Improvement of capacitance activity for Cu‐doped Ni‐based metal–organic frameworks by adding potassium hexacyanoferrate into KOH electrolyte

Cu‐doped Ni‐based metal–organic frameworks (MOFs) nanomaterials fabricated through a one‐pot hydrothermal reaction were characterized, and their performance as supercapacitor electrode materials was further studied for the first time. The results indicated that the doping of foreign metals and the introduction of K₃[Fe(CN)₆] in the KOH electrolyte significantly improve the performance of the supercapacitor. The results indicated that the Ni_2.6Cu_0.4 MOFs material shows the highest specific capacitance (1282 F g^?1 at 1 A g^?1 in mixed 2 M KOH and 0.1 M K₃[Fe(CN)₆]) and optimal capacitance retention (85.7% after 2000 cycles). This work provides a feasible optimization strategy for the construction of MOFs‐based supercapacitor electrode materials with excellent performance, and also provides a reliable experimental and theoretical basis for practical industrial production.     

Entropic effect implication for change in polymer coils swelling state in the demixing enthalpy recovery of aqueous poly(vinyl methyl ether) solutions

Time‐dependent demixing enthalpy recovery behavior of aqueous poly(vinyl methyl ether) (PVME) solutions exhibits distinct recovery characteristics in three concentration regions. The absence of recovery behavior below a water concentration of 38.3 wt % indicates that the PVME coil is in a globular state. The typically sigmoidal recovery behavior of demixing enthalpy above 38.3 wt % is ascribed to the reswelling of the collapsed polymer coils induced by the entropic effect. The increase in difference between the upper and lower limits indicates the continued swelling of the PVME coils. Above 65 wt %, a dominant diluting effect can be observed, and a much longer phase separation time is needed to reach the expected lower limit. In contrast, the recovery of demixing enthalpy in a wide range of water concentration (from 38.3 to 90 wt %) exhibits the same feature. The infrared spectroscopy results are in agreement with the above macroscopic differential scanning calorimetry results. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2019 , 57, 142–151     

Synthesis,cytotoxicity, apoptosis and cell cycle arrest of a monoruthenium(II)-substituted Dawson polyoxotungstate

By 5-h reaction of cis-[Ru^IICl₂(DMSO)₄] (M2) with K₁₀[α₂-P₂W₁₇O₆₁] (M3) in ice-cooled, HCl-acidic aqueous solution, a water-soluble 1:2-type diamagnetic ruthenium(II) complex of formula K₁₈[Ru^II(DMSO)₂(P₂W₁₇O₆₁)₂]·35H₂O (M1) was unexpectedly obtained as an analytically pure, homogeneous tan-colored solid, in which two DMSO ligands are coordinated to the ruthenium(II) atom. The cytotoxic potential of the complex was tested on C33A, DLD-1, and HepG-2 cancer cells and human normal embryonic lung fibroblasts cell MRC-5; the viability of the treated cells was evaluated by MTT assay. The mode of cell death was assessed by morphological study of DNA damage and apoptosis assays. Compound M1 induced cell death in a dose-dependent manner, and the mode of cell death was essentially apoptosis though necrosis was also noticed. Cell cycle analysis by flow cytometry indicated that M1 caused cell cycle arrest and accumulated cells in S phase.     

Novel palladium nanoparticles supported on β‐cyclodextrin@graphene oxide as magnetically recyclable catalyst for Suzuki–Miyaura cross‐coupling reaction with two different approaches in bio‐based solvents

A novel nanocatalyst was designed and prepared. Initially, the surface of magnetic graphene oxide (M‐GO) was modified using thionyl chloride, tris(hydroxymethyl)aminomethane and acryloyl chloride as linkers which provide reactive C═C bonds for the polymerization of vinylic monomers. Separately, β‐cyclodextrin (β‐CD) was treated with acryloyl chloride to provide a modified β‐CD. Then, in the presence methylenebisacrylamide as a cross‐linker, monomers of modified β‐CD and acrylamide were polymerized on the surface of the pre‐prepared M‐GO. Finally, palladium acetate and sodium borohydride were added to this composite to afford supported palladium nanoparticles. This fabricated nanocomposite was fully characterized using various techniques. The efficiency of this easily separable and reusable heterogeneous catalyst was successfully examined in Suzuki–Miyaura cross‐coupling reactions of aryl halides and boronic acid as well as in modified Suzuki–Miyaura cross‐coupling reactions of N‐acylsuccinimides and boronic acid in green media. The results showed that the nanocatalyst was efficient in coupling reactions for direct formation of the corresponding biphenyl as well as benzophenone derivatives in green media based on bio‐based solvents. In addition, the nanocatalyst was easily separable, using an external magnet, and could be reused several times without significant loss of activity under the optimum reaction conditions.     

CoFe2O4@SiO2‐CPTES‐Guanidine‐Cu(II): A novel and reusable nanocatalyst for the synthesis of 2,3‐dihydroquinazolin‐4(1H)‐ones and polyhydroquinolines and oxidation of sulfides

CoFe₂O₄@SiO₂‐CPTES‐Guanidine‐Cu(II) magnetic nanoparticles were synthesized and used as a new, inexpensive and efficient heterogeneous catalyst for the synthesis of polyhydroquinolines and 2,3‐dihydroquinazoline‐4(1H)‐ones and for the oxidation of sulfides. The structure of this nanocatalyst was characterized using Fourier transform infrared spectroscopy, scanning electron microscopy, energy‐dispersive X‐ray spectroscopy, vibrating sample magnetometry, thermogravimetric analysis, X‐ray diffraction and inductively coupled plasma optical emission spectrometry. Simple preparation, high catalytic activity, simple operation, high yields, use of green solvents, easy magnetic separation and reusability of the catalyst are some of the advantages of this protocol.     

