Metastable de-excitation spectroscopy and density functional theory study of the selective oxidation of crotyl alcohol over Pd(111)

The extremely surface sensitive technique of metastable de-excitation spectroscopy (MDS) has been utilized to probe the bonding and reactivity of crotyl alcohol over Pd(111) and provide insight into the selective oxidation pathway to crotonaldehyde. Auger de-excitation (AD) of metastable He (23S) atoms reveals distinct features associated with the molecular orbitals of the adsorbed alcohol, corresponding to emission from the hydrocarbon skeleton, the O n nonbonding, and C═C π states. The O n and C═C π states of the alcohol are reversed when compared to those of the aldehyde. Density functional theory (DFT) calculations of the alcohol show that an adsorption mode with both C═C and O bonds aligned somewhat parallel to the surface is energetically favored at a substrate temperature below 200 K. Density of states calculations for such configurations are in excellent agreement with experimental MDS measurements. MDS revealed oxidative dehydrogenation of crotyl alcohol to crotonaldehyde between 200 and 250 K, resulting in small peak shifts to higher binding energy. Intramolecular changes lead to the opposite assignment of the first two MOs in the alcohol versus the aldehyde, in accordance with DFT and UPS studies of the free molecules. Subsequent crotonaldehyde decarbonylation and associated propylidyne formation above 260 K could also be identified by MDS and complementary theoretical calculations as the origin of deactivation and selectivity loss. Combining MDS and DFT in this way represents a novel approach to elucidating surface catalyzed reaction pathways associated with a “real-world” practical chemical transformation, namely the selective oxidation of alcohols to aldehydes.

Are there theory of mind regions in the brain? A review of the neuroimaging literature

There have been many functional imaging studies of the brain basis of theory of mind (ToM) skills, but the findings are heterogeneous and implicate anatomical regions as far apart as orbitofrontal cortex and the inferior parietal lobe. The functional imaging studies are reviewed to determine whether the diverse findings are due to methodological factors. The studies are considered according to the paradigm employed (e.g., stories vs. cartoons and explicit vs. implicit ToM instructions), the mental state(s) investigated, and the language demands of the tasks. Methodological variability does not seem to account for the variation in findings, although this conclusion may partly reflect the relatively small number of studies. Alternatively, several distinct brain regions may be activated during ToM reasoning, forming an integrated functional "network." The imaging findings suggest that there are several "core" regions in the network-including parts of the prefrontal cortex and superior temporal sulcus-while several more "peripheral" regions may contribute to ToM reasoning in a manner contingent on relatively minor aspects of the ToM task. © 2008 Wiley-Liss, Inc.

Larger foraminiferal biostratigraphy, systematics and paleoenvironments of the Avon Park Formation and Ocala Limestone, Highlands County, Florida

This study investigates the use of larger foraminifera in determining the biostratigraphy of the Avon Park Formation and the Ocala Limestone in central Florida. Sedimentary rocks of the Avon Park Formation are the oldest exposed deposits in the state of Florida, and together with the Ocala Limestone comprise a part of the confining unit of the Floridan Aquifer, a major source of Florida's water supply. ^ Material from the ROMP 29A core collected by the U.S. Geological Survey was evaluated and compared to previous studies of the biostratigraphy of the formations. The larger foraminifera of the Avon Park Formation were examined in thin section, and those of the Ocala Limestone were free specimens. The larger foraminifera from both units were described and identified, and the biostratigraphy determined. The morphological features of the larger foraminifera of the Ocala Limestone were measured and analyzed at various depths within the ROMP 29A core.^ The Avon Park Formation contains predominantly the shallow-water, conical foraminifera Fallotella cookei, Fallotella floridana, Pseudochrysalidina floridana, Coleiconus christianaensis, Coleiconus sp. A, Coskinolina sp. A, Coskinolina sp. B, Fallotella sp. A, Fallotella sp. B, Fabularia vaughani and larger miliolids. ^ The Ocala Limestone contains a different, deeper water assemblage that included the larger foraminifera Heterostegina ocalana, Lepidocyclina ocalana varieties, Lepidocyclina chaperi, Lepidocyclina pustulosa, Nummulites willcoxi, Nummulites striatoreticulatus, Nummulites floridensis and Pseudophragmina spp. A, B, and C. The age of the Avon Park Formation was corroborated by the occurrence of the biomarker echinoid Neolaganum dalli as Eocene, and the Ocala Limestone also contained Eocene larger foraminifera with Eocene to possibly Oligocene calcareous nannofossils. The distribution of the larger foraminifera of the Avon Park Formation was correlated with the subtidal and peritidal zones of the continental shelf. Analyses of variance showed that the changes in measurements of the morphology in Heterostegina ocalana, Lepidocyclina spp. and Nummulites spp. were correlated with change in the depositional environments.^

