Ring opening polymerization of lactides and lactones by multimetallic alkyl zinc complexes derived from the acids Ph₂C(X)CO₂2H (X = OH, NH₂ )

The reaction of the dialkylzinc reagents R₂Zn with the acids 2,2-Ph₂C(X)(CO₂H), where X = NH₂, OH, i.e. 2,2′-diphenylglycine (dpgH) or benzilic acid (benzH2), in toluene at reflux temperature afforded the tetra-nuclear ring complexes [RZn(dpg)]₄, where R = Me (1), Et (2), 2-CF₃C₆H₄ (3), and 2,4,6-F₃C₆H₂ (4); complex 2 has been previously reported. The crystal structures of 1·(2MeCN), 3 and 4·(4(C₇H₈)·1.59(H₂O)) are reported, along with that of the intermediate compound (2-CF₃C₆H₄)3B·MeCN and the known compound [ZnCl₂(NCMe)₂]. Complexes 1–4, together with the known complex [(ZnEt)₃(ZnL)₃(benz)₃] (5; L = MeCN), have been screened, in the absence of benzyl alcohol, for their potential to act as catalysts for the ring opening polymerization (ROP) of ε-caprolactone (ε-CL), δ-valerolactone (δ-VL) and rac-lactide (rac-LA); the co-polymerization of ε-CL with rac-LA was also studied. Complexes 3 and 4 bearing fluorinated aryls at zinc were found to afford the highest activities

Padronização de uma bateria para a avaliação de fatores de risco psicossociais trabalhistas em trabalhadores colombianos

A battery of questionnaires to assess psychosocial risk factors at work was developed in 2010 in response to Resolution 2646 created by the Colombian Ministry of Social Protection. However, this battery presents some theoretical and practical limitations. A new battery of instruments has been designed and validated that includes instruments and risk indicators of the demand-control-social support and the effort-reward imbalance models. Other factors, not included in these models, but that Resolution 2646 suggests should be assessed, have also been added, and with this additional information, the new battery allows us to also calculate a “global indicator” of demand, control, and social support; family and social risk conditions, coping and personality; and health and wellbeing. The new battery was administered to a sample of 16,095 workers from different occupations and representative Colombian regions. An analysis of the various domains indicates that internal consistency of the various scales is high. The new battery has the following properties: it is simple to use in paper format or when administered by computer, it enables comparison between occupations, it offers unified scores for each variable, and provides information to assess the risk factors suggested by Resolution 2646. In addition, it will make it possible to compare the results obtained when analyzing Colombian workers with those obtained from studies of workers from other countries.Em 2010, desenvolveu-se uma bateria de instrumentos para avaliar fatores psicossociais trabalhistas de risco para a saúde, em resposta à Resolução 2 646 do Ministério da Proteção Social da Colômbia. Contudo, esta conta com algumas limitações que, a partir da construção e da validação de uma nova bateria, neste estudo se pretendem superar. Além disso, a nova bateria oferece recursos adicionais para a avaliação desses fatores: a presente bateria incorpora os instrumentos e os indicadores centrais dos modelos demanda-controle-apoio social e desiquilíbrio esforço-recompensa e os fatores internos do trabalho não considerados nesses modelos, mas que a Resolução considera necessários, mediram-se com testes preexistentes ou desenvolvidos pelos autores. Com os dados coletados, é possível calcular indicadores globais de demanda, controle e apoio social; além de condições familiares e sociais de risco, enfrentamento, personalidade e indicadores de saúde e bem-estar. Para a validação, a bateria foi aplicada a uma amostra de 16 095 trabalhadores de diferentes cargos e municípios colombianos. As anál i ses de consistência interna e validade permitem afirmar que a bateria é simples de aplicar em papel ou digital, permitirá comparar cargos, obter pontuações unificadas por variável, oferecer um diagnóstico de um número importante das variáveis sugeridas na Resolução bem como permitirá comparar os resultados dos trabalhadores colombianos com os de outros países. Palavras-chave: fatores trabalhistas de risco psicossocial, Resolução 2 646 de 2008, modelo demanda-controle-apoio social, modelo desiquilíbrio esforço-recompensa, estresse profissional, avaliação.En 2010 se desarrolló una batería de instrumentos para evaluar factores psicosociales laborales de riesgo para la salud, en respuesta a la Resolución 2646 de 2008 del Ministerio de la Protección Social de Colombia. Sin embargo, esta cuenta con algunas limitaciones que, a partir de la construcción y validación de una nueva batería, en el presente estudio se buscan superar. La nueva batería ofrece recursos adicionales para la evaluación de estos factores: incorpora los instrumentos e indicadores centrales de los modelos demanda-control-apoyo social y desequilibrio esfuerzo-recompensa, y los factores intralaborales no contemplados en dichos modelos, pero que la Resolución considera necesarios, se midieron con pruebas preexistentes o desarrolladas por los autores. Con los datos recolectados es posible calcular indicadores globales de demanda, control y apoyo social; además de condiciones familiares y sociales de riesgo, afrontamiento, personalidad e indicadores de salud y bienestar. Para la validación, la batería se aplicó a una muestra de 16.095 trabajadores de diferentes ocupaciones y municipios colombianos. Los análisis de consistencia interna y validez permiten afirmar que la batería es sencilla de aplicar en papel o por computador, permitirá comparar ocupaciones, obtener puntuaciones unificadas por variable, ofrecer un diagnóstico de un número importante de las variables sugeridas en la Resolución y comparar los resultados de los trabajadores colombianos con los de otros países