New lower bounds on the radius of spatial analyticity for the KdV equation

The radius of spatial analyticity for solutions of the KdV equation is studied. It is shown that the analyticity radius does not decay faster than $t^{?1/4}$ as time t goes to infinity. This improves the works of Selberg and da Silva (2017) [30] and Tesfahun (2017) [34]. Our strategy mainly relies on a higher order almost conservation law in Gevrey spaces, which is inspired by the I-method.     

Convergence of solutions for the fractional Cahn–Hilliard system

This paper deals with the Cauchy–Dirichlet problem for the fractional Cahn–Hilliard equation. The main results consist of global (in time) existence of weak solutions, characterization of parabolic smoothing effects (implying under proper condition eventual boundedness of trajectories), and convergence of each solution to a (single) equilibrium. In particular, to prove the convergence result, a variant of the so-called ?ojasiewicz–Simon inequality is provided for the fractional Dirichlet Laplacian and (possibly) non-analytic (but $C^1$) nonlinearities.     

Dose‐dependent exposure profile and metabolic characterization of notoginsenoside R1 in rat plasma by ultra‐fast liquid chromatography–electrospray ionization–tandem mass spectrometry

Notoginsenoside R₁ (NGR₁), a diagnostic protopanaxatriol‐type (ppt‐type) saponin in Panax notoginseng, possesses potent biological activities including antithrombotic, anti‐inflammatory, neuron protection and improvement of microcirculation, yet its pharmacokinetics and metabolic characterization as an individual compound remain unclear. The aim of this study was to investigate the exposure profile of NGR₁ in rats after oral and intravenous administration and to explore the metabolic characterization of NGR₁. A simple and sensitive ultra‐fast liquid chromatographic–tandem mass spectrometric method was developed and validated for the quantitative determination of NGR₁ and its major metabolites, and for characterization of its metabolic profile in rat plasma. The blood samples were precipitated with methanol, quantified in a negative multiple reaction monitoring mode and analyzed within 6.0 min. Validation parameters (linearity, precision and accuracy, recovery and matrix effect, stability) were within acceptable ranges. After oral administration, NGR₁ exhibited dose‐independent exposure behaviors with t_1/2 over 8.0 h and oral bioavailability of 0.25–0.29%. A total of seven metabolites were characterized, including two pairs of epimers, 20(R)‐notoginsenoside R₂/20(S)‐notoginsenoside R₂ and 20(R)‐ginsenoside Rh₁/20(S)‐ginsenoside Rh₁, with the 20(R) form of saponins identified for the first time in rat plasma. Five deglycometabolites were quantitatively determined, among which 20(S)‐notoginsenoside R₂, ginsenoside Rg₁, ginsenoside F₁ and protopanaxatriol displayed relatively high exploration, which may partly explain the pharmacodynamic diversity of ginsenosides after oral dose.     

Kinetics and mechanism of trichloroisocyanuric acid/NaNO2-triggered nitration of aromatic compounds under acid-free and Vilsmeier-Haack conditions

Kinetics and mechanism of nitration of aromatic compounds using trichloroisocyanuric acid (TCCA)/NaNO₂, TCCA-N,N-dimethyl formamide (TCCA-DMF)/NaNO₂, and TCCA-N,N-dimethyl acetamide (TCCA-DMA)/NaNO₂ under acid-free and Vilsmeier-Haack conditions. Reactions followed second-order kinetics with a first-order dependence on [Phenol] and [Nitrating agent] ([TCCA], [(TCCA-DMF)], or [(TCCA-DMA)] >> [NaNO₂]). Reaction rates accelerated with the introduction of electron-donating groups and retarded with electron-withdrawing groups, but did not fit well into the Hammett's theory of linear free energy relationship or its modified forms like Brown-Okamoto or Yukawa-Tsuno equations. Rate data were analyzed by Charton's multiple linear regression analysis. Isokinetic temperature (β) values, obtained from Exner's theory for different protocols, are 403.7 K (TCCA-NaNO₂), 365.8 K (TCCA-DMF)/NaNO₂, and 358 K (TCCA-DMA)/NaNO₂. These values are far above the experimental temperature range (303-323 K), indicating that the enthalpy factors are probably more important in controlling the reaction.     

A-posteriori KAM theory with optimal estimates for partially integrable systems

In this paper we present a-posteriori KAM results for existence of d-dimensional isotropic invariant tori for n-DOF Hamiltonian systems with additional $n?d$ independent first integrals in involution. We carry out a covariant formulation that does not require the use of action-angle variables nor symplectic reduction techniques. The main advantage is that we overcome the curse of dimensionality avoiding the practical shortcomings produced by the use of reduced coordinates, which may cause difficulties and underperformance when quantifying the hypotheses of the KAM theorem in such reduced coordinates. The results include ordinary and (generalized) iso-energetic KAM theorems. The approach is suitable to perform numerical computations and computer assisted proofs.