Estudio teórico de la isomerización del ácido maleico en ácido fumárico: un enfoque basado en el concepto de superficie de energía potencial

A comparative study based on potential energy surfaces (PES) of 2-butanedioic and hypothetic 2-butanedioic/HCl acids is useful for understanding the maleic acid isomerization. The PES enables locating conformers of minimum energy, intermediates of reactions and transition states. From contour diagrams, a set of possible reaction paths are depicted interconnecting the proposed structures. The study was carried out in absentia and in the presence of the catalyst (HCl), using an solvatation model provided by the Gaussian software package. Clearly, the effect of HCl is given by new reaction paths with lower energetic barriers in relation to the reaction without catalyzing.

Exploración estocástica de las superficies de energía potencial de dímeros cis-trans y trans-trans del ácido fórmico

Potential energy surface (PES) of cis-trans and trans-trans formic acid dimers were sampled using a stochastic method, and the geometries, energies, and vibrational frequencies were computed at B3LYP/6-311++G(3df,2p) level of theory. The results show that molar free energy of dimerization deviated up to 108.4% when basis set superposition error (BSSE) and zero-point energy (ZPE) were not considered. For cis-trans dimers, C=O and O - H bond weakened, whereas C - O bonds strengthened due to dimerization. Also, trans-trans FA dimers did not show a trend regarding strengthening or weakening of the C=O, O - H and C - O bonds.

Sydämen sulatuksia ihmiselle

Sisältö: Kehoitus armahtamaan kanssa-luotuja ; Ihmisen arwo ; Luotuen arwo ; Linnun pesä.

Exploring Adaptive Implementation of On-Chip Networks

As technology geometries have shrunk to the deep submicron regime, the communication delay and power consumption of global interconnections in high performance Multi- Processor Systems-on-Chip (MPSoCs) are becoming a major bottleneck. The Network-on- Chip (NoC) architecture paradigm, based on a modular packet-switched mechanism, can address many of the on-chip communication issues such as performance limitations of long interconnects and integration of large number of Processing Elements (PEs) on a chip. The choice of routing protocol and NoC structure can have a significant impact on performance and power consumption in on-chip networks. In addition, building a high performance, area and energy efficient on-chip network for multicore architectures requires a novel on-chip router allowing a larger network to be integrated on a single die with reduced power consumption. On top of that, network interfaces are employed to decouple computation resources from communication resources, to provide the synchronization between them, and to achieve backward compatibility with existing IP cores. Three adaptive routing algorithms are presented as a part of this thesis. The first presented routing protocol is a congestion-aware adaptive routing algorithm for 2D mesh NoCs which does not support multicast (one-to-many) traffic while the other two protocols are adaptive routing models supporting both unicast (one-to-one) and multicast traffic. A streamlined on-chip router architecture is also presented for avoiding congested areas in 2D mesh NoCs via employing efficient input and output selection. The output selection utilizes an adaptive routing algorithm based on the congestion condition of neighboring routers while the input selection allows packets to be serviced from each input port according to its congestion level. Moreover, in order to increase memory parallelism and bring compatibility with existing IP cores in network-based multiprocessor architectures, adaptive network interface architectures are presented to use multiple SDRAMs which can be accessed simultaneously. In addition, a smart memory controller is integrated in the adaptive network interface to improve the memory utilization and reduce both memory and network latencies. Three Dimensional Integrated Circuits (3D ICs) have been emerging as a viable candidate to achieve better performance and package density as compared to traditional 2D ICs. In addition, combining the benefits of 3D IC and NoC schemes provides a significant performance gain for 3D architectures. In recent years, inter-layer communication across multiple stacked layers (vertical channel) has attracted a lot of interest. In this thesis, a novel adaptive pipeline bus structure is proposed for inter-layer communication to improve the performance by reducing the delay and complexity of traditional bus arbitration. In addition, two mesh-based topologies for 3D architectures are also introduced to mitigate the inter-layer footprint and power dissipation on each layer with a small performance penalty.

