Development of a Chitosan/Nickel Phthalocyanine Composite Based Conductometric Micro-sensor for Methanol Detection

Thin-film composite of chitosan/nickel phthalocyanine (NiPc) was electrochemically deposited on the fingers of interdigitated gold electrodes, applying chronoamperometric polymerization technique. The presence of crystallized NiPc in the chitosan was confirmed by EDX and FTIR analysis. Acetone, ethanol, and methanol gas-sensing properties of the films prepared at optimum conditions were studied at atmospheric temperature, through differential measurements at an optimized frequency of 10 kHz, using a lock-in amplifier. The conductometric sensor presents the highest sensitivity of 60.2 μS.cm⁻¹(v/v) for methanol and 700 ppm as the limit of detection. For validation, the methanol content of a commercial rubbing alcohol was determined.     

On the reactions of methyl radicals with nitrilotris(methylenephosphonic-acid) complexes in aqueous solutions

Abstract

The reactions of methyl radicals with M^II-(ntp)(H₂O)₂ complexes were studied. The formation of an unstable intermediate (ntp)(H₂O)M^III-CH₃ is observed. This reaction is an equilibrium process, i.e. the M^III-C bond decomposes via homolysis. The (ntp)(H₂O)M^III-CH₃ complexes isomerize to a more stable form. The results compared to those obtained in analogous reactions of the M^II-(nta)(H₂O)₂ complexes were shown to be similar with one exception – for the nta complexes no isomerization process is observed.     

Electrochemical and electrophoretic coatings of medical implants by nanomaterials

Journal of Solid State Electrochemistry - The demand for medical implants has rapidly increased over the last decades. These artificial devices should possess various properties such as...     

Self‐assembled polyurea macromer nanodispersion and resulting hybrid polyurea‐acrylic emulsions and films

A polyurea macromer (PUM) was synthesized and dispersed in basic conditions to form self‐assembled nanoparticles (<20 nm dispersions, up to 30 wt % aq. soln.). These nanoparticles enabled surfactant‐free emulsion polymerization to form hybrid polyurea‐acrylic particles despite the absence of a measureable water‐soluble fraction. The T_g of the starting PUM material was a strong function of the PUM's extent of neutralization and hydration (varying between 100 °C and >175 °C) due to changes in hydrogen and ionic bonding. Two separate hybrid polyurea‐acrylic emulsion systems were prepared: one by direct polymerization of (meth)acrylic monomers in the presence of the nanodispersion and a second by a physical blend of PUM nanodispersion with an acrylic latex control. The direct polymerization method resulted in a hybrid emulsion particle size that developed by a mechanism resembling conventional emulsion polymerization and was unlike that described for seeded polyurethane dispersion systems. Film hardness was shown to increase with increasing coating thickness for the hybrid film prepared by direct polymerization. The resulting mechanical properties could be explained by applying mechanical models for a composite foam structure. These results were unprecedented for normal elastomer films. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019, 57, 1373–1388     

Large‐Scale Synthesis of Enantiopure Molecular Cages: Chiroptical and Recognition Properties

A convenient and efficient gram‐scale synthesis for enantiopure hemicryptophane–tren (tren=tris(2‐aminoethyl)amine) derivatives has been developed. The four‐step synthesis is based on the optical resolution of a key intermediate, cyclotriveratrylene, for which the energy barrier for racemization has been measured to ensure that no racemization occurs during the two last steps of the synthetic pathway. The assignments of the absolute configurations have been performed by electronic circular dichroism and the enantiopurity was determined by NMR spectroscopy in the presence of enantiopure camphor sulfonic acid. To highlight the interest of such compounds, the recognition of norephedrine neurotransmitter was investigated and showed a remarkable enantioselectivity towards the C₃ symmetrical hosts. Finally, this highly modular synthetic pathway was used to provide eight enantiopure hemicryptophanes with different sizes, shapes, and functionalities. These results underline the high potential of this approach, which could lead to many applications in chiral recognition or asymmetric supramolecular catalysis.     

