Utilização do D-manitol em síntese orgânica

D-mannitol is used in several fields including food, pharmaceuticals, cosmetics and textiles being an important carbohydrate found widespread in nature. Due to its chirality, it is largely used in organic synthesis with several applications, such as ligands, polymers, chiral pool, for preparation of small chiral building blocks, key intermediates in total synthesis. In this context, the aim of this review is to highlights recent applications of D-mannitol, especially in total synthesis.

Quiralidade em moléculas e cristais

The present contribution describes some concepts of stereochemistry and chirality in molecules and crystals. This paper also reports on the development of a simple and fast experiment to prepare and recognize conglomerate and true racemate of tartaric acid produced by mechanic mixture of commercial enantiomers and recristalization. Optical activity and melting point of mixtures are also used in the analysis.

Evolução biomolecular homoquiral: a origem e a amplificação da quiralidade nas moléculas da vida

The fact that biologically relevant molecules exist only as one of the two enantiomers is a fascinating example of complete symmetry breaking of chirality and has long intrigued our curiosity. The origin of this selective chirality has remained a fundamental enigma with regard to the origin of life since the time of Pasteur, 160 years ago. The symmetry breaking processes, which include autocatalytic crystallization, asymmetric autocatalysis, spontaneous crystallization, adsorption and polymerization of amino acids on mineral surfaces, provide new insights into the origin of biomolecular homochirality.

Methane combustion kinetic rate constants determination: an ill-posed inverse problem analysis

Methane combustion was studied by the Westbrook and Dryer model. This well-established simplified mechanism is very useful in combustion science, for computational effort can be notably reduced. In the inversion procedure to be studied, rate constants are obtained from [CO] concentration data. However, when inherent experimental errors in chemical concentrations are considered, an ill-conditioned inverse problem must be solved for which appropriate mathematical algorithms are needed. A recurrent neural network was chosen due to its numerical stability and robustness. The proposed methodology was compared against Simplex and Levenberg-Marquardt, the most used methods for optimization problems.

Tratamento de dados censurados em estudos ambientais

Due to the inherent limitations of the analytical methods of measurement, environmental exposure data often present observations described as below a certain detection limit, also called left-censored data. Censored data directly interferes in almost all types of statistical analyzes, including descriptive parameters, hypothesis testing, confidence intervals, correlations and regressions. In this work, we investigated the performance of the main classes of methods from major publications available in the literature, considering their advantages and limitations. Some criteria for selecting the best method of dealing with censored data are presented.

Fatigue analysis of brackets with and without scallop for bridge and other deck structure using effective notch stress.

Due to functional requirement of a structural detail brackets with and without scallop are frequently used in bridges, decks, ships and offshore structure. Scallops are designed to serve as passage way for fluids, to reduce weld length and plate distortions. Moreover, scallops are used to avoid intersection of two or more welds for the fact that there is the presence of inventible inherent initial crack except for full penetrated weld and the formation of multi-axial stress state at the weld intersection. Welding all around the scallop corner increase the possibility of brittle fracture even for the case the bracket is not loaded by primary load. Avoiding of scallop will establish an initial crack in the corner if bracket is welded by fillet welds. If the two weld run pass had crossed, this would have given a 3D residual stress situation. Therefore the presences and absence of scallop necessitates the 3D FEA fatigue resistance of both types of brackets using effective notch stress approach ( ). FEMAP 10.1 with NX NASTRAN was used for the 3D FEA. The first and main objective of this research was to investigate and compare the fatigue resistance of brackets with and without scallop. The secondary goal was the fatigue design of scallops in case they cannot be avoided for some reason. The fatigue resistance for both types of brackets was determined based on approach using 1 mm fictitiously rounded radius based on IIW recommendation. Identical geometrical, boundary and loading conditions were used for the determination and comparison of fatigue resistance of both types of brackets using linear 3D FEA. Moreover the size effect of bracket length was also studied using 2D SHELL element FEA. In the case of brackets with scallop the flange plate weld toe at the corner of the scallop was found to exhibit the highest and made the flange plate weld toe critical for fatigue failure. Whereas weld root and weld toe at the weld intersections were the highly stressed location for brackets without scallop. Thus weld toe for brackets with scallop, and weld root and weld toe for brackets without scallop were found to be the critical area for fatigue failure. Employing identical parameters on both types of brackets, brackets without scallop had the highest except for full penetrated weld. Furthermore the fatigue resistance of brackets without scallop was highly affected by the lack of weld penetration length and it was found out that decreased as the weld penetration was increased. Despite the fact that the very presence of scallop reduces the stiffness and also same time induce stress concentration, based on the 3D FEA it is worth concluding that using scallop provided better fatigue resistance when both types of brackets were fillet welded. However brackets without scallop had the highest fatigue resistance when full penetration weld was used. This thesis also showed that weld toe for brackets with scallop was the only highly stressed area unlike brackets without scallop in which both weld toe and weld root were the critical locations for fatigue failure when different types of boundary conditions were used. Weld throat thickness, plate thickness, scallop radius, lack of weld penetration length, boundary condition and weld quality affected the fatigue resistance of both types of brackets. And as a result, bracket design procedure, especially welding quality and post weld treatment techniques significantly affect the fatigue resistance of both type of brackets.

