Gas-Phase Acylium Ion Transfer Reactions Mediated by a Proton Shuttle Mechanism

The mechanism and the energy profile of the gas-phase reaction that mimics esterification under acidic conditions have been investigated at different levels of theory. These reactions are known to proceed with rate constants close to the collision limit in the gas-phase and questions have been raised as to whether the typical addition-elimination mechanism via a tetrahedral intermediate can explain the ease of these processes. Because these reactions are common to many organic and biochemical processes it is important to understand the intrinsic reactivity of these systems. Our calculations at different levels of theory reveal that a stepwise mechanism via a tetrahedral species is characterized by energy barriers that are inconsistent with the experimental results. For the thermoneutral exchange between protonated acetic acid and water and the exothermic reaction of protonated acetic acid and methanol our calculations show that these reactions proceed initially by a proton shuttle between the carbonyl oxygen and the hydroxy oxygen of acetic acid mediated by water, or methanol, followed by displacement at the acylium ion center. These findings suggest that the reactions in the gas-phase should be viewed as an acylium ion transfer reaction. (C) 2010 Wiley Periodicals, Inc. Int J Quantum Chem 111: 1596-1606, 2011

The sustainability revolution : A societal paradigm shift - ethos, innovation, government transformation

The Sustainability revolution: A societal paradigm shift – ethos, innovation, governance transformation This paper identifies several key mechanisms that underlie major paradigm shifts. After identifying four such mechanisms, the article focuses on one type of transformation which has a prominent place in the sustainability revolution that the article argues is now taking place. The transformation is piecemeal, incremental, diffuse – in earlier writings referred to as ”organic”. This is a more encompassing notion than grassroots, since the innovation and transformation processes may be launched and developed at multiple levels through diverse mechanisms of discovery and development. Major features of the sustainability revolution are identified and comparisons made to the industrial revolution.

Alumni @ Large

Alumni notes Newsmakers Milestones Maine's Bilingual Education Dynamo: Grayce Hall Studley '61 Voyage of Discovery: Stephen Orlov '71 The Picture of Health: Bianca Belcher '03 Obituaries

Fatores-chave na qualidade de sistemas de home broker : uma análise teórico-empírica

This work has as main objective the development of a key factors¿ model for the quality of Home Broker systems. An explanatory research was performed, based on a quantitative approach. To achieve this goal, some theoretical models of technology acceptance (TAM, TRA, TPB and IDT), reliability and quality of service were reviewed. It was proposed an extended key factors¿ model and developed a questionnaire, which was the research instrument used in this study. The questionnaire was applied over the Internet, from which was obtained a participation of 113 valid respondents, all of them users of Home Broker system. Once performed the data collection, statistical tests were used for the Factorial Analysis in order to achieve a definitive model. The key factors found were Perceived Usefulness, Perceived Ease of Use, Subjective Norms, Compatibility, Reliability and Relative Advantage. Some hypotheses from the model were also tested to investigate the relationship between the importance given to the factors and the resulting degree of satisfaction about quality of service. As a result of the study, a key factors¿ model for the quality of Home Broker systems was established, and identified that the factor Compatibility" has more explanatory power than the others."

Os fatores que influenciaram o download gratuito de música na Internet

A disseminação do formato mp3 como padrão para arquivos de música, aliada ao crescimento da Internet, fez surgir uma poderosa rede de distribuição de música online. A extrema disponibilidade, diversidade de escolha e facilidade de acesso para quem possui banda larga em seus computadores fez crescer o download de músicas pela Internet, revolucionando o mundo fonográfico. O objetivo geral deste estudo é identificar quais fatores, na perspectiva do consumidor, têm maior influência no download gratuito de música pela Internet através de uma pesquisa exploratória de duas fases. Na primeira fase, qualitativa, foram realizadas entrevistas não estruturadas com usuários e consumidores de redes peer-to-peer de download de música pela Internet e entrevista semi-estruturada com um ex-executivo da indústria fonográfica. Na fase seguinte, quantitativa, foram aplicados questionários estruturados a pessoas que efetuam download de música pela Internet. Adotou-se a regressão linear múltipla como modelo para interpretar os dados colhidos junto à amostra e testar as hipóteses relacionadas as variáveis: acessibilidade ao produto, percepção de injustiça no preço e faixa etária. Os resultados sugerem a não rejeição das três hipóteses estudadas.

