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121.
Caleb J. Hiller Dr. Chi Chung Lee Dr. Martin T. Stiebritz Lee A. Rettberg Prof. Dr. Yilin Hu 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(10):2389-2395
Nitrogenase utilizes an ATP-dependent reductase to deliver electrons to its catalytic component to enable two important reactions: the reduction of N2 to NH4+, and the reduction of CO to hydrocarbons. The two nitrogenase-based reactions parallel the industrial Haber–Bosch and Fischer–Tropsch processes, yet they occur under ambient conditions. As such, understanding the enzymatic mechanism of nitrogenase is crucial for the future development of biomimetic strategies for energy-efficient production of valuable chemical commodities. Mechanistic investigations of nitrogenase has long been hampered by the difficulty to trap substrates and intermediates relevant to the nitrogenase reactions. Recently, we have successfully captured CO on the Azotobacter vinelandii V-nitrogenase via two approaches that alter the electron fluxes in a controlled manner: one approach utilizes an artificial electron donor to trap CO on the catalytic component of V-nitrogenase in the resting state; whereas the other employs a mismatched reductase component to reduce the electron flux through the system and consequently accumulate CO on the catalytic component of V-nitrogenase. Here we summarize the major outcome of these recent studies, which not only clarified the catalytic relevance of the one-CO (lo-CO) and multi-CO (hi-CO) bound states of nitrogenase, but also pointed to a potential competition between N2 and CO for binding to the same pair of reactive Fe sites across the sulfur belt of the cofactor. Together, these results highlight the utility of these strategies in poising the cofactor at a well-defined state for substrate- or intermediate-trapping via controlled alteration of electron fluxes, which could prove beneficial for further elucidation of the mechanistic details of nitrogenase-catalyzed reactions. 相似文献
122.
Fengfeng Chi Yanguang Qin Shaoshuai Zhou Xiantao Wei Yonghu Chen Changkui Duan Min Yin 《Current Applied Physics》2017,17(1):24-30
In order to clarify the site occupancy of rare-earth ions in rare-earth doped perovskite materials, the un-doped pure CaTiO3 and Eu3+-doped CaTiO3 samples with a series of Ca/Ti ratio were synthesized via high-temperature solid-state reaction method. X-ray diffraction (XRD) powder patterns confirm that the crystal structure keeps invariant at various Ca/Ti ratios. Measurement results of unit-cell parameters and X-ray photoelectron spectroscopy (XPS) indicate that Eu3+ ions enter into the Ca2+ site. The high-resolution photoluminescence spectra of Eu3+ ions at 20 K in all samples did not witness a significant change under the excitation at different wavelength, implying that Eu3+ ions occupy only one type of site. Considering the small spectral splitting range of 5D0 → 7F2 transition and the large intensity ratio of 5D0 → 7F2/5D0 → 7F1, it can be concluded that Eu3+ occupies Ca2+ site with larger coordinate numbers rather than Ti4+ site. 相似文献
123.
A model study of DNA-directed peptide ligation has been developed by transferring fluorescent reporting group from small molecule thioester to a DNA strand (template DNA) in the presence of a thiol-functionalized DNA strand (auxiliary DNA), mimicking the Native Chemical Ligation (NCL) reaction. This DNA-directed transfer shows dependence on the sequence complementarity of the two DNA strands, with in situ generated 4-thiolphenylmethyl functionalized oligonucleotide as the auxiliary DNA strand, under mild basic condition (pH=8.5), and with tris(2-carboxyethyl) phosphine hydrochloride (TCEP) as a reducing agent. Reactions with different amino acid α-thioesters resulted in varied transfer efficiencies from glycine to α-substituted amino acids. This study has provided the basic foundation to use DNA-programmed chemistry toward the chemical synthesis or unnatural modification of protein molecules. 相似文献
124.
Dr. Xiong‐Jie Jiang Dr. Janet T. F. Lau Dr. Qiong Wang Prof. Dennis K. P. Ng Prof. Pui‐Chi Lo 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(24):8273-8281
A diiodo distyryl boron dipyrromethene (BODIPY) core was conjugated to two ferrocenyl quenchers through acid‐labile ketal and/or thiol‐cleavable disulfide linkers, of which the fluorescence and photosensitizing properties were significantly quenched through a photoinduced electron‐transfer process. The two symmetrical analogues that contained either the ketal or disulfide linkers could only be activated by a single stimulus, whereas the unsymmetrical analogue was responsive to dual stimuli. Upon interaction with acid and/or dithiothreitol (DTT), these linkers were cleaved selectively. The separation of the BODIPY core and the ferrocenyl moieties restored the photoactivities of the former in phosphate buffered saline and inside the MCF‐7 breast cancer cells, rendering these compounds as potential activable photosensitizers for targeted photodynamic therapy. The dual activable analogue exhibited the greatest enhancement in intracellular fluorescence intensity in both an acidic environment (pH 5) and the presence of DTT (4 mm ). Its photocytotoxicity against MCF‐7 cells also increased by about twofold upon preincubation with 4 mm of DTT. The activation of this compound was also demonstrated in nude mice bearing a HT29 human colorectal carcinoma. A significant increase in fluorescence intensity in the tumor was observed over 9 h after intratumoral injection. 相似文献
125.
