Platinum Group Metals and Their Oxides in Semiconductor Photosensitisation BASIC PRINCIPLES, METAL PHOTODEPOSITION AND WATER PHOTOSPLITTING REACTIONS

The basic principles of semiconductor photochemistry, particularly using titania as a semiconductor photocatalyst, are discussed. When a platinum group metal or its oxide is deposited onto the surface of a sensitised semiconductor the overall efficiency of the reactions it takes part in are often improved, especially when the deposits are used as hydrogen and oxygen catalysts, respectively. Methods of depositing metal or metal oxide are examined, and a particular focus is given to a photodeposition process that uses a sacrificial electron donor. Platinum group metal and platinum group metal oxide coated semiconductor photocatalysts are prominent in heterogeneous systems that are capable of the photoreduction, oxidation and cleavage of water. There is a recent renaissance in work on water-splitting semiconductor-sensitised photosystems, but there are continued concerns over their irreproducibility, longevity and photosynthetic nature.

Toenail trace element status and risk of Barrett's oesophagus and oesophageal adenocarcinoma. Results from the FINBAR study

Trace elements have been cited as both inhibitory and causative agents of cancer but importantly exposure to them is potentially modifiable. Our study aimed to examine toenail trace element status and risk of Barrett's oesophagus (BO) and oesophageal adenocarcinoma (OAC). Toenail clippings from each hallux were obtained from 638 participants of the FINBAR (Factors Influencing the Barrett's Adenocarcinoma Relationship) study comprising 221 healthy controls, 98 reflux oesophagitis, 182 BO and 137 OAC cases. The concentrations of eight toenail trace elements were determined using instrumental neutron activation analysis. Using multivariable adjusted logistic regression analysis, odds ratios (OR) and 95% confidence intervals (CIs) were calculated within tertiles of trace element concentrations. A twofold increased risk of BO was observed, but not OAC, among individuals in the highest tertile of toenail zinc status OR 2.21 (95% CI, 1.11-4.40). A higher toenail selenium status was not associated with risk of OAC OR 0.94 (95% CI, 0.44-2.04) or BO OR 0.89 (95% CI, 0.37-2.12). A borderline significant increased risk of BO was detected with a higher toenail cobalt concentration, OR 1.97 (95% CI, 1.01-3.85). No association was found between toenail levels of chromium, cerium, mercury and OAC or BO risk. This is the first case-control study to investigate a variety of trace elements in relation to OAC and BO risk. Despite antioxidant and proapoptotic properties, no associations were found with selenium. Higher concentrations of toenail zinc and cobalt were associated with an increased BO risk, but not OAC. These findings need confirmation in prospective analysis.

Minimizing side reactions in chemoenzymatic dynamic kinetic resolution: organometallic and material strategies

Chemoenzymatic dynamic kinetic resolution (DKR) of rac-1-phenyl ethanol into R-1-phenylethanol acetate was investigated with emphasis on the minimization of side reactions. The organometallic hydrogen transfer (racemization) catalyst was varied, and this was observed to alter the rate and extent of oxidation of the alcohol to form ketone side products. The performance of highly active catalyst [(pentamethylcyclopentadienyl) IrCl2(1-benzyl,3-methyl-imidazol-2-ylidene)] was found to depend on the batch of lipase B used. The interaction between the bio- and chemo-catalysts was reduced by employing physical entrapment of the enzyme in silica using a sol-gel process. The nature of the gelation method was found to be important, with an alkaline method preferred, as an acidic method was found to initiate a further side reaction, the acid catalyzed dehydration of the secondary alcohol. The acidic gel was found to be a heterogeneous solid acid.

