Validity of the acoustic approximation in full-waveform seismic crosshole tomography

Acoustic waveform inversions are an increasingly popular tool for extracting subsurface information from seismic data. They are computationally much more efficient than elastic inversions. Naturally, an inherent disadvantage is that any elastic effects present in the recorded data are ignored in acoustic inversions. We investigate the extent to which elastic effects influence seismic crosshole data. Our numerical modeling studies reveal that in the presence of high contrast interfaces, at which P-to-S conversions occur, elastic effects can dominate the seismic sections, even for experiments involving pressure sources and pressure receivers. Comparisons of waveform inversion results using a purely acoustic algorithm on synthetic data that is either acoustic or elastic, show that subsurface models comprising small low-to-medium contrast (?30%) structures can be successfully resolved in the acoustic approximation. However, in the presence of extended high-contrast anomalous bodies, P-to-S-conversions may substantially degrade the quality of the tomographic images. In particular, extended low-velocity zones are difficult to image. Likewise, relatively small low-velocity features are unresolved, even when advanced a priori information is included. One option for mitigating elastic effects is data windowing, which suppresses later arriving seismic arrivals, such as shear waves. Our tests of this approach found it to be inappropriate because elastic effects are also included in earlier arriving wavetrains. Furthermore, data windowing removes later arriving P-wave phases that may provide critical constraints on the tomograms. Finally, we investigated the extent to which acoustic inversions of elastic data are useful for time-lapse analyses of high contrast engineered structures, for which accurate reconstruction of the subsurface structure is not as critical as imaging differential changes between sequential experiments. Based on a realistic scenario for monitoring a radioactive waste repository, we demonstrated that acoustic inversions of elastic data yield substantial distortions of the tomograms and also unreliable information on trends in the velocity changes.

Efficacy, safety and tolerability of linezolid containing regimens in treating MDR-TB and XDR-TB: systematic review and meta-analysis.

Linezolid is used off-label to treat multidrug-resistant tuberculosis (MDR-TB) in absence of systematic evidence. We performed a systematic review and meta-analysis on efficacy, safety and tolerability of linezolid-containing regimes based on individual data analysis. 12 studies (11 countries from three continents) reporting complete information on safety, tolerability, efficacy of linezolid-containing regimes in treating MDR-TB cases were identified based on Preferred Reporting Items for Systematic Reviews and Meta-Analyses guidelines. Meta-analysis was performed using the individual data of 121 patients with a definite treatment outcome (cure, completion, death or failure). Most MDR-TB cases achieved sputum smear (86 (92.5%) out of 93) and culture (100 (93.5%) out of 107) conversion after treatment with individualised regimens containing linezolid (median (inter-quartile range) times for smear and culture conversions were 43.5 (21-90) and 61 (29-119) days, respectively) and 99 (81.8%) out of 121 patients were successfully treated. No significant differences were detected in the subgroup efficacy analysis (daily linezolid dosage ≤600 mg versus >600 mg). Adverse events were observed in 63 (58.9%) out of 107 patients, of which 54 (68.4%) out of 79 were major adverse events that included anaemia (38.1%), peripheral neuropathy (47.1%), gastro-intestinal disorders (16.7%), optic neuritis (13.2%) and thrombocytopenia (11.8%). The proportion of adverse events was significantly higher when the linezolid daily dosage exceeded 600 mg. The study results suggest an excellent efficacy but also the necessity of caution in the prescription of linezolid.

Kinetics of selective oxidation of lactose to lactobionic acid over Pd-active carbon catalyst

