Evaluation of group electronegativities and hardness (softness) of group 14 elements and containing functional groups through density functional theory and correlation with NMR spectra data

Quantum Chemical calculations for group 14 elements of Periodic Table (C, Si, Ge, Sn, Pb) and their functional groups have been carried out using Density Functional Theory (DFT) based reactivity descriptors such as group electronegativities, hardness and softness. DFT calculations were performed for a large series of tetracoordinated Sn compounds of the CH3SnRR'X type, where X is a halogen and R and R' are alkyl, halogenated alkyl, alkoxy, or alkyl thio groups. The results were interpreted in terms of calculated electronegativity and hardness of the SnRR'X groups, applying a methodology previously developed by Geerlings and coworkers (J. Phys. Chem. 1993, 97, 1826). These calculations allowed to see the regularities concerning the influence of the nature of organic groups RR' and inorganic group X on electronegativities and hardness of the SnRR'X groups; in this case, it was found a very good correlation between the electronegativity of the fragment and experimental 119Sn chemical shifts, a property that sensitively reflects the change in the valence electronic structure of molecules. This work was complemented with the study of some compounds of the EX and ER types, where E= C, Si, Ge, Sn and R= CH3, H, which was performed to study the influence that the central atom has on the electronegativity and hardness of molecules, or whether these properties are mainly affected for the type of ligand bound to the central atom. All these calculations were performed using the B3PW91 functional together with the 6-311++G** basis set level for H, C, Si, Ge, F, Cl and Br atoms and the 3-21G for Sn and I atoms.

The notion of process in nonstandard theory and in Whiteheadian metaphysics

In this article I intend to show that certain aspects of A.N. Whitehead's philosophy of organism and especially his epochal theory of time, as mainly exposed in his well-known work Process and Reality, can serve in clarify the underlying assumptions that shape nonstandard mathematical theories as such and also as metatheories of quantum mechanics. Concerning the latter issue, I point to an already significant research on nonstandard versions of quantum mechanics; two of these approaches are chosen to be critically presented in relation to the scope of this work. The main point of the paper is that, insofar as we can refer a nonstandard mathematical entity to a kind of axiomatical formalization essentially 'codifying' an underlying mental process indescribable as such by analytic means, we can possibly apply certain principles of Whitehead's metaphysical scheme focused on the key notion of process which is generally conceived as the becoming of actual entities. This is done in the sense of a unifying approach to provide an interpretation of nonstandard mathematical theories as such and also, in their metatheoretical status, as a formalization of the empirical-experimental context of quantum mechanics.

Network connectance and autonomy analyses of the photosynthetic apparatus in tropical tree species from different successional groups under contrasting irradiance conditions

Biological systems are complex dynamical systems whose relationships with environment have strong implications on their regulation and survival. From the interactions between plant and environment can emerge a quite complex network of plant responses rarely observed through classical analytical approaches. The objective of this current study was to test the hypothesis that photosynthetic responses of different tree species to increasing irradiance are related to changes in network connectances of gas exchange and photochemical apparatus, and alterations in plant autonomy in relation to the environment. The heat dissipative capacity through daily changes in leaf temperature was also evaluated. It indicated that the early successional species (Citharexylum myrianthum Cham. and Rhamnidium elaeocarpum Reiss.) were more efficient as dissipative structures than the late successional one (Cariniana legalis (Mart.) Kuntze), suggesting that the parameter deltaT (T ºCair - T ºCleaf) could be a simple tool in order to help the classification of successional classes of tropical trees. Our results indicated a pattern of network responses and autonomy changes under high irradiance. Considering the maintenance of daily CO2 assimilation, the tolerant species (C. myrianthum and R. elaeocarpum) to high irradiance trended to maintain stable the level of gas exchange network connectance and to increase the autonomy in relation to the environment. On the other hand, the late successional species (C. legalis) trended to lose autonomy, decreasing the network connectance of gas exchange. All species showed lower autonomy and higher network connectance of the photochemical apparatus under high irradiance.

Alternative banking: theory and evidence from Europe

Since financial liberalization in the 1980s, non-profit maximizing, stakeholder-oriented banks have outperformed private banks in Europe. This article draws on empirical research, banking theory and theories of the firm to explain this apparent anomaly for neo-liberal policy and contemporary market-based banking theory. The realization of competitive advantages by alternative banks (savings banks, cooperative banks and development banks) has significant implications for conceptions of bank change, regulation and political economy.