Control Of Electron Transport Research Articles

Imaging and controlling electron transport inside a quantum ring

Traditionally, the understanding of quantum transport, coherent and ballistic1, relies on the measurement of macroscopic properties such as the conductance. While powerful when coupled to statistical theories, this approach cannot provide a detailed image of "how electrons behave down there". Ideally, understanding transport at the nanoscale would require tracking each electron inside the nano-device. Significant progress towards this goal was obtained by combining Scanning Probe Microscopy (SPM) with transport measurements2-7. Some studies even showed signatures of quantum transport in the surrounding of nanostructures4-6. Here, SPM is used to probe electron propagation inside an open quantum ring exhibiting the archetype of electron wave interference phenomena: the Aharonov-Bohm effect8. Conductance maps recorded while scanning the biased tip of a cryogenic atomic force microscope above the quantum ring show that the propagation of electrons, both coherent and ballistic, can be investigated in situ, and even be controlled by tuning the tip potential.

Adjustment of leaf photosynthesis to shade in a natural canopy: rate parameters

ABSTRACTThe present study was performed to investigate the adjustment of the rate parameters of the light and dark reactions of photosynthesis to the natural growth light in leaves of an overstorey species, Betula pendula Roth, a subcanopy species, Tilia cordata P. Mill., and a herb, Solidago virgaurea L., growing in a natural plant community in Järvselja, Estonia. Shoots were collected from the site and individual leaves were measured in a laboratory applying a standardized routine of kinetic gas exchange, Chl fluorescence and 820 nm transmittance measurements. These measurements enabled the calculations of the quantum yield of photosynthesis and rate constants of excitation capture by photochemical and non‐photochemical quenchers, rate constant for P700+ reduction via the cytochrome b6f complex with and without photosynthetic control, actual maximum and potential (uncoupled) electron transport rate, stomatal and mesophyll resistances for CO2 transport, Km(CO2) and Vm of ribulose‐bisphosphate carboxylase‐oxygenase (Rubisco) in vivo. In parallel, N, Chl and Rubisco contents were measured from the same leaves. No adjustment toward higher quantum yield in shade compared with sun leaves was observed, although relatively more N was partitioned to the light‐harvesting machinery in shade leaves (H. Eichelmann et al., 2004). The electron transport rate through the Cyt b6f complex was strongly down‐regulated under saturating light compared with darkness, and this was observed under atmospheric, as well as saturating CO2 concentration. In vivo Vm measurements of Rubisco were lower than corresponding reported measurements in vitro, and the kcat per reaction site varied widely between leaves and growth sites. The correlation between Rubisco Vm and the photosystem I density was stronger than between Vm and the density of Rubisco active sites. The results showed that the capacity of the photosynthetic machinery decreases in shade‐adjusted leaves, but it still remains in excess of the actual photosynthetic rate. The photosynthetic control systems that are targeted to adjust the photosynthetic rate to meet the plant's needs and to balance the partial reactions of photosynthesis, down‐regulate partial processes of photosynthesis: excess harvested light is quenched non‐photochemically; excess electron transport capacity of Cyt b6f is down‐regulated by ΔpH‐dependent photosynthetic control; Rubisco is synthesized in excess, and the number of activated Rubisco molecules is controlled by photosystem I‐related processes. Consequently, the nitrogen contained in the components of the photosynthetic machinery is not used at full efficiency. The strong correlation between leaf nitrogen and photosynthetic performance is not due to the nitrogen requirements of the photosynthetic apparatus, but because a certain amount of energy must be captured through photosynthesis to maintain this nitrogen within a leaf.

