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1.
Redox Communication within Multinuclear Iron–Sulfur Complexes Related to Electronic Interplay in the Active Site of [FeFe]Hydrogenase 下载免费PDF全文
Kai‐Ti Chu Dr. Yu‐Chiao Liu Yi‐Lan Huang Dr. Gene‐Hsiang Lee Dr. Mei‐Chun Tseng Prof. Ming‐Hsi Chiang 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(18):6852-6861
The one‐electron oxidations of a Fe2 complex lead to the formation of a persistent metal‐stabilized thiyl radical Fe2 species, mixed‐valent Fe4, and Fe8 complexes. The unpaired spin in the Fe2 radical species delocalizes over the Fe2 and the aromatic dithiolate, mostly on the terminal sulfur. The subsequent dimerization of the singly oxidized Fe2 to the Fe4 retains the partial thiyl radical character. For an analogue with less steric hindrance, the π–π stacking interaction between the dithiolato aromatic rings induces generation of the Fe8, in which process electronic structures of the species are modulated through reducing the thiyl radical to the thiolate. Electronic reorganization repeats when the Fe8 is converted to Fe4. Electronic interplay in the complexes decreases the energy gap of frontier MOs and buffers electronic impacts upon redox events. Easier accessible redox potentials and increased stability of the species are facilitated. The results demonstrate that electronic versatility of the benzenedithiolate exerts pronounced influences on electronic and coordination structure of the metal complexes. 相似文献
2.
Characterization of Novel Aminobenzylcantharidinimides and Related Imides by Proton NMR Spectra and Their Effects on NO Induction 下载免费PDF全文
Ing‐Jy Tseng Pen‐Yuan Lin Shiow‐Yunn Sheu Wan‐Ni Tung Ching‐Tung Lin Mei‐Hsiang Lin 《中国化学会会志》2015,62(1):59-63
Various acidic anhydrides including cantharidin were converted into corresponding aminobenzylcantharidinimide 3a and analogous imides 3b~k (at the ortho, meta, and para positions) with 35%~87% yields by reacting with aminobenzylamines and triethylamine. The two methyl side chains of cantharidinimides 3ao , 3am , and 3ap, and related imides had more than two chiral centers; the lone pair of electrons of nitrogen displayed a different chemical shift and coupling constant in H‐NMR spectra when the amino group of benzylamine was in the ortho position. These cantharidinimides had parent aniline, pyridine, and naphthalene plane structures, and the primary amine nucleophilicity and basicity might reflect the inductive electron’s negative effect on chemical shifts. We prepared cantharidinimides by heating the reactants cantharidin 1a , aliphatic and aromatic acid anhydrides, primary benzylic amines, and aniline derivatives to ca. 200 °C with 3 mL of dry toluene, and 1~2 mL of triethylamine in high‐pressure sealed tubes (Buchi glasuster 0032) to produce cantharidinimides and their analogues in good yields. The para‐aminobenzylic imides showed greater inhibition of nitric oxide (NO) synthesis by NO synthase (NOS) than did ortho‐ and meta‐aminobenzylic imides. Compound 3fp , para‐aminobenzylic norbonane‐imide, had the most potent effect on inducible NOS among the tested compounds and showed 35% inhibition. 相似文献
3.
Inside Back Cover: A Reversible Proton Relay Process Mediated by Hydrogen‐Bonding Interactions in [FeFe]Hydrogenase Modeling (Chem. Eur. J. 31/2015) 下载免费PDF全文
4.
