Composition Space Analysis in the Development of Copper Molybdate Hybrids Decorated by a Bifunctional Pyrazolyl/1,2,4-Triazole Ligand

A bitopic ligand, 4-(3,5-dimethylpyrazol-4-yl)-1,2,4-triazole (Hpz-tr) (1), containing two different heterocyclic moieties was employed for the design of copper(II)–molybdate solids under hydrothermal conditions. In the multicomponent CuII/Hpz-tr/MoVI system, a diverse set of coordination hybrids, [Cu(Hpz-tr)2SO4]·3H2O (2), [Cu(Hpz-tr)Mo3O10] (3), [Cu4(OH)4(Hpz-tr)4Mo8O26]·6H2O (4), [Cu(Hpz-tr)2Mo4O13] (5), and [Mo2O6(Hpz-tr)]·H2O (6), was prepared and characterized. A systematic investigation of these systems in the form of a ternary crystallization diagram approach was utilized to show the influence of the molar ratios of starting reagents, the metal (CuII and MoVI) sources, the temperature, etc., on the reaction products outcome. Complexes 2–4 dominate throughout a wide crystallization range of the composition triangle, while the other two compounds 5 and 6 crystallize as minor phases in a narrow concentration range. In the crystal structures of 2–6, the organic ligand behaves as a short [N–N]-triazole linker between metal centers Cu···Cu in 2–4, Cu···Mo in 5, and Mo···Mo in 6, while the pyrazolyl function remains uncoordinated. This is the reason for the exceptional formation of low-dimensional coordination motifs: 1D for 2, 4, and 6 and 2D for 3 and 5. In all cases, the pyrazolyl group is involved in H bonding (H-donor/H-acceptor) and is responsible for π–π stacking, thus connecting the chain and layer structures in more complicated H-bonding architectures. These compounds possess moderate thermal stability up to 250–300 °C. The magnetic measurements were performed for 2–4, revealing in all three cases antiferromagnetic exchange interactions between neighboring CuII centers and long-range order with a net moment below Tc of 13 K for compound 4.

Chemical and isotope composition of rocks from the Omgon Range, Western Kamchatka coastal area

Hypabyssal rocks of the Omgon Range, Western Kamchatka that intrude Upper Albian-Lower Campanian deposits of the Eurasian continental margin belong to three coeval (62.5-63.0 Ma) associations: (1) ilmenite gabbro-dolerites, (2) titanomagnetite gabbro-dolerites and quartz microdiorites, and (3) porphyritic biotite granites and granite-aplites. Early Paleocene age of ilmenite gabbro-dolerites and biotite granites was confirmed by zircon and apatite fission-track dating. Ilmenite and titanomagnetite gabbro-dolerites were produced by multilevel fractional crystallization of basaltic melts with, respectively, moderate and high Fe-Ti contents and contamination of these melts with rhyolitic melts of different compositions. Moderate- and high-Fe-Ti basaltic melts were derived from mantle spinel peridotite variably depleted and metasomatized by slab-derived fluid prior to melting. The melts were generated at variable depths and different degrees of melting. Biotite granites and granite aplites were produced by combined fractional crystallization of a crustal rhyolitic melt and its contamination with terrigenous rocks of the Omgon Group. The rhyolitic melts were likely derived from metabasaltic rocks of suprasubduction nature. Early Paleocene hypabyssal rocks of the Omgon Range were demonstrated to have been formed in an extensional environment, which dominated in the margin of the Eurasian continent from Late Cretaceous throughout Early Paleocene. Extension in the Western Kamchatka segment preceded the origin of the Western Koryakian-Kamchatka (Kinkil') continental-margin volcanic belt in Eocene time. This research was conducted based on original geological, mineralogical, geochemical, and isotopic (Rb-Sr) data obtained by the authors.