Green tea supplementation increases glutathione and plasma antioxidant capacity in adults with the metabolic syndrome

Green tea, a popular polyphenol-containing beverage, has been shown to alleviate clinical features of the metabolic syndrome. However, its effects in endogenous antioxidant biomarkers are not clearly understood. Thus, we tested the hypothesis that green tea supplementation will upregulate antioxidant parameters (enzymatic and nonenzymatic) in adults with the metabolic syndrome. Thirty-five obese participants with the metabolic syndrome were randomly assigned to receive one of the following for 8 weeks: green tea (4 cups per day), control (4 cups water per day), or green tea extract (2 capsules and 4 cups water per day). Blood samples and dietary information were collected at baseline (0 week) and 8 weeks of the study. Circulating carotenoids (a-carotene, ß-carotene, lycopene) and tocopherols (a-tocopherol, ?-tocopherol) and trace elements were measured using high-performance liquid chromatography and inductively coupled plasma mass spectroscopy, respectively. Serum antioxidant enzymes (glutathione peroxidase, glutathione, catalase) and plasma antioxidant capacity were measured spectrophotometrically. Green tea beverage and green tea extract significantly increased plasma antioxidant capacity (1.5 to 2.3 µmol/L and 1.2 to 2.5 µmol/L, respectively; P <.05) and whole blood glutathione (1783 to 2395 µg/g hemoglobin and 1905 to 2751 µg/g hemoglobin, respectively; P <.05) vs controls at 8 weeks. No effects were noted in serum levels of carotenoids and tocopherols and glutathione peroxidase and catalase activities. Green tea extract significantly reduced plasma iron vs baseline (128 to 92 µg/dL, P <.02), whereas copper, zinc, and selenium were not affected. These results support the hypothesis that green tea may provide antioxidant protection in the metabolic syndrome.

Stability and performance enhancements of Electrokinetic-Fenton soil remediation

Electrokinetic process is a potential in situ soil remediation process which transports the contaminants via electromigration and electroosmosis. For organic compounds contaminated soil, Fenton’s reagent is utilized as a flushing agent in electrokinetic process (Electrokinetic-Fenton) so that removal of organic contaminants could be achieved by in situ oxidation/destruction. However, this process is not applied widely in industries as the stability issue for Fenton’s reagent is the main drawback. The aim of this mini review is to summarize the developments of Electrokinetic-Fenton process on enhancing the stability of Fenton’s reagent and process efficiency in past decades. Generally, the enhancements are conducted via four paths: (1) chemical stabilization to delay H2O2 decomposition, (2) increase of oxidant availability by monitoring injection method for Fenton’s reagent, (3) electrodes operation and iron catalysts and (4) operating conditions such as voltage gradient, electrolytes and H2O2 concentration. In addition, the types of soils and contaminants are also showing significant effect as the soil with low acid buffering capacity, adequate iron concentration, low organic matter content and low aromatic ring organic contaminants generally gives better efficiency.

Arsenic(III,V) adsorption onto charred dolomite: charring optimization and batch studies

In this work, the removal of arsenic from aqueous solutions onto thermally processed dolomite is investigated. The dolomite was thermally processed (charred) at temperatures of 600, 700 and 800 degrees C for 1, 2, 4 and 8 h. Isotherm experiments were carried out on these samples over a wide pH range. A complete arsenic removal was achieved over the pH range studied when using the 800 degrees C charred dolomite. However, at this temperature, thermal degradation of the dolomite weakens its structure due to the decomposition of the magnesium carbonate, leading to a partial dissolution. For this reason, the dolomitic sorbent chosen for further investigations was the 8 h at 700 degrees C material. Isotherm studies indicated that the Langmuir model was successful in describing the process to a better extent than the Freundlich model for the As(V) adsorption on the selected charred dolomite. However, for the As(III) adsorption, the Freundlich model was more successful in describing the process. The maximum adsorption capacities of charred dolomite for arsenite and arsenate ions are 1.846 and 2.157 mg/g, respectively. It was found that both the pseudo first- and second-order kinetic models are able to describe the experimental data (R-2 > 0.980). The data suggest the charring process allows dissociation of the dolomite to calcium carbonate and magnesium oxide, which accelerates the process of arsenic oxide and arsenic carbonate precipitation. (C) 2014 Elsevier B.V. All rights reserved.

