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Platinum dissolution and deposition in the polymer electrolyte membrane of a PEM fuel cell as studied by potential cycling.

The behavior of platinum dissolution and deposition in the polymer electrolyte membrane of a membrane-electrode-assembly (MEA) for a proton-exchange membrane fuel cell (PEMFC) was studied using potential cycling experiment and high-resolution transmission electron microscopy (HRTEM). The electrochemically active surface area decreased depending on the cycle number and the upper potential limit. Platinum deposition was observed in the polymer electrolyte membrane near a cathode catalyst layer. Platinum deposition was accelerated by the presence of hydrogen transported through the membrane from an anode compartment. Platinum was transported across the membrane and deposited on the anode layer in the absence of hydrogen in the anode compartment. This deposition was also affected by the presence of oxygen in the cathode compartment.

Chemical Phenomena↗

Two temporally synthesized charge subunits interact to form the five isoforms of cottonseed (Gossypium hirsutum) catalase.

Five charge isoforms of tetrameric catalase were isolated from cotyledons of germinated cotton (Gossypium hirsutum L.) seedlings. Denaturing isoelectric focusing of the individual isoforms in polyacrylamide gels indicated that isoforms A (most anodic) and E (most cathodic) consisted of one subunit of different charge, whereas isoforms B, C and D each consisted of a mixture of these two subunits. Thus the five isoforms apparently were formed through combinations of two subunits in different ratios. Labelling cotyledons in vivo with [35S]methionine at three daily intervals in the dark, and translation in vivo of polyadenylated RNA isolated from cotyledons at the same ages, revealed synthesis of two different subunits. One of the subunits was synthesized in cotyledons at all ages studied (days 1-3), whereas the other subunit was detected only at days 2 and 3. This differential expression of two catalase subunits helped explain previous results from this laboratory showing that the two anodic forms (A and B) found in maturing seeds were supplemented with three cathodic forms (C-E) after the seeds germinated. These subunit data also helped clarify our new findings that proteins of isoforms A, B and C (most active isoforms) accumulated in cotyledons of plants kept in the dark for 3 days, then gradually disappeared during the next several days, whereas isoforms D and E (least active isoforms) remained in the cells. This shift in isoform pattern occurred whether seedlings were kept in the dark or exposed to continuous light after day 3, although exposure to light enhanced this process. These sequential molecular events were responsible for the characteristic developmental changes (rise and fall) in total catalase activity. We believe that the isoform changeover is physiologically related to the changeover in glyoxysome to leaf-type-peroxisome metabolism.

Blotting, Western↗

Cleaning effectiveness of root canal irrigation with electrochemically activated anolyte and catholyte solutions: a pilot study.

AIM: The aim of this study was to evaluate the potential of electrochemically activated (ECA) anolyte and catholyte solutions to clean root canals during conventional root canal preparation. METHODOLOGY: Twenty extracted single-rooted human mature permanent teeth were allocated randomly into four groups of five teeth. The pulp chambers were accessed and the canals prepared by hand with conventional stainless steel endodontic instruments using a double-flared technique. One or other of the following irrigants was used during preparation: distilled water, 3% NaOCl, anolyte neutral cathodic (ANC) (300 mg L-1 of active chlorine), and a combination of anolyte neutral cathodic (ANC) (300 mg L-1 of active chlorine) and catholyte. The teeth were split longitudinally and the canal walls examined for debris and smear layer by scanning electron microscopy. SEM photomicrographs were taken separately in the coronal, middle and apical parts of canal at magnification of x800 to evaluate the debridement of extracellular matrix and at a magnification of x2500 to evaluate the presence of smear layer. RESULTS: Irrigation with distilled water did not remove debris in the apical part of canals and left a continuous and firm smear layer overlying compressed low-mineralized predentine. All chemically active irrigants demonstrated improved cleaning potential compared to distilled water. The quality of loose debris elimination was similar for NaOCl and the anolyte ANC solution. The combination of anolyte ANC and catholyte resulted in improved cleaning, particularly in the apical third of canals. The evaluation of smear layer demonstrated that none of the irrigants were effective in its total removal; however, chemically active irrigants affected its surface and thickness. Compared to NaOCl, the ECA solutions left a thinner smear layer with a smoother and more even surface. NaOCl enhanced the opening of tubules predominantly in the coronal and middle thirds of canals, whereas combination of ANC and catholyte resulted in more numerous open dentine tubules throughout the whole length of canals. CONCLUSIONS: Irrigation with electrochemically activated solutions cleaned root canal walls and may be an alternative to NaOCl in conventional root canal treatment. Further investigation of ECA solutions for root canal irrigation is warranted.