Laktoosi eli maitosokeri on tärkein ainesosa useimpien nisäkkäiden tuottamassa maidossa. Sitä erotetaan herasta, juustosta ja maidosta. Laktoosia käytetään elintarvike- ja lääketeollisuuden raaka-aineena monissaeri tuotteissa. Lääketeollisuudessa laktoosia käytetään esimerkiksi tablettien täyteaineena. Hapettamalla laktoosia voidaan valmistaa laktobionihappoa, 2-keto-laktobionihappoa ja laktuloosia. Laktobionihappoa käytetään biohajoavien pintojen ja kosmetiikkatuotteiden valmistuksessa, sekä sisäelinten säilöntäliuoksissa, joissa laktobionihappo estää happiradikaalien aiheuttamien kudosvaurioiden syntymistä. Tässä työssä laktoosia hapetettiin laktobionihapoksi sekoittimella varustetussa laboratoriomittakaavaisessa panosreaktorissa käyttäenkatalyyttinä palladiumia aktiivihiilellä. Muutamissa kokeissa katalyytin promoottorina käytettiin vismuttia, joka hidastaa katalyytin deaktivoitumista. Työn tarkoituksena oli saada lisää tietoa laktoosin hapettamisen kinetiikasta. Laktoosin hapettumisessa laktobionihapoksi havaittiin selektiivisyyteen vaikuttavan muunmuassa reaktiolämpötila, paine, pH ja käytetyn katalyytin määrä. Katalyyttiä kierrättämällä eri kokeiden välillä saatiin paremmat konversiot, selektiivisyydet ja saannot. Parhaat koetulokset saatiin hapetettaessa synteettisellä ilmalla 60 oC lämpötilassa ja 1 bar paineessa. Tehdyissä kokeissa pH:n säätö tehtiin manuaalisesti, joten pH ei pysynyt koko ajan haluttuna. Laktoosin konversio oli parhaimmillaan 95 %. Laktobionihapon suhteellinen selektiivisyys oli 100% ja suhteellinen saanto 100 %. Kinetiikan matemaattinen mallinnus tehtiin Modest-ohjelmalla käyttäen kokeista saatuja mittaustuloksia.Ohjelman avulla estimoitiin parametreja ja saatiin matemaattinen malli reaktorille. Tässä työssä tehtiin kineettinen mallinnus myös ravistelureaktorissa tehdyille laktoosin hapetuskokeille, missä pH pysyi koko ajan haluttuna 'in-situ' titrauksen avulla. Työn yhteydessä selvitettiin myös mahdollisuutta käyttää monoliittikatalyyttejä laktoosin hapetusreaktiossa.

Selective catalytic reduction of nitrogen oxides with ammonia in forced unsteady state reactors - Case based reasoning and mathematical model simulation reasoning

