Hydrogen-bonded and π-stacked nickel(II) thiosemicarbazone complexes: Synthesis,spectral and structural studies

Transition Metal Chemistry - Mixed ligand Ni(II) complexes were synthesized from triphenylphosphine and S-methyl- or S-ethyl-isothiosemicarbazone ligands derived from...     

Formation of phthalocyanines deprotonated forms and their interaction with Zn Ions in the system 1,8-diazabicyclo[5.4.0]undec-7-ene-acetonitrile at 298 K

The formation of deprotonated forms of tetra(t-butyl)phthalocyanine ((H₂ tButPc) and octa(pentoxy)-phthalocyanine (H₂OAmPc) in the system acetonitrile-1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) at 298 K was studied by the method of spectrophotometric titration. With increasing DBU concentration sequential formation occurs of both mono- and douby deprotonated forms. The introduction of pentoxy groups into the fused benzene rings leads to a significant decrease in the acidity of the tetrapyrrole macrocycle compared with the tert-butyl substitution. The interaction of douby deprotonated forms of the phthalocyanines with zinc diacetate leads to the formation of metal complexes, the chelation constant of the latter is shown to correlate with the acidity of NH-protons in the nucleus of the macrocycle. For the chelation of more acidic tetra(t-butyl)-phthalocyanine an equimolar concentrations of zinc diacetate is sufficient, while the less acidic octa(pentoxy)-phthalocyanine requires almost 6-fold excess.     

Solution properties,unperturbed dimensions,and chain flexibility of poly(1‐adamantyl acrylate)

Poly(1‐adamantyl acrylate) (PAdA) exhibits much higher glass transition and degradation temperatures than other polyacrylates. However, the quantitative evaluation of the stiffness of this polymer chain has not been reported previously. In this study, the dilute solution properties and conformational characteristics of PAdA were evaluated using viscometry and scattering techniques. The unperturbed dimensions of this polymer were evaluated using the Burchard–Stockmayer–Fixman extrapolation and the touched‐bead wormlike chain model. The PAdA chain has a comparable persistence length, diameter per bead and characteristic ratio to poly(methyl methacrylate) and polystyrene. All these results indicate that PAdA is less flexible than common polyacrylates. In addition, the second virial coefficients (A₂) of PAdA in different solvents obtained by static light scattering were compared. Among the solvents investigated, tetrahydrofuran is a moderate solvent. Radius of gyration of a polymer sample in the various solvents ranged from 16.8 to 30.3 nm. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2017 , 55, 1526–1531     

Magnetic properties of neutron irradiated RPV steel

The neutron irradiated reactor pressure vessel (RPV) steels at various dose of 0–10¹⁸ n/cm² have been studied with Mössbauer, x-ray diffraction, and VSM. The Mössbauer data shows that the value of magnetic hyperfine field of Fe atom that exist at martensite is 330 kOe at site 1 and 305 kOe at site 2. At room temperature, the total absorption area of Mössbauer spectra with respect to irradiation of neutron is constant for the dose of 0–10¹⁶ n/cm², while over the dose of 0–10¹⁷ n/cm² the absorption area decreases rapidly. But the doublet area for the dose of 0–10¹⁶ n/cm² is constant, while over the dose of 10¹⁷ n/cm² it increases with increasing the fluence level of neutron. The coercivity and remanence of the neutron irradiated samples do not change significantly. But the maximum induction decreases by 5% at 10¹⁸ n/cm², compared with that of the as-received sample.     

The Reaction of Ninhydrin with Trimethylbenzenes under Friedel-Crafts Reaction Conditions

The reaction of ninhydrin with 1,2,3- and 1,2,4-trimethylbenzene in the presence of H₂SO₄ or AlCl₃ afforded 2-monoaryl and 2,2-diaryl-1,3-indanedione derivatives as the major products. With 1,3,5-trimethylbenzene as the arene nucleophile, either a reduction product or an indenoindanone derivative was obtained depending upon the catalyst employed in the reaction.     

