Understanding the Grafting of Telechelic Polymers on a Solid Substrate to Form Loops

Recent experimental and theoretical studies have demonstrated that relative to singly tethered chains, the presence of polymer loops at interfaces significantly improves interfacial properties such as adhesion, friction, and wettability. In the present study, a simple system was studied to examine the formation of polymeric loops on a solid surface, where the grafting of carboxylic acid terminated telechelic polystyrene from the melt to an epoxy functionalized silicon is chosen. The impact of telechelic molecular weight, grafting temperature, and surface functionality on the telechelic attachment process is studied. It was found that grafting of the telechelic to the surface at both ends to form loops is the primary product of this grafting process. Moreover, examination of the kinetics of the grafting process indicates that it is reaction controlled. Fluorescence tagging of the dangling ends of singly bound chains provides a mechanism to monitor their time evolution during grafting, and these results indicate that the grafting process is accurately described by recent Monte Carlo simulation work. The results also provide a method to control the extent of loop formation at interfaces and therefore provide an opportunity to further understand the role of the loops in the interfacial properties in multicomponent polymer systems.

Theoretical and Experimental Studies in Nuclear Magnetic Resonance

Nuclear magnetic resonance (NMR) is a tool used to probe the physical and chemical environments of specific atoms in molecules. This research explored small molecule analogues to biological materials to determine NMR parameters using ab initio computations, comparing the results with solid-state NMR measurements. Models, such as dimethyl phosphate (DMP) for oligonucleotides or CuCl for the active site of the protein azurin, represented computationally unwieldy macromolecules. 31P chemical shielding tensors were calculated for DMP as a function of torsion angles, as well as for the phosphate salts, ammonium dihydrogen phosphate (ADHP), diammonium hydrogen phosphate, and magnesium dihydrogen phosphate. The computational DMP work indicated a problem with the current standard 31P reference of 85% H3PO4(aq.). Comparison of the calculations and experimental spectra for the phosphate salts indicated ADHP might be a preferable alternative as a solid state NMR reference for 31P. Experimental work included magic angle spinning experiments on powder samples using the UNL chemistry department’s Bruker Avance 600 MHz NMR to collect data to determine chemical shielding anisotropies. For the quadrupolar nuclei of copper and scandium, the electric field gradient was calculated in diatomic univalent metal halides, allowing determination of the minimal level of theory necessary to compute NMR parameters for these nuclei.

Melting Alpine Glaciers Enrich High-Elevation Lakes with Reactive Nitrogen

Alpine glaciers have receded substantially over the last century in many regions of the world. Resulting changes in glacial runoff not only affect the hydrological cycle, but can also alter the physical (i.e., turbidity from glacial flour) and biogeochemical properties of downstream ecosystems. Here we compare nutrient concentrations, transparency gradients, algal biomass, and fossil diatom species richness in two sets of high-elevation lakes: those fed by snowpack melt alone (SF lakes) and those fed by both glacial and snowpack meltwaters (GSF lakes). We found that nitrate (NO3-) concentrations in the GSF lakes were 1-2 orders of magnitude higher than in SF lakes. Although nitrogen (N) limitation is common in alpine lakes, algal biomass was lower in highly N-enriched GSF lakes than in the N-poor SF lakes. Contrary to expectations, GSF lakes were more transparent than SF lakes to ultraviolet and equally transparent to photosynthetically active radiation.Sediment diatom assemblages had lower taxonomic richness in the GSF lakes, a feature that has persisted over the last century. Our results demonstrate that the presence of glaciers on alpine watersheds more strongly influences NO3- concentrations in high-elevation lake ecosystems than any other geomorphic or biogeographic characteristic.

Admiralty Bay Benthos Diversity-A census of a complex polar ecosystem

A thorough census of Admiralty Bay benthic biodiversity was completed through the synthesis of data, acquired from more than 30 years of observations. Most of the available records arise from successive Polish and Brazilian Antarctic expeditions organized since 1977 and 1982, respectively, but also include new data from joint collecting efforts during the International Polar Year (2007-2009). Geological and hydrological characteristics of Admiralty Bay and a comprehensive species checklist with detailed data on the distribution and nature of the benthic communities are provided. Approximately 1300 species of benthic organisms (excluding bacteria, fungi and parasites) were recorded from the bay`s entire depth range (0-500 m). Generalized classifications and the descriptions of soft-bottom and hard-bottom invertebrate communities are presented. A time-series analysis showed seasonal and interannual changes in the shallow benthic communities, likely to be related to ice formation and ice melt within the bay. As one of the best studied regions in the maritime Antarctic Admiralty Bay represents a legacy site, where continued, systematically integrated data sampling can evaluate the effects of climate change on marine life. Both high species richness and high assemblage diversity of the Admiralty Bay shelf benthic community have been documented against the background of habitat heterogeneity. (C) 2010 Elsevier Ltd. All rights reserved.