On the institution of the moral subject: on the commander and the commanded in Nietzsche's discussion of law

The article discusses how Nietzsche understands the institution of law and morals in distinction to Kant and the Christian tradition. It argues that Nietzsche to a large extent is inspired by the paradigm-shift toward a evolutionary biological thinking introduced by several of his peers in the late 19th century, among else F. A. Lange, who sees this shift as a sobering scientific-materialistic alternative to Kant. In Nietzsche, the Kantian moral imperative is replaced with a notion of a morality emerging thanks to historical, or pre-historical, civilizational processes, imposed on a feebleminded human without any inherent rational dispositions to obey Law. It is also a process, which rather than universalizing the human, splits it in a duality where one part obeys old immediate self-interests and another part obeys new 'commands,' having been shouted 'into the ear' by a so-called 'commander.' The compliance with law takes two radically different forms in Nietzsche: servile and mediocre individuals need to be exposed to discipline and punishment in order to adopt Law; while so-called 'sovereign' individuals are able to impose law upon themselves. The figure of the 'sovereign' has consequently been an issue for vigorous debate in especially the Anglo-Saxon tradition of Nietzsche research, since his apparent 'respect for law' and 'sense of duty' reiterate typical Kantian qualities. Relating to these discussions, I suggest that Nietzsche's 'sovereign' (in one context) is identical his 'commander' (in other contexts). When the 'sovereign' as such imposes law upon himself and others, his act is conventional and arbitrary (like language in Saussure), and is rather irrational than rational as in Kant. His will is not a good will, nor a rational will with a vision of human autonomy. His command of himself and others is a performative, thus without truth-value (like illocutionary speech-acts in Austin and Searle).

Makt som fullmakt : ett vårdvetenskapligt perspektiv

The aim of this study is to deepen understanding and knowledge of the concepts and phenomenaof power and authority from the standpoint of caring science. The overall questions of the research are: What is power? What is authority? How do power and authority manifest themselves in the context of caring? How are power and authorityto be understood as caring science concepts? The overall research inception is determination of the concepts in accordance with the hermeneutic approach based on Eriksson's model. The process of understanding follows Gadamer's (1999) hermeneutics. The thesis consists of three part studies. An ontological determinationof the character of the concepts is carried out where a hermeneutic interpretation is made of texts in the Old and the New Testaments in the Bible. The pragmatic features of the concepts are studied on the basis of nurses' written stories of authority and patients' written stories of power and authority. Beside the review of literature concerning power and authority a qualitative meta-analysis ofthe concept and the phenomenon of empowerment are made. The ontological determination shows how a human being's power is the authority to hold every living thing in trust, to tend and care life. To anyone using this authority, serving onesfellow-being is the purpose. Understanding the pragmatical features of authority in the stories of nurses reveals the life-giving nature of serving. By serving the nurse draws near her true mission as a human being, her authority to care for life with love. The service of the nurse and her ability to see and confirm the patient's otherness creates confidence and results in her authority. The nursedoes not abandon the responsibility associated with authority. When the patientdoes not entrust the nurse with authority the nurse employs her inherent authority to alleviate the suffering of the patient. The pragmatical features of the concepts of power and authority in the patients' stories indicate how the nurse puts her power to an improper use if she only makes use of the authority conferred by the hierarchy of power in the organisation, assumes all power and fails to use her faculty for loving care. Patients feel that their existence is threatened when the nurse tries to deprive them of their authority; they experience homelessness, despair and impotence. Patients' struggle for existence and absolute dignity deprives their health processes of strength, and their suffering becomes unbearable. Patients recognize their vitality when encountering a nurse who uses her authority to alleviate the patients' suffering. The power of compassion is strong, and the patients' dignity is recreated when they are able to serve fellowpatients or nurses. The purpose of human life can be understood as the use of one's own inner power and strength. Love.

