GLOBAL AND LOCAL REACTIVITY DESCRIPTORS FOR PICLORAM HERBICIDE: A THEORETICAL QUANTUM STUDY

In this work, we studied the reactivity of picloram in the aqueous phase at the B3LYP/6-311++G(2d,2p) and MP2/6-311++G(2d,2p) levels of theory through global and local reactivity descriptors. The results obtained at the MP2 level indicate that the cationic form of picloram exhibits the highest hardness while the anionic form is the most nucleophilic. From the Fukui function values, the most reactive site for electrophilic and free radical attacks are on the nitrogen in the pyridine ring. The more reactive sites for nucleophilic attacks are located on the nitrogen atom of the amide group and on the carbon atoms located at positions 2 and 3 in the pyridine ring.

CHEMICAL CONSTITUENTS, ANTI-INFLAMMATORY, AND FREE-RADICAL SCAVENGING ACTIVITIES OF Guettarda viburnoides CHAM. & SCHLTDL. (RUBIACEAE)

Chemical investigation of Guettarda viburnoides (leaves) led to the isolation of ursolic acid, uncaric acid, secoxyloganin, and grandifloroside, along with a mixture of quercetin-3-O-β-D-galactopyranoside and quercetin-3-O-β-D-glucopyranoside, and of β-sitosterol and stigmasterol. The structures of the isolated compounds were elucidated on the basis of their NMR data. The crude extract, ethyl acetate fraction, aqueous-methanol fraction, and grandifloroside showed significant DPPH free-radical scavenging activities with IC50 ranging from 18.92 to 26.47 µg mL-1. The topical administration of the crude extract and fractions markedly reduced the croton oil-induced mice ear edema in 67.0%-99.0%. Inhibition of tissue MPO activity was also observed, which demonstrated an anti-inflammatory effect of the G. viburnoides species.

AVALIAÇÃO DO RADICAL N,N-DIETIL-1,4-FENILENODIAMINO (DEPD•+) COMO SONDA ESPECTROFOTOMÉTRICA PARA DETERMINAÇÃO DA CAPACIDADE ANTIOXIDANTE EM BEBIDAS

AbstractMany well-established methods for determining the antioxidant capacities in several samples have been described in literature. However, DPPH (2,2-diphenyl-1-picrylhydrazyl) and ABTS (2,2'-azino-bis(3-ethylbenzothiazoline-6-sulphonic acid)) are the main two methods that utilize radicals as spectrophotometric probes for analysis. Nevertheless, these methods have certain limitations because of their slower kinetics, solvent polarity effects, the hydrophilicity and lipophilicity of the compounds, chemical costs, etc. In this study, a spectrophotometric method for determining the antioxidant capacity in beverages was developed based on an exploration of the cation radical derived from DEPD. This method was based on the oxidation of aromatic amines with Fe(III) ions at pH 4.0, which leads to their corresponding purple cation radicals (DEPD•+) with λmax values at 500 and 540 nm. The addition of an antioxidant after the formation of the radical leads to a reduction in color intensity that is proportional to the antioxidant concentration in the medium. Results obtained using this method were compared with the Folin-Ciocalteau, ABTS and DPPH methods in terms of applications in wines, teas, and infusions samples. Linear correlation analysis at a 95% confidence level was employed to compare the results, which were in good agreement with a correlation coefficient of r > 0.9000. Thus, the developed method was simple, accurate, and consistent with other assays for the determination of the total amount of phenolic compounds and antioxidant capacity.

Electron transfer by singlet excited state of porphyn and electron acceptor affinity in rigid medium: photoacoustic phase angle analysis

Photoacoustic spectroscopy provides information about both amplitude and phase of the response of a system to an optical excitation process. This paper presents the studies of the phase in the electron transfer process between octaethylporphyn (OEP) and quinone molecules dispersed in a polymeric matrix. It was observed a tendency in the phase behavior to small values only in the spectral region near to 620 nm, while for shorter wavelength did not show any tendency. These measurements suggested that the electron transfer to acceptor occurred with the participation of octaethylporphyn singlet excited state.

