Kinetic considerations of ion selectivity coefficients of ion-selective electrodes based on neutral carriers

Ion selectivity coefficients of ion-selective electrodes based on neutral carriers are described by means of a mixed potential model of ion transport reactions at the aqueous solution/ion-sensitive membrane interface. The decrease in ion selectivity can be explained by the deviations from the equilibrium conditions, which arise from the ionic partial current across the interface, but the proposed correspondence of the exchange current density of ion transfer reactions with the ion selectivity coefficients is rationalized only for certain conditions of the kinetic parameters. The ion selectivity for liquid membrane transport is discussed starting from three different rate-determining steps. It is shown that the potentiometric selectivities of ion-selective electrodes and the transport selectivities are correlated when the ionic transfer across the aqueous solution/ membrane interface is fast compared with the complex ion transport through the membrane. The significance of a kinetic approach for the design of neutral carriers for ion-selective electrodes is stressed.     

Monitoring local spatial distribution of Mg2+, pH and ionic currents

Micro ion-selective electrode techniques can analyze concentration of particular ions at the solid–liquid interface from the side of solution being an alternative, or a complement, to methods based on potential and current changes across the interface. We report the successful application of ion-selective micro-electrodes for mapping local activity of Mg²⁺ and H⁺ (by scanning ion-selective electrode technique, SIET) as well as local ionic current density measurements (by scanning vibrating electrode technique, SVET) over the surface of Mg-based alloy in aqueous chloride-containing solution. The local concentration of Mg²⁺ ions dissolved due to corrosion from artificial defects and pH changes together with cathodic and anodic currents are measured by combination of two selective and one vibrating microelectrodes. Combination of these techniques in one experiment gives a powerful tool for investigation mechanisms and kinetics of electrochemical corrosion processes in micro-confined zones.     

A flow injection system for measurement of chemical response time of microelectrodes

A system for the measurement of the chemical response time (response to a rapid change in ionic activity) of ion-selective microelectrodes is described. The system is based on the flow injection technique. Results are presented for microchloride and potassium ion-selective field effect transistors. It is shown that these devices are sufficiently fast to study transient intracellular processes occurring on a time scale of a few seconds.     

Utilization of photoinduced charge-separated state of donor-acceptor-linked molecules for regulation of cell membrane potential and ion transport

The control of ion transport across cell membranes by light is an attractive strategy that allows targeted, fast control of precisely defined events in the biological membrane. Here we report a novel general strategy for the control of membrane potential and ion transport by using charge-separation molecules and light. Delivery of charge-separation molecules to the plasma membrane of PC12 cells by a membranous nanocarrier and subsequent light irradiation led to depolarization of the membrane potential as well as inhibition of the potassium ion flow across the membrane. Photoregulation of the cell membrane potential and ion transport by using charge-separation molecules is highly promising for control of cell functions.     

离子选择性微电极用于原位测量离子扩散系数

扩散系数是描述物质扩散过程的重要参数,而用膜池法、放射性或荧光示踪法、分子动力学模拟等现有方法无法原位进行生物体系中离子扩散系数的实时测量。 本文利用离子选择性微电极响应迅速、高选择性、高灵敏度、高空间分辨率、对样品无污染等优势,通过分析单个植物细胞原生质体在培养液中破裂时所形成的离子浓度脉冲信号,建立了相应的点源扩散模型,推导出了描述离子浓度随时间变化的理论公式,并通过该公式对实验测得的脉冲信号进行拟合,得到了离子的扩散系数,从而建立了一种用离子选择性微电极原位测定离子扩散系数的新方法,并将其应用于芦荟细胞原生质体破裂时离子扩散系数的测定,得到了Ca²⁺、Na⁺和K⁺的扩散系数分别为(6.51±0.12)×10^-6、(2.93±0.15)×10^-5和(3.03±0.35)×10^-5 cm²/s。 对比发现,拟合得到的Ca²⁺、Na⁺和K⁺扩散系数均略高于已报道的数值(纯水中),这一现象的产生可能是因为原生质体是在低渗液中吸水膨胀,细胞膜内压力升高产生内外压力差,该压力差会加速细胞破裂时离子的扩散。 这一方法对生物体系无干扰,较好地解决了生物体系中离子扩散系数原位实时测量的难题。     

Potentiometric behavior of ion-selective electrodes to large cationic species modulated by decyl alcohol

The effect of 1-decanol on the potentiometric response of three ion-selective electrodes to large cationic species is analyzed. The electrodes were constructed with plasticized PVC membranes. The results suggest that 1-decanol alters the ionic transport through the membrane/water interface to an extent that depends on the strength of the active ion pair. The water solubility of the cation, its molecular weight, and the size of the ion pair seem to be relevant factors in this type of behavior. The potentiometric selectivity coefficients are also dependent on the presence of 1-decanol in the membrane. These results are similar to those already described in ion-selective electrodes with membranes capable of sensing anionic benzene sulfonate-type systems. Thus, the effect of the alcohol appears to be general by affecting mainly the membrane surface polarity.     

