Light-induced Electron Transfer from Tris(2,2′-bipyridine)ruthenium(II)2+ to a Nickeldithiolene in Homogeneous and Heterogeneous Systems

1982 ◽  
Vol 37 (11) ◽  
pp. 1253-1258 ◽  
Author(s):  
Rudolf Frank ◽  
Hermann Rau
Keyword(s):  
Electron Transfer ◽  
Electron Transport ◽  
Quantum Yield ◽  
Anionic Surfactants ◽  
Ruthenium Complex ◽  
Direct Electron Transfer ◽  
Heterogeneous Systems ◽  
Micelle Formation ◽  
Homogeneous System ◽  
Compartment System

We have investigated the reduction of Nickel-tetraphenyldithiolene by 2-aminonaphthalene with Ru(bipy)32+ as a photocatalyst and found a quantum yield of approximately 1 % for the conditions of our homogeneous system. The lifetime of Ru(bipy)32+ is increased from 600 to 800 ns when micelle formation in aqueous solutions of anionic surfactants takes place. No such change.in lifetime is found in nonionic micelles. In a three compartment system the light driven electron transport from one aqueous compartment containing the Ru(bipy)32+/EDTA system through a membrane containing Ni-dithiolene in an organic solvent to tbe second aqueous compartment containing Na3[Fe(CN)6] is investigated. It is shown that direct electron transfer from the excited ruthenium complex to Ni-dithiolene across the phase boundary can be effected by the action of an anionic surfactant.

scholarly journals Response of Photosynthetic Performance to Drought Duration and Re-Watering in Maize

Agronomy ◽  
2020 ◽  
Vol 10 (4) ◽  
pp. 533
Author(s):  
Yuying Jia ◽  
Wanxin Xiao ◽  
Yusheng Ye ◽  
Xiaolin Wang ◽  
Xiaoli Liu ◽  
...  
Keyword(s):  
Electron Transfer ◽  
Electron Transport ◽  
Energy Dissipation ◽  
Quantum Yield ◽  
Photosynthetic Electron Transport ◽  
Photosynthetic Performance ◽  
Electron Acceptors ◽  
Drought Duration ◽  
Acceptor Side ◽  
Antioxidase Activity

The drought tolerance and capacity to recover after drought are important for plant growth and yield. In this study, two maize lines with different drought resistance were used to investigate the effects of different drought durations and subsequent re-watering on photosynthetic capacity, electron transfer and energy distribution, and antioxidative defense mechanisms of maize. Under short drought, maize plants decreased stomatal conductance and photosynthetic electron transport rate, and increased NPQ (Non-photochemical quenching) to dissipate excess excitation energy in time and protect the photosynthetic apparatus. With the increased drought duration, NPQ, antioxidase activity, PItotal (total performance index), ∆I/Io, ψEo (quantum yield for electron transport), φEo (efficiency/probability that an electron moves further than QA−), δRo (efficiency/probability with which an electron from the intersystem electron carriers is transferred to reduce end electron acceptors at the PSI acceptor side) and φRo (the quantum yield for the reduction of the end electron acceptors at the PSI acceptor side) were significantly reduced, while Y(NO) (quantum yield of nonregulated energy dissipation) and MDA (malondialdehyde) began to quickly increase. The photosynthetic rate and capacity of photosynthetic electron transport could not recover to the level of the plants subjected to normal water status after re-watering. These findings indicated that long drought damaged the PSI (photosystem I) and PSII (photosystem II) reaction center and decreased the electron transfer efficiency, and this damage could not be recovered by re-watering. Different drought resistance and recovery levels of photosynthetic performance were achieved by different maize lines. Compared with D340, D1798Z had higher NPQ and antioxidase activity, which was able to maintain functionality for longer in response to progressive drought, and it could also recover at more severe drought after re-watering, which indicated its higher tolerance to drought. It was concluded that the capacity of the energy dissipation and antioxidant enzyme system is crucial to mitigate the effects caused by drought, and the capacity to recover after re-watering was dependent on the severity and persistence of drought, adaptability, and recovery differences of the maize lines. The results provide a profound insight to understand the maize functional traits’ responses to drought stresses and re-watering.

