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1.
Sci Rep ; 10(1): 3786, 2020 Mar 02.
Article in English | MEDLINE | ID: mdl-32123211

ABSTRACT

The Kibi Plateau in the active Japanese Islands consists of mainly Permian to Cretaceous rocks that have been deeply weathered into a red soil, comprising a peneplain with U-shaped valley. Systematic geological analyses of the Eocene fluvial deposits revealed the paleo-rivers that existed in the eastern Asian continent and streamed out to the paleo-Pacific Ocean. Each paleo-river is traced in a flow line shape without any significant vertical and horizontal displacement. The Eocene shallow marine sediments in a possible coastal region have no relevant inclination. These geological data strongly suggest that the Kibi Plateau has been a stable-coherent tectonic unit since the Eocene through the opening of the Japan Sea and the associated quick rotation of SW Japan in the Middle Miocene. The Kibi Plateau region with a thick crust over 30 km existed as a stable eastern segment of the Asian continent in the Eocene. The Kibi Plateau tectonic unit drifted to the south without any destruction due to the peripheral successive tectonic events such as the Philippine Sea plate subduction and the reactivation of Median Tectonic Line. No subduction related arc volcanism since the Eocene has also influenced to preserve the stable tectonic unit.

2.
Molecules ; 23(3)2018 Mar 05.
Article in English | MEDLINE | ID: mdl-29510575

ABSTRACT

The fac-Ir(ppy)3 complex, where ppy denotes 2-phenylpyridine, is one of the well-known luminescent metal complexes having a high quantum yield. However, there have been no specific molecular design guidelines for color tuning. For example, it is still unclear how its optical properties are changed when changing substitution groups of ligands. Therefore, in this study, differences in the electronic structures and optical properties among several substituted fac-Ir(ppy)3 derivatives are examined in detail by density functional theory (DFT) and time-dependent DFT (TD-DFT) calculations. On the basis of those results, we present rational design guidelines for absorption and emission color tuning by modifying the species of substituents and their substitution positions.


Subject(s)
Coordination Complexes/chemical synthesis , Iridium/chemistry , Pyridines/chemistry , Color , Drug Design , Guidelines as Topic , Ligands , Luminescence , Luminescent Measurements , Molecular Structure , Quantum Theory , Structure-Activity Relationship
3.
Appl Environ Microbiol ; 84(7)2018 04 01.
Article in English | MEDLINE | ID: mdl-29374031

ABSTRACT

Sphingobium sp. strain SYK-6 converts four stereoisomers of arylglycerol-ß-guaiacyl ether into achiral ß-hydroxypropiovanillone (HPV) via three stereospecific reaction steps. Here, we determined the HPV catabolic pathway and characterized the HPV catabolic genes involved in the first two steps of the pathway. In SYK-6 cells, HPV was oxidized to vanilloyl acetic acid (VAA) via vanilloyl acetaldehyde (VAL). The resulting VAA was further converted into vanillate through the activation of VAA by coenzyme A. A syringyl-type HPV analog, ß-hydroxypropiosyringone (HPS), was also catabolized via the same pathway. SLG_12830 (hpvZ), which belongs to the glucose-methanol-choline oxidoreductase family, was isolated as the HPV-converting enzyme gene. An hpvZ mutant completely lost the ability to convert HPV and HPS, indicating that hpvZ is essential for the conversion of both the substrates. HpvZ produced in Escherichia coli oxidized both HPV and HPS and other 3-phenyl-1-propanol derivatives. HpvZ localized to both the cytoplasm and membrane of SYK-6 and used ubiquinone derivatives as electron acceptors. Thirteen gene products of the 23 aldehyde dehydrogenase (ALDH) genes in SYK-6 were able to oxidize VAL into VAA. Mutant analyses suggested that multiple ALDH genes, including SLG_20400, contribute to the conversion of VAL. We examined whether the genes encoding feruloyl-CoA synthetase (ferA) and feruloyl-CoA hydratase/lyase (ferB and ferB2) are involved in the conversion of VAA. Only FerA exhibited activity toward VAA; however, disruption of ferA did not affect VAA conversion. These results indicate that another enzyme system is involved in VAA conversion.IMPORTANCE Cleavage of the ß-aryl ether linkage is the most essential process in lignin biodegradation. Although the bacterial ß-aryl ether cleavage pathway and catabolic genes have been well documented, there have been no reports regarding the catabolism of HPV or HPS, the products of cleavage of ß-aryl ether compounds. HPV and HPS have also been found to be obtained from lignin by chemoselective catalytic oxidation by 2,3-dichloro-5,6-dicyano-1,4-benzoquinone/tert-butyl nitrite/O2, followed by cleavage of the ß-aryl ether with zinc. Therefore, value-added chemicals are expected to be produced from these compounds. In this study, we determined the SYK-6 catabolic pathways for HPV and HPS and identified the catabolic genes involved in the first two steps of the pathways. Since SYK-6 catabolizes HPV through 2-pyrone-4,6-dicarboxylate, which is a building block for functional polymers, characterization of HPV catabolism is important not only for understanding the bacterial lignin catabolic system but also for lignin utilization.


Subject(s)
Ethers/metabolism , Genes, Bacterial/genetics , Sphingomonadaceae/genetics , Escherichia coli/genetics , Escherichia coli/metabolism , Microorganisms, Genetically-Modified/genetics , Microorganisms, Genetically-Modified/metabolism , Sphingomonadaceae/metabolism
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