Unambiguous assessments of reaction paths for selected pericyclic reactions

Four commonplace concerted reactions are examined using (i) correlation diagrams, (ii) frontier molecular orbital analyses for transition states, (iii) Zimmerman-Dewar analyses for transition states and (iv) modified Zimmerman-Dewar analyses for transition states. Only the latter approach is consistently satisfactory.

Dependência das vias de dissociação unimolecular com a energia interna da molécula de éter dimetílico

Internal energy dependence of the competitive unimolecular dissociation channels of dimethyl ether were studied with the statistical RRKM formalism. The C-O and C-H fission reactions and the 1,2-H and 1,3-H shifts, and 1,1-H2 and 1,3-H2 molecular eliminations are discussed as a function of energy dependence of k a(E*), the microcanonical rate constant for production of transition states. C-O fission is the dominant process while reaction channels involving C-H fission, 1,1-H2 and 1,3-H2 elimination and production of MeOH should be competitive at energies around 400 kJ mol-1. The less favorable process is the channel of CH4 formation.

Estudio teórico de la isomerización del ácido maleico en ácido fumárico: un enfoque basado en el concepto de superficie de energía potencial

A comparative study based on potential energy surfaces (PES) of 2-butanedioic and hypothetic 2-butanedioic/HCl acids is useful for understanding the maleic acid isomerization. The PES enables locating conformers of minimum energy, intermediates of reactions and transition states. From contour diagrams, a set of possible reaction paths are depicted interconnecting the proposed structures. The study was carried out in absentia and in the presence of the catalyst (HCl), using an solvatation model provided by the Gaussian software package. Clearly, the effect of HCl is given by new reaction paths with lower energetic barriers in relation to the reaction without catalyzing.

Gas-phase solvolysis type reactions of SiCl3+ cations

Gas-phase SiCl3+ ions undergo sequential solvolysis type reactions with water, methanol, ammonia, methylamine and propylene. Studies carried out in a Fourier Transform mass spectrometer reveal that these reactions are facile at 10-8 Torr and give rise to substituted chlorosilyl cations. Ab initio and DFT calculations reveal that these reactions proceed by addition of the silyl cation to the oxygen or nitrogen lone pair followed by a 1,3-H migration in the transition state. These transition states are calculated to lie below the energy of the reactants. By comparison, hydrolysis of gaseous CCl3+ is calculated to involve a substantial positive energy barrier.

Hückel and Möbius annulenes: relationships between their Hückel-level orbitals and their Hückel-level energies

The problem of convenient access to quantitative Hückel-level descriptions of Möbius and Hückel annulenes for undergraduate lectures about aromaticity is discussed. Frost circle, Zimmerman circle, double circle and Langler semicircular mnemonics are described. The relationship between spectra (complete sets of secular equation roots) for an isoconjugate pair of Hückel and Möbius annulenes and the corresponding acyclic polyene with one less carbon is fully developed. In addition to providing an alternative path to exact spectrum roots, this relationship provides immediate access to almost half of the eigenfunctions for an isoconjugate annulene pair. The remaining eigenfunctions may be obtained very easily.

Mao's steps in Monroe's backyard: towards a United States-China hegemonic struggle in Latin America?

Contrary to what could be expected given the United States' historical hegemony of Latin America, growing Chinese influence in this region has not led to a dispute between China and the US. Despite activism of hard-line groups in the United States, both parties have faced the issue with noticeable pragmatism. This attitude could be explained by three variables: the US political negligence towards Latin America in the Post-Cold War, the focus of Sino-Latin American relations on economic rather than geopolitical or ideological affairs, and the scanty relevance of the region in the top priorities of overall Washington-Beijing relations.

Chinese energy policy progress and challenges in the transition to low carbon development, 2006-2013

If the world is not to jeopardize the chances for human life on Earth, climate change must be mitigated; therefore, achieving low carbon development is crucial. China is the world's greatest GHG emitter, energy producer and energy consumer; investigating its energy-climate policy developments and international positions are of utmost importance to understand and tackle current stumbling blocks of the global energy and climate governance.

