Electron and Proton Transfers around the b/f Complex in Chloroplasts: Modelling the Constraints on Q-cycle Activity

1988 ◽  
Vol 15 (4) ◽  
pp. 567 ◽  
Author(s):  
AB Hope ◽  
DB Matthews
Keyword(s):  
Reduction Potential ◽  
Slow Phase ◽  
Single Turnover ◽  
Reduction Potentials ◽  
Q Cycle ◽  
Proton Transfers ◽  
Proton Uptake ◽  
Time Standard ◽  
Electron Transfers ◽  
Stimulation Of

The requirements for the operation of a Q-cycle in thylakoids are discussed. A computer model is described in which the state of reduction of components of the b/f complex is followed, single turnover at a time. Standard reduction potentials from the literature were assigned to the cytochrome b563 molecules; those for the second electron oxidation of plastoquinol at p-sites, and for the reduction of plastoquone at n-sites, were found by optimising the predicted stimulation of proton uptake by valinomycin. The stimulation has been attributed to uptake by doubly reduced plastoquinone at b/f complexes, a process thought to continue only if the membrane potential (ΔV) is kept low by ionophores. ΔV was simulated in the model via the electrochromic signal; its effect on electron transfers in the b/f complex was incorporated by modifying the reduction potentials. The extent of valinomycin stimulation of proton uptake, its dependence on [valinomycin] and flash frequency, the slow phase of the electrochromic signal and the extent of cytochrome b reduction were predicted by the model when the standard reduction potential for the p-site was set at -0.05 to -0.08 V. with that for the n-site at about 0 V.

Further Studies of Proton Translocations in Chloroplasts After Single-Turnover Flashes. I. Proton Uptake

1983 ◽  
Vol 10 (5) ◽  
pp. 363 ◽  
Author(s):  
AB Hope ◽  
DB Matthews
Keyword(s):  
Ionic Strength ◽  
Electron Flow ◽  
External Solution ◽  
Half Time ◽  
Cycle Model ◽  
Single Turnover ◽  
Q Cycle ◽  
Proton Uptake ◽  
Factor Α ◽  
Light Flashes

Damped, binary oscillations were observed in proton uptake by class C pea chloroplasts given a train of light flashes. The oscillation at pH 7.8 is predictable if the species accepting protons is either the doubly reduced secondary acceptor B�- or a plastoquinone PQ- from the pool, if 0.29 of the secondary acceptor is B- in dark-adapted chloroplasts and if a miss factor α = 0.12 governs the amval of electrons at B or B- after a flash. The rate of proton uptake was measured with varied pH, ionic strength and temperature. The half-time was 95 ms at pH 7.8 and 21°C. Using double flashes separated by variable intervals showed that the species able to accept protons was generated (t½) about 0.8 ms after a flash. The results are consistent with protons from the external solution reacting relatively slowly with univalent anions, which have earlier promptly supplied protons to B2- or PQ2-. Under conditions of cyclic and of non-cyclic electron flow, H+/e- stoichiometries were 1.1 and 1.0 respectively, and so the results do not support a Q-cycle model for pea chloroplasts.

Further Studies of Proton Translocations in Chloroplasts After Single-Turnover Flashes. II. Proton Deposition

1984 ◽  
Vol 11 (4) ◽  
pp. 267 ◽  
Author(s):  
AB Hope ◽  
DB Matthews
Keyword(s):  
Electron Acceptor ◽  
Water Oxidation ◽  
Electron Flow ◽  
Neutral Red ◽  
S Phase ◽  
Cyclic Electron Flow ◽  
Slow Phase ◽  
Single Turnover ◽  
Q Cycle ◽  
Average Size

The deposition of protons in the inside spaces of pea class C chloroplasts was studied by means of the acidification of neutral red measured spectrophotometrically, with the outside space buffered. Careful kinetic analysis of such signals revealed three components, during non-cyclic electron flow induced by single-turnover flashes. These components included a 'slow' phase not emphasized in previous studies. The half-times of these phases were: 'Fast', < 1 ms (not resolved); 'Intermediate', 13-25 ms with added electron acceptor or 4 ms without; and 'Slow', 70-90 ms. Under conditions for cyclic electron flow only the I phase remained; it was the same magnitude as the I phase in non-cyclic flow, and its half-time was c. 3 ms. The F phase, which is usually attributed to protons from the oxidation of water, increased in average size with number of flashes (taken four flashes at a time) and was not fully patent until more than 20 flashes. The size of the I phase, which is usually attributed to protons from the oxidation of plastohydroquinone, when measured in a sequence of flashes to dark-adapted suspensions under non- cyclic conditions, had a binary oscillation in phase with the oscillation in proton uptake reported previously. It was concluded that protons leave PQH2 two at a time on alternate flashes. The S phase (average in 10 test flashes) was reduced by fast preflashes; an origin near photosystem II is suggested. The S phase may imply a small pool of proton-sequestering ability near the water oxidation site, or a number of other possibilities. In steady-state conditions, the ratio of the protons from PQH2 to those from water was 1.0 under all conditions examined except in the absence of added electron acceptor, when it was as high as 1.6. This was the only condition apparently indicating a Q-cycle, with infrequent single-turnover flashes.