Use of stochastic web patterns to control electron transport in semiconductor superlattices

Chaotic electron transport has been explored in a variety of semiconductor structures in which the transition to chaos occurs by the gradual and progressive destruction of stable orbits in response to an increasing perturbation. There is also a much rarer type of chaos, known as non-KAM dynamics, which switches on and off abruptly when the temporal frequency of the perturbation reaches certain critical values. This type of chaotic motion is of great interest due to diverse applications in the theory of plasma physics, tokamak fusion, turbulent fluid dynamics, ion traps, and quasicrystals, but has not yet been realized in experiment. Here, we show that electrons in a superlattice miniband with a tilted magnetic field provide an experimentally-accessible non-KAM system and, moreover, that this unusual type of chaotic dynamics can produce strong resonant enhancement of the electron drift velocity. The onset of chaos is characterized by the formation of intricate “stochastic web” patterns in the electron phase space. These webs delocalize the electron orbits, thereby generating strong resonant peaks in our calculated drift velocity versus electric field characteristics.

Synthesis of Diode Molecules and Their Sequential Assembly to Control Electron Transport

Sequenzielle Entschützung und Immobilisierung ermöglichte die Synthese von Thiophen-Thiazol-Diblockoligomeren mit zwei unterschiedlichen Thiolschutzgruppen. Eine Untersuchung des I/V-Verhaltens dieser Diblockoligomere zwischen zwei Goldelektroden (siehe Beipiel) zeigt, dass die Orientierung der Gleichrichtung durch ihre Anordnung zwischen den Elektroden gesteuert wird.

Synthesis of diode molecules and their sequential assembly to control electron transport.

A sequential deprotection and immobilization procedure was enabled by the synthesis of two thiophene–thiazole diblock oligomers with two different thiol protection groups. Investigation of the I/V behaviors of these diblock molecules between two gold electrodes (see picture) showed that the rectifying direction was controlled by their orientation between the electrodes.

Iron bound to the high-affinity Mn-binding site of the oxygen-evolving complex shifts the pK of a component controlling electron transport via Y(Z).

Flash-probe fluorescence spectroscopy was used to compare the pH dependence of charge recombination between Y(Z)(*) and Q(a)(-) in Mn-depleted, photosystem II membranes [PSII(-Mn)] and in membranes with the high-affinity (HA(Z)) Mn-binding site blocked by iron [PSII(-Mn,+Fe); Semin, B. K., Ghirardi, M. L., and Seibert, M. (2002) Biochemistry 41, 5854-5864]. The apparent half-time for fluorescence decay (t(1/2)) in PSII(-Mn) increased from 9 ms at pH 4.4 to 75 ms at pH 9.0 [with an apparent pK (pK(app)) of 7.1]. The actual fluorescence decay kinetics can be fit to one exponential component at pH <6.0 (t(1/2) = 9.5 ms), but it requires an additional component at pH >6.0 (t(1/2) = 385 ms). Similar measurements with PSII(-Mn,+Fe) membranes show that iron binding has little effect on the maximum and minimum t(1/2) values measured at alkaline and acidic pHs but that it does shift the pK(app) from 7.1 to 6.1 toward the more acidic pK(app) value typical of intact membranes. Light-induced Fe(II) blocking of the PSII(-Mn) membrane is accompanied by a decrease in buffer Fe(II) concentration. This decrease was not the result of Fe(II) binding, but rather of its oxidation at two sites, the HA(Z) site and the low-affinity site. Mössbauer spectroscopy at 80 K on PSII(-Mn,+Fe) samples, prepared under conditions providing the maximal blocking effect but minimizing the amount of nonspecifically bound iron cations, supports this conclusion since this method detected only Fe(III) cations bound to the membranes. Correlation of the kinetics of Fe(II) oxidation with the blocking parameters showed that blocking occurs after four to five Fe(II) cations were oxidized at the HA(Z) site. In summary, the blocking of the HA(Z) Mn-binding site by iron in PSII(-Mn) membranes not only prevents the access of exogenous donors to Y(Z) but also partially restores the properties of the hydrogen bond net found in intact PS(II), which in turn controls the rate of electron transport to Y(Z).

A nanometre-scale electronic switch consisting of a metal cluster and redox-addressable groups.

