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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.
The Eastern Sierras Pampeanas are mainly composed of Neoproterozoic-early Palaeozoic metamorphic complexes whose protoliths were sedimentary sequences deposited along the western margin of Gondwana. South of the Sierra de Aconquija, Eastern Sierras Pampeanas, a voluminous metamorphic complex crops out. It is mainly composed of schists, gneisses, marbles, calk-silicate schists, thin layers of amphibolites intercalated with the marbles and granitic veins. The new data correlate the Sierra de Aconquija with others metamorphic units that crop out to the south, at the middle portion of the Sierra de Ancasti. Bulk rock composition reflects originally shales, iron rich shales, wackes, minor litharenites and impure limestones as its protoliths. Moreover, comparisons with the northern Sierra de Aconquija and from La Majada (Sierra de Ancasti) show similar composition. Amphibolites have a basaltic precursor, like those from the La Majada (Sierra de Ancasti) ones. The analyzed metamorphic sequence reflects low to moderate weathering conditions in the sediments source environment and their chemical composition would be mainly controlled by the tectonic setting of the sedimentary basin rather than by the secondary sorting and reworking of older deposits. The sediments composition reveal relatively low maturity, nevertheless the Fe - shale and the litharenite show a tendency of minor maturity among them. The source is related to an acid one for the litharenite protolith and a more basic to intermediate for the other rocks, suggesting a main derivation from intermediate to felsic orogen. The source of the Fe shales may be related to and admixture of the sediments with basic components. Overall the composition point to an upper continental crust as the dominant sediment source for most of the metasedimentary rocks. The protolith of the amphibolites have basic precursors, related to an evolving back-arc basin. The chemical data in combination with the specific sediment association (wackes, shales, Fe-shales and minor litharenites) are characteristic for turbidity currents deposits along tectonically active region. They are also commonly associated with calcareous clays (marbles), commonly observed in the evolution of basins with slope and shelf derived carbonate turbidites. The amphibolites members are probably derived from lava-flows synchronous with the sedimentation during the basin evolution. The basin was controlled by a continental island arc possible evolving to a back-arc setting, as indicated for the mixed nature of the inferred source. The metasedimentary sequence from the Cuesta de La Chilca have petrographic, structural and strong chemical similarities, building a north-south striking belt from the north of the Sierra de Aconquija and to the south along the Sierra de Ancasti (La Majada area). The observed similarities allow to present this portion of the Eastern Sierras Pampeanas as a crustal block that records the sedimentary sequences developed along the geodynamic context of the southwestern margin of Gondwana during the Neoproterozoic and Early Palaeozoic. (C) 2017 Elsevier Ltd. All rights reserved.
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.
Novel metal-doped bacteriostatic hybrid clay composites for point-of-use disinfection of water
(2017)
This study reports the facile microwave-assisted thermal preparation of novel metal-doped hybrid clay composite adsorbents consisting of Kaolinite clay, Carica papaya seeds and/or plantain peels (Musa paradisiaca) and ZnCl2. Fourier Transformed IR spectroscopy, X-ray diffraction, Scanning Electron Microscopy and Brunauer-Emmett-Teller (BET) analysis are employed to characterize these composite adsorbents. The physicochemical analysis of these composites suggests that they act as bacteriostatic rather than bacteriacidal agents. This bacterostactic action is induced by the ZnO phase in the composites whose amount correlates with the efficacy of the composite. The composite prepared with papaya seeds (PS-HYCA) provides the best disinfection efficacy (when compared with composite prepared with Musa paradisiaca peels-PP-HYCA) against gram-negative enteric bacteria with a breakthrough time of 400 and 700 min for the removal of 1.5 x10(6) cfu/mL S. typhi and V. cholerae from water respectively. At 10(3) cfu/mL of each bacterium in solution, 2 g of both composite adsorbents kept the levels the bacteria in effluent solutions at zero for up to 24 h. Steam regeneration of 2 g of bacteria-loaded Carica papaya prepared composite adsorbent shows a loss of ca. 31% of its capacity even after the 3rd regeneration cycle of 25 h of service time. The composite adsorbent prepared with Carica papaya seeds will be useful for developing simple point-of-use water treatment systems for water disinfection application. This composite adsorbent is comparatively of good performance and shows relatively long hydraulic contact times and is expected to minimize energy intensive traditional treatment processes.
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 mu g/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
This study is focused on the analysis of volcanic deposits that crop out at the middle portion of the Las Planchadas range, northern part of the Famatina System in Argentina. These volcanic rocks are records of an Ordovician effusive basaltic volcanism that took place under subaqueous marine conditions. Along the study area crop out an Arenigian volcanic and volcaniclastic rocks succession with massive and autoclastic lavas, hyaloclastites of basaltic composition and volcaniclastic sandstones and mudstones. Large volumes of the volcanic deposits were strongly affected by fragmentation processes during their subaqueous emplacement and in situ accumulated as basaltic breccias. The same volcanic-volcaniclastic association crops out to the south of the Las Planchadas range, forming a basaltic belt with similar characteristics. The geochemical features of the basalts are compatible with depleted mid-ocean ridge basalt (MORB)-like source for the magma, with contribution of subducted related components such as water rich marine hemipelagic sediments, compatible with a back arc geotectonic setting developed along the northern part of the Famatina System during the Arenigian.
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.
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.