Distance Education in the Professionalization of People with Disability and Prison Inmates

This paper illustrates the impact of the Universidad Estatal a Distancia  (UNED, by its Spanish acronym) in supporting and professionalizing the vulnerable groups of the Costa Rican society, including prison inmates, persons with physical disability, individuals from remote areas, among others.  This study attempts to answer this type of questions: What kind of support has been provided to these sectors?  What are the challenges faced by distance education universities to succeed?  How does UNED have solved these challenges?  What is the impact of the Universidad Estatal a Distancia on the Costa Rican society for the professionalization of its population?  Documentation and statistics have been used in the study; in addition, two people who graduated from UNED were selected to illustrate the type of cases the University serves.(1) Translator’s note: It refers to the “Costa Rican Distance Education State University”.

Time-Dependent Density Functional Molecular Orbital and Excited State Calculations on Bis(porphyrinyl)butadiynes in the Monocationic, Neutral, Monoanionic, and Dianionic Oxidation States

We report a theoretical study of the multiple oxidation states (1+, 0, 1−, and 2−) of a meso,meso-linked diporphyrin, namely bis[10,15,20-triphenylporphyrinatozinc(II)-5-yl]butadiyne (4), using Time-Dependent Density Functional Theory (TDDFT). The origin of electronic transitions of singlet excited states is discussed in comparison to experimental spectra for the corresponding oxidation states of the close analogue bis{10,15,20-tris[3‘,5‘-di-tert-butylphenyl]porphyrinatozinc(II)-5-yl}butadiyne (3). The latter were measured in previous work under in situ spectroelectrochemical conditions. Excitation energies and orbital compositions of the excited states were obtained for these large delocalized aromatic radicals, which are unique examples of organic mixed-valence systems. The radical cations and anions of butadiyne-bridged diporphyrins such as 3 display characteristic electronic absorption bands in the near-IR region, which have been successfully predicted with use of these computational methods. The radicals are clearly of the “fully delocalized” or Class III type. The key spectral features of the neutral and dianionic states were also reproduced, although due to the large size of these molecules, quantitative agreement of energies with observations is not as good in the blue end of the visible region. The TDDFT calculations are largely in accord with a previous empirical model for the spectra, which was based simplistically on one-electron transitions among the eight key frontier orbitals of the C4 (1,4-butadiyne) linked diporphyrins.