Quantification of the Effect of an External Magnetic Field on Water Oxidation with Cobalt Oxide Anodes.

Here, we quantify the effect of an external magnetic field (β) on the oxygen evolution reaction (OER) for a cobalt oxide|fluorine-doped tin oxide coated glass (CoO|FTO) anode. A bespoke apparatus enables us to precisely determine the relationship between magnetic flux density (β) and OER activity at the surface of a CoO|FTO anode. The apparatus includes a strong NdFeB magnet ( = 450 ± 1 mT) capable of producing a magnetic field of 371 ± 1 mT at the surface of the anode.

Microwatt-Resolution Calorimeter for Studying the Reaction Thermodynamics of Nanomaterials at High Temperature and Pressure.

Calorimetry of reactions involving nanomaterials is of great current interest, but requires high-resolution heat flow measurements and long-term thermal stability. Such studies are especially challenging at elevated reaction pressures and temperatures. Here, we present an instrument for measuring the enthalpy of reactions between gas-phase reactants and milligram scale nanomaterial samples.

Strain Influences the Hydrogen Evolution Activity and Absorption Capacity of Palladium.

Strain engineering can increase the activity and selectivity of an electrocatalyst. Tensile strain is known to improve the electrocatalytic activity of palladium electrodes for reduction of carbon dioxide or dioxygen, but determining how strain affects the hydrogen evolution reaction (HER) is complicated by the fact that palladium absorbs hydrogen concurrently with HER. We report here a custom electrochemical cell, which applies tensile strain to a flexible working electrode, that enabled us to resolve how tensile strain affects hydrogen absorption and HER activity for a thin film palladium electrocatalyst.

Revisiting the cold case of cold fusion.

The 1989 claim of 'cold fusion' was publicly heralded as the future of clean energy generation. However, subsequent failures to reproduce the effect heightened scepticism of this claim in the academic community, and effectively led to the disqualification of the subject from further study. Motivated by the possibility that such judgement might have been premature, we embarked on a multi-institution programme to re-evaluate cold fusion to a high standard of scientific rigour.

Facets and vertices regulate hydrogen uptake and release in palladium nanocrystals.

Crystal facets, vertices and edges govern the energy landscape of metal surfaces and thus the chemical interactions on the surface. The facile absorption and desorption of hydrogen at a palladium surface provides a useful platform for defining how metal-solute interactions impact properties relevant to energy storage, catalysis and sensing. Recent advances in in operando and in situ techniques have enabled the phase transitions of single palladium nanocrystals to be temporally and spatially tracked during hydrogen absorption.

High-temperature high-pressure calorimeter for studying gram-scale heterogeneous chemical reactions.

We present an instrument for measuring pressure changes and heat flows of physical and chemical processes occurring in gram-scale solid samples under high pressures of reactive gases. Operation is demonstrated at 1232 °C under 33 bars of pure hydrogen. Calorimetric heat flow is inferred using a grey-box non-linear lumped-element heat transfer model of the instrument.

Bill Arnold and calorimetric measurements of the quantum requirement of photosynthesis-once again ahead of his time.

The approach of photocalorimetry to decide on the true quantum requirement of photosynthesis - one of the main issues of the research in the first half of the century and a source of a bitter debate - is described. Bill Arnold's original approach to get into the true answer is reflected from the point of view of present day calorimetric techniques.

Light adaptation of cyclic electron transport through Photosystem I in the cyanobacterium Synechococcus sp. PCC 7942.

Photosystem I-driven cyclic electron transport was measured in intact cells of Synechococcus sp PCC 7942 grown under different light intensities using photoacoustic and spectroscopic methods. The light-saturated capacity for PS I cyclic electron transport increased relative to chlorophyll concentration, PS I concentration, and linear electron transport capacity as growth light intensity was raised. In cells grown under moderate to high light intensity, PS I cyclic electron transport was nearly insensitive to methyl viologen, indicating that the cyclic electron supply to PS I derived almost exclusively from a thylakoid dehydrogenase.

Changes in the cyanobacterial photosynthetic apparatus during acclimation to macronutrient deprivation.

When the cyanobacterium Synechococcus sp. Strain PCC 7942 is deprived of an essential macronutrient such as nitrogen, sulfur or phosphorus, cellular phycobiliprotein and chlorophyll contents decline. The level of β-carotene declines proportionately to chlorophyll, but the level of zeaxanthin increases relative to chlorophyll.

Acclimation of the Photosynthetic Apparatus to Growth Irradiance in a Mutant Strain of Synechococcus Lacking Iron Superoxide Dismutase.

The acclimation of the photosynthetic apparatus to growth irradiance in a mutant strain of Synechococcus sp. PCC 7942 lacking detectable iron superoxide dismutase activity was studied. The growth of the mutant was inhibited at concentrations of methyl viologen 4 orders of magnitude smaller than those required to inhibit the growth of the wild-type strain.

Electron transport and photophosphorylation by Photosystem I in vivo in plants and cyanobacteria.

Recently, a number of techniques, some of them relatively new and many often used in combination, have given a clearer picture of the dynamic role of electron transport in Photosystem I of photosynthesis and of coupled cyclic photophosphorylation. For example, the photoacoustic technique has detected cyclic electron transport in vivo in all the major algal groups and in leaves of higher plants. Spectroscopic measurements of the Photosystem I reaction center and of the changes in light scattering associated with thylakoid membrane energization also indicate that cyclic photophosphorylation occurs in living plants and cyanobacteria, particularly under stressful conditions.

Characterization of damage to photosystems I and II in a cyanobacterium lacking detectable iron superoxide dismutase activity.

