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The selective oxidation of alkane and olefin moieties are reactions of fundamental importance in both chemical synthesis and biology. Nature efficiently catalyzes the oxidation of hydrocarbons using iron-dependent enzymes, which operate through the mediation of oxoiron(IV) or oxoiron(V) species. In the quest for chemo, regio and stereoselective transformations akin to those taking place in nature, bioinspired iron catalysts have been developed and understanding their mechanism of action has become a particularly relevant area of research. While a prominent advance in the preparation and characterization of oxoiron(IV) species has been accomplished, oxoiron(V) species remain exceedingly rare, presumably because the high reactivity that makes them particularly interesting also makes them difficult to observe. This review summarizes the advances in the field, focusing in synthetic systems for which the oxoiron(V) species relevant in these transformations have been directly detected and spetroscopically characterized.  相似文献   
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A fundamental practice in process engineering is monitoring the state dynamics of a system. Unfortunately, observability of some states is related to high costs, time, and efforts. The mechanistic event recognition (MER) aims to detect an event (defined as a change of the system with specific significance to the operation of the process) that cannot be directly observed but has some predictable effect on the dynamics of the systems. MER attempts to apply fault diagnosis techniques using mechanistic “recognition” models to describe the process. A systematic method for building recognition models using optimal experimental design tools is presented. As proof of concept, the MER approach to detect organic matter depletion in sequencing batch reactors, measuring only ammonia, dissolved oxygen, and nitroxides is applied. The event, that is, consumption of organic matter to a level below 50 gCOD/m3, was successfully detected even though microbial activity is known to continue after organic matter depletion. © 2014 American Institute of Chemical Engineers AIChE J, 60: 3460–3472, 2014  相似文献   
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Indoor exposure to air contaminants penetrating from the outdoor environment depends on a number of key processes and parameters such as the ventilation rate, the geometric characteristics of the indoor environment, the outdoor concentration and the indoor removal mechanisms. In this study two alternative methods are used, an analytical and a numerical one, in order to study the time lag and the reduction of the variances of the indoor concentrations, and to estimate the deposition rate of the air contaminants in the indoor environment employing both indoor and outdoor measurements of air contaminants. The analytical method is based on a solution of the mass balance equation involving an outdoor concentration pulse which varies sinusoidally with the time, while the numerical method involves the application of the MIAQ indoor air quality model assuming a triangular pulse. The ratio of the fluctuation of the indoor concentrations to the outdoor ones and the time lag were estimated for different values of the deposition velocity, the ventilation rate and the duration of the outdoor pulse. Results have showed that the time lag between the indoor and outdoor concentrations is inversely proportional to the deposition and ventilation rates, while is proportional to the duration of the outdoor pulse. The decrease of the ventilation and the deposition rate results in a rapid decrement of the variance ratio of indoor to outdoor concentrations and to an increment of the variance ratio, respectively. The methods presented here can be applied for gaseous species as well as for particulate matter. The nomograms and theoretical relationships that resulted from the simulation results and the analytical methods respectively were used in order to study indoor air phenomena. In particular they were used for the estimation of SO2 deposition rate. Implications of the studied parameters to exposure studies were estimated by calculating the ratio of the indoor exposure to the exposure outdoors. Limitations of the methods were explored by testing various scenarios which are usually met in the indoor environment. Strong indoor emissions, intense chemistry and varying ventilation rates (opening and closing of the windows) were found to radically influence the time lag and fluctuation ratios.  相似文献   
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Novel configurations of fractional‐order filter topologies, realized through the employment of the concept of companding filtering, are introduced in this paper. As a first step, the design procedure is presented in a systematic algorithmic way, while in the next step, the basic building blocks of sinh‐domain and log‐domain integrators are presented. Because of the employment of metal–oxide–semiconductor (MOS) transistors operated in the subthreshold region, the derived filter structures offer the capability for operation in an ultra‐low‐voltage environment. In addition, because of the offered resistorless realizations, the proposed topologies are reconfigurable, in the sense that the order of the filter could be chosen through appropriate bias current sources. The performance of the derived fractional‐order filters has been evaluated through simulation and comparison results using the Analog Design Environment of the Cadence software and MOS transistor parameters provided by the Taiwan Semiconductor Manufacturing Company (TSMC) 180‐nm complementary MOS (CMOS) process. Copyright © 2014 John Wiley & Sons, Ltd.  相似文献   
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Scientometrics - This paper presents an analysis of the anti-vaccination movement’s referencing of research articles on the topic of vaccination in the social media network Twitter. Drawing...  相似文献   
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Bulletin of Engineering Geology and the Environment - This present paper presents an adopted methodology for Micro Tunnel Boring Machine (TBM) selection, based on the results of a...  相似文献   
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