Study of the potential response of solid-state chloride electrodes at low concentration ranges

Ion-selective electrodes based on silver chloride precipitates have been investigated in the low concentration range, by use of a specially designed cell of small volume. Electrode potential measurements and silver determinations in the corresponding solutions by atomic-absorption spectrometry were made. The results prove that the potential response of these ion-selective electrodes in the low concentration ranges is governed by inequality of the ion concentrations in the boundary zone of the test solution contacting the electrode membrane. This is a result of adsorption-desorption processes, a dissolution process followed by recrystallization of the silver chloride at the electrode membrane surface, and photoreduction of silver ions at the electrode surface.     

Characterization of proton transport across a waveguide-supported lipid bilayer

Cellular energy transduction processes are often driven by transmembrane ion gradients, and numerous artificial biomembrane systems have been developed that allow for chemically or light-induced charge transport into/out of liposomes. Liposomal architectures, however, are not readily interfaced to a solid-state transducer. Formation of an ion gradient across a planar-supported membrane, "wired" to a substrate electrode, may ultimately allow utilization of the potential energy to drive other electrochemical processes. Described here is a novel conductive polymer/planar waveguide assembly that provides for highly sensitive transduction of proton transport across a planar-supported lipid bilayer (PSLB). A quinone proton shuttle is embedded in the PSLB, which is coupled to the planar optical waveguide electrode through a pH-sensitive, self-assembled conductive polymer film. Interfacial potential and absorbance changes in the conductive polymer film provide for sensitive characterization of transmembrane proton transport. The general and flexible nature of this architecture makes it adaptable to many different types of transmembrane transport chemistries, particularly light-activated systems.     

Ion channel formation from a calix[4]arene amide that binds HCl

The ion transport activity of calix[4]arene tetrabutylamide 1,3-alt 2 was studied in liposomes, planar lipid bilayers, and HEK-293 cells. These experiments, when considered together with (1)H NMR and X-ray crystallography data, indicate that calix[4]arene tetrabutylamide 2 (1) forms ion channels in bilayer membranes, (2) mediates ion transport across cell membranes at positive holding potential, (3) alters the pH inside liposomes experiencing a Cl(-) gradient, and (4) shows a significant Cl(-)/SO(4)(2)(-) transport selectivity. An analogue, calix[4]arene tetramethylamide 1, self-assembles in the presence of HCl to generate solid-state structures with chloride-filled and water-filled channels. Structureminus signactivity studies indicate that the hydrophobicity, amide substitution, and macrocyclic framework of the calixarene are essential for HCl binding and transport. Calix[4]arene tetrabutylamide 2 is a rare example of an anion-dependent, synthetic ion channel.     

Synthesis and Characterization of Thiacalix[4] arene Derivatives with Polymerisable Groups

Introduction Calixarenes are versatile host molecules for molecular recognition and supram olecular assembly be-cause its functional groups can be readily introduced in-to the phenolic OH or the para position to realize a wide variety of functions[1-5].     

冠醚对生物化学影响的研究(Ⅲ)——五种冠醚化合物对小麦幼苗根系吸收与运转42K、24Na、45Ca离子的影响

本文用放射性同位素⁴²K、²⁴Na、⁴⁵Ca作示踪,配以P^K、P^Na离子选择电极测量溶液的电导率和电位变化。研究五种冠醚化合物对南大八号小麦幼苗根系吸收与运转无机离子(K⁺、Na⁺、Ca^艹)的作用。实验结果表明,五种冠醚化合物对小麦幼苗根系具有不同程度的促进吸收和加速运转K⁺、Na⁺、Ca^艹的作用,其中以1号冠醚化合物作用最为明显,在K⁺、Na⁺、Ca⁺艹>中对K⁺的作用最为突出。     

The influence of Triton X-100 ionophorous detergent on the transport kinetics of the tetramethylammonium cation through the human erythrocyte membrane

Triton X-100 facilitates the transport of tetramethylammonium cations (TMA⁺) through the human erythrocyte membrane in vitro. These changes manifest themselves as the disappearance of the characteristic minimum of the function erythrocyte electrophoretic mobility plotted versus time, normally observed in the presence of TMA⁺ ions. The incorporation of Triton X-100 molecules into the erythrocyte membrane induces both an increase in lipid phase fluidity and a decrease in cell glycoprotein coat viscosity. However, the resultant enhancement of the rate of penetration of TMA⁺ ions across the lipid phase seems to be greater than the enhancement of their migration rate across the glycoprotein coat. Triton X-100 also induces changes in the membrane potential, which depend on the ionic content of the extracellular medium. These changes are probably too small to affect TMA⁺ ion transport across the membrane significantly.     