Modelo estendido de adoção da tecnologia de comunicação pessoal de voz pela internet

Estudos científicos têm demonstrado a existência de diversos fatores de influência sobre o processo de adoção de Tecnologia da Informação. Vários aspectos potencializadores das intenções de uso das tecnologias parecem estar presentes nas decisões sobre a adoção de tecnologia como, por exemplo, vantagens relativas obtidas pelo uso da tecnologia, conhecimento requerido para operação dos sistemas, facilidade e utilidade uso da tecnologia, entre outros. No entanto, há estudos que demonstram que o processo de adoção de tecnologia pode não ser explicado, somente, por aspectos financeiros e mercadológicos, mas englobar fatores endógenos que interferem nas decisões dos usuários sobre o uso de tecnologias de informação. Teorias e modelos de adoção de tecnologias conseguem explicar uma parcela dos motivos que levam os indivíduos a se comportarem de acordo com o uso de uma determinada tecnologia. Por exemplo: hábito individual, conectividade e conveniência podem influenciar as preferências de uso de uma determinada tecnologia de informação. De acordo com estas teorias, é possível analisar as influências que os indivíduos percebem e consideram nas decisões como justificativas sobre o uso de tecnologias de comunicação pessoal, além da busca exclusiva por resultados econômicos. Observa-se que um dos segmentos de tecnologia que apresenta condições de diferentes ofertas e múltiplas funcionalidades se refere ao segmento de tecnologias de comunicação de voz no qual o usuário pode se comunicar por meio de linhas telefônicas fixas, móveis, Internet, entre outras formas. Para a operacionalização de uma análise de adoção de tecnologia que englobe múltiplas interações de influências ao usuário, optou-se pela contextualização do estudo com foco na tecnologia de comunicação de voz pela Internet – VOIP, pois quando comparada com outras tecnologias de comunicação, adiciona-se que a gratuidade de ligações entre usuários de um mesmo sistema pode ser apresentada como um dos benefícios econômicos principais, aliada a outros benefícios provindos da telefonia em si. Os resultados obtidos por esta pesquisa confirmam a influência de diversos fatores posicionados em diferentes dimensões e proporcionam conclusões relevantes à adoção das tecnologias de comunicação de voz sobre Internet. Conclui-se que as percepções individuais sobre as características da tecnologia, a rede de contatos do usuário, hábito de uso e incentivos comerciais destinados ao uso de outras tecnologias de comunicação podem formar uma rede de influências à adoção da telefonia VOIP frente às percepções sobre os benefícios que podem ser obtidos com o uso desta aplicação.

Ecoparques empresariais e vantagem competitiva: um estudo sobre o polo verde tecnológico do Rio de Janeiro

Ecoparques Empresariais são novos arranjos empresariais coletivos para uma maior sustentabilidade em nível local. Nesse sentido e pautado pelas discussões em Estratégias Socioambientais Competitivas, o presente estudo buscou analisar quais fatores de vantagem competitiva estão associados a esses empreendimentos. Após a elaboração de um estudo exploratório foi selecionado, por tipicidade e acessibilidade, o Polo Verde Tecnológico do Rio de Janeiro como contexto para condução de um estudo de caso. Especificamente, as unidades de análise foram duas empresas que terão centros de pesquisa no polo, General Electric e L'Oréal. Adicionalmente, atendendo ao critério de multidisciplinaridade para estudos de caso e, em se tratando de arranjos fisicamente localizados, optou-se pela Teoria da Localização como teoria explicativa complementar. Com base nesses dois corpos teóricos foi definido um quadro conceitual utilizado na posterior análise qualitativa. Essa análise que contou com uma triangulação de dados, revelou que a principal vantagem percebida pelas empresas é a proximidade dos mercados consumidores, seguida do apoio do governo, o ambiente de negócios e a disponibilidade de capital intelectual. As questões socioambientais, por sua vez, foram tidas como uma responsabilidade, sendo a competitividade uma questão secundária. Todavia, foram reconhecidos potenciais ganhos dessa estratégia, como reputação, inovação, aumento de produtividade e redução de riscos.