Reaction Mechanisms of Inorganic and Organometallic Systems

2007 ◽  
Author(s):  
Robert B. Jordan
Keyword(s):  
Electron Transfer ◽  
Heterogeneous Systems ◽  
Asymmetric Hydrogenation ◽  
Pressure Effects ◽  
General Level ◽  
Hydrogenation Catalysts ◽  
Methyl Transferase ◽  
Transfer Region ◽  
Previous Edition ◽  
Oxide Synthase

This third edition retains the general level and scope of earlier editions, but has been substantially updated with over 900 new references covering the literature through 2005, and 140 more pages of text than the previous edition. In addition to the general updating of materials, there is new or greatly expanded coverage of topics such as Curtin-Hammett conditions, pressure effects, metal hydrides and asymmetric hydrogenation catalysts, the inverted electron-transfer region, intervalence electron transfer, photochemistry of metal carbonyls, methyl transferase and nitric oxide synthase. The new chapter on heterogeneous systems introduces the basic background to this industrially important area. The emphasis is on inorganic examples of gas/liquid and gas/liquid/solid systems and methods of determining heterogeneity.

scholarly journals Electrical characteristics of amyloid beta peptides in vertical junctions

2021 ◽  
Vol 13 (1) ◽  
Author(s):  
Sohyeon Seo ◽  
Jinju Lee ◽  
Jungsue Choi ◽  
G. Hwan Park ◽  
Yeseul Hong ◽  
...  
Keyword(s):  
Electron Transfer ◽  
Electron Transport ◽  
Amyloid Beta ◽  
Field Effect Transistors ◽  
Brain Diseases ◽  
Electrical Characteristics ◽  
Transport Pathway ◽  
Sequence Dependence ◽  
Aβ Oligomers ◽  
Aβ Peptides

AbstractAssembled amyloid beta (Aβ) peptides have been considered pathological assemblies involved in human brain diseases, and the electron transfer or electron transport characteristics of Aβ are important for the formation of structured assemblies. Here, we report the electrical characteristics of surface-assembled Aβ peptides similar to those observed in Alzheimer’s patients. These characteristics correlate to their electron transfer characteristics. Electrical current–voltage plots of Aβ vertical junction devices show the Aβ sequence dependence of the current densities at both Aβ monomers (mono-Aβs) and Aβ oligomers (oli-Aβs), while Aβ sequence dependence is not clearly observed in the electrical characteristics of Aβ planar field effect transistors (FETs). In particular, surface oligomerization of Aβ peptides drastically decreases the activity of electron transfer, which presents a change in the electron transport pathway in the Aβ vertical junctions. Electron transport at oli-Aβ junctions is symmetric (tunneling/tunneling) due to the weak and voltage-independent coupling of the less redox-reactive oli-Aβ to the contacts, while that at mono-Aβ junctions is asymmetric (hopping/tunneling) due to redox levels of mono-Aβ voltage-dependently coupled with contact electrodes. Consequently, through vertical junctions, the sequence- and conformation-dependent electrical characteristics of Aβs can reveal their electron transfer activities.

scholarly journals Over-expression of an electron transport protein OmcS provides sufficient NADH for d-lactate production in cyanobacterium

2021 ◽  
Vol 14 (1) ◽  
Author(s):  
Hengkai Meng ◽  
Wei Zhang ◽  
Huawei Zhu ◽  
Fan Yang ◽  
Yanping Zhang ◽  
...  
Keyword(s):  
Electron Transfer ◽  
Electron Transport ◽  
Lactate Production ◽  
Transport Protein ◽  
Dominant Form ◽  
Photosynthetic Production ◽  
Reducing Equivalent ◽  
Excess Electrons ◽  
Novel Strategy ◽  
Electron Transport Protein

Abstract Background An efficient supply of reducing equivalent is essential for chemicals production by engineered microbes. In phototrophic microbes, the NADPH generated from photosynthesis is the dominant form of reducing equivalent. However, most dehydrogenases prefer to utilize NADH as a cofactor. Thus, sufficient NADH supply is crucial to produce dehydrogenase-derived chemicals in cyanobacteria. Photosynthetic electron is the sole energy source and excess electrons are wasted in the light reactions of photosynthesis. Results Here we propose a novel strategy to direct the electrons to generate more ATP from light reactions to provide sufficient NADH for lactate production. To this end, we introduced an electron transport protein-encoding gene omcS into cyanobacterium Synechococcus elongatus UTEX 2973 and demonstrated that the introduced OmcS directs excess electrons from plastoquinone (PQ) to photosystem I (PSI) to stimulate cyclic electron transfer (CET). As a result, an approximately 30% increased intracellular ATP, 60% increased intracellular NADH concentrations and up to 60% increased biomass production with fourfold increased d-lactate production were achieved. Comparative transcriptome analysis showed upregulation of proteins involved in linear electron transfer (LET), CET, and downregulation of proteins involved in respiratory electron transfer (RET), giving hints to understand the increased levels of ATP and NADH. Conclusions This strategy provides a novel orthologous way to improve photosynthesis via enhancing CET and supply sufficient NADH for the photosynthetic production of chemicals.

scholarly journals Ruthenium-based PACT agents based on bisquinoline chelates: synthesis, photochemistry, and cytotoxicity

