Optical properties of Al‐doped ZnO thin films deposited by two different sputtering methods

Aluminum‐doped zinc oxide (AZO) thin films were deposited on sapphire (002) and glass substrates by two different sputtering techniques radio frequency magnetron cosputtering of AZO and ZnO targets and sputtering of an AZO target. The dependence of the photoluminescence (PL) and transmittance properties of the AZO films deposited by cosputtering and sputtering on the AZO/ZnO target power ratio, R and the O₂/Ar flow ratio, r were investigated, respectively. Only a deep level emission peak appears in the PL spectra of cosputtered AZO films whereas both UV emission and deep level emission peaks are observed in the PL spectra of sputtered AZO films. The absorption edges in the transmittance spectra of the AZO films shift to the lower wavelength region as R and r increase. Also effects of crystallinity, surface roughness, PL on the transmittance of the AZO films were explained using the X‐ray diffraction (XRD), atomic force microscopy (AFM), and PL analysis results. (© 2006 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Effects of cooling rate and post-heat treatment on properties of ZnO thin films deposited by sol-gel method

Sol-gel spin-coated ZnO thin films are cooled with different rates after the pre-heat treatment. Atomic force microscopy (AFM), X-ray diffraction (XRD), Raman, and photoluminescence (PL) were carried out to investigate the effects of the cooling rate during pre-heat treatment on structural and optical properties of the ZnO thin films. The ZnO thin films cooled slowly exhibit mountain chain structure while the ones cooled rapidly have smooth surface. The ZnO thin films cooled rapidly have higher c-axis orientation compared to the ones cooled slowly. The narrower and the higher near-band-edge emission (NBE) peaks are observed in the ZnO thin films cooled rapidly.     

Hydration of nitriles: an examination in terms of No Barrier Theory

Nitriles pose an interesting problem to the explanatory powers of organic chemistry because, despite the favorable overall thermodynamics of hydrolysis to the corresponding amides, the reactions are inherently slow. The rate determining step is hydration of the nitrile to give the imidic acid, which quickly tautomerizes to the amide. In terms of Marcus Theory, the intrinsic barriers for acid and base‐catalyzed hydration are higher for nitriles than for amides, which are themselves slow reactions. It is remarkable that hydration of a nitrile, for which the free energy change is close to zero except for polyhaloacetonitriles, is much slower than hydration of an amide, which is energetically unfavorable. This can be explained by No Barrier Theory in terms of the high energetic cost of the geometrical distortions in “one thing at a time” corner species. There are no experimental equilibrium constants for this initial hydration step, so we have determined them computationally. The free energy change for the initial hydration is small; it is the fast and energetically downhill second step, tautomerization to the amide, which makes the overall hydrolysis of nitrile to amide thermodynamically favorable. Very few of the pK_a values needed in the acid and base‐catalyzed mechanisms are known, so we used linear free energy relations and treat the parent pK_a values as adjustable parameters. This procedure leads to pK_a values in accord with expectation based on such data as are available and permits calculation of rate constants in satisfactory agreement with experiment. Copyright © 2013 John Wiley & Sons, Ltd.     

Elemental surface enrichment in flame synthesis: A mechanism associated with particle melting-solidification

Elemental surface enrichment is important for functionalities of flame-synthesized particle materials, but its mechanism is poorly understood. In this paper, a mechanism associated with particle melting-solidification is proposed based on an experimental study. Y₂O₃:Eu particles were generated by flame assisted spray pyrolysis (FASP), using H₂/O₂ flames or H₂/air flames. The particles were analyzed by transmission electron microscopy (TEM), X-ray diffraction (XRD), inductively coupled plasma mass spectrometry (ICP-MS), and X-ray photoelectron spectroscopy (XPS). H₂/O₂ flames resulted in particles with Eu surface enrichment, i.e. the surface Eu concentration was several times higher than the overall Eu concentration; there was no elemental surface enrichment in particles from H₂/air flames. The Eu surface enrichment in H₂/O₂ flames was attributed to elemental partitioning during solidification of molten Y₂O₃:Eu particles; in H₂/air flames the particles did not melt and hence there was no elemental surface enrichment. The findings of this study suggest that elemental surface enrichment may be a common phenomenon for binary metal oxide particles that experience melting-solidification. Such particles should be examined for elemental surface enrichment, both for understanding their functionality and for their potential biological effects.     