Chlorine↗

The study of jaw reflexes evoked by electrical stimulation of the lip: the importance of stimulus intensity and polarity.

The aim of this study was to investigate whether reported differences in the patterns of jaw reflexes which can be evoked by electrical stimulation of the lip might be related to the intensity or polarity of the stimuli. Constant-current stimuli were applied through bipolar electrodes clipped across the lower lip of 14 subjects while EMG recordings were made from a masseter muscle. During stimulation, the subjects sustained a level of masseter activity equivalent to 10% of their maximum. The stimuli were applied as multiples of sensory threshold. The EMGs were analysed following rectification, averaging and smoothing. A sequence of inhibitory, excitatory, inhibitory and excitatory responses could be produced in the muscle by both polarities of stimuli. The latencies of these four responses were generally in the ranges 10-20, 25-40, 40-55 and 80-100 ms, respectively. These latencies, particularly for the last two responses, tended to decrease at higher intensities of stimulation. The threshold for the long-latency inhibition was significantly lower than that for the short-latency inhibition when the cathode was outside the mouth but not when it was inside the mouth. In addition, the long-latency excitation had the lowest threshold of the four responses regardless of stimulus polarity. Since nerves are excited particularly around a cathode, we interpret these results as showing that stimulation of nerves supplying the skin outside the mouth evokes predominately long-latency jaw reflexes whereas shorter latency responses can be evoked by stimulating nerves supplying oral mucosa. Furthermore, long latency excitatory reflexes seem to be the most easily evoked by stimulation of the lip.

Adult↗

The hemoglobin system of the brown moray Gymnothorax unicolor: structure/function relationships.

The Gymnothorax unicolor hemoglobin system is characterized by two components, called cathodic and anodic on the basis of their isoelectric point, which were separated by ion-exchange chromatography. The oxygen-binding properties of the purified components were studied in the absence and presence of chloride and/or GTP or ATP in the pH range 6.5-8.0. Stripped cathodic hemoglobin showed a small reverse Bohr effect, high oxygen affinity, and low co-operativity; the addition of chloride only caused a small decrease in oxygen affinity. In the presence of GTP or ATP, the oxygen affinity was dramatically reduced, the co-operativity increased, and the reverse Bohr effect abolished. Stripped anodic hemoglobin is characterized by both low oxygen affinity and co-operativity, and displayed a normal Bohr effect; the addition of chloride increased co-operativity, whereas ATP and GTP significantly modulated oxygen affinity at acidic pH values, enhancing the Bohr effect and giving rise to the Root effect. The complete amino-acid sequences of the alpha and beta chains of both hemoglobins were established; the molecular basis of the functional properties of the hemoglobins is discussed in the light of the primary structure and compared with those of other fish hemoglobins.

Allosteric Regulation↗

Saccadic eye movements evoked by microstimulation of striate cortex.

