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A facile one-pot synthesis for preparing thermosensitive, luminescent gold nanodots with diameters of 1-2 nm is presented. The influence of the alkyl chain length of the surface ligands (alkyl thiols) on the optical properties of the gold nanodots was investigated. The synthesized gold nanodots show strong thermosensitive photoluminescence. A photoluminescence quantum yield of 16.6% was observed at room temperature, which could be improved to a value of 28.6% when cooling the gold nanodot solutions to -7 degrees C. The synthesized thermosensitive, luminescent gold nanodots are interesting candidates for optoelectronic devices, medical imaging, sensing, or security labels.
The sensing potential of CuO nanoparticles synthesized via. precipitation from a water/ionic liquid precursor (ILP) mixture was investigated. The particles have a moderate surface area of 66 m(2)/g after synthesis, which decreases upon thermal treatment to below 5 m(2)/g. Transmission electron microscopy confirms crystal growth upon annealing, likely due to sintering effects. The as-synthesized particles can be used for ethanol sensing. The respective sensors show fast response and recovery times of below 10 s and responses greater than 2.3 at 100 ppm of ethanol at 200 degrees C, which is higher than any CuO-based ethanol sensor described so far.
Orbitolinids are larger foraminifera widespread in Lower Cretaceous shallow-water carbonates of the Tethyan realm. They are among the most important fossil groups used for Biostratigraphy. Despite this and although the structural features of the group have been described in detail, very little is known about the composition of their agglutinated test and the process by which they selected foreign grains. In this study, the test of Orbitolina d'Orbigny, 1850 (subgenus Mesorbitolina Schroeder, 1962) from Aptian shallow-water carbonate deposits of southern Italy has been studied in detail. We combine petrographic techniques (optical microscope and SEM) with energy-dispersive x-ray spectrometry (EDS), electron probe microanalyzer (EPMA), X-ray diffraction and Raman spectroscopy analyses.
The results show that the test of Mesorbitolina is composed of carbonate and non-carbonate agglutinated grains with the latter distributed across the test with a specific pattern, moving from the marginal to the central zone. In the marginal zone, non-carbonate grains are found only in the epidermis and along the septa which are composed of quartz, with smaller amounts of illite/muscovite and K-feldspar grains. In the central zone of the test, non-carbonate grains are distributed in two ways. Coarse grains of quartz and K-feldspar are abundant and randomly placed in the endoskeleton embedded in a mosaic of minute carbonate grains. Flat grains, mainly of illite/muscovite constitute the external part of the septa. Our observations indicate that Mesorbitolina did select and place agglutinated grains across its test, mainly according to their shape, whereas it did not select particles according to grain size. The distribution of agglutinated particles according to their mineralogical composition shows some contradictory evidence and therefore, at the moment, grain selection in function of mineralogy cannot be completely confirmed or ruled out. Analogies in the test composition of Mesorbitolina specimens from coeval deposits from different areas of southern Italy indicate that the features of their agglutinated test are typical characters of the genus Mesorbitolina. However, it is still unclear what advantage was obtained by the foraminifer by the described test features.
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.
Extremely rare veinlets and reaction textures composed of symplectites of olivine (similar to Fo(43-55)) + plagioclase +/- spinel +/- ilmenite, associated with more common pyroxene + plagioclase and amphibole + plagioclase varieties, are preserved within eclogites and garnet pyroxenites in the Moldanubian Zone of the Bohemian Massif. Thermodynamic modelling integrated with conventional geothermometry conducted on an eclogite reveals that the symplectite-forming stage occurred at high T (similar to 850 degrees C) and low P (< 6 and > 2 center dot 5 kbar). The development of the different symplectite types reflects reactions that took place in micro-scale domains. The breakdown of high-P garnet controlled the formation of olivine-bearing and amphibole + plagioclase symplectites, whereas breakdown of high-P omphacite led to formation of pyroxene + plagioclase symplectites. In addition, post-eclogite facies but pre-symplectite stage porphyroblastic amphibole and phlogopite were also replaced by olivine-bearing symplectites. Material transfer calculations and thermodynamic modelling indicate that the formation of different symplectite types was linked despite their different bulk compositions. For example, the olivine-bearing symplectites gained Fe +/- Mg, whereas adjacent amphibole + plagioclase and pyroxene + plagioclase symplectites show losses in Fe and Mg; Al, Si and Ca were also variably exchanged. The olivine-bearing symplectites were particularly sensitive to Na despite the small concentration of this element. In eclogites where Na was readily available, the plagioclase composition in the olivine-bearing symplectites shifted from pure anorthite to bytownite, with the less calcic feldspar partitioning Si and inhibiting the formation of orthopyroxene. This regional high-T, low-P granulite-facies symplectite overprint may have been caused by advective heat loss from rapidly exhumed high-T, high-P granulitic bodies (Gfohl Unit) that were emplaced into and over the middle crust (Monotonous and Varied Series) during Carboniferous continent-continent collision.
