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The catalytic function of the previously synthesized and characterized [(L)MoFe(3)S(4)Cl(3)](2)(-)(,3)(-) clusters (L = tetrachlorocatecholate, citrate, citramalate, methyliminodiacetate, nitrilotriacetate, thiodiglycolate) and of the [MoFe(3)S(4)Cl(3)(thiolactate)](2)(4)(-) and [(MoFe(3)S(4)Cl(4))(2)(&mgr;-oxalate)](4)(-) clusters in the reduction of N(2)H(4) to NH(3) is reported. In the catalytic reduction, which is carried out at ambient temperature and pressure, cobaltocene and 2,6-lutidinium chloride are supplied externally as electron and proton sources, respectively. In experiments where the N(2)H(4) to the [(L)MoFe(3)S(4)Cl(3)](n)()(-) catalyst ratio is 100:1, and over a period of 30 min, the reduction proceeds to 92% completion for L = citrate, 66% completion for L = citramalate, and 34% completion for L = tetrachlorocatecholate. The [Fe(4)S(4)Cl(4)](2)(-) cluster is totally inactive and gives only background ammonia measurements. Inhibition studies with PEt(3) and CO as inhibitors show a dramatic decrease in the catalytic efficiency. These results are consistent with results obtained previously in our laboratory and strongly suggest that N(2)H(4) activation and reduction occur at the Mo site of the [(L)MoFe(3)S(4)Cl(3)](2)(-)(, 3)(-) clusters. A possible pathway for the N(2)H(4) reduction on a single metal site (Mo) and a possible role for the carboxylate ligand are proposed. The possibility that the Mo-bound polycarboxylate ligand acts as a proton delivery "shuttle" during hydrazine reduction is considered. 相似文献
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Analytical methodology was developed and validated for the determination of spiroxamine residues in grapes, must, and wine by gas chromatography/ion trap-mass spectrometry (GC/IT-MS). Two extraction procedures were used: the first involved grapes, must, and wine extraction with alkaline cyclohexane-dichloromethane (9 + 1, v/v) solution, and the second grape extraction with acetone, dichloromethane, and petroleum ether. In both procedures, the extract was centrifuged, evaporated to dryness, and reconstituted in cyclohexane or 2,2,4-trimethylpentane-toluene (9 + 1, v/v), respectively. Spiroxamine diastereomers A and B were determined by GC/IT-MS, and a matrix effect was observed in the case of grapes but not in must and wine. Recovery of spiroxamine from fortified samples at 0.02 to 5.0 mg/kg ranged from 78-102% for grapes and must, with relative standard deviation (RSD) <13%; for red and white wines, recoveries ranged from 90 to 101% with RSD <9%. The limit of quantification was 0.02 mg/kg for grapes, must, and wine or 0.10 mg/kg for grapes, depending on the extraction procedure used. 相似文献
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Many cities all over the world are making large investments for the construction of big network infrastructures, in order to offer to local public organizations, businesses and citizens high speed connectivity, and on top of them useful e-services, aiming to achieve various social and economic objectives. The value generated from these costly ‘digital city’ investments is actually the value provided to the citizens and businesses by the e-services that will be developed and run on these network infrastructures. This paper proposes and validates a structured methodology for assessing and improving e-services developed in digital cities. The proposed methodology assesses the various types of value generated by an e-service, and also the relations among them, allowing a more structured evaluation, a deeper understanding of the value generation process and also identification and prioritization of the improvements that should be made in the e-service with the usually scarce resources in municipalities. This methodology is applied for the evaluation of an e-learning service developed in the Greek city of Karlovassi for young citizens, and also for the prioritization of the necessary improvements in it. The above application provided positive and encouraging evidence concerning the validity, usefulness and applicability of the proposed method. 相似文献
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Jörg Fliege Konstantinos Kaparis Banafsheh Khosravi 《European Journal of Operational Research》2012,217(2):233-240
Operations research techniques have been used in the space industry since its infancy, and various competing methods and codes, with widely varying characteristics, have been used over time. This survey is intended to give an overview of current application cases of different operations research techniques and methodologies in the domain of space engineering and space science. 相似文献
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Diblock copolymers of polystyrene‐b‐poly(1,3‐cyclohexadiene) exhibiting unique three‐phase microdomain morphologies 下载免费PDF全文
Konstantinos Misichronis Jihua Chen Jong K. Kahk Adam Imel Mark Dadmun Kunlun Hong Nikos Hadjichristidis Jimmy W. Mays Apostolos Avgeropoulos 《Journal of Polymer Science.Polymer Physics》2016,54(16):1564-1572
The synthesis and molecular characterization of a series of conformationally asymmetric polystyrene‐block‐poly(1,3‐cyclohexadiene) (PS‐b‐PCHD) diblock copolymers (PCHD: ~90% 1,4 and ~10% 1,2), by sequential anionic copolymerization high vacuum techniques, is reported. A wide range of volume fractions (0.27 ≤ ?PS ≤ 0.91) was studied by transmission electron microscopy and small‐angle X‐ray scattering in order to explore in detail the microphase separation behavior of these flexible/semiflexible diblock copolymers. Unusual morphologies, consisting of PCHD core(PCHD‐1,4)–shell(PCHD‐1,2) cylinders in PS matrix and three‐phase (PS, PCHD‐1,4, PCHD‐1,2) four‐layer lamellae, were observed suggesting that the chain stiffness of the PCHD block and the strong dependence of the interaction parameter χ on the PCHD microstructures are important factors for the formation of this unusual microphase separation behavior in PS‐b‐PCHD diblock copolymers. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016 , 54, 1564–1572 相似文献
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Morgan A. Higgins Christopher R. Maroon Jacob Townsend Xinyi Wang Konstantinos D. Vogiatzis Brian K. Long 《Journal of polymer science. Part A, Polymer chemistry》2020,58(18):2644-2653
Polymeric membranes have shown tremendous promise for the separation of CO2 from flue gas streams. However, few systematic studies have been conducted to better understand the impact that chemical functionalities have on membrane-based gas separation performance. To address this gap, we herein describe the synthesis and gas separation performance of a series of vinyl-addition polynorbornenes bearing various CO2-philic functional groups. To facilitate direct comparison between functional groups, each material was designed to maintain a common polymer backbone. Though the incorporation of CO2-philic moieties within a dense polymeric membrane is frequently hypothesized to enhance CO2 solubility, and thereby increase CO2/N2 selectivity, our results demonstrate that the incorporation of CO2-philic groups onto a common polymer backbone do not necessarily result in increased gas separation performance. Experimental and computational results demonstrate that the incorporation of amidoxime groups onto a polynorbornene backbone increase CO2/N2 selectivity, whereas commonly employed ethereal side chains only increased permeability. 相似文献