Catalytic Reduction of Hydrazine to Ammonia with MoFe(3)S(4)-Polycarboxylate Clusters. Possible Relevance Regarding the Function of the Molybdenum-Coordinated Homocitrate in Nitrogenase

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.     

Determination of spiroxamine residues in grapes, must, and wine by gas chromatography/ion trap-mass spectrometry

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.     

A structured methodology for assessing and improving e-services in digital cities

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.     

Improvements in the Synthesis of the Third-Generation EGFR Inhibitor Osimertinib

Osimertinib, a third generation potent and specific EGFR inhibitor is an important drug against many forms of cancer. It was synthesized by an improved and highly efficient protocol, revisiting the classical synthetic process and modifying parameters, such as solvents, temperature, reagents, and reaction time. A cost-effective, environmentally friendly methodology for the synthesis of osimertinib was established, which gave shorter reaction times, saved labor by eliminating purification steps through column chromatography, and enhanced yields. Four of the seven steps in total, were proceeded quantitatively or almost quantitatively (ca. 98 %). This synthetic protocol provides a very high overall yield, up to 68 %. In addition, the entire approach enables the preparation of osimertinib analogues and could be extended in the synthesis of other structurally similar bioactive compounds.     

Operations research in the space industry

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.     

Diblock copolymers of polystyrene‐b‐poly(1,3‐cyclohexadiene) exhibiting unique three‐phase microdomain morphologies

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