Nickel (II) tetrapyridyl complexes as electrocatalysts and precatalysts for water oxidation

Two nickel complexes, [Ni(tpen)](ClO₄)₂.0.5CH₃COCH₃ ( 1 ) and [Ni(tpbn)](ClO₄)₂ ( 2 ), of tetrapyridyl ligands N,N,N′,N′-tetrakis(2-pyridyl-methyl)-1,2-ethanediamine (tpen) and N,N,N′,N′-tetrakis(2-pyridyl-methyl)-1,4-butanediamine (tpbn) were prepared and their catalysis for water oxidation reaction (WOR) studied. In 0.1 M phosphate buffer solution (PBS) of pH 8.0, complex 1 is a homogeneous molecular catalyst with an overpotential of ~440 mV and a Faradaic efficiency of 89%. At pH ≥ 9.0, complex 1 degraded gradually during the catalytic process and formed NiO_x composite (nickel oxide with general formula Ni_xO_yH_z) active for WOR. In contrast, complex 2 deteriorated under measured conditions (pH 8.0–12.0) and formed NiO_x composite active for WOR. The NiO_x composite derived from 1 in 0.1 M PBS at pH 11.0 showed an activity with an overpotential of ~500 mV, a Tafel slope of ~90 mV/decade and a Faradaic efficiency of 97%. Mechanisms were proposed for water oxidation catalyzed by 1 and 2 . This work revealed that the catalytic activity of the nickel complexes was related to the flexibility of the tetrapyridyl ligands and the adaptability of the coordination sphere of the nickel(II) center.     

Dinuclear gold (I)-di-N-heterocyclic carbene complexes: syntheses,structure, density functional theory calculation and photoluminescence study

The synthesis and characterizations for a series of dinuclear gold (I)-di-NHC complexes, 1–8 through the trans-metalation method of their respective silver (I)-di-NHC complexes, i–viii are reported (where NHC = N-heterocyclic carbene). The successful complexation of a series of unusual non-symmetrical and symmetrical di-NHC ligands, 3,3'-(ethane-1,2-diyl)-1-alkylbenzimidazolium-1'-butylbenzimidazolium (with alkyl = methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, benzyl) with the gold (I) ions are suggested by elemental analysis, Fourier transform-infrared, ¹H- and ¹³C-NMR data. The ¹³C-NMR spectra of 1–8 show a singlet sharp peak in the range of 190.00–192.00 ppm, indicating the presence of a carbene carbon that bonded to the gold (I) ion. From single crystal X-ray diffraction data, the structure of complex 6 with the formula of [di-NHC-Au (I)]₂·2PF₆ is obtained [where NHC = 3,3'-(ethane-1,2-diyl)-1-hexylbenzimidazolium-1'-butylbenzimidazolium]. The photophysical study in solid state of 6 displays an intense photoluminescence with a strong emission maxima, λ_em = 480 nm, upon excitation at 340 nm at room temperature. Interestingly, the emission maximum at 77 K shows a structural character with a strong peak at 410 nm, a medium at 433 nm and a weak at 387 nm, accompanied by a tail band to about 500 nm.     

Nano-sized Cu(II) and Zn(II) complexes and their use as a precursor for synthesis of CuO and ZnO nanoparticles: A study on their sonochemical synthesis,characterization, and DNA-binding/cleavage,anticancer, and antimicrobial activities

Two new divalent copper (C1) and zinc (C2) chelates having the formulae [M(PIMC)₂] (where M = Cu(II), Zn(II) and PIMC = Ligand [(E)-3-(((3-hydroxypyridin-2-yl)imino)methyl)-4H-chromen-4-one] were obtained and characterized by several techniques. Structures and geometries of the synthesized complexes were judged based on the results of alternative analytical and spectral tools supporting the proposed formulae. IR spectral data confirmed the coordination of the ligands to the copper and zinc centers as monobasic tridentate in the enol form. Thermal analysis, UV-Vis spectra and magnetic moment confirmed the geometry around the copper center to be tetrahedral, square pyramidal and octahedral. Study of the binding ability of the synthesized compounds with Circulating tumor DNA (CT-DNA) bas been evaluated applying UV-Vis spectral titration and viscosity measurements. The copper and zinc oxides were achieved from the copper and zinc nano-particles structures Schiff base complexes as the raw material after calcination for 5 hr at 600°C. On the other hand, synthesized of C1 and C2 NPs were used as suitable precursors to the preparation of CuO and ZnO NPs. Finally, the synthesized of the two complexes exhibited enhanced activity against the tested bacterial (Staphylococcus aureus and Escherichia Coli) and fungal strains (Candida albicans and Aspergillus fumigatus) as compared to HPIMC. Among all these synthesized compounds, C1 exhibits good cleaving ability compared to other newly synthesized C2.     