Mosaic image of the artificial light produced by Berlin on the night of September 11, 2010 observed from an altitude of 10,000 ft

Aerial observations of light pollution can fill an important gap between ground based surveys and nighttime satellite data. Terrestrially bound surveys are labor intensive and are generally limited to a small spatial extent, and while existing satellite data cover the whole world, they are limited to coarse resolution. This paper describes the production of a high resolution (1 m) mosaic image of the city of Berlin, Germany at night. The dataset is spatially analyzed to identify themajor sources of light pollution in the city based on urban land use data. An area-independent 'brightness factor' is introduced that allows direct comparison of the light emission from differently sized land use classes, and the percentage area with values above average brightness is calculated for each class. Using this methodology, lighting associated with streets has been found to be the dominant source of zenith directed light pollution (31.6%), although other land use classes have much higher average brightness. These results are compared with other urban light pollution quantification studies. The minimum resolution required for an analysis of this type is found to be near 10 m. Future applications of high resolution datasets such as this one could include: studies of the efficacy of light pollution mitigation measures, improved light pollution simulations, economic and energy use, the relationship between artificial light and ecological parameters (e.g. circadian rhythm, fitness, mate selection, species distributions, migration barriers and seasonal behavior), or the management of nightscapes. To encourage further scientific inquiry, the mosaic data is freely available at Pangaea.

Mad Men, The Sopranos and The American Way of Life. The history of the capital in two times

Don Draper (Mad Men, Matthew Weiner, AMC: 2007-2015) actively colaborates in the birth and consolidationof a model of consumer society without realizing the enormous lie he is telling himself. Tony Soprano(The Sopranos, David Chase, HBO: 1999-2007) desperately grasps the wreckage of that ideal imageof effort and self-improvement which is not only disappearing but was actually never coherent or real.This article does a comparative textual, sociological, and discursive analysis these two characters as arepresentation of the evolution of the discourse of capitalism in the second half of the 20th century, that is,the artificiality of the hegemonic discourse of “pursuit of happiness” as the main myth in post-war NorthAmerican neoliberalism.

The Worsening of the employment and work conditions and its relationship to the self-perceived health in European working population. Relevance and effects of the latest socioeconomic crisis

The recent crisis of the capitalistic economic system has altered the working conditions and occupations in the European Union. The recession situation has accelerated trends and has brought transformations that have been observed before. Changes have not looked the same way in all the countries of the Union. The social occupation norms, labour relations models and the type of global welfare provision can help underline some of these inequalities. Poor working conditions can expose workers to situations of great risk. This is one of the basic assumptions of the theoretical models and analytical studies of the approach to the psychosocial work environment. Changes in working conditions of the population seems to be important to explain in the worst health states. To observe these features in the current period of economic recession it has made a comparative study of trend through the possibilities of the European Working Conditions Survey in the 2005 and 2010 editions. It has also set different multivariate logistic regression models to explore potential partnerships with the worst conditions of employment and work. It seems that the economic crisis has intensified changes in working conditions and highlighted the effects of those conditions on the poor health of the working population. This conclusion can’t be extended for all EU countries; some differences were observed in terms of global welfare models.