The application of forced unsteady-state reactors in case of selective catalytic reduction of nitrogen oxides (NOx) with ammonia (NH3) is sustained by the fact that favorable temperature and composition distributions which cannot be achieved in any steady-state regime can be obtained by means of unsteady-state operations. In a normal way of operation the low exothermicity of the selective catalytic reduction (SCR) reaction (usually carried out in the range of 280-350°C) is not enough to maintain by itself the chemical reaction. A normal mode of operation usually requires supply of supplementary heat increasing in this way the overall process operation cost. Through forced unsteady-state operation, the main advantage that can be obtained when exothermic reactions take place is the possibility of trapping, beside the ammonia, the moving heat wave inside the catalytic bed. The unsteady state-operation enables the exploitation of the thermal storage capacity of the catalyticbed. The catalytic bed acts as a regenerative heat exchanger allowing auto-thermal behaviour when the adiabatic temperature rise is low. Finding the optimum reactor configuration, employing the most suitable operation model and identifying the reactor behavior are highly important steps in order to configure a proper device for industrial applications. The Reverse Flow Reactor (RFR) - a forced unsteady state reactor - corresponds to the above mentioned characteristics and may be employed as an efficient device for the treatment of dilute pollutant mixtures. As a main disadvantage, beside its advantages, the RFR presents the 'wash out' phenomena. This phenomenon represents emissions of unconverted reactants at every switch of the flow direction. As a consequence our attention was focused on finding an alternative reactor configuration for RFR which is not affected by the incontrollable emissions of unconverted reactants. In this respect the Reactor Network (RN) was investigated. Its configuration consists of several reactors connected in a closed sequence, simulating a moving bed by changing the reactants feeding position. In the RN the flow direction is maintained in the same way ensuring uniformcatalyst exploitation and in the same time the 'wash out' phenomena is annulated. The simulated moving bed (SMB) can operate in transient mode giving practically constant exit concentration and high conversion levels. The main advantage of the reactor network operation is emphasizedby the possibility to obtain auto-thermal behavior with nearly uniformcatalyst utilization. However, the reactor network presents only a small range of switching times which allow to reach and to maintain an ignited state. Even so a proper study of the complex behavior of the RN may give the necessary information to overcome all the difficulties that can appear in the RN operation. The unsteady-state reactors complexity arises from the fact that these reactor types are characterized by short contact times and complex interaction between heat and mass transportphenomena. Such complex interactions can give rise to a remarkable complex dynamic behavior characterized by a set of spatial-temporal patterns, chaotic changes in concentration and traveling waves of heat or chemical reactivity. The main efforts of the current research studies concern the improvement of contact modalities between reactants, the possibility of thermal wave storage inside the reactor and the improvement of the kinetic activity of the catalyst used. Paying attention to the above mentioned aspects is important when higher activity even at low feeding temperatures and low emissions of unconverted reactants are the main operation concerns. Also, the prediction of the reactor pseudo or steady-state performance (regarding the conversion, selectivity and thermal behavior) and the dynamicreactor response during exploitation are important aspects in finding the optimal control strategy for the forced unsteady state catalytic tubular reactors. The design of an adapted reactor requires knowledge about the influence of its operating conditions on the overall process performance and a precise evaluation of the operating parameters rage for which a sustained dynamic behavior is obtained. An apriori estimation of the system parameters result in diminution of the computational efforts. Usually the convergence of unsteady state reactor systems requires integration over hundreds of cycles depending on the initial guess of the parameter values. The investigation of various operation models and thermal transfer strategies give reliable means to obtain recuperative and regenerative devices which are capable to maintain an auto-thermal behavior in case of low exothermic reactions. In the present research work a gradual analysis of the SCR of NOx with ammonia process in forced unsteady-state reactors was realized. The investigation covers the presentationof the general problematic related to the effect of noxious emissions in the environment, the analysis of the suitable catalysts types for the process, the mathematical analysis approach for modeling and finding the system solutions and the experimental investigation of the device found to be more suitable for the present process. In order to gain information about the forced unsteady state reactor design, operation, important system parameters and their values, mathematical description, mathematicalmethod for solving systems of partial differential equations and other specific aspects, in a fast and easy way, and a case based reasoning (CBR) approach has been used. This approach, using the experience of past similarproblems and their adapted solutions, may provide a method for gaining informations and solutions for new problems related to the forced unsteady state reactors technology. As a consequence a CBR system was implemented and a corresponding tool was developed. Further on, grooving up the hypothesis of isothermal operation, the investigation by means of numerical simulation of the feasibility of the SCR of NOx with ammonia in the RFRand in the RN with variable feeding position was realized. The hypothesis of non-isothermal operation was taken into account because in our opinion ifa commercial catalyst is considered, is not possible to modify the chemical activity and its adsorptive capacity to improve the operation butis possible to change the operation regime. In order to identify the most suitable device for the unsteady state reduction of NOx with ammonia, considering the perspective of recuperative and regenerative devices, a comparative analysis of the above mentioned two devices performance was realized. The assumption of isothermal conditions in the beginningof the forced unsteadystate investigation allowed the simplification of the analysis enabling to focus on the impact of the conditions and mode of operation on the dynamic features caused by the trapping of one reactant in the reactor, without considering the impact of thermal effect on overall reactor performance. The non-isothermal system approach has been investigated in order to point out the important influence of the thermal effect on overall reactor performance, studying the possibility of RFR and RN utilization as recuperative and regenerative devices and the possibility of achieving a sustained auto-thermal behavior in case of lowexothermic reaction of SCR of NOx with ammonia and low temperature gasfeeding. Beside the influence of the thermal effect, the influence of the principal operating parameters, as switching time, inlet flow rate and initial catalyst temperature have been stressed. This analysis is important not only because it allows a comparison between the two devices and optimisation of the operation, but also the switching time is the main operating parameter. An appropriate choice of this parameter enables the fulfilment of the process constraints. The level of the conversions achieved, the more uniform temperature profiles, the uniformity ofcatalyst exploitation and the much simpler mode of operation imposed the RN as a much more suitable device for SCR of NOx with ammonia, in usual operation and also in the perspective of control strategy implementation. Theoretical simplified models have also been proposed in order to describe the forced unsteady state reactors performance and to estimate their internal temperature and concentration profiles. The general idea was to extend the study of catalytic reactor dynamics taking into account the perspectives that haven't been analyzed yet. The experimental investigation ofRN revealed a good agreement between the data obtained by model simulation and the ones obtained experimentally.

