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Understanding the mechanisms responsible for generating different phases and morphologies of calcium phosphate by elastin-like recombinamers is supreme for bioengineering of advanced multifunctional materials. The generation of such multifunctional hybrid materials depends on the properties of their counterparts and the way in which they are assembled. The success of this assembly depends on the different approaches used, such as recombinant DNA technology and click chemistry. In the present work, an elastin-like recombinamer bearing lysine amino acids distributed along the recombinamer chain has been cross-linked via Huisgen [2 + 3] cycloaddition. The recombinamer contains the SN(A)15 peptide domains inspired by salivary statherin, a peptide epitope known to specifically bind to and nucleate calcium phosphate. The benefit of using click chemistry is that the hybrid elastin-like-statherin recombinamers cross-link without losing their fibrillar structure. Mineralization of the resulting hybrid elastin-like-statherin recombinamer hydrogels with calcium phosphate is described. Thus, two different hydroxyapatite morphologies (cauliflower- and plate-like) have been formed. Overall, this study shows that crosslinking elastin-like recombinamers leads to interesting matrix materials for the generation of calcium phosphate composites with potential applications as biomaterials.
Six N-alkylpyridinium salts [CnPy](2)[MCl4] (n = 4 or 12 and M = Co, Cu, Zn) were synthesized, and their structure and thermal properties were studied. The [C4Py](2)[MCl4] compounds are monoclinic and crystallize in the space group P2(1)/n. The crystals of the longer chain analogues [C12Py](2)[MCl4] are triclinic and crystallize in the space group P (1) over bar. Above the melting temperature, all compounds are ionic liquids (ILs). The derivatives with the longer C12 chain exhibit liquid crystallinity and the shorter chain compounds only show a melting transition. Consistent with single-crystal analysis, electron paramagnetic resonance spectroscopy suggests that the [CuCl4](2-) ions in the Cu-based ILs have a distorted tetrahedral geometry.
The effect of cellulose-based polyelectrolytes on biomimetic calcium phosphate mineralization is described. Three cellulose derivatives, a polyanion, a polycation, and a polyzwitterion were used as additives. Scanning electron microscopy, X-ray diffraction, IR and Raman spectroscopy show that, depending on the composition of the starting solution, hydroxyapatite or brushite precipitates form. Infrared and Raman spectroscopy also show that significant amounts of nitrate ions are incorporated in the precipitates. Energy dispersive X-ray spectroscopy shows that the Ca/P ratio varies throughout the samples and resembles that of other bioinspired calcium phosphate hybrid materials. Elemental analysis shows that the carbon (i.e., polymer) contents reach 10% in some samples, clearly illustrating the formation of a true hybrid material. Overall, the data indicate that a higher polymer concentration in the reaction mixture favors the formation of polymer-enriched materials, while lower polymer concentrations or high precursor concentrations favor the formation of products that are closely related to the control samples precipitated in the absence of polymer. The results thus highlight the potential of (water-soluble) cellulose derivatives for the synthesis and design of bioinspired and bio-based hybrid materials.
Six N-alkylpyridinium salts [CnPy](2)[MCl4] (n = 4 or 12 and M = Co, Cu, Zn) were synthesized, and their structure and thermal properties were studied. The [C4Py](2)[MCl4] compounds are monoclinic and crystallize in the space group P2(1)/n. The crystals of the longer chain analogues [C12Py](2)[MCl4] are triclinic and crystallize in the space group P (1) over bar. Above the melting temperature, all compounds are ionic liquids (ILs). The derivatives with the longer C12 chain exhibit liquid crystallinity and the shorter chain compounds only show a melting transition. Consistent with single-crystal analysis, electron paramagnetic resonance spectroscopy suggests that the [CuCl4](2-) ions in the Cu-based ILs have a distorted tetrahedral geometry.
Mesoporous carbon/iron carbide hybrid materials with surface areas reaching 800 m(2) g(-1) were synthesized via an exotemplating route using monolithic mesoporous silica as template and the ionic liquid 1-butyl-3-methylimidazolium tetrachloridoferrate(III) [Bmim][FeCl4] as carbon and iron source. After heat treatment (750 degrees C under argon) of the [Bmim][FeCl4] precursor confined within the silica matrix, the silica exotemplate was removed with HF leaving the mesoporous C/Fe3C hybrid behind. The surface areas and the pore sizes depend on the exotemplate and the surface areas a significantly larger than any other surface area reported for C/Fe3C hybrid materials so far. The approach is thus a prototype for the synthesis of high-surface area iron carbide-based hybrid materials with potential application in catalysis.
The present work gives a detailed analysis of the metamorphic and structural evolution of the back-arc portion of the Famatinian Orogen exposed in the southern Sierra de Aconquija (Cuesta de La Chilca segment) in the Sierras Pampeanas Orientales (Eastern Pampean Sierras). The Pampeanas Orientales include from north to south the Aconquija, Ambato and Ancasti mountains. They are mainly composed of middle to high grade metasedimentary units and magmatic rocks.