Identification of extractives and polysaccharides as foulants in membrane filtration of pulp and paper mill effluents

The search for new renewable materials has intensified in recent years. Pulp and paper mill process streams contain a number of potential compounds which could be used in biofuel production and as raw materials in the chemical, food and pharmaceutical industries. Prior to utilization, these compounds require separation from other compounds present in the process stream. One feasible separation technique is membrane filtration but to some extent, fouling still limits its implementation in pulp and paper mill applications. To mitigate fouling and its effects, foulants and their fouling mechanisms need to be well understood. This thesis evaluates fouling in filtration of pulp and paper mill process streams by means of polysaccharide model substance filtrations and by development of a procedure to analyze and identify potential foulants, i.e. wood extractives and carbohydrates, from fouled membranes. The model solution filtration results demonstrate that each polysaccharide has its own fouling mechanism, which also depends on the membrane characteristics. Polysaccharides may foul the membranes by adsorption and/or by gel/cake layer formation on the membrane surface. Moreover, the polysaccharides interact, which makes fouling evaluation of certain compound groups very challenging. Novel methods to identify wood extractive and polysaccharide foulants are developed in this thesis. The results show that it is possible to extract and identify wood extractives from membranes fouled in filtration of pulp and paper millstreams. The most effective solvent was found to be acetone:water (9:1 v/v) because it extracted both lipophilic extractives and lignans at high amounts from the fouled membranes and it was also non-destructive for the membrane materials. One hour of extraction was enough to extract wood extractives at high amounts for membrane samples with an area of 0.008 m2. If only qualitative knowledge of wood extractives is needed a simplified extraction procedure can be used. Adsorption was the main fouling mechanism in extractives-induced fouling and dissolved fatty and resin acids were mostly the reason for the fouling; colloidal fouling was negligible. Both process water and membrane characteristics affected extractives-induced fouling. In general, the more hydrophilic regenerated cellulose (RC) membrane fouled less that the more hydrophobic polyethersulfone (PES) and polyamide (PA) membranes independent of the process water used. Monosaccharide and uronic acid units could also be identified from the fouled synthetic polymeric membranes. It was impossible to analyze all monosaccharide units from the RC membrane because the analysis result obtained contained degraded membrane material. One of the fouling mechanisms of carbohydrates was adsorption. Carbohydrates were not potential adsorptive foulants to the sameextent as wood extractives because their amount in the fouled membranes was found to be significantly lower than the amount of wood extractives.

Caracterização da pulverização de fungicida na cultura do trigo com pontas hidráulicas e atomizadores rotativos de discos

O objetivo deste trabalho foi avaliar as características de pulverização de pontas hidráulicas e atomizadores rotativos de discos, utilizando diferentes volumes de calda, na cultura do trigo, bem como seus rendimentos operacionais. Foram realizados dois experimentos, nas safras agrícolas de 2009 e 2010. No primeiro ano, utilizou-se da cultivar Fundacep 30, e no segundo das cultivares Pampeano e Nova Era. As pontas testadas foram do tipo leque e cone vazio, ambas com volume de calda de 120 L ha-1, e atomizadores rotativos de discos utilizando baixo volume oleoso (BVO®), com volumes de calda de 24 e 34 L ha-1. Os parâmetros avaliados foram densidade de gotas (DG) e diâmetro mediano volumétrico (DMV) nos terços superior, médio e inferior, através da análise de cartões hidrossensíveis. Também foi calculada a capacidade operacional para os tratamentos. Os resultados mostraram que os atomizadores rotativos de disco com 24 L ha-1 apresentaram a maior DG no terço superior; entretanto, não houve diferença entre os tratamentos para os demais terços avaliados. Atomizadores rotativos de disco apresentaram gotas de menor DMV em comparação com as pontas hidráulicas, sendo que estas apresentaram grande heterogeneidade de gotas. A maior capacidade de campo operacional foi obtida com uso de atomizadores rotativos de disco, devido ao menor volume de calda utilizado por este equipamento.

