Formation of a crosslinked POSS network by an unusual hydrosilylation: Thermo‐oxidative stabilization of the α‐cristobalite phase in its amorphous regions

A semicrystalline inorganic–organic hybrid crosslinked network containing polyhedral oligomeric silsesquioxane (POSS) cores was constructed by the unusual hydrosilylation of the terminal vinyl groups of an internal acetylene‐containing silane linker by a POSS monomer. Products from the thermal treatments of this network in either argon or air at 250, 550, and 1000 °C, respectively, were characterized by Fourier transform infrared, Solid‐state ¹³C and ²⁹Si magic angle spinning NMR, X‐ray diffraction and XPS analyses. The highly symmetrically functionalized POSS silica clusters, in the fluorite silica phase, in the network were found to remain unchanged on thermal treatment possibly due to the shielding of the silica core by the functionalities and a cancellation of thermal stresses on the silica core. Stabilization of the metastable α‐cristobalite phase, which is typically formed on cooling by a β‐ to α‐transition of the β‐cristobalite phase formed above 1400 °C, was observed in the amorphous regions in the network sample treated only to 1000 °C in air. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Hybrid inorganic–organic poly(carborane‐siloxane‐arylacetylene) structural isomers with in‐chain aromatics: Synthesis and properties

Structural isomers of thermo‐oxidatively stable poly(carborane‐siloxane‐arylacetylene) (PCSAA), namely, m‐PCSAA and p‐PCSAA, were synthesized by the reaction of the dimagnesium salts of m‐diethynylbenzene or p‐diethynylbenzene with 1,7‐bis(chlorotetramethyldisiloxyl)‐m‐carborane. The developed polymers have exceptional thermo‐oxidative properties similar to their diacetylene counterpart poly(carborane‐siloxane‐acetylene), PCSA. Thermal treatment of either of the PCSAAs results in a fully crosslinked thermoset by 500 °C resulting from the cycloaddition reactions involving the acetylene and aryl functionalities and subsequent formation of bridging disilylmethylene entities as discerned from Fourier transform infrared, ¹³C and ²⁹Si solid‐state NMR, and XPS studies. X‐ray diffraction analysis revealed that the thermosets obtained from p‐PCSAA possess enhanced crystallinity when compared to that obtained from m‐PCSAA possibly due to more efficient packing interactions of the p‐diethynylbenzene groups during thermoset formation. The presence of the aryl groups in the backbone of the PCSAAs' chains appeared to have enhanced the storage and bulk moduli of their thermosets when compared to the thermoset of PCSA. Dielectric studies of m‐PCSAA and p‐PCSAA revealed segmental relaxation peaks, α, above their glass transition temperatures with p‐PCSAA exhibiting a broader peak with a slower relaxation rate than m‐PCSAA. © 2013 Wiley Periodicals, Inc.^? J. Polym. Sci., Part A: Polym. Chem. 2013, 51, 2638–2650     

The synthesis of a fluorinated phthalocyanine

The reaction of perfluoroalkylcopper with 4-iodophthalonitrile provides a convenient route to fluorinated phthalonitriles which readily form phthalocyanines in the presence of stannous chloride dihydrate.During the course of preparing 4-perfluoroheptylphthalonitrile $\text{1}$, a secondary reaction was observed when the reaction time was extended beyond two hours. This reaction involves the interaction of the orthodinitrile with copper and/or cuprous iodide to afford the phthalocyanine nucleus. This coaction is portrayed by the appearance of a green color in the reaction media.     

Testimony of the Correlation Between the Reactive Histidine Residue and the Arginase Catalytic Mechanism Using a Biochromatographic Concept and Mutagenesis Experiments

In a previous paper (Bagnost et al., J Chromatogr B Analyt Technol Biomed Life Sci 853:38–46, 2007), an arginase chromatographic support was developed to study the association mechanism of arginase (an enzyme which can reduce endothelial dysfunction and blood pressure rising in spontaneously hypertensive rats) with nor-NOHA a potential inhibitor of its activity. In this report mutagenesis experiments associated with this biochromatographic approach confirmed that the active-site residue Hist 141 is protonated as imidazolium cation. Hist 141 could function as a general acid to protonate the leaving amino group of l-ornithine during catalysis.     

