Soluble aromatic polyamide bearing ether linkages: synthesis and characterization

Soluble aromatic polyamide chains were prepared by reacting 4–4′-oxydianiline with isophthaloyl chloride in dimethylacetamide. To quench the HCl produced during the polymerization reaction, a stoichiometric amount of triethylamine was added. The precipitates formed were separated leaving behind clear polyamide resin. Thin and transparent film was obtained by evaporating the solvent and was subjected for Fourier transform infrared (IR), nuclear magnetic resonance (NMR), gel permeation chromatography, thermogravimetric analysis, differential scanning calorimetry, water absorption, and mechanical analyses. The transparent film was found to be soluble in dimethylacetamide, dimethyl sulfoxide, and dimethylformamide. IR and NMR spectroscopic analyses confirmed the structure of the polyamide while the gel permeation chromatography revealed the formation of a high-molecular-weight polymer. Thermogravimetry, differential scanning calorimetry, water absorption, and mechanical testing were also performed to further verify its physical properties. A soluble aromatic polyamide was successfully synthesized by solution polymerization and characterized. The polyamide has film-forming property, and the film is transparent, mechanically strong, and thermally stable.     

Deacetylcephalosporin C production in Penicillium chrysogenum by expression of the isopenicillin N epimerization, ring expansion, and acetylation genes

Penicillium chrysogenum npe6 lacking isopenicillin N acyltransferase activity is an excellent host for production of different beta-lactam antibiotics. We have constructed P. chrysogenum strains expressing cefD1, cefD2, cefEF, and cefG genes cloned from Acremonium chrysogenum. Northern analysis revealed that the four genes were expressed in P. chrysogenum. The recombinant strains TA64, TA71, and TA98 secreted significant amounts of deacetylcephalosporin C, but cephalosporin C was not detected in the culture broths. DAC-acetyltransferase activity was found in all transformants containing the cefG gene. HPLC analysis of cell extracts showed that transformant TA64, TA71, and TA98 accumulate intracellularly deacetylcephalosporin C and, in the last strain (TA98), also cephalosporin C. Mass spectra analysis confirmed that transformant TA98 synthesize true deacetylcephalosporin C and cephalosporin C. Even when accumulated intracellularly, cephalosporin C was not found in the culture broth.     

Pyrazole complexes as anion receptors: effects of changing the metal, the pyrazole substitution pattern, and the number of pyrazole ligands

Compound cis,fac-[Mo(eta3-allyl)(CO)2(Hdmpz)3]BAr'4 (1) (Hdmpz = 3,5-dimethylpyrazole, Ar' = 3,5-bis(trifluoromethyl)phenyl) undergoes rapid substitution of one of the pyrazole ligands by anions, including the low nucleophilic ReO4-, a reaction that afforded [Mo(OReO3)(eta3-allyl)(CO)2(Hdmpz)2] (2), structurally characterized by X-ray diffraction. The new compounds fac-[Mn(CO)3(Hdmpz)3]BAr'4 (4a) and fac-[Mn(CO)3(HtBupz)3]BAr'4 (4b) (HtBupz = 3(5)-tert-butylpyrazole) also undergo pyrazole substitution with most anions, and the product from the reaction with nitrate was crystallographically characterized. Compounds 4a,b were found to be substitutionally stable toward perrhenate, and the adducts [Mn(CO)3(Hdmpz)3].[ReO4] (7a) and [Mn(CO)3(HtBupz)3].[ReO4].[Bu4N].[BAr'4] (7b), crystallographically characterized, display hydrogen bonds between one of the perrhenate oxygens and the N-H groups of two of the pyrazole ligands. The structurally similar adduct [Re(CO)3(Hdmpz)3].[ReO4] (8) was found to result from the interaction of [Re(CO)3(Hdmpz)3]BAr'4 with perrhenate. The reaction of [Re(OTf)(CO)5] with 3,5-dimethylpyrazole (Hdmpz) afforded [Re(CO)5(Hdmpz)]OTf (9). The reaction of 9 with Hdmpz and NaBAr'4 yielded [Re(CO)4(Hdmpz)2]BAr'4 (10), which was found to be unstable toward chloride anion. In contrast, the new compound fac,cis-[Re(CO)3(CNtBu)(Hdmpz)2]BAr'4 (11) is stable in solution in the presence of different anions. Binding constants for 11 with chloride, bromide, and nitrate are 1-2 orders of magnitude lower than those found for these anions and rhenium tris(pyrazole) hosts, indicating that the presence of the third pyrazole ligand is crucial. Compounds fac-[Re(CO)3(HPhpz)3]BAr'4 (14) (HPhpz = 3(5)-phenylpyrazole) and fac-[Re(CO)3(HIndz)3]BAr'4 (15) (HIndz = indazole) are, in terms of anion binding strength and selectivity, inferior to those with dimethylpyrazole or tert-butylpyrazole ligands.     