Adoção de governo eletrônico no Brasil: a perspectiva do usuário do Programa Nota Fiscal Paulista

A intensa utilização da tecnologia da informação (TI) por todos os setores disseminou-se também na Administração Pública. A utilização da TI aliada à internet como ferramenta de gestão pública é denominada governo eletrônico e tem como objetivos qualificar melhor a prestação dos serviços e possibilitar aos cidadãos uma participação mais efetiva no processo político. O presente estudo buscou investigar o contexto do governo eletrônico no Brasil e apresenta um modelo de adoção baseado numa iniciativa de informatização de mecanismos de controle fiscal do Estado de São Paulo. O objetivo geral da tese foi estudar quais são os elementos que influenciam a utilização do governo eletrônico no Brasil, por meio de um estudo no programa Nota Fiscal Paulista (NFP). A metodologia envolveu técnicas do método qualitativo, pelo uso de opiniões de especialistas, associadas a procedimentos do método quantitativo, por meio de um survey aplicado em 715 usuários da NFP. A análise utilizou modelagem por equações estruturais. Os resultados contribuem para as pesquisas em TI, apresentando um modelo que reforça e amplia os estudos anteriores sobre adoção tecnológica e os estudos de governo eletrônico, acrescentando um modelo em um novo contexto ainda pouco explorado. No caso da NFP, os fatores testados e que influenciam no processo de adoção são: Benefício Percebido, Facilidade de Uso Percebida, Influências Sociais, Segurança Percebida, Confiança e Hábito. Em termos práticos, a pesquisa auxilia na compreensão da participação e do envolvimento dos cidadãos na fase atual de desenvolvimento de governo eletrônico no Brasil. Com melhor esclarecimento da influência dessa tecnologia na vida pessoal e profissional dos usuários, é possível elevar a qualidade da prestação dos serviços para atender às demandas da sociedade. Isto posto, auxilia também na implantação mais rápida do programa em outros contextos administrativos para o governo eletrônico, gerando informações úteis para os principais pontos a se considerar para ampliar a adesão dos cidadãos e ter mais chance de sucesso na implantação.

Impactos da adoção de sistemas de informação no judiciário: pesquisa com usuários do sistema processual virtual em um juizado especial federal

The Information Technology (IT) is increasing his applicability to business, both private and public companies. It is necessary the adequate use of the new technologies and get cooperation and technology acceptance of the system. People tend to resist to the changes, contributing so that the technology is rejected or even it is not recognized as promoting of the changes. This study is relevant and aim to evaluate the impacts of new technologies, considering their users as fundamental factors in the change process. The survey analyzed the advantages and the barriers of the system use in three federal special judicial of Rio Grande do Norte, with data collected in May of 2007, through the application of questionnaires to thirty eight users of the virtual system CRETA. The users' perception was evaluated, under the optics of five variables: efficiency, image, agility, ease of use and quality. Starting from the obtained results, it was evidenced that the implementation of the system felt accordingly the expected and it reached the objectives intended that were: the velocity and efficiency in the path of the lawsuits, larger productivity, resulting in a better quality of the final work introduced to the citizen and proportionate an improvement in the organizational image of the judiciary power

Fatores que influenciam a aceitação de práticas avançadas de gestão de segurança da informação: um estudo com gestores públicos estaduais no Brasil

This study examines the factors that influence public managers in the adoption of advanced practices related to Information Security Management. This research used, as the basis of assertions, Security Standard ISO 27001:2005 and theoretical model based on TAM (Technology Acceptance Model) from Venkatesh and Davis (2000). The method adopted was field research of national scope with participation of eighty public administrators from states of Brazil, all of them managers and planners of state governments. The approach was quantitative and research methods were descriptive statistics, factor analysis and multiple linear regression for data analysis. The survey results showed correlation between the constructs of the TAM model (ease of use, perceptions of value, attitude and intention to use) and agreement with the assertions made in accordance with ISO 27001, showing that these factors influence the managers in adoption of such practices. On the other independent variables of the model (organizational profile, demographic profile and managers behavior) no significant correlation was identified with the assertions of the same standard, witch means the need for expansion researches using such constructs. It is hoped that this study may contribute positively to the progress on discussions about Information Security Management, Adoption of Safety Standards and Technology Acceptance Model

Fatores críticos de sucesso como antecedentes da aceitação de um sistema de informação em uma universidade federal