Further Studies of Proton Translocations in Chloroplasts After Single-Turnover Flashes. III. Conditions for the Operation of an Apparent Q-Cycle in Thylakoids

1985 ◽  
Vol 12 (4) ◽  
pp. 387 ◽  
Author(s):  
AB Hope ◽  
L Handley ◽  
DB Mathews
Keyword(s):  
Electric Field ◽  
Electron Acceptor ◽  
Electron Flow ◽  
Cytochrome B6 ◽  
Single Turnover ◽  
Ph Values ◽  
Maximal Stimulation ◽  
Q Cycle ◽  
Proton Uptake ◽  
Transverse Electron

The proton-to-electron ratio in pea thylakoids, considering proton uptake with ferricyanide as electron acceptor, was reconfirmed as 1 in periods of single-turnover (<0.5 �s, 2-3 mJ) flashes delivered at 5-50 Hz and at pH values 6.4-8.3. Addition of valinomycin in the presence of K+ increased proton uptake in a way depending on [val], flash frequency and flash number. A maximal stimulation by valinomycin of up to about 1.8× controls was observed in fresh preparations. Half-maximal stimulation was caused by c. 2 nM valinomycin at 10-20 Hz, at c. 3 Hz with 10 nM valinomycin, and after c. five flashes at 50 Hz with 10 nM valinomycin. The results are discussed in terms of recent models for the Q-cycle. It is suggested that such a cycle operates in chloroplasts only when the intramembrane electric field induced in a series of flashes is kept small by the presence of valinomycin. Preliminary observations of 'P518', the thylakoid component probably indicating the electric field, are consistent with this idea. This field may control the transverse electron flow between the two cytochrome b6 molecules in the b/f complexes.

scholarly journals Spectral Probe for Electron Transfer and Addition Reactions of Azide Radicals with Substituted Quinoxalin-2-Ones in Aqueous Solutions

2021 ◽  
Vol 22 (2) ◽  
pp. 633
Author(s):  
Konrad Skotnicki ◽  
Slawomir Ostrowski ◽  
Jan Cz. Dobrowolski ◽  
Julio R. De la Fuente ◽  
Alvaro Cañete ◽  
...  
Keyword(s):  
Electron Transfer ◽  
Aqueous Solutions ◽  
Absorption Spectra ◽  
Density Functional ◽  
Reduction Potential ◽  
Biological Significance ◽  
Radical Cations ◽  
Basis Sets ◽  
Double Bonds ◽  
Reduction Potentials

The azide radical (N3●) is one of the most important one-electron oxidants used extensively in radiation chemistry studies involving molecules of biological significance. Generally, it was assumed that N3● reacts in aqueous solutions only by electron transfer. However, there were several reports indicating the possibility of N3● addition in aqueous solutions to organic compounds containing double bonds. The main purpose of this study was to find an experimental approach that allows a clear assignment of the nature of obtained products either to its one-electron oxidation or its addition products. Radiolysis of water provides a convenient source of one-electron oxidizing radicals characterized by a very broad range of reduction potentials. Two inorganic radicals (SO4●−, CO3●−) and Tl2+ ions with the reduction potentials higher, and one radical (SCN)2●− with the reduction potential slightly lower than the reduction potential of N3● were selected as dominant electron-acceptors. Transient absorption spectra formed in their reactions with a series of quinoxalin-2-one derivatives were confronted with absorption spectra formed from reactions of N3● with the same series of compounds. Cases, in which the absorption spectra formed in reactions involving N3● differ from the absorption spectra formed in the reactions involving other one-electron oxidants, strongly indicate that N3● is involved in the other reaction channel such as addition to double bonds. Moreover, it was shown that high-rate constants of reactions of N3● with quinoxalin-2-ones do not ultimately prove that they are electron transfer reactions. The optimized structures of the radical cations (7-R-3-MeQ)●+, radicals (7-R-3-MeQ)● and N3● adducts at the C2 carbon atom in pyrazine moiety and their absorption spectra are reasonably well reproduced by density functional theory quantum mechanics calculations employing the ωB97XD functional combined with the Dunning’s aug-cc-pVTZ correlation-consistent polarized basis sets augmented with diffuse functions.

scholarly journals A Three-Step Approach to Estimation of Reduction Potentials of Natural Mixtures of Antioxidants Based on DPPH Test; Illustration for Catechins and Cocoa