Asymptotic and structural properties of special cases of the Wright function arising in probability theory

This analysis paper presents previously unknown properties of some special cases of the Wright function whose consideration is necessitated by our work on probability theory and the theory of stochastic processes. Specifically, we establish new asymptotic properties of the particular Wright function 1Ψ1(ρ, k; ρ, 0; x) = X∞ n=0 Γ(k + ρn) Γ(ρn) x n n! (|x| < ∞) when the parameter ρ ∈ (−1, 0)∪(0, ∞) and the argument x is real. In the probability theory applications, which are focused on studies of the Poisson-Tweedie mixtures, the parameter k is a non-negative integer. Several representations involving well-known special functions are given for certain particular values of ρ. The asymptotics of 1Ψ1(ρ, k; ρ, 0; x) are obtained under numerous assumptions on the behavior of the arguments k and x when the parameter ρ is both positive and negative. We also provide some integral representations and structural properties involving the ‘reduced’ Wright function 0Ψ1(−−; ρ, 0; x) with ρ ∈ (−1, 0) ∪ (0, ∞), which might be useful for the derivation of new properties of members of the power-variance family of distributions. Some of these imply a reflection principle that connects the functions 0Ψ1(−−;±ρ, 0; ·) and certain Bessel functions. Several asymptotic relationships for both particular cases of this function are also given. A few of these follow under additional constraints from probability theory results which, although previously available, were unknown to analysts.

Using Quantitative Methods to Explore Political Leverage, Trade Policy, and Food Security: A Case Study of the Middle East

This dissertation explores why some states consistently secure food imports at prices higher than the world market price, thereby exacerbating food insecurity domestically. I challenge the idea that free market economics alone can explain these trade behaviors, and instead argue that states take into account political considerations when engaging in food trade that results in inefficient trade. In particular, states that are dependent on imports of staple food products, like cereals, are wary of the potential strategic value of these goods to exporters. I argue that this consideration, combined with the importing state’s ability to mitigate that risk through its own forms of political or economic leverage, will shape the behavior of the importing state and contribute to its potential for food security. In addition to cross-national analyses, I use case studies of the Gulf Cooperation Council states and Jordan to demonstrate how the political tools available to these importers affect their food security. The results of my analyses suggest that when import dependent states have access to forms of political leverage, they are more likely to trade efficiently, thereby increasing their potential for food security.

Experimental and numerical studies of hydrodynamic interaction of two bodies in waves

This thesis focuses on experimental and numerical studies of the hydrodynamic interaction between two vessels in close proximity in waves. In the model tests, two identical box-like models with round corners were used. Regular waves with the same wave steepness and different wave frequencies were generated. Six degrees of freedom body motions and wave elevations between bodies were measured in a head sea condition. Three initial gap widths were examined. In the numerical computations, a panel-free method based seakeeping program, MAPS0, and a panel method based program, WAMIT, were used for the prediction of body motions and wave elevations. The computed body motions and wave elevations were compared with experimental data.

Status of Endangered and Threatened Sand Area Species of the Illinois Flora

This study was undertaken to determine the distribution and habitat requirements of many of the endangered and threatened plant species associated with the sand deposits of Illinois. Approximately 70 species of endangered and threatened plants are known to grow in these deposits. The habitat fidelity and natural community types were determined for 40 of these species that are restricted to these glacial drift sand habitats. Plant community types, associated species, moisture requirements, and other data concerning each of the plant species were determined by reviewing the pertinent literature, searching the Illinois Department of Natural Resources Natural Heritage Database, through discussions with botanists and natural heritage biologists, examination of herbarium specimens, and our studies of the vegetation of the Illinois sand deposits. Throughout the course of these studies, most of the nature preserves, state parks, and identified natural areas in the sand regions were visited on numerous occasions and vegetation surveys undertaken. The information presented in this paper could allow rare plant conservation in Illinois to become more proactive by encouraging the selection of sites where in situ conservation efforts could be conducted by state, local, and nongovernmental organizations.