In recent decades the public sector comes under pressure in order to improve its performance. The use of Information Technology (IT) has been a tool increasingly used in reaching that goal. Thus, it has become an important issue in public organizations, particularly in institutions of higher education, determine which factors influence the acceptance and use of technology, impacting on the success of its implementation and the desired organizational results. The Technology Acceptance Model - TAM was used as the basis for this study and is based on the constructs perceived usefulness and perceived ease of use. However, when it comes to integrated management systems due to the complexity of its implementation,organizational factors were added to thus seek further explanation of the acceptance of such systems. Thus, added to the model five TAM constructs related to critical success factors in implementing ERP systems, they are: support of top management, communication, training, cooperation, and technological complexity (BUENO and SALMERON, 2008). Based on the foregoing, launches the following research problem: What factors influence the acceptance and use of SIE / module academic at the Federal University of Para, from the users' perception of teachers and technicians? The purpose of this study was to identify the influence of organizational factors, and behavioral antecedents of behavioral intention to use the SIE / module academic UFPA in the perspective of teachers and technical users. This is applied research, exploratory and descriptive, quantitative with the implementation of a survey, and data collection occurred through a structured questionnaire applied to a sample of 229 teachers and 30 technical and administrative staff. Data analysis was carried out through descriptive statistics and structural equation modeling with the technique of partial least squares (PLS). Effected primarily to assess the measurement model, which were verified reliability, convergent and discriminant validity for all indicators and constructs. Then the structural model was analyzed using the bootstrap resampling technique like. In assessing statistical significance, all hypotheses were supported. The coefficient of determination (R ²) was high or average in five of the six endogenous variables, so the model explains 47.3% of the variation in behavioral intention. It is noteworthy that among the antecedents of behavioral intention (BI) analyzed in this study, perceived usefulness is the variable that has a greater effect on behavioral intention, followed by ease of use (PEU) and attitude (AT). Among the organizational aspects (critical success factors) studied technological complexity (TC) and training (ERT) were those with greatest effect on behavioral intention to use, although these effects were lower than those produced by behavioral factors (originating from TAM). It is pointed out further that the support of senior management (TMS) showed, among all variables, the least effect on the intention to use (BI) and was followed by communications (COM) and cooperation (CO), which exert a low effect on behavioral intention (BI). Therefore, as other studies on the TAM constructs were adequate for the present research. Thus, the study contributed towards proving evidence that the Technology Acceptance Model can be applied to predict the acceptance of integrated management systems, even in public. Keywords: Technology

Fatores que influenciam a intenção de compra online: aplicação de um modelo adaptado de aceitação da tecnologia para o comércio eletrônico

This research aims to understand the factors that influence intention to online purchase of consumers, and to identify between these factors those that influence the users and the nonusers of electronic commerce. Thus, it is an applied, exploratory and descriptive research, developed in a quantitative model. Data collection was done through a questionnaire administered to a sample of 194 graduate students from the Centre for Applied Social Sciences of UFRN and data analysis was performed using descriptive statistics, confirmatory factorial analysis and simple and multiple linear regression analysis. The results of descriptive statistics revealed that respondents in general and users of electronic commerce have positive perceptions of ease of use, usefulness and social influence about buying online, and intend to make purchases on Internet over the next six months. As for the non-users of electronic commerce, they do not trust the Internet to transact business, have negative perceptions of risk and social influence over purchasing online, and does not intend to make purchases on Internet over the next six months. Through confirmatory factorial analysis six factors were set up: behavioral intention, perceived ease of use, perceived usefulness, perceived risk, trust and social influence. Through multiple regression analysis, was observed that all these factors influence online purchase intentions of respondents in general, that only the social influence does not influence the intention to continue buying on the Internet from users of electronic commerce, and that only trust and social influence affect the intention to purchase online from non-users of electronic commerce. Through simple regression analysis, was found that trust influences perceptions of ease of use, usefulness and risk of respondents in general and users of electronic commerce, and that trust does not influence the perceptions of risk of non-users of electronic commerce. Finally, it was also found that the perceived ease of use influences perceived usefulness of the three groups. Given this scenario, it was concluded that it is extremely important that organizations that work with online sales know the factors that influence consumers purchasing intentions in order to gain space in their market

Crenças normativas e comportamentais e suas influências na intenção de adoção de um sistema de informação: um estudo na área de compras da UFPA