Geochemical signatures of metasedimentary rocks of high-pressure granulite facies and their relation with partial melting: Carvalhos Klippe, Southern Brasilia Belt, Brazil

High-grade metasedimentary rocks can preserve geochemical signatures of their sedimentary protolith if significant melt extraction did not occur. Retrograde reaction textures provide the main evidence for trapped melt in the rock fabrics. Carvalhos Klippe rocks in Southern Brasilia Orogen, Brazil, present a typical high-pressure granulite assemblage with evidence of mica breakdown partial melting (Ky + Grt + Kfs +/- Bt +/- Rt). The metamorphic peak temperatures obtained by Zr-in-Rt and ternary feldspar geothermometers are between 850 degrees C and 900 degrees C. The GASP bane peak pressure obtained using grossular rich garnet core is 16 kbar. Retrograde reaction textures in which the garnet crystals are partially to totally replaced by Bt + Qtz +/- Fsp intergrowths are very common in the Carvalhos Klippe rocks. These reactions are interpreted as a result of interactions between residual phases and trapped melt during the retrograde path. In the present study the geochemical signatures of three groups of Carvalhos Klippe metasedimentary rocks are analysed. Despite the high metamorphic grade these three groups show well-defined geochemical features and their REE patterns are similar to average compositions of post-Archean sedimentary rocks (PAAS, NASC). The high-pressure granulite facies Grt-Bt-Pl gneisses with immature arenite (wacke, arkose or lithic-arenite) geochemical signatures present in the Carvalhos Klippe are compared to similar rocks in amphibolite facies from the same tectonic framework (Andrelandia Nappe System). The similar geochemical signatures between Grt-Bt-Pl gneisses metamorphosed in high-pressure granulite facies and Grt-Bt-Pl-Qtz schists from the Andrelandia and Liberdade Nappes, with minimal to absent melting conditions, are suggestive of low rates of melt extraction in these high-grade rocks. The rocks with pelitic compositions most likely had higher melt extraction and even under such circumstances nevertheless tend to show REE patterns similar to average compositions of post-Archean sedimentary rocks (PAAS, NASC). (C) 2012 Elsevier Ltd. All rights reserved.

Incorporation of PbF2 into Heavy Metal Oxide Borate Glasses. Structural Studies by Solid State NMR

A series of heavy metal oxide (HMO) glasses with composition 26.66B(2)O(3)-16GeO(2)-4 Bi2O3-(53.33-x)PbO-xPbF2 (0 <= x <= 40) were prepared and characterized with respect to their bulk (glass transition and crystallization temperatures, densities, molar volumes) and spectroscopic properties. Homogeneous glasses are formed up to x = 30, while crystallization of beta-PbF2 takes place at higher contents. Substitution of PbO by PbF2 shifts the optical band gap toward higher energies, thereby extending the UV transmission window significantly toward higher frequencies. Raman and infrared absorption spectra can be interpreted in conjunction with published reference data. Using B-11 and F-19 high-resolution solid state NMR as well as B-11/F-19 double resonance methodologies, we develop a quantitative structural description of this material. The fraction of four-coordinate boron is found to be moderately higher compared to that in glasses with the same PbO/B2O3 ratios, suggesting some participation of PbF2 in the network transformation process. This suggestion is confirmed by the F-19 NMR spectra. While the majority of the fluoride ions is present as ionic fluoride, similar to 20% of the fluorine inventory acts as a network modifier, resulting in the formation of four-coordinate BO3/2F- units. These units can be identified by F-19{B-11} rotational echo double resonance and B-11{F-19} cross-polarization magic angle spinning (CPMAS) data. These results provide the first unambiguous evidence of B-F bonding in a PbF2-modified glass system. The majority of the fluoride ions are found in a lead-dominated environment. F-19-F-19 homonuclear dipolar second moments measured by spin echo decay spectroscopy are quantitatively consistent with a model in which these ions are randomly distributed within the network modifier subdomain consisting of PbO, Bi2O3, and PbF2. This model, which implies both the features of atomic scale mixing with the network former borate species and some degree of fluoride ion clustering is consistent with all of the experimental data obtained on these glasses.