126.
Abstract 1,1′-Dihydroxyethyl-2,2′-biimidazole has been used as a copolymerizing monomer with the diglycidyl ether of bisphenol A in the preparation of biimidazole-containing epoxy polymers. Polymerization reactions were studied in bulk, with and without catalyst, and in N,N-dimethylforma-mide and anisole solvents, with and without catalyst. FT-IR and NMR spectra, molecular weight, thermal and solubility characteristics were obtained. Polymers isolated as amorphous light brown solids were found to be only sparingly soluble in THF or in highly polar nitrogen-containing solvents (DMF, NMP, pyridine). These materials exhibited molecular weights up to 37 000 for SnC14-catalyzed polymerization carried out in DMF. A glass-transition temperature of 391°C was observed for polymers obtained under uncatalyzed solventless conditions. The glass transition temperature was 373°C for product obtained under SnC14-catalyzed, solventless conditions. Thermogravimetric analysis in air of polymers obtained under varying solvent and catalyst conditions showed less than 25% weight loss below 330°C and greater than 75% weight loss above 400°C. 相似文献
127.
128.
Phthalocyanines have been used as photodynamic therapy (PDT) agents because of their uniquely favorable optical properties and high photostability. They have been shown to be highly successful for the treatment of cancer through efficient singlet‐oxygen (1O2) production. However, due to their hydrophobic properties, the considerations of solubility and cellular location have made understanding their photophysics in vitro and in vivo difficult. Indeed, many quantitative assessments of PDT reagents are undertaken in purely organic solvents, presenting challenges for interpreting observations during practical application in vivo. With steady‐state and time‐resolved laser spectroscopy, we show that for axial ligated silicon phthalocyanines in aqueous media, both the water:lipophile ratio and the pH have drastic effects on their photophysics, and ultimately dictate their functionality as PDT drugs. We suggest that considering the presented photophysics for PDT drugs in aqueous solutions leads to guidelines for a next generation of even more potent PDT agents. 相似文献
129.
Prof. Dr. Minghuey Shieh Chun‐Hsien Yu Yen‐Yi Chu Yu‐Wen Guo Chung‐Yi Huang Kai‐Jieah Hsing Pei‐Chi Chen Chung‐Feng Lee 《化学:亚洲杂志》2013,8(5):963-973
The reactions of E powder (E=S, Se) with a mixture of Cr(CO)6 and Mn2(CO)10 in concentrated solutions of KOH/MeOH produced two new mixed Cr? Mn? carbonyl clusters, [E2CrMn2(CO)9]2? (E=S, 1 ; Se, 2 ). Clusters 1 and 2 were isostructural with one another and each displayed a trigonal‐bipyramidal structure, with the CrMn2 triangle axially capped by two μ3‐E atoms. The analogous telluride cluster, [Te2CrMn2(CO)9]2? ( 3 ), was obtained from the ring‐closure of Te2Mn2 ring complex [Te2Mn2Cr2(CO)18]2? ( 4 ). Upon bubbling with CO, clusters 2 and 3 were readily converted into square‐pyramidal clusters, [E2CrMn2(CO)10]2? (E=Se, 5 ; Te, 6 ), accompanied with the cleavage of one Cr? Mn bond. According to SQUID analysis, cluster 6 was paramagnetic, with S=1 at room temperature; however, the Se analogue ( 5 ) was spectroscopically proposed to be diamagnetic, as verified by TD‐DFT calculations. Cluster 6 could be further carbonylated, with cleavage of the Mn? Mn bond to produce a new arachno‐cluster, [Te2CrMn2(CO)11]2? ( 7 ). The formation and structural isomers, as well as electrochemistry and UV/Vis absorption, of these clusters were also elucidated by DFT calculations. 相似文献
130.
Chi Fang Ting Xiong Jie Hou Jing Wei Gu Mei Hu Sheng 《Journal of Dispersion Science and Technology》2013,34(4):604-610
Amidoxime (AO)/amine co-functionalized polypropylene fiber adsorbents were prepared. The all-polymeric structures were characterized by using Fourier transform infrared spectroscopy (FTIR), optical microscope, contact angle meter and electron spin resonance (ESR) analysis methods, confirming the grafting, modification, and amidoximation stages gravimetrically, spectroscopically, and visually. The properties for the removal of uranyl(VI) from aqueous solutions were investigated. For amidoxime (AO) fiber, high adsorption rate was observed within the first 30 minutes and the plateau value of 40.6% uranium loading (0.0812 mg/g) was reached at around 30 minutes. The adsorption equilibrium for AO/amine fiber was attained within 20 minutes, resulting in the adsorption of 92.6% uranium loading (0.185 mg/g). The percentage of adsorption increases with increasing pH value (2–6), reaches a maximum at pH 6.0 and then remains almost constant for AO/amine fiber, whereas reduces slightly for AO fiber. 相似文献