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531.
Diego Cesario Mariagrazia Fortino Tiziana Marino Francesca Nunzi Nino Russo Emilia Sicilia 《Journal of computational chemistry》2019,40(8):944-951
The effects on the activity of thyroxine (T4) due to the chalcogen replacement in a series of peri-substituted naphthalenes mimicking the catalytic function of deiodinase enzymes are computationally examined using density functional theory. In particular, T4 inner-ring deiodination pathways assisted by naphthyl-based models bearing two tellurols and a tellurol-thiol pair in peri-position are explored and compared with the analogous energy profiles for the naphthalene mimic having two selenols. The presence of a halogen bond (XB) in the intermediate formed in the first step and involved in the rate-determining step of the reaction is assumed to facilitate the process increasing the rate of the reaction. The rate-determining step calculated energy barrier heights allow rationalizing the experimentally observed superior catalytic activity of tellurium containing mimics. Charge displacement analysis is used to ascertain the presence and the role of the electron density charge transfer occurring in the rate-determining step of the reaction, suggesting the incipient formation or presence of a XB interaction. © 2019 Wiley Periodicals, Inc. 相似文献
532.
Burcin Bozal‐Palabiyik Mariagrazia Lettieri Bengi Uslu Giovanna Marrazza 《Electroanalysis》2019,31(8):1458-1464
In this study, we report the development of a sensitive label‐free impedimetric sensor based on molecularly imprinted polymer (MIP) as biomimetic receptor coupled with screen‐printed electrodes (SPEs) for the detection of vascular endothelial growth factor (VEGF). Firstly, electropolymerization of o‐phenylenediamine (o‐PD) in the presence of VEGF molecule by cyclic voltammetry was performed onto graphite screen‐printed electrodes. The solvent extraction of the target was then carried out. The MIP based sensor was characterized by electrochemical techniques and scanning electron microscopy (SEM). Using optimized experimental conditions, the single‐use MIP‐based sensor showed a good analytical performance for VEGF detection from 20 to 200 pg mL?1 with limit of detection of 0.08 pg mL?1. Finally, the developed MIP‐based sensor in human serum samples was also tested. 相似文献
533.
Stefania Pragliola Chiara Costabile Mariagrazia Napoli Gaetano Guerra Pasquale Longo 《Macromolecular Symposia》2006,234(1):128-138
Olefin-diene copolymerizations in the presence of C2 symmetric zirconocene rac-[CH2(3-tert-butyl-1-indenyl)2]ZrCl2/MAO catalytic system have been reported and rationalized by experimental and molecular modeling studies. Ethene gives 1,2-cyclopropane and 1,2-cyclopentane, 1,3-cyclobutane, and 1,3-cyclopentane units in copolymerization with 1,3-butadiene, 1,4-pentadiene, and 1,5-hexadiene, respectively. Propene-1,3-butadiene copolymerizations lead to 1,2 and 1,4 butadiene units and to a low amount of 1,2-cyclopropane units. 相似文献
534.
535.
Michele Bianchi Janetti 《Transport in Porous Media》2018,122(3):633-645
This paper deals with the double-constraint methodology for calibration of steady-state groundwater flow models. The methodology is based on updating the hydraulic conductivity of the model domain by comparing the results of two forward groundwater flow models: a model in which known fluxes are specified as boundary conditions and a model in which known heads are specified as boundary conditions. A new zone-integrated double-constraint approach is presented by partitioning the model domain in zones with presumed constant hydraulic conductivity (soft data), and the double-constraint methodology is reformulated accordingly. The feasibility of the method is illustrated by a practical case study involving a numerical steady-state groundwater flow model with about 3 million grid blocks, subdivided into four zones corresponding to the major hydrogeological formations. The results of the zone-integrated double-constraint method for estimating the horizontal and vertical hydraulic conductivities of the zones compare favourably with a classical model calibration based on minimisation of the differences between calculated and measured heads, while the double-constraint method proves to be more robust and computationally less cumbersome. 相似文献
536.
Diederik Aerts Massimiliano Sassoli de Bianchi Sandro Sozzo 《International Journal of Theoretical Physics》2017,56(12):3727-3739
The quantum formalism can be completed by assuming that density operators also represent genuine states. An ‘extended Bloch representation’ (EBR) then results, in which not only the states but also the measurement-interactions can be described. Consequently, the Born rule can be obtained as an expression that quantifies the lack of knowledge about the measurement-interaction that is each time actualized, during a measurement. Entanglement can also be consistently described in the EBR, as it remains compatible with the principle according to which a composite entity exists only if its components also exist, and therefore are in well-defined states. 相似文献
537.
Diederik Aerts Jonito Aerts Arguëlles Lester Beltran Lyneth Beltran Massimiliano Sassoli de Bianchi Sandro Sozzo Tomas Veloz 《International Journal of Theoretical Physics》2017,56(12):3744-3756
The ‘conjunction fallacy’ has been extensively debated by scholars in cognitive science and, in recent times, the discussion has been enriched by the proposal of modeling the fallacy using the quantum formalism. Two major quantum approaches have been put forward: the first assumes that respondents use a two-step sequential reasoning and that the fallacy results from the presence of ‘question order effects’; the second assumes that respondents evaluate the cognitive situation as a whole and that the fallacy results from the ‘emergence of new meanings’, as an ‘effect of overextension’ in the conceptual conjunction. Thus, the question arises as to determine whether and to what extent conjunction fallacies would result from ‘order effects’ or, instead, from ‘emergence effects’. To help clarify this situation, we propose to use the World Wide Web as an ‘information space’ that can be interrogated both in a sequential and non-sequential way, to test these two quantum approaches. We find that ‘emergence effects’, and not ‘order effects’, should be considered the main cognitive mechanism producing the observed conjunction fallacies. 相似文献
538.
539.
A generalized Bloch sphere, in which the states of a quantum entity of arbitrary dimension are geometrically represented, is investigated and further extended, to also incorporate the measurements. This extended representation constitutes a general solution to the measurement problem, inasmuch it allows to derive the Born rule as an average over hidden-variables, describing not the state of the quantum entity, but its interaction with the measuring system. According to this modelization, a quantum measurement is to be understood, in general, as a tripartite process, formed by an initial deterministic decoherence-like process, a subsequent indeterministic collapse-like process, and a final deterministic purification-like process. We also show that quantum probabilities can be generally interpreted as the probabilities of a first-order non-classical theory, describing situations of maximal lack of knowledge regarding the process of actualization of potential interactions, during a measurement. 相似文献
540.
Eugenio Bianchi 《General Relativity and Gravitation》2014,46(2):1-23
In this paper we calculate the Bondi mass of asymptotically flat spacetimes with interacting electromagnetic and scalar fields. The system of coupled Einstein–Maxwell–Klein–Gordon equations is investigated and corresponding field equations are written in the spinor form and in the Newman–Penrose formalism. Asymptotically flat solution of the resulting system is found near null infinity. Finally we use the asymptotic twistor equation to find the Bondi mass of the spacetime and derive the Bondi mass-loss formula. We compare the results with our previous work (Bi?ák et al. in Class Quantum Gravity 27(17):175011, 2010) and show that, unlike the conformal scalar field, the (Maxwell–)Klein–Gordon field has negatively semi-definite mass-loss formula. 相似文献