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Interactions of surface-confined DNA with acid-activated mitomycin C.

The anti-cancer drug mitomycin C (MC) was acid-activated and its interaction with single-stranded calf thymus DNA, immobilized at the surface of the hanging mercury drop electrode (DNA-modified HMDE) was studied by cyclic voltammetry. It was found that immersion of the DNA-modified electrode in a solution of acid-activated MC (at pH 3.9) for a short time (usually 1 min) at open current circuit, followed by transfer of the electrode in a neutral blank background electrolyte, resulted in a decrease of the anodic peak G (due to guanine residues in DNA) and in the formation of a reversible couple at approx. -0.44 V. The potential of the cathodic peak was approx. 50 mV more negative than the cathodic peak of the acid-activated MC obtained under the same conditions in the absence of DNA. No changes of peak G occurred and only a very small cathodic peak appeared if the DNA-modified electrode was immersed in an MC solution not exposed to acid pH. On the basis of these results and additional experiments, including dependence on concentration, time and pH during the interaction of MC with DNA at the electrode surface, we concluded that acid-activated MC is covalently bound to guanine residues in DNA immobilized at the electrode surface and that the quinone group in the DNA-MC adduct is reversibly reduced at the electrode.

Animals↗

A new method to control electrolytes pH by circulation system in electrokinetic soil remediation.

To simultaneously avoid a decrease of electro-osmotic flow by hydrogen ions and to increase heavy metal precipitation due to hydroxide ions, simulated electrokinetic remediation was conducted in saturated kaolinite specimens loaded with lead(II) using an electrolyte circulation method to control electrolyte pH. At an electrolyte circulation rate of 1.1 ml/min, it was possible to increase the anolyte pH from 2 to 4 and decrease the catholyte pH from 12 to 8. Using electrolyte circulation, it was observed that the rate of decrease of clay pH due to the change of electrolyte pH was reduced. As a result, the operable period was extended and the removal efficiency for lead(II) was also increased. It was observed that most of the effluent lead(II) from the cathode compartment was electroplated onto the cathode and that residual effluent lead(II) did not precipitate onto, or adsorb to, the clay at the anode compartment during circulation. Therefore, there was no need to treat the electrolyte because there was virtually no effluent from the cathode compartment in the circulation system. It was also found that the electrolyte volume required to sustain the electrolytic reaction was sufficient for the whole electrokinetic remediation process.

Electrochemistry↗

Removal and degradation of phenol in a saturated flow by in-situ electrokinetic remediation and Fenton-like process.

In this laboratory study, a sandy loam soil saturated with phenol solution was treated by in-situ electrokinetics-Fenton process incorporated with a permeable reactive wall of scrap iron powder (SIP). The soil was contaminated and saturated with aqueous phenol solution of 90-115 mg/kg in concentration. It was then placed in a soil cell. The soil cell was assembled with an anode reservoir and a cathode reservoir at its ends. A bed of SIP (1.05-32.69 g) was inserted in the soil cell at a distance of 5 cm from the anode reservoir compartment. For the test runs, 0.3% H(2)O(2) was used as the anode reservoir fluid, whereas de-ionized water was used as the cathode reservoir fluid. An electric gradient of 1 V/cm was applied to enhance the saturated flow in the soil cell for a period of 10 days. Experimental results have shown that the electroosmotic (EO) flow quantity decreased as the amount of SIP increased. This phenomenon was in good agreement with the results showing the value of EO permeability increased with a decreasing amount of SIP. Results also showed that throughout the test period the cumulative, consumed mass of H(2)O(2) in the anode reservoir increased as the amount of SIP decreased. On the other hand, the cumulative, increased mass of phenol in the cathode reservoir was found to increase with a decreasing amount of SIP. Meanwhile, the residual phenol concentration in the soil cell was found to decrease with a decreasing amount of SIP. When 1.05 g scrap iron powder was used, an overall removal and destruction efficiency of phenol of 99.7% was obtained. Therefore, it is evident that an in-situ combined technology of electrokinetic remediation and Fenton-like process is capable of simultaneously removing and degrading the phenol in a saturated flow.

