Greener Alternatives to Selected Organic Oxidation Reactions

The study of green chemistry is dedicated to eliminating or reducing toxic waste. One route to accomplish this goal is to explore alternative reaction conditions and parameters resulting in the development of more benign synthetic routes and reagents. The primary focus of this research is to find optimal reaction conditions for the oxidation of a primary alcohol to an aldehyde. As a case study, the oxidation of benzyl alcohol to benzaldehyde, a common industrial process, was examined. Traditionally carried out using the Jones Reagent, commonly referred to as chromium (IV) oxide or chromium trioxide (CrO3) in sulphuric acid, a great deal of research went into utilizing less toxic reagents, such as MnO2 or KMnO4 supported on a clay base. This research has led to an improvement on these alternatives, using a lithium chloride (LiCl) catalyst in a montmorillonite K10 clay solid phase, together with the oxidizing agent hydrogen peroxide, as even greener alternatives to these traditional oxidizing agents. Experiments were carried out to determine the lifetime of this LiCl/clay system as compared to MnO2 and KMnO4, to investigate its ability to catalyze the oxidation of other aromatic alcohols (such as 4-methoxybenzyl alcohol and diphenylmethanol), and to further improve the system’s adherence to green chemistry principles. Green solvent alternatives were examined by replacing the toluene solvent with dimethylcarbonate (DMC), and reaction conditions were optimized to improve product yield. It was determined that the LiCl/H2O2 system was, in most cases, equally as effective at catalyzing the oxidation of benzyl alcohol to benzaldehyde. Although the catalyst and oxidizing agent eliminated the toxic waste generated from chromium reagents, it offered significant challenges in product isolation, because of an aqueous-organic phase separation.

Uma vida de relações falhadas: continuidade ou mudança?: estudo sobre a herança psíquica e os desamores narcísicos na vida adulta

Este estudo propôs-se investigar, como os Esquemas Iniciais Desadaptativos (EIDs) concebidos pelo indivíduo e a sua representação dos Estilos Parentais (EPs), influenciam na escolha amorosa da vida adulta considerando os relacionamentos amorosos de reparação narcísica: Submisso-Idealizador, Eufórico-Idealizante e Evitante-Desnarcisante. A amostra constituiu-se por 225 (jovens) adultos/as portugueses/as, entre os 23 e 63 anos, que tivessem tido ou possuíssem na altura do estudo uma relação amorosa. A investigação de natureza quantitativa utilizou como instrumentos o: Inventário de Tipos de Relacionamento Amoroso (ITRA), Questionário de Esquemas (QE) e Questionário de Estilos Parentais (QEP). Segundo os resultados, evidenciou-se a associação de EIDs0F 1 e EPs1F 2 mais precoces e rígidos (incondicionais) aos três tipos de relacionamento amoroso, verificou-se uma herança psíquica trans-geracional com conteúdos individuais e relacionais mantidos e apurou-se a necessidade de o sujeito procurar relações fornecedoras de uma imagem mais completa do seu self desestruturado, concluindo-se que houve uma continuidade de relações falhadas; Abstract: A lifetime of failed relationships: continuity or change? Study about the psychic heritage and narcissistic unlove in adulthood. This study proposes to investigate, how the Early Maladaptive Schemas (EIDs) conceived by the individual and, their representation about the Parental Styles (EPs), influence the choice of adulthood loving relationships considering the romantic relationships of narcissistic repair: Submissive-Idealizer, Euphoric-Idealizing and Avoidant-Devaluate. The sample consisted of 225 Portuguese (young) adults, between 23 and 63 years old, who have had or maintained at the time of the study a loving relationship. The quantitative research used as instruments the: Inventory Types of Loving Relationship (ITRA), Schema Questionnaire (QE) and Parental Styles Questionnaire (QEP). According to the results, it showed the association of more early and rigid (unconditional) EIDs2F 3 and EPs3F 4 with the three types of love relationship, it was found a trans-generational psychic inheritance with individual and relational content maintained and found out the need for the subject pursuit for supplier relations of a more complete image of your self unstructured, concluding that there was a continuity of failed relationships.

