Long Distance Electron Transfer at the Metal/Alkanethiol/Ionic Liquid Interface

The rate constants of simple electron transfer (ET) reactions in room temperature ionic liquids (ILs) available now are rather high, typically at the edge of experimental accuracy. To consider ET phenomena in these media in view of theory developed earlier for molecular solvents, it is crucial to provide quantitative comparison of experimental kinetic data for certain reactions. We report this comparison for ferrocene/ferrocenium reaction. The ET distance is fixed by Au surface modification by alkanethiol self-assembled monolayers, which were characterized by in situ scanning tunneling microscopy. The dependence of ln kapp on barrier thickness in the range of ca. 6–20 Å is linear, with a slope typical for the same plots in aqueous media. This result confirms diabatic mode of Fc oxidation at long distance. The data for shorter ET distances point to the adiabatic regime of ET at a bare gold surface, although more detailed computational studies are required to justify this conclusion.

A longitudinal cross-country study of entrepreneurial orientation

As recent research documents, there has been an impressive effort of studying the entrepreneurial orientation construct and its nomological role. However, most research has been very context specific and based on the analyses of cross-sectional information. We study causal performance effects from entrepreneurial orientation and its key dimensions in two economic contexts–developed and emerging markets. Gathering data on a sample of 94 firms in developed market context and 108 in emerging market context at two time-points we explore our hypotheses. The results suggest that in a developed economy entrepreneurial orientation has a positive impact on firm performance, whereas in the emerging market context this effect is negative. Furthermore, we assess the contribution of each dimension to the aggregate construct and reveal the importance of risk-taking in both contexts. Finally, we highlight the role of environmental dynamism and explain its varying effect

Reactions of CF3-enones with arenes under superelectrophilic activation: a pathway to trans-1,3-diaryl-1-CF3-indanes, new cannabinoid receptor ligands

4-Aryl-1,1,1-trifluorobut-3-en-2-ones ArCH[double bond, length as m-dash]CHCOCF3 (CF3-enones) react with arenes in excess of Brønsted superacids (TfOH, FSO3H) to give, stereoselectively, trans-1,3-diaryl-1-trifluoromethyl indanes in 35-85% yields. The reaction intermediates, the O-protonated ArCH[double bond, length as m-dash]CHC(OH(+))CF3 and the O,C-diprotonated ArHC(+)CH2C(OH(+))CF3 species, have been studied by means of (1)H, (13)C, (19)F NMR, and DFT calculations. Both types of the cations may participate in the reaction, depending on their electrophilicity and electron-donating properties of the arenes. The formation of CF3-indanes is a result of cascade reaction of protonated CF3-enones to form chemo-, regio- and stereoselectively three new C-C bonds. The obtained trans-1,3-diaryl-1-trifluoromethyl indanes were investigated as potential ligands for cannabinoid receptors CB1 and CB2 types. The most potent compound showed sub-micromolar affinity for both receptor subtypes with a 6-fold selectivity toward the CB2 receptor with no appreciable cytotoxicity toward SHSY5Y cells.

Living benthic foraminifers in bottom sediments of the southeastern Kandalaksha Bay (White Sea)

Analysis of composition and distribution of benthic foraminifers in six samples of bottom sediments obtained in the southeast Kandalaksha Bay of the White Sea at water depths of 20 to 155 m revealed their dependence on lithology and different hydrological characteristics. It is shown that living foraminifers populating relatively shallow areas of the bay (20-60 m), which are bathed by seasonally warmed intermediate water with temperature 0.7-1.5°C and salinity 26 per mil, are characterized by high abundance (250-750 specimens/10 ccm of wet sediment) and prevalence of agglutinated species (Eggerella advena, Recurvoides turbinatus, and others). Deeper (155 m) where cold and relatively saline deep water occurs (-1.4°C, 29.5 per mil), abundance is an order lower (30 specimens/10 ccm) and is dominated by calcareous taxa Cassidulina reniforme, an Arctic cold resistant species.

Geochemical parameters of sediments and water of the Black Sea, data of Cruise 8 of R/V Vityaz-2

The book presents results of comprehensive geological investigations carried out during Cruise 8 of R/V "Vityaz-2" to the western part of the Black Sea in 1984. Systematic studies in the Black Sea during about hundred years have not weakened interest in the sea. Lithological and geochemical studies of sediments in estuarine areas of the Danube and the Kyzyl-Irmak rivers, as well as in adjacent parts of the deep sea and some other areas were the main aims of the cruise. Data on morphological structures of river fans, lithologic and chemical compositions of sediments in the fans and their areal distribution, forms of occurrence of chemical elements, role of organic matter and gases in sedimentation and diagenesis are given and discussed in the book.

