Efficient alkane hydroxylation catalysis of nickel(ii) complexes with oxazoline donor containing tripodal tetradentate ligands

2020 ◽  
Vol 49 (18) ◽  
pp. 6108-6118
Author(s):  
Ikumi Terao ◽  
Sena Horii ◽  
Jun Nakazawa ◽  
Masaya Okamura ◽  
Shiro Hikichi

Nickel(ii) complexes with oxazoline-based tripodal ligands are efficient catalysts for alkane oxidation, and reaction rates and oxidizing position selectivity are controlled by the structural properties of the substituent groups on the ligands.

2002 ◽  
Vol 716 ◽  
Author(s):  
You-Seok Suh ◽  
Greg Heuss ◽  
Jae-Hoon Lee ◽  
Veena Misra

AbstractIn this work, we report the effects of nitrogen on electrical and structural properties in TaSixNy /SiO2/p-Si MOS capacitors. TaSixNy films with various compositions were deposited by reactive sputtering of TaSi2 or by co-sputtering of Ta and Si targets in argon and nitrogen ambient. TaSixNy films were characterized by Rutherford backscattering spectroscopy and Auger electron spectroscopy. It was found that the workfunction of TaSixNy (Si>Ta) with varying N contents ranges from 4.2 to 4.3 eV. Cross-sectional transmission electron microscopy shows no indication of interfacial reaction or crystallization in TaSixNy on SiO2, resulting in no significant increase of leakage current in the capacitor during annealing. It is believed that nitrogen retards reaction rates and improves the chemical-thermal stability of the gate-dielectric interface and oxygen diffusion barrier properties.


2017 ◽  
Vol 83 (21) ◽  
Author(s):  
Jie-Liang Liang ◽  
Yuan Gao ◽  
Zheng He ◽  
Yong Nie ◽  
Meng Wang ◽  
...  

ABSTRACT n-Alkanes are ubiquitous in nature and are widely used by microorganisms as carbon sources. Alkane hydroxylation by alkane monooxygenases is a critical step in the aerobic biodegradation of n-alkanes, which plays important roles in natural alkane attenuation and is used in industrial and environmental applications. The alkane oxidation operon, alkW1-alkX, in the alkane-degrading strain Dietzia sp. strain DQ12-45-1b is negatively autoregulated by the TetR family repressor AlkX via a product positive feedback mechanism. To predict the gene regulation mechanism, we determined the 3.1-Å crystal structure of an AlkX homodimer in a non-DNA-bound state. The structure showed traceable long electron density deep inside a hydrophobic cavity of each monomer along the long axis of the helix bundle, and further gas chromatography-mass spectrometry analysis of AlkX revealed that it contained the Escherichia coli-derived long-chain fatty acid molecules as a ligand. Moreover, an unusual structural feature of AlkX is an extra helix, α6′, forming a lid-like structure with α6 covering the inducer-binding pocket and occupying the space between the two symmetrical DNA-binding motifs in one dimer, indicating a distinct conformational transition mode in modulating DNA binding. Sequence alignment of AlkX homologs from Dietzia strains showed that the residues involved in DNA and inducer binding are highly conserved, suggesting that the regulation mechanisms of n-alkane hydroxylation are possibly a common characteristic of Dietzia strains. IMPORTANCE With n-alkanes being ubiquitous in nature, many bacteria from terrestrial and aquatic environments have evolved n-alkane oxidation functions. Alkane hydroxylation by alkane monooxygenases is a critical step in the aerobic biodegradation of n-alkanes, which plays important roles in natural alkane attenuation and petroleum-contaminating environment bioremediation. The gene regulation of the most common alkane hydroxylase, AlkB, has been studied widely in Gram-negative bacteria but has been less explored in Gram-positive bacteria. Our previous study showed that the TetR family regulator (TFR) AlkX negatively autoregulated the alkane oxidation operon, alkW1-alkX, in the Gram-positive strain Dietzia sp. strain DQ12-45-1b. Although TFRs are one of the most common transcriptional regulator families in bacteria, the TFR involved in n-alkane metabolism has been reported only recently. In this study, we determined the crystal structure of AlkX, which implies a distinct DNA/ligand binding mode. Our results shed light upon the regulation mechanism of the common alkane degradation process in nature.


Author(s):  
V. Annamalai ◽  
L.E. Murr

Economical recovery of copper metal from leach liquors has been carried out by the simple process of cementing copper onto a suitable substrate metal, such as scrap-iron, since the 16th century. The process has, however, a major drawback of consuming more iron than stoichiometrically needed by the reaction.Therefore, many research groups started looking into the process more closely. Though it is accepted that the structural characteristics of the resultant copper deposit cause changes in reaction rates for various experimental conditions, not many systems have been systematically investigated. This paper examines the deposit structures and the kinetic data, and explains the correlations between them.A simple cementation cell along with rotating discs of pure iron (99.9%) were employed in this study to obtain the kinetic results The resultant copper deposits were studied in a Hitachi Perkin-Elmer HHS-2R scanning electron microscope operated at 25kV in the secondary electron emission mode.


1996 ◽  
Vol 1 (3) ◽  
pp. 200-205 ◽  
Author(s):  
Carlo Umiltà ◽  
Francesca Simion ◽  
Eloisa Valenza

Four experiments were aimed at elucidating some aspects of the preference for facelike patterns in newborns. Experiment 1 showed a preference for a stimulus whose components were located in the correct arrangement for a human face. Experiment 2 showed a preference for stimuli that had optimal sensory properties for the newborn visual system. Experiment 3 showed that babies directed their attention to a facelike pattern even when it was presented simultaneously with a non-facelike stimulus with optimal sensory properties. Experiment 4 showed the preference for facelike patterns in the temporal hemifield but not in the nasal hemifield. It was concluded that newborns' preference for facelike patterns reflects the activity of a subcortical system which is sensitive to the structural properties of the stimulus.


1998 ◽  
Vol 08 (PR2) ◽  
pp. Pr2-47-Pr2-50
Author(s):  
O. Crisan ◽  
J. M. Le Breton ◽  
F. Machizaud ◽  
A. Jianu ◽  
J. Teillet ◽  
...  

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