Proton-Coupled Electron Flow in Protein Redox Machines

Electron transfer (ET) reactions are fundamental steps in biological redox processes. Respiration is a case in point: at least 15 ET reactions are required to take reducing equivalents from NADH, deposit them in O_2, and generate the electrochemical proton gradient that drives ATP synthesis. Most of these reactions involve quantum tunneling between weakly coupled redox cofactors (ET distances > 10 Å) embedded in the interiors of folded proteins. Here we review experimental findings that have shed light on the factors controlling these distant ET events. We also review work on a sensitizer-modified copper protein photosystem in which multistep electron tunneling (hopping) through an intervening tryptophan is orders of magnitude faster than the corresponding single-step ET reaction.If proton transfers are coupled to ET events, we refer to the processes as proton coupled ET, or PCET, a term introduced by Huynh and Meyer in 1981. Here we focus on two protein redox machines, photosystem II and ribonucleotide reductase, where PCET processes involving tyrosines are believed to be critical for function. Relevant tyrosine model systems also will be discussed

Texture transitions in the liquid crystalline alkyloxybenzoic acid 6OBAC

The 4,n-alkyloxybenzoic acid 6OBAC has a very rich variety of crystalline structures and two nematic sub-phases, characterised by different textures. It is a material belonging to a family of liquid crystals formed by hydrogen bonded molecules, the 4,n-alkyloxybenzoic acids indicates the homologue number). The homologues with n ranging from 7 to 13 display both smectic C and N phases. In spite of the absence of a smectic phase, 6OBAC exhibits two sub-phases with different textures, as it happens in other materials of the homologue series which possess the smectic phase. This is the first material that exhibits a texture transition in a nematic phase directly originated from a crystal phase. Here we present the results of an image processing assisted optical investigation to characterise the textures and the transitions between textures. This processing is necessary to discriminate between crystal modifications and nematic sub-phases.Comment: 12 pages, 10 figure

Mechanism of H_2 Evolution from a Photogenerated Hydridocobaloxime

Proton transfer from the triplet excited state of brominated naphthol to a difluoroboryl bridged Co^I-diglyoxime complex, forming Co^(III)H, was monitored via transient absorption. The second-order rate constant for Co^(III)H formation is in the range (3.5−4.7) × 10^9 M^(−1) s^(−1), with proton transfer coupled to excited-state deactivation of the photoacid. Co^(III)H is subsequently reduced by excess Co^I-diglyoxime in solution to produce Co^(II)H (k_(red) = 9.2 × 10^6 M^(−1) s^(−1)), which is then protonated to yield Co^(II)-diglyoxime and H_2

An automatic lightning detection and photographic system

Conventional 35-mm camera is activated by an electronic signal every time lightning strikes in general vicinity. Electronic circuit detects lightning by means of antenna which picks up atmospheric radio disturbances. Camera is equipped with fish-eye lense, automatic shutter advance, and small 24-hour clock to indicate time when exposures are made

Conformational profiling of a G-rich sequence within the c-KIT promoter

G-quadruplexes (G4) within oncogene promoters are considered to be promising anticancer targets. However, often they undergo complex structural rearrangements that preclude a precise description of the optimal target. Moreover, even when solved structures are available, they refer to the thermodynamically stable forms but little or no information is supplied about their complex multistep folding pathway. To shed light on this issue, we systematically followed the kinetic behavior of a G-rich sequence located within the c-KIT proximal promoter (kit2) in the presence of monovalent cations K + and Na + . A very short-lived intermediate was observed to start the G4 folding process in both salt conditions. Subsequently, the two pathways diverge to produce distinct thermodynamically stable species (parallel and antiparallel G-quadruplex in K + and Na + , respectively). Remarkably, in K + -containing solution a branched pathway is required to drive the wild type sequence to distribute between a monomeric and dimeric G-quadruplex. Our approach has allowed us to identify transient forms whose relative abundance is regulated by the environment; some of them were characterized by a half-life within the timescale of physiological DNA processing events and thus may represent possible unexpected targets for ligands recognition

Thermal design of the space shuttle external tank

The shuttle external tank thermal design presents many challenges in meeting the stringent requirements established by the structures, main propulsion systems, and Orbiter elements. The selected thermal protection design had to meet these requirements, and ease of application, suitability for mass production considering low weight, cost, and high reliability. This development led to a spray-on-foam (SOFI) which covers the entire tank. The need and design for a SOFI material with a dual role of cryogenic insulation and ablator, and the development of the SOFI over SLA concept for high heating areas are discussed. Further issuses of minimum surface ice/frost, no debris, and the development of the TPS spray process considering the required quality and process control are examined

Fixed Point and Aperiodic Tilings

An aperiodic tile set was first constructed by R.Berger while proving the undecidability of the domino problem. It turned out that aperiodic tile sets appear in many topics ranging from logic (the Entscheidungsproblem) to physics (quasicrystals) We present a new construction of an aperiodic tile set that is based on Kleene's fixed-point construction instead of geometric arguments. This construction is similar to J. von Neumann self-reproducing automata; similar ideas were also used by P. Gacs in the context of error-correcting computations. The flexibility of this construction allows us to construct a "robust" aperiodic tile set that does not have periodic (or close to periodic) tilings even if we allow some (sparse enough) tiling errors. This property was not known for any of the existing aperiodic tile sets.Comment: v5: technical revision (positions of figures are shifted

A Markov chain model to enhanced the weather simulation capabilities of an operations and maintenance tool for a wave energy array

Operations and maintenance is a vital area of research in the push to make wave energy a commercial reality. A tool has previously been developed by Pelamis Wave Power to obtain reliable estimates for operational expenditure and ensure smooth running of wave energy arrays. Wave Energy Scotland is now tasked with the future development of this operations and maintenance tool. One of its key inputs is the wave and wind data used to simulate weather windows suitable for marine access. This paper details the creation and validation of a Markov Chain Model to enhance the weather simulation capabilities of the tool. This will ensure that the operations and maintenance strategy of wave energy arrays is modelled more realistically, resulting in an increased confidence in cost estimates and logistical arrangements.The author would like to thank the academic supervisors of this IDCORE project for their contributions, advice and support. Similar thanks must go to the engineers, past and present, who have dedicated their time to the Pelamis project. The industrial supervisor deserves a special mention, without her experience and guidance this study would not have been a success. The author would also like the IDCORE programme and its funding bodies, in particular the ETP (Energy Technology Partnership), for their support

Fuel cell research - An investigation of non- steady-state operation Final report, 1 Jun. 1963 - 1 Jun. 1965

Application of galanostatic studies to fuel cell electrodes - effects of pulsed loading on fuel cell operatio