Quantum chemistry and in situ FTir spectroscopy studies on potential-dependent properties of CO adsorbed on Pt electrodes

The electronic and vibrational properties of CO adsorbed on Pt electrodes at different potentials have been studied, by using methods of self-consistent-charge discrete variational Xa (SCC-DV-Xa) cluster calculations and in situ FTir spectroscopy. Two new models have been developed and verified to be successful: (1) using a "metallic state cluster" to imitate a metal (electrode) surface; and (2) charging the cluster and shifting its Fermi level (e{lunate}) to simulate, according to the relation of -d e{lunate}e dE, quantitatively the variation of the electrode potential (E). It is shown that the binding of PtCO is dominated by the electric charge transfer of dp ? 2p, while that of s ? Pt is less important in this binding. The electron occupancy of the 2p orbital of CO weakens the CO bond and decreases the v. Variation of E mainly influences the charge transfer process of dp ? 2p, but hardly influences that of s ? Pt. A linear potential-dependence of v has been shown and the calculated dv/dE = 35.0 cm V. All results of calculations coincide with the ir experimental data. © 1993.

Risk assessment of neonatal excipient exposure:Lessons from food safety and other areas

Newborn babies can require significant amounts of medication containing excipients intended to improve the drug formulation. Most medicines given to neonates have been developed for adults or older children and contain excipients thought to be safe in these age groups. Many excipients have been used widely in neonates without obvious adverse effects. Some excipients may be toxic in high amounts in which case they need careful risk assessment. Alternatively, it is conceivable that ill-founded fears about excipients mean that potentially useful medicines are not made available to newborn babies. Choices about excipient exposure can occur at several stages throughout the lifecycle of a medicine, from product development through to clinical use. Making these choices requires a scalable approach to analysing the overall risk. In this contribution we examine these issues.

The influence of market deregulation on fast food consumption and body mass index:A cross-national time series analysis

Objective
To investigate the effect of fast food consumption on mean population body mass index (BMI) and explore the possible influence of market deregulation on fast food consumption and BMI.

Methods
The within-country association between fast food consumption and BMI in 25 high-income member countries of the Organisation for Economic Co-operation and Development between 1999 and 2008 was explored through multivariate panel regression models, after adjustment for per capita gross domestic product, urbanization, trade openness, lifestyle indicators and other covariates. The possible mediating effect of annual per capita intake of soft drinks, animal fats and total calories on the association between fast food consumption and BMI was also analysed. Two-stage least squares regression models were conducted, using economic freedom as an instrumental variable, to study the causal effect of fast food consumption on BMI.

Findings
After adjustment for covariates, each 1-unit increase in annual fast food transactions per capita was associated with an increase of 0.033 kg/m2 in age-standardized BMI (95% confidence interval, CI: 0.013–0.052). Only the intake of soft drinks – not animal fat or total calories – mediated the observed association (β: 0.030; 95% CI: 0.010–0.050). Economic freedom was an independent predictor of fast food consumption (β: 0.27; 95% CI: 0.16–0.37). When economic freedom was used as an instrumental variable, the association between fast food and BMI weakened but remained significant (β: 0.023; 95% CI: 0.001–0.045).

Conclusion
Fast food consumption is an independent predictor of mean BMI in high-income countries. Market deregulation policies may contribute to the obesity epidemic by facilitating the spread of fast food.

Self-assembly of hybrid organic–inorganic polyoxovanadates: functionalised mixed-valent clusters and molecular cages’

Herein we report the intra- and inter-molecular assembly of a {V5O9} subunit. This mixed-valent structural motif can be stabilised as [V5O9(L1–3)4]5−/9− (1–3) by a range of organoarsonate ligands (L1–L3) whose secondary functionalities influence its packing arrangement within the crystal structures. Variation of the reaction conditions results in the dodecanuclear cage structure [V12O14(OH)4(L1)10]4− (4) where two modified convex building units are linked via two dimeric {O4VIV(OH)2VIVO4} moieties. Bi-functional phosphonate ligands, L4–L6 allow the intramolecular connectivity of the {V5O9} subunit to give hybrid capsules [V10O18(L4–6)4]10− (5–7). The dimensions of the electrophilic cavities of the capsular entities are determined by the incorporated ligand type. Mass spectrometry experiments confirm the stability of the complexes in solution. We investigate and model the temperature-dependent magnetic properties of representative complexes 1, 4, 6 and 7 and provide preliminary cell-viability studies of three different cancer cell lines with respect to Na8H2[6]·36H2O and Na8H2[7]·2DMF·29H2O.

