Electron transfer gating

The PSII complex contains two distinct plastoquiaones that act ia series. The first is the mentioned above the second, Qg, is reversibly associated with a 30—34 kDa polypeptide ia the PSII cote. This secondary quiaone acceptor polypeptide is the most rapidly tumed-over proteia ia thylakoid membranes (41,46). It serves as a two-electron gate and connects the single-electron transfer events of the reaction center with the pool of free... 

Current research aims at high efficiency PHB materials with both the high speed recording and high recording density that are required for future memory appHcations. To achieve this aim, donor—acceptor electron transfer (DA-ET) as the hole formation reaction is adopted (177). Novel PHB materials have been developed in which spectral holes can be burnt on sub- or nanosecond time scales in some D-A combinations (178). The type of hole formation can be controlled and changed between the one-photon type and the photon-gated two-photon type (179). 

Chi Q, Farver O, Ulstrup J (2005) Long-range protein electron transfer observed at the singlemolecule level in situ mapping of redox-gated tunneling resonance. Proc Natl Acad Sci USA 102 16203-16208... 

Fig. 13. Representative Trumpet Plots for the [3Fe-4S]+/0 couple in native and D15N mutant forms of Azotobacter vinelandii ferredoxin I adsorbed on a PGE electrode. The plots for D15N also show the fits based on k0 t = 2.5 s-1. Note the intermediate region of the plot (pH 5.50) in which an oxidation peak is not observed because ET is gated. Data points shown in red are for the pH values indicated whereas data points shown in blue are for the uncoupled electron-transfer reaction occurring at pH > pffoiuater- Reproduced from Ref. (33) by permission of the Royal Society of Chemistry.

Keywords Luminescence m Fluorescence m Phosphorescence a Sensors a Switches a Logic Gates a Supramolecular Systems a Truth Tables a Photoinduced Electron Transfer a Molecular-Level Devices... 

The standard formalisms for describing ET processes assume that in reactions such as Eqs. (1) and (2) there is but a single stable conformational form for each of the precursor and successor electron-transfer states. However, for a system that displays two (or more) alternative stable conformations with different ET rates, dynamic conformational equilibrium can modulate the ET rates. Major protein conformational changes can occur at rates that are competitive with observed rates of ET [9], and such gating [10] may occur in non-rigid complexes such as that between zinc cytochrome c peroxidase (ZnCcP) and cytochrome c (see below) or even within cytochrome c [5]. 

The fact that ET and conformational reactions thus are sequential (Scheme III), and not concerted, is an important factor in efforts to disentangle eonforma-tional and electron-transfer influences, because standard detection methods monitor only the ET event, and not conformational changes within one electronic state. In many, if not most, instances the measured time course of a single gated ET reaction is likely to be indistinguishable from a reaction without gating. 

As discussed later, if binding can occur at more than one site, then more than one rate may occur. Alternatively, if the sites interconvert, this interconversion may modulate the electron transfer rate by modulating the distance. This would represent one limiting example of gated electron transfer as discussed by Hoffman and Ratner [4], and demonstrated by Pardue [5]. 

Oike T, Kurata T, Takimiya K et al (2005) Polyether-bridged sexithiophene as a complexa-tion-gated molecular wire for intramolecular photoinduced electron transfer. J Am Chem Soc 127 15372-15373... 

Davis WB, Ratner MA, Wasielewski MR (2001) Conformational gating of long distance electron transfer through wire-like bridges in donor-bridge-acceptor molecules. J Am Chem Soc 123 7877-7886... 

Figure 9. (a) Schematic representation of the five-module format of a photoactive triad which is switchable only by the simultaneous presence of a pair of ions. This design involves the multiple application of the ideas in Figure 1. The four distinct situations are shown. Note that the presence of each guest ion in its selective receptor only suppresses that particular electron transfer path. The mutually exclusive selectivity of each receptor is symbolized by the different hole sizes. All electron transfer activity ceases when both guest ions have been received by the appropriate receptors. The case is an AND logic gate at the molecular scale. While this uses only two ionic inputs, the principle established here should be extensible to accommodate three inputs or more, (b) An example illustrating the principles of part (a) from an extension of the aminomethyl aromatic family. The case shown applies to the situation (iv) in part (a) where both receptors are occupied. It is only then that luminescence is switched "on". Protons and sodium ions are the relevant ionic inputs.

