Search results for "Caliza"

A molecular electron density theory study for [3 + 2] cycloaddition reactions of 1‐pyrroline ‐1‐oxide with disubstituted acetylenes leading to bicycl…

2020

Theoretical study on the molecular mechanism of the [5 + 2] vs. [4 + 2] cyclization mediated by Lewis acid in the quinone system

2013

[EN] The thermal and Lewis acid (LA) catalyzed cyclizations of quinone 1 involved in the synthesis of Colombiasin A and Elipsaterosin B have been theoretically studied using DFT methods at the B3LYP/6-311G(d,p) computational level. B3LYP calculations suggest that the formal endo [4 + 2] cycloadduct allowing the synthesis of Colombiasin A is preferentially formed under thermal conditions, while in the presence of the BF3 LA catalyst the formal [5 + 2] cycloadduct is seen, allowing the synthesis of Elipsaterosin B. The BF3 LA catalyst not only accelerates the nucleophilic attack on the C2 carbon of the quinone framework through a more polar C-C bond formation, but also provokes a different el…

Understanding the regioselectivity in hetero Diels–Alder reactions. An ELF analysis of the reaction between nitrosoethylene and 1-vinylpyrrolidine

2013

[EN] The regioselectivity in the hetero Diels-Alder reaction between nitrosoethylene 1 and 1-vinylpyrrolidine 2 has been studied by a comparative ELF bonding analysis along the IRC of the endo/ortho and endo/meta regioisomeric channels at the B3LYP/6-31G*. level. Along the most favorable endo/ortho regioisomeric channel, the C-C sigma bond is first formed by coupling of two pseudoradical centers located at the most electrophilic carbon of 1 and the most nucleophilic center of 2. Formation of these relevant pseudoradical centers, which depend on the total charge transfer process along the polar reaction, and not on the approach mode of each reagent, is well characterized by analysis of the a…

Energetics of hydride and electron pair attachment to EX30/+ (E=B, C, Al, Si and X=F, Cl, Br, I) and the study of bonding trends among EX30/+, EX32−/…

2004

Abstract A theoretical gas-phase “ligand-free” or “electron pair affinity” (EPA) approach, based on CCSD(T)/(SDB-)cc-pVTZ//MP2/(SDB-)cc-pVTZ electronic structure calculations, is introduced as a possible means for determining Lewis acidity trends among planar EX30/+ (E = B, C, Al, Si; X = F, Cl, Br, I) species. In this treatment, the free electron pair is considered to be an extreme Lewis base. The calculated EPA values are compared with experimental Lewis acidities, previously calculated fluoride ion affinity (FIA) and hydride ion affinity (HA) trends, and are found to exhibit reasonable correlations in all cases. The bonding in the planar and trigonal pyramidal conformations of EX30/+ and…

Nature of the ring-closure process along the rearrangement of octa-1,3,5,7-tetraene to cycloocta-1,3,5-triene from the perspective of the electron lo…

2011

We analyze the behavior of the energy profile of the ring-closure process for the transformation of (3Z,5Z)-octa-1,3,5,7-tetraene 5 to (1Z,3Z,5Z)-cycloocta-1,3,5-triene 6 through a combination of electron localization function (ELF) and catastrophe theory (CT). From this analysis, concepts such as bond breaking/forming processes, formation/annihilation of lone pairs, and other electron pair rearrangements arise naturally through the reaction progress simply in terms of the different ways of pairing up the electrons. A relationship between the topology and the nature of the bond breaking/forming processes along this rearrangement is reported. The different domains of structural stability of …

Finite elements augmented with embedded interphases for application in quasi-brittle materials

2022

Quasi-brittle materials mainly fail under shear or tensile stress state. When the stress limit is reached, fractures propagate and the stress-strain relation exhibits a softening branch until failure. In the framework of finite elements, discrete crack models and continuous smeared crack models have been implemented to best capture material’s response. In this ambit, we propose a strategy based on the Augmented Finite Element Method (A-FEM, [1]), which can be placed among the discrete crack models, since intra-element weak discontinuity is considered and modelled through a zero-thickness interphase model (IPH, [2, 3]). The original element is in practice divided in two elastic sub-elements …

Optimizing the MAC Protocol in Localization Systems Based on IEEE 802.15.4 Networks

2017

Radio frequency signals are commonly used in the development of indoor localization systems. The infrastructure of these systems includes some beacons placed at known positions that exchange radio packets with users to be located. When the system is implemented using wireless sensor networks, the wireless transceivers integrated in the network motes are usually based on the IEEE 802.15.4 standard. But, the CSMA-CA, which is the basis for the medium access protocols in this category of communication systems, is not suitable when several users want to exchange bursts of radio packets with the same beacon to acquire the radio signal strength indicator (RSSI) values needed in the location proce…

Low stiffness variation in structural systems: identification and localization

2008

When a very low damage occurs, the undamaged structural response totally overlaps the damaged one either in time domain or in frequency domain; on the other hand, by considering some characteristics of the analytical signal, such as the phase, it has been possible to develop a damage identification procedure that allows the identification and localization of damage even if the structure experiences multiple damages at the same time. This procedure is also robust with respect to the presence of measuring noise. In order to assess the validity of the proposed damage identification procedure, numerical applications on single degree of freedom and 2 DOF and 4 DOF are presented using data record…

Preliminary analysis of warehouse localization systems based on RFID technology

2010

In the industrial warehouse design domain, today's computerized information systems have gained a relevant interest due to the issues related to asset tracking and traceability. In such context, the employment of new information technologies on warehouse management systems has opened new business opportunities due to the sensible price reduction in the last years. This paper focuses on the technical issues related to the realization of wireless localization systems for warehouses, which are necessary for the implementation of random allocation policies, and in particular investigates the opportunities offered by RFID technology in such context. The enforcement of random allocation policies …

Born Global Firms, Internet, and New Forms of Internationalization

2013

Although Internet is widely acknowledged to facilitate the rapid internationalization of born global firms (BGs), it is less known how such firms actually go about it. The current chapter specifically explores Internet-enabled internationalization (IEI) in the context of BGs. Based on e-adoption, international marketing and internationalization literatures, a conceptualization of IEI modes is suggested along three key dilemmas, assumed to underlie IEI mode configurations, including - functionality, localization and service directness. Three cases of Internet-enabled internationalizing born global firms (IEI BGs) from small open economies are then presented, as part of an effort towards conc…