War, food rationing, and socioeconomic inequality in Germany during the First World War

Germany experienced a devastating period during the First World War due to severely restricted import possibilities and a general shortage of foodstuffs. This study uses the heights of some 4,000 individuals who served during the Second World War to quantify biological living standards from the 1900s to the 1920s, and focuses primarily on socioeconomic inequality during this period. The results suggest that generally the upper social strata, measured by fathers' occupation, exhibited the tallest average height, followed by the middle and lower classes. These socioeconomic differences became more pronounced during the First World War when the rationing system provided a limited food supply. Wealthier individuals were able to purchase additional foodstuffs on black markets. Therefore, children from upper-class families experienced only a small decline in average height compared to their counterparts from the middle and lower social strata.

Irradiation of oxygen and water ices at by 4 keV singly and doubly charged ions; sputtering and molecular synthesis

The icy surfaces of dust grains in the Interstellar Medium and those of comets, satellites and Kuiper Belt Objects are continuously exposed tophoton and charged particle irradiation. These energetic particles maysputter and induce chemical changes in the ices and the underlyingsurfaces.In the present work 258 nm thick O2 and H2O ices were deposited at 10 K with the thickness measured by a laser interferometer method. Asimple model fit to the reflected laser intensity as measured by aphotodiode detector enabled the refractive index of the ices to bedetermined. The ices were then irradiated with various singly and doublycharged ions such as He+, 13C+, N+, O+ , Ar+, 13C2+, N2+ and O2+ at 4keV. The decrease in ice thickness as a function of ion dose wasmonitored by a laser interferometer and the model used to determine thesputtering yield as shown in Figure 1.In the case of O2 ice thesputtering yields increased with increasing ion mass in good agreementwith a model calculation [Fama, J, Shi, R.A Baragiola, Surface Sci.,602, 156 (2007)]. In the case of O2 ice, O2+ has a significant lowersputtering yield when compared to O+. The sputtering yields for O2 icewere found to be at least 9 times larger compared to those for H2O ice.For H2O ice the sputter yields for C, N and O ions were found todecrease with increasing mass. Doubly charged C, N and O ions which werefound to have the same sputtering yield as the singly charged ionswithin the experimental errors. A preliminary TPD study was carried outusing a QMS to detect the desorbed species from water ice afterirradiation by 6 × 10^15 ions of 13C+ and 13C2+. The formation of13CO and 13CO2 was observed with the yield of 13CO almost of a factor of100 larger than of 13CO2. This is in contrast to our earlier work whereonly CO¬2 was observed.

The Application of Computational Chemistry and Chemometrics to Developing a Method for Online Monitoring of Polymer Degradation in the Manufacture of Bioresorbable Medical Implants

Bioresorbable polymers such as PLA have an important role to play in the development of temporary implantable medical devices with significant benefits over traditional therapies. However, development of new devices is hindered by high manufacturing costs associated with difficulties in processing the material. A major problem is the lack of insight on material degradation during processing. In this work, a method of quantifying degradation of PLA using IR spectroscopy coupled with computational chemistry and chemometric modeling is examined. It is shown that the method can predict the quantity of degradation products in solid-state samples with reasonably good accuracy, indicating the potential to adapt the method to developing an on-line sensor for monitoring PLA degradation in real-time during processing.

Chemistry and Mechanism of Alizarin Red S and Methylene Blue Biosorption onto Olive Stone: Equilibrium and Kinetic

The biosorption process of anionic dye Alizarin Red S (ARS) and cationic dye methylene blue (MB) as a function of solution pH, initial concentration and contact time onto olive stone (OS) biomass has been investigated. The main objectives of the current study are to: (i) study the chemistry and the mechanism of ARS and MB biosorption onto olive stone and the type of OS–ARS, MB interactions occurring, (ii) study the biosorption equilibrium and kinetic experimental data required for the design and operation of column reactors. Equilibrium biosorption isotherms and kinetics were also examined. Experimental equilibrium data were fitted to four different isotherms by non-linear regression method, however, the biosorption experimental data for ARS and MB dyes were well interpreted by the Temkin and Langmuir isotherms, respectively. The maximum monolayer adsorption capacity for ARS and MB dyes were 109.0 and 102.6 mg/g, respectively. The kinetic data of the two dyes could be better described by the pseudo second-order model. The data showed that olive stone can be effectively used for removing dyes from wastewater.