2021 ◽  
Author(s):  
Anja Busemann ◽  
Ingrid Flaspohler ◽  
Xue-Quan Zhou ◽  
Claudia Schmidt ◽  
Sina K. Goetzfried ◽  
...  
Keyword(s):  
Quantum Yield ◽  
Singlet Oxygen ◽  
Cancer Cells ◽  
Cellular Uptake ◽  
Ruthenium Complex ◽  
Human Cancer ◽  
Light Irradiation ◽  
Quantum Yields ◽  
Light Activation ◽  
Human Cancer Cells

AbstractThe known ruthenium complex [Ru(tpy)(bpy)(Hmte)](PF6)2 ([1](PF6)2, where tpy = 2,2’:6’,2″-terpyridine, bpy = 2,2’-bipyridine, Hmte = 2-(methylthio)ethanol) is photosubstitutionally active but non-toxic to cancer cells even upon light irradiation. In this work, the two analogs complexes [Ru(tpy)(NN)(Hmte)](PF6)2, where NN = 3,3'-biisoquinoline (i-biq, [2](PF6)2) and di(isoquinolin-3-yl)amine (i-Hdiqa, [3](PF6)2), were synthesized and their photochemistry and phototoxicity evaluated to assess their suitability as photoactivated chemotherapy (PACT) agents. The increase of the aromatic surface of [2](PF6)2 and [3](PF6)2, compared to [1](PF6)2, leads to higher lipophilicity and higher cellular uptake for the former complexes. Such improved uptake is directly correlated to the cytotoxicity of these compounds in the dark: while [2](PF6)2 and [3](PF6)2 showed low EC50 values in human cancer cells, [1](PF6)2 is not cytotoxic due to poor cellular uptake. While stable in the dark, all complexes substituted the protecting thioether ligand upon light irradiation (520 nm), with the highest photosubstitution quantum yield found for [3](PF6)2 (Φ[3] = 0.070). Compounds [2](PF6)2 and [3](PF6)2 were found both more cytotoxic after light activation than in the dark, with a photo index of 4. Considering the very low singlet oxygen quantum yields of these compounds, and the lack of cytotoxicity of the photoreleased Hmte thioether ligand, it can be concluded that the toxicity observed after light activation is due to the photoreleased aqua complexes [Ru(tpy)(NN)(OH2)]2+, and thus that [2](PF6)2 and [3](PF6)2 are promising PACT candidates. Graphic abstract

scholarly journals Amperometric Biosensors Based on Direct Electron Transfer Enzymes

Molecules ◽  
2021 ◽  
Vol 26 (15) ◽  
pp. 4525
Author(s):  
Franziska Schachinger ◽  
Hucheng Chang ◽  
Stefan Scheiblbrandner ◽  
Roland Ludwig
Keyword(s):  
Electron Transfer ◽  
Electrode Materials ◽  
Direct Electron Transfer ◽  
Accurate Determination ◽  
Direct Electrochemistry ◽  
Product Analysis ◽  
Amperometric Biosensors ◽  
Chemical Surface ◽  
Fusion Enzymes ◽  
Cost Efficient

The accurate determination of analyte concentrations with selective, fast, and robust methods is the key for process control, product analysis, environmental compliance, and medical applications. Enzyme-based biosensors meet these requirements to a high degree and can be operated with simple, cost efficient, and easy to use devices. This review focuses on enzymes capable of direct electron transfer (DET) to electrodes and also the electrode materials which can enable or enhance the DET type bioelectrocatalysis. It presents amperometric biosensors for the quantification of important medical, technical, and environmental analytes and it carves out the requirements for enzymes and electrode materials in DET-based third generation biosensors. This review critically surveys enzymes and biosensors for which DET has been reported. Single- or multi-cofactor enzymes featuring copper centers, hemes, FAD, FMN, or PQQ as prosthetic groups as well as fusion enzymes are presented. Nanomaterials, nanostructured electrodes, chemical surface modifications, and protein immobilization strategies are reviewed for their ability to support direct electrochemistry of enzymes. The combination of both biosensor elements—enzymes and electrodes—is evaluated by comparison of substrate specificity, current density, sensitivity, and the range of detection.

scholarly journals Enhancement of Direct Electron Transfer in Graphene Bioelectrodes Containing Novel Cytochrome c Variants with Optimized Heme Orientation

2021 ◽  
pp. 107818
Author(s):  
Miriam Izzo ◽  
Silvio Osella ◽  
Margot Jacquet ◽  
Małgorzata Kiliszek ◽  
Ersan Harputlu ◽  
...  
Keyword(s):  
Electron Transfer ◽  
Cytochrome C ◽  
Direct Electron Transfer
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