Experiments were performed to assess the excitability of neural elements activated while inducing saccadic eye movements electrically from different cortical layers of striate cortex (area V1) in rhesus monkeys. Excitability was assessed by measuring current thresholds, saccadic latencies, chronaxies, and the effectiveness of anode-first vs. cathode-first pulses. Minimum current thresholds for the evocation of saccades (i.e. less than 5 microA) were observed when the deepest layers of V1 were stimulated. The shortest saccadic latencies were also observed at these depths. The shortest latency at 10 times the threshold current was 49 ms on average. The chronaxies of the elements mediating saccades were less in deep V1 (i.e. 0.17 ms) than in superficial V1 (i.e. 0.23 ms). Anode-first pulses were more effective at evoking saccades from superficial V1, whereas cathode-first pulses were more effective at evoking saccades from deep V1. These results indicate that the excitability properties of superficial and deep V1 are distinct for the generation of saccades. Moreover, the excitability of elements mediating saccades in V1 of monkeys is comparable to that of elements mediating phosphenes in human V1.

Animals↗

Determination of standard electrode potential E(o) for chronic platinum and gold electrodes in rat muscle: implications for biosensors and the "anode" of bipolar pacing.

Pacemaker electrode surface modification by organosilane and organic self-assembled monolayer strategies creates a possible new variable in pacemaker electrode behavior. Because all of these chemical surface coatings are unstable at extremes of potential, the potential to which the electrode relaxes (between pacing pulses) becomes extremely important. The authors measured this potential for platinum (Pt) and gold (Au) relevant for their use as anode (or cathode) in a bipolar pacing system and from this potential the standard electrode potential, E(o) was determined. Thirty-Four determinations were made by a null current three-electrode potentiostatic technique of 2.45 mm2 platinum or gold electrodes implanted chronically in blood perfused muscle in a spontaneously breathing rat. Linear voltage sweeps were performed while monitoring current with voltage at null current determined repeatedly at varying scan rates and limits. Electrode potential varied between -388 +/- 19 mV (vs Ag/Ag+) for platinum and -388 +/- 55 mV for gold electrodes. Hysteresis was observed in all sweeps (P < 0.008, Fisher's exact) and measured 61 +/- 17 mV (anodic) and 25 +/- 3 mV (cathodic) with steep dependence on polarity (P < 0.001, t-test). The findings were independent of the materials' electronic work function. E(o) versus normal hydrogen electrode (NHE) were thus -166 mV (platinum) and -166 mV (gold). Because the most common bipolar system, uses platinum as anode, these results are directly applicable to current pacing technology. Provided low thresholds are achievable with novel surface modified electrodes, the small range of variation of E(o), and the particular mean value observed, are both compatible with function, provided care is used during electrode testing to avoid surface disruption. These results are significant also for biosensors that use similar surface modification methodologies.

Animals↗

Electrokinetic movement of Escherichia coli in capillaries.

The movement of Escherichia coli K-12 has been studied in capillaries with an 8 microm inside diameter under a DC electric field. At low applied voltages (< 0.2 V cm(-1)), bacterial motility is the predominant mode of motion, with bacteria swimming, tumbling and moving unidirectionally towards the anode and the cathode, although a significant difference between the mean moving speeds towards the two electrodes was observed. When the electric field was removed, the mean swimming speeds were the same for both directions. At higher voltages, all the cells were swept by electro-osmotic flow exclusively towards the cathode.

Capillaries↗

[Biophysical foundations in the application of electromagnetic fields in the modification of osteogenesis].

The interactions between bone-forming cells and the extracellular processes determining the mineralisation of the osteoid with electric and/or magnetic fields is the elementary prerequisite. The magnetic or electric field or the combination of both, as well as their time related intensity are discussed as the stimulating factors. When using electric current there is a physical process to be considered. This process consists of changes of metabolites caused by the cathodic electrode reaction which may gain influence on the metabolism of bone-forming cells and the mineralisation. According to the results of this investigation the bone-producing effect of the cathodic electrode reaction saturates+ at a geometric current density of about 0.4 microA/mm2. Apart from the changes of metabolites produced by the electric current there are electric polarizations in front of interfaces and cell membranes due to local ion concentrations caused by even very weak electric fields.

Animals↗

Separation of hydrogenase-catalyzed hydrogen-evolution system from electron-donating system by means of enzymic electric cell technique.

