Catalytic asymmetric transfer hydrogenation of ketones: recent advances

In this review, we consider the main processes for the asymmetric transfer hydrogenation of ketones from 2008 up today. The most effective organometallic compounds (derived from Ru, Rh, Ir, Fe, Os, Ni, Co, and Re) and chiral ligands (derived from amino alcohols, diamines, sulfur- and phosphorus-containing compounds, as well as heterocyclic systems) will be shown paying special attention to functionalized substrates, tandem reactions, processes under non-conventional conditions, supported catalysts, dynamic kinetic resolutions, the use of water as a green solvent, theoretical and experimental studies on reaction mechanisms, enzymatic processes, and finally applications to the total synthesis of biologically active organic molecules.

SYSTEM DYNAMICS MODELING AS A QUANTITATIVE-QUALITATIVE FRAMEWORK FOR SUSTAINABLE WATER RESOURCES MANAGEMENT: INSIGHTS FOR WATER QUALITY POLICY IN THE GREAT LAKES REGION

Early water resources modeling efforts were aimed mostly at representing hydrologic processes, but the need for interdisciplinary studies has led to increasing complexity and integration of environmental, social, and economic functions. The gradual shift from merely employing engineering-based simulation models to applying more holistic frameworks is an indicator of promising changes in the traditional paradigm for the application of water resources models, supporting more sustainable management decisions. This dissertation contributes to application of a quantitative-qualitative framework for sustainable water resources management using system dynamics simulation, as well as environmental systems analysis techniques to provide insights for water quality management in the Great Lakes basin. The traditional linear thinking paradigm lacks the mental and organizational framework for sustainable development trajectories, and may lead to quick-fix solutions that fail to address key drivers of water resources problems. To facilitate holistic analysis of water resources systems, systems thinking seeks to understand interactions among the subsystems. System dynamics provides a suitable framework for operationalizing systems thinking and its application to water resources problems by offering useful qualitative tools such as causal loop diagrams (CLD), stock-and-flow diagrams (SFD), and system archetypes. The approach provides a high-level quantitative-qualitative modeling framework for "big-picture" understanding of water resources systems, stakeholder participation, policy analysis, and strategic decision making. While quantitative modeling using extensive computer simulations and optimization is still very important and needed for policy screening, qualitative system dynamics models can improve understanding of general trends and the root causes of problems, and thus promote sustainable water resources decision making. Within the system dynamics framework, a growth and underinvestment (G&U) system archetype governing Lake Allegan's eutrophication problem was hypothesized to explain the system's problematic behavior and identify policy leverage points for mitigation. A system dynamics simulation model was developed to characterize the lake's recovery from its hypereutrophic state and assess a number of proposed total maximum daily load (TMDL) reduction policies, including phosphorus load reductions from point sources (PS) and non-point sources (NPS). It was shown that, for a TMDL plan to be effective, it should be considered a component of a continuous sustainability process, which considers the functionality of dynamic feedback relationships between socio-economic growth, land use change, and environmental conditions. Furthermore, a high-level simulation-optimization framework was developed to guide watershed scale BMP implementation in the Kalamazoo watershed. Agricultural BMPs should be given priority in the watershed in order to facilitate cost-efficient attainment of the Lake Allegan's TP concentration target. However, without adequate support policies, agricultural BMP implementation may adversely affect the agricultural producers. Results from a case study of the Maumee River basin show that coordinated BMP implementation across upstream and downstream watersheds can significantly improve cost efficiency of TP load abatement.

Potential mitigation of midwest grass-finished beef production emissions with soil carbon sequestration in the United States of America

