Exploring the intrinsic polar [4?+?2+] cycloaddition reactivity of gaseous carbosulfonium and carboxonium ions

Gas-phase reactions of model carbosulfonium ions (CH3-S+?=?CH2; CH3CH2-S+?=?CH2 and Ph-S+?=?CH2) and an O-analogue carboxonium ion (CH3-O+?=?CH2) with acyclic (isoprene, 1,3-butadiene, methyl vinyl ketone) and cyclic (1,3-cyclohexadiene, thiophene, furan) conjugated dienes were systematically investigated by pentaquadrupole mass spectrometry. As corroborated by B3LYP/6-311?G(d,p) calculations, the carbosulfonium ions first react at large extents with the dienes forming adducts via simple addition. The nascent adducts, depending on their stability and internal energy, react further via two competitive channels: (1) in reactions with acyclic dienes via cyclization that yields formally [4?+?2+] cycloadducts, or (2) in reactions with the cyclic dienes via dissociation by HSR loss that yields methylenation (net CH+ transfer) products. In great contrast to its S-analogues, CH3-O+?=?CH2 (as well as C2H5-O+?=?CH2 and Ph-O+?=?CH2 in reactions with isoprene) forms little or no adduct and proton transfer is the dominant reaction channel. Isomerization to more acidic protonated aldehydes in the course of reaction seems to be the most plausible cause of the contrasting reactivity of carboxonium ions. The CH2?=?CH-O+?=?CH2 ion forms an abundant [4?+?2+] cycloadduct with isoprene, but similar to the behavior of such alpha,beta-unsaturated carboxonium ions in solution, seems to occur across the C?=?C bond. Copyright (c) 2012 John Wiley & Sons, Ltd.

A hearing report from Brazil

The past several decades, the need for hearing health services is still great, especially in the northeast, the Amazonian, and the southern regions Brazil, officially Federative Republic of Brazil, is the largest Portuguese-speaking country, and the fifth largest country in the world by population and by land. The vast land not only brings rich natural resources but also large varieties of exotic vegetation and wildlife. One hundred and ninety-three million inhabitants live in five geographical regions with diverse cultural practices influenced by immigrants from Italy, Spain, Japan, Germany, and other countries. Brazilian people generally are warm-hearted, very welcoming, and resilient. They are optimistic and creative despite having encountered many economic downturns and political challenges throughout history. A bachelor's degree is the entry level for the profession. As only 19 percent of the population aged 18–24 years have access to higher education, the competition for admissions is fierce, especially in government institutions. High school students need to pass tests of general knowledge in a national examination and a university-specific examination. Government educational institutions offer good education without charging tuition. The majority of scientific papers are also produced by scholars working in government institutions. Private institutions are generally ranked lower in academic rigor (Behlau and Gasparini, 2006), except for a few top-ranking institutions. The fields of speech-language pathology and audiology are marked by rapid changes in recent years. Currently, there are 104 undergraduate programs recognized by the Ministry of Education and distributed in all but three federal states of Brazil.