CHRONOMETRY OF LATE ENEOLITHIC AND ‘EARLY BRONZE’ CULTURES IN THE MIDDLE DNIESTER AREA: INVESTIGATIONS OF THE YAMPIL BARROW COMPLEX

The paper discusses the 2010-2015 studies of the radiocarbon chronology of Podolia ‘barrow cultures’ on the left bank of the middle dniester . The studies have relied on series of 14 C dates for the Klembivka 1, Pidlisivka 1, Porohy 3a and Prydnistryanske 1 sites determined in Kyiv and Poznań laboratories . They are the first attempt to construct a regional (‘Yampil’) radiocarbon scale for ‘Early Bronze’ funerary rites (4th/3rd-2nd millennium BC) as practised by barrow builders – the communities of the Tripolye and Yamnaya cultures – and the secondary barrow users – the designers of necropolises located on barrows – belonging to the Catacomb, Babyno and Noua cultures.

Decorative tiles between Brazil and Europe: the case of the Santa Catharina factory

Abstract It was in the first decade of the twentieth century that the first white china Factory was implemented in Brazil. Fruit of the association between the Sao Paulo Aristocracy and the Italian Romeo Ranzini, this factory was responsible for producing significant amounts of crockery in industrial moulds in sao Paulo, Brazil. It was also the first factory to produce decorative tiles that would be part of the architecture of the public buildings built between 1919 and 1922 in Commemoration of the Centennial of the Brazilian Independence. Known as The Santa Catharina Factory, this factory was inaugurated in 1913 with the participation of Italian immigrants and German technologies for the development of its first manufacturing activities. As a result of a number of economic, political and social matters that started in the previous century in the city of Sao Paulo, The Santa Catharina factory played an important role in industrial development as regards the production of national white china and was used as a model for the construction of new ceramic factories in Sao Paulo. After acquired by Matarazzo industries in 1927, had closed their activities in 1937. This research is based on the identification and analysis of the first tiles produced in Brazil by the Santa Catharina Factory, which were part of the architectural decorations of the buildings built in Sao Paulo to the celebration of the Centennial of the Brazilian Independence. Designed by Victor Dubugras, The Largo da Memoria (located in the city of Sao Paulo) and the buildings located in the "Paths of the Sea" road marked the beginning of Brazilian industrialization and the emergence of Neocolonial Movement in architecture of Sao Paulo. Studies of the first national patterns of decorative tiles approach a subject poorly researched by experts in tiled studies in Brazil, although in this case these tiles have represented not only an important milestone in the national industrialization, but also have demarcated the significant changes in architectural and decorative practices in the country in the early twentieth century; RESUMÈ: C'est durant la premiere decennie du XXe siecle que la premiere usine de porcelaine blanche fut implant& au Bresil. Elle fut le fruit de l'association entre l'aristocratie de Sao Paulo et l'italien Romeo Ranzini. L'usine produisait une quantite signifiante de porcelaine sur le territoire industriel de Sao Paulo. Ce fut egalement la premiere usine a produire des carreaux decoratifs qui sont aujourd'hui visibles dans l'architecture des batiments publics construit entre 1919 et 1922, pour la commemoration du centenaire de l'independance bresilienne. Connue sous le nom de Santa Catharina, cette usine fut inaugure en 1912. Elle fut construite par des émigrés Italiens, et utilisa pour la technologie allemande pour so production. En tant que resultat d'un certain nombre de questions economiques, politiques et sociales qui ont &butes durant le siecle precedent dans la ville de Sao Paulo, l'usine Santa Catharina a joue un role important dans le developpement industriel de la production de porcelaine blanche nationale et a ete utilise comme modele pour la construction de nouvelles usines de ceramique a Sao Paulo. Apres avoir ete achete par l'industrie Matarazzo en 1927, elle cessa ses activites en 1937. Cette recherche est basee sur l'identification et l'analyse des premiers carreaux decoratifs fabriques au Bresil par l'usine Santa Catharina, qui etait une partie des decorations architecturales des batiments construits a Sao Paulo pour la celebration du centenaire de l'Independance Bresilienne. Connue par Victor Dubugras, le "Largo da Memoria" (situe dans la ville de Sao Paulo), et les batiments situes sur le "Path of the Sea", ont marque le debut de l'industrialisation bresilienne et l'emergence d'un mouvement neocolonialiste dans l'architecture de Sao Paolo. L'etude des premiers modeles nationaux de carreaux decoratifs est un sujet peut etudie par les experts bresiliens, bien qu'ils furent un jalon importante pour l'industrialisation nationale. Its ont egalement entrains des changements importants dans les pratiques architecturales, et decoratives au sein du pays au XXe siecle. Mots-cles: Ceramique - carreaux decoratifs — L'usine Santa Catharina, Bresil - Production de carreaux; RIASSUNTO: Nel primo decennio del Novecento vide luce la prima fabbrica di ceramica di porcellana in Brasile. Frutto dell'associazione tra l'aristocrazia Paulista e l'italiano Romeo Ranzini, questa fabbrica fu responsabile della produzione di notevoli quantita di ceramica di porcellana mediante stampi industriali nella citta di San Paolo, Brasile. Fu anche la prima fabbrica a produrre azulejos che avrebbero poi fatto parte dell'architettura degli edifici pubblici costruiti tra it 1919 ed it 1922, per la commemorazione del Centenario dell'indipendenza Brasiliana. Conosciuta come Fabbrica di Santa Catharina, questa fu inaugurata nel 1913, con la partecipazione di immigrati italiani e con l'impiego di tecnologie tedesche per lo sviluppo delle sue prime attivita produttive. Risultato di una serie di cambiamenti economici, politici e sociali, che ebbero inizio nel secolo precedente nella citta di San Paolo, la Fabbrica di Santa Catharina svolse un ruolo importante nello sviluppo industriale per quanto riguarda la produzione di ceramica di porcellana nazionale e fu adottata come modello per la costruzione di nuove fabbriche a San Paolo. Successivamente, fu acquisita dalle industrie Matarazzo nel 1927, vedendo poi chiudersi le sue attivita nel 1937. Questa ricerca si basa sull'identificazione e l'analisi dei primi azulejos prodotti in Brasile dalla Fabbrica di Santa Catharina che fecero parte delle decorazioni architettoniche degli edifici costruiti a San Paolo per la commemorazione del Centenario dell'indipendenza Brasiliana. Progettati da Victor Dubugras, it Largo da Mem(Via (situato nella citta di San Paolo) e gli edifici che si trovano nei Caminhos do Mar marcarono l'inizio dell'industrializzazione brasiliana e la nascita del Movimento Neocolonial dell'architettura Paulista. Gli studi dei primi modelli di azulejos nazionali affrontano un argomento poco studiato dagli esperti in azulejaria in Brasile, nonostante rappresentino un importante avvenimento dell'industrializzazione nazionale, ma segnano anche i cambiamenti di significative pratiche architettoniche e decorative nel Paese nel primo Novecento. Parole chiave: Ceramica - porcellana - La fabbrica di Santa Catharina - Produzione di ceramica .