The enzyme superoxide dismutase is ubiquitous in aerobic organisms where it plays a major role in alleviating oxygen-radical toxicity. An insertion mutation introduced into the iron superoxide dismutase locus (designated sodB) of the cyanobacterium Synechococcus sp. PCC 7942 created a mutant strain devoid of detectable iron superoxide dismutase activity.

Simultaneous photoreduction and photooxidation of cytochrome b-559 in Photosystem II treated with carbonylcyanide-m-chlorophenylhydrazone.

The possibility of a Photosystem II (PS II) cyclic electron flow via Cyt b-559 catalyzed by carbonylcyanide m-chlorophenylhydrazone (CCCP) was further examined by studying the effects of the PS II electron acceptor 2,6-dichloro-p-benzoquinone (DCBQ) on the light-induced changes of the redox states of Cyt b-559. Addition to barley thylakoids of micromolar concentrations of DCBQ completely inhibited the changes of the absorbance difference corresponding to the photoreduction of Cyt b-559 observed either in the presence of 10 μM ferricyanide or after Cyt b-559 photooxidation in the presence of 2 μM CCCP. In CCCP-treated thylakoids, the concentration of photooxidized Cyt b-559 decreased as the irradiance of actinic light increased from 2 to 80 W m(-2) but remained close to the maximal concentration (0.

Enhanced susceptibility of the oxidized and unprotonated forms of high potential cytochrome b-559 toward DCMU.

The nature of interaction of cytochrome b-559 high potential (HP) with electron transport on the reducing side of photosystem II was investigated by measuring the susceptibility of cytochrome b-559HP to 3-(3,4-dichlorophenyl)-1,1-dimethylurea (DCMU) under different conditions. Submicromolar DCMU concentrations decreased the rate of absorbance change corresponding to cytochrome b-559HP photoreduction while the amplitude was lowered at higher concentrations (up to 10 μM). Appreciable extents of cytochrome b-559HP photoreduction were observed at DCMU concentrations which completely abolished the electron transport from water to methyl viologen under the same experimental conditions.

Light Energy Distribution in the Brown Alga Macrocystis pyrifera (Giant Kelp).

The brown alga Macrocystis pyrifera (giant kelp) was studied by a combination of fluorescence spectroscopy at 77 kelvin, room temperature modulated fluorimetry, and photoacoustic techniques to determine how light energy is partitioned between photosystems I and II in states 1 and 2. Preillumination with farred light induced the high fluorescence state (state 1) as determined by fluorescence emission spectra measured at 77K and preillumination with green light produced a low fluorescence state (state 2). Upon transition from state 1 to state 2, there was an almost parallel decrease of all of the fluorescence bands at 693, 705, and 750 nanometers and not the expected decrease of fluorescence of photosystem II and increase of fluorescence in photosystem I.

A gas-permeable photoacoustic cell.

A photoacoustic cell assembly is described that is permeable to CO2 and other gases but not water vapor. As a replacement for the usually employed solid cover, this cell uses a cover containing a small fritted glass disk that holds a small piece of 6.4 μm Teflon film against the sample.

Photoacoustic measurements in vivo of energy storage by cyclic electron flow in algae and higher plants.

Energy storage by cyclic electron flow through photosystem I (PSI) was measured in vivo using the photoacoustic technique. A wide variety of photosynthetic organisms were considered and all showed measurable energy storage by PSI-cyclic electron flow except for higher plants using the C-3 carbon fixation pathway. The capacity for energy storage by PSI-cyclic electron flow alone was found to be small in comparison to that of linear and cyclic electron flows combined but may be significant, nonetheless, under conditions when photosystem II is damaged, particularly in cyanobacteria.

Cytochrome c-553 is not required for photosynthetic activity in the cyanobacterium Synechococcus.

In cyanobacteria, the water-soluble cytochrome c-553 functions as a mobile carrier of electrons between the membrane-bound cytochrome b6-f complex and P-700 reaction centers of Photosystem I. The structural gene for cytochrome c-553 (designated cytA) of the cyanobacterium Synechococcus sp. PCC 7942 was cloned, and the deduced amino acid sequence was shown to be similar to known cyanobacterial cytochrome c-553 proteins.

The effect of light intensity on the assay of the low temperature limit of photosynthesis using msec delayed light emission.

Steady state millisecond delayed fluorescence (DLE) of intact leaves and cyanobacterial cells was measured continuously with a Becquerel-type phosphoroscope while cooling from the growth temperature to near 0°C or heating from the low to high temperature at about 1°C/min. The temperature of maximum DLE depended upon light intensity. In Anacystis grown at 28 and 38°C DLE maximum occurred near 15 and 23°C, respectively, which are the temperatures where thylakoid membrane lipids have been shown to pass from the liquid crystalline to the mixed solid-liquid crystalline state in these cyanobacteria.

Low and High Temperature Limits to PSII : A Survey Using trans-Parinaric Acid, Delayed Light Emission, and F(o) Chlorophyll Fluorescence.

Many studies have shown that membrane lipids of chilling-sensitive plants begin lateral phase separation (i.e. a minor component begins freezing) at chilling temperatures and that chilling-sensitive plants are often of tropical origin.

Superconducting bi-ca-sr-cu-o fibers grown by the laser-heated pedestal growth method.

Superconducting fibers of several compositions including the nominal composition Bi(2)CaSrCu(2)O(8) have been grown by means of the laser-heated pedestal growth method. The influence of starting composition and growth conditions on structure and superconducting properties is discussed. The a-b planes of the material are parallel to the fiber axis (along the growth direction), providing the ideal condition for conduction along the copper-oxygen planes.