Limiting conditions of yielding for anisotropic materials

Summary The known Limiting Conditions of Yielding presuppose homogeneity andisotropy of the material. Formulas for anisotropic materials have been proposed: but they cannot be applied to all practical applications. The Limiting Condition of Yielding already proposed by the A. for isotropic materials can easily be extended to materials with different mechanical properties in different directions: the formulas obtained confirm the particular cases and the particular formulas already known for isotropic materials. The various solutions proposed by the A. for anisotropic bodies are usually represented by paraboloids whose characteristics obviously depend on the experimental parameters.

---

Sommario Le condizioni di plastificazione che si conoscono presuppongono omogeneità eisotropia del materiale. Per corpi anisotropi sono state proposte espressioni che non possono essere applicate in casi riguardanti le pratiche applicazioni. La condizione di plastificazione proposta dall'A. per i corpi isotropi può essere con opportune trasformazioni adattata a materiali presentanti differenti proprietà meccaniche nelle tre direzioni principali: le formule che se ne ottengono confermano i casi particolari e le formule già note per i corpi isotropi. Le soluzioni proposte dall'A. per i corpi anisotropi sono rappresentate in genere da paraboloidi le cui caratteristiche dipendono ovviamente dai parametri sperimentali.

---

     

Preferential protonation and methylation at the nitrogen atoms of N,N-dimethylamino derivatives of pyridine

The relative reactivity toward protonation and methylation of the two nitrogen atoms in N,N-dimethylaminopyridines has been examined by ¹H NMR. The ring position of the dimethylamino group has no influence on protonation, which occurs in all the derivatives at the heterocyclic nitrogen. The N-methylation reaction does not follow a homogeneous behaviour, occurring at the exocyclic nitrogen in the 2-substituted dimethylamino derivative. The electronic characteristics of the molecules, determined by MO calculations at a semi-empirical level, indicate that both protonation and methylation should occur at the heterocyclic nitrogen; the calculated relative stabilites, however, of the N-protonated and N-methylated forms are in full agreement with the experimental results, and it appears that the anomalous behaviour of 2-dimethylaminopyridine in the N-methylation reaction is caused by steric factors.     

A system approach to the optimal health-care districting

The paper presents a methodology for partitioning a given region in geographical areas in such a way as to insure an optimal allocation of the available health services. Two steps compose the proposed approach. In the first step, via mathematical programming one determines optimal hospital districts by taking into account demand and capacity, measured in number of hospital-beds. In the second step, one determines health-districts by aggregating together hospital districts, by taking into account lower and upper bounds for the population in each district and the existence of districts with a different nature (political, educational, etc.). A case study is presented for the Italian province of Cosenza. Although developed within the context of health-care services, the approach is general enough to be applicable also to the partition in a given region of other social services, i.e. school districts.     

The influence of ligand field effects on the magnetic exchange of high-spin Co(II)-semiquinonate complexes

[Co(Me(4)cyclam)(tropolonate)](PF(6)) was synthesised and structurally characterised. Its electronic and W-band EPR spectra have been analysed by means of the angular overlap calculation of the Spin Hamiltonian parameters that provided also a satisfactory reproduction of the temperature dependence of the magnetic susceptibility. The present results can be interpreted assuming a pseudo-octahedral character for the Co(II) center. This prompted us to reconsider the model formerly used for the analysis of the magnetic coupling between hs-Co(II) and the paramagnetic o-semiquinonate ligand in the corresponding derivatives [Co(Me(4)cyclam)(PhenSQ)](PF(6)) and [Co(Me(4)cyclam)(DTBSQ)](PF(6)). These results indicate that the effect of the magnetic coupling is active only below 50 K and that a more refined model of exchange coupling between Co(II) and semiquinonato ligands is needed to quantitatively analyze the magnetic behaviour of this class of systems.     

Solution phase synthesis of a library of tetrasubstituted pyrrole amides

An efficient strategy for the solution-phase parallel synthesis of a library of pyrrole-amides is described. Key reactions include functional homologation of beta-ketoesters with a set of aldehydes followed by oxidation to produce a series of differently substituted 1,4-dicarbonyl compounds. Rapid cyclization using a microwave-assisted Paal-Knorr reaction provided a set of 24 pyrrole esters that were further functionalized through a trimethylaluminum-mediated aminolysis to obtain a larger library of 288 diverse pyrrole-3-amides. The tetrasubstitution allows a good exploration of the chemical space around the central pyrrole core. The last step was entirely automated with a Bohdan Myriad personal synthesizer.     

Microwaves make hydroformylation a rapid and easy process

[reaction: see text] Hydroformylation of alkenes can be carried out in a few minutes under microwave activation at a relatively low pressure (40 psi) using commercially available catalysts and ligands. The 80 mL vial of a Discover microwave oven was connected to a cylinder of CO and H2, and after filling the reactor at 40 psi, a mixture of an alkene, the Wilkinson catalyst, and XANTPHOS was submitted to microwave irradiation giving, after 4 min, high conversion into the corresponding aldehyde without formation of the isomerized alkene.     

EEG topography-specific BOLD changes: a continuous EEG-fMRI study in a patient with focal epilepsy

Blood oxygenation level dependent (BOLD) response related to interictal activity was evaluated in a patient with post-traumatic focal epilepsy at repeated continuous electroencephalogram (EEG)-functional magnetic resonance imaging examinations. Lateralized interictal EEG activity induced a main cluster of activation co-localized with the anatomical lesion. Spreading of EEG interictal activity to both frontal lobes evoked bilateral clusters of activation indicating that topography of BOLD response might depend on the spatial distribution of epileptiform activity.