Validation of the haemoglobin colour scale for screening blood donors in Malawi

Background In 2009 Malawi introduced a new protocol to screen potential blood donors for anaemia, using the WHO Haemoglobin Colour Scale (HCS) for initial screening. Published studies of the accuracy of the HCS to screen potential blood donors show varying levels of accuracy and opinion varies whether this is an appropriate screening test. The aim of the study was to assess the validity of the HCS, as a screening test, by comparison to HemoCue in potential blood donors in Malawi. Study design and Methods This was a blinded prospective study in potential blood donors aged over 18 years, at Malawi Blood Transfusion Service in Blantyre, Malawi. Capillary blood samples were analysed using the HCS and HemoCue, independent of each other. The sensitivity and specificity of correctly identifying ineligible blood donors (Hb≤12g/dL) were calculated. Results From 242 participants 234 (96.7%) were correctly allocated and 8 (3.3%), were wrongly allocated on the basis of the Haemoglobin Colour Scale (HCS) compared to HemoCue, all were subjects that were wrongly accepted as donors when their haemoglobin results were ≤12.0g/dL. This gave a sensitivity of 100% and specificity of 96.7% to detect donor eligibilty. The negative predictive value of the HCS was 100% but the positive predictive value to identify ineligible donors on the basis of anaemia was only 20%. Conclusions Initial screening with the HCS correctly predicts eligibility for blood donation in the majority of potential blood donors at considerable cost saving compared with use of HemoCue as the first line anaemia screening test, however, by this method a small number of anaemic patients were allowed to donate blood.