Electric Stimulation↗

Prototypes using metal, carbon fiber and composite field emission sources modulated by a laser beam.

Field emission of electrons from a variety of metallic, carbon fiber and composite metal-insulator micropoint cathodes was employed in this study. Tungsten, carbon fiber and ZrC tips, were studied using a field emission microscope. These cathodes were characterized and the current-voltage (I-V) characteristics were determined. A variety of surface treatment procedures were carried out to increase the stability of emission. These electron sources were mounted in sealed prototype field emission tubes, while others were tested under medium, high and UHV conditions. The emission current switch-on phenomenon was found with all non-metallic cathodes. The emitters were then subjected to a square wave-modulated, maximally focused laser diode beam (lambda = 658 nm, 30mW). The beam impedance (approximately 1 Gohms) and the anode capacitance (approximately 10 pF) act as a low-pass filter.

Journal Article↗

Electrically evoked single-fiber action potentials from cat: responses to monopolar, monophasic stimulation.

We recorded action potentials from single auditory-nerve fibers of cats using monophasic current pulses delivered by a monopolar intracochlear electrode. These simple stimuli provided a means of investigating basic properties and hypotheses of electrical excitation. Standard micropipette recording techniques were used. Responses to anodic (positive) and cathodic (negative) stimulus pulses were recorded separately to evaluate stimulus polarity effects. Mean spike (action potential) latency was polarity dependent, with greater latencies for cathodic stimulation. Threshold stimulus level was also polarity dependent, with relatively lower cathodic thresholds. Both effects are consistent with trends reported in the compound action potential. Variability in single-fiber latency (i.e., jitter) was dependent upon stimulus polarity. In contrast, the slope of single-fiber input-output functions failed to show a clear polarity dependence, although such trends have been seen in the compound action potential data. We also observed a relatively greater degree of adaptation over time with anodic stimulation. Bimodal post-stimulus-time histograms were recorded in a small number (2%) of fibers, supporting the hypothesis that both the peripheral (dendritic) and central axonal processes are excitable with the same stimulus polarity, in a limited number of cases. This observation, together with analyses of interactions among measures of latency, threshold, and jitter, is consistent with the hypothesis that, with monopolar intracochlear stimulation, most fibers are stimulated at axonal (modiolar) sites and a minority of fibers nearest the electrode are stimulable at their peripheral processes.

Action Potentials↗

Electrochemical study of nisoldipine: analytical application in pharmaceutical forms and photodegradation.

The anodic and cathodic behavior of nisoldipine, 3-isobutyl-5-methyl-1,4-dihydro-2,6-dimethyl-4-(2-nitrophenyl)pyridine-3 ,5-dicarboxylate, are reported. This drug belongs to the nitroaryl-1,4-dihydropyridine family, known as calcium channel antagonist and employed in therapeuticalls as peripheral and cerebral vasodilators, in the treatment of the arterial hypertension. The cathodic response corresponds to the reduction of the nitroaromatic group to generate the hydroxylamine derivative. The study by dc and d.p.p. reveals the appearance of four signals depending on pH: Signal I (pH 1-11.5) R - NO2 + 4H+ + 4e- --> R - NHOH + H2O; Signal II (pH 1-5) R - N+H2OH + 2H+ + 2e- --> RN+H3 + H2O; Signal III (pH > 11.5) R - NO2 + e- <--> R - NO2.-; Signal IV (pH > 11.5) R - NO2.- + 3e- + 4H+ --> R - NHOH. In contrast, the anodic response corresponds to the oxidation of the 1,4-dihydropyridine ring to generate the corresponding pyridine derivative. Both, cathodic (d.p.p.) and anodic signals (d.p.v.) were employed to develop analytical methodology for the determination of the drug. The repeatability of the measurements for both methods was adequate with R.S.D. of 1.4% (n = 10) and 2.1% (n = 10) for d.p.p. and d.p.v., respectively. Also recovery studies, 103.8% (R.S.D. 2.65%) by d.p.p. and 98.7% (R.S.D. 2.1%) by d.p.v. show that the accuracy and precision of the developed methods were adequate. The analytical methods were successfully applied to the determination of nisoldipine in both tablets and capsules. In addition, a preliminary study of the photostability of nisoldipine (using both UV and artificial day light) was completed. The identity of the main electroactive photodegradation products by GC with spectrometry detection is provided.