Effect of heating vermiculites on extractability of phosphorus and some essential plant micronutrients

The study assessed the effect of heating vermiculites on extractability of phosphorus, iron, zinc and manganese with respect to their potential agricultural use. Of these elements, phosphorus was from apatite and monazite that occur as accessory minerals in vermiculites. Vermiculites were heated at 15-800 degrees C and digested by acetic acid for extracting phosphorus and diethylene triamine pentaacetic acid (DTPA) for extracting zinc, iron and manganese. Phosphorus in the extract was analysed by a flow injection method while zinc, iron and manganese were measured by atomic absorption spectrometry. The results showed that heating vermiculites to 400 C enhanced extractability of phosphorus from apatite and monazite to a level of 335 mg kg(-1). Further heating to 800 degrees C reduced extractable phosphorus to less than 75 mg kg(-1). Maximum extractable zinc, iron and manganese found were 2.7, 19.1 and 22.9 mg kg(-1), respectively, values that are beneficial and tolerable by most plants. Thus, it was concluded that heating vermiculites to

Hydroprocessing of waste cooking oil over a dispersed nano catalyst: Kinetics study and temperature effect

The kinetics of hydrodeoxygenation of waste cooking oil (WCO) is investigated with unsupported CoMoS catalysts. A kinetic model is established and a comprehensive analysis of each reaction pathway is carried out. The results show that hydrodecarbonylation/decarboxylation (HDC) routes are the predominant reaction pathways in the elimination of oxygen, with the rate constant three times as high as that of hydrodeoxygenation (HDO). However, the HDC activity of the CoMoS catalyst deactivates due to gradual loss of sulfur from the catalyst. HDO process is insensitive to the sulfur deficiency. The kinetic modeling shows that direct hydrodecarbonylation of fatty acids dominates the HDC routes and, in the HDO route, fatty acids are transferred to aldehydes/alcohols and then to C-18 hydrocarbons, a final product, and the reduction of acids is the rate limiting step. The HDO route via alcohols is dominant over aldehydes due to a significantly higher reaction rate constant. The difference of C-18/C-17 ratio in unsupported and supported catalysts show that a support with Lewis acid sites may play an important role in the selectivity for the hydrodeoxygenation pathways and promoting the final product quality

Electroless nickel composite (Ni-P/SiC) coating - A study on interface and corrosion characteristic

Surface behaviour is of paramount importance as failure and degradation tend to initiate from the surface. Electroless composite coating (NiP/SiC) was developed using SiC as reinforcing particles. As heat treatment plays a vital role in electroless nickel coating owing to the changes in microstructure, phase structure and mechanical properties, an insight at the interface changes in chemistry and micromechanical behaviour was investigated using scanning electron microscopy (SEM) and energy dispersive X-ray (EDX) and microindentation techniques. Corrosion performance was analysed using electrochemical impedance spectroscopy (EIS). Absence of zinc and migration of copper at the interface was detected. Brittleness and microcracks was seen long the interface when indenting at load of 500 gf (Vickers). Corrosion performance is weaker than particles free coating. However, a thin blanket of NiP could enhance the resistance to corrosive medium.

Late-time spectral line formation in Type IIb supernovae, with application to SN 1993J, SN 2008ax, and SN 2011dh

We investigate line formation processes in Type IIb supernovae (SNe) from 100 to 500 days post-explosion using spectral synthesis calculations. The modelling identifies the nuclear burning layers and physical mechanisms that produce the major emission lines, and the diagnostic potential of these. We compare the model calculations with data on the three best observed Type IIb SNe to-date - SN 1993J, SN 2008ax, and SN 2011dh. Oxygen nucleosynthesis depends sensitively on the main-sequence mass of the star and modelling of the [O I] lambda lambda 6300, 6364 lines constrains the progenitors of these three SNe to the M-ZAMS = 12-16 M-circle dot range (ejected oxygen masses 0.3-0.9 M-circle dot), with SN 2011dh towards the lower end and SN 1993J towards the upper end of the range. The high ejecta masses from M-ZAMS greater than or similar to 17 M-circle dot progenitors give rise to brighter nebular phase emission lines than observed. Nucleosynthesis analysis thus supports a scenario of low-to-moderate mass progenitors for Type IIb SNe, and by implication an origin in binary systems. We demonstrate how oxygen and magnesium recombination lines may be combined to diagnose the magnesium mass in the SN ejecta. For SN 2011dh, a magnesium mass of 0.02-0.14 M-circle dot is derived, which gives a Mg/O production ratio consistent with the solar value. Nitrogen left in the He envelope from CNO burning gives strong [N II] lambda lambda 6548, 6583 emission lines that dominate over Ha emission in our models. The hydrogen envelopes of Type IIb SNe are too small and dilute to produce any noticeable H alpha emission or absorption after similar to 150 days, and nebular phase emission seen around 6550 angstrom is in many cases likely caused by [N II] lambda lambda 6548, 6583. Finally, the influence of radiative transport on the emergent line profiles is investigated. Significant line blocking in the metal core remains for several hundred days, which affects the emergent spectrum. These radiative transfer effects lead to early-time blueshifts of the emission line peaks, which gradually disappear as the optical depths decrease with time. The modelled evolution of this effect matches the observed evolution in SN 2011dh.