New hybrid clay adsorbent based on kaolinite clay and Carica papaya seeds with improved cation exchange capacity (CEC), rate of heavy metal ion uptake, and adsorption capacity for heavy metal ions were prepared. The CEC of the new material is ca. 75 meq/100 g in spite of the unexpectedly low surface area (approximate to 19 m(2)/g). Accordingly, the average particle size of the hybrid clay adsorbent decreased from over 200 to 100 pm. The hybrid clay adsorbent is a highly efficient adsorbent for heavy metals. With an initial metal concentration of 1 mg/L, the hybrid clay adsorbent reduces the Cd2+, Ni2+, and Pb2+ concentration in aqueous solution to <= 4, <= 7 and <= 20 mu g/L, respectively, from the first minute to over 300 min using a fixed bed containing 2 g of adsorbent and a flow rate of approximate to 7 mL/min. These values are (with the exception of Pb2+) in line with the WHO permissible limits for heavy metal ions. In a cocktail solution of Cd2+, and Ni2+, the hybrid clay shows a reduced rate of uptake but an increased adsorption capacity. The CEC data suggest that the adsorption of Pb2+, Cd2+, and Ni2+ on the hybrid clay adsorbent is essentially due to ion exchange. This hybrid clay adsorbent is prepared from materials that are abundant and by a simple means that is sustainable, easily recovered from aqueous solution, nonbiodegradable (unlike numerous biosorbent), and easily regenerated and is a highly efficient alternative to activated carbon for water treatment.
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.
The present article is among the first reports on the effects of poly(ampholyte)s and poly(betaine)s on the biomimetic formation of calcium phosphate. We have synthesized a series of di- and triblock copolymers based on a non-ionic poly(ethylene oxide) block and several charged methacrylate monomers, 2-(trimethylammonium)ethyl methacrylate chloride, 2-((3-cyanopropyl)-dimethylammonium)ethyl methacrylate chloride, 3-sulfopropyl methacrylate potassium salt, and [2-(methacryloyloxy)ethyl]dimethyl-(3-sulfopropyl)ammonium hydroxide. The resulting copolymers are either positively charged, ampholytic, or betaine block copolymers. All the polymers have very high molecular weights of over 106 g mol−1. All polymers are water-soluble and show a strong effect on the precipitation and dissolution of calcium phosphate. The strongest effects are observed with triblock copolymers based on a large poly(ethylene oxide) middle block (nominal Mn = 100 000 g mol−1). Surprisingly, the data show that there is a need for positive charges in the polymers to exert tight control over mineralization and dissolution, but that the exact position of the charge in the polymer is of minor importance for both calcium phosphate precipitation and dissolution.
The present article is among the first reports on the effects of poly(ampholyte)s and poly(betaine)s on the biomimetic formation of calcium phosphate. We have synthesized a series of di- and triblock copolymers based on a non-ionic poly(ethylene oxide) block and several charged methacrylate monomers, 2-(trimethylammonium)ethyl methacrylate chloride, 2-((3-cyanopropyl)-dimethylammonium)ethyl methacrylate chloride, 3-sulfopropyl methacrylate potassium salt, and [2-(methacryloyloxy)ethyl]dimethyl-(3-sulfopropyl)ammonium hydroxide. The resulting copolymers are either positively charged, ampholytic, or betaine block copolymers. All the polymers have very high molecular weights of over 106 g mol−1. All polymers are water-soluble and show a strong effect on the precipitation and dissolution of calcium phosphate. The strongest effects are observed with triblock copolymers based on a large poly(ethylene oxide) middle block (nominal Mn = 100 000 g mol−1). Surprisingly, the data show that there is a need for positive charges in the polymers to exert tight control over mineralization and dissolution, but that the exact position of the charge in the polymer is of minor importance for both calcium phosphate precipitation and dissolution.