At the south end of the Sierra de Aconquija, along an east to west segment extending over nearly 10 km (Cuesta de La Chilca), large volumes of metasedimentary rocks crop out. The eastern metasediments were defined as members of the El Portezuelo Metamorphic-Igneous Complex (EPMIC) or Eastern block and the western ones relate to the Quebrada del Molle Metamorphic Complex (QMMC) or Western block. The two blocks are divided by the La Chilca Shear Zone, which is reactivated as the Rio Chanarito fault.
The EPMIC, forming the hanging wall, is composed of schists, gneisses and rare amphibolites, calc- silicate schists, marbles and migmatites. The rocks underwent multiple episodes of deformation and a late high strain-rate episode with gradually increasing mylonitization to the west. Metamorphism progrades from a M-1 phase to the peak M-3, characterized by the reactions: Qtz + Pl + Bt +/- Ms -> Grt + Bt(2) + Pl(2) +/- Sil +/- Kfs, Qtz + Bt + Sil -> Crd + Kfs and Qtz + Grt + Sil -> Crd. The M-3 assemblage is coeval with the dominant foliation related to a third deformational phase (D-3).
The QMMC, forming the foot wall, is made up of fine-grained banded quartz - biotite schists with quartz veins and quartz-feldspar-rich pegmatites. To the east, schists are also overprinted by mylonitization. The M-3 peak assemblage is quartz + biotite + plagioclase +/- garnet +/- sillimanite +/- muscovite +/- ilmenite +/- magnetite +/- apatite.
The studied segment suffered multiphase deformation and metamorphism. Some of these phases can be correlated between both blocks. D-1 is locally preserved in scarce outcrops in the EPMIC but is the dominant in the QMMC, where S-1 is nearly parallel to S-0. In the EPMIC, D-2 is represented by the S-2 foliation, related to the F-2 folding that overprints S-1, with dominant strike NNW - SSE and high angles dip to the E. D-3 in the EPMIC have F-3 folds with axis oblique to S-2; the S-3 foliation has striking NW - SE dipping steeply to the E or W and develops interference patterns. In the QMMC, S-2 (D-2) is a discontinuous cleavage oblique to S-1 and transposed by S-3 (D-3), subparallel to S-1. Such structures in the QMMC developed at subsolidus conditions and could be correlated to those of the EPMIC, which formed under higher P-T conditions. The penetrative deformation D-2 in the EPMIC occurred during a prograde path with syntectonic growth of garnet reaching P-T conditions of 640 degrees C and 0.54 GPa in the EPMIC. This stage was followed by a penetrative deformation D-3 with syn-kinematic growth of garnet, cordierite and plagioclase. Peak P-T conditions calculated for M-3 are 710 degrees C and 0.60 GPa, preserved in the western part of the EPMIC, west of the unnamed fault.
The schists from the QMMC suffered the early low grade M-1 metamorphism with minimum PT conditions of ca 400 degrees C and 0.35 GPa, comparable to the fine schists (M-1) outcropping to the east. The D-2 deformation is associated with the prograde M-2 metamorphism. The penetrative D-3 stage is related to a medium grade metamorphism M-3, with peak conditions at ca 590 degrees C and 0.55 GPa.
The superimposed stages of deformation and metamorphism reaching high P-T conditions followed by isothermal decompression, defining a clockwise orogenic P-T path. During the Lower Paleozoic, folds were superimposed and recrystallization as well as partial melting at peak conditions occurred. Similar characteristics were described from the basement from other Famatinian-dominated locations of the Sierra de Aconquija and other ranges of the Sierras Pampeanas Orientales.
Pseudotachylyte veins frequently associated with mylonites and ultramylonites occur within migmatitic paragneisses, metamonzodiorites, as well as felsic and mafic granulites at the base of the section of the Hercynian lower crust exposed in Calabria (Southern Italy). The crustal section is tectonically superposed on lower grade units. Ultramylonites and pseudotachylytes are particularly well developed in migmatitic paragneisses, whereas sparse fault-related pseudotachylytes and thin mylonite/ultramylonite bands occur in granulite-facies rocks. The presence of sillimanite and clinopyroxene in ultramylonites and mylonites indicates that relatively high-temperature conditions preceded the formation of pseudotachylytes. We have analysed pseudotachylytes from different rock types to ascertain their deep crustal origin and to better understand the relationships between brittle and ductile processes during deformation of the deeper crust. Different protoliths were selected to test how lithology controls pseudotachylyte composition and textures. In migmatites and felsic granulites, euhedral or cauliflower-shaped garnets directly crystallized from pseudotachylyte melts of near andesitic composition. This indicates that pseudotachylytes originated at deep crustal conditions (> 0.75 GPa). In mafic protoliths, quenched needle-to-feather-shaped high-alumina orthopyroxene occurs in contact with newly crystallized plagioclase. The pyroxene crystallizes in garnet-free and garnet-bearing veins. The simultaneous growth of orthopyroxene and plagioclase as well as almandine, suggests lower crustal origin, with pressures in excess of 0.85 GPa. The existence of melts of different composition in the same vein indicates the stepwise, non-equilibrium conditions of frictional melting. Melt formed and intruded into pre-existing anisotropies. In mafic granulites, brittle faulting is localized in a previously formed thin high-temperature mylonite bands. migmatitic gneisses are deformed into ultramylonite domains characterized by s-c fabric. Small grain size and fluids lowered the effective stress on the c planes favouring a seismic event and the consequent melt generation. Microstructures and ductile deformation of pseudotachylytes suggest continuous ductile flow punctuated by episodes of high-strain rate, leading to seismic events and melting.