Calcium Channel Blockers↗

Recruitment by motor nerve root stimulators: significance for implant design.

Three paraplegics have been implanted with stimulators of the lumbar anterior roots. Twelve roots were trapped in slots, each with three electrodes, a central cathode and two anodes, but the anodes in all the slots were connected together to reduce the number of wires. Cross-talk between roots was observed at lower levels than expected. Cross-talk was assessed from the ratio of the root's threshold to the threshold of the contralateral response (expected ratio: 72). Two hypothetical reasons for this low ratio were: that the cathode current was not equally shared by the anodes; or that the contralateral responses were reflex. Experiments showed that neither explanation was valid. The ratio of the contralateral to ipsilateral threshold for individual slots (K(1)) was sometimes low because the ipsilateral threshold was high. By taking the ratio of the lowest contralateral response to lowest ipsilateral response, for all roots in each subject (K(2)), the ratio should approach the theoretical value. However, for the two subjects with small slots, it was 7.9 and 15.3, much less than 72, suggesting that the original theory was incorrect. Approximate calculations of the activation function suggest that the reason may be that roots which run close to a slot, but not through it, may pass through a virtual anode region outside the ends of the slots, and that anodal break stimulation in those regions causes the cross-talk. Our estimate is that this cross-talk would be expected to occur at intensities above 5.3 times the cathodal threshold. If the roots are stimulated in pairs, below the levels of cross-talk, experimental results show that the moments obtained in response are additive to within 5%.

Artifacts↗

Rotational temperature of nitrogen glow discharge obtained by optical emission spectroscopy.

Measurements of rotational temperature as low as several hundred Kelvin have been measured using optical emission spectroscopy (OES) in nitrogen direct current (DC) glow discharge. The strongest band of the first negative system of nitrogen was chosen to deduce the rotational temperature at four different positions in nitrogen DC glow discharge, the back of cathode; cathode sheath; positive column; and anode glow. In positive column the rotational temperature increased apparently with the increasing discharge voltage from 500 to 1000 V when the pressure was 10 Pa. But with pressure of 20 Pa the rotational temperature in positive column increased slightly with the increase of discharge voltage. On the contrary, the rotational temperature in cathode sheath took reverse tendencies when the discharge voltage varies from 500 to 1000 V. As regard the anode glow, the rotational temperature at 10 Pa decreased with the increase of discharge voltage, but that at pressure of 20 Pa increased. We attribute the different tendencies of the rotational temperature to the different discharge statues at different pressures. When the discharge voltage varies from 500 to 1100 V, the discharge with pressure of 10 Pa is normal glow and that with 20 Pa is abnormal glow.

Nitrogen↗

Interaction effects of galvanic vestibular stimulation and head position on the soleus H reflex in humans.

OBJECTIVES: The objective of this study is to measure the influence of galvanic vestibular stimulation and head-on-body alignment on the soleus H-reflex in prone human subjects. METHODS: We studied changes in the amplitude of the right soleus H-reflex to monopolar monaural galvanic stimulation in 10 healthy prone lying subjects. Trials were randomly administered according to head position (left or right) and stimulus polarity (anode or cathode). We also investigated the influence of the conditioning stimuli by examining the amplitude of the H-reflex based on head position without galvanic stimulation. A one-way and two-way repeated measures analysis of variance were used to compare the mean amplitudes of the test and conditioned H-reflexes. RESULTS: The greatest facilitation was observed when the head was turned to the left and coupled with cathodal stimulation. The largest inhibitory effect was found when the head was turned to the right and paired with anodal stimulation. However, when head left was paired with anodal stimulation or head right was coupled with cathodal stimulation, only minimal changes in amplitude were observed. CONCLUSIONS: The results demonstrate that there is an interaction between head position and galvanic stimulus polarity when measuring the excitability of the soleus motoneuron pool in prone lying subjects.