An enzymic electric cell was constructed in which the anode was composed of a zinc plate inserted in aqueous NH(4)Cl solution and the cathode was composed of an electrode made of a glassy carbon stick inserted in a reaction mixture containing cytochrome c(3) hydrogenase (H(2):ferricytochrome c(3) oxidoreductase, EC 1.12.2.1) and methylviologen under an atmosphere of N(2). When the circuit was closed, the electric cell formulated as [Formula: see text] was composed, and hydrogenase-catalyzed H(2)-evolution was observed in the cathode of the cell with concomitant flow of an electric current. Thus, the hydrogenase-catalyzed reaction and the electron-donating reaction proceeded at different parts of the cell. This enables us to protect the hydrogenase from the byproducts of the electron-donating system, which might be hazardous to the enzyme.

Journal Article↗

Two HLA-linked loci controlling the fourth component of human complement.

An electrophoretic polymorphism of the fourth component of human complement (C4) is described. Three patterns of bands of C4 were observed in EDTA plasma from a panel of unrelated blood donors and family members by using the technique of immunofixation electrophoresis. These patterns consisted of four fast-moving anodal bands (F), four slow-moving cathodal bands (S), or a combination of both the F and S bands (FS). The C4 patterns of bands were observed in EDTA plasma and not in serum. Family studies showed that this polymorphism of C4 did not segregate with HLA histocompatibility genes in a fashion governed by two codominant alleles at a single genetic locus. The family data are in agreement with the hypothesis that two different genetic loci control the electrophoretic patterns of C4. One locus controls the presence (F) or absence (f0) of the four anodal (F) bands and the other controls the presence (S) or absence (s0) of the four cathodal (S) bands. The C4F and C4S loci are both closely linked to HLA-B.

Complement C4↗

The Ras/Raf-1/MEK1/ERK signaling pathway coupled to integrin expression mediates cholinergic regulation of keratinocyte directional migration.

The physiologic mechanisms that determine directionality of lateral migration are a subject of intense research. Galvanotropism in a direct current (DC) electric field represents a natural model of cell re-orientation toward the direction of future migration. Keratinocyte migration is regulated through both the nicotinic and muscarinic classes of acetylcholine (ACh) receptors. We sought to identify the signaling pathway mediating the cholinergic regulation of chemotaxis and galvanotropism. The pharmacologic and molecular modifiers of the Ras/Raf-1/MEK1/ERK signaling pathway altered both chemotaxis toward choline and galvanotropism toward the cathode in a similar way, indicating that the same signaling steps were involved. The galvanotropism was abrogated due to inhibition of ACh production by hemicholinium-3 and restored by exogenously added carbachol. The concentration gradients of ACh and choline toward the cathode in a DC field were established by high-performance liquid chromatographic measurements. This suggested that keratinocyte galvanotaxis is, in effect, chemotaxis toward the concentration gradient of ACh, which it creates in a DC field due to its highly positive charge. A time-course immunofluorescence study of the membrane redistribution of ACh receptors in keratinocytes exposed to a DC field revealed rapid relocation to and clustering at the leading edge of alpha7 nicotinic and M(1) muscarinic receptors. Their inactivation with selective antagonists or small interfering RNAs inhibited galvanotropism, which could be prevented by transfecting the cells with constitutively active MEK1. The end-point effect of the cooperative signaling downstream from alpha7 and M(1) through the MEK1/ERK was an up-regulated expression of alpha(2) and alpha(3) integrins, as judged from the results of real-time PCR and quantitative immunoblotting. Thus, alpha7 works together with M(1) to orient a keratinocyte toward direction of its future migration. Both alpha7 and M(1) apparently engage the Ras/Raf/MEK/ERK pathway to up-regulate expression of the "sedentary" integrins required for stabilization of the lamellipodium at the keratinocyte leading edge.

Acetylcholine↗

A novel technique for isolation of pure sperm heads from disintegrated mammalian spermatozoa.