Geochemistry on rocks from Shackleton Range

During the GEISHA expedition (Geologische Expedition in die Shackleton Range 1987/88), the Pioneers Escarpment was visited and sampled extensively for the first time. Most of the rock types encountered represent amphibolite facies metamorphics, but evidence for granulite facies conditions was found in cores of garnet. These conditions must have been at least partly reached during the peak of metamorphism. For the Pioneers Escarpment a varicolored succession of sedimentary and bimodal volcanic origin is typical. It comprises: quartzites muscovite quartzite, sericite quartzite, fuchsite quartzite, garnet-quartz schists etc.; pelites: mica schists and plagioclase or plagioclase-microcline gneisses, aluminous schists; marls and carbonates: grey meta-limestones, carbonaceous quartzites, but also pure white, often fine-grained, saccharoidal marble, or a variety of tremolite marble, olivine (forsterite) marble, diopside-clinopyroxene-tremolite marble, etc.; basic volcanic rocks: amphibole fels, amphibolite schist, garnet amphibolite, and acidic to intermediate volcanic rocks: garnet-biotite schist, epidote-biotite-plagioclase gneiss, microcline gneiss. These rocks are considered to be a supracrustal unit, called the Pioneers Group. In the easternmost parts of the Pioneers Escarpment, e.g. at Vindberget, nonmetamorphic shales, sandstones and greywackes crop out, which are cover rocks of possibly Jurassic age. These metasediments, which represent a quartz-pelite-carbonate (QPC) association, indicate that deposition took place on a stable shelf, i.e. on the submerged rim of a craton. Marine shallow-water sedimentation including marls and aluminous clays form the protoliths. The volcanics may be part of a bimodal volcanics-arkose-conglomerate (BVAC) association. Geochemical analyses support the assumption of volcanic protoliths. This is demonstrated especially by the elevated amounts of the immobile, incompatible high-field-strength elements (HFSE) Nb, Ta, Ti, Y, and Zr encountered in some of the gneisses. Microscopic investigation suggests the existence of ortho-amphibolites. This is confirmed by the geochemistry. A bimodal volcanic association is evident. The amphibolites plot in both the tholeiite and calc-alkaline fields. The acidic volcanics are mainly rhyolitic. The sediments and volcanics were subjected to conditions of 10-11 kbar and 600°C during the peak of metamorphism, i.e. granulite facies metamorphism, which can be deduced from the Fe mole ratios of 0.71-0.73 in the garnet cores. Due to the relatively low temperatures, no anatectic melting took placc. The rims of the garnets show a Fe mole ratio of 0.84-0.86, and the coexisting mineral association garnet-biotite-staurolite-kyanite indicate amphibolite facies. The thermobarometry shows P-T conditions of 5-6 kbar and 570-580°C for this stage. The metamorphic history indicates deep burial at depths down to 35 km (subduction?) i.e. high pressure metamorphism, followed by pressure release due to uplift associated with retrograde metamorphism. This may have happened during a pre-Ross metamorphic event or orogeny. The Ross Orogeny at about 500 Ma probably just led to the weak greenschist facies overprint that is evident in the rocks of the Pioneers Group. Finally, sedimentation resumed in the area of the present Shackleton Range, or at least in the eastern part of the Pioneers Escarpment, probably when detritus from erosion of the basement (Read Group and Pioneers Group) was deposited, forming sandstones and greywackes of possibly Jurassic age. There is no indication that these sediments belong to the former Turnpike Bluff Group.