Adult↗

Conditions for accurate Karl Fischer coulometry using diaphragm-free cells.

Factors influencing the extent of formation of oxidizable reduction products in coulometric cells used for Karl Fischer (KF) determination of water were investigated. For methanolic KF reagents buffered with imidazole (Im) or diethanolamine (DEA) (separately or in combination), three parameters were found to be of outmost importance: the cathodic current density, the pH, and the concentration of protonated base (ImH+ or DEAH+). For reagents buffered with only Im, the relative formation of oxidizable reduction products varied in the range 2-40%; i.e., 51-70 micrograms of water was found for a 50 micrograms water sample, depending on the above-mentioned parameters. The lowest values were observed for reagents having a pH around 10 in combination with cathodic current densities in the range 2000-5000 mA cm-2. For all the Imbuffered reagents investigated, the addition of modifiers such as chloroform, hexanol, and carbon tetrachloride was found to decrease the formation of oxidizable reduction products significantly. For example, a reagent buffered at pH 10 containing 1 M hexanol gave less than 0.3% formation in the current density interval from 200 to 4000 mA cm-2. The best reagents based on the above-mentioned modifiers were tested in the continuous coulometric mode with errors typically in the interval 0-0.5% using optimum conditions. One prerequisite for obtaining such small errors with diaphragm-free continuous coulometry is to use a cathode area no larger than 0.002 cm2. For some of the reagents based on both Im and DEA, the formation of oxidizable reduction products was close to zero at certain current densities, although the analytical performance was not as good as for the reagents buffered solely by Im due to longer conditioning and titration times.

Buffers↗

Electrochemical hydrodehalogenation of 2,4-dibromophenolin paraffin oil using a solid polymer electrolyte reactor.

A new technology for remediation of halogenated organics-oil systems, which can cause serious environmental problems, has been demonstrated using the electrochemical hydrodehalogenation of 2,4-dibromophenol (DBP) in paraffin oil in a solid polymer electrolyte reactor. The reactor has been evaluated in terms of cathode materials and structure and the ratio of the cathode surface area to the solution volume. A cathode of titanium minimesh with a palladium electrocatalyst produced by electrodeposition was particularly effective. Current efficiencies of up to 85% and percentage of DBP removal of up to 62%, space-time yields of up to 7.6 kg DBP m(-3) h(-1), and energy consumption as low as 1.6 kW h (kg of DBP)(-1) were achieved. The reactor showed stable operation for periods of up to 170 h. The results demonstrated that electroreduction could be an alternative technology to electrooxidation forthe treatment of wastes and toxic halogenated compounds, making the process simpler in comparison to electrooxidation.

Electrochemistry↗

Production of electricity during wastewater treatment using a single chamber microbial fuel cell.

Microbial fuel cells (MFCs) have been used to produce electricity from different compounds, including acetate, lactate, and glucose. We demonstrate here that it is also possible to produce electricity in a MFC from domestic wastewater, while atthe same time accomplishing biological wastewater treatment (removal of chemical oxygen demand; COD). Tests were conducted using a single chamber microbial fuel cell (SCMFC) containing eight graphite electrodes (anodes) and a single air cathode. The system was operated under continuous flow conditions with primary clarifier effluent obtained from a local wastewater treatment plant. The prototype SCMFC reactor generated electrical power (maximum of 26 mW m(-2)) while removing up to 80% of the COD of the wastewater. Power output was proportional to the hydraulic retention time over a range of 3-33 h and to the influent wastewater strength over a range of 50-220 mg/L of COD. Current generation was controlled primarily by the efficiency of the cathode. Optimal cathode performance was obtained by allowing passive air flow rather than forced air flow (4.5-5.5 L/min). The Coulombic efficiency of the system, based on COD removal and current generation, was < 12% indicating a substantial fraction of the organic matter was lost without current generation. Bioreactors based on power generation in MFCs may represent a completely new approach to wastewater treatment. If power generation in these systems can be increased, MFC technology may provide a new method to offset wastewater treatment plant operating costs, making advanced wastewater treatment more affordable for both developing and industrialized nations.