Evidence-based entrepreneurship: Cumulative science, action principles, and bridging the gap between science and practice

10.1561/0300000044Foundations and Trends in Entrepreneurship811-6

Polychromatic solar energy conversion in pigment-protein chimeras that unite the two kingdoms of (bacterio)chlorophyll-based photosynthesis

Natural photosynthesis can be divided between the chlorophyll-containing plants, algae and cyanobacteria that make up the oxygenic phototrophs and a diversity of bacteriochlorophyll-containing bacteria that make up the anoxygenic phototrophs. Photosynthetic light harvesting and reaction centre proteins from both kingdoms have been exploited for solar energy conversion, solar fuel synthesis and sensing technologies, but the energy harvesting abilities of these devices are limited by each protein’s individual palette of pigments. In this work we demonstrate a range of genetically-encoded, self-assembling photosystems in which recombinant plant light harvesting complexes are covalently locked with reaction centres from a purple photosynthetic bacterium, producing macromolecular chimeras that display mechanisms of polychromatic solar energy harvesting and conversion. Our findings illustrate the power of a synthetic biology approach in which bottom-up construction of photosystems using naturally diverse but mechanistically complementary components can be achieved in a predictable fashion through the encoding of adaptable, plug-and-play covalent interfaces

Sustaining Electron Transfer Pathways Extends Biohybrid Photoelectrode Stability to Years

The exploitation of natural photosynthetic enzymes in semi-artificial devices constitutes an attractive and potentially sustainable route for the conversion of solar energy into electricity and solar fuels. However, the stability of photosynthetic proteins after incorporation in a biohybrid architecture typically limits the operational lifetime of biophotoelectrodes to a few hours. Here, we demonstrate ways to greatly enhance the stability of a mesoporous electrode coated with the RC-LH1 photoprotein from Rhodobacter sphaeroides. By preserving electron transfer pathways, we extended operation under continuous high-light to 33 days, and operation after storage to over two years. Coupled with large photocurrents that reached peak values of 4.6 mA cm−2, the optimized biophotoelectrode produced a cumulative output of 86 C cm−2, the largest reported performance to date. Our results demonstrate that the factor limiting stability is the architecture surrounding the photoprotein, and that biohybrid sensors and photovoltaic devices with operational lifetimes of years are feasible

Mainline and Peripheral Agriculture: Toward Generic Classification of Farms

An examination of the state of the art in the classification of farms indicates a need for more work. Classification of farms by size has been widely used and found serviceable. In a capitalistic social system, such as the United States, the most appropriate measure of the relative contributions of farms of different sizes appears to be the market value of products they sell. Accordingly, a preliminary generic typology of U.S. farms, based on published data, is proposed in which Mainline, Marginal, and Peripheral types are identified

Region Spherical Harmonic Magnetic Modeling from Near-Surface and Satellite-Altitude Anomlaies

The compiled near-surface data and satellite crustal magnetic measured data are modeled with a regionally concentrated spherical harmonic presentation technique over Australia and Antarctica. Global crustal magnetic anomaly studies have used a spherical harmonic analysis to represent the Earth's magnetic crustal field. This global approach, however is best applied where the data are uniformly distributed over the entire Earth. Satellite observations generally meet this requirement, but unequally distributed data cannot be easily adapted in global modeling. Even for the satellite observations, due to the errors spread over the globe, data smoothing is inevitable in the global spherical harmonic presentations. In addition, global high-resolution modeling requires a great number of global spherical harmonic coefficients for the regional presentation of crustal magnetic anomalies, whereas a lesser number of localized spherical coefficients will satisfy. We compared methods in both global and regional approaches and for a case where the errors were propagated outside the region of interest. For observations from the upcoming Swarm constellation, the regional modeling will allow the production a lesser number of spherical coefficients that are relevant to the region of interes

Just Bone Tired: Equine Bone Stress

The field of biophotoelectrochemistry and its application in biophotovoltaics and biosensors has gained more and more attention in recent years. Knowledge of the redox potentials of the catalytically active protein cofactors in biophotovoltaic devices is crucial for accurate modelling and in discerning the mechanisms of their operation. Here, for the first time, we used spectroelectrochemical methods to investigate thermodynamic parameters of a biophotoelectrode in situ. We determined redox potentials of two elements of the system: the primary electron donor in photosynthetic reaction centers (RCs) of the bacterium Rhodobacter sphaeroides and osmium-complex based redox mediators that are bound to a hydrogel matrix. We observe that the midpoint potential of the primary donor is shifted towards more positive potentials in comparison to literature data for RCs solubilized in buffered water solution, likely due to interaction with the polymer matrix. We also demonstrate that the osmium-complex modified redox polymer efficiently wires the RCs to the electrode, maintaining a high Internal Quantum Efficiency with approximately one electron per two photons generated (IQE=50±12%). Overall, this biophotoelectrode may be attractive for controlling the redox state of the protein when performing other types of experiments, e.g. time resolved absorption or fluorescence measurements, in order to gain insights into kinetic limitations and thereby help in the rational design of bioelectronic devices