Kroppen som bärare av hälsa och lidande

The overall aim of this study is to seek new knowledge and deeper understanding of the body as a phenomenon from a caring science point of view. By means of a hermeneutic definition, the body is studied on a contextual as well as an ontological level in order to create a deeper understanding for human beings in relation to health and suffering. The study focuses of the body as a perspective of human beings. It is important for the knowledge growth in caring science to create a deeper understanding for the body, thus making it possible to understand patients in nursing care. The overall methodology is a hermeneutic definition which covers a contextual and an ontological concept definition. In the three empirical studies, Giorgi’s phenomenological method was used. The first empirical study comprises twelve students’ statements about experiences of their body in different situatons in life. The second study is composed of interviews with fifteen patients who had been afflicted by illness and been subjected to surgical treatment. In the third empirical study, ten patients who had been cared for in perioperative nursing care were interviewed. In the data analysis, the essential meaning of the body as a phenomenon is described, along with its variations and nuances. In the ontological determination of the body, an etymologic and semantic analysis is carried out, as well as a qualitative analysis of ideas, where the material is comprised of chosen texts on the body from different perspectives. In the concluding analysis the results were synthesized. The result of the first empirical study shows that a body is expressive and manifests movement in its striving for dignity. The body harbours language and inherent powers to cope with the unexpected, as well as feelings of anxiety, fear and powerlessness. The second study shows that the body is experienced as mysterious when it is afflicted by illness, but it is also found mysterious as an opponent to man and life. A battle is fought between the illness that breaks down the body, and human beings fighting to keep their unity whole. The body appears as a prison and a host for a threatening illness. The body bears a feeling of powerlessness when it is changed by illness and suffering. In a care and treatment context, the body is objectified by the patient and the caregiver. It is the illness that forces the patient to sacrifice parts of the body in order to once again become whole in the unity. The third study shows that the patient in a perioperative nursing context delivers him-/herself over to the hands of the caregiver, who defends and protects body and life. The patient experiences a sense of well-being when the caretaker receives him/her and protects the body from dangers. Suffering is alleviated when the patients are allowed to talk about what has happened in their body. The result of the semantic analysis shows that the body as a concept is described as bending around the human soul and spirit. Linguistically, dimensions like corporeal, shape, totality, unity and mortal clay, are described. Different ideas about the body described it as: a material animate part of man, active and demanding, something that perceives its surrounding world and as a subjective body of senses, thoughts and language. Ideas about the body also describe it as a biological and physiological, living organism, submitted to the laws of nature, a passive apparatus and a socially constructed gender. The results of the different studies were synthesized and reflected against a caring science perspective. The research has created a deeper understanding for the body as a material abode and as an entity of body, soul and spirit.

Experiences in using a structured method in finding and defining new innovations: the strategic options approach

Investment decision-making on far-reaching innovation ideas is one of the key challenges practitioners and academics face in the field of innovation management. However, the management practices and theories strongly rely on evaluation systems that do not fit in well with this setting. These systems and practices normally cannot capture the value of future opportunities under high uncertainty because they ignore the firm’s potential for growth and flexibility. Real options theory and options-based methods have been offered as a solution to facilitate decision-making on highly uncertain investment objects. Much of the uncertainty inherent in these investment objects is attributable to unknown future events. In this setting, real options theory and methods have faced some challenges. First, the theory and its applications have largely been limited to market-priced real assets. Second, the options perspective has not proved as useful as anticipated because the tools it offers are perceived to be too complicated for managerial use. Third, there are challenges related to the type of uncertainty existing real options methods can handle: they are primarily limited to parametric uncertainty. Nevertheless, the theory is considered promising in the context of far-reaching and strategically important innovation ideas. The objective of this dissertation is to clarify the potential of options-based methodology in the identification of innovation opportunities. The constructive research approach gives new insights into the development potential of real options theory under non-parametric and closeto- radical uncertainty. The distinction between real options and strategic options is presented as an explanans for the discovered limitations of the theory. The findings offer managers a new means of assessing future innovation ideas based on the frameworks constructed during the course of the study.