Consensus and Confusion in Molluscan Trees: Evaluating Morphological and Molecular Phylogenies

Mollusks are the most morphologically disparate living animal phylum, they have diversified into all habitats, and have a deep fossil record. Monophyly and identity of their eight living classes is undisputed, but relationships between these groups and patterns of their early radiation have remained elusive. Arguments about traditional morphological phylogeny focus on a small number of topological concepts but often without regard to proximity of the individual classes. In contrast, molecular studies have proposed a number of radically different, inherently contradictory, and controversial sister relationships. Here, we assembled a dataset of 42 unique published trees describing molluscan interrelationships. We used these data to ask several questions about the state of resolution of molluscan phylogeny compared to a null model of the variation possible in random trees constructed from a monophyletic assemblage of eight terminals. Although 27 different unique trees have been proposed from morphological inference, the majority of these are not statistically different from each other. Within the available molecular topologies, only four studies to date have included the deep-sea class Monoplacophora; but 36.4% of all trees are not significantly different. We also present supertrees derived from 2 data partitions and 3 methods, including all available molecular molluscan phylogenies, which will form the basis for future hypothesis testing. The supertrees presented here were not constructed to provide yet another hypothesis of molluscan relationships, but rather to algorithmically evaluate the relationships present in the disparate published topologies. Based on the totality of available evidence, certain patterns of relatedness among constituent taxa become clear. The internodal distance is consistently short between a few taxon pairs, particularly supporting the relatedness of Monoplacophora and the chitons, Polyplacophora. Other taxon pairs are rarely or never found in close proximity, such as the vermiform Caudofoveata and Bivalvia. Our results have specific utility for guiding constructive research planning in order to better test relationships in Mollusca as well as other problematic groups. Taxa with consistently proximate relationships should be the focus of a combined approach in a concerted assessment of potential genetic and anatomical homology, while unequivocally distant taxa will make the most constructive choices for exemplar selection in higher-level phylogenomic analyses.

LC- HRMS based metabolomics in food safety and doping control – DeTECH21

Issues surrounding the misuse of prohibited and licensed substances in animals destined for food production and performance sport competition continue to be an enormous challenge to regulatory authorities charged with enforcing their control. Efficient analytical strategies are implemented to screen and confirm the presence of a wide range of exogenous substances in various biological matrices. However, such methods rely on the direct measurement of drugs and/or their metabolites in a targeted mode, allowing the detection of restricted number of compounds. As a consequence, emerging practices, in particular the use of natural hormones, designer drugs and low-dose cocktails, remain difficult to handle from a control point of view. A new SME-led FP7 funded project, DeTECH21, aims to overcome current limitations by applying an untargeted metabolomics approach based on liquid chromatography coupled to high resolution mass spectrometry and bioinformatic data analysis to identify bovine and equine animals which have been exposed to exogenous substances and assist in the identification of administered compounds. Markerbased strategies, dealing with the comprehensive analysis of metabolites present in a biological sample (urine/plasma/tissue), offer a reliable solution in the areas of food safety and animal sport doping control by effective, high-throughput and sensitive detection of exogenously administered agents. Therefore, the development of the first commercially available forensic test service based on metabolomics profiling will meet 21st century demands in animal forensics.

Stout: Cloudy's Atomic and Molecular Database

We describe a new atomic and molecular database we developed for use in the spectral synthesis code Cloudy. The design of Stout is driven by the data needs of Cloudy, which simulates molecular, atomic, and ionized gas with kinetic temperatures and densities spanning the low-to high-density limits. The radiation field between photon energies 10−8 Ry and 100 MeV is considered, along with all atoms and ions of the lightest 30 elements, and ~102 molecules. For ease of maintenance, the data are stored in a format as close as possible to the original data sources. Few data sources include the full range of data we need. We describe how we fill in the gaps in the data or extrapolate rates beyond their tabulated range. We tabulate data sources both for the atomic spectroscopic parameters and for collision data for the next release of Cloudy. This is not intended as a review of the current status of atomic data, but rather a description of the features of the database which we will build upon.