The study aims to identify the factors that influence the behavior intention to adopt an academic Information System (SIE), in an environment of mandatory use, applied in the procurement process at the Federal University of Pará (UFPA). For this, it was used a model of innovation adoption and technology acceptance (TAM), focused in attitudes and intentions regarding the behavior intention. The research was conducted a quantitative survey, through survey in a sample of 96 administrative staff of the researched institution. For data analysis, it was used structural equation modeling (SEM), using the partial least squares method (Partial Least Square PLS-PM). As to results, the constructs attitude and subjective norms were confirmed as strong predictors of behavioral intention in a pre-adoption stage. Despite the use of SIE is required, the perceived voluntariness also predicts the behavior intention. Regarding attitude, classical variables of TAM, like as ease of use and perceived usefulness, appear as the main influence of attitude towards the system. It is hoped that the results of this study may provide subsidies for more efficient management of the process of implementing systems and information technologies, particularly in public universities

Aceitação e uso de ambiente virtual de aprendizagem no contexto de um curso de capacitação para servidores públicos

This study aimed to examine how students perceives the factors that may influence them to attend a training course offered in the distance virtual learning environment (VLE) of the National School of Public Administration (ENAP). Thus, as theoretical basis it was used the Unified Theory of Acceptance and Use of Technology (UTAUT), the result of an integration of eight previous models which aimed to explain the same phenomenon (acceptance/use of information technology). The research approach was a quantitative and qualitative. To achieve the study objectives were made five semi-structured interviews and an online questionnaire (websurvey) in a valid sample of 101 public employees scattered throughout the country. The technique used to the analysis of quantitative data was the structural equation modeling (SEM), by the method of Partial Least Square Path Modeling (PLS-PM). To qualitative data was the thematic content analysis. Among the results, it was found that, in the context of public service, the degree whose the individual believes that the use of an AVA will help its performance at work (performance expectancy) is a factor to its intended use and also influence its use. Among the results, it was found that the belief which the public employee has in the use of a VLE as a way to improve the performance of his work (performance expectation) was determinant for its intended use that, in turn, influenced their use. It was confirmed that, under the voluntary use of technology, the general opinion of the student s social circle (social influence) has no effect on their intention to use the VLE. The effort expectancy and facilitating conditions were not directly related to the intended use and use, respectively. However, emerged from the students speeches that the opinions of their coworkers, the ease of manipulate the VLE, the flexibility of time and place of the distance learning program and the presence of a tutor are important to their intentions to do a distance learning program. With the results, it is expected that the managers of the distance learning program of ENAP turn their efforts to reduce the impact of the causes of non-use by those unwilling to adopt voluntarily the e-learning, and enhance the potentialities of distance learning for those who are already users

A rede de marcação e recaptura: o caso de borboletas do gênero heliconius

(The Mark and Recapture Network: a Heliconius case study). The current pace of habitat destruction, especially in tropical landscapes, has increased the need for understanding minimum patch requirements and patch distance as tools for conserving species in forest remnants. Mark recapture and tagging studies have been instrumental in providing parameters for functional models. Because of their popularity, ease of manipulation and well known biology, butterflies have become model in studies of spatial structure. Yet, most studies on butterflies movement have focused on temperate species that live in open habitats, in which forest patches are barrier to movement. This study aimed to view and review data from mark-recapture as a network in two species of butterfly (Heliconius erato and Heliconius melpomene). A work of marking and recapture of the species was carried out in an Atlantic forest reserve located about 20km from the city of Natal (RN). Mark recapture studies were conducted in 3 weekly visits during January-February and July-August in 2007 and 2008. Captures were more common in two sections of the dirt road, with minimal collection in the forest trail. The spatial spread of captures was similar in the two species. Yet, distances between recaptures seem to be greater for Heliconius erato than for Heliconius melpomene. In addition, the erato network is more disconnected, suggesting that this specie has shorter traveling patches. Moving on to the network, both species have similar number of links (N) and unweighed vertices (L). However, melpomene has a weighed network 50% more connections than erato. These network metrics suggest that erato has more compartmentalized network and restricted movement than melpomene. Thus, erato has a larger number of disconnected components, nC, in the network, and a smaller network diameter. The frequency distribution of network connectivity for both species was better explained by a Power-law than by a random, Poissom distribution, showing that the Power-law provides a better fit than the Poisson for both species. Moreover, the Powerlaw erato is much better adjusted than in melpomene, which should be linked to the small movements that erato makes in the network