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A giant hybrid organic-inorganic octahedron from a narrow rim carboxylate calixarene.
2020
Here we discovered an unprecedented giant octahedral coordination compound bearing 16 Zn2+, 12 Na+, 8 O2-, 4 OH-, 13 H2O and 6 L4- ligands [L4- = fully deprotonated tetra(carboxymethoxy)calix[4]arene]. Its structure was elucidated by single-crystal X-ray diffraction, wavelength-dispersive X-ray spectroscopy and MALDI-TOF mass spectrometry. This compound, Zn8Na6L6⊃Zn8Na6O8(OH)4(H2O)13 (external⊃internal), has eight tetrahedral zinc ions forming the coordination vertices of an outermost cube where carboxylate groups from the sodium calixarenes are anchored. Its core consists of eight Zn2+, six Na+, eight O2-, and four OH- distributed over three layers, besides thirteen coordinated H2O molecul…
Functionalization of P3HT with Various Mono- and Multidentate Anchor Groups
2018
Due to its favorable optoelectronic properties and the accessibility via Grignard metathesis (GRIM) polymerization, poly(3-hexylthiophene) (P3HT) is one of the most applied conjugated polymers. The ‘living' nature of GRIM polymerization enables the modification of the polymer and the installation of desired properties. In the present study, two versatile approaches for the synthesis of anchor group-modified P3HT have been developed, which enable the functionalization of various inorganic nanoparticles. Depending on the polymerization conditions, mono- and bifunctional ethynyl-terminated P3HT or solely monofunctionalized aldehyde-terminated P3HT was synthesized. Afterwards, the quantitative …
Polyethylene composites filled with n‐alkyl‐functionalized siloxane‐silsesquioxane resins and sol‐gel silicas
2019
High‐density polyethylene (HDPE) composites filled with silicon‐based fillers were prepared by melt blending. The use of non‐functionalized and n‐octyl‐functionalized siloxane‐silsesquioxane resins and the sol‐gel silicas as fillers allowed us to evaluate the influence of functionalization of the fillers on the properties of the composites. The melting and crystallization temperatures of the composites were found to be only slightly affected by the addition of the silicon‐based fillers. In turn, the crystallization degree values were increased, in particular for the materials containing non‐functionalized fillers. The free‐volume properties of the composites did not change significantly in …
Morphological Characterisation of Bacterial Cellulose-Starch Nanocomposites
2008
Acetobacter sp. growing medium was modified in order to produce bacterial cellulose (BC) nanocomposites using a bottom-up technique that allowed starch to be introduced into the cellulose network. The BC-starch mats were hot-pressed to obtain nanocomposites sheets. Morphological characterisation was carried out using Atomic Force Microscopy and Environmental Scanning Electron Microscopy. The images obtained from microscopy were then processed using image analysis. Network properties, such as mesh size and fibre orientation were characterised. Fracture surfaces of these new nanocomposites were analysed.
Synthesis of chemisorbed imidazolium and phosphonium cations by reaction of ionic liquid precursors with silica.
2010
The reaction of four different basic ionic liquid precursors with Aerosil®300 is presented. Chemisorbed imidazolium and phosphonium cations, with silanolate anions as part of the silicatic support, were obtained and investigated with various solid state NMR techniques.
Recognition and sensing of fluoride anion.
2009
Fluoride anion recognition is attracting a mounting interest in the scientific community due to its duplicitous nature. It is a useful chemical for many industrial applications, and it has been used in human diet, but, recently it has been accused for several human pathologies. Here we describe the ample panorama of different approaches the chemists world-wide have employed to face the challenge of fluoride binding, and we outline some of the research which in our view can contribute to the development of this field, especially when fluoride binding has to be achieved in highly competitive protic solvents and water.
An efficient synthesis of new fluorinated uracil derivativesElectronic supplementary information (ESI) available: general procedures for the preparat…
2003
A series of potentially biologically active fluorinated uracil derivatives has been prepared in three steps from oxazolines and fluorinated nitriles with good chemical yields.
Uranium( iv ) cyclobutadienyl sandwich compounds: synthesis, structure and chemical bonding
2019
The 1 : 1 reactions of uranium(IV) tetrakis(borohydride) with the sodium and potassium salts of the cyclobutadienyl anion [C4(SiMe3)4]2− (Cb′′′′) produce the half-sandwich complexes [Na(12-crown-4)2][U(η4-Cb′′′′)(BH4)3] and [U(η4-Cb′′′′)(μ-BH4)3{K(THF)2}]2. In the 1 : 2 reaction of U(BH4)4 with Na2Cb′′′′, formation of [U(η4-Cb′′′′)(η3-C4H(SiMe3)3-κ-(CH2SiMe2)(BH4))]− reveals that a Cb′′′′ ligand undergoes an intramolecular deprotonation, resulting in an allyl/tuck-in bonding mode. A computational study reveals that the uranium–Cb′′′′ bonding has an appreciable covalent component with contributions from the uranium 5f and 6d orbitals. peerReviewed
Non-covalent graphene nanobuds from mono- and tripodal binding motifs.
2017
Graphene nanobuds were prepared via the non-covalent anchoring of C60-based molecules endowed with one or three pyrene units, respectively. TGA, FTIR, UV-Vis and TEM investigations confirmed the formation of nanohybrids. For the two molecular derivatives, striking differences were determined in their interaction with graphene or carbon surfaces by Raman, cyclic voltammetry and molecular mechanics calculations, revealing the important role of pyrene adsorption in modulating the electronic properties of the nanohybrids.
Rhodium catalyzed oxidative coupling of salicylaldehydes with diazabicyclic olefins: a one pot strategy involving aldehyde C–H cleavage and π-allyl c…
2013
An efficient one pot strategy for the synthesis of cyclopentene fused chromanone derivatives through the direct oxidative coupling of salicylaldehydes with bicyclic olefins in the presence of a rhodium-copper catalyst system is described. This is the first report on the ring opening-ring closing of bicyclic hydrazines via metal catalyzed oxidative coupling reaction.