Bioelectric Energy Sources↗

Destruction of gas-phase trichloroethylene in a modified fuel cell.

A conventional fuel cell was used as a catalytic reactor to treat soil vapor extraction (SVE) gases contaminated with trichloroethylene (TCE). The SVE gases are fed to the cathode side of the fuel cell, where TCE is reduced to ethane and hydrochloric acid. The results obtained suggest that TCE reduction occurs by a catalytic reaction with hydrogen that is re-formed on the cathode's surface beyond a certain applied cell potential. Substantial conversion of TCE is obtained, even when competing oxygen reduction occurs in the cathode. The process has been modeled successfully by conceptualizing the flow passage in the fuel cell as a plug flow reactor.

Catalysis↗

Effects of membrane cation transport on pH and microbial fuel cell performance.

Due to the excellent proton conductivity of Nafion membranes in polymer electrolyte membrane fuel cells (PEMFCs), Nafion has been applied also in microbial fuel cells (MFCs). In literature, however, application of Nafion in MFCs has been associated with operational problems. Nafion transports cation species other than protons as well, and in MFCs concentrations of other cation species (Na+, K+, NH4+, Ca2+, and Mg2+) are typically 10(5) times higher than the proton concentration. The objective of this study, therefore, was to quantify membrane cation transport in an operating MFC and to evaluate the consequences of this transport for MFC application on wastewaters. We observed that during operation of an MFC mainly cation species other than protons were responsible for the transport of positive charge through the membrane, which resulted in accumulation of these cations and in increased conductivity in the cathode chamber. Furthermore, protons are consumed in the cathode reaction and, consequently, transport of cation species other than protons resulted in an increased pH in the cathode chamber and a decreased MFC performance. Membrane cation transport, therefore, needs to be considered in the development of future MFC systems.

Bacteria↗

Light-driven OR and XOR programmable chemical logic gates.

Photoelectrodes made of nanocrystalline titanium dioxide modified with various pentacyanoferrates exhibit unique photoelectrochemical properties; photocurrent direction can be switched from anodic to cathodic and vice versa upon changes in photoelectrode potential and incident light wavelength (PhotoElectrochemical Photocurrent Switching, PEPS effect). At certain potentials, anodic photocurrent generated upon UV irradiation has the same intensity as the cathodic photocurrent generated upon visible irradiation. Under these conditions, simultaneous irradiation with UV and visible light results in compensation of anodic and cathodic photocurrents, and zero net photocurrent is observed. This process can be used for construction of unique light-driven chemical logic gates.

Journal Article↗

Electrochemical actuation of growing copper dendrimers in water.

We report the observation of electrochemical actuation in growing dendritic fibers made of self-assembled copper nanostructures (of 100 nm or less in diameter), on the metallic cathode of an ordinary aqueous electrochemical cell. This could be achieved when a copper anode and another metal cathode is placed in aqueous solution of either dilute HCl or CuSO(4), or CuCl(2), or H(2)O, and upon application of a DC voltage in the range of 1.5-12.0 V. The actuation could be observed with an on-off cycle of the applied voltage in the above range. The phenomenon was also observed with the growth of bimetallic structures using a number of electrolytes such as Ag(NO(3)), Pb(NO(3))(2), CoCl(2), NiCl(2), CdCl(2), ZnCl(2), and HAuCl(4). The fibrous structures remained stretched as they grew longer with time in the presence of an applied voltage. The extent of actuation was dependent on the applied voltage, the concentration of Cu(2+) ions in the solution, and also on ions such as Na(+), which did not get deposited at the cathode. The observed phenomena under different conditions have been explained on the basis of electrocapillarity.

Journal Article↗

Pore charge distribution considerations in human epidermal membrane electroosmosis.