Stopping power dependence of nitrogen sputtering yields in copper nitride films under swift-ion irradiation: Exciton model approach

Nitrogen sputtering yields as high as 104 atoms/ion, are obtained by irradiating N-rich-Cu3N films (N concentration: 33 ± 2 at.%) with Cu ions at energies in the range 10?42 MeV. The kinetics of N sputtering as a function of ion fluence is determined at several energies (stopping powers) for films deposited on both, glass and silicon substrates. The kinetic curves show that the amount of nitrogen release strongly increases with rising irradiation fluence up to reaching a saturation level at a low remaining nitrogen fraction (5?10%), in which no further nitrogen reduction is observed. The sputtering rate for nitrogen depletion is found to be independent of the substrate and to linearly increase with electronic stopping power (Se). A stopping power (Sth) threshold of ?3.5 keV/nm for nitrogen depletion has been estimated from extrapolation of the data. Experimental kinetic data have been analyzed within a bulk molecular recombination model. The microscopic mechanisms of the nitrogen depletion process are discussed in terms of a non-radiative exciton decay model. In particular, the estimated threshold is related to a minimum exciton density which is required to achieve efficient sputtering rates.

Organizational determinants of substantive sustainability reporting practices: the role of company-level fit

As sustainability reporting (SR) practices have being increasingly adopted by corporations over the last twenty years, most of the existing literature on SR has stressed the role of external determinants (such as institutional and stakeholder pressures) in explaining this uptake. However, given that recent evidence points to a broader range of motives and uses (both external and internal) of SR, we contend that its role within company-level activities deserves greater academic attention. In order to address this research gap, this paper seeks to provide a more detailed examination of the organizational characteristics acting as drivers and/or barriers of SR integration within corporate sustainability practices at the company-level. More specifically, we suggest that substantive SR implementation can be predicted by assessing the level of fit between the organization and the SR framework being adopted. Building on this hypothesis, our theoretical model defines three forms of fit (technical, cultural and political) and identifies organizational characteristics associated to each of these fits. Finally, implications for academic research, businesses and policy-makers are derived.

Symbolic vs substantive sustainability reporting: examining the role of company-level characteristics

As sustainability reporting (SR) practices have being increasingly adopted by corporations over the last twenty years, most of the existing literature on SR has stressed the role of external determinants (such as institutional and stakeholder pressures) in explaining this uptake. However, given that recent evidence points to a broader range of motives and uses (both external and internal) of SR, we contend that its role within company-level activities deserves greater academic attention. In order to address this research gap, this paper seeks to provide a more integrated perspective of both institutional and efficiency explanations of SR dynamics, as well as to highlight the role of company-level characteristics in explaining its contribution to sustainability management practices. More specifically, we suggest that substantive SR implementation can be predicted by assessing the level of fit between the organization and the SR framework being adopted. Building on this idea, our theoretical model defines three forms of fit (technical, cultural and political) and identifies organizational characteristics associated to each of these fits. Finally, implications for academic research, businesses and policy-makers are derived.

Chaperone-facilitated copper binding is a property common to several classes of familial amyotrophic lateral sclerosis-linked superoxide dismutase mutants

Mutations in Cu, Zn superoxide dismutase (SOD1) cause the neurodegenerative disease familial amyotrophic lateral sclerosis from an as-yet-unidentified toxic property(ies). Analysis in Saccharomyces cerevisiae of a broad range of human familial amyotrophic lateral sclerosis–linked SOD1 mutants (A4V, G37R, G41D, H46R, H48Q, G85R, G93C, and I113T) reveals one property common to these mutants (including two at residues that coordinate the catalytic copper): Each does indeed bind copper and scavenge oxygen-free radicals in vivo. Neither decreased copper binding nor decreased superoxide scavenging activity is a property shared by all mutants. The demonstration that shows that all mutants tested do bind copper under physiologic conditions supports a mechanism of SOD1 mutant-mediated disease arising from aberrant copper-mediated chemistry catalyzed by less tightly folded (and hence less constrained) mutant enzymes. The mutant enzymes also are shown to acquire the catalytic copper in vivo through the action of CCS, a specific copper chaperone for SOD1, which in turn suggests that a search for inhibitors of this SOD1 copper chaperone may represent a therapeutic avenue.

