Synthesis of Novel Tridentate 5-Arylazosalicylaldehyde Thiosemicarbazone Derivatives and Their Complexes with Copper(II)

Russian Journal of General Chemistry - Herein, novel 5-arylazosalicylaldehyde thiosemicarbazone derivatives (H2L1–12) and their copper(II) complexes have been synthesized and characterized by...     

Surface-Initiated RAFT Polymerization of 2,3-Dimethyl-1,3-butadiene on Silica Nanoparticles for Matrix-free Methyl Rubber Nanocomposites

Reversible addition-fragmentation chain transfer (RAFT) polymerization of 2,3-dimethyl-1,3-butadiene (DMB) in solution and on the surface of silica nanoparticles was investigated and PDMB-grafted silica nanoparticles (PDMB-g-SiO₂ NPs) with different chain densities and molecular weights were prepared. The kinetic studies of DMB polymerization mediated by silica anchored RAFT agents at different graft densities were investigated and compared to the polymerization mediated by the corresponding free RAFT agent. The PDMB-g-SiO₂ NPs were cured to prepare rubbery films and obtain matrix-free nanocomposites, which exhibited a good dispersion of silica nanoparticles and improved mechanical properties compared to the unfilled crosslinked rubber. © 2020 Wiley Periodicals, Inc. J. Polym. Sci. 2020 , 58, 417–427     

Carriers-assisted Enhanced Ferromagnetism in Al-doped ZnMnO Nano-crystallites

Zn_0.95-xAl_xMn_0.05O (x=0, 0.03, 0.05, and 0.07) dilute magnetic semiconductor materials have been synthesized by sol-gel auto-combustion technique. The effect of Al doping on the structural, electrical, and magnetic properties has been investigated. X-ray diffraction studies demonstrate the existence of single phase characteristic hexagonal wurtzite type crystal structure, similar to the host ZnO, in all the synthesized compositions. Although, the microscopic images revealed that the grains were clustered, yet some individual grains could be seen to have hexagonal texture. Electrical resistivity was observed to decrease with the rise of temperature up to 450 oC, depicting the characteristic semiconductor behavior. Room temperature ferromagnetic behavior was observed in all the compositions. The value of saturation magnetization increased with the increase of Al concentration in ZnMnO system referred to the gradual enhancement of free carriers.     

Structural, electrical, electronic and optical properties of melanin films

We present thick, uniform and rather flat melanin films obtained using spray deposition. The morphology of the films was investigated using Scanning Electron Microscopy (SEM) and Atomic Force Microscopy (AFM). Temperature-dependent electrical resistance of melanin thin films evidenced a semiconductor-like character and a hysteretic behavior linked to an irreversible process of water molecule desorption from the melanin film. X-ray Photoelectron Spectroscopy (XPS) was carried out to analyze the role of the functional groups in the primary and secondary structure of the macromolecule, showing that the contribution of the 5,6-dihydroxyindole-2-carboxylic acid (DHICA) subunit to the molecule is about 35%. Comparison of the optical absorption of the thick (800nm) and thin (80nm) films showed a spectral change when the thickness increases. From in vacuum photoconductivity (PC) measured at controlled temperatures, we suggest that the melanin films exhibit a possible charge transport mechanism by means of delocalized states along the stacked planar secondary structure.     

Improved bounds on the radius and curvature of the K$ \pi$ scalar form factor and implications to low-energy theorems

We obtain stringent bounds in the 〈r ² -c plane where these are the scalar radius and the curvature parameters of the scalar K form factor, respectively, using analyticity and dispersion relation constraints, the knowledge of the form factor from the well-known Callan-Treiman point , as well as at , which we call the second Callan-Treiman point. The central values of these parameters from a recent determination are accomodated in the allowed region provided the higher loop corrections to the value of the form factor at the second Callan-Treiman point reduce the one-loop result by about 3% with . Such a variation in magnitude at the second Callan-Treiman point yields 0.12 fm² 〈r ² 0.21 fm²and 0.56 GeV^-4 c 1.47 GeV^-4and a strong correlation between them. A smaller value of shifts both bounds to lower values.     

Remarkably Slow Rotation about a Single Bond between an sp3‐Hybridised Carbon Atom and an Aromatic Ring without ortho Substituents

Look, no ortho substituents! A series of polycycles were prepared by using a three‐component Joullié–Ugi reaction. The rate of rotation about the bond between a highly hindered bridgehead and a phenyl ring with no ortho substituents was measured, and was highly dependent on the substitution. Rotamer half‐lives of up to 21 h at 298 K were observed (see figure). Rotamers resulting from this restricted rotation were isolated for the first time.

     

Preparation and properties of new ortho-linked polyamide-imides bearing ether, sulfur, and trifluoromethyl linkages

A CF₃-containing diamine, 2,2′-thiobis-[4-methyl(2-trifluoromethyl)4-aminophenoxy) phenyl ether] (DA), was successfully synthesized from 2-2′-sulfide-bis-(4-methyl phenol) and 2-chloro-5-nitrobenzotrifluoride. The sulfur containing diimide-diacid (DIDA) was prepared by condensation reaction of diamine DA and trimellitic anhydride. A series of novel organic-soluble polyamide-imides (PAIs) bearing flexible ether and sulfide links, electron-withdrawing trifluoromethyl groups and ortho-phenylene units were synthesized from DIDA, by direct polycondensation with various aromatic diamines in N-methyl-2-pyrrolidone using triphenyl phosphite and pyridine as a condensing agent in the presence of dehydrating agent (LiCl). The polyamide-imides were obtained in high yields and possessed inherent viscosities in the range of 0.42-0.95 dL g⁻¹. All of the polymers were amorphous in nature, showed outstanding solubility and could be easily dissolved in amide-type polar aprotic solvents (e.g., N-methyl-2-pyrrolidone, N,N-dimethylacetamide, and N,N-dimethylformamide) and even dissolved in less polar solvents (e.g., pyridine and tetrahydrofuran). They showed good thermal stability with glass transition temperatures between 195-245 °C, 10% weight loss temperatures in excess of 485 °C, and char yields more than 50% at 700 °C in nitrogen atmosphere. Moreover, these PAIs possessed low refractive indexes (n = 1.57-1.59) and low birefringence (Δ ≈ 0.02) due to the trifluoromethyl pendent groups and thioether bridged ortho-catenated aromatic rings that interrupt chain packing and increase free volume.     

Synthesis of some pyridine, thiopyrimidine, and isoxazoline derivatives based on the pyrrole moiety

Abstract  

Condensation of 2-acetylpyrrole with 5-methylfuran-2-carboxyaldehyde and 4-chlorobenzaldehyde in 20% NaOH give the corresponding 2-chalconylpyrroles. Some new 2-alkoxy-3-cyano-4,6-diarylpyridines were synthesized by condensation of chalcones with malononitrile, followed by cyclization in sodium alkoxide. The reactivity of chalcones towards nitrogen nucleophiles such as thiourea and hydroxylamine hydrochloride to provide thiopyrimidines and isoxazolines was investigated.