So-called bottom-up fabrication methods aim to assemble and integrate molecular components exhibiting specific functions into electronic devices that are orders of magnitude smaller than can be fabricated by lithographic techniques. Fundamental to the success of the bottom-up approach is the ability to control electron transport across molecular components. Organic molecules containing redox centres-chemical species whose oxidation number, and hence electronic structure, can be changed reversibly-support resonant tunnelling and display promising functional behaviour when sandwiched as molecular layers between electrical contacts, but their integration into more complex assemblies remains challenging. For this reason, functionalized metal nanoparticles have attracted much interest: they exhibit single-electron characteristics (such as quantized capacitance charging) and can be organized through simple self-assembly methods into well ordered structures, with the nanoparticles at controlled locations. Here we report scanning tunnelling microscopy measurements showing that organic molecules containing redox centres can be used to attach metal nanoparticles to electrode surfaces and so control the electron transport between them. Our system consists of gold nanoclusters a few nanometres across and functionalized with polymethylene chains that carry a central, reversibly reducible bipyridinium moiety. We expect that the ability to electronically contact metal nanoparticles via redox-active molecules, and to alter profoundly their tunnelling properties by charge injection into these molecules, can form the basis for a range of nanoscale electronic switches.

Molecular control over Au/GaAs diodes

The use of molecules to control electron transport is an interesting possibility, not least because of the anticipated role of molecules in future electronic devices. But physical implementations using discrete molecules are neither conceptually simple nor technically straightforward (difficulties arise in connecting the molecules to the macroscopic environment). But the use of molecules in electronic devices is not limited to single molecules, molecular wires or bulk material. Here we demonstrate that molecules can control the electrical characteristics of conventional metal-semiconductor junctions, apparently without the need for electrons to be transferred onto and through the molecules. We modify diodes by adsorbing small molecules onto single crystals of n-type GaAs semiconductor. Gold contacts were deposited onto the modified surface, using a 'soft' method to avoid damaging the molecules. By using a series of multifunctional molecules whose dipole is varied systematically, we produce diodes with an effective barrier height that is tuned by the molecule's dipole moment. These barrier heights correlate well with the change in work function of the GaAs surface after molecular modification. This behaviour is consistent with that of unmodified metal-semiconductor diodes, in which the barrier height can depend on the metal's work function.

Regulation of the photosynthetic electron transport chain.

The regulation of electron transport between photosystems II and I was investigated in the plant Silene dioica L. by means of measurement of the kinetics of reduction of P(700) following a light-to-dark transition. It was found that, in this species, the rate constant for P(700) reduction is sensitive to light intensity and to the availability of CO(2). The results indicated that at 25 degrees C the rate of electron transport is down-regulated by approximately 40-50% relative to the maximum rate achievable in saturating CO(2) and that this down-regulation can be explained by regulation of the electron transport chain itself. Measurements of the temperature sensitivity of this rate constant indicated that there is a switch in the rate-limiting step that controls electron transport at around 20 degrees C: at higher temperatures, CO(2) availability is limiting; at lower temperatures some other process regulates electron transport, possibly a diffusion step within the electron transport chain itself. Regulation of electron transport also occurred in response to drought stress and sucrose feeding. Measurements of non-photochemical quenching of chlorophyll fluorescence did not support the idea that electron transport is regulated by the pH gradient across the thylakoid membrane, and the possibility is discussed that the redox potential of a stromal component may regulate electron transport.Keywords: DeltapH. Electron transport. Photosynthesis. Photosynthetic control. Redox regulation. Silene (photosynthesis)

Flat thin CRT based on controlled electron transport through insulating structures

