Rate of proton transport

The excellent prospects of PEFCs as well as the undesirable dependence of current PEMs on bulk-like water for proton conduction motivate the vast research in materials synthesis and experimental characterization of novel PEMs. A major incentive in this realm is the development of membranes that are suitable for operation at intermediate temperatures (120-200°C). Inevitably, aqueous-based PEMs for operation at higher temperatures (T > 90°C) and low relative humidity have to attain high rates of proton transport with a minimal amount of water that is tightly bound to a stable host polymer.33 37,40,42,43 yj-jg development of new PEMs thus warrants efforts in understanding of proton and water transport phenomena under such conditions. We will address this in Section 6.7.3. 

The properties are as follows, (i) The activity of the protein (i.e. the inward transport of protons) is inhibited by ATP. (ii) The activity of the protein is increased by the presence of long-chain fatty acids, since they relieve the ATP inhibition, (iii) When mitochondria, isolated from brown adipose tissue, are incubated in the presence of fatty acids, there is a sharp increase in the rates of electron transfer, substrate utilisation and oxygen consumption, whereas the rate of ATP generation remains low. These studies indicate that the rate of proton transport, by the uncoupling protein, depends on the balance between the concentrations of ATP and fatty acids, (iv) In adipocytes isolated from brown adipose tissue, the rate of oxygen consumption (i.e. electron transfer) is increased in the presence of catecholamines. 

Electrodes were fabricated with catalyst layers containing platinum-ruthenium alloys and platinum-ruthenium oxide. Membrane electrode assemblies were fabricated with such cells, and the performance was evaluated in a full cell configuration. Although ruthenium oxide is a proton conductor and is expected to enhance the rate of proton transport from the interface during methanol oxidation, no noticeable improvement in activity of the catalyst layer was observed by addition of ruthenium oxide. The role of other metal oxides such as tungsten oxide will be investigated next year, along with evaluation of non-noble metal catalysts based on nickel, titanium, and zirconium. 

To minimize the cell potential losses due to the rate of proton transport and reactant gas permeation in the depth of the electro catalyst layer, this layer should be made reasonably thin. At the same time, the metal active surface area should be maximized, for which the Pt particles should be as small as possible [1]. 

The factor 2 exhibits the Tafel slope doubling at high currents resulting from insufficient rate of proton transport in the CCL. In dimensional form. Equation 4.133 reads... 

The resistivity Red, Equation 4.219 is proportional to the CCL proton resistivity Ici/O yp)- The reason is seen in Figure 4.26 At high current, the peak of the ORR rate shifts away from the membrane, which means that protons need to be transported more deeply into the CCL (Figure 4.26c). In addition, the overpotential r]ox is very high so that the rate of ORR itself does not limit the cathode performance. In this situation, proton transport is the rate-determining process, that is, the rates of electrochemical conversion appear to be much higher than the rate of proton transport. In addition, methanol crossover reduces the resistivity (4.219), since the MOR provides protons in-place, without the need of transporting them from the membrane. 

In this section, a one-dimensional, through-plane model of a DMFC anode is constructed (Kulikovsky, 2013a). The model takes into account the finite rate of proton transport in the ACL, the two-step kinetics of the MOR (4.224), (4.225) and the potential loss resulting from the methanol transport in the ABL. 

Structure and water sorption characteristics of fuel cell media determine their transport properties. The dynamic properties of water determine microscopic transport mechanisms and diffusion rates of protons in PEM and CLs. Protons must be transported at sufficiently high rates, away from or toward the active Pt catalyst in anode and cathode catalyst layers, respectively. Effective rates of proton transport in nanoporous PEM and CLs result from a convolution of microscopic transport rates of protons with random network properties of aqueous pathways. Accounting for the geometry of these materials, namely, their external surface area and thickness, gives their resistances. 

In rat liver mitochondria, in state 4, the AP was estimated to be about 220 mV, with the membrane potential representing about 90% of this (Nicholls, 1974 Appendix 3). Similar values have been reported for human and rat skeletal muscle mitochondria in state 4 (Stumpf et al., 1982). The control of the rate of electron transport is not only determined by the availability of ADP, but also of Pj oxidizable substrates, and oxygen. There is evidence for futile cycling of protons in intact normal rat hepatocytes (Brand et al., 1993). Recently, Porter and Brand (1993) found a correlation between the proton permeability of the inner membrane of liver mitochondria and body size in animals from the mouse (20 g) to horses (150 kg) with a decrease in permeability with increasing weight of several-fold at a constant... 