Electron migration in DNA matrix: an electron transfer reaction

This paper brings an active and provocative area of current research. It describes the investigation of electron transfer (ET) chemistry in general and ET reactions results in DNA in particular. Two DNA intercalating molecules were used: Ethidium Bromide as the donor (D) and Methyl-Viologen as the acceptor (A), the former intercalated between DNA bases and the latter in its surface. Using the Perrin model and fluorescence quenching measurements the distance of electron migration, herein considered to be the linear spacing between donor and acceptor molecule along the DNA molecule, was obtained. A value of 22.6 (± 1.1) angstroms for the distance and a number of 6.6 base pairs between donor and acceptor were found. In current literature the values found were 26 angstroms and almost 8 base pairs. DNA electron transfer is considered to be mediated by through-space interactions between the p-electron-containing base pairs.

Role of culture in knowledge transfer and sharing - case ERP implementation

The main objective of this study was to examine how culture influences knowledge transfer and sharing within multicultural ERP project implementation in China. The main interest was to explain how national culture and knowledge are linked by understanding how culture influences knowledge transfer and sharing in a project organization. The other objective of this work was to discuss what Chinese cultural characteristic inhibit and en-hance knowledge sharing in ERP project. The perspective of this study was qualitative and the empirical material was collected from theme interviews among Stora Enso employees. Conclusion of this thesis is that Finns have a very direct style of communication and sharing knowledge whereas Chinese respect face shaving and indirect communication. Another conclusion is that knowledge sharing does not “just happen”, it is needed that project members understand national culture to get all project members commitment to project. In China most important is understand local business processes and understand role of trust and guanxi.

Leaf-Targeted Ferredoxin-NADP+-Oxidoreductase (FNR): Electron Transfer Properties and Thylakoid Association in Arabidopsis thaliana

Photosynthetic reactions are divided in two parts: light-driven electron transfer reactions and carbon fixation reactions. Electron transfer reactions capture solar energy and split water molecules to form reducing energy (NADPH) and energy-carrying molecules (ATP). These end-products are used for fixation of inorganic carbon dioxide into organic sugar molecules. Ferredoxin-NADP⁺ oxidoreductase (FNR) is an enzyme that acts at the branch point between the electron transfer reactions and reductive metabolism by catalyzing reduction of NADP+ at the last step of the electron transfer chain. In this thesis, two isoforms of FNR from A rabidopsis thaliana, FNR1 and FNR2, were characterized using the reverse genetics approach. The fnr1 and fnr2 mutant plants resembled each other in many respects. Downregulation of photosynthesis protected the single fnr mutant plants from excess formation of reactive oxygen species (ROS), even without significant upregulation of antioxidative mechanisms. Adverse growth conditions, however, resulted in phenotypic differences between fnr1 and fnr2. While fnr2 plants showed downregulation of photosynthetic complexes and upregulation of antioxidative mechanisms under low-temperature growth conditions, fnr1 plants had the wild-type phenotype, indicating that FNR2 may have a specific role in redistribution of electrons under unfavorable conditions. The heterozygotic double mutant (fnr1xfnr2) was severely devoid of chloroplastic FNR, which clearly restricted photosynthesis. The fnr1xfnr2 plants used several photoprotective mechanisms to avoid oxidative stress. In wild-type chloroplasts, both FNR isoforms were found from the stroma, the thylakoid membrane, and the inner envelope membrane. In the absence of the FNR1 isoform, FNR2 was found only in the stroma, suggesting that FNR1 and FNR2 form a dimer, by which FNR1 anchors FNR2 to the thylakoid membrane. Structural modeling predicted formation of an FNR dimer in complex with ferredoxin. In this thesis work, Tic62 was found to be the main protein that binds FNR to the thylakoid membrane, where Tic62 and FNR formed high molecular weight complexes. The formation of such complexes was shown to be regulated by the redox state of the chloroplast. The accumulation of Tic62-FNR complexes in darkness and dissociation of complexes from the membranes in light provide evidence that the complexes may have roles unrelated to photosynthesis. This and the high viability of fnr1 mutant plants lacking thylakoid-bound FNR indicate that the stromal pool of FNR is photosynthetically active.