Beef production can be environmentally detrimental due in large part to associated enteric methane (CH4) production, which contributes to climate change. However, beef production in well-managed grazing systems can aid in soil carbon sequestration (SCS), which is often ignored when assessing beef production impacts on climate change. To estimate the carbon footprint and climate change mitigation potential of upper Midwest grass-finished beef production systems, we conducted a partial life cycle assessment (LCA) comparing two grazing management strategies: 1) a non-irrigated, lightly-stocked (1.0 AU/ha), high-density (100,000 kg LW/ha) system (MOB) and 2) an irrigated, heavily-stocked (2.5 AU/ha), low-density (30,000 kg LW/ha) system (IRG). In each system, April-born steers were weaned in November, winter-backgrounded for 6 months and grazed until their endpoint the following November, with average slaughter age of 19 months and a 295 kg hot carcass weight. As the basis for the LCA, we used two years of data from Lake City Research Center, Lake City, MI. We included greenhouse gas (GHG) emissions associated with enteric CH4, soil N2O and CH4 fluxes, alfalfa and mineral supplementation, and farm energy use. We also generated results from the LCA using the enteric emissions equations of the Intergovernmental Panel on Climate Change (IPCC). We evaluated a range of potential rates of soil carbon (C) loss or gain of up to 3 Mg C ha-1 yr-1. Enteric CH4 had the largest impact on total emissions, but this varied by grazing system. Enteric CH4 composed 62 and 66% of emissions for IRG and MOB, respectively, on a land basis. Both MOB and IRG were net GHG sources when SCS was not considered. Our partial LCA indicated that when SCS potential was included, each grazing strategy could be an overall sink. Sensitivity analyses indicated that soil in the MOB and IRG systems would need to sequester 1 and 2 Mg C ha-1 yr-1 for a net zero GHG footprint, respectively. IPCC model estimates for enteric CH4 were similar to field estimates for the MOB system, but were higher for the IRG system, suggesting that 0.62 Mg C ha-1 yr-1 greater SCS would be needed to offset the animal emissions in this case.

Nuevos estilos de liderazgo en la organización

A lo largo del tiempo se aborda el liderazgo desde las posturas propias del comportamiento organizacional y la gestión humana. Desde un principio se basaba el liderazgo como un sujeto (líder), más adelante se tuvo en cuenta la parte situacional, es decir cómo afecta el entorno a la empresa y por último, es de principal interés el liderazgo organizacional. Dicho esto,en el contexto actual, un mundo globalizado y en que el mercado se vuelve más exigente, las organizaciones deben adaptarse y adecuarse rápidamente a los nuevos requerimientos para sobrevivir (Chiavenato, 2002) . Esta investigación tiene como fin explorar reconocer y demostrar como el mundo de los negocios es dinámico y exige cambiar para mejorar e incursionar estrategias que garanticen la perdurabilidad de una empresa, debido a esto se analizan diferentes empresas exitosas y perdurables en el tiempo ubicadas en la ciudad de Nueva York ,el cómo y porque la gestión humana, su talento humano en una organización debe ser valorado como personas dotadas de capacidades y habilidades que trabajan en conjunto por un bien común y así mismo ,la relación y el impacto que tiene con los diferentes estilos de liderazgos, por lo tanto ,si una compañía desea mostrarse y ser exitosa en el mercado, primeramente debe estar bien estructurada y fuerte por dentro , es decir, la relación directa con su talento humano.

Complex Transition to Cooperative Behavior in a Structured Population Model

Cooperation plays an important role in the evolution of species and human societies. The understanding of the emergence and persistence of cooperation in those systems is a fascinating and fundamental question. Many mechanisms were extensively studied and proposed as supporting cooperation. The current work addresses the role of migration for the maintenance of cooperation in structured populations. This problem is investigated in an evolutionary perspective through the prisoner's dilemma game paradigm. It is found that migration and structure play an essential role in the evolution of the cooperative behavior. The possible outcomes of the model are extinction of the entire population, dominance of the cooperative strategy and coexistence between cooperators and defectors. The coexistence phase is obtained in the range of large migration rates. It is also verified the existence of a critical level of structuring beyond that cooperation is always likely. In resume, we conclude that the increase in the number of demes as well as in the migration rate favor the fixation of the cooperative behavior.

Evolutionary branching in deme-structured populations.

Adaptive dynamics shows that a continuous trait under frequency dependent selection may first converge to a singular point followed by spontaneous transition from a unimodal trait distribution into a bimodal one, which is called "evolutionary branching". Here, we study evolutionary branching in a deme-structured population by constructing a quantitative genetic model for the trait variance dynamics, which allows us to obtain an analytic condition for evolutionary branching. This is first shown to agree with previous conditions for branching expressed in terms of relatedness between interacting individuals within demes and obtained from mutant-resident systems. We then show this branching condition can be markedly simplified when the evolving trait affect fecundity and/or survival, as opposed to affecting population structure, which would occur in the case of the evolution of dispersal. As an application of our model, we evaluate the threshold migration rate below which evolutionary branching cannot occur in a pairwise interaction game. This agrees very well with the individual-based simulation results.

