the ice surface, whereas in the bulk, their transport is facilitated by thermal diffusion process. The finding suggests that chlorine activation reactions of hydrogen chloride for polar stratospheric ice particles occur at the surface of ice within a depth of at most a few molecular layers, rather than in the bulk phase.

• Transactions of the Korean hydrogen and new energy society
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• v.10 no.4
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• pp.197-210
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• 1999

The hydrogen storage performance and electrochemical properties of $Zr_{1-X}Ti_X(Mn_{0.2}V_{0.2}Ni_{0.6})_{1.8}$(X=0.0, 0.2, 0.4, 0.6) alloys are investigated. The relationship between discharge performance and alloy characteristics such as P-C-T characteristics and crystallographic parameters is also discussed. All of these alloys are found to have mainly a C14-type Laves phase structure by X-ray diffraction analysis. As the mole fraction of Ti in the alloy increases, the reversible hydrogen storage capacity decreases while the equilibrium hydrogen pressure of alloy increases. Furthermore, the discharge capacity shows a maxima behavior and the rate-capability is increased, but the cycling durability is rapidly degraded with increasing Ti content in the alloy. In order to analyze the above phenomena, the phase distribution, surface composition, and dissolution amount of alloy constituting elements are examined by S.E.M., A.E.S. and I.C.P. respectively. The decrease of secondary phase amount with increasing Ti content in the alloy explains that the micro-galvanic corrosion by multiphase formation is little related with the degradation of the alloys. The analysis of surface composition shows that the rapid degradation of Ti-substituted Zr base alloy electrode is due to the growth of oxygen penetration layer. After comparing the radii of atoms and ions in the electrolyte, it is clear that the electrode surface becomes more porous, and that is the source of growth of oxygen penetration layer while accelerating the dissolution of alloy constituting elements with increasing Ti content. Consequently, the rapid degradation (fast growth of the oxygen-penetrated layer) with increasing Ti substitution in Zr-based alloy is ascribed to the formation of porous surface oxide through which the oxygen atom and hydroxyl ion with relatively large radius can easily transport into the electrode surface.

• Membrane Journal
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• v.26 no.2
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• pp.152-158
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• 2016

The Chlor-alkali (CA) membrane cell is a major electrolysis system to produce valued chemicals such as chlorine gas and sodium hydroxide. The CA membrane process has been attracted in the industries, since it has relatively low energy consumption when compared with other CA processes. The key component in CA process is perfluorinated sulfonic acid ionomer membranes, which provide ion-selectivity and barrier properties to produced gases. Unfortunately, there is limited information to determine which factors should be satisfied for CA applications. In this study, the influences of PFSA membranes on CA performances are disclosed. They include ion transport behaviors, gas evolution capability, and chemical/electrochemical resistances under CA operation conditions.

• Membrane Journal
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• v.30 no.6
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• pp.433-442
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• 2020

In this study, in order to build a molecular dynamics simulation model of ionomer for water electrolysis, an ionomer model that reflects the characteristics of a water electrolysis system in which excess water molecules exist was compared to an ionomer built according to the conventional simulation method of the fuel cells membrane. The final ionomer MD models have a strong phase separation and water channel that is one of the important characteristics of the perfluorinated ionomer, and are stable and water-insoluble under excessive water and high temperature conditions. In the ionomer MD models built in this study, the excess water molecules decrease an ion conductivity due to the dilution of ions, but increase a hydrogen diffusivity. Therefore, it is necessary to design the molecular structure of ionomers for water electrolysis in experimental studies as well as molecular dynamics studies according to the characteristics of the water electrolysis system reported in this study.

• Tuberculosis and Respiratory Diseases
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• v.40 no.3
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• pp.236-249
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• 1993

Background: Among the injurious agents to which the lung airspaces are constantly exposed are reactive species of oxygen. It has been widely believed that reactive oxygen species may be implicated in the etiology of lung injuries. In order to elucidated how this oxidant causes lung cell injury, we investigated the effects of exogenous $H_2O_2$ on alveolar epithelial barrier characteristics. Methods: Rat type II alveolar epithelial cells were plated onto tissue culture-treated polycarbonate membrane filters. The resulting confluent monolayers on days 3 and 4 were mounted in a modified Ussing chamber and bathed on both sides with HEPES-buffered Ringer solution. The changes in short-circuit current (Isc) and monolayer resistance (R) in response to the exogenous hydroperoxide were measured. To determine the degree of cellular catalase participation in protection against $H_2O_2$ injury to the barrier, experiments were repeated in the presence of 20 mM aminotriazole (ATAZ, an inhibitor of catalase) in the same bathing fluid as the hydroperoxide. Results: These monolayers have a high transepithelial resistance (>2000 ohm-$cm^2$) and actively transport $Na^+$ from apical fluid. $H_2O_2$(0-100 mM) was then delivered to either apical or basolateral fluid. Resulting indicated that $H_2O_2$ decreased Isc and R gradually in dose-dependent manner. The effective concentration of apical $H_2O_2$ at which Isc (or R) was decreased by 50% at one hour ($ED_{50}$) was about 4 mM. However, basolateral $H_2O_2$ exposure led to $ED_{50}$ for Isc (and R) of about 0.04 mM. Inhibition of cellular catalase yielded $ED_{50}$ for Isc (and R) of about 0.4 mM when $H_2O_2$ was given apically, while $ED_{50}$ for basolateral exposure to $H_2O_2$ did not change in the presence of ATAZ. The rate of $H_2O_2$ consumption in apical and basolateral bathing fluids was the same, while cellualr catalase activity rose gradually with time in culture. Conclusion: Our data suggest that basolateral $H_2O_2$ may affect directly membrane component (e.g., $Na^+,\;K^+$-ATPase) located on the basolateral cell surface. Apical $H_2O_2$, on the other hand, may be largely degraded by catalase as it passes through the cells before reaching these membrane components. We conclude that alveolar epithelial barrier integrity as measured by Isc and R are compromised by $H_2O_2$ being relatively sensitive to basolateral (and insensitive to apical) $H_2O_2$.