External knowledge transfer mechanisms in service business acquisition

In knowledge-intensive economy an effective knowledge transfer is a part of the firm’s strategy to achieve a competitive advantage in the market. Knowledge transfer related to a variety of mechanisms depends on the nature of knowledge and context. The topic is, however, very little empirical studied and there is a research gap in scientific literature. This study examined and analyzed external knowledge transfer mechanisms in service business and especially in the context of acquisitions. The aim was to find out what kind of mechanisms was used when the buyer began to transfer data e.g. their own agendas and practices to the purchased units. Another major research goal was to identify the critical factors which contributed to knowledge transfer through different mechanisms. The study was conducted as a multiple-case study in a consultative service business company, in its four business units acquired by acquisition, in various parts of the country. The empirical part of the study was carried out as focus group interviews in each unit, and the data were analyzed using qualitative methods. The main findings of this study were firstly the nine different knowledge transfer mechanisms in service business acquisition: acquisition management team as an initiator, unit manager as a translator, formal training, self-directed learning, rooming-in, IT systems implementation, customer relationship management, codified database and ecommunication. The used mechanisms brought up several aspects as giving the face to changing, security of receiving right knowledge and correctly interpreted we-ness atmosphere, and orientation to use more consultative touch with customers. The study pointed out seven critical factors contributed to different mechanisms: absorption, motivation, organizational learning, social interaction, trust, interpretation and time resource. The two last mentioned were new findings compared to previous studies. Each of the mechanisms and the related critical factors contributed in different ways to the activity in different units after the acquisition. The role of knowledge management strategy was the most significant managerial contribution of the study. Phenomenon is not recognized enough although it is strongly linked in knowledge based companies. The recognition would help to develop a better understanding of the business through acquisitions, especially in situations such as where two different knowledge strategies combines in new common company.

Analysis on firm innovation boundaries

Innovation has been widely recognized as an important driver of firm competitiveness, and the firm’s internal research and development (R&D) activities are often considered to have a critical role in innovation activities. Internal R&D is, however, not the source of innovation as firms may tap into knowledge necessary for innovation also through various types of sourcing agreements or by collaborating with other organizations. The objective of this study is to analyze the way firms go about organizing efficiently their innovation boundaries. Within this context, the analysis is focused, firstly, on the relation between innovation boundaries and firm innovation performance and, secondly, on the factors explaining innovation boundary organization. The innovation literature recognizes that the sources of innovation depend on the nature of technology but does not offer a sufficient tool for analyzing innovation boundary options and their efficiency. Thus, this study suggests incorporating insights from transaction cost economics (TCE) complemented with dynamic governance costs and benefits into the analysis. The thesis consists of two parts. The first part introduces the background of the study, research objectives, an overview of the empirical studies, and the general conclusions of the study. The second part is formed of five publications. The overall results firstly indicate that although the relation between firm innovation boundary options is partly industry sector-specific, the firm level search strategies and knowledge transfer capabilities are important for innovation performance independently of the sector. Secondly, the results show that the attributes suggested by TCE alone do not offer a sufficient explanation of innovation boundary selection, especially under conditions of high levels of (radical) uncertainty. Based on the results, the dynamic governance cost and benefit framework complements the static TCE when firm innovation boundaries are scrutinized.

Motivational Influences on Transfer: Dimensions and Boundary Conditions

The focus of this dissertation is the motivational influences on transfer in higher education and professional training contexts. To estimate these motivational influences, the dissertation includes seven individual studies that are structured in two parts. Part I, Dimensions, aims at identifying the dimensionality of motivation to transfer and its structural relations with training-related antecedents and outcomes. Part II, Boundary Conditions, aims at testing the predictive validity of motivation theories used in contemporary training research under different study conditions. Data in this dissertation was gathered from multi-item questionnaires, which were analyzed differently in Part I and Part II. Studies in Part I employed exploratory and confirmatory factor analysis, structural equation modeling, partial least squares (PLS) path modeling, and mediation analysis. Studies in Part II used artifact distribution meta-analysis, (nested) subgroup analysis, and weighted least squares (WLS) multiple regression. Results demonstrate that motivation to transfer can be conceptualized as a three-dimensional construct, including autonomous motivation to transfer, controlled motivation to transfer, and intention to transfer, given a theoretical framework informed by expectancy theory, self-determination theory, and the theory of planned behavior. Results also demonstrate that a range of boundary conditions moderates motivational influences on transfer. To test the predictive validity of expectancy theory, social cognitive theory, and the theory of goal orientations under different study settings, a total of 17 boundary conditions were meta-analyzed, including age; assessment criterion; assessment source; attendance policy; collaboration among trainees; computer support; instruction; instrument used to measure motivation; level of education; publication type; social training context; SS/SMC bias; study setting; survey modality; type of knowledge being trained; use of a control group; and work context. Together, the findings cumulated in this thesis support the basic premise that motivation is centrally important for transfer, but that motivational influences need to be understood from a more differentiated perspective than commonly found in the literature, in order to account for several dimensions and boundary conditions. The results of this dissertation across the seven individual studies are reflected in terms of their implications for theory development and their significance for training evaluation and the design of training environments. Limitations and directions to take in future research are discussed.