Business intelligence viewpoint on managerial decision-making : Ill-structured problems and decision support systems

Vaikka liiketoimintatiedon hallintaa sekä johdon päätöksentekoa on tutkittu laajasti, näiden kahden käsitteen yhteisvaikutuksesta on olemassa hyvin rajallinen määrä tutkimustietoa. Tulevaisuudessa aiheen tärkeys korostuu, sillä olemassa olevan datan määrä kasvaa jatkuvasti. Yritykset tarvitsevat jatkossa yhä enemmän kyvykkyyksiä sekä resursseja, jotta sekä strukturoitua että strukturoimatonta tietoa voidaan hyödyntää lähteestä riippumatta. Nykyiset Business Intelligence -ratkaisut mahdollistavat tehokkaan liiketoimintatiedon hallinnan osana johdon päätöksentekoa. Aiemman kirjallisuuden pohjalta, tutkimuksen empiirinen osuus tunnistaa liiketoimintatiedon hyödyntämiseen liittyviä tekijöitä, jotka joko tukevat tai rajoittavat johdon päätöksentekoprosessia. Tutkimuksen teoreettinen osuus johdattaa lukijan tutkimusaiheeseen kirjallisuuskatsauksen avulla. Keskeisimmät tutkimukseen liittyvät käsitteet, kuten Business Intelligence ja johdon päätöksenteko, esitetään relevantin kirjallisuuden avulla – tämän lisäksi myös dataan liittyvät käsitteet analysoidaan tarkasti. Tutkimuksen empiirinen osuus rakentuu tutkimusteorian pohjalta. Tutkimuksen empiirisessä osuudessa paneudutaan tutkimusteemoihin käytännön esimerkein: kolmen tapaustutkimuksen avulla tutkitaan sekä kuvataan toisistaan irrallisia tapauksia. Jokainen tapaus kuvataan sekä analysoidaan teoriaan perustuvien väitteiden avulla – nämä väitteet ovat perusedellytyksiä menestyksekkäälle liiketoimintatiedon hyödyntämiseen perustuvalle päätöksenteolle. Tapaustutkimusten avulla alkuperäistä tutkimusongelmaa voidaan analysoida tarkasti huomioiden jo olemassa oleva tutkimustieto. Analyysin tulosten avulla myös yksittäisiä rajoitteita sekä mahdollistavia tekijöitä voidaan analysoida. Tulokset osoittavat, että rajoitteilla on vahvasti negatiivinen vaikutus päätöksentekoprosessin onnistumiseen. Toisaalta yritysjohto on tietoinen liiketoimintatiedon hallintaan liittyvistä positiivisista seurauksista, vaikka kaikkia mahdollisuuksia ei olisikaan hyödynnetty. Tutkimuksen merkittävin tulos esittelee viitekehyksen, jonka puitteissa johdon päätöksentekoprosesseja voidaan arvioida sekä analysoida. Despite the fact that the literature on Business Intelligence and managerial decision-making is extensive, relatively little effort has been made to research the relationship between them. This particular field of study has become important since the amount of data in the world is growing every second. Companies require capabilities and resources in order to utilize structured data and unstructured data from internal and external data sources. However, the present Business Intelligence technologies enable managers to utilize data effectively in decision-making. Based on the prior literature, the empirical part of the thesis identifies the enablers and constraints in computer-aided managerial decision-making process. In this thesis, the theoretical part provides a preliminary understanding about the research area through a literature review. The key concepts such as Business Intelligence and managerial decision-making are explored by reviewing the relevant literature. Additionally, different data sources as well as data forms are analyzed in further detail. All key concepts are taken into account when the empirical part is carried out. The empirical part obtains an understanding of the real world situation when it comes to the themes that were covered in the theoretical part. Three selected case companies are analyzed through those statements, which are considered as critical prerequisites for successful computer-aided managerial decision-making. The case study analysis, which is a part of the empirical part, enables the researcher to examine the relationship between Business Intelligence and managerial decision-making. Based on the findings of the case study analysis, the researcher identifies the enablers and constraints through the case study interviews. The findings indicate that the constraints have a highly negative influence on the decision-making process. In addition, the managers are aware of the positive implications that Business Intelligence has for decision-making, but all possibilities are not yet utilized. As a main result of this study, a data-driven framework for managerial decision-making is introduced. This framework can be used when the managerial decision-making processes are evaluated and analyzed.