Mu‐Huan Chi Chun‐Hsien Su Ming‐Hsiang Cheng Pei‐Yun Chung Chi‐How Peng Jiun‐Tai Chen 《Macromolecular rapid communications》2016,37(24):2037-2044
To manipulate the functions of nanomaterials more precisely for diverse applications, the controllability and critical influencing factors of their properties must be thoroughly investigated. In this work, the macroscopic and microscopic effects are studied on the photophysical properties of various pyrene‐ended poly(styrene‐block‐methyl methacrylate) nanostructures. Fluorescent polymer nanospheres, nanorods, and nanotubes are prepared by different template‐based methods using anodic aluminum oxide membranes. Chain arrangements and conformations are determined as the key factors affecting the photophysical properties of the fluorescent polymer nanostructures. This work not only gives a deeper understanding of the effects on the photophysical properties of polymer nanomaterials influenced by morphologies, chain arrangements, and chain conformations, but also provides a reference for designing proper fluorescent nanostructures for specific applications.
5.
Cheng Hung Chu Ming Lun Tseng Jie Chen Pin Chieh Wu Yi‐Hao Chen Hsiang‐Chu Wang Ting‐Yu Chen Wen Ting Hsieh Hui Jun Wu Greg Sun Din Ping Tsai 《Laser \u0026amp; Photonics Reviews》2016,10(6):986-994
We propose all‐dielectric metasurfaces that can be actively re‐configured using the phase‐change material Ge2Sb2Te5 (GST) alloy. With selectively controlled phase transitions on the composing GST elements, metasurfaces can be tailored to exhibit varied functionalities. Using phase‐change GST rod as the basic building block, we have modelled metamolecules with tunable optical response when phase change occurs on select constituent GST rods. Tunable gradient metasurfaces can be realized with variable supercell period consisting of different patterns of the GST rods in their amorphous and crystalline states. Simulation results indicate a range of functions can be delivered, including multilevel signal modulating, near‐field coupling of GST rods, and anomalous reflection angle controlling. This work opens up a new space in exploring active meta‐devices with broader applications that cannot be achieved in their passive counterparts with permanent properties once fabricated.
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The reaction of the thiocarbamoyl‐molybdenum complex [Mo(CO)2(η2‐SCNMe2)(PPh3)2Cl] 1 , with EtOCS2K and C4H8NCS2NH4 in dichloromethane at room temperature yielded the seven coordinated ethyldithiocarbonate thiocarbamoyl‐molybdenum complex [Mo(CO)2(η2‐S2COEt)(η2‐SCNMe2)(PPh3)] 2 , and the dithiocarbamate thiocarbamoyl‐molybdenum complex [Mo(CO)2(η2‐S2CNC4H8)(η2‐SCNMe2)(PPh3)] 3 . The geometry around the metal atom of compounds 2 and 3 are capped octahedrons as revealed by X‐ray diffraction analyses. The thiocarbamoyl and ethyldithiocarbonate or pyrrolidinyldithiocarbamate ligands coordinate to the molybdenum metal center through the carbon and sulfur and two sulfur atoms, respectively. Structure parameters, NMR, IR and Mass spectra are in agreement with the crystal chemistry of the two compounds. 相似文献
9.
Jayachandran Jayakumar Kanniyappan Parthasarathy Yi‐Hsiang Chen Tai‐Hua Lee Shih‐Ching Chuang Chien‐Hong Cheng 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2014,126(37):10047-10050
A new method for the synthesis of highly substituted naphthyridine‐based polyheteroaromatic compounds in high yields proceeds through rhodium(III)‐catalyzed multiple C H bond cleavage and C C and C N bond formation in a one‐pot process. Such highly substituted polyheteroaromatic compounds have attracted much attention because of their unique π‐conjugation, which make them suitable materials for organic semiconductors and luminescent materials. Furthermore, a possible mechanism, which involves multiple chelation‐assisted ortho C H activation, alkyne insertion, and reductive elimination, is proposed for this transformation. 相似文献
10.
In this study, an improved process for the synthesis of etorphine and dihydroetorphine from codeine with an overall yield of 2.7% and 1.5% respectively is described. The structure of 19‐propylthevinol 7 was verfied by X‐ray structure analysis. This result is promising for synthesizing various morphine‐based drugs. 相似文献