Silaffin Peptides as a Novel Signal Enhancer for Gravimetric Biosensors

Application of biomimetic silica formation to gravimetric biosensors has been conducted for the first time. As a model system, silaffin peptides fused with green fluorescent protein (GFP) were immobilized on a gold quartz crystal resonator for quartz crystal microbalances using a self-assembled monolayer. When a solution of silicic acid was supplied, silica particles were successfully deposited on the Au surface, resulting in a significant change in resonance frequency (i.e., signal enhancement) with the silaffin–GFP. However, frequency was not altered when bare GFP was used as a control. The novel peptide enhancer is advantageous because it can be readily and quantitatively conjugated with sensing proteins using recombinant DNA technology. As a proof of concept, this study shows that the silaffin domains can be employed as a novel and efficient biomolecular signal enhancer for gravimetric biosensors.     

Improved optical and electrical properties of sol–gel-derived boron-doped zinc oxide thin films

Sol–gel spin-coating was used to grow zinc oxide (ZnO) thin films doped with 0–2.5 at.% B on quartz substrates. The structural, optical, and electrical properties of the thin films were investigated using field-emission scanning electron microscopy, X-ray diffraction (XRD), photoluminescence (PL), ultraviolet–visible spectroscopy, and van der Pauw Hall-effect measurements. All the thin films had deposited well onto the quartz substrates and exhibited granular morphology. The average crystallite size, lattice constants, residual stress, and lengths of the bonds in the crystal lattice of the thin films were calculated from the XRD data. The PL spectra showed near-band-edge (NBE) and deep-level emissions, and B doping varied the PL properties and increased the efficiency of the NBE emission. The optical transmittance spectra for the undoped ZnO and boron-doped zinc oxide (BZO) thin films show that the optical transmittance of the BZO thin films was significantly higher than that of the undoped ZnO thin films in the visible region of the spectra and that the absorption edge of the BZO thin films was blue-shifted. In addition, doping the ZnO thin films with B significantly varied the absorption coefficient, optical band gap, Urbach energy, refractive index, extinction coefficient, single-oscillator energy, dispersion energy, average oscillator strength, average oscillator wavelength, dielectric constant, and optical conductivity of the BZO thin films. The Hall-effect data suggested that B doping also improved the electrical properties such as the carrier concentration, mobility, and resistivity of the thin films.     

Designed Synthesis of Well‐Defined Pd@Pt Core–Shell Nanoparticles with Controlled Shell Thickness as Efficient Oxygen Reduction Electrocatalysts

Improving the electrocatalytic activity and durability of Pt‐based catalysts with low Pt content toward the oxygen reduction reaction (ORR) is one of the main challenges in advancing the performance of polymer electrolyte membrane fuel cells (PEMFCs). Herein, a designed synthesis of well‐defined Pd@Pt core–shell nanoparticles (NPs) with a controlled Pt shell thickness of 0.4–1.2 nm by a facile wet chemical method and their electrocatalytic performances for ORR as a function of shell thickness are reported. Pd@Pt NPs with predetermined structural parameters were prepared by in situ heteroepitaxial growth of Pt on as‐synthesized 6 nm Pd NPs without any sacrificial layers and intermediate workup processes, and thus the synthetic procedure for the production of Pd@Pt NPs with well‐defined sizes and shell thicknesses is greatly simplified. The Pt shell thickness could be precisely controlled by adjusting the molar ratio of Pt to Pd. The ORR performance of the Pd@Pt NPs strongly depended on the thickness of their Pt shells. The Pd@Pt NPs with 0.94 nm Pt shells exhibited enhanced specific activity and higher durability compared to other Pd@Pt NPs and commercial Pt/C catalysts. Testing Pd@Pt NPs with 0.94 nm Pt shells in a membrane electrode assembly revealed a single‐cell performance comparable with that of the Pt/C catalyst despite their lower Pt content, that is the present NP catalysts can facilitate low‐cost and high‐efficient applications of PEMFCs.