STATE-AND-TRANSITION MODELING AND ADAPTIVE MANAGEMENT: TOOLS FOR FUTURE CO-DEVELOPMENT OF MADAGASCAR’S NATURAL RESOURCES AND PEOPLE

Madagascar’s terrestrial and aquatic ecosystems have long supported a unique set of ecological communities, many of whom are endemic to the tropical island. Those same ecosystems have been a source of valuable natural resources to some of the poorest people in the world. Nevertheless, with pride, ingenuity and resourcefulness, the Malagasy people of the southwest coast, being of Vezo identity, subsist with low development fishing techniques aimed at an increasingly threatened host of aquatic seascapes. Mangroves, sea grass bed, and coral reefs of the region are under increased pressure from the general populace for both food provisions and support of economic opportunity. Besides purveyors and extractors, the coastal waters are also subject to a number of natural stressors, including cyclones and invasive, predator species of both flora and fauna. In addition, the aquatic ecosystems of the region are undergoing increased nutrient and sediment runoff due, in part, to Madagascar’s heavy reliance on land for agricultural purposes (Scales, 2011). Moreover, its coastal waters, like so many throughout the world, have been proven to be warming at an alarming rate over the past few decades. In recognizing the intimate interconnectedness of the both the social and ecological systems, conservation organizations have invoked a host of complimentary conservation and social development efforts with the dual aim of preserving or restoring the health of both the coastal ecosystems and the people of the region. This paper provides a way of thinking more holistically about the social-ecological system within a resiliency frame of understanding. Secondly, it applies a platform known as state-and-transition modeling to give form to the process. State-and-transition modeling is an iterative investigation into the physical makeup of a system of study as well as the boundaries and influences on that state, and has been used in restorative ecology for more than a decade. Lastly, that model is sited within an adaptive management scheme that provides a structured, cyclical, objective-oriented process for testing stakeholders cognitive understanding of the ecosystem through a pragmatic implementation and monitoring a host of small-scale interventions developed as part of the adaptive management process. Throughout, evidence of the application of the theories and frameworks are offered, with every effort made to retool conservation-minded development practitioners with a comprehensive strategy for addressing the increasingly fragile social-ecological systems of southwest Madagascar. It is offered, in conclusion, that the seascapes of the region would be an excellent case study worthy of future application of state-and-transition modeling and adaptive management as frameworks for conservation-minded development practitioners whose multiple projects, each with its own objective, have been implemented with a single goal in mind: preserve and protect the state of the supporting environment while providing for the basic needs of the local Malagasy people.

The impact of bandwidth in structured interviewing and criterion stability in predicting and assessing manager performance across transition and maintenance stages

The current study examined the role of three important components in the use of structured employment interviewing in performance prediction: construct bandwidth, observed communication skill, and the stability/dynamicity of performance criteria over time. A matched sample of 242 hospitality managers was derived from a field data set provided by a large hospitality management organization. Interview data and two years of performance appraisal data were provided. Bandwidth analysis demonstrated only minimal differences in prediction between matched predictor-criterion pairs compared with predictor to overall aggregate ratings (unmatched). The communication skill analysis revealed that this interviewer rated observation significantly predicted a number of the individual performance dimensions as well as overall performance over time. Of the five interview items, the strongest overall predictor of performance was interviewer rated communication skill. The stability/dynamicity analyses demonstrated the performance criteria to be generally stable over the two year period examined, which provides support for the long held notion that performance criteria is stabile over time. However, there were two exceptions. The interview dimension customer service orientation had shifting relationships over time with four of the criteria over the two year period. The performance criteria employee development also demonstrated some instability in its relationships with predictors. Thus, some evidence of dynamicity in performance criteria was revealed. Interestingly, both of the most noteworthy findings in the study involved items that were rated differently than the others in the study. The rated interview item communication skill and the rated performance criteria client satisfaction were ratings that involved a more direct level of observation. Additional analyses also revealed evidence of a general factor of performance. These two themes are more fully covered in the discussion.