The feasibility is demonstrated of a flat thin cathode ray tube with insulating supports inside the envelope to withstand the atmospheric pressure. The supports are actively used to guide the electrons from the cathodes to the phosphor screen. The electrons are transported through the insulating structures by a self-regulating secondary emission process, provided a sufficiently high voltage is applied between the entrance and the exit of the structures. The local potentials are automatically adjusted by charge deposition on the insulating walls until a situation is established characterized by the property that the local average secondary emission coefficient is equal to one everywhere in the structure. The flat thin CRT with these insulating internal supports has a thickness of about 1 cm for any display size and a relatively low mass. Large displays have been realized showing a good performance: brightness, contrast, colour purity and power dissipation are comparable to or better than obtained with conventional cathode ray tubes. Some other interesting applications based on the same phenomenon are briefly discussed: an electron ‘fibre’, an electron source with high current density and a beam switch.

Suppression of ballistic electron transmission through a semiconductor II-structure by an external transverse electric field

We have conducted numerical studies of ballistic electron transport in a semiconductor II-structure when an external transverse electric field is applied. The device conductance as a function of electron energy and the strength of the transverse electric field is calculated on the basis of tight-binding Green's function formalism. The calculations show that a relatively weak electric field can induce very large decrease in the electron transmission across the structure. When the transverse electric field is sufficiently strong, electrons can hardly be transported through the device. Thus the performance of the device can be greatly improved for it is much easier to control electron transport through the device with an external transverse electric field.

Iron at the cell surface controls both DNA synthesis and plasma membrane redox system

Addition of the impermeable iron II chelator bathophenanthroline disulfonate (BPS) to cultured Chinese hamster lung fibroblast (CCL 39 cells) inhibits DNA synthesis but not protein synthesis or cytoplasmic alkalinization, when cell growth is initiated with growth factors such as EGF plus insulin, thrombin, or ceruloplasmin. The BPS inhibition is reversed by addition of stoichiometric ferrous iron at stoichiometric concentration. BPS does not inhibit cell growth stimulated by fetal calf serum. The effect of the BPS differs from the inhibition of growth by hydroxyurea which acts on the ribonucleotide reductase. The BPS treatment leads to release of iron from the cells as determined by BPS iron II complex formation over 90 min. Cells treated with BPS just during starvation period cannot re-initiate DNA synthesis after mitogen stimulation even if BPS is removed from the medium and cells are previously washed. BPS treatment also inhibits transplasma membrane electron which is restored by incubation of cells with 10 μM ferric ammonium citrate. Growth factor stimulation of DNA synthesis is restored by addition of 1 μM ferrous ammonium sulfate or ferric ammonium citrate, or 0.1 μM diferric transferrin. Copper, cobalt, nickel, zinc, gallium, aluminum, or apotransferrin cannot restore the activity. The BPS effect is consistent with removal of iron from a site on the cell surface which controls electron transport and DNA synthesis.

Polycrystalline thin film ZnSexTe1-x: preparation and properties

ZnSexTe1-x films were prepared by co-evaporating ZnSe and ZnTe powders from a two-zone hot wall evaporation jig onto glass substrates. The optical band gaps for different x were determined and this showed a bowing behaviour. The refractive indices and extinction coefficients have been determined as a function of wavelength. Variations of surface roughness with composition and microstructural details were also reported. Grain boundary scattering effects were found to be a dominant factor controlling electron transport processes in these films.

Oxygen production and consumption by chloroplasts in situ and in vitro as studied with microscopic spin label probes

A new spin-label oximetry approach able to measure the oxygen partial pressure in complex photosynthetic systems has been developed using bovine serum albumin (BSA)-coated light paraffin oil particles containing cholestane spin label (CSL). Paraffin oil particles protect the spin label against the action of chemically active metabolites. The amplitude of the electron paramagnetic resonance (EPR) signal from CSL measured at a saturating microwave power is sensitive to the concentration of oxygen. We demonstrate here the ability of this method to monitor the kinetics of light-induced oxygen production in situ, i.e., in the interior of a bean leaf. The oxygen release, observed during leaf illumination with continuous light, exhibits an overshoot that correlates with the well-known nonmonotonous behavior of the Photosystem I reaction center, P700. Short-term illumination of isolated bean chloroplasts, suspended in the presence of the electron mediator methylviologen, induces a reversible uptake of oxygen. However, after prolonged illumination, chloroplasts lose their ability to regenerate oxygen in the dark. The exhaustion of oxygen (and oxygen active forms) is accompanied by the loss of CSL paramagnetism and the capacity to photooxidize P700. Comparison of the kinetics of P700 redox transients with oximetric data demonstrates that oxygen concentration is the essential factor controlling electron transport in leaves and isolated chloroplasts.

