Selectivity in cycloadditions-IX: Cycloadditions of nitrile oxides to indoles. Reactivity and regiochemistry

Cycloadditions of benzonitrile oxide and mesitonitrile oxide to N-methylindole and indole yield the acid sensitive cycloadducts 1 a-d with high regioselectivity. With N-carbethoxyindole the stable cycloadducts 1 e,f and minor amounts of the regioisomeric 2 e,f are isolated. The electron withdrawing substituent reduces both the regioselectivity and the reactivity of the cycloadditions.Frontier orbital considerations, based on MINDO/3 calculations, allow elucidation of the observed changes in reactivity and regiochemistry.     

Review of aminopolycarboxylic acids–based metal complexes application to water and wastewater treatment by (photo-)Fenton process at neutral pH

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Regioselective Hydration of Alkynes by Iron(III) Lewis/Brønsted Catalysis

The triflimide iron(III) salt [Fe(NTf₂)₃] promotes the direct hydration of terminal and internal alkynes with very good Markovnikov regioselectivities and high yields. The enhanced carbophilic Lewis acidity of the Fe^III cation mediated by the weakly‐coordinating triflimide anion is crucial for the catalytic activity. The iron(III) metal salt can be recycled in the form of the OPPh₃/[Fe(NTf₂)₃] system with similar activity and selectivity. However, spectroscopic and kinetic studies show that [Fe(NTf₂)₃] hydrolyzes under the reaction conditions and that catalytically less active Brønsted species are formed, which points to a Lewis/Brønsted co‐catalysis. This triflimide‐based catalytic system is regioselective for the hydration of internal aryl‐alkynes and opens the door to a new synthetic route to alkyl ketophenones. As a proof of concept, the synthesis of two antipsychotics Haloperidol and Melperone, with general butyrophenone‐like structure, is shown.     

Polymerization of (E)‐1,3‐Pentadiene and (E)‐2‐methyl‐1,3‐pentadiene with neodymium catalysts: Examination of the factors that affect the stereoselectivity

(E)‐1,3‐Pentadiene (EP) and (E)‐2‐methyl‐1,3‐pentadiene (2MP) were polymerized to cis‐1,4 polymers with homogeneous and heterogeneous neodymium catalysts to examine the influence of the physical state of the catalyst on the polymerization stereoselectivity. Data on the polymerization of (E)‐1,3‐hexadiene (EH) are also reported. EP and EH gave cis‐1,4 isotactic polymers both with the homogeneous and with the heterogeneous system, whereas 2MP gave an isotactic cis‐1,4 polymer with the heterogeneous catalyst and a syndiotactic cis‐1,4 polymer, never reported earlier, with the homogeneous one. For comparison, the results obtained with the soluble CpTiCl₃‐based catalyst (Cp = cyclopentadienyl), which gives cis‐1,4 isotactic poly(2MP), are examined. A tentative interpretation is given for the mechanism of the formation of the stereoregular polymers obtained and a complete NMR characterization of the cis‐1,4‐syndiotactic poly(2MP) is reported. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013, 51, 3227–3232     

Ionic electroactive polymer metal composites: Fabricating,modeling, and applications of postsilicon smart devices

Smart systems adapt to the surrounding environments in a number of ways. They are capable to scavenge energy from available sources, sense and elaborate external stimuli and adequately react. Electro Active Polymers are playing a main role in the realization of smart systems for applications if fields such as bio inspired and autonomous robotics, medicine, and aerospace. This paper focus on the possibility to use Ionic Polymer Metal Composites as a class of materials relevant to the realization of post silicon smart systems. The three main aspects of this new technology, i.e., fabrication methods, modeling, and applications are described with emphasis to most recent results. Attention is given to main challenges and shortcomings to be solved for technology, modelling, and control of IPMC based devices that need to be solved before this new technology can be fully exploited in real world applications. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2013     

Free-radical selective functionalization of 1,4-naphthoquinones by perfluorodiacyl peroxides

Perfluoroalkyl radicals, generated by thermal decomposition of perfluorodiacyl peroxides, react selectively with quinone rings of 1,4-naphthoquinones. In the presence of a non-conjugated alkene such as 1-hexene, perfluoroalkyl radicals add to the double bonds of the olefin forming a radical adduct, which selectively adds to the naphthoquinone ring. Several perfluorodiacyl peroxides have been synthesized and used for the direct and alkene-mediated functionalization of naphthoquinones. Geometrical parameters and electron density topology of all perfluorodiacyl peroxides have been calculated by the density functional formalism and quantum theory of atoms in molecules to attempt a rationalization of the experimental reactivity.     

Impact of Matrix Metalloproteinase-9 during Periodontitis and Cardiovascular Diseases

Matrix metalloproteinase-9 (MMP-9) has been shown to play a key role in endothelial function and perhaps pivotal in the correlation between periodontal disease and cardiovascular disease (CVD). For the study, the impact of MMP-9 of periodontitis and CVD on serum and saliva concentrations was analyzed. For the study patients with periodontitis (n = 31), CVD (n = 31), periodontitis + CVD (n = 31), and healthy patients (n = 31) were enrolled. Clinical and demographic characteristics as well as serum and salivary MMP-9 were evaluated. MMP-9 concentrations in serum and saliva were statistically elevated in patients with CVD (p < 0.01) and in patients with periodontitis plus CVD (p < 0.001) compared to patients with periodontitis and healthy subjects. Multivariate regression analysis showed that c-reactive protein (hs-CRP) was the only significant predictor for MMP-9 serum (p < 0.001), whereas hs-CRP (p < 0.001) and total cholesterol (p = 0.029) were the statistically significant salivary MMP-9 predictors. This study evidenced that patients with CVD and periodontitis + CVD presented elevated MMP-9 concentrations in serum and saliva compared to patients with periodontitis and healthy subjects. Furthermore, hs-CRP was a negative predictor of serum and salivary MMP-9.     

Reactivity of Aliphatic and Phenolic Hydroxyl Groups in Kraft Lignin towards 4,4′ MDI

Several efforts have been dedicated to the development of lignin-based polyurethanes (PU) in recent years. The low and heterogeneous reactivity of lignin hydroxyl groups towards diisocyanates, arising from their highly complex chemical structure, limits the application of this biopolymer in PU synthesis. Besides the well-known differences in the reactivity of aliphatic and aromatic hydroxyl groups, experimental work in which the reactivity of both types of hydroxyl, especially the aromatic ones present in syringyl (S-unit), guaiacyl (G-unit), and p-hydroxyphenyl (H-unit) building units are considered and compared, is still lacking in the literature. In this work, the hydroxyl reactivity of two kraft lignin grades towards 4,4′-diphenylmethane diisocyanate (MDI) was investigated. ³¹P NMR allowed the monitoring of the reactivity of each hydroxyl group in the lignin structure. FTIR spectra revealed the evolution of peaks related to hydroxyl consumption and urethane formation. These results might support new PU developments, including the use of unmodified lignin and the synthesis of MDI-functionalized biopolymers or prepolymers.