Browsing by Subject "ALUMINUM"

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  • Collins, Scott; Hasan, Galib; Joshi, Anuj; McIndoe, J. Scott; Linnolahti, Mikko (2021)
    Density functional theory calculations on neutral sheet models for methylaluminoxane (MAO) indicate that these structures, containing 5-coordinate and 4-coordinate Al, are likely precursors to ion-pairs seen during the hydrolysis of trimethylaluminum (Me3Al) in the presence of donors such as octamethyltrisiloxane (OMTS). Ionization by both methide ([Me](-)) and [Me2Al](+) abstraction, involving this donor, were studied by polarizable continuum model calculations in fluorobenzene (PhF) and o-difluorobenzene (DFB) media. These studies suggest that low MW, 5-coordinate sheets ionize by [Me2Al](+) abstraction, while [Me](-) abstraction from Me3Al-OMTS is the likely process for higher MW 4-coordinate sheets. Further, comparison of anion stabilities per mole of aluminoxane repeat unit (MeAlO)(n), suggest that anions such as [(MeAlO)(7)(Me3Al)(4)Me](-)=[7,4](-) are especially stable compared to higher homologues, even though their neutral precursors are unstable.
  • Kögler, Martin; Paul, Andrea; Anane, Emmanuel; Birkholz, Mario; Bunker, Alex; Viitala, Tapani; Maiwald, Michael; Junne, Stefan; Neubauer, Peter (2018)
    The application of Raman spectroscopy as a monitoring technique for bioprocesses is severely limited by a large background signal originating from fluorescing compounds in the culture media. Here, we compare time-gated Raman (TG-Raman)-, continuous wave NIR-process Raman (NIR-Raman), and continuous wave micro-Raman (micro-Raman) approaches in combination with surface enhanced Raman spectroscopy (SERS) for their potential to overcome this limit. For that purpose, we monitored metabolite concentrations of Escherichia coli bioreactor cultivations in cell-free supernatant samples. We investigated concentration transients of glucose, acetate, AMP, and cAMP at alternating substrate availability, from deficiency to excess. Raman and SERS signals were compared to off-line metabolite analysis of carbohydrates, carboxylic acids, and nucleotides. Results demonstrate that SERS, in almost all cases, led to a higher number of identifiable signals and better resolved spectra. Spectra derived from the TG-Raman were comparable to those of micro-Raman resulting in well-discernable Raman peaks, which allowed for the identification of a higher number of compounds. In contrast, NIR-Raman provided a superior performance for the quantitative evaluation of analytes, both with and without SERS nanoparticles when using multivariate data analysis. (c) 2018 American Institute of Chemical Engineers
  • Lammel, Daniel R.; Barth, Gabriel; Ovaskainen, Otso; Cruz, Leonardo M.; Zanatta, Josileia A.; Ryo, Masahiro; de Souza, Emanuel M.; Pedrosa, Fabio O. (2018)
    Background: pH is frequently reported as the main driver for prokaryotic community structure in soils. However, pH changes are also linked to "spillover effects" on other chemical parameters (e.g., availability of Al, Fe, Mn, Zn, and Cu) and plant growth, but these indirect effects on the microbial communities are rarely investigated. Usually, pH also co-varies with some confounding factors, such as land use, soil management (e.g., tillage and chemical inputs), plant cover, and/or edapho-climatic conditions. So, a more comprehensive analysis of the direct and indirect effects of pH brings a better understanding of the mechanisms driving prokaryotic (archaeal and bacterial) community structures. Results: We evaluated an agricultural soil pH gradient (from 4 to 6, the typical range for tropical farms), in a liming gradient with confounding factors minimized, investigating relationships between prokaryotic communities (16S rRNA) and physical-chemical parameters (indirect effects). Correlations, hierarchical modeling of species communities (HMSC), and random forest (RF) modeling indicated that both direct and indirect effects of the pH gradient affected the prokaryotic communities. Some OTUs were more affected by the pH changes (e.g., some Actinobacteria), while others were more affected by the indirect pH effects (e.g., some Proteobacteria). HMSC detected a phylogenetic signal related to the effects. Both HMSC and RF indicated that the main indirect effect was the pH changes on the availability of some elements (e.g., Al, Fe, and Cu), and secondarily, effects on plant growth and nutrient cycling also affected the OTUs. Additionally, we found that some of the OTUs that responded to pH also correlated with CO2, CH4, and N2O greenhouse gas fluxes. Conclusions: Our results indicate that there are two distinct pH-related mechanisms driving prokaryotic community structures, the direct effect and "spillover effects" of pH (indirect effects). Moreover, the indirect effects are highly relevant for some OTUs and consequently for the community structure; therefore, it is a mechanism that should be further investigated in microbial ecology.
  • Jogiaas, Taivo; Kull, Mikk; Seemen, Helina; Ritslaid, Peeter; Kukli, Kaupo; Tamm, Aile (2020)
    Nanolaminates of ZrO2 and HfO2 were grown by atomic layer deposition, using metal halides and water as precursors, on silicon and fused quartz substrates at 300 degrees C. The crystalline phase composition, optical refraction, and mechanical performance of the multilayers were influenced by the relative contents of the constituent metal oxides. The crystal growth in as-deposited HfO2 dominantly led to the monoclinic phase, whereas ZrO2 was partially crystallized as its metastable and hard tetragonal polymorph. The hardness and elasticity of the nanolaminate structures could be modified by varying the amounts of either oxide contributing to the crystallographic order formed in the solid films. The refractive indexes depended on the nanolaminate structure.
  • Vaalama, Anu; Hartikainen, Helina; Vallius, Henry; Lukkari, Kaarina (2019)
    Phosphorus (P) exchange in clayey mud sediments was investigated with desorption-sorption isotherms at 22 coastal sites in the eutrophied brackish Gulf of Finland, the Baltic Sea. The aim was to gain information on P sorption potential and pattern of oxygenated surface sediments and to elucidate factors explaining them. Modified Freundlich equation was fitted to the isotherm data and used for calculation of the P exchange parameters EPC0 (equilibrium P concentration at zero net sorption), k(E)(PC0), k(15) and k(100) (P buffering capacities at early, middle and high sorption stages, respectively). They were further used to assess the P sorption potential and pattern of the sediments. Sediment properties explaining the P sorption potential at different sorption stages were identified.The greatest sorption potentials were recorded in originally poorly oxic sediments in the inner archipelago with accumulated fine particulate material, high in adsorbents for P, transported from the watersheds. After oxygenation, they were high in amorphous Fe-oxyhydroxides, which explained their efficient P sorption (k(EPC0) > 1.32 I g(-1)). Poorer P sorption (k(EPC0) 0.45-0.84 I g(-1)) was recorded in fine sediments abundant in Al-oxyhydroxides, presumably due to their higher original P occupation degree. The lowest sorption potentials were found in the outer archipelago sediments. Their lowest specific surface areas and highest original P contents referred to scarcity of adsorbents and high occupation degree of the existing ones. These results suggest that the coastal clayey mud sediments investigated possess high P sorption potential, which can be markedly diminished by eutrophication-induced hypoxia but recovered if oxygen conditions improve.