Modelo de análise técnico-tática do jogo de handebol : necessidades, perspectivas e implicações de um modelo de interpretação das situações de jogo em tempo real

Universidade Estadual de Campinas . Faculdade de Educação Física

Transition amplitude for two-time physics

We present the transition amplitude for a particle moving in a space with two times and D space dimensions having an Sp(2, R) local symmetry and an SO(D, 2) rigid symmetry. It was obtained from the BRST-BFV quantization with a unique gauge choice. We show that by constraining the initial and final points of this amplitude to lie on some hypersurface of the D + 2 space the resulting amplitude reproduces well-known systems in lower dimensions. This work provides an alternative way to derive the effects of two-time physics where all the results come from a single transition amplitude.

Magnetic-field-induced transition in a wide parabolic well superimposed with a superlattice

We study a Al(x)Ga(x-1)As parabolic quantum well (PQW) with GaAs/Al(x)Ga(x-1)As square superlattice. The magnetotransport in PQW with intentionally disordered short-period superlattice reveals a surprising transition from electrons distribution over whole parabolic well to independent-layer states with unequal density. The transition occurs in the perpendicular magnetic field at Landau filling factor v approximate to 3 and is signaled by the appearance of the strong and developing fractional quantum Hall (FQH) states and by the enhanced slope of the Hall resistance. We attribute the transition to the possible electron localization in the x-y plane inside the lateral wells, and formation of the FQH states in the central well of the superlattice, driven by electron-electron interaction.

Magnetotransport in a wide parabolic well superimposed with a superlattice

The electron properties of artificially disordered superlattices embedded in a wide AlGaAs parabolic well were investigated in a strong magnetic field. We demonstrated that in the extreme quantum limit the interlayer disorder results in formation of a new correlated phase. A nearly uniform electron distribution over the superlattice wells was found in a weak magnetic field. However, a nonuniform phase with partially localized electrons, representing well-developed fractional quantum Hall effect features, was observed in high magnetic field (at the filling factor v < 1). A distinct magnetic field-induced transition separates these two phases. (C) 2011 American Institute of Physics. [doi:10.1063/1.3576134]

Delocalization-localization transition of plasmons in random (GaAs)(m)(Al(0.3)Ga(0.7)As)(6) superlattices

The transition of plasmons from propagating to localized state was studied in disordered systems formed in GaAs/AlGaAs superlattices by impurities and by artificial random potential. Both the localization length and the linewidth of plasmons were measured by Raman scattering. The vanishing dependence of the plasmon linewidth on the disorder strength was shown to be a manifestation of the strong plasmon localization. The theoretical approach based on representation of the plasmon wave function in a Gaussian form well accounted for by the obtained experimental data.

The role of electron localization in the atomic structure of transition-metal 13-atom clusters: the example of Co(13), Rh(13), and Hf(13)

The crystalline structure of transition-metals (TM) has been widely known for several decades, however, our knowledge on the atomic structure of TM clusters is still far from satisfactory, which compromises an atomistic understanding of the reactivity of TM clusters. For example, almost all density functional theory (DFT) calculations for TM clusters have been based on local (local density approximation-LDA) and semilocal (generalized gradient approximation-GGA) exchange-correlation functionals, however, it is well known that plain DFT fails to correct the self-interaction error, which affects the properties of several systems. To improve our basic understanding of the atomic and electronic properties of TM clusters, we report a DFT study within two nonlocal functionals, namely, the hybrid HSE (Heyd, Scuseria, and Ernzerhof) and GGA + U functionals, of the structural and electronic properties of the Co(13), Rh(13), and Hf(13) clusters. For Co(13) and Rh(13), we found that improved exchange-correlation functionals decrease the stability of open structures such as the hexagonal bilayer (HBL) and double simple-cubic (DSC) compared with the compact icosahedron (ICO) structure, however, DFT-GGA, DFT-GGA + U, and DFT-HSE yield very similar results for Hf(13). Thus, our results suggest that the DSC structure obtained by several plain DFT calculations for Rh(13) can be improved by the use of improved functionals. Using the sd hybridization analysis, we found that a strong hybridization favors compact structures, and hence, a correct description of the sd hybridization is crucial for the relative energy stability. For example, the sd hybridization decreases for HBL and DSC and increases for ICO in the case of Co(13) and Rh(13), while for Hf(13), the sd hybridization decreases for all configurations, and hence, it does not affect the relative stability among open and compact configurations.