Frequency-Domain and Wide-Pulse Time-Domain Measurements of Lanthanide Luminescence and Lanthanide-Based Resonance Energy Transfer

Resonance energy transfer (RET) is a non-radiative transfer of the excitation energy from the initially excited luminescent donor to an acceptor. The requirements for the resonance energy transfer are: i) the spectral overlap between the donor emission spectrum and the acceptor absorption spectrum, ii) the close proximity of the donor and the acceptor, and iii) the suitable relative orientations of the donor emission and the acceptor absorption transition dipoles. As a result of the RET process the donor luminescence intensity and the donor lifetime are decreased. If the acceptor is luminescent, a sensitized acceptor emission appears. The rate of RET depends strongly on the donor–acceptor distance (r) and is inversely proportional to r6. The distance dependence of RET is utilized in binding assays. The proximity requirement and the selective detection of the RET-modified emission signal allow homogeneous separation free assays. The term lanthanide-based RET is used when luminescent lanthanide compounds are used as donors. The long luminescence lifetimes, the large Stokes’ shifts and the intense, sharply-spiked emission spectra of the lanthanide donors offer advantages over the conventional organic donor molecules. Both the organic lanthanide chelates and the inorganic up-converting phosphor (UCP) particles have been used as donor labels in the RET based binding assays. In the present work lanthanide luminescence and lanthanide-based resonance energy transfer phenomena were studied. Luminescence lifetime measurements had an essential role in the research. Modular frequency-domain and time-domain luminometers were assembled and used successfully in the lifetime measurements. The frequency-domain luminometer operated in the low frequency domain ( 100 kHz) and utilized a novel dual-phase lock-in detection of the luminescence. One of the studied phenomena was the recently discovered non-overlapping fluorescence resonance energy transfer (nFRET). The studied properties were the distance and temperature dependences of nFRET. The distance dependence was found to deviate from the Förster theory and a clear temperature dependence was observed whereas conventional RET was completely independent of the temperature. Based on the experimental results two thermally activated mechanisms were proposed for the nFRET process. The work with the UCP particles involved the measurement of the luminescence properties of the UCP particles synthesized in our laboratory. The goal of the UCP particle research is to develop UCP donor labels for binding assays. In the present work the effect of the dopant concentrations and the core–shell structure on the total up-conversion luminescence intensity, the red–green emission ratio, and the luminescence lifetime was studied. Also the non-radiative nature of the energy transfer from the UCP particle donors to organic acceptors was demonstrated for the first time in aqueous environment and with a controlled donor–acceptor distance.

Effective diffusivity and convective mass transfer coefficient during the drying of bananas

In this article, a methodology is used for the simultaneous determination of the effective diffusivity and the convective mass transfer coefficient in porous solids, which can be considered as an infinite cylinder during drying. Two models are used for optimization and drying simulation: model 1 (constant volume and diffusivity, with equilibrium boundary condition), and model 2 (constant volume and diffusivity with convective boundary condition). Optimization algorithms based on the inverse method were coupled to the analytical solutions, and these solutions can be adjusted to experimental data of the drying kinetics. An application of optimization methodology was made to describe the drying kinetics of whole bananas, using experimental data available in the literature. The statistical indicators enable to affirm that the solution of diffusion equation with convective boundary condition generates results superior than those with the equilibrium boundary condition.