Non-Markovian Dynamics in Continuous Variable Quantum Systems

The present manuscript represents the completion of a research path carried forward during my doctoral studies in the University of Turku. It contains information regarding my scientific contribution to the field of open quantum systems, accomplished in collaboration with other scientists. The main subject investigated in the thesis is the non-Markovian dynamics of open quantum systems with focus on continuous variable quantum channels, e.g. quantum Brownian motion models. Non-Markovianity is here interpreted as a manifestation of the existence of a flow of information exchanged by the system and environment during the dynamical evolution. While in Markovian systems the flow is unidirectional, i.e. from the system to the environment, in non-Markovian systems there are time windows in which the flow is reversed and the quantum state of the system may regain coherence and correlations previously lost. Signatures of a non-Markovian behavior have been studied in connection with the dynamics of quantum correlations like entanglement or quantum discord. Moreover, in the attempt to recognisee non-Markovianity as a resource for quantum technologies, it is proposed, for the first time, to consider its effects in practical quantum key distribution protocols. It has been proven that security of coherent state protocols can be enhanced using non-Markovian properties of the transmission channels. The thesis is divided in two parts: in the first part I introduce the reader to the world of continuous variable open quantum systems and non-Markovian dynamics. The second part instead consists of a collection of five publications inherent to the topic.

Computational modeling for irrigated agriculture planning. Part II: risk analysis

Techniques of evaluation of risks coming from inherent uncertainties to the agricultural activity should accompany planning studies. The risk analysis should be carried out by risk simulation using techniques as the Monte Carlo method. This study was carried out to develop a computer program so-called P-RISCO for the application of risky simulations on linear programming models, to apply to a case study, as well to test the results comparatively to the @RISK program. In the risk analysis it was observed that the average of the output variable total net present value, U, was considerably lower than the maximum U value obtained from the linear programming model. It was also verified that the enterprise will be front to expressive risk of shortage of water in the month of April, what doesn't happen for the cropping pattern obtained by the minimization of the irrigation requirement in the months of April in the four years. The scenario analysis indicated that the sale price of the passion fruit crop exercises expressive influence on the financial performance of the enterprise. In the comparative analysis it was verified the equivalence of P-RISCO and @RISK programs in the execution of the risk simulation for the considered scenario.

Uncertainties of the 137Cs technique for validation of soil redistribution modelling in a semiarid meso-scale watershed

Scarcity of long-term series of sediment-related variables has led watershed managers to apply mathematical models to simulate sediment fluxes. Due to the high efforts for installation and maintenance of sedimentological gauges, tracers have been pointed out as an alternative to validate soil redistribution modelling. In this study, the 137Cs technique was used to assess the WASA-SED model performance at the Benguê watershed (933 km²), in the Brazilian semiarid. Qualitatively, good agreement was found among the 137Cs technique and the WASA-SED model results. Nonetheless, quantitatively great differences, up to two orders of magnitude, were found between the two methods. Among the uncertainties inherent to the 137Cs technique, definition of the reference inventory seems to be a major source of imprecision. In addition, estimations of water and sediment fluxes with mathematical models usually also present high uncertainty, contributing to the quantitative differences of the soil redistribution estimates with the two methods.