The role of van der Waals interactions in the case of H2 adsorption on ruthenium (0001) surface

Computational material science with the Density Functional Theory (DFT) has recently gained a method for describing, for the first time the non local bonding i.e., van der Waals (vdW) bonding. The newly proposed van der Waals-Density Functional (vdW-DF) is employed here to address the role of non local interactions in the case of H2 adsorption on Ru(0001) surface. The later vdW-DF2 implementation with the DFT code VASP (Vienna Ab-initio Simulation Package) is used in this study. The motivation for studying H2 adsorption on ruthenium surface arose from the interest to hydrogenation processes. Potential energy surface (PES) plots are created for adsorption sites top, bridge, fcc and hcp, employing the vdW-DF2 functional. The vdW-DF yields 0.1 eV - 0.2 eV higher barriers for the dissociation of the H2 molecule; the vdW-DF seems to bind the H2 molecule more tightly together. Furthermore, at the top site, which is found to be the most reactive, the vdW functional suggests no entrance barrier or in any case smaller than 0.05 eV, whereas the corresponding calculation without the vdW-DF does. Ruthenium and H2 are found to have the opposite behaviors with the vdW-DF; Ru lattice constants are overestimated while H2 bond length is shorter. Also evaluation of the CPU time demand of the vdW-DF2 is done from the PES data. From top to fcc sites the vdW-DF computational time demand is larger by 4.77 % to 20.09 %, while at the hcp site it is slightly smaller. Also the behavior of a few exchange correlation functionals is investigated along addressing the role of vdW-DF. Behavior of the different functionals is not consistent between the Ru lattice constants and H2 bond lengths. It is thus difficult to determine the quality of a particular exchange correlation functional by comparing equilibrium separations of the different elements. By comparing PESs it would be computationally highly consuming.

Metsänhakkuiden vaikutukset merikotkan (Haliaeetus albicilla) pesintään

Suomen merikotkapopulaatio kasvaa ja levittäytyy saaristosta mantereen puolelle. Sen seurauksena tehometsätalouden intressit ja merikotkan pesimähabitaattien suojelutarve törmäävät yhä useammin. Tämän tutkimuksen tavoitteena oli tuottaa tuloksia, joiden perusteella voidaan laatia entistä tarkemmat ohjeet pesien huomioonottamisesta metsätaloustoimenpiteiden yhteydessä. Käytin tutkimusaineistona WWF:n merikotkatyöryhmän vuosittain keräämiä pesimätietoja sekä metsänkäyttöilmoituksista kokoamiani hakkuutietoja vuosilta 2000–2009. Tarkastelin yleistettyjen lineaaristen sekamallien avulla säteeltään 600-metrisen pesäalueen hakkuiden vaikutusta mm. pesinnän jatkumiseen samalla pesällä ja pesimäyritysten onnistumiseen. Havaitsin, että edellisvuoden pesinnän epäonnistuminen lisää merikotkien pesänvaihtotodennäköisyyttä, ja uudistushakkuuaukot pesäalueella lisäävät tätä epäonnistumisen jälkeistä pesänvaihtoherkkyyttä. Merikotkat ovat kuitenkin monissa tapauksissa pesineet ja myös onnistuneet pesinnässään hyvinkin lähellä hakkuuaukkoa. Pesäalueen hakkuut pesimäkauden ulkopuolella eivät siis haittaa ainakaan kaikkien merikotkayksilöiden pesinnän aloitusta tai pesimäyrityksen onnistumista. Uudistushakkuutapahtuma pesäalueella laskee vähintään suuntaa-antavasti samanaikaisen tai seuraavan pesinnän onnistumistodennäköisyyttä. Reviireillä, joiden ytimessä on hakkuita, pesinnän väliinjättövuosia on ainakin suuntaa-antavasti enemmän kuin hakkaamattomilla reviireillä. Hakkuiden haittavaikutuksista huolimatta poikastuotto on niilläkin reviireillä, joiden ytimessä on hakkuita, niin hyvä, että populaatio kasvaa. Nykyisen tasoinen hakkuuhäiriö ei siis uhkaa merikotkien suotuisan suojelun tasoa. Tutkimukseni perusteella pidän ELY-keskuksen käyttämää 50–100 metrin levyistä näkyvyyden mukaan sovellettavaa suojavyöhykettä sopivana pesimäkauden ulkopuolisille hakkuille. Varsinaisesti en saanut näyttöä tämänkään suojavyöhykkeen tarpeellisuudesta, mutta aineisto ei ollut edes sopiva näin lähellä pesää olevien hakkuiden vaikutusten tilastolliseen testaamiseen. Sen sijaan näyttää melko varmalta, että ainakaan isompi suojavyöhyke ei ole tarpeen merikotkan suotuisan suojelun tason varmistamiseksi. Hakkuuaineiston ajoitusongelmien vuoksi en voi ottaa kantaa pesimäkautisen suojavyöhykkeen leveyteen. Merikotkapopulaation kasvun myötä lajin uhanalaisluokitus saattaa lähivuosina muuttua, mikä vaikuttanee myös pesimähabitaattien suojaan lainsäädännössä. Siinäkin tilanteessa tämä tutkimus auttanee vapaaehtoisen suojelun toteutusta.