The nebular spectra of SN 2012aw and constraints on stellar nucleosynthesis from oxygen emission lines

We present nebular-phase optical and near-infrared spectroscopy of the Type IIP supernova SN 2012aw combined with non-local thermodynamic equilibrium radiative transfer calculations applied to ejecta from stellar evolution/explosion models. Our spectral synthesis models generally show good agreement with the ejecta from a M_ZAMS = 15 M_⊙progenitor star. The emission lines of oxygen, sodium, and magnesium are all consistent with the nucleosynthesis in a progenitor in the 14-18 M_⊙ range.We also demonstrate how the evolution of the oxygen cooling lines of [O I] λ5577, [O I] λ6300, and [O I] λ6364 can be used to constrain the mass of oxygen in the non-molecularly cooled ashes to < 1 M_⊙, independent of the mixing in the ejecta. This constraint implies that any progenitor model of initial mass greater than 20 M_⊙ would be difficult to reconcile with the observed line strengths. A stellar progenitor of around M_ZAMS = 15 M_⊙ can consistently explain the directly measured luminosity of the progenitor star, the observed nebular spectra, and the inferred pre-supernova mass-loss rate.We conclude that there is still no convincing example of a Type IIP supernova showing the nucleosynthesis products expected from an M_ZAMS > 20 M_⊙ progenitor. © 2014 The Author. Published by Oxford University Press on behalf of the Royal Astronomical Society.

Adaptor protein-2 sigma subunit mutations causing familial hypocalciuric hypercalcaemia type 3 (FHH3) demonstrate genotype-phenotype correlations, codon bias and dominant-negative effects

The adaptor protein-2 sigma subunit (AP2sigma;2) is pivotal for clathrin-mediated endocytosis of plasma membrane constituents such as the calcium-sensing receptor (CaSR). Mutations of the AP2sigma;2 Arg15 residue result in familial hypocalciuric hypercalcaemia type 3 (FHH3), a disorder of extracellular calcium (Ca<inf>o</inf>²⁺) homeostasis. To elucidate the role of AP2sigma;2 in Ca<inf>o</inf>²⁺ regulation, we investigated 65 FHH probands, without other FHH-associated mutations, for AP2sigma;2 mutations, characterized their functional consequences and investigated the genetic mechanisms leading to FHH3. AP2sigma;2 mutations were identified in 17 probands, comprising 5 Arg15Cys, 4 Arg15His and 8 Arg15Leu mutations. A genotype-phenotype correlation was observed with the Arg15Leu mutation leading to marked hypercalcaemia. FHH3 probands harboured additional phenotypes such as cognitive dysfunction. All three FHH3-causing AP2sigma;2 mutations impaired CaSR signal transduction in a dominant-negative manner. Mutational bias was observed at the AP2sigma;2 Arg15 residue as other predicted missense substitutions (Arg15Gly, Arg15Pro and Arg15Ser), which also caused CaSR loss-of-function, were not detected in FHH probands, and these mutations were found to reduce the numbers of CaSR-expressing cells. FHH3 probands had significantly greater serum calcium (sCa) and magnesium (sMg) concentrations with reduced urinary calcium to creatinine clearance ratios (CCCR) in comparison with FHH1 probands with CaSR mutations, and a calculated index of sCa × sMg/100 × CCCR, which was ≥ 5.0, had a diagnostic sensitivity and specificity of 83 and 86%, respectively, for FHH3. Thus, our studies demonstrate AP2sigma;2 mutations to result in a more severe FHH phenotype with genotype-phenotype correlations, and a dominant-negative mechanism of action with mutational bias at the Arg15 residue.