“IT’S ALL RIGHT”. Multimodal rightward spatial bias modified by age and praxis

The general goal of the present work was to study whether spatial perceptual asymmetry initially observed in linguistic dichotic listening studies is related to the linguistic nature of the stimuli and/or is modality-specific, as well as to investigate whether the spatial perceptual/attentional asymmetry changes as a function of age and sensory deficit via praxis. Several dichotic listening studies with linguistic stimuli have shown that the inherent perceptual right ear advantage (REA), which presumably results from the left lateralized linguistic functions (bottom-up processes), can be modified with executive functions (top-down control). Executive functions mature slowly during childhood, are well developed in adulthood, and decline as a function of ageing. In Study I, the purpose was to investigate with a cross-sectional experiment from a lifespan perspective the age-related changes in top-down control of REA for linguistic stimuli in dichotic listening with a forced-attention paradigm (DL). In Study II, the aim was to determine whether the REA is linguistic-stimulus-specific or not, and whether the lifespan changes in perceptual asymmetry observed in dichotic listening would exist also in auditory spatial attention tasks that put load on attentional control. In Study III, using visual spatial attention tasks, mimicking the auditory tasks applied in Study II, it was investigated whether or not the stimulus-non-specific rightward spatial bias found in auditory modality is a multimodal phenomenon. Finally, as it has been suggested that the absence of visual input in blind participants leads to improved auditory spatial perceptual and cognitive skills, the aim in Study IV was to determine, whether blindness modifies the ear advantage in DL. Altogether 180-190 right-handed participants between 5 and 79 years of age were studied in Studies I to III, and in Study IV the performance of 14 blind individuals was compared with that of 129 normally sighted individuals. The results showed that only rightward spatial bias was observed in tasks with intensive attentional load, independent of the type of stimuli (linguistic vs. non-linguistic) or the modality (auditory vs. visual). This multimodal rightward spatial bias probably results from a complex interaction of asymmetrical perceptual, attentional, and/or motor mechanisms. Most importantly, the strength of the rightward spatial bias changed as a function of age and augmented praxis due to sensory deficit. The efficiency of the performance in spatial attention tasks and the ability to overcome the rightward spatial bias increased during childhood, was at its best in young adulthood, and decreased as a function of ageing. Between the ages of 5 and 11 years probably at first develops movement and impulse control, followed by the gradual development of abilities to inhibit distractions and disengage attention. The errors especially in bilateral stimulus conditions suggest that a mild phenomenon resembling extinction can be observed throughout the lifespan, but especially the ability to distribute attention to multiple targets simultaneously decreases in the course of ageing. Blindness enhances the processing of auditory bilateral linguistic stimuli, the ability to overcome a stimulus-driven laterality effect related to speech sound perception, and the ability to direct attention to an appropriate spatial location. It was concluded that the ability to voluntarily suppress and inhibit the multimodal rightward spatial bias changes as a function of age and praxis due to sensory deficit and probably reflects the developmental level of executive functions.

En gestaltning av individens erfarenhetsbaserade kunskap inom diabetesvården

The aim of this study is to form the experience-based knowledge of diabetics. The broader intent is to be able to transform this experience-based knowledge as an asset within caring. In this study, a theoretical contact for the empirical data is presented through phronesis, i.e. practical wisdom. Phronesis can be seen as the most suitable form of knowledge to be able to deepen the individual's understanding of experiencebased knowledge. For this research, hermeneutic phenomenology was chosen. Abductive reasoning was the method chosen to approach the data collected through repeated deep interviews with individuals with personal experience of diabetes and the use of insulin pumps. The abductive approach fascilitates a broader interpretation of the primary empirical results via a theory of philosophy of science, such as phronesis, the life-world and the negativity of the experience. The latent message of the empirical data is thereby also additionally highlighted. The synthesis reveals that experience-based knowledge arrives with time, it is personified and praxis-oriented, and before this time, the knowledge and security must be provided by the established care, by people close to the individual or by other external sources. The experience-based knowledge has strenghts and weaknesses. The knowledge is further categorized by the individual's ability to discern and make judgement. Additionally, the experience-based kowledge is a reflecting and action-based knowledge striving to improve the care provided. The experience-based knowledge held by the individual is potentially a great instrument towards improving general knowledge with possible practical applications within the diabetic care. Furthermost, in practical suggestions to fascilitate care. In generally applying knowledge gathered from the individual's experiental point of view, there are inherent risks. These risks could potentially be eliminated through the adoption of a concept where the established care could function as a quality guarantor. A concept taking into account the experiencebased knowledge as a source of information and knowledge in the care for diabetics. Co-created knowledge and understanding is a position found in both self-care and pump-treatment. It is also found through the optimal application of the experience-based knowledge of the individual as well as the knowledge found within the established care, in order to fascilitate well-being. This as expressed by the individual's phronesis-based knowledge.