Effects of iron-ore particles on propagule release, growth and photosynthetic performance of Sargassum vulgare C. Agardh (Phaeophyta, Fucales)

The effect of iron-ore particles on the propagule release and growth of Sargassum vulgare C. Agardh was tested under treatments with different concentrations of iron-ore particles: 0.1, 1.0, 10.0 g.L-1 and a solution of 10.0 g.L-1 of filtered iron-ore. Filtered seawater was used as control. Photosynthesis vs. irradiance (P-I) curves were calculated for S. vulgare in the presence of iron-ore and in seawater. There was no significant difference in the number of propagules released by the receptacles or in the percentage of zygote formation among the treatments. The released propagules acted like aggregation centers for the particles, those more heavily coated with iron (10.0 g.L-1) exhibiting the highest sinking velocity (32.6 ± 9.8 mm.s-1). No difference in the percentage of embryo survival was detected during the first week in culture. After four weeks the embryos grew in all treatments. Maximum frond development (5.3 ± 0.8 mm) was observed in treatment of seawater enriched with Provasoli's medium (PES) while initial filoids did not develop in three treatments without PES and with iron-ore (0.1 g.L-1, 1.0 g.L-1 and 10.0 g.L-1). The values for Pmax, alpha and respiration showed no significant differences between the P-I curves. The calculated value for I K was 106.26 µmol.m-2.s-1 to the control curve and 981.49 µmol.m-2.s-1 to the iron-ore curve. The results indicate that the iron-ore particles in high concentration reduce the growth of S. vulgare as they recovered the embryos, juveniles and young plants. In contrast, the presence of the particles did not affect the release of gametes, percentage of zygote formation or the percentage of embryo survival.

Formação de calos e regeneração de segmentos apicais de Hypnea musciformis (Wulfen) Lamouroux (Gigartinales, Rhodophyta): obtenção de culturas axênicas e efeitos da concentração do ágar

