Bi Fe O 3 (BFO), Ti(2%)-doped BFO (BFTO), Zn(2%)-doped BFO (BFZO), as well as Ti (1%) and Zn (1%) codoped BFO (BFTZO) films were deposited on Pt∕Ti∕SiO2∕Si substrates by using a metal organic decomposition process. Well saturated P-E hysteresis loops can be obtained in BFZO and BFTZO films due to their lower leakage currents compared to those of BFO and BFTO films. In comparison with BFZO film, BFTZO film exhibits a much larger remanent polarization (Pr∼84μC∕cm2), a lower coercive field (2Ec∼570kV∕cm), as well as stronger charge-retaining ability and fatigue resistance. These phenomena can be explained based on the formation of the defect complexes between the acceptors and oxygen vacancies in the films.
Abstract. Synthetic polycrystalline ice was sheared at temperatures of −5, −20 and −30 ∘C, to different shear strains, up to γ=2.6, equivalent to a maximum stretch of 2.94 (final line length is 2.94 times the original length). Cryo-electron backscatter diffraction (EBSD) analysis shows that basal intracrystalline slip planes become preferentially oriented parallel to the shear plane in all experiments, with a primary cluster of crystal c axes (the c axis is perpendicular to the basal plane) perpendicular to the shear plane. In all except the two highest-strain experiments at −30 ∘C, a secondary cluster of c axes is observed, at an angle to the primary cluster. With increasing strain, the primary c-axis cluster strengthens. With increasing temperature, both clusters strengthen. In the −5 ∘C experiments, the angle between the two clusters reduces with strain. The c-axis clusters are elongated perpendicular to the shear direction. This elongation increases with increasing shear strain and with decreasing temperature. Highly curved grain boundaries are more prevalent in samples sheared at higher temperatures. At each temperature, the proportion of curved boundaries decreases with increasing shear strain. Subgrains are observed in all samples. Microstructural interpretations and comparisons of the data from experimentally sheared samples with numerical models suggest that the observed crystallographic orientation patterns result from a balance of the rates of lattice rotation (during dislocation creep) and growth of grains by strain-induced grain boundary migration (GBM). GBM is faster at higher temperatures and becomes less important as shear strain increases. These observations and interpretations provide a hypothesis to be tested in further experiments and using numerical models, with the ultimate goal of aiding the interpretation of crystallographic preferred orientations in naturally deformed ice.
A series of symmetrical donor-acceptor-donor (D-A-D) chromophores bearing various electron-withdrawing groups, such as quinoxaline (Qx), benzo[g]quinoxaline (BQ), phenazine (Pz), benzo[b]phenazine (BP), thieno[3,4-b]pyrazine (TP), and thieno[3,4-b]quinoxaline (TQ), has been designed and synthesized. Intramolecular charge transfer (ICT) interactions can be found for all the chromophores due to the electron-withdrawing properties of the two imine nitrogens in the pyrazine ring and the electron-donating properties of the other two amine nitrogens in the two triphenylamines. Upon the fusion of either benzene or thiophene ring on the pyrazine acceptor unit, the ICT interactions are strengthened, which results in the bathochromically shifted ICT band. Moreover, the thiophene ring is superior to the benzene ring in enlarging the ICT interaction and expanding the absorption spectrum. Typically, when a thiophene ring is fused on the Qx unit in DQxD, a near-infrared dye is realized in simple chromophore DTQD, which displays the maximum absorption wavelength at 716 nm with the threshold over 900 nm. This is probably due to the enhanced charge density on the acceptor moiety and better orbital overlap, as revealed by theoretical calculation. These results suggest that extending the conjugation of a pyrazine acceptor in an orthogonal direction to the D-A-D backbone can dramatically improve the ICT interactions.
Enzymatic sensors possess high selectivity but suffer from some limitations such as instability, complicated modified procedure, and critical environmental factors, which stimulate the development of more sensitive and stable nonenzymatic electrochemical sensors. Herein, a novel nonenzymatic electrochemical sensor is proposed based on a new zinc porphyrin-fullerene (C60) derivative (ZnP-C60), which was designed and synthesized according to the conformational calculations and the electronic structures of two typical ZnP-C60 derivatives of para-ZnP-C60 (ZnP(p)-C60) and ortho-ZnP-C60 (ZnP(o)-C60). The two derivatives were first investigated by density functional theory (DFT) and ZnP(p)-C60 with a bent conformation was verified to possess a smaller energy gap and better electron-transport ability. Then ZnP(p)-C60 was entrapped in tetraoctylammonium bromide (TOAB) film and modified on glassy carbon electrode (TOAB/ZnP(p)-C60/GCE). The TOAB/ZnP(p)-C60/GCE showed four well-defined quasi-reversible redox couples with extremely fast direct electron transfer and excellent nonenzymatic sensing ability. The electrocatalytic reduction of H2O2 showed a wide linear range from 0.035 to 3.40 mM, with a high sensitivity of 215.6 μA mM(-1) and a limit of detection (LOD) as low as 0.81 μM. The electrocatalytic oxidation of nitrite showed a linear range from 2.0 μM to 0.164 mM, with a sensitivity of 249.9 μA mM(-1) and a LOD down to 1.44 μM. Moreover, the TOAB/ZnP(p)-C60/GCE showed excellent stability and reproducibility, and good testing recoveries for analysis of the nitrite levels of river water and rainwater. The ZnP(p)-C60 can be used as a novel material for the fabrication of nonenzymatic electrochemical sensors.
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