Covalent Grafting of BPin functions on Carbon Nanotubes and Chan–Lam–Evans Post-Functionalization

The chemical functionalization of carbon nanotubes is often a prerequisite prior to their use in various applications. The covalent grafting of 4,4,5,5-tetramethyl-1,3,2-dioxaborolane (BPin) functional groups directly on the surface of multi- and single-walled carbon nanotubes, activated by nucleophilic addition of nBuLi, was carried out. Thermogravimetric analysis (TGA) coupled with mass spectrometry, Raman spectroscopy, X-ray photoelectron spectroscopy (XPS) and time-of-flight secondary ions mass spectrometry (ToF-SIMS) confirmed the efficiency of this methodology and proved the integrity and covalent grafting of the BPin functional groups. These groups were further reacted with various nucleophiles in the presence of a copper(II) source in the conditions of the aerobic Chan–Lam–Evans coupling. The resulting materials were characterized by TGA, XPS and ToF-SIMS. This route is efficient, reliable and among the scarce reactions that enable the direct grafting of heteroatoms at carbonaceous material surfaces.     

Design,Synthesis, and Phenotypic Profiling of Pyrano‐Furo‐Pyridone Pseudo Natural Products

Natural products (NPs) inspire the design and synthesis of novel biologically relevant chemical matter, for instance through biology‐oriented synthesis (BIOS). However, BIOS is limited by the partial coverage of NP‐like chemical space by the guiding NPs. The design and synthesis of “pseudo NPs” overcomes these limitations by combining NP‐inspired strategies with fragment‐based compound design through de novo combination of NP‐derived fragments to unprecedented compound classes not accessible through biosynthesis. We describe the development and biological evaluation of pyrano‐furo‐pyridone (PFP) pseudo NPs, which combine pyridone‐ and dihydropyran NP fragments in three isomeric arrangements. Cheminformatic analysis indicates that the PFPs reside in an area of NP‐like chemical space not covered by existing NPs but rather by drugs and related compounds. Phenotypic profiling in a target‐agnostic “cell painting” assay revealed that PFPs induce formation of reactive oxygen species and are structurally novel inhibitors of mitochondrial complex I.     

Synthesis,Electrochemistry, and Photophysics of Aza‐BODIPY Porphyrin Dyes

The synthesis of dyad and triad aza‐BODIPY‐porphyrin systems in two steps starting from an aryl‐substituted aza‐BODIPY chromophore is described. The properties of the resulting aza‐BODIPY‐porphyrin conjugates have been extensively investigated by means of electrochemistry, spectroelectrochemistry, and absorption/emission spectroscopy. Fluorescence measurements have revealed a dramatic loss of luminescence intensity, mainly due to competitive energy transfer and photoinduced electron transfer involving charge separation followed by recombination.     

Thermodynamic study of transthyretin association (wild‐type and senile forms) with heparan sulfate proteoglycan: pH effect and implication of the reactive histidine residue

The tetramer destabilization of transthyretin into monomers and its fibrillation are phenomena leading to amyloid deposition. Heparan sulfate proteoglycan (HSPG) has been found in all amyloid deposits. A chromatographic approach was developed to compare binding parameters between wild‐type transthyretin (wtTTR) and an amyloidogenic transthyretin (sTTR). Results showed a greater affinity of sTTR for HSPG at pH 7.4 compared with wtTTR owing to the monomeric form of sTTR. Analysis of the thermodynamic parameters showed that van der Waals interactions were involved at the complex interface for both transthyretin forms. For sTTR, results from the plot representing the number of protons exchanged vs pH showed that the binding mechanism was pH‐dependent with a critical value at a pH 6.5. This observation was due to the protonation of a histidine residue as an imidazolium cation, which was not accessible when TTR was in its tetrameric structure. At pH >6.5, dehydration at the binding interface and several contacts between nonpolar groups of sTTR and HSPG were also coupled to binding for an optimal hydrogen‐bond network. At pH <6.5, the protonation of the His residue from sTTR monomer when pH decreased broke the hydrogen‐bond network, leading to its destabilization and thus producing slight conformational changes in the sTTR monomer structure. Copyright © 2014 John Wiley & Sons, Ltd.     

Thermoset modified with polyethersulfone: Characterization and control of the morphology

Thermoset (TS) epoxy resins can be toughened with a thermoplastic (TP) for high-performance applications. The final structure morphology has to be controlled to achieve high mechanical properties and high impact resistance. Four polyethersulfone-modified epoxy resins are considered. They consist of different epoxy monomer structure (TGAP, triglycidyl-p-aminophenol and TGDDM, tetraglycidyl diaminodiphenylmethane) and a fixed amount of thermoplastic, and they are cured with two different amounts of curing agent. A reaction-induced phase separation occurs for all formulations generating morphologies, different in shapes and scales. The aim is to control the final morphology and in particular its dominant length scale. This morphology depends on the phase separation process, from the initiation to its final stage. The initiation relies on the relative miscibility of the components and on the stoichiometry between epoxy and curing agent. The kinetics depends on the viscosity of the systems. The different morphologies are characterized by electron microscopy or neutron scattering. Dynamic mechanical analysis allows confirming the presence of a phase separation even when it is not observable by electron microscopy. Vermicular morphologies with few hundreds nanometer width are obtained for the systems containing the TGAP as epoxy monomer. Systems formulated with TGDDM presents morphologies on much smaller scale of order a few tens of nanometers. We interpret the different sizes of the morphologies as a consequence of a larger viscosity for the TGDDM systems as compared to the TGAP ones rather than by a latter initiation of phase separation.