Linear diacetylene polymers containing bis(dimethylsilyl) phenyl and/or bis-(tetramethyldisiloxane) carborane residues: Their synthesis,characterization and thermal and oxidative properties

A series of inorganic-organic linear diacetylenic hybrid polymers ( 5a–e ) were prepared by the polycondensation reaction of 1,4-dilithiobutadiyne with 1,4-bis(dimethylchlorosilyl)benzene and/or 1,7-bis(tetramethylchlorodisiloxane)-m-carborane. Their structures were characterized using FTIR, and ¹³C and ¹H NMR spectroscopies, and their thermal and oxidative properties were evaluated by DSC and TGA analyses. The hybrid polymers exhibited solubility in common organic solvents and were viscous liquids or low melting solids at room temperature. Broad prominent exotherms, attributed to reaction of the diacetylenic units, were observed by DSC in the 306°C to 354°C temperature range. When 5a–e were analyzed by TGA to 1000°C under nitrogen, weight retention between 79 and 86% were obtained. Ageing studies, performed at elevated temperatures in air on a thermoset and a ceramic obtained from polymer 5b , showed this system to have excellent thermal and oxidative stability. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35 : 2387–2391, 1997     

β-Phosphorus Hyperfine Coupling Constant in Nitroxides: Conformational Effects in 6-Membered Ring Nitroxides

Recently, we reported a significant solvent effect on the phosphorus hyperfine coupling constant a _P in β-phosphorylated 6-membered ring nitroxides (?a _P = 24 G in Org. Biomol. Chem. 2015). Thus, it led us to investigate the effect of solvent for several 6-membered ring nitroxides. Although smaller than mentioned above, a change of 5–7 G in a _P with the polarity of solvent was still observed for these nitroxides. As for other β-phosphorylated nitroxides, a _N increases with the polarity/polarizability π* and the Hydrogen Bond Donating α properties of the solvent whereas a _P exhibits the reverse trends. The change of a _P with the solvent depends a lot on a subtle interplay between the destabilizing steric hindrance due to the bulkiness of the substituents and the stabilizing hyperconjugation interactions SOMO → σ*_C–P between the anti-bonding orbitals of the C–P bond and the SOMO.     

Lipid-bound apolipoproteins in tyrosyl radical-oxidized HDL stabilize ABCA1 like lipid-free apolipoprotein A-I

Background  

ATP-binding cassette transporter A1 (ABCA1) mediates the lipidation of exchangeable apolipoproteins, the rate-limiting step in the formation of high density lipoproteins (HDL). We previously demonstrated that HDL oxidized ex vivo by peroxidase-generated tyrosyl radical (tyrosylated HDL, tyrHDL) increases the availability of cellular cholesterol for efflux and reduces the development of atherosclerosis when administered to apolipoprotein E-deficient mice as compared to treatment with control HDL.     

Detecting causal relations in time series with the new cross Markov Matrix technique

Nowadays, scientists are increasingly asked to investigate problems, which require the analysis of irregular, chaotic, non-stationary and corrupted time series. Assessing the causal relations between such signals is particularly challenging and, in many instances, interventions and experiments are impossible or impractical. The present work is a contribution to the development of indicators to quantify the mutual influences between time series. The criterion is called Cross Markov Matrix and belongs to the strand of techniques based on the conversion of time series into complex networks and the subsequent analysis of their topological properties. The proposed indicator is quite competitive with the available tools and can complement them very effectively. Indeed, all techniques have their strong and weak points and therefore corroborating the conclusions with mathematically independent methods is a recommended practice. The properties of the Cross Markov Matrix have been investigated with the help of a systematic series of numerical tests using synthetic data. The potential of the approach is then substantiated by the analysis of various real-life examples, ranging from environmental and global climate problems to the mutual influence between media coverage of Brexit and the pound-euro exchange rate.