Epigenetics and alternative splicing

Dissertação de Mestrado, Oncobiologia: Mecanismos Moleculares do Cancro, Departamento de Ciências Biomédicas e Medicina, Universidade do Algarve, 2015

'Ephemerality’ in game development: opportunitiees and challenges

Ephemeral Computation (Eph-C) is a newly created computation paradigm, the purpose of which is to take advantage of the ephemeral nature (limited lifetime) of computational resources. First we speak of this new paradigm in general terms, then more specifically in terms of videogame development. We present possible applications and benefits for the main research fields associated with videogame development. This is a preliminary work which aims to investigate the possibilities of applying ephemeral computation to the products of the videogame industry. Therefore, as a preliminary work, it attempts to serve as the inspiration for other researchers or videogame developers.

Wireless Sensor Network Deployment

Wireless Sensor Networks (WSNs) are widely used for various civilian and military applications, and thus have attracted significant interest in recent years. This work investigates the important problem of optimal deployment of WSNs in terms of coverage and energy consumption. Five deployment algorithms are developed for maximal sensing range and minimal energy consumption in order to provide optimal sensing coverage and maximum lifetime. Also, all developed algorithms include self-healing capabilities in order to restore the operation of WSNs after a number of nodes have become inoperative. Two centralized optimization algorithms are developed, one based on Genetic Algorithms (GAs) and one based on Particle Swarm Optimization (PSO). Both optimization algorithms use powerful central nodes to calculate and obtain the global optimum outcomes. The GA is used to determine the optimal tradeoff between network coverage and overall distance travelled by fixed range sensors. The PSO algorithm is used to ensure 100% network coverage and minimize the energy consumed by mobile and range-adjustable sensors. Up to 30% - 90% energy savings can be provided in different scenarios by using the developed optimization algorithms thereby extending the lifetime of the sensor by 1.4 to 10 times. Three distributed optimization algorithms are also developed to relocate the sensors and optimize the coverage of networks with more stringent design and cost constraints. Each algorithm is cooperatively executed by all sensors to achieve better coverage. Two of our algorithms use the relative positions between sensors to optimize the coverage and energy savings. They provide 20% to 25% more energy savings than existing solutions. Our third algorithm is developed for networks without self-localization capabilities and supports the optimal deployment of such networks without requiring the use of expensive geolocation hardware or energy consuming localization algorithms. This is important for indoor monitoring applications since current localization algorithms cannot provide good accuracy for sensor relocation algorithms in such indoor environments. Also, no sensor redeployment algorithms, which can operate without self-localization systems, developed before our work.

Temporal solitonic crystals and non-Hermitian informational lattices

Clusters of temporal optical solitons—stable self-localized light pulses preserving their form during propagation—exhibit properties characteristic of that encountered in crystals. Here, we introduce the concept of temporal solitonic information crystals formed by the lattices of optical pulses with variable phases. The proposed general idea offers new approaches to optical coherent transmission technology and can be generalized to dispersion-managed and dissipative solitons as well as scaled to a variety of physical platforms from fiber optics to silicon chips. We discuss the key properties of such dynamic temporal crystals that mathematically correspond to non-Hermitian lattices and examine the types of collective mode instabilities determining the lifetime of the soliton train. This transfer of techniques and concepts from solid state physics to information theory promises a new outlook on information storage and transmission.

Beginner's guide to fishing

With some basic knowledge and minimum skill, a beginning angler can embark on a lifetime of fun, relaxation and camaraderie with other anglers. Discussed in this booklet are several styles of fishing, types of rods, reels, knots, baits, lures, freshwater fish and aquatic habitats. You’ll find tips to improve your skills and prepare you for a fun, exciting and successful fishing trip. You’ll also learn ways to protect your aquatic resources.