ATPase also catalyzed a passive Rb -Rb exchange, the rate of which was comparable to the rate of active Rb efflux. This suggested that the K-transporting step of H,K-ATPase is not severely limited by a K -occluded enzyme form, as was observed for Na,K-ATPase. Skrabanja et al. [164] also described the reconstitution of choleate solubilized H,K-ATPase into phosphatidylcholine-cholesterol liposomes. With the use of a pH electrode to measure the rate of H transport they observed not only an active transport, which is dependent on intravesicular K, but also a passive H exchange. This passive transport process, which exhibited a maximal rate of 5% of the active transport process, could be inhibited by vanadate and the specific inhibitor omeprazole, giving evidence that it is a function of gastric H,K-ATPase. The same authors demonstrated, by separation of non-incorporated H,K-ATPase from reconstituted H,K-ATPase on a sucrose gradient, that H,K-ATPase transports two protons and two ions per hydrolyzed ATP [112]. 

Many parameters can be monitored, for example, free-ion concentrations, membrane potentials, activities of specific enzymes, rate of proton generation, transport of signaling molecules, and gene expression. 

Current estimates are that three protons move into the matrix through the ATP-synthase for each ATP that is synthesized. We see below that one additional proton enters the mitochondrion in connection with the uptake of ADP and Pi and export of ATP, giving a total of four protons per ATP. How does this stoichiometry relate to the P-to-O ratio When mitochondria respire and form ATP at a constant rate, protons must return to the matrix at a rate that just balances the proton efflux driven by the electron-transport reactions. Suppose that 10 protons are pumped out for each pair of electrons that traverse the respiratory chain from NADH to 02, and 4 protons move back in for each ATP molecule that is synthesized. Because the rates of proton efflux and influx must balance, 2.5 molecules of ATP (10/4) should be formed for each pair of electrons that go to 02. The P-to-O ratio thus is given by the ratio of the proton stoichiometries. If oxidation of succinate extrudes six protons per pair of electrons, the P-to-O ratio for this substrate is 6/4, or 1.5. These ratios agree with the measured P-to-O ratios for the two substrates. 

In 1982, /Mert-butyl-cal i x n larenes were studied by Izatt et al. for their capacity to transport cesium from an alkaline medium ([MOH] = 1M) through bulk liquid membranes made of a mixture of diluents able to dissolve these compounds methylene chloride, carbon tetrachloride, and dichloromethane. Experiments were carried out using p-tert-calix[8]arene to measure the rate of cesium transport under conditions of varying source pH. The values of the transport rate, small below a pH of 12, rise rapidly beyond this value, hence confirming that a proton is removed from the ligand in the complexation process. Under such conditions, tetramer, hexamer, and octamer (n = 4, 6, and 8, respectively) display a high selectivity for cesium over the other... 

Figure 1. The channels which can be available for proton release in different cells. These may be activated by ligands attached to receptors or signals generated by the electron transport system. The electron transport across the membrane can also be accompanied by proton movement, depending on the orientation of electron transport, but th is movement would be I imited because of the slow rate of electron transport compared to the rapid rate which can be elicited through channels. Any possible relation of oxidase control to the H+-ATPase or the H -K+-ATPase has not been tested by inhibitors such as bafilomycin or omeprazole, respectively (Swallow et al., 1990).

The intrinsic catalytic properties of enzymes are modified either during immobilization or after they were immobilized [25-27], In heterogeneous catalysis such as is carried out by immobilized enzymes, the rate of reaction is determined not simply by pH, temperature and substrate solution, but by the rates of proton, heat and substrate transport, through the support matrix to the immobilized enzyme. In order to estimate this last phenomenon, we have studied the internal mass transfer limitation both in hexane and in SC C02, with different enzymatic support sizes. 

The functional and morphological heterogeneity of a lamellar system of chloroplasts indicates that pH values in different compartments (in granal and intergranal thylakoids) differ. This type of structure makes it difficult to measure local pH values at different sites. Therefore, mathematical models taking into account the spatial structure of chloroplasts provide a tool for studying the effect of diffusion restrictions on pH distributions over the thy lakoid on the rates of electron transport, proton transport, and ATP synthesis. The rate of ATP synthesis depends on the osmotic properties of a chloroplast-incubation medium and, therefore, on topological factors. 

Extremely hydrophobic monomers do not polymerize well via macroemulsion polymerization due to their very low rates of monomer transport across the aqueous phase. Obviously, these monomers can be polymerized much more effectively in a miniemulsion system. One example of this is provided by Landfester et al. [320]. In this paper,fluoroalkyl acrylates are polymerized in a miniemulsion with low levels of a protonated surfactant. When fluorinated monomers were copolymerized with standard hydrophobic and hydrophilic monomers, either core-shell structures or statistical copolymers were formed. 

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