Biochemical studies of postsynaptic density signaling proteins with a focus on synaptic GTPase activating protein and PDZ domains

Memory storage in the brain involves adjustment of the strength of existing synapses and formation of new neural networks. A key process underlying memory formation is synaptic plasticity, the ability of excitatory synapses to strengthen or weaken their connections in response to patterns of activity between their connected neurons. Synaptic plasticity is governed by the precise pattern of Ca²⁺ influx through postsynaptic N-methyl-D-aspartate-type glutamate receptors (NMDARs), which can lead to the activation of the small GTPases Ras and Rap. Differential activation of Ras and Rap acts to modulate synaptic strength by promoting the insertion or removal of 2-amino-3-(3-hydroxy-5-methyl-isoxazol-4-yl)propanoic acid receptors (AMPARs) from the synapse. Synaptic GTPase activating protein (synGAP) regulates AMPAR levels by catalyzing the inactivation of GTP-bound (active) Ras or Rap. synGAP is positioned in close proximity to the cytoplasmic tail regions of the NMDAR through its association with the PDZ domains of PSD-95. SynGAP’s activity is regulated by the prominent postsynaptic protein kinase, Ca²⁺/calmodulin-dependent protein kinase II (CaMKII) and cyclin-dependent kinase 5 (CDK5), a known binding partner of CaMKII. Modulation of synGAP’s activity by phosphorylation may alter the ratio of active Ras to Rap in spines, thus pushing the spine towards the insertion or removal of AMPARs, subsequently strengthening or weakening the synapse. To date, all biochemical studies of the regulation of synGAP activity by protein kinases have utilized impure preparations of membrane bound synGAP. Here we have clarified the effects of phosphorylation of synGAP on its Ras and Rap GAP activities by preparing and utilizing purified, soluble recombinant synGAP, Ras, Rap, CaMKII, CDK5, PLK2, and CaM. Using mass spectrometry, we have confirmed the presence of previously identified CaMKII and CDK5 sites in synGAP, and have identified novel sites of phosphorylation by CaMKII, CDK5, and PLK2. We have shown that the net effect of phosphorylation of synGAP by CaMKII, CDK5, and PLK2 is an increase in its GAP activity toward HRas and Rap1. In contrast, there is no effect on its GAP activity toward Rap2. Additionally, by assaying the GAP activity of phosphomimetic synGAP mutants, we have been able to hypothesize the effects of CDK5 phosphorylation at specific sites in synGAP. In the course of this work, we also found, unexpectedly, that synGAP is itself a Ca²⁺/CaM binding protein. While Ca²⁺/CaM binding does not directly affect synGAP activity, it causes a conformational change in synGAP that increases the rate of its phosphorylation and exposes additional phosphorylation sites that are inaccessible in the absence of Ca²⁺/CaM.

The postsynaptic density (PSD) is an electron-dense region in excitatory postsynaptic neurons that contains a high concentration of glutamate receptors, cytoskeletal proteins, and associated signaling enzymes. Within the PSD, three major classes of scaffolding molecules function to organize signaling enzymes and glutamate receptors. PDZ domains present in the Shank and PSD-95 scaffolds families serve to physically link AMPARs and NMDARs to signaling molecules in the PSD. Because of the specificity and high affinity of PDZ domains for their ligands, I reasoned that these interacting pairs could provide the core components of an affinity chromatography system, including affinity resins, affinity tags, and elution agents. I show that affinity columns containing the PDZ domains of PSD-95 can be used to purify active PDZ domain-binding proteins to very high purity in a single step. Five heterologously expressed neuronal proteins containing endogenous PDZ domain ligands (NMDAR GluN2B subunit Tail, synGAP, neuronal nitric oxide synthase PDZ domain, cysteine rich interactor of PDZ three and cypin) were purified using PDZ domain resin, with synthetic peptides having the sequences of cognate PDZ domain ligands used as elution agents. I also show that conjugation of PDZ domain-related affinity tags to Proteins Of Interest (POIs) that do not contain endogenous PDZ domains or ligands does not alter protein activity and enables purification of the POIs on PDZ domain-related affinity resins.