O ROMANCE HISTÓRICO E A PROBLEMÁTICA DO DISTANCIAMENTO TEMPORAL ENTRE O FATO NARRADO E O PERÍODO DE VIDA DO AUTOR

The article discusses the great controversy over the time gap between the narrated fact and the author’s life period in the concept of the historical romance. For many literary critics, perhaps most of them, it is necessary that the action of the novel, or at least most of it, happens in a period of time before the lifetime of the novelist, and for others, this criteria is too rigid and outdated. Therefore and taking into consideration that George Lukacs, the first theorist of historical novel, placed Balzac in the group of novelists as one of the followers of Walter Scott’s techniques, stating that the French novelist “created a superior type and so far unknown historical novel, which is a representation of this as history, this article presents a reflection on the controversy, checking whether there is really need that the temporal distance has a greater relevance than the dialogue with history and its representation in the characterization of a historical novel.

The user query based learning system for lifetime prediction of metallic components

Real-World Data Mining Applications generally do not end up with the creation of the models. The use of the model is the final purpose especially in prediction tasks. The problem arises when the model is built based on much more information than that the user can provide in using the model. As a result, the performance of model reduces drastically due to many missing attributes values. This paper develops a new learning system framework, called as User Query Based Learning System (UQBLS), for building data mining models best suitable for users use. We demonstrate its deployment in a real-world application of the lifetime prediction of metallic components in buildings

Development of lifetime warranty policies and models for estimating costs

In today's fiercely competitive products market, product warranty has started playing an important role. The warranty period offered by the manufacturer/dealer has been progressively increasing since the beginning of the 20th Century. Currently, a large number of products are being sold with long-term warranty policies in the form of extended warranty, warranty for used products, service contracts and lifetime warranty policies. Lifetime warranties are relatively a new concept. The modelling of failures during the warranty period and the costs for such policies are complex since the lifespan in these policies are not defined well and it is often difficult to tell about life measures for the longer period of coverage due to usage pattern/maintenance activities undertaken and uncertainties of costs over the period. This paper focuses on defining lifetime, developing lifetime warranty policies and models for predicting failures and estimating costs for lifetime warranty policies.

Assessment of lifetime cumulative sun exposure using a self-administered questionnaire : reliability of two approaches

Few studies have evaluated the reliability of lifetime sun exposure estimated from inquiring about the number of hours people spent outdoors in a given period on a typical weekday or weekend day (the time-based approach). Some investigations have suggested that women have a particularly difficult task in estimating time outdoors in adulthood due to their family and occupational roles. We hypothesized that people might gain additional memory cues and estimate lifetime hours spent outdoors more reliably if asked about time spent outdoors according to specific activities (an activity-based approach). Using self-administered, mailed questionnaires, test-retest responses to time-based and to activity-based approaches were evaluated in 124 volunteer radiologic technologist participants from the United States: 64 females and 60 males 48 to 80 years of age. Intraclass correlation coefficients (ICC) were used to evaluate the test-retest reliability of average number of hours spent outdoors in the summer estimated for each approach. We tested the differences between the two ICCs, corresponding to each approach, using a t test with the variance of the difference estimated by the jackknife method. During childhood and adolescence, the two approaches gave similar ICCs for average numbers of hours spent outdoors in the summer. By contrast, compared with the time-based approach, the activity-based approach showed significantly higher ICCs during adult ages (0.69 versus 0.43, P = 0.003) and over the lifetime (0.69 versus 0.52, P = 0.05); the higher ICCs for the activity-based questionnaire were primarily derived from the results for females. Research is needed to further improve the activity-based questionnaire approach for long-term sun exposure assessment. (Cancer Epidemiol Biomarkers Prev 2009;18(2):464–71)