Electron transport processes in conductor‐filled polymers

AbstractThis article contends that three distinct physical processes control electron transport in conductor‐filled polymer systems. Percolation is required to explain the macroscopic conduction in the disordered medium. Quantum mechanical tunneling (possibly quantum fluctuation augmented) is needed to describe conduction between adjacent conductive particles at the microscopic level. And, thermal expansion is invoked to deduce constituent volume densities and microscopic tunnel lengths. Each of these mechanisms is given a mathematical form. The ansatz is used to predict resistivity vs. temperature and resistivity vs. conductor‐filling fraction functions. Successes and deficiencies of the theory are discussed with respect to experimental data and theoretical considerations.

PH effects on light dependence of the stoichiometry of proton influx and efflux to electron transport in spinach chloroplasts

Initial and steady state rates of proton transport at low light intensity have been measured and compared with steady state rates of electron transport in the pH range of 6.0-7.6 in envelope-free spinach chloroplasts. At pH 6-7, the H(+)/e(-) values computed using the initial rate of proton transport varied with light intensity, from a value of 2 at low light to almost 5 at high light. In contrast, the H(+)/e(-) values computed using the steady state rate of proton transport did not show a dependence on light intensity, having a constant value of 1.7±0.2. Likewise, at pH 7.6, the H(+)/e(-) ratio, computed using either the initial or steady state rates of proton transport did not vary with light intensity but was constant at H(+)/e(-)=1.7±0.1. Analysis of the light dependence of electron and proton transport allowed determination of (a) the quantam requirements of transport, (b) the rates of transport at light saturation, and (c) H(+)/e(-) ratios for initial and steady state proton transport. Extrapolating the initial proton transport to zero light, we found that both H(+)/photon and H(+)/e(-) values were not strongly dependent on pH, approaching a near constant value of 2.0. Using the initial rate of proton transport extrapolated to saturating light intensity we found the H(+)/e(-) ratio to be strongly pH-dependent. We suggest that internal pH controls electron transport at high light intensities. The true stoichiometry is reflected only in measurements taken at low light using the initial proton transport data. Our findings and interpretation reconcile some conflicting data in the literature regarding the pH-dependence of the H(+)/e(-) ratio and support the concept that internal pH controls noncyclic electron transport.

Phospholipid requirements for the reconstitution of complex-III vesicles exhibiting controlled electron transport

Phospholipid requirements for the reconstitution of Complex-III vesicles exhibiting respiratory control (electron-transport control) were studied. Vesicles prepared from pure phosphatidylethanolamine gave maximal control ratios. Phosphatidylcholine alone did not support respiratory control, although these vesicles were capable of maintaining stable K+-diffusion gradients. Apparently Complex III cannot insert into a bilayer of phosphatidylcholine. Formation of mixed phosphatidylcholine/phosphatidylethanolamine (6:1, w/w) vesicles was sufficient, however, to allow Complex-III insertion and to restore respiratory control. Mixtures of acidic phospholipids with either phosphatidylethanolamine or phosphatidylcholine did not improve respiratory control over that obtained with pure phosphatidylethanolamine. Phosphatidylethanolamine from bovine heart mitochondria, soya beans or Escherichia coli was equally effective in reconstituting respiratory control, suggesting that the specificity is referable to the head group and not to the fatty-acid moiety.