The phenomenon of differential charge distribution on sperm surface membrane has been utilised here in a low e.m.f. (electro motive force) capillary electrophoresis system to effect separation of sperm heads from disintegrated mixed spermatozoal subfractions. Washed caudal sperm of goat (Black Bengal variety) and ejaculated washed human sperm were fractionated by sonication into head, mid-piece and tail portions. Routine techniques of density gradient centrifugation on Percoll and/or sucrose were performed with sonicated spermatozoa for separation into their respective subfractions. The products obtained were not free of contamination in either case. Mixed sperm fractions when subjected to the afore mentioned modified capillary electrophoresis technique only the head pieces exhibited high affinity for migration towards the cathode terminal. With this method around 50% of the total sperm heads were separated and collected in absolutely pure form at the cathode side within 2 hrs. at 150 volts (V) and 1.5 milliampere (mA) current at 37.5 degrees C. A 4 cm. long capillary tube with a bore size 1.2 mm. was used for this purpose.

Animals↗

Geochemical reconnaissance of heavy metals in kaolin after electrokinetic remediation.

The development or implementation of electrokinetic soil remediation technique requires a good knowledge of how the contaminants are retained within the soil-water system. This paper investigates the speciation and extent of migration of the heavy metals, Cr(VI), Cr(III), Ni(II), and Cd(II), during electrokinetic soil remediation. A geochemical assessment of how the contaminants are held within the kaolin soil under induced electric potential is made by using the equilibrium model MINEQL+. The study is performed for three different contaminant cases: the Cr(VI) existing alone in the soil, the Cr(VI) combined with Ni(II) and Cd(II) in the soil, and the Cr(VI) combined with Ni(II) and Cd(II) in the soil in the presence of a reducing agent (sulfide). The adsorption of the studied metals by kaolin was implemented as an electrostatic behavior. FITEQL 4.0 model was used to determine the equilibrium constants of the electrostatic adsorption model of kaolin for the studied metals by optimizing the experimental titration and adsorption data of kaolin. This study showed that the initial speciation of the contaminants in the soil prior to the electrokinetic treatment depends on the type and amounts of contaminants present as well as on the presence of the co-contaminants or any reducing agent. Moreover, the extent of migration of the contaminants is strongly dependent on their initial speciation prior electrokinetic treatment. This study also showed that adsorption and precipitation are the significant hindering mechanisms for the removal of heavy metals from kaolin soil during electrokinetic treatment. The adsorption and precipitation forms of Cr(III), Ni(II), and Cd(II) increased near the cathode and decreased near the anode, whereas the adsorption form of Cr(VI) increased near the anode as well as in the middle region. However, the precipitation form of Cr(III), Ni(II), and Cd(II) as Cr2O3 or Cr(OH)3, Ni(OH)2, and Cd(OH)2, respectively, dominates over their adsorption form as they get closer to the cathode. Overall this study demonstrates that the electrolysis reactions control contaminant speciation and distribution in the soil during electrokinetic remediation because of the generated variations in pH and redox potential in the soil as a result of these reactions.

Chemical Precipitation↗

Enhancing electrokinetic remediation of cadmium- contaminated soils with stepwise moving anode method.