Tb3Pd2, Er3Pd2 and Er6Co5–x: structural variations and bonding in rare‐earth‐richer binary intermetallics

The three binary Tb/Er‐rich transition metal compounds Tb₃Pd₂ (triterbium dipalladium), Er₃Pd₂ (trierbium dipalladium) and Er₆Co_5–x (hexaerbium pentacobalt) crystallize in the space groups Pbam (Pearson symbol oP20), P4/mbm (tP10) and P6₃/m (hP22), respectively. Single crystals of Tb₃Pd₂ and Er₆Co_5–x suitable for X‐ray structure analysis were obtained using rare‐earth halides as a flux. Tb₃Pd₂ adopts its own structure type, which can be described as a superstructural derivative of the U₃Si₂ type, which is the type adopted by Er₃Pd₂. Compound Er₆Co_5–x belongs to the Ce₆Co_2–xSi₃ family. All three compounds feature fused tricapped {TR₆} (R = rare‐earth metal and T = transition metal) trigonal prismatic heterometallic clusters. R₃Pd₂ is reported to crystallize in the U₃Si₂ type; however, our more detailed structure analysis reveals that deviations occur with heavier R elements. Similarly, Er₆Co_5–x was assumed to be stoichiometric Er₄Co₃ = Er₆Co_4.5. Our studies reveal that it has a single defective transition‐metal site leading to the composition Er₆Co_4.72(2). LMTO (linear muffin‐tin orbital)‐based electronic structure calculations suggest the strong domination of heteroatomic bonding in all three structures.     

The pentacene films on the glass/ITO surface: structure and optical properties

Abstract

The structure, morphology and optical transmittance spectra of pentacene films on the (glass/ITO) surface were studied. The films were grown by two methods - the thermal vacuum deposition (TVD) and pulsed laser deposition (PLD). The electron diffraction pattern from thermally deposited pentacene films confirms their polycrystalline structure while the diffraction pattern of PLD-coated layers has a diffusion character. The results obtained showed that layers deposited by the TVD method has an optical spectrum that is characteristic for the pentacene film in contrary to the layers deposited by the PLD method. It is found a sensitivity of the optical transmittance of pentacene films to the ammonia action, which may be used for development the optical gas sensor.     

Photosensitive organic-inorganic hybrid structures based on porous silicon

Abstract

In this study, the photovoltaic organic-inorganic structures were created by deposition of poly(3,4-ethylenedioxythiophene) film doped by poly(styrenesulfonate) and reduced graphene oxide on the porous silicon/silicon substrate. Formation of the hybrid structure was confirmed by means of atomic-force microscopy and Fourier transform infrared spectroscopy. The current-voltage characteristics of the obtained structures were studied. It was found the increase of electrical conductivity and photo-induced signal in organic-inorganic structures. Temporal parameters and spectral characteristics of photoresponse in the 400–1100?nm wavelength range were investigated. The widening of spectral photosensitivity in a short-wavelength range due to light absorption in various layers of the multijunction structure in comparison with single crystal silicon was revealed.     

Wave-based vibration control of large cable net structures

Large cable net structures have been widely applied in aerospace engineering due to the feature of light-weight, high packaging efficiency, and high thermal stability. Structural vibrations induced by a variety of disturbances are inevitable in the space environment, resulting in the requirement of effective vibration control strategies for large cable net structures. Since the large cable net structures have many closely spaced vibrational modes in the range of low frequencies, traditional modal based control may cause modal truncation and spillover problems. In this paper, a wave-based boundary control strategy is adopted and its effectiveness to control the vibration of cable net structures is investigated, by transfer function analysis and numerical methods. It is found that the structural vibration can be absolutely resisted by applying the wave-based boundary controllers onto all the exterior nodes, when disturbances come from the external boundaries of the cable net. Our results in this paper can provide a theoretical basis for the vibration control of large cable net structures.     

