Photocatalytic E→Z Contra-Thermodynamic Isomerization of Vinyl Silanes with Lewis Base

Herein, we disclosed the contra-thermodynamic E→Z isomerization of alkenyl silanes, according to the in situ formation of a chromophoric species, in the presence of rac-BINAP as the catalyst. The reaction carried out in DMSO or CH₃CN under irradiation at 405 nm allowed the interconversion of the E-isomers into the Z-congeners in good to excellent yields and outstanding Z/E selectivities, on 18 examples. Finally, the mechanism of this E→Z isomerization was studied to get insight into the reaction mechanism.     

Redox‐responsive core cross‐linked micelles of poly(ethylene oxide)‐b‐poly(furfuryl methacrylate) by Diels‐Alder reaction for doxorubicin release

Redox‐responsive core cross‐linked (CCL) micelles of poly(ethylene oxide)‐b‐poly(furfuryl methacrylate) (PEO‐b‐PFMA) block copolymers were prepared by the Diels‐Alder click‐type reaction. First, the PEO‐b‐PFMA amphiphilic block copolymer was synthesized by the reversible addition‐fragmentation chain transfer polymerization. The hydrophobic blocks of PFMA were employed to encapsulate the doxorubicin (DOX) drug, and they were cross‐linked using dithiobismaleimidoethane at 60 °C without any catalyst. Under physiological circumstance, the CCL micelles demonstrated the enhanced structural stability of the micelles, whereas dissociation of the micelles took place rapidly through the breaking of disulfide bonds in the cross‐linking linkages under reduction environment. The core‐cross‐linked micelles showed fine spherical distribution with hydrodynamic diameter of 68 ± 2.9  nm. The in vitro drug release profiles presented a slight release of DOX at pH 7.4, while a significant release of DOX was observed at pH 5.0 in the presence of 1,4‐dithiothreitol. MTT assays demonstrated that the block copolymer did not have any practically cytotoxicity against the normal HEK293 cell line while DOX‐loaded CCL micelles exhibited a high antitumor activity towards HepG2 cells. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 3741–3750     

Supercritical fluid chromatography and two-dimensional supercritical fluid chromatography of polar car lubricant additives with neat CO(2) as mobile phase

Car lubricant additives are added to mineral or synthetic base stocks to improve viscosity and resistance to oxidation of the lubricant and to limit wear of engines. Their total amount in the commercial lubricant varies from a few percents to 20-25%. As they belong to various chemical classes and are added to a very complex medium, the base stock, their detailed chromatographic analysis is very difficult and time consuming as it should involve sample treatment and preparative scale separations in order to simplify the sample. The aim of this work is to determine the feasibility of the separation of low molecular weight lubricant additives using various packed columns with pure CO(2) as a mobile phase to enable implementation of flame ionisation detection as universal detector. This is part of a hypernated system including more sophisticated specific detectors, such as AED, FTIR or MS to obtain detailed structural information of compounds. This paper is devoted to the comparison of some stationary phases supposed to provide hydrocarbon group type separation (silica and normal phase) or separations on alkyl-bonded silica in non-aqueous mode of some selected classes of additives in test mixtures or in base stocks. Adsorption chromatography allows partial separation of additives from the base stocks while the direct elution of test additives can only be obtained on reversed phase supports having a very efficient silanol group protection so the interaction of the more polar compounds is much reduced. A two-dimensional scheme of analysis is also described. It combines adsorption chromatography to separate most of the polar additives from the base stock and alkyl-bonded silica for more detailed separation of the additives. However, overlapping between groups of compounds and the lack of resolution between some additives and the base stock should be addressed by the implementing of selective detectors.     

Designing liquid-crystalline dendronised hexa-adducts of [60]fullerene via click chemistry

ABSTRACT

Liquid-crystalline [60]fullerodendrimers were constructed via click chemistry based on the reaction between hexa-adducts of [60]fullerene (C₆₀) bearing 12 azide groups and alkyne-terminated cyanobiphenyl dendrons of first- and second-generation. The structure of all the new compounds was confirmed by IR, UV, ¹H and ¹³C NMR spectroscopies and mass spectrometry. The mesomorphic properties were studied by polarised optical microscopy, differential scanning calorimetry and small-angle X-ray scattering. The hexa-adduct of C₆₀ functionalised with the first-generation dendrons gave rise to the formation of a smectic A phase and a rectangular columnar phase (c2mm symmetry) while the hexa-adduct of C₆₀ decorated with the second-generation dendrons displayed only a rectangular columnar phase (c2mm symmetry). Our results show that the hexa-adduct of C₆₀ is a unique synthetic platform for the design of fullerodendrimers and dendronised materials.     

Highly sensitive fluorescent sensor targeting CuCl2 based on thiophene attached anthracene compound (TA)

A novel thiophene attached anthracene (TA) based fluorescent compound was designed and synthesized. The TA showed a high quantum yield (Qy = 0.34) in regard to fluorescence. We applied this TA compound to detect specific metal compound and found that it could identify CuCl₂ from other metals through dramatic fluorescence change at λ_max = 460 nm. It showed strong quenching fluorescence property with CuCl₂ while with other metal compounds it exhibited strong blue fluorescence emission. UV/Vis absorption spectroscopy clearly demonstrated that the quenching property of TA at λ_max = 460 nm was due to overlapping of the fluorescence peak of TA at λ_max = 460 nm and the absorption band of CuCl₂ (from 190 nm to 525 nm). Binding constant (K′), which was 0.0895 mM^?2, indicated a complexation ratio between TA and CuCl₂ as 1:2 and this interaction induced quenching property.     

