Palladium-Catalyzed Decarboxylative and Decarbonylative Transformations in the Synthesis of Fine and Commodity Chemicals

Decarboxylation and decarbonylation are important reactions in synthetic organic chemistry, transforming readily available carboxylic acids and their derivatives into various products through loss of carbon dioxide or carbon monoxide. In the past few decades, palladium-catalyzed decarboxylative and decarbonylative reactions experienced tremendous growth due to the excellent catalytic activity of palladium. Development of new reactions in this category for fine and commodity chemical synthesis continues to draw attention from the chemistry community.

The Stoltz laboratory has established a palladium-catalyzed enantioselective decarboxylative allylic alkylation of β-keto esters for the synthesis of α-quaternary ketones since 2005. Recently, we extended this chemistry to lactams due to the ubiquity and importance of nitrogen-containing heterocycles. A wide variety of α-quaternary and tetrasubstituted α-tertiary lactams were obtained in excellent yields and exceptional enantioselectivities using our palladium-catalyzed decarboxylative allylic alkylation chemistry. Enantioenriched α-quaternary carbonyl compounds are versatile building blocks that can be further elaborated to intercept synthetic intermediates en route to many classical natural products. Thus our chemistry enables catalytic asymmetric formal synthesis of these complex molecules.

In addition to fine chemicals, we became interested in commodity chemical synthesis using renewable feedstocks. In collaboration with the Grubbs group, we developed a palladium-catalyzed decarbonylative dehydration reaction that converts abundant and inexpensive fatty acids into value-added linear alpha olefins. The chemistry proceeds under relatively mild conditions, requires very low catalyst loading, tolerates a variety of functional groups, and is easily performed on a large scale. An additional advantage of this chemistry is that it provides access to expensive odd-numbered alpha olefins.

Finally, combining features of both projects, we applied a small-scale decarbonylative dehydration reaction to the synthesis of α-vinyl carbonyl compounds. Direct α-vinylation is challenging, and asymmetric vinylations are rare. Taking advantage of our decarbonylative dehydration chemistry, we were able to transform enantioenriched δ-oxocarboxylic acids into quaternary α-vinyl carbonyl compounds in good yields with complete retention of stereochemistry. Our explorations culminated in the catalytic enantioselective total synthesis of (–)-aspewentin B, a terpenoid natural product featuring a quaternary α-vinyl ketone. Both decarboxylative and decarbonylative chemistries found application in the late stage of the total synthesis.

A importância da gestão de riscos e controles internos como respostas a riscos empresariais

O principal objetivo deste estudo foi verificar a importância da gestão de riscos e controles internos como resposta a riscos empresariais. A relevância do assunto é respaldada na crescente necessidade apresentada pelas empresas para mitigar seus riscos empresarias com objetivo de enfrentar o mundo globalizado e a acirrada concorrência, além de buscar diferencial na qualidade de gestão empresarial e proporcionar maior valor agregado a seus acionistas. Adicionalmente, foram realizadas pesquisas de mercado, sobre assuntos afins ao tema principal, por meio de aplicação de questionários junto a Unidades de Relacionamento com investidores de grandes empresas brasileiras e a empregados de empresas de auditorias independentes com grande experiência de mercado, permitindo ao leitor visão panorâmica da situação atual dos referidos temas. A metodologia utilizada foi a pesquisa documental e bibliográfica, com utilização de documentos de trabalho e relatórios de consultorias privadas e uso de material acessível ao público em geral como livros, artigos, dissertações, seminários e legislações publicados. Como conclusão, é apresentada seleção contemplando 15 importantes lições.

Validação dos processos envolvidos na obtenção do polissacarídeo capsular de Haemophilus influenzae tipo b conjugado com toxóide tetânico utilizado para produção de vacina

Haemophilus influenzae tipo b (Hib) é a principal causa de pneumonia bacteriana e meningite em crianças com menos de 5 anos de idade. A doença pode ser prevenida através da vacinação com uma vacina conjugada polissacarídeo-proteína, uma vez que a vacina de polissacarídeo não é eficaz. Desde 1999, o Ministério da Saúde incluiu a vacina conjugada Hib na rotina do calendário de imunização para crianças rotineiramente. Sendo este um processo de grande importância para as pessoas e demanda de produção significativa para o governo brasileiro, é necessário que os processos estejam de acordo com as normas nacionais e internacionais de regulamentação e devem ser validados. Uma operação validada assegura a produção de lotes uniformes que atendem as especificações exigidas, consequentemente, garantindo ao fabricante a capacidade de proporcionar um produto de qualidade. O trabalho propõe o desenvolvimento de uma metodologia que evidencie e garanta o processo de produção de um conjugado de polissacarídeo-proteína pelo método de conjugação química e que será produzido de forma consistente e de acordo com as suas especificações pré-definidas. Os atributos de qualidade garantem o não desabastecimento da vacina Haemophilus influenzae tipo b por desvios de processo, o que contribui com aumento do valor agregado ao produto em questão. Portanto, a metodologia de validação foi aplicada ao estudo de validação. O estudo baseou-se em três etapas. A primeira foi baseada em análise de parâmetros do processo de conjugação química para mapear e estabelecer intervalos críticos de controle quanto a estes parâmetros, a segunda fase foi realizada com a produção de três lotes consecutivos, em escala industrial, com monitorização regular dos parâmetros críticos mapeados anteriormente. A fase final consistiu em amostras recolhidas, em tempo pré-determinado, durante o processo de produção e de controle do produto final em tamanho 50% a mais que na rotina de produção. Estas amostras foram analisadas utilizando os métodos de análise que foram anteriormente validados, a fim de garantir a reprodutibilidade dos resultados. A robustez do processo foi assegurada uma vez que todos os parâmetros do processo avaliados apresentaram resultados dentro do padrão de conformidade com os resultados de controle determinados durante o processo, e no produto final para a população de amostragem dentro de especificações definidas pelas metodologias analíticas validadas garantindo os resultados. O trabalho proposto assegura status de processo validado para o conjugado polissacarídeo-proteína com excepcionais rendimentos obtidos, combinado com características químicas bem definidas

