Armed Groups and Violence in Paraguay

Armed violence in Paraguay is not a recent phenomenon. During the second half of the XX Century, Paraguay saw the rise of a larger number of underground, revolutionary movements that sought the overthrow of the Alfredo Stroessner’s (1954-1989) government. From among those movements emerged the Partido Patria Libre (or, Free Fatherland, also known for its acronym PPL), made up of a two branches: one legal and the other one, operational. The latter was based on people’s power, as represented by “Ejército del Pueblo Paraguayo” (or, the Paraguayan People’s Army, with acronym EPP). After EPP broke with PPL in March 2008, this Marxist-oriented revolutionary project, which was apparently oriented to put an end to the social, political and economic inequalities in Paraguay, began to carry out markedly criminal activities, which included bank robberies, kidnappings, assassinations, terrorist attacks and armed confrontations. Its strategies and modus operandi utilized by the Armed Revolutionary Forces of Colombia (FARC). Paraguay features a farm sector in a state of crisis, in which cattle-ranchers, peasants and agro-exporting companies live in a constant strife. The Paraguayan Departments that are the most affected by this situation are Concepciόn, San Pedro, Canindeyú y Caazapá, which also suffer from a weak government presence. This deficiency has made these departments ripe for drug-trafficking activity by Brazilian groups such as Primer Comando Capital (i.e., First Capital command), also PCC and Comando Vermelho, (i.e., The Red Command). That is why many peasants, now recruited by EPP, have joined the drug-trafficking business and that, not only as marihuana growers but as “campanas” (i.e., early warning sentinels) for the organization. This helps shape their attitudes for their future involvement in all areas of drug-trafficking. Paraguayan society is the result of social inequity and inequality, such as those resulting from a lack of opportunity. Although Paraguay has successfully recovered from the last world economic crisis, economic growth, by itself, does not ensure an improvement in the quality of life. As long as such economic and social gaps persist and the government fails to enact the policies that would result in a more just society and toward EPP neutralization or containment, the latter is bound to grow stronger. In this context, the situation in Paraguay calls for more research into the EPP phenomenon. It would also seem necessary for Paraguay to promote an open national debate that includes all sectors of society in order to raise consciousness and to induce society to take actual steps to eliminate the EPP, as well as any other group that might arise in the immediate future. EPP has strong connections with the Frente Patriόtico Manuel Rodríguez in Chile and other armed groups and peasant movements in other countries of this region. Although most governments in the region are aware that the armed struggle is not a solution to current problems, it might be worth it to hold a regional debate about armed or insurgent groups in Latin American to seek common strategies and cooperation on dealing with them since the expansion of these armed groups is a problem for all.

Relative basicities of free base porphyrins; understanding the role of macrocyclic distortion

Porphyrins have been the center of numerous investigations in different areas of chemistry, geochemistry, and the life sciences. In nature the conformation of the porphyrin macrocycle varies, depending on the function of its apoenzyme. It is believed that the conformation of the porphyrin ring is necessary for the enzyme to achieve its function and modify its reactivity. It is important to understand how the conformation of the porphyrin ring will influence its properties. ^ In synthetic porphyrins particular conformations and ring deformations can be achieved by peripheral substitution, metallation, core substitution, and core protonation among other alterations of the macrocycle. The macrocyclic distortions will affect the ring current, the ability of pyrroles to intramolecularly hydrogen bond and the relative basicity of each of the porphyrins. To understand these effects different theoretical models are used. The ground state structure of each of 19 free base porphyrins is determined using molecular mechanics (MM+) and semiempirical methods (PM3). The energetics of deformation of the macrocyclic core is calculated by carrying out single point energy calculations for the conformation achieved by each synthetic compound. Enthalpies of solution and enthalpies of protonation of 10 porphyrins with varying degrees of macrocyclic deformation and varying electron withdrawing groups in the periphery are determined using solution calorimetry. Using Hess's Law, the relative basicity of each of the different free base porphyrins is calculated. NMR results are described, including the determination of free energies of activation of ring tautomerization and hydrogen bonding for several compounds. It was found that in the absence of electronic effects, the greater macrocyclic deformation, the greater the basicity of the porphyrins. This basicity is attenuated by the presence of electron withdrawing groups and ability to of the macrocycle to intramolecularly hydrogen bond. ^

Relative basicities of free base porphyrins : understanding the role of macrocyclic distortion

Porphyrins have been the center of numerous investigations in different areas of chemistry, geochemistry, and the life sciences. In nature the conformation of the porphyrin macrocycle varies, depending on the function of its apoenzyme. It is believed that the conformation of the porphyrin ring is necessary for the enzyme to achieve its function and modify its reactivity. It is important to understand how the conformation of the porphyrin ring will influence its properties. In synthetic porphyrins particular conformations and ring deformations can be achieved by peripheral substitution, metallation, core substitution, and core protonation among other alterations of the macrocycle. The macrocyclic distortions will affect the ring current, the ability of pyrroles to intramolecularly hydrogen bond and the relative basicity of each of the porphyrins. To understand these effects different theoretical models are used. The ground state structure of each of 19 free base porphyrins is determined using molecular mechanics (MM+) and semiempirical methods (PM3). The energetics of deformation of the macrocyclic core is calculated by carrying out single point energy calculations for the conformation achieved by each synthetic compound. Enthalpies of solution and enthalpies of protonation of 10 porphyrins with varying degrees of macrocyclic deformation and varying electron withdrawing groups in the periphery are determined using solution calorimetry. Using Hess's Law, the relative basicity of each of the different free base porphyrins is calculated. NMR results are described, including the determination of free energies of activation of ring tautomerization and hydrogen bonding for several compounds. It was found that in the absence of electronic effects, the greater macrocyclic deformation, the greater the basicity of the porphyrins. This basicity is attenuated by the presence of electron withdrawing groups and ability to of the macrocycle to intramolecularly hydrogen bond.