Water transfer from São Francisco river to semiarid northeast of Brazil: technical data, environmental impacts, survey of opinion about the amount to be transferred

The transposition of the São Francisco River is considered one of the greatest engineering works in Brazil of all time since it will cross an extensive agricultural region of continental dimensions, involving environmental impacts, water, soil, irrigation, water payment and other multidisciplinary themes. Taking into account its importance, this subject was incorporated into a discipline of UFSCar (Federal University of São Carlos - Brazil) named "Pollution and Environmental Impacts". It was noted strong reaction against the project, even before the presentation. To allow a critical analysis, the first objective was to compile the main technical data and environmental impacts. The second objective was to detect the three most important aspects that cause reaction, concluding for the following reasons: assumption that the volume of water to be transferred was much greater than it actually is proposed in the project; lack of knowledge about similar project already done in Brazil; the idea that the artificial canal to be built was much broader than that proposed by the project. The participants' opinion about "volume to be transferred" was raised quantitatively four times: 2-undergraduate students; 1-graduate; 1-outside community. The average resulted 14 times larger than that proposed in the project, significant according to t-test. It was concluded that the reaction to water transfer project is due in part to the ignorance combined with a preconceived idea that tend to overestimate the magnitude of environmental impacts.

Interposição jejunal após gastrectomia total radical por adenocarcinoma gástrico

Realizamos um estudo retrospectivo do tratamento cirúrgico do adenocarcinoma gástrico por uma gastrectomia total radical, com reconstrução do trânsito esofagoduodenal pela interposição de uma alça jejunal pediculada. Revisão de trabalhos nacionais e estrangeiros relacionados ao tratamento do adenocarcinoma gástrico pela gastrectomia total radical. De acordo com a operabilidade relacionada ao paciente e à ressecabilidade, à lesão primária e sua evolução, 126 pacientes foram submetidos à interposição de um segmento de alça jejunal após gastrectomia total radical. Ressecção oncológica total do estômago e sistematizada reconstrução técnica do reservatório gástrico e do trânsito esofagoduodenal. Nossos casos evoluíram de maneira satisfatória, não fugindo daqueles estudados na literatura. Ênfase especial foi dada ao procedimento técnico, mais anatômico e muito mais funcional, restituindo ao operado um neoestômago e um trânsito esôfago-intestinal através do duodeno. A interposição de uma alça jejunal pediculada entre o esôfago terminal e a segunda porção do duodeno age como neo-reservatório gástrico. Evita o refluxo esofágico e direciona o bolo alimentar para o delgado através do duodeno, trânsito anatômico e funcional capaz de proporcionar melhor qualidade de vida ao gastrectomizado total.

Influência da linfadenectomia radical (D2) na morbidade e mortalidade da ressecção curativa do carcinoma gástrico

A despeito da controvérsia existente na literatura com relação aos benefícios da linfadenectomia na sobrevida dos doentes submetidos a ressecções curativas para tratamento do adenocarcinoma gástrico, é inegável que a linfadenectomia ampliada (nível II na classificação japonesa) contribui para o melhor estadiamento e prognóstico destes pacientes. Este procedimento permite-nos melhor identificar aqueles pacientes que têm pior prognóstico e oferecer-lhes novas formas de terapia adjuvante. Como o principal argumento para a não realização de cirurgias mais alargadas é que estas são acompanhadas de maior morbidade e mortalidade, os autores estudaram prospectivamente parâmetros relacionados a esses índices nas gastrectomias com linfadenectomia nível 11 (D2) que tiveram intenção curativa. Para tanto, estudaram-se a taxa de mortalidade, o tempo operatório, as unidades de glóbulos transfundidas, as complicações e o tempo de internação pós-operatória. Entre dezembro de 1992 e fevereiro de 1997 foram internados 86 pacientes com diagnóstico de adenocarcinoma gástrico, dos quais, em 27, atendidos por uma mesma equipe interessada no tratamento destes tumores, houve ressecção cirúrgica com intenção curativa e o tratamento consistiu de gastrectomia acompanhada de linfadenectomia D2. A gastrectomia subtotal foi realizada em 17 doentes, a total em três e a total ampliada em sete. Nove doentes tinham tumores superficiais. Não houve mortalidade entre os pacientes submetidos a ressecções D2; o tempo médio operatório foi de 208,7 minutos; receberam em média 0,2 unidades de glóbulos e a incidência de complicações foi de 33,3%. A permanência hospitalar pós-operatória média foi de 8,6 dias. Foram estudados 854 linfonodos, dos quais 22,1% eram positivos para tumor metastático. Os autores concluem que a dissecção D2 pode ser feita de forma segura e não deve ser evitada por causa do risco de complicações. Permite estadiamento anatomopatológico mais preciso e melhor avaliação do prognóstico destes pacientes.