This paper proposed an innovative approach by stepwise moving anode towards cathode to enhance the cadmium (Cd) removal from soil during the process of electrokinetic (EK) remediation. Fixed anode tests and moving anode tests were carried out for 60 hours to compare their performances. The anode-cathode spacing was 21 cm. Constant voltage grade of 1.0 V cm(-1) was applied in this study. The parameters included pH, electrical conductivity, current, Cd concentration and speciation distributions, energy consumptions, etc. It was found that the pH values in the moving anode tests were relatively lower than those of the fixed tests. In the moving anode test, the removal efficiency of Cd in the soils at the fraction of S4 was enhanced by 54.9% compared with that of the fixed anode tests. After 60 hours of treatment, approximately 80% of the spiked soils (100.63 mg x kg(-1) of Cd) in the system were successfully remedied in the moving anode tests; and the mean removal efficiency was 73% for actual field-contaminated soil (54.26 mg x kg(-1) of Cd). It is effective to remedy actual contaminated soils. In addition, the cumulative energy consumptions were 59.29 kWhm(-3) and 31.52 kWhm(-3) for the fixed and moving tests, respectively. The results revealed that the Cd removal efficiency was improved by the moving anode method. Moreover, less energy was consumed in the moving test. The proposed approach does not need to introduce extra chemicals nor adjust the pH in the system to enhance the Cd removal by EK remediation. The basic idea proposed in this paper provides a novel and environmental friendly method to enhance the EK remediation of heavy metals contaminated soils.

Cadmium↗

Sustainable approach for leachate treatment: electricity generation in microbial fuel cell.

Electricity generation from landfill leachate was examined by using both a dual-chamber microbial fuel cell (MFC) and a single chamber MFC. Experimental results showed that the maximum power density of 2060.19 mW/m3 in the dual-chamber MFC and that of 6817.4 mW/m3 in the single chamber MFC were obtained. It was recognized that the difference in internal resistance for two MFC systems was the main reason for resulting in the difference of power generation. Power generation as function of chemical oxygen demand (COD) in single chamber MFC showed a Monod-type relationship with Pmax of 5920.96 mW/m3 and Ks of 251.39 mg/L at an external resistance of 500 Omega. Cyclic voltammetry showed that electrons were directly transferred onto the anode by bacteria in biofilms, rather than self-produced mediators of bacteria in the solutions. At low COD concentration, electricity generation was limited by the anode due to kinetic limitation; while at high COD concentration, the cathode was shown to have more significant effects on the electricity generation than the anode. COD in leachate could be removed when it increases, mainly because oxygen diffused from the cathode was substantially reduced by aerobic or anoxic bacteria in the anode chamber, leading to the substrate loss. Removal of ammonium-nitrogen was not observed in the single chamber MFC. This novel technology provides an economical route for electricity energy recovery in leachate treatment.

Bacteria↗

Electrochemical remediation of trichloroethene-contaminated groundwater using palladized iron oxides.

The objective of this study is to develop electrochemically-enhanced dechlorination of trichloroethene (TCE) using palladized iron oxides minerals for ex situ remediation of contaminated groundwaters. A bench-scale column packed with the palladized iron oxide media connected to a cathode and an anode embedded in a carbon pad was prepared for flow through column tests. Contaminated groundwaters with about 14-16 mg/L TCE were passed from the cathode side to the anode side of the column while the system was supplied with direct current. All of the TCE in the groundwater was dechlorinated even after 300 pore volumes were passed. Furthermore, intermediate reaction products, dichloroethene isomers and vinyl chloride, were not detected in the treated water.

Electrochemistry↗

Membrane-related specializations associated with acetylcholine receptor aggregates induced by electric fields.

The localization of membrane-associated specializations (basal lamina and cytoplasmic density) at sites of acetylcholine receptor (AChR) aggregation is consistent with an involvement of these structures in receptor stabilization. We investigated the occurrence of these specializations in association with AChR aggregates that develop at the cathode-facing edge of Xenopus muscle cells during exposure to a DC electric field. The cultures were labeled with a fluorescent conjugate of alpha-bungarotoxin and the receptor distribution on selected cells was determined before and after exposure to the field. In thin sections taken from the same cells, the cathode-facing edge was characterized by plaques of basal lamina and cytoplasmic density co-extensive with sarcolemma of increased density. In sections cut in a plane similar to the fluorescence image, it was possible to demonstrate that the specializations were concentrated at areas of field-induced AChR aggregation, and at receptor clusters existing on control cells. This finding further indicates that these structures participate in AChR stabilization, and that the mechanisms involved in AChR aggregation that result from field exposure and nerve contact may be similar.

Animals↗