A Dependency Parsing Approach to Biomedical Text Mining

Biomedical research is currently facing a new type of challenge: an excess of information, both in terms of raw data from experiments and in the number of scientific publications describing their results. Mirroring the focus on data mining techniques to address the issues of structured data, there has recently been great interest in the development and application of text mining techniques to make more effective use of the knowledge contained in biomedical scientific publications, accessible only in the form of natural human language. This thesis describes research done in the broader scope of projects aiming to develop methods, tools and techniques for text mining tasks in general and for the biomedical domain in particular. The work described here involves more specifically the goal of extracting information from statements concerning relations of biomedical entities, such as protein-protein interactions. The approach taken is one using full parsing—syntactic analysis of the entire structure of sentences—and machine learning, aiming to develop reliable methods that can further be generalized to apply also to other domains. The five papers at the core of this thesis describe research on a number of distinct but related topics in text mining. In the first of these studies, we assessed the applicability of two popular general English parsers to biomedical text mining and, finding their performance limited, identified several specific challenges to accurate parsing of domain text. In a follow-up study focusing on parsing issues related to specialized domain terminology, we evaluated three lexical adaptation methods. We found that the accurate resolution of unknown words can considerably improve parsing performance and introduced a domain-adapted parser that reduced the error rate of theoriginal by 10% while also roughly halving parsing time. To establish the relative merits of parsers that differ in the applied formalisms and the representation given to their syntactic analyses, we have also developed evaluation methodology, considering different approaches to establishing comparable dependency-based evaluation results. We introduced a methodology for creating highly accurate conversions between different parse representations, demonstrating the feasibility of unification of idiverse syntactic schemes under a shared, application-oriented representation. In addition to allowing formalism-neutral evaluation, we argue that such unification can also increase the value of parsers for domain text mining. As a further step in this direction, we analysed the characteristics of publicly available biomedical corpora annotated for protein-protein interactions and created tools for converting them into a shared form, thus contributing also to the unification of text mining resources. The introduced unified corpora allowed us to perform a task-oriented comparative evaluation of biomedical text mining corpora. This evaluation established clear limits on the comparability of results for text mining methods evaluated on different resources, prompting further efforts toward standardization. To support this and other research, we have also designed and annotated BioInfer, the first domain corpus of its size combining annotation of syntax and biomedical entities with a detailed annotation of their relationships. The corpus represents a major design and development effort of the research group, with manual annotation that identifies over 6000 entities, 2500 relationships and 28,000 syntactic dependencies in 1100 sentences. In addition to combining these key annotations for a single set of sentences, BioInfer was also the first domain resource to introduce a representation of entity relations that is supported by ontologies and able to capture complex, structured relationships. Part I of this thesis presents a summary of this research in the broader context of a text mining system, and Part II contains reprints of the five included publications.

L'expérience sociale de la conversion au bodybuilding

Cette thèse propose d'étudier les carrières des adeptes des salles de musculation afin de comprendre comment certains d'entre eux organisent progressivement leur existence autour du bodybuilding. Nos observations issues d'une ethnographie d'une salle de musculation et de trente entretiens semi-directifs menés avec différents profils d'adeptes en Suisse romande, suggèrent que l'emprise du bodybuilding sur les individus résulte de phénomènes assimilables à des conversions. Deux voies de conversion, « consonante » et « introspective », ont été identifiées. Elles correspondent à des usages distincts de la musculation qui n'ont pas les mêmes conséquences sur les parcours de vie des pratiquant(e)s. Si les conversions consonantes stabilisent les parcours de vie en renforçant un statut professionnel, les conversions introspectives les infléchissent significativement. En outre, cette perspective de recherche offre un nouvel éclairage sur le façonnement des représentations et des pratiques de santé, les processus de normalisation des pharmacopraxis et les rapports sociaux de sexe en présence. -- This thesis aims to study gym-goers' careers in order to understand how some of them progressively organise their lives around bodybuilding. Our observations, drawn from an ethnography of a gym and thirty semi-structured interviews with different profiles of gym enthusiasts in French-speaking Switzerland, suggest that the grip that bodybuilding takes on individuals results from phenomena akin to conversions. Two paths to conversion - consonant and introspective - are identified. They correspond to distinct uses of bodybuilding, which do not have the same consequences in the practitioners' life courses. While consonant conversions stabilise life courses by reinforcing an occupational status, introspective conversions inflect them significantly. Furthermore, this research perspective provides new insights into the shaping of health norms (representations and practices), the process of normalisation of pharmacopraxia and the gender relations identified.