Dietary exposure to aflatoxin and micronutrient status among young children from Guinea

SCOPE: Aflatoxin exposure coincides with micronutrient deficiencies in developing countries. Animal feeding studies have postulated that aflatoxin exposure may be exacerbating micronutrient deficiencies. Evidence available in human subjects is limited and inconsistent. The aim of the study was to investigate the relationship between aflatoxin exposure and micronutrient status among young Guinean children.

METHOD AND RESULTS: A total of 305 children (28.8 ± 8.4 months) were recruited at groundnut harvest (rainy season), of which 288 were followed up 6 months later post-harvest (dry season). Blood samples were collected at each visit. Aflatoxin-albumin adduct levels were measured by ELISA. Vitamin A, vitamin E and β-carotene concentrations were measured using HPLC methods. Zinc was measured by atomic absorption spectroscopy. Aflatoxin exposure and micronutrient deficiencies were prevalent in this population and were influenced by season, with levels increasing between harvest and post-harvest. At harvest, children in the highest aflatoxin exposure group, compared to the lowest, were 1.98 (95%CI: 1.00, 3.92) and 3.56 (95%CI: 1.13, 11.15) times more likely to be zinc and vitamin A deficient.

CONCLUSION: Although children with high aflatoxin exposure levels were more likely to be zinc and vitamin A deficient, further research is necessary to determine a cause and effect relationship. 

The Mass of Kepler-93b and The Composition of Terrestrial Planets

Kepler-93b is a 1.478 ± 0.019 R ⊕ planet with a4.7 day period around a bright (V = 10.2), astroseismicallycharacterized host star with a mass of 0.911 ± 0.033 M⊙ and a radius of 0.919 ± 0.011 R⊙. Based on 86 radial velocity observations obtainedwith the HARPS-N spectrograph on the Telescopio Nazionale Galileo and 32archival Keck/HIRES observations, we present a precise mass estimate of4.02 ± 0.68 M ⊕. The corresponding high densityof 6.88 ± 1.18 g cm-3 is consistent with a rockycomposition of primarily iron and magnesium silicate. We compareKepler-93b to other dense planets with well-constrained parameters andfind that between 1 and 6 M ⊕, all dense planetsincluding the Earth and Venus are well-described by the same fixed ratioof iron to magnesium silicate. There are as of yet no examples of suchplanets with masses >6 M ⊕. All known planets inthis mass regime have lower densities requiring significant fractions ofvolatiles or H/He gas. We also constrain the mass and period of theouter companion in the Kepler-93 system from the long-term radialvelocity trend and archival adaptive optics images. As the sample ofdense planets with well-constrained masses and radii continues to grow,we will be able to test whether the fixed compositional model found forthe seven dense planets considered in this paper extends to the fullpopulation of 1-6 M ⊕ planets.Based on observations made with the Italian Telescopio Nazionale Galileo(TNG) operated on the island of La Palma by the Fundación GalileoGalilei of the INAF (Istituto Nazionale di Astrofisica) at the SpanishObservatorio del Roque de los Muchachos of the Instituto de Astrofisicade Canarias.

Highlights from Faraday Discussion: Designing New Heterogeneous Catalysts, London, UK, April 2016

The Faraday Discussion on the design of new heterogeneous catalysts took place from 4-6 April 2016 in London, United Kingdom. It brought together world leading scientists actively involved in the synthesis, characterisation, modelling and testing of solid catalysts, attracting more than one hundred delegates from a broad spectrum of backgrounds and experience levels-academic and industrial researchers, experimentalists and theoreticians, and students. The meeting was a reflection of how big of an impact the ability to control and design catalysts with specific properties for particular processes can potentially have on the chemical industry, environment, economy and society as a whole. In the following, we give an overview of the topics covered during this meeting and briefly highlight the content of each presentation.