The aim of this study was to assess the extent to which a model with pores having only net negative charges would adequately describe transdermal electroosmosis in human epidermal membrane (HEM) at neutral pH. Such information would enhance the predictive value of the modified Nernst-Planck model for transdermal iontophoresis, in addition to providing insights regarding the likelihood of significant pore charge distribution in HEM. Baseline results (the control) obtained from 0.1 to 0.4 V anodal and cathodal electroosmosis experiments with synthetic polycarbonate membranes (Nuclepore membranes), using radiolabeled urea and mannitol as the model permeants, demonstrated that such a membrane system can be modeled by the electrokinetic (electroosmosis) theory with the assumption of the pores possessing only negative charges. The studies with HEM were carried out at low voltage (</=0.5 V) where alterations in the barrier properties of HEM were minimal and at higher voltages (>/approximately = 1.0 V) where significant field-induced pore formation in HEM occurred. In both the low and high voltage studies, radiolabeled urea, mannitol, and water were employed as permeants in cathodal and anodal iontophoresis experiments. The results of the low voltage iontophoresis experiments suggest significant pore charge distribution in HEM (a significant deviation between the predictions from the single pore charge type assumption and the experimental data). Under the higher applied voltage conditions (>/approximately = 1.0 V), results from anodal and cathodal electroosmosis studies were consistent with the model in which the HEM has only pores that are net negatively charged.

Algorithms↗

Underpotential deposition of hydrogen on benzene-modified Pt(111) in aqueous H2SO4.

The Pt(111) electrode is modified by an overlayer of C6H6 (ads) upon its cycling in the 0.05-0.80 V range in aq H2SO4 + 1 mM C6H6. The C6H6 (ads) overlayer significantly changes the underpotential-deposited H (H(UPD)) and anion adsorption, and cyclic-voltammetry (CV) profiles show a sharp cathodic peak and an asymmetric anodic one in the 0.05-0.80 V potential range. The C6H6 (ads) layer blocks the (bi)sulfate adsorption but facilitates the adsorption of one monolayer of H(UPD). Cycling of the benzene-modified Pt(111) in benzene-free aq 0.05 H2SO4 from 0.05 to 0.80 V results in a partial desorption of C6H6 (ads) and in a partial recovery of the CV profile characteristic of an unmodified Pt(111). The peak potential of the cathodic and anodic feature is independent of the scan rate, s (10 < or = s < or = 100 mV s(-1)), and the peak current density increases linearly with an increase of the scan rate. Temperature variation modifies the peak potential and current density but does not affect the charge density of the cathodic or anodic feature. Temperature-dependent studies allow us to determine the thermodynamic state function for the H(UPD) adsorption and desorption. Delta G degrees(ads)(H(UPD))assumes values from -4 to -12 kJ mol(-1), while has values from 9 to 14 kJ mol(-1). The values of delta Delta G degrees (delta Delta G degrees = delat Delta G degrees(ads) + delta Delta D degrees(des)) decrease almost linearly from 6 kJ mol(-1) at theta(H(UPD) --> 0 to 0 kJ mol(-1) at theta(H(UPD) --> 1. The nonzero values of delta Delta G degrees testify that the adsorbing and desorbing H(UPD) adatoms interact with an energetically different substrate. The lateral interactions changed from repulsive (omega = 29 kJ mol(-1) at theta(H(UPD) --> 0) to attractive (omega = -28 kJ mol(-1) at theta(H(UPD) --> 1) as the H(UPD) coverage increases. The values of delta S degrees(ads)(H(UPD)) increase from 19 to 56 J K(-1) mol(-1), while those of delta S degrees(des)(H(UPD)) decrease from 45 to -30 J K(-1) mol(-1) with an increase of H(UPD) coverage. The values of delta H degrees(des)(H(UPD)) and delta H degrees(des)(H(UPD)) vary from 0 to 27 kJ mol(-1). The Pt(111)-H(UPD) surface bond energy at the benzene-modified Pt(111) electrode falls in the 191-218 kJ mol(-1) range and is weaker than in the case of the unmodified Pt(111) electrode in the same electrolyte.

Journal Article↗