Poly(vinyl chloride) membrane cesium ion-selective electrodes based on lipophilic calix[6]arene tetraester derivatives

New lipophilic tetraesters of calix[6]arene and calix[6]diquinone are investigated as cesium ion-selective ionophores in poly(vinyl chloride) membrane electrodes. For an ion-selective electrode based on calix[6]arene tetraester I, the linear response is 1x10(-6)-1x10(-1) M of Cs(+) concentrations. The selectivity coefficients for cesium ion over alkali, alkaline earth and ammonium ions are determined. The detection limit (log a (Cs (+))=-6.31) and the selectivity coefficient (log k (Cs (+),Rb (+))(pot )=-1.88) are obtained for polymeric membrane electrode containing calix[6]arene tetraester I.     

Parameters influencing transport across conducting electroactive polymer membranes

The parameters which influence electrochemically facilitated transport of electroinactive ions across conducting electroactive polymer membranes have been investigated. The design of membranes and the materials used as well as transport cells and systems have been addressed to improve selectivity and flux. Polypyrrole-para-toluenesulfonate (PPy-pTS) was compared with the copolymer of pyrrole with 3-carboxy-4-methylpyrrole (PPy/PCMP-pTS) and their different chemistries resulted in different membrane selectivities for ions. Platinum mesh was found to be the most suitable auxiliary electrode material and its placement in the cell chamber(s) facilitated ion incorporation/expulsion at the membrane working electrode. This enhanced the flux of ion transport. The flux can also further enhanced by narrowing the distance between the membrane working electrode and the platinum mesh auxiliary electrode(s), and/or by stirring to improve the hydrodynamics. An alternative cell design, namely a dual membrane flow through cell, also proved to be more efficient for ion transport. Good connection geometry to the membrane as well as the application of a square wave pulsed potential waveform to the membrane was found to be essential for achieving high and sustainable flux in ion transport.     

Stationary electrodiffusion–adsorption processes in membranes including diffuse double layer effects: A network approach

Ion transport across membranes with surface charge due to ion adsorption, including the diffuse double layer effects, is analysed using the network simulation method. The membrane system under study is a multilayer one constituted by a membrane and two diffusion boundary layers on both sides of the membrane. The ion transport processes are described by the Nernst–Planck and Poisson equations not only in the membrane–solution interfaces, but also in the membrane bulk and in the two diffusion boundary layers. The membrane has a negative surface charge due to an anion adsorption process. The structure of the equilibrium diffuse double layers and the steady-state current–voltage characteristic have been analysed for the case of an adsorption process described by a Langmuir-type adsorption isotherm. The evolution of the electric potential difference across the membrane system in the equilibrium state of the system as a function of the bathing concentrations, have been also analysed.     

Microelectrode for potassium ions based on a neutral carrier and comparison of its characteristics with a cation exchanger sensor

A potassium-selective liquid-membrane microelectrode based on valinomycin is described. Tip diameters of about 2 μm as well as high discrimination against Na⁺, H₃O⁺, acetylcholine and some other quaternary ammonium ions, allow the intracellular measurement of potassium ion activity changes. The inherently high membrane resistance of the neutral carrier-based microelectrodes is reduced by adding a lipophilic charge carrier to the valinomycin. Results are compared with those of classical microelectrodes.     

Enzymes Immobilized by Microencapsulation Within Spherical Ultrathin Polymeric Membranes

Biological cells in nature have diameters of about 7 to 50 μm, with a cell membrane of about 0.01 μm in thickness. This means that the total membrane area available for diffusion can be extremely large in comparison to the volume and that the cell membrane can also be very thin without the loss of mechanical strength. In addition, rapid mixing is possible within the individual microscopic compartments. Biological cells have very complex and selective enzyme systems to act on substrates crossing the cell membrane. Artificial cells in the form of spherical ultrathin polymeric membrane envelopes containing enzymes have been prepared in this laboratory with some of these properties [1-3]. Detailed papers and upadated information published since then on this subject have been described in a recent monograph [4].