Synthesis,characterization, duplex-DNA interactions,and anticancer activities of novel octahedral [Ni(phen)2(dppz-idzo)]2+ and [Co(phen)2(dppz-idzo)]3+ complexes

Two new octahedral [Ni(phen)₂(dppz-idzo)]²⁺ and [Co(phen)₂(dppz-idzo)]³⁺ complexes have been synthesized and characterized by CHN analysis, electrospray ionization-MS, nuclear magnetic resonance, and UV–Vis spectra. The DNA-binding ability of these complexes was spectrophotometrically, hydrodynamically, and electrophoretically evaluated which indicated that they strongly intercalate into the DNA double helix, and that both induced severe DNA damage in the presence of peroxide. The complexes also showed strong antiproliferative effect against HepG2 and MDA-MB-231 cells. By contrast, they were found to be inactive against the MCF-7 cell line. The ligand itself was found to be inactive against the cells tested.     

Green synthesis and characterizations of Nickel oxide nanoparticles using leaf extract of Rhamnus virgata and their potential biological applications

In the present report, Nickel oxide nanoparticles (NiONPs) were synthesized using Rhamnus virgata (Roxb.) (Family: Rhamnaceae) as a potential stabilizing, reducing and chelating agent. The formation, morphology, structure and other physicochemical properties of resulting NiONPs were characterized by Ultra violet spectroscopy, X‐ray diffraction (XRD), Fourier Transform Infrared analysis (FTIR), Scanning electron microscopy (SEM), Energy‐dispersive‐spectroscopy (EDS), Transmission electron microscopy (TEM), Raman spectroscopy and dynamic light scattering (DLS). Detailed in vitro biological activities revealed significant therapeutic potential for NiONPs. The antimicrobial efficacy of biogenic NiONPs was demonstrated against five different gram positive and gram negative bacterial strains. Klebsiella pneumoniae and Pseudomonas aeruginosa (MIC: 125 μg/mL) were found to be the least susceptible and Bacillus subtilis (MIC: 31.25 μg/mL) was found to be the most susceptible strain to NiONPs. Biogenic NiONPs were reported to be highly potent against HepG2 cells (IC₅₀: 29.68 μg/ml). Moderate antileishmanial activity against Leishmania tropica (KMH₂₃) promastigotes (IC₅₀: 10.62 μg/ml) and amastigotes (IC₅₀: 27.58 μg/ml) cultures are reported. The cytotoxic activity was studied using brine shrimps and their IC₅₀ value was recorded as 43.73 μg/ml. For toxicological assessment, NiONPs were found compatible towards human RBCs (IC₅₀: > 200 μg/ml) and macrophages (IC₅₀: > 200 μg/ml), deeming particles safe for various applications in nanomedicines. Moderate antioxidant activities: total antioxidant capacity (TAC) (51.43%), 2,2‐diphenyl‐1‐picrylhydrazyl (DPPH) activity (70.36%) and total reducing power (TRP) (45%) are reported for NiONPs. In addition, protein kinase and alpha amylase inhibition assays were also performed. Our results concluded that Rhamnus virgata synthesized NiONPs could find important biomedical applications with low cytotoxicity to normal cells.     

NIFTy 3 – Numerical Information Field Theory: A Python Framework for Multicomponent Signal Inference on HPC Clusters

NIFTy , “Numerical Information Field Theory,” is a software framework designed to ease the development and implementation of field inference algorithms. Field equations are formulated independently of the underlying spatial geometry allowing the user to focus on the algorithmic design. Under the hood, NIFTy ensures that the discretization of the implemented equations is consistent. This enables the user to prototype an algorithm rapidly in 1D and then apply it to high‐dimensional real‐world problems. This paper introduces NIFTy  3, a major upgrade to the original NIFTy  framework. NIFTy  3 allows the user to run inference algorithms on massively parallel high performance computing clusters without changing the implementation of the field equations. It supports n‐dimensional Cartesian spaces, spherical spaces, power spaces, and product spaces as well as transforms to their harmonic counterparts. Furthermore, NIFTy  3 is able to handle non‐scalar fields, such as vector or tensor fields. The functionality and performance of the software package is demonstrated with example code, which implements a mock inference inspired by a real‐world algorithm from the realm of information field theory. NIFTy  3 is open‐source software available under the GNU General Public License v3 (GPL‐3) at https://gitlab.mpcdf.mpg.de/ift/NIFTy/tree/NIFTy_3 .