Simple and rapid synthesis of ternary polyaniline/titanium oxide/graphene by simultaneous TiO<Subscript>2</Subscript> generation and aniline oxidation as hybrid materials for supercapacitor applications

This paper reports a simple methodology for the synthesis of a polyaniline/titanium oxide/graphene hybrid (Pani/TiO₂/GN) using a simple methodology, and their application as a supercapacitor electrode material for energy storage. The Pani/TiO₂/GN hybrid was prepared by a simple approach by simultaneous generation of Pani and TiO₂ in situ from aniline and titanium iso-propoxide, respectively, in the presence of GN under ice bath conditions. The incorporation of GN improved the electrical conductivity of Pani and helped to decrease the charge transfer resistance, whereas TiO₂ generation by an in situ method increased the surface area considerably and enhanced the capacitance of the Pani/TiO₂/GN hybrid. TEM showed that Pani and TiO₂ were well incorporated and coated on the GN successfully. The shift of the peaks in the FTIR spectrum and XRD pattern of the Pani/TiO₂/GN hybrid compared to their pure counterparts suggested that TiO₂ and Pani had been perfectly coated on the GN, and there was a strong interaction among Pani, GN, and TiO₂ particles. The electrochemical performance of the as-prepared Pani/TiO₂/GN hybrid electrode showed a high specific capacitance of 403.2 F g^?1 at a current density of 2 A g^?1 and excellent cycling stability for up to 1000 cycles. This suggested that the effective incorporation of GN and TiO₂ into Pani and the high surface area could simultaneously increase the electrochemical capacitance and cyclic stability of the Pani/TiO₂/GN hybrid, leading to superior electrochemical performance.

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Graphical abstract The electrochemical performance of as-prepared Pani/TiO₂/GN hybrid electrode showed a high specific capacitance of 403.2 F g^?-1 at a current density of 2 A g^?-1 and excellent cycling stability for up to 1000 cycles. This suggested that the effective incorporation of GN and TiO₂ into Pani and the high surface area could simultaneously increase the electrochemical capacitance and cycle stability of the Pani/TiO₂/GN hybrid, leading to superior electrochemical performance.

     

The Influence of Dopant Concentration on Optical-Electrical Features of Quantum Dot-Sensitized Solar Cell

In this study, TiO₂/CdS/Cd_xCu_1−xSe, TiO₂/CdS/Cd_xMn_1−xSe, and TiO₂/CdS/Cd_xAg_2−2xSe thin films were synthesized by chemical bath deposition for the fabrication of photoanode in quantum-dot-sensitized solar cells. As a result, the structural properties of the thin films have been studied by X-ray diffraction, which confirmed the zinc Blende structure in the samples. The optical films were researched by their experimental absorption spectra with different doping concentrations. Those results were combined with the Tauc correlation to estimate the absorption density, the band gap energy, valence band and conduction band positions, steepness parameter, and electron–phonon interaction. Furthermore, the electrical features, electrochemical impedance spectrum and photocurrent density curves were carried out. The result was used to explain the enhancing performance efficiency.     

The Inhibitory Effects of Plant Derivate Polyphenols on the Main Protease of SARS Coronavirus 2 and Their Structure–Activity Relationship

The main protease (M^pro) is a major protease having an important role in viral replication of the severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2), the novel coronavirus that caused the pandemic of 2020. Here, active M^pro was obtained as a 34.5 kDa protein by overexpression in E. coli BL21 (DE3). The optimal pH and temperature of M^pro were 7.5 and 37 °C, respectively. M^pro displayed a K_m value of 16 μM with Dabcyl-KTSAVLQ↓SGFRKME-Edans. Black garlic extract and 49 polyphenols were studied for their inhibitory effects on purified M^pro. The IC₅₀ values were 137 μg/mL for black garlic extract and 9–197 μM for 15 polyphenols. The mixtures of tannic acid with puerarin, daidzein, and/or myricetin enhanced the inhibitory effects on M^pro. The structure–activity relationship of these polyphenols revealed that the hydroxyl group in C3′, C4′, C5′ in the B-ring, C3 in the C-ring, C7 in A-ring, the double bond between C2 and C3 in the C-ring, and glycosylation at C8 in the A-ring contributed to inhibitory effects of flavonoids on M^pro.     

Channel effect in isomeric ratio of 137m,gCe produced in different nuclear reactions

This work presents the experimental study of the isomeric ratio of ^137mCe–^137gCe produced in ¹³⁸Ce(γ, n) ^137m,gCe photonuclear reaction, in neutron capture reaction ¹³⁶Ce(n, γ) ^137m,gCe and in the two simultaneous reactions ¹³⁸Ce(γ, n) ^137m,gCe and ¹³⁶Ce(n, γ) ^137m,gCe in the mixed photon—neutron field by the activation method. The investigated samples were irradiated at the bremsstrahlung photon flux, in the epithermal and thermal-epithermal neutron beam and in the mixed photon-neutron field constructed at the electron accelerator Microtron MT-25 of the Flerov Laboratory of Nuclear Reaction, Joint Institute for Nuclear Research, Dubna, Russia. The results were analyzed, discussed and compared with those of other authors to examine the role of the channel effect in nuclear reaction and provide the nuclear data for theoretical model interpretation of nuclear reactions.

     

An Armijo-type method for pseudomonotone equilibrium problems and its applications

We present a new algorithm for solving equilibrium problems, where the underlying bifunctions are pseudomonotone and not necessarily Lipschitz-type continuous. The algorithm is based on the auxiliary problem principle and the Armijo-type linesearch techniques. Convergence properties of the algorithms are established, among them the global convergence is proved under few assumptions. Applications to generalized variational inequalities and some numerical results are reported.