Spherical and monodispersed sub‐micrometer sized particles of organic–inorganic hybrids were prepared by means of a sol–gel non‐emulsion method using the biopolymer κ‐carrageenan and the alkoxysilane 3‐isocyanatopropyltriethoxysilane (ICPTES). The structural characterization of the carrageenan–silica hybrid particles was performed by using FTIR spectroscopy and solid‐state 29Si and 13C NMR spectroscopy and confirmed that κ‐carrageenan was covalently linked to the siliceous network via urethane bonds. Zeta‐potential measurements indicate the hybrids were functionalized on the surface with sulfonate groups from the polysaccharide. These hybrids display thermal sensitivity, which is of great relevance for biomedical applications such as drug encapsulation and thermally controlled drug‐delivery systems.
Although paraquat has been banned in European countries, this herbicide is still used all over the world, thanks to its low-cost, high-efficiency, and fast action. Because paraquat is highly toxic to humans and animals, there is interest in mitigating the consequences of its use, namely by implementing removal procedures capable of curbing its environmental and health risks. This research describes new magnetic nanosorbents composed of magnetite cores functionalized with bio-hybrid siliceous shells, that can be used to uptake paraquat from water using magnetically-assisted procedures. The biopolymers κ-carrageenan and starch were introduced into the siliceous shells, resulting in two hybrid materials, Fe3O4@SiO2/SiCRG and Fe3O4@SiO2/SiStarch, respectively, that exhibit a distinct surface chemistry. The Fe3O4@SiO2/SiCRG biosorbents displayed a superior paraquat removal performance, with a good fitting to the Langmuir and Toth isotherm models. The maximum adsorption capacity of paraquat for Fe3O4@SiO2/SiCRG biosorbents was 257 mg·g−1, which places this sorbent among the best systems for the removal of this herbicide from water. The interesting performance of the κ-carrageenan hybrid, along with its magnetic properties and good regeneration capacity, presents a very efficient way for the remediation of water contaminated with paraquat.
crystalline phase.2,17 Here, we demonstrate that copper sulphide NCs can be prepared through a single-source approach by thermolysis of Cu(II) dialkyldithiocarbamate complexes in ILs. Furthermore, the photocatalytic activity of the ensuing copper sulphide nanomaterials have been evaluated using rhodamine B (RhB) solutions under visible-light irradiation with the assistance of hydrogen peroxide.
Experimental
Reagents and methodsCopper nitrate tri-hydrate (Carlo Erba, 99.5%), dibutylamine (Sigma-Aldrich, 99%), carbon disulphide (Panreac), sodium hydroxide (Acros Organics, 98.5%), sodium diethyldithiocarbamate trihydrate (Sigma-Aldrich), oleylamine (SigmaAldrich) and 30% (w/w) aqueous hydrogen peroxide (Riedel-deHäen) were used as received. The ionic liquids trihexyl(tetradecyl) phosphonium dicyanamide, [TDTHP]
Functionality in nanoengineered materials has been usually explored on structural and chemical compositional aspects of matter that exist in such solid materials. It is well known that the absence of solid matter is also relevant and the existence of voids confined in the nanostructure of certain particles is no exception. Indeed, over the past decades, there has been great interest in exploring hollow nanostructured materials that besides the properties recognized in the dense particles also provide empty spaces, in the sense of condensed matter absence, as an additional functionality to be explored. As such, the chemical synthesis of hollow nanostructures has been driven not only for tailoring the size and shape of particles with well-defined chemical composition, but also to achieve control on the type of hollowness that characterize such materials. This review describes the state of the art on late developments concerning the chemical synthesis of hollow nanostructures, providing a number of examples of materials obtained by distinct strategies. It will be apparent by reading this progress report that the absence of solid matter determines the functionality of hollow nanomaterials for several technological applications.
The controlled release of pesticides using hydrogel vehicles is an important procedure to limit the amount of these compounds in the environment, providing an effective way for crop protection. A key-step in the formulation of new materials for these purposes encompasses the monitoring of available pesticides in the gel matrix under variable working conditions. In this work, we report a series of bionanocomposites made of Ag nanoparticles (NPs) and gelatine A for the surface enhanced Raman scattering (SERS) detection of sodium diethyldithiocarbamate (EtDTC) as a pesticide model. These studies demonstrate the effectiveness of these substrates for the detection of EtDTC in aqueous solutions in a concentration as low as 10(-5) M. We have monitored the Raman signal enhancement of this analyte in bionanocomposites having an increasing amount of gelatine due to their relevance in formulating hydrogels of variable gel strengths. Under these conditions, the bionanocomposites have shown an effective SERS activity using EtDTC, demonstrating their effectiveness in the qualitative detection of this analyte. Finally, experiments involving the release of EtDTC from Ag/gelatine samples have been monitored by SERS, which attest the potential of this spectroscopic method in the laboratorial monitoring of hydrogels for pesticide release.
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