Utilização do TEMPO (N-oxil-2,2,6,6-tetrametilpiperidina) na oxidação de álcoois primários e secundários

The oxidation of alcohols to obtain ketones, aldehydes or carboxylic acids is a fundamental transformation in organic synthesis and many reagents are known for these conversions. However, there is still a demand for mild and selective reagents for the oxidation of alcohols in the presence of other functional groups. As an alternative, the nitroxyl radical TEMPO (2,2,6,6-tetramethylpiperidine-N-oxyl) has been demonstrated to be a useful reagent for the transformation of alcohols. The oxidation of alcohols using TEMPO is often efficient, fast, selective, made in mild conditions and can tolerate sensitive functional groups. In this article we report different methodologies using TEMPO in the oxidation of alcohols.

Optimal Traffic Grooming in WDM using Lighttours

Recent developments in optical communications have allowed simpler optical devices to improve network resource utilization. As such, we propose adding a lambda-monitoring device to a wavelength-routing switch (WRS) allowing better performance when traffic is routed and groomed. This device may allow a WRS to aggregate traffic over optical routes without incurring in optical-electrical-optical conversion for the existing traffic. In other words, optical routes can be taken partially to route demands creating a sort of "lighttours". In this paper, we compare the number of OEO conversions needed to route a complete given traffic matrix using either lighttours or lightpaths

Operational Cost Reduction in WDM Networks using Lighttours

Wavelength division multiplexing (WDM) networks have been adopted as a near-future solution for the broadband Internet. In previous work we proposed a new architecture, named enhanced grooming (G+), that extends the capabilities of traditional optical routes (lightpaths). In this paper, we compare the operational expenditures incurred by routing a set of demands using lightpaths with that of lighttours. The comparison is done by solving an integer linear programming (ILP) problem based on a path formulation. Results show that, under the assumption of single-hop routing, almost 15% of the operational cost can be reduced with our architecture. In multi-hop routing the operation cost is reduced in 7.1% and at the same time the ratio of operational cost to number of optical-electro-optical conversions is reduced for our architecture. This means that ISPs could provide the same satisfaction in terms of delay to the end-user with a lower investment in the network architecture

All-Optical Unicast/Multicast Routing in WDM Networks

Optical transport networks (OTN) must be prepared in terms of better resource utilization, for accommodating unicast and multicast traffic together. Light-trees have been proposed for supporting multicast connections in OTN. Nevertheless when traffic grooming is applied in light-trees, resources can be underutilized as traffic can be routed to undesirable destinations in order to avoid optical-electrical-optical (OEO) conversions. In this paper, a novel architecture named S/G light- tree for supporting unicast/multicast connections is proposed. The architecture allows traffic dropping and aggregation in different wavelengths without performing OEO conversions. A heuristic that routes traffic demands using less wavelengths by taking advantage of the proposed architecture is designed as well. Simulation results show that the architecture can minimize the number of used wavelengths and OEO conversions when compared to light-trees