Silencing of KIF14 interferes with cell cycle progression and cytokinesis by blocking the p27Kip1 ubiquitination pathway in hepatocellular carcinoma

Although it has been suggested that kinesin family member 14 (KIF14) has oncogenic potential in various cancers, including hepatocellular carcinoma (HCC), the molecular mechanism of this potential remains unknown. We aimed to elucidate the role of KIF14 in hepatocarcinogenesis by knocking down KIF14 in HCC cells that overexpressed KIF14. After KIF14 knockdown, changes in tumor cell growth, cell cycle and cytokinesis were examined. We also examined cell cycle regulatory molecules and upstream Skp1/Cul1/F-box (SCF) complex molecules. Knockdown of KIF14 resulted in suppression of cell proliferation and failure of cytokinesis, whereas KIF14 overexpression increased cell proliferation. In KIF14-silenced cells, the levels of cyclins E1, D1 and B1 were profoundly decreased compared with control cells. Of the cyclin-dependent kinase inhibitors, the p27^Kip1 protein level specifically increased after KIF14 knockdown. The increase in p27^Kip1 was not due to elevation of its mRNA level, but was due to inhibition of the proteasome-dependent degradation pathway. To explore the pathway upstream of this event, we measured the levels of SCF complex molecules, including Skp1, Skp2, Cul1, Roc1 and Cks1. The levels of Skp2 and its cofactor Cks1 decreased in the KIF14 knockdown cells where p27^Kip1 accumulated. Overexpression of Skp2 in the KIF14 knockdown cells attenuated the failure of cytokinesis. On the basis of these results, we postulate that KIF14 knockdown downregulates the expression of Skp2 and Cks1, which target p27^Kip1 for degradation by the 26S proteasome, leading to accumulation of p27^Kip1. The downregulation of Skp2 and Cks1 also resulted in cytokinesis failure, which may inhibit tumor growth. To the best of our knowledge, this is the first report that has identified the molecular target and oncogenic effect of KIF14 in HCC.     

Synthesis,Characterization, Self‐Assembly,Gelation, Morphology and Computational Studies of Alkynylgold(III) Complexes of 2,6‐Bis(benzimidazol‐2′‐yl)pyridine Derivatives

A novel class of alkynylgold(III) complexes of the dianionic ligands derived from 2,6‐bis(benzimidazol‐2′‐yl)pyridine (H₂bzimpy) derivatives has been synthesized and characterized. The structure of one of the complexes has also been determined by X‐ray crystallography. Electronic absorption studies showed low‐energy absorption bands at 378–466 nm, which are tentatively assigned as metal‐perturbed π–π* intraligand transitions of the bzimpy^2? ligands. A computational study has been performed to provide further insights into the nature of the electronic transitions for this class of complexes. One of the complexes has been found to show gelation properties, driven by π–π and hydrophobic–hydrophobic interactions. This complex exhibited concentration‐ and temperature‐dependent ¹H NMR spectra. The morphology of the gel has been characterized by transmission electron microscopy (TEM) and scanning electron microscopy (SEM).     

The quenching of nucleon yields in the nonmesonic weak decay of Λ -hypernuclei and the three-body weak decay process

Recent exclusive coincidence measurements of non-mesonic weak decays (NMWD) reported for the ratio of the partial decay width of neutron-induced-to-proton-induced NMWD, Γ_n/Γ_p , values of 0.45±0.11±0.03 and 0.51±0.13±0.04 for 5lam and ¹² _Λ C , respectively. These observations agree well with the improved theoretical Γ_n/Γ_p ratios which are in the range of 0.3-0.7. It appears that the long-standing discrepancy between the experimental and theoretical values of Γ_n/Γ_p has finally been solved. However, when compared to the results of intra-nuclear cascade (INC) calculations, the observed numbers of both single nucleons and coincident nucleon pairs are strongly quenched. The quenching of the proton yield observed previously has been interpreted as an increase of the Γ_n/Γ_p ratio. On the other hand, significant contributions from the two-nucleon-induced three-body process ΛNN → nNN are predicted. Indeed, the angular correlation of the emitted nucleon pairs in the NMWD of ¹² _Λ C showed not only decay events in back-to-back kinematics, but also events with non-back-to-back kinematics. In this paper we show that the difficulties to extract the correct Γ_n/Γ_p ratio from the proton spectra is related to the three-body weak-interaction process which strongly quenches the nucleon yields.     

Interfacial structure and properties in polystyrene/epoxy bilayer films

The interfacial structure and properties of immiscible deuterated polystyrene (dPS)/epoxy bilayer films were investigated with neutron reflectivity as functions of the composition of the epoxy layer, the thickness of the dPS layer, and the annealing time. We have found that the interfacial width and its growth rate depend strongly on the compositions of the epoxy layer but only weakly on the thickness of the dPS layer. The effect of the resin/crosslinker composition on the interfacial width and its growth rate is likely due to the different near‐surface structures that result for different epoxy stoichiometries. For an ultra‐thin dPS film (thickness = 2R_g), the data suggest a slight suppression of the growth of the interfacial width that could be due to confinement effects for the long‐chain molecules such as have been previously reported for a thickness of less than approximately 4R_g, where R_g is the radius of gyration of polymer molecules. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 40: 2653–2660, 2002     

Synthesis and photochemical properties of trans‐2‐(2‐aryl‐ or heteroarylvinyl)‐4,5‐dichloropyridazin‐3(2H)‐ones

trans‐2‐(2‐Aryl‐ or heteroarylvinyl)‐4,5‐dichloropyridazin‐3(2H)‐ones 3 were synthesized from 4,5‐dichloropyridazin‐3(2H)‐one via 2 step. The photochemical behavior of 3 in THF, methylene chloride, acetonitrile and methanol is dependent on the kind of aryl or heterocyclic ring and the solvent polarity