Proceedings ◽  
2019 ◽  
Vol 11 (1) ◽  
pp. 4 ◽  
Author(s):  
Barbara Kusznierewicz ◽  
Monika Baranowska ◽  
Klaudia Suliborska ◽  
Wojciech Chrzanowski ◽  
Agnieszka Bartoszek
Keyword(s):  
Electrochemical Properties ◽  
Plant Extracts ◽  
Reduction Potential ◽  
Correlation Equation ◽  
Complex Mixtures ◽  
Test Results ◽  
Reduction Potentials ◽  
Dpph Test

The aim of this study is to propose a methodology to assess electrochemical properties of complex mixtures of antioxidants, such as plant extracts, based on the results of simple and popular DPPH test. The first, most difficult step, involves determinations of standard reduction potentials (E0) for the series of purified compounds (here catechins). The next step is the calculation of stoichiometric values (n10) based on the results of DPPH test for the same compounds. Finally, a correlation equation is formulated, which is then employed to estimate “cumulative reduction potential” (Ec) for the mixture of interest (here cocoa) using DPPH test results.

scholarly journals One-Electron Reduction Potentials: Calibration of Theoretical Protocols for Morita–Baylis–Hillman Nitroaromatic Compounds in Aprotic Media

Molecules ◽  
2018 ◽  
Vol 23 (9) ◽  
pp. 2129 ◽  
Author(s):  
Amauri Francisco da Silva ◽  
Antonio João da Silva Filho ◽  
Mário Vasconcellos ◽  
Otávio Luís de Santana
Keyword(s):  
Cyclic Voltammetry ◽  
Biological Activity ◽  
Chemical Structure ◽  
Reduction Potential ◽  
Chemical Reactivity ◽  
Nitroaromatic Compounds ◽  
Reduction Potentials ◽  
Electron Reduction ◽  
The One ◽  
Antileishmanial Activities

Nitroaromatic compounds—adducts of Morita–Baylis–Hillman (MBHA) reaction—have been applied in the treatment of malaria, leishmaniasis, and Chagas disease. The biological activity of these compounds is directly related to chemical reactivity in the environment, chemical structure of the compound, and reduction of the nitro group. Because of the last aspect, electrochemical methods are used to simulate the pharmacological activity of nitroaromatic compounds. In particular, previous studies have shown a correlation between the one-electron reduction potentials in aprotic medium (estimated by cyclic voltammetry) and antileishmanial activities (measured by the IC50) for a series of twelve MBHA. In the present work, two different computational protocols were calibrated to simulate the reduction potentials for this series of molecules with the aim of supporting the molecular modeling of new pharmacological compounds from the prediction of their reduction potentials. The results showed that it was possible to predict the experimental reduction potential for the calibration set with mean absolute errors of less than 25 mV (about 0.6 kcal·mol−1).

Further Studies of Proton Translocations in Chloroplasts After Single-Turnover Flashes. IV. Effects of Cytochrome b/f Complex Inhibitors on Proton Uptake and Cytochrome b6 Turnover

1987 ◽  
Vol 14 (1) ◽  
pp. 47 ◽  
Author(s):  
AB Hope ◽  
S Birch ◽  
DB Matthews
Keyword(s):  
Electron Transport ◽  
Photosystem Ii ◽  
Reduction Rate ◽  
Maximum Effect ◽  
Phenol Red ◽  
Cytochrome B6 ◽  
Oxidation Rates ◽  
Single Turnover ◽  
Proton Uptake ◽  
Reduction And Oxidation

The effects of the substances 2-n-heptyl- and 2-n-nonyl-4-hydroxyquinoline N-oxide (HQNO, NQNO), and antimycin A (AMA) on proton uptake stimulated by a 10-20 Hz train of single-turnover flashes given to pea thylakoids were investigated. Electron transport was from H2O to ferricyanide ('oxidising conditions') and the pH indicator of proton uptake was phenol red. All three of HQNO, NQNO and AMA inhibited proton uptake in control conditions, with concentrations (c½) for half-maximum effect of 1.7, 0.1 and 5 �M, respectively. The valinomycin-stimulated proton uptake, which has been attributed to Q-cycle activity in thylakoids, was more sensitive to HQNO and NQNO, with c½ of 0.6 and < 0.05 �M respectively. AMA had the same or less relative effect on proton uptake in the presence of valinomycin as in its absence. In oxidising conditions the maximum extent of flash-induced cytochrome (cyt) b6 reduction was 7-9% of the total present (which was 2 molecules/620 chlorophylls), as an average during 10 flashes, valinomycin being always added to reduce interference from the electrochromic effect. The average half- time for this reduction was 3.4 ms, while that for oxidation was 420 ms. The amount of cyt b6 reduced was increased by NQNO to a maximum of 14-19%, the c½ being 0.05 �M. Reduction and oxidation rates were both diminished by NQNO. In reducing conditions [electrons from duroquinol to methyl viologen, 3-(3,4-dichlorophenyl)-l,l- dimethylurea added to inhibit photosystem II], the cytochrome b6 was 12-16% reduced during flashes at 0.5-1 Hz, with half-times of 3.1 and 21 ms for reduction and oxidation, respectively. NQNO increased the percentage reduced to a maximum of 34-45, with a c½ of 0.05 �M. The diminution of the oxidation rate of cyt b6 was similarly related to [NQNO] but that of the reduction rate had a c½ of -1 �M. The findings on proton uptake are seen as consistent with HQNO and NQNO inhibiting at the Qc sites on cyt b/f complexes, at QB sites near photosystem II with less specificity and possibly at Q2 sites during the first few turnovers. Data for AMA indicated that it does not inhibit at Qc. Electron transport from H2O to methyl purple was more sensitive to NQNO for the first few turnovers (c½ 0.1 �M) than in the steady state (c½ - 1 �M).