Detrimental Ni(0) transfer in Kumada catalyst transfer polycondensation of benzo[2,1‐b:3,4‐b']dithiophene

This article deals with the Kumada Catalyst Transfer Polycondensation (KCTP) of 4,7‐dioctylbenzo[2,1‐b:3,4‐b']dithiophene ( BDP‐Oct ) using Ni(II) catalyst or In/cat combination. A combination of MALDI MS, GPC, and ³¹P NMR spectroscopy is used to reveal the failure of the KCTP of this particular monomer. Intermolecular transfer reactions to monomer appeared to prevent the formation of polymer. This result is remarkable, since isomeric benzo[1,2‐b:4,5‐b']dithiophene polymerizes in a controlled way. The presence of a “non‐aromatic double bond” in annulated monomers is discussed. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 1706–1712     

Synthesis of Redox-Active Photochromic Phenanthrene Derivatives

A phenanthrene unit has been functionalized by several methylthiophene units in order to bring it a photochromic behavior. These compounds were characterized by NMR, absorption and emission spectroscopies, theoretical calculations as well as cyclic voltammetry. The association of a phenanthrene group with a photochromic center could open the door to a new generation of organic field-effect transistors.     

Intertwined Detection and Recognition Roles of Tetrazine in Synergistic Anion-π and H-bond Based Anion Receptor

The intrinsic properties of tetrazine as a π-anion receptor and as an on/off recognition probe merged with H-bond ability of an urea motif into a single architecture constitutes a new generation of well-defined anion receptors. Complexation properties directly benefit from the dual and synergistic contribution of tetrazine and urea. In this study, we report on the synthesis and assessment of binding properties to anions of diverse geometries. Association constants have been predicted by theoretical calculations and evaluated by multiple and complementary experimental techniques including electrospray-mass tandem spectroscopy, NMR, UV-visible, steady state fluorescence spectroscopies and time resolved fluorescence. These results provide the basis for a better understanding of both the complexation and the anion-dependent quenching mechanism.     

3-O-Sulfation of Heparan Sulfate Enhances Tau Interaction and Cellular Uptake

Prion-like transcellular spreading of tau in Alzheimer's Disease (AD) is mediated by tau binding to cell surface heparan sulfate (HS). However, the structural determinants for tau–HS interaction are not well understood. Microarray and SPR assays of structurally defined HS oligosaccharides show that a rare 3-O-sulfation (3-O-S) of HS significantly enhances tau binding. In Hs3st1^−/− (HS 3-O-sulfotransferase-1 knockout) cells, reduced 3-O-S levels of HS diminished both cell surface binding and internalization of tau. In a cell culture, the addition of a 3-O-S HS 12-mer reduced both tau cell surface binding and cellular uptake. NMR titrations mapped 3-O-S binding sites to the microtubule binding repeat 2 (R2) and proline-rich region 2 (PRR2) of tau. Tau is only the seventh protein currently known to recognize HS 3-O-sulfation. Our work demonstrates that this rare 3-O-sulfation enhances tau–HS binding and likely the transcellular spread of tau, providing a novel target for disease-modifying treatment of AD and other tauopathies.     

A Multi‐Addressable Switch Based on the Dimethyldihydropyrene Photochrome with Remarkable Proton‐Triggered Photo‐opening Efficiency

A series of photochromic derivatives based on the trans‐10b,10c‐dimethyl‐10b,10c‐dihydropyrene (DHP, “closed form”) skeleton has been synthesized and their photoisomerization leading to the corresponding cyclophanediene (CPD, “open form”) isomers has been investigated by UV/Vis and ¹H NMR spectroscopies. Substitution of the DHP core with electron‐withdrawing pyridinium groups was found to have major effects on the photoisomerization efficiency, the most remarkable examples being to enhance the quantum yield of the opening reaction and to allow fast and quantitative conversions at much lower radiant energies. This effect was rationalized by theoretical calculations. We also show that the reverse reaction, that is, going from the open form to the closed form, can be electrochemically triggered by oxidation of the CPD unit and that the photo‐opening properties of pyridine‐substituted DHPs can be efficiently tuned by protonation, the system behaving as a multi‐addressable molecular switch. These multi‐addressable photochromes show promise for the development of responsive materials.