Culturas axênicas de Hypnea musciformis (Wulfen) Lamouroux foram estabelecidas em meio de Provasoli (PES) sólido com diferentes concentrações de ágar (0,4%, 0,6%, 0,8% e 1,0%) para avaliar o seu efeito na formação de calos e na regeneração de plantas. O cultivo em meio sólido induziu a formação de quatro tipos de calos (apical - CApi, lateral 1 - CLat1, lateral 2 - CLat2 e basal - CBas), os quais são constituídos internamente por proliferações unisseriadas pigmentadas. O tipo CApi foi o mais freqüente (taxa de 5,3 calos por explante em 1,0% de ágar). A maior biomassa das plântulas regeneradas (7,4 g) foi alcançada a partir de calos cultivados a 1,0% de ágar. A formação dos quatro tipos de calos é um dado inédito e indica que as diferentes concentrações de ágar no meio apresentam efeitos morfogenéticos no crescimento dos calos e na regeneração de segmentos apicais em H. musciformis

Growth of red and green strains of the tropical agarophyte Gracilaria cornea J. Agardh (Gracilariales, Rhodophyta) in laboratory

Gracilaria cornea J. Agardh is an important agarophyte occurring in the western Atlantic Ocean. Green colour individuals of G. cornea were found in a natural population, growing next to red individuals, which were more common. Due to the importance of colour strains in genetic and intraspecific variability studies, this work aimed to characterize the red and green strains evaluating different nutritional and light conditions. Red and green gametophytes were cultivated at 14:10 light: dark cycle, with alternating aeration periods of 30 min. Two different enriched solutions were tested: von Stosch (VSS) at concentrations reduced to 12.5% and 25%; and Provasoli (PES) at concentrations reduced to 25% and 50%, and 100%. Red and green gametophytes were cultivated at the irradiance of 45 mumol photons m-2 s-1. In another experiment utilizing PES 100%, two sources of light (Osram 40 W daylight fluorescent tubes and Sylvania Designer 3,500 tubes) were tested at irradiances of 90 and 180 mumol photons m-2 s-1. Growth rates (GR) were evaluated for five weeks. Gametophytes developed few branches and reproductive structures were not induced. Differences were not observed between GR of red and green strains in the conditions tested. GR were higher in VSS 12.5% (8.4% day-1) than in 25% (7.1% day-1), suggesting an adaptation of the species to low nutrient concentrations. GR were higher at 180 (9.0% day-1) than at 90 mumol photons m-2 s-1 (6.3% day-1). These results suggest that G. cornea should be cultivated in laboratory at high irradiances and low nutrient concentrations. These data will be useful in future genetic and physiological studies of the species.

Spectroscopic Studies of III-V Semiconductor Materials for Improved Devices

Defects in semiconductor crystals and at their interfaces usually impair the properties and the performance of devices. These defects include, for example, vacancies (i.e., missing crystal atoms), interstitials (i.e., extra atoms between the host crystal sites), and impurities such as oxygen atoms. The defects can decrease (i) the rate of the radiative electron transition from the conduction band to the valence band, (ii) the amount of charge carriers, and (iii) the mobility of the electrons in the conduction band. It is a common situation that the presence of crystal defects can be readily concluded as a decrease in the luminescence intensity or in the current flow for example. However, the identification of the harmful defects is not straightforward at all because it is challenging to characterize local defects with atomic resolution and identification. Such atomic-scale knowledge is however essential to find methods for reducing the amount of defects in energy-efficient semiconductor devices. The defects formed in thin interface layers of semiconductors are particularly difficult to characterize due to their buried and amorphous structures. Characterization methods which are sensitive to defects often require well-defined samples with long range order. Photoelectron spectroscopy (PES) combined with photoluminescence (PL) or electrical measurements is a potential approach to elucidate the structure and defects of the interface. It is essential to combine the PES with complementary measurements of similar samples to relate the PES changes to changes in the interface defect density. Understanding of the nature of defects related to III-V materials is relevant to developing for example field-effect transistors which include a III-V channel, but research is still far from complete. In this thesis, PES measurements are utilized in studies of various III-V compound semiconductor materials. PES is combined with photoluminescence measurements to study the SiO2/GaAs, SiNx/GaAs and BaO/GaAs interfaces. Also the formation of novel materials InN and photoluminescent GaAs nanoparticles are studied. Finally, the formation of Ga interstitial defects in GaAsN is elucidated by combining calculational results with PES measurements.