Spectroelectrochemical Study of the Photoinduced Catalytic Formation of 4,4′-Dimercaptoazobenzene from 4-Aminobenzenethiol Adsorbed on Nanostructured Copper

Surface-enhanced raman scattering (SERS) spectra of self-assembled monolayers of 4-aminobenzenethiol (4-ABT) on copper (Cu) and silver (Ag) surfaces decorated with Cu and Ag nanostructures, respectively, have been obtained with lasers at 532, 632.8, 785, and 1064 nm. Density functional theory (DFT) has been used to obtain calculated vibrational frequencies of the 4-ABT and 4,4′-dimercaptoazobenzene (4,4′-DMAB) molecules adsorbed on model Cu surfaces. The features of the SERS spectra depend on the electrode potential and the type and power density of the laser. SERS spectra showed the formation of the 4,4′-DMAB on the nanostructured Cu surface independently of the laser employed. For the sake of comparison SERS spectra of a self-assembled monolayer of the 4-ABT on Ag surfaces decorated with Ag nanostructures have been also obtained with the same four lasers. When using the 532 and 632.8 nm lasers, the 4,4′-DMAB is formed on Cu surface at electrode potentials as low as −1.0 V (AgCl/Ag) showing a different behavior with respect to Ag (and others metals such as Au and Pt). On the other hand, the surface-enhanced infrared reflection absorption (SEIRA) spectra showed that in the absence of the laser excitation the 4,4′-DMAB is not produced from the adsorbed 4-ABT on nanostructured Cu in the whole range of potentials studied. These results point out the prevalence of the role of electron–hole pairs through surface plasmon activity to explain the obtained SERS spectra.

Gold Company Claims, Witwatersrand, South Africa, 1895 (Raster Image)

This layer is a georeferenced raster image of the historic paper map entitled: Bacon's new map of the Witwatersrand goldfields in the districts of Pretoria and Heidelberg, Transvaal, S. A. R. : shewing the main and other reefs, with the farms, gold mining company's claims and concessions : from information in the Surveyor-General's Department. It was published by G. W. Bacon & Co. in 1895. Scale [ca. 1:88,992].The image inside the map neatline is georeferenced to the surface of the earth and fit to the Universal Transverse Mercator (UTM Zone 35S, meters, WGS 1984) projected coordinate system. All map collar and inset information is also available as part of the raster image, including any inset maps, profiles, statistical tables, directories, text, illustrations, index maps, legends, or other information associated with the principal map. This map shows features such as drainage, roads, railroads, cities and other human settlements, administrative boundaries, farms, homesteads, main reefs, other reefs, probable connections, and mills. Includes also notes and inset: "Enlarged map of the farms Lanlaagte, Turffontein, Dornfontein & Elandsfontein, shewing the boundaries of the principal deep level gold mining coys. on the Witwatersrand goldfields" and a geological profile of the area north of Magaliesberg to the south of Witwatersrange.This layer is part of a selection of digitally scanned and georeferenced historic maps from the Harvard Map Collection. These maps typically portray both natural and manmade features. The selection represents a range of originators, ground condition dates, scales, and map purposes.

Report to the President by the Emergency Board ... to investigate and report in respect to the dispute between the Duluth, Missabe & Iron Range Railway Co., Chicago & North Western Railway, Great Northern Railway, Minneapolis, St. Paul & Sault Ste. Marie Railway, and certain of their employees as represented by the Brotherhood of Railway and Steamship Clerks, Freight Handlers, Express, and Station Employees.

Cover title.

Wind tunnel test[s] and further analysis of [the] floating wing fuel tanks for helicopter range extension.

"Contract no. DA44-177-TC-550."

Sunday school selections : comprising a wide range of reading and recitations adapted to church and Sunday school entertainments and to all gatherings of a moral or religious character /

Mode of access: Internet.

The Newtonian system of philosophy : adapted to the capacities of young ladies and gentlemen, and familiarized and made entertaining, by objects with which they are intimately acquainted : being the substance of six letters, read to a select company of friends /

Cf. Roscoe, S. Newbery, J348(8)