We report on a new series of isoreticular frameworks based on zinc and 2-substituted imidazolate-4-amide-5-imidate (IFP-14, IFP=imidazolate framework Potsdam) that form one-dimensional, microporous hexagonal channels. Varying R in the 2-substitued linker (R=Me (IFP-1), Cl (IFP-2), Br (IFP-3), Et (IFP-4)) allowed the channel diameter (4.01.7 angstrom), the polarisability and functionality of the channel walls to be tuned. Frameworks IFP-2, IFP-3 and IFP-4 are isostructural to previously reported IFP-1. The structures of IFP-2 and IFP-3 were solved by X-ray crystallographic analyses. The structure of IFP-4 was determined by a combination of PXRD and structure modelling and was confirmed by IR spectroscopy and 1H MAS and 13C CP-MAS NMR spectroscopy. All IFPs showed high thermal stability (345400?degrees C); IFP-1 and IFP-4 were stable in boiling water for 7 d. A detailed porosity analysis was performed on the basis of adsorption measurements by using various gases. The potential of the materials to undergo specific interactions with CO2 was investigated by measuring the isosteric heats of adsorption. The capacity to adsorb CH4 (at 298 K), CO2 (at 298 K) and H2 (at 77 K) at high pressure were also investigated. In situ IR spectroscopy showed that CO2 is physisorbed on IFP-14 under dry conditions and that both CO2 and H2O are physisorbed on IFP-1 under moist conditions.
Background. Metal recycling factories (MRFs) have developed rapidly in Nigeria as recycling policies have been increasingly embraced. These MRFs are point sources for introducing potentially toxic elements (PTEs) into environmental media. Objectives. The aim of this study was to determine the constituents (elemental and mineralogy) of the wastes (slag and particulate matter, (PM)) and soils around the MRFs and to determine the level of pollution within the area. Methods. Sixty samples (30 slag samples, 15 soil samples and 15 PM samples) were collected for this study. The soils, slag and PM samples were analyzed for elemental constituents using inductively coupled plasma optical emission spectrometry. Mineralogy of the PM was determined using scanning electron microscope-energy dispersive spectroscopy (SEM-EDS), and soil mineralogy was determined by an X-ray diffractometer (XRD). Results. The results of the soil analyses revealed the following concentrations for the selected metals in mg/kg include lead (Pb) (21.0-2399.0), zinc (Zn) (56.0-4188.0), copper (Cu) (10.0-1470.0), nickel (Ni) (6.0-215.0), chromium (Cr) (921.0-1737.0) and cadmium (Cd) (below detectable limit (Bdl)-18.1). For the slags the results were Pb (68.0-.333.0), Zn (1364.0-3062), Cu (119.0-1470.0), Ni (12.0-675.0), Cr (297-1737) and Cd (Bdl-15.8). The results in µg/g for the metal analysis in PM were Pb (4.6-160.0), Zn (18.0-471.0), Cu (2.5-11.0), Ni (0.8-4.2), and Cr (2.5-11.0), while Cd was undetected. The slags are currently utilized for filling the foundations of buildings and roads, providing additional pathways for the introduction of PTEs into the environment from the suspended materials generated from mechanical breakdown of the slags. Conclusions. The MRFs were found to have impacted the quality of environmental media through the introduction of PTEs, impairing soil quality, in addition to PM, which can have detrimental health consequences. Further studies on the health implications of these pollutants and their impacts on human health are needed. Competing Interests. The authors declare no competing financial interests
The central European Bohemian Massif has undergone over two centuries of scientific investigation which has made it a pivotal area for the development and testing of modern geological theories. The discovery of melt inclusions in high-grade rocks, either crystallized as nanogranitoids or as glassy inclusions, prompted the re-evaluation of the area with an ‘inclusionist’ eye. Melt inclusions have been identified in a wide range of rocks, including felsic/perpotassic granulites, migmatites, eclogites and garnet clinopyroxenites, all the result of melting events albeit over a wide range of pressure/temperature conditions (800–1000°C/0.5–5 GPa). This contribution provides an overview of such inclusions and discusses the qualitative and quantitative constraints they provide for melting processes, and the nature of melts and fluids involved in these processes. In particular, data on trace-element signatures of melt inclusions trapped at mantle depths are presented and discussed. Moreover, experimental re-homogenization of nanogranitoids provided microstructural criteria allowing assessment of the conditions at which melt and host are mutually stable during melting. Overall this work aims to provide guidelines and suggestions for petrologists wishing to explore the fascinating field of melt inclusions in metamorphic terranes worldwide, based on the newest discoveries from the still-enigmatic Bohemian Massif.