Salvaged single-unit cord blood transplantation for 26 patients with hematologic malignancies not in remission

Treatments for patients with hematologic malignancies not in remission are limited, but a few clinical studies have investigated the effects of salvaged unrelated cord blood transplantation (CBT). We retrospectively studied 19 patients with acute leukemia, 5 with myelodysplastic syndrome (MDS with refractory anemia with excess blasts [RAEB]), and 2 with non-Hodgkin's lymphoma who received 1 CBT unit ≤2 loci human leukocyte antigen (HLA)-mismatched after undergoing myeloablative conditioning regimens between July 2005 and July 2014. All of them were in non-remission before transplantation. The infused total nucleated cell (TNC) dose was 4.07 (range 2.76-6.02)×107/kg and that of CD34+ stem cells was 2.08 (range 0.99-8.65)×105/kg. All patients were engrafted with neutrophils that exceeded 0.5×109/L on median day +17 (range 14-37 days) and had platelet counts of >20×109/L on median day +35 (range 17-70 days). Sixteen patients (61.5%) experienced pre-engraftment syndrome (PES), and six (23.1%) patients progressed to acute graft-versus-host disease (GVHD). The cumulative incidence rates of II-IV acute GVHD and chronic GVHD were 50% and 26.9%, respectively. After a median follow-up of 27 months (range 5-74), 14 patients survived and 3 relapsed. The estimated 2-year overall survival (OS), disease-free survival (DFS), and non-relapse mortality (NRM) rates were 50.5%, 40.3%, and 35.2%, respectively. Salvaged CBT might be a promising modality for treating hematologic malignancies, even in patients with a high leukemia burden.

Perfil sensorial e aceitabilidade de diferentes formulações de pão de queijo

Pão de queijo é produto tradicionalmente mineiro. Sua produção vem crescendo muito, expandindo-se inclusive para o mercado externo. Entretanto, ainda não existe um padrão de qualidade. No presente estudo, análise descritiva quantitativa foi aplicada para levantar atributos sensoriais que melhor definem modificações na aparência, aroma, sabor e textura quando alguns ingredientes são variados na formulação do pão de queijo. Sete formulações foram avaliadas por uma equipe de provadores treinados, dezoito atributos sensoriais foram definidos. Após um período de treinamento, os provadores avaliaram as amostras através de delineamento de blocos incompletos balanceados usando escala não estruturada de 9cm. As mesmas foram também avaliadas em relação a aceitabilidade através da escala hedônica de 9 pontos, por 70 consumidores de pães de queijo. Os resultados foram analisados através da ANOVA, seguida pelo teste de Tukey. As amostras apresentaram diferença significativa (p<0,05) em todos os atributos avaliados. Não houve aceitação significativa (p>0,05) entre as amostras que se situaram entre os termos hedônicos "gostei ligeiramente" e "gostei muito".

Efeito de adição de diferentes sais de cálcio nas características da massa e na elaboração de pão francês

O objetivo deste trabalho foi estudar os efeitos da adição do sulfato de cálcio, carbonato de cálcio e fosfato de cálcio dibásico nas características físicas e reológicas da farinha de trigo e na qualidade de pão francês. Utilizou-se a quantidade de sais de cálcio que correspondesse a 100% da IDR de adulto por 100g de pão. Na farinha foram realizadas análises de cor, teor de glúten, farinografia, alveografia e extensigrafia. O pão francês elaborado foi analisado quanto a seu volume específico e conceito global. O enriquecimento com cálcio melhorou a cor da farinha e os resultados satisfatórios obtidos na reologia das massas e com os pães mostraram que se pode utilizar qualquer uma das três fontes para se elaborar pão enriquecido com cálcio.