Deposition of polyaniline on RVC electrodes: effect of substrate thickness

Polyaniline films, obtained by either chemical or electrochemical deposition on reticulated vitreous carbon (RVC), were investigated as a function of the substrate thickness. The electrochemical properties of these RVC/Pani electrodes were assessed by cyclic voltammetry and electrochemical impedance spectroscopy (EIS), whereas the morphology of the Pani films on RVC was analyzed by scanning electron microscopy (SEM). The cyclic voltammetric results revealed that the oxidation/reduction charges for electrodeposited polyaniline decrease as the RVC thickness is increased. Conversely, the charge densities for the chemically deposited films do not present a significant dependence on the substrate thickness. Two time constants, appearing in all the EIS spectra, indicate that an ohmic drop effect within the RVC substrate affects the polymer electrodeposition and the electrochemical behavior of the obtained electrodes. Therefore, an electric equivalent circuit considering the different electrochemical environments at the outer and inner RVC surfaces was proposed to analyze the EIS data.     

Selenium methylselenocysteine protects human hepatoma HepG2 cells against oxidative stress induced by tert-butyl hydroperoxide

Selenium methylselenocysteine (Se-MeSeCys) is a common selenocompound in the diet with a tested chemopreventive effect. This study investigated the potential protective effect of Se-MeSeCys against a chemical oxidative stress induced by tert-butyl hydroperoxide (t-BOOH) on human hepatoma HepG2 cells. Speciation of selenium derivatives by liquid chromatography–inductively coupled plasma mass spectrometry depicts Se-MeSeCys as the only selenocompound in the cell culture. Cell viability (lactate dehydrogenase) and markers of oxidative status—concentration of reduced glutathione (GSH) and malondialdehyde (MDA), generation of reactive oxygen species (ROS) and activity of the antioxidant enzymes glutathione peroxidase (GPx) and glutathione reductase (GR)—were evaluated. Pretreatment of cells with Se-MeSeCys for 20 h completely prevented the enhanced cell damage, MDA concentration and GR and GPx activity and the decreased GSH induced by t-BOOH but did not prevent increased ROS generation. The results show that treatment of HepG2 cells with concentrations of Se-MeSeCys in the nanomolar to micromolar range confers a significant protection against an oxidative insult.     

The Potential Role of Polyphenols in Modulating Mitochondrial Bioenergetics within the Skeletal Muscle: A Systematic Review of Preclinical Models

Polyphenols are naturally derived compounds that are increasingly being explored for their various health benefits. In fact, foods that are rich in polyphenols have become an attractive source of nutrition and a potential therapeutic strategy to alleviate the untoward effects of metabolic disorders. The last decade has seen a rapid increase in studies reporting on the bioactive properties of polyphenols against metabolic complications, especially in preclinical models. Various experimental models involving cell cultures exposed to lipid overload and rodents on high fat diet have been used to investigate the ameliorative effects of various polyphenols against metabolic anomalies. Here, we systematically searched and included literature reporting on the impact of polyphenols against metabolic function, particularly through the modulation of mitochondrial bioenergetics within the skeletal muscle. This is of interest since the skeletal muscle is rich in mitochondria and remains one of the main sites of energy homeostasis. Notably, increased substrate availability is consistent with impaired mitochondrial function and enhanced oxidative stress in preclinical models of metabolic disease. This explains the general interest in exploring the antioxidant properties of polyphenols and their ability to improve mitochondrial function. The current review aimed at understanding how these compounds modulate mitochondrial bioenergetics to improve metabolic function in preclinical models on metabolic disease.     

Hydrothermal Preparation of Ni3S4/CoS2 Composite Electrocatalytic Materials for High Performance Counter Electrodes of Dye-Sensitized Solar Cells

Journal of Cluster Science - A facile one step synthetic hydrothermal route was used to fabricate the Pt free Ni3S4/CoS2 heterostructure counter electrode and study the photovoltaic characteristics...     

Asymptotic Behavior of Positive Solutions of a Nonlinear Combined p-Laplacian Equation

For p > 1, we establish existence and asymptotic behavior of a positive continuous solution to the following boundary value problem $$\left\{\begin{array}{ll}\frac{1}{A} \left( A\Phi _{p}(u^{\prime})\right) ^{\prime}+a_{1}(r)u^{\alpha _{1}}+a_{2}(r)u^{\alpha _{2}}=0, \, {\rm in}\, (0,\infty ),\\ {\rm lim}_{r\rightarrow 0} A\Phi _{p}(u^{\prime})(r)=0, {\rm lim}_{r\rightarrow \infty } u(r)=0,\end{array}\right.$$ where \({\alpha _{1}, \alpha _{2} < p -1, \Phi _{p}(t) = t|t| ^{p-2},A}\) is a positive differentiable function and a ₁, a ₂ are two positive functions in \({C_{\rm loc}^{\gamma}((0, \infty )), 0 < \gamma < 1,}\) satisfying some appropriate assumptions related to Karamata regular variation theory. Also, we obtain an uniqueness result when \({\alpha _{1}, \alpha _{2} \in (1-p,p-1)}\) . Our arguments combine a method of sub and supersolutions with Karamata regular variation theory.