Parameters of population dynamics and energetics of ctenophore Mnemiopsis leidyi in Sevastopol Bay from January 1995 to March 1996

Population dynamics of abundance and biomass were studied and specific production of population of ctenophore Mnemiopsis leidyi was estimated in the Sevastopol Bay from January 1995 to March 1996. The ctenophores achieved maximum abundance and biomass in July during period of intensive reproduction. Young specimens (<5 mm) contributed during that period as much as 50-87% to total abundance of population. Annually averaged daily specific growth rate was 0.039. Growth, food consumption, and rate of filtration were measured in a laboratory under two concentrations of food (Acartia clausi and Moina micrura: 60 and 100 specimens per liter, 0.35 and 0.60 mg wet weight/l). Both concentrations sustained growth of animals with dry weight less than 20 mg. However these concentrations were insufficient to sustain growth of larger ctenophores. Specific growth rate of the ctenophores with dry weight <20 mg under favorable food conditions was 0.20-0.30 l/day. Specific growth rate of the ctenophores in the Sevastopol Bay never exceeded 0.093 l/day, mean biomass of fodder zooplankton in the bay being 90 mg/m**3 in terms of wet weight. Hence a conclusion was made that population of M. leidyi in the bay was limited by lack of food.

Rocks and minerals from the Strakhov Fracture Zone, 4°N Mid-Atlantic Ridge

Geological-geophysical data obtained during Cruises 7, 11, and 12 of R/V Akademic Nikolay Strakhov (1989-1991) within the international project EQUARIDGE in the Strakhov Fracture Zone region (4°N) are presented. The trough of the fracture is interpreted as an open extension joint, a graben produced by stretching along the axis of the Mid-Atlantic Ridge. Bedrock studies showed that typical mid-ocean tholeiitic basalts occur within the narrow (60 nm wide) axial rift zone, whereas igneous rocks not typical for the ocean were found on the eastern and western flank plateaus. This allows to suppose that a reworked relict continental-type basement of pre-Upper Jurassic age possibly exists beneath the flank plateaus, within the segment under discussion. The above data correspond to the hypothesis of E. Bonatti about nonspreading nature of the basement of Mid-Atlantic Ridge within the equatorial segment and the Strakhov Fracture Zone.

Composition of recent carbonate bottom sediments from the Guiana shelf an off the West Africa

This work was based on a study of the upper layer of recent carbonate bottom sediments of the Atlantic Ocean. Biogenic carbonate of recent sediments is represented by metastable and stable minerals. In the ocean metastable phases can exist indefinitely long, but the structure of polymorphism determines inevitability of transformation of metastable phases into stable ones. This transformation occurs in the solid phase. In the absence of a critical point between the two phases of the transition process is not available for study by microscopic methods. It is estimated indirectly by studying the nature and extent of changes in mineral and chemical compositions. With aging of sediments their mineral composition alters in direction of increasing contents of resistant minerals. Fine grained sediments and fractions are subject to more intensive effects of early diagenesis processes, rather than coarse ones; this is reflected in their mineral composition. Regularities of distribution of carbonate minerals in size fractions consistent with the direction of polymorphic transformations in calcium carbonate. Such transformations can occur in a particular dimension of grains. Concrete grain size depends on environmental conditions. This situation explains presence of metastable biogenic carbonates at different depths of the ocean and suggests presence of diagenetic calcite in sediments occurring below expected for each case depth of the transition.

Bitumoids and methane in bottom sediments of the northeast Black Sea

Complex investigations of recent and ancient Black Sea sediments from the outer shelf, continental slope, and deep-water basin of the Russian Black Sea sector have been carried out. Samples were collected during Cruise 100 of R/V Professor Shtokman organized by the P.P. Shirshov Institute of Oceanology (March 2009) and expedition of UZHMORGEO (summer 2006). Rates of the main anaerobic processes during diagenesis (sulfate reduction, dark CO2 assimilation, methanogenesis, and methane oxidation) were studied for the first time in sediment cores of the studied area. Two peaks in the rate of microbial processes and two sources of these processes were identified: the upper peak near the water-sediment contact is related to solar energy (OM substrate of the water column) and the lower peak at the base of ancient Black Sea sediments with high(>1 mmol) methane concentration related to energy of anaerobic methane oxidation. New labile OM formed during this process is utilized by other groups of microorganisms. According to experimental data, daily rate of anaerobic methane oxidation is many times higher than that of methanogenesis, which unambiguously indicates migration nature of the main part of methane.

Methane and microbiological processes in the Barents Sea

Biogeochemical cycle of methane in the Barents Sea was studied using isotope geochemistry to determine rates of microbial methane oxidation. It was established that microbiological processes (glucose consumption, 14CO2 assimilation, sulfate reduction, and slow methane oxidation) in oxidized surface and weakly reduced sediments are marked by only insignificant change in SO4 concentration and absence of notable increase of total alkalinity and N/NH4 downward sediment cores. Microbial methane productivity was 0.111x10**6 mol/day. Taking into account volume of the water column, microbial methane consumption therein can be as much as 1.8x10**6 mol/day.