Discourses of cyberspace securitization in Brazil and in the United States

Abstract This paper uses the framework of the Copenhagen School to understand the process of securitization of cyberspace, exploring how something in such sphere becomes a threat. Seeking to contribute to the debate, this study analyses the securitization discourses of Brazil and of the United States from Hansen and Nissenbaum's (2009) theorization about the existence of a specific sector for cybersecurity. To comprehend the securitization of cyberspace in these terms allows not only to identify distinct levels of securitization, but also to capture the dynamics of cyber threats, distinguishing them from those existent in other sectors, as well as to trace distinctions between tendencies of securitization and militarization.

Forty Years of the United Nations General Assembly Resolution 3379 (XXX) on Zionism and Racism: the Brazilian Vote as an instance of United States - Brazil Relations

Abstract In 1975, Brazil voted in favor of the United Nations General Assembly resolution 3379 (XXX), equating Zionism with a form of racism. Focusing on the decision-making process of president Ernesto Geisel's (1974-1979) foreign policy, "responsible pragmatism", this article discusses how the ultimate decision to vote in favor of resolution was taken taking into account mainly US-Brazil relationship.

The European Union and the Member States: two different perceptions of border

Abstract In this article we analyze two different perceptions of border inside Europe. On the one hand, we have the perception idealized by the European Union as an international organization, which believes that states benefit more from cooperation and dilution of borders in a common space than from keeping its borders as a symbol of its sovereignty. On the other hand, we have the European member states, taken individually, with particular interests and goals that, given the threat of illegal immigration, which is currently felt in the large-scale Europe, adopt a realistic perception of the border, and look at each territory as a space that needs protection from external threats. Following this argument, we reason that the current construction of walls in several European countries reflects the rebirth of a realistic perception of the border, and this is one more challenge for Europe regarding its unity and solidarity. Is this the end of the Schengen Agreement? What is going to happen to the European project if each state unilaterally adopts a strategy to deal with illegal immigration and refugees that are coming to Europe? Can immigration lead to a retrocession of the EU idealist significance of border?

Composite synthetic hydroxyapatite 30%, in two physical states, as dermal filler

The aim of this study was to evaluate the response to the implantation of synthetic hydroxyapatite 30% (HAP-91®) in different physical states as dermal filler. Eighteen New Zealand rabbits were used, distributed randomly into two equal groups and then divided into three groups according to the postoperative period at 8, 21 and 49 days. One mL of HAP-91®, fluid and viscous, was implanted in the subcutaneous tissue, 1 cm proximal to the cranial crest of the right scapula. The thickness of the skin was measured before and after implantation and for the following 15 days. Pain sensitivity assessment was conducted, assigning the following scores: 0 - when the animal allowed the touch of the implant area and expressed no signs of pain; 1 - when the animal allowed the touch, but pain reaction occurred, like increase of the respiratory rate or attempt to escape; 2 - when the animal did not allow the touch to the implanted area. At 8, 21 and 49 days, biopsy of the implanted area was performed. No difference was observed between the thickness of the skin (p>0.05) and all animals received a score 0 for soreness. Histological analysis did not reveal any obvious inflammatory process, showing a predominance of mononuclear cells in samples of eight days and tissue organization around the biomaterial with a tendency to encapsulation. The results indicate that HAP-91®, both viscous and fluid, is biocompatible and suitable for dermal filling.

Current trends in the global tourism industry: evidence from the United States

Tourism is one of the largest U.S. industries, serving millions of international and domestic tourists yearly. Tourists visit the U.S. to see natural wonders, cities, historic landmarks, and entertainment venues. Americans seek similar attractions as well as recreation and vacation areas. Tourism competes in the global market, so it is important to understand current trends in the U.S. travel industry. Therefore, this article offers insight into important trends and suggests strategies for policy makers involved in the travel and tourism industry.