scholarly journals Mutually Isomeric 2- and 4-(3-Nitro-1,2,4-triazol-1-yl)pyrimidines Inspired by an Antimycobacterial Screening Hit: Synthesis and Biological Activity against the ESKAPE Panel of Pathogens

Antibiotics ◽  
2020 ◽  
Vol 9 (10) ◽  
pp. 666
Author(s):  
Sergey Chuprun ◽  
Dmitry Dar’in ◽  
Elizaveta Rogacheva ◽  
Liudmila Kraeva ◽  
Oleg Levin ◽  
...  
Keyword(s):  
Cyclic Voltammetry ◽  
Antibacterial Activity ◽  
Reduction Potential ◽  
Gram Negative ◽  
Reduction Potentials ◽  
Apparent Correlation ◽  
Electron Reduction ◽  
Activity Loss ◽  
Eskape Pathogens ◽  
Bioactivity Profile

Starting from the structure of antimycobacterial screening hit OTB-021 which was devoid of activity against ESKAPE pathogens, we designed, synthesized and tested two mutually isomeric series of novel simplified analogs, 2- and 4-(3-nitro-1,2,4-triazol-1-yl)pyrimidines, bearing various amino side chains. These compounds demonstrated a reverse bioactivity profile being inactive against M. tuberculosis while inhibiting the growth of all ESKAPE pathogens (with variable potency patterns) except for Gram-negative P. aeruginosa. Reduction potentials (E1/2, V) measured for selected compounds by cyclic voltammetry were tightly grouped in the −1.3–−1.1 V range for a reversible single-electron reduction. No apparent correlation between the E1/2 values and the ESKAPE minimum inhibitory concentrations was established, suggesting possible significance of other factors, besides the compounds’ reduction potential, which determine the observed antibacterial activity. Generally, more negative E1/2 values were displayed by 2-(3-nitro-1,2,4-triazol-1-yl)pyrimidines, which is in line with the frequently observed activity loss on moving the 3-nitro-1,2,4-triazol-1-yl moiety from position 4 to position 2 of the pyrimidine nucleus.

scholarly journals Comparison of the Greenhouse Gas Emission Reduction Potential of Energy Communities

Energies ◽  
2019 ◽  
Vol 12 (23) ◽  
pp. 4440 ◽  
Author(s):  
Wouter Schram ◽  
Atse Louwen ◽  
Ioannis Lampropoulos ◽  
Wilfried van Sark
Keyword(s):  
Greenhouse Gas ◽  
Emission Reduction ◽  
Reduction Potential ◽  
Greenhouse Gas Emission ◽  
Heat Pumps ◽  
Solar Irradiation ◽  
Ghg Emission ◽  
Reduction Potentials ◽  
Emission Reduction Potential ◽  
Energy Sharing

In this research, the greenhouse gas (GHG) emission reduction potentials of electric vehicles, heat pumps, photovoltaic (PV) systems and batteries were determined in eight different countries: Austria, Belgium, France, Germany, Italy, the Netherlands, Portugal and Spain. Also, the difference between using prosuming electricity as a community (i.e., energy sharing) and prosuming it as an individual household was calculated. Results show that all investigated technologies have substantial GHG emission reduction potential. A strong moderating factor is the existing electricity generation mix of a country: the GHG emission reduction potential is highest in countries that currently have high hourly emission factors. GHG emission reduction potentials are highest in southern Europe (Portugal, Spain, Italy) and lowest in countries with a high share of nuclear energy (Belgium, France). Hence, from a European GHG emission reduction perspective, it has most impact to install PV in countries that currently have a fossil-fueled electricity mix and/or have high solar irradiation. Lastly, we have seen that energy sharing leads to an increased GHG emission reduction potential in all countries, because it leads to higher PV capacities.

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