G+: Enhanced Traffic Grooming in WDM Mesh Networks using Lighttours

In this article, a new technique for grooming low-speed traffic demands into high-speed optical routes is proposed. This enhancement allows a transparent wavelength-routing switch (WRS) to aggregate traffic en route over existing optical routes without incurring expensive optical-electrical-optical (OEO) conversions. This implies that: a) an optical route may be considered as having more than one ingress node (all inline) and, b) traffic demands can partially use optical routes to reach their destination. The proposed optical routes are named "lighttours" since the traffic originating from different sources can be forwarded together in a single optical route, i.e., as taking a "tour" over different sources towards the same destination. The possibility of creating lighttours is the consequence of a novel WRS architecture proposed in this article, named "enhanced grooming" (G+). The ability to groom more traffic in the middle of a lighttour is achieved with the support of a simple optical device named lambda-monitor (previously introduced in the RingO project). In this article, we present the new WRS architecture and its advantages. To compare the advantages of lighttours with respect to classical lightpaths, an integer linear programming (ILP) model is proposed for the well-known multilayer problem: traffic grooming, routing and wavelength assignment The ILP model may be used for several objectives. However, this article focuses on two objectives: maximizing the network throughput, and minimizing the number of optical-electro-optical conversions used. Experiments show that G+ can route all the traffic using only half of the total OEO conversions needed by classical grooming. An heuristic is also proposed, aiming at achieving near optimal results in polynomial time

Estudo da influência do solvente, carboidrato e ácido graxo na síntese enzimática de ésteres de açúcares

The aim of this work was to gain knowledge of enzymatic processes for the synthesis fatty acid esters of sugar, with the objective to develop an enzymatic process for the preparation of non-toxic biodegradable surface-active agents derived entirely from renewable resources. A wide range of data were collected for reaction conditions involving different sugars (glucose, fructose and sucrose), fatty acids (oleic, palmitic, lauric), solvents (hexane, heptane and t-butanol) and different sources of lipases in both free and immobilized forms. As a solvent t-butanol provided the best conditions to create a catalytic liquid phase in which the reaction occurs. Sugars were preferentially esterified in the following order: fructose > glucose > sucrose, depending on the enzyme preparation. For fructose no influence was found concerning de acyl donor and similar rates were achieved for all tested fatty acids. Ester synthesis was maximized for substrates containing fructose, lauric or oleic acids, t-butanol and lipase from porcine pancreas immobilized on polysiloxane-polyvinyl alcohol particles. Under such conditions molar conversions were higher than 50%.

Polimerização de estireno utilizando compostos organolantanídeos ativados por MAO

In an attempt to improve the performance of organolanthanide catalysts we investigated the use of the industrially important cocatalyst methylaluminoxane (MAO) to activate organolanthanide compounds in olefin polymerization. The catalytic systems LnBrCp2(THF)2/MAO (Cp=cyclopentadienyl) and LnBrCp*2THF/MAO (Cp*= pentamethylcyclopentadienyl), Ln=Pr and Yb, were active in styrene polymerization but inactive in ethylene and propylene polymerization. These systems produced atactic polystyrene with conversions of up to 8.2% (PrBrCp*2THF, Al/Ln=200, T=80ºC, t=4 h) in toluene. In the absence of solvent, the conversion is 26.0% (1.5 h) and the molar mass of the atactic polystyrene is almost ten times higher (43 kg/mol).

Bioreduction of substituted a-tetralones promoted by Daucus carota root

The bioreduction of a series of substituted a-tetralones, carried out using Daucus carota root (carrot), afforded the corresponding homochiral a-tetralols in variable conversions (9 to 90%) and excellent enantiomeric excesses. Two of the assayed a-tetralones were resistant to the bioreduction conditions. The absolute configurations of four a-tetralols were assigned as being (S), by comparison to the (S)-enantiomers obtained by kinetic resolution promoted by CALB-catalysed acetylation. Additionally, the new 5-methoxy-6-methyl-1-tetralone was synthesized in seven steps from 3-methylsalicylic acid.

Transformações biológicas: contribuições e perspectivas

In a moment that amazingly advances are being reached on the development of technologies to obtain high value chemical compounds as polymers, fine chemicals, pharmaceutical industry intermediates and chemical entities, we cannot refuse that a meaningful progress is due to the maturing in knowledge of biological transformations. Biocatalysis and biotransformations are being widespread applied to generate processes and products with incredible success. In this review article we present the main contributions of biotechnology and biological catalytic processes to Chemistry, the most important evolution steps on enzymatic transformations, how it has being applied and which are the perspectives to academic and industrial environments. We also would like to stimulate the community to step out research in biotechnology applicable to chemical and pharmaceutical industries, trying to achieve what we believe to be the ideal layout: integrating chemical transformations, enzymatic conversions and fermentation processes.