The economics of happiness : a lifetime perspective

The three studies in this thesis focus on happiness and age and seek to contribute to our understanding of happiness change over the lifetime. The first study contributes by offering an explanation for what was evolving to a ‘stylised fact’ in the economics literature, the U-shape of happiness in age. No U-shape is evident if one makes a visual inspection of the age happiness relationship in the German socio-economic panel data, and, it seems counter-intuitive that we just have to wait until we get old to be happy. Eliminating the very young, the very old, and the first timers from the analysis did not explain away regression results supporting the U-shape of happiness in age, but fixed effect analysis did. Analysis revealed found that reverse causality arising from time-invariant individual traits explained the U-shape of happiness in age in the German population, and the results were robust across six econometric methods. Robustness was added to the German fixed effect finding by replicating it with the Australian and the British socio-economic panel data sets. During analysis of the German data an unexpected finding emerged, an exceedingly large negative linear effect of age on happiness in fixed-effect regressions. There is a large self-reported happiness decline by those who remain in the German panel. A similar decline over time was not evident in the Australian or the British data. After testing away age, time and cohort effects, a time-in-panel effect was found. Germans who remain in the panel for longer progressively report lower levels of happiness. Because time-in-panel effects have not been included in happiness regression specifications, our estimates may be biased; perhaps some economics of the happiness studies, that used German panel data, need revisiting. The second study builds upon the fixed-effect finding of the first study and extends our view of lifetime happiness to a cohort little visited by economists, children. Initial analysis extends our view of lifetime happiness beyond adulthood and revealed a happiness decline in adolescent (15 to 23 year-old) Australians that is twice the size of the happiness decline we see in older Australians (75 to 86 yearolds), who we expect to be unhappy due to declining income, failing health and the onset of death. To resolve a difference of opinion in the literature as to whether childhood happiness decreases, increases, or remains flat in age; survey instruments and an Internet-based survey were developed and used to collect data from four hundred 9 to 14 year-old Australian children. Applying the data to a Model of Childhood Happiness revealed that the natural environment life-satisfaction domain factor did not have a significant effect on childhood happiness. However, the children’s school environment and interactions with friends life-satisfaction domain factors explained over half a steep decline in childhood happiness that is three times larger than what we see in older Australians. Adding personality to the model revealed what we expect to see with adults, extraverted children are happier, but unexpectedly, so are conscientious children. With the steep decline in the happiness of young Australians revealed and explanations offered, the third study builds on the time-invariant individual trait finding from the first study by applying the Australian panel data to an Aggregate Model of Average Happiness over the lifetime. The model’s independent variable is the stress that arises from the interaction between personality and the life event shocks that affect individuals and peers throughout their lives. Interestingly, a graphic depiction of the stress in age relationship reveals an inverse U-shape; an inverse U-shape that looks like the opposite of the U-shape of happiness in age we saw in the first study. The stress arising from life event shocks is found to explain much of the change in average happiness over a lifetime. With the policy recommendations of economists potentially invoking unexpected changes in our lives, the ensuing stress and resulting (un)happiness warrant consideration before economists make policy recommendations.

Assessing the impacts of lifetime sun exposure on skin damage and skin aging using a non-invasive method

Background: Ultraviolet radiation exposure during an individuals' lifetime is a known risk factor for the development of skin cancer. However, less evidence is available on assessing the relationship between lifetime sun exposure and skin damage and skin aging. Objectives: This study aims to assess the relationship between lifetime sun exposure and skin damage and skin aging using a non-invasive measure of exposure. Methods: We recruited 180 participants (73 males, 107 females) aged 18-83 years. Digital imaging of skin hyper-pigmentation (skin damage) and skin wrinkling (skin aging) on the facial region was measured. Lifetime sun exposure (presented as hours) was calculated from the participants' age multiplied by the estimated annual time outdoors for each year of life. We analyzed the effects of lifetime sun exposure on skin damage and skin aging. We adjust for the influence of age, sex, occupation, history of skin cancer, eye color, hair color, and skin color. Results: There were non-linear relationships between lifetime sun exposure and skin damage and skin aging. Younger participant's skin is much more sensitive to sun exposure than those who were over 50 years of age. As such, there were negative interactions between lifetime sun exposure and age. Age had linear effects on skin damage and skin aging. Conclusion: The data presented showed that self reported lifetime sun exposure was positively associated with skin damage and skin aging, in particular, the younger people. Future health promotion for sun exposure needs to pay attention to this group for skin cancer prevention messaging. (C) 2012 Elsevier B.V. All rights reserved.