NADPH oxidation and NO synthesis by the enzyme, it supports a role for reduction of the heme iron in catalysis, and may explain why NOS functions only as an NADPH-dependent reductase in the absence of bound calmodulin (Klatt et ai, 1993). The mechanism of calmodulin gating is envisioned to involve a conformational change between the reductase and oxygenase domains of NOS, such that an electron transfer between the terminal flavin and heme iron becomes possible. Calmodulin may also have a distinct role within the NOS reductase domain, in that its binding dramatically increases reductase activity of the enzyme toward cytochrome c (Klatt et al., 1993 Heinzel et al., 1992). However, it is clear that several other NOS functions occur independent of calmodulin, including the binding of L-arginine and NADPH, and transfer of NADPH-derived electrons into the flavins (Abu-Soud and Stuehr, 1993). 

Photoinduced electron transfer processes involving electron donor (D) and acceptor (A) components can be tuned via redox reactions. Namely, the excited-state properties of fluorophores can be manipulated by either oxidation of electron donors or reduction of electron acceptors. Also, the oxidized and the reduced species show different properties compared to the respective electron donors and acceptors. By making use of these properties of electron donors and acceptors, a number of molecular switches and logic gates have been described in recent years. In the following, we will introduce these redox-controlled molecular switches according to the redox centers. 

If the system under consideration possesses non-adiabatic electronic couplings within the excited-state vibronic manifold, the latter approach no longer is applicable. Recently, we have developed a simple model which allows for the explicit calculation of RF s for electronically nonadiabatic systems coupled to a heat bath [2]. The model is based on a phenomenological dissipation ansatz which describes the major bath-induced relaxation processes excited-state population decay, optical dephasing, and vibrational relaxation. The model has been applied for the calculation of the time and frequency gated spontaneous emission spectra for model nonadiabatic electron-transfer systems. The predictions of the model have been tested against more accurate calculations performed within the Redfield formalism [2]. It is natural, therefore, to extend this... 

If M is unstable then ipb/fpf will be less than unity. Its magnitude will depend upon the scan rate, the value of the first-order constant k, and the conditions of the experiment. At fast scan rates the ratio ipb/ ip, may approach one if the time gate for the decomposition of M is small compared with the half-life of M-, (In 2jk). As the temperature is lowered, the magnitude of k may be sufficiently decreased for full reversible behaviour to be observed. The decomposition of M- could involve the attack of a solution species upon it, e.g. an electrophile. In such cases, ipb/ipf, will of course be dependent upon the concentration of the particular substrate (under pseudo-first-order conditions, k is kapparent). Quantitative cyclic voltammetric and related techniques allow the evaluation of the rate constants for such electrochemical—chemical, EC, processes. At the limit, the electron-transfer process is completely irreversible if k is sufficiently large with respect to the rate of heterogeneous electron transfer the electrochemical and chemical steps are concerted on the time-scale of the cyclic voltammetric experiment.1-3... 

The mechanism of proton translocation in complexes I and IV is not yet understood. Here, the electron-transfer reactions may cause protein conformational changes that open gates for proton movement first on one side of the membrane and then on the other. 

Pogozelski WK, Tullius TD (1998) Oxidative strand scission of nucleic acids Routes initiated by hydrogen abstraction from the sugar moiety. Chem Rev 98 1089-1107 Poole JS, Eladad CM, Platz MJ, Fredin ZP, Pickard L, Guerrero EL, Kesser M, Chowdhury G, Kotande-niya D, Gates KS (2002) Photochemical electron transfer reactions of tirapazamine. Photochem Photobiol 75 339-345... 

De Silva et al. [28] prepared a naphthalene derivative (3) with logic functions (Scheme 1). Here, the bromonaphthalene unit exhibits phosphorescence in the presence of both the calcium ion and (3-CD [28], However, without them, oxygen quenches the phosphorescence of 2-bromonaphthalene phosphor because the protection effect of (3-CD is absent and photoinduced electron transfer from the tetracarboxylate receptor to the 2-bromonaphthalene phosphor occurs. Thus, phosphorescence output occurs only when the calcium ion and (3-CD inputs are active. The operation of these two inputs with a phosphorescence output corresponds to the AND logic function. The input to the NOT gate is oxygen. In the presence of oxygen without either calcium or (3-CD, the AND gate is disabled. 

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