Integrating remote sensing products and GIS tools to support marine spatial management in West Hawai'i

Marine protected areas (MPAs) represent a form of spatial management, and geospatial information on living marine resources and associated habitat is extremely important to support best management practices in a spatially discrete MPA. Benthic habitat maps provide georeferenced information on the geomorphic structure and biological cover types in the marine environment. This information supports an enhanced understanding of ecosystem function and species habitat utilization patterns. Benthic habitat maps are most useful for marine management and spatial planning purposes when they are created at a scale that is relevant to management actions. We sought to improve the resolution of existing benthic habitat maps created during a regional mapping effort in Hawai`i. Our results complemented these existing regional maps and provided more detailed, finer-scale habitat maps for a network of MPAs in West Hawai`i. The map products created during this study allow local planners and managers to extract information at a spatial scale relevant to the discrete management units, and appropriate for local marine management efforts on the Kona Coast. The resultant benthic habitat maps were integrated in a geographic information system (GIS) that also included aerial imagery, underwater video, MPA regulations, summarized ecological data and other relevant and spatially explicit information. The integration of the benthic habitat maps with additional “value added” geospatial information into a dynamic GIS provide a decision support tool with pertinent marine resource information available in one central location and support the application of a spatial approach to the management of marine resources. Further, this work can serve as a case study to demonstrate the integration of remote sensing products and GIS tools at a fine spatial scale relevant to local-level marine spatial planning and management efforts.

Recent advances in fish processing and product development

There are good possibilities for expanding the consumer sector in both the traditional and nontraditional marine products. Frozen shrimp continues to be the item of highest demand in foreign markets. Individual quick frozen (IQF) prawns which are indeed value added products and have already penetrated international markets elicit export incentive from development agencies like the Marine Products Export Development Authority. With the projected potential of 1.8 lakh tonnes of cephalopods against the current yield of 13,000 tonnes, there are good prospects of increasing exports of frozen squid and cuttlefish. The technology of packing fish in retortable pouches as an alternative to canning has now been perfected. Salted fish mince has good market potential in India and abroad.

Preparation of an extruded fish snack using twin screw extruder and the storage characteristics of the product

A value-added extruded fish product was prepared with corn flour (80%) and fish (sciaenid) powder (20%), using a twin-screw extruder. The effect of different parameters like moisture, temperature, fish powder concentration, speed of the extruder and die-diameter on expansion ratio and crisp texture were studied. The storage characteristics of the final product were studied using three different types of packaging under nitrogen flushing. The study revealed that aluminum foil is the best packaging material to keep the product acceptable for more than three months.

Status of the shrimp sector in Bangladesh in the context of HACCP and trade issues: a review

Shrimp culture in Bangladesh has emerged as an important aquaculture industry over the last three decades although its culture in greater parts of the farming area is done in traditional ways. In the meantime, the government of Bangladesh has taken necessary measures along with the private sectors to increase production, upgrade processing industries and to promote export performance. Long supply chain in raw material collection, inadequate infrastructure facilities, poor level of cool chain and lack of adequate HACCP-based training on hygiene and sanitation of different groups of people involved in the field level are the main problems of quality loss of raw materials. Shortage of raw materials results in poor capacity utilization of the processing plants. The growth of bagda (P. monodon) hatchery has expanded rapidly over the last few years, remaining mostly concentrated in Cox's Bazar region is enough to meet the target production. However, there is a shortage of pelleted shrimp feed in Bangladesh. A large number of export processors are now producing increasing amounts of value-added products such as individually quick-frozen, peeled and divined, butterfly cut shrimp, as well as cooked products. The export earnings from value added products is about half of the total export value. About 95% of total fish products are exported to European countries, USA and Japan and the remaining to the Southeast Asia and the Middle East. Most of the EU approved shrimp processing industries have been upgraded with laboratory facilities and provided HACCP training to their workers. As of now, HACCP is applied on the processing plants, but to ensure the quality of raw materials and to reduce risks, shrimp farms are also required to adopt HACCP plan. There is increased pressure time to time from importing countries for fish processors to establish effective quality assurance system in processing plants. Fish Inspection and Quality Control (FIQC) of the Department of Fisheries while having moderately equipped laboratories with chemical, bio-chemical and microbiological testing facilities and qualified technical personnel, the creation of facilities for testing of antibiotics is underway. FIQC mainly supervises quality aspects of the processing plants and has little or no control over raw material supply chains from farm to processing plants. Bangladesh export consignments sometimes face rejection due to reported poor quality of the products. Three types of barriers are reported for export of shrimp to EU countries. These are:(1) government participation in trade and restrictive practices (state aid, countervailing duties, state trading enterprises, government monopoly practices), customs and administrative entry procedures (anti-dumping duties, customs valuation, classification, formalities, rules of origin); (2) technical barriers to trade or TBT (technical regulations, standards, testing, certification arrangement); (3) specific limitations (quantitative restrictions, import licensing, embargoes, exchange control, discriminatory sourcing, export restraints, measures to regulate domestic prices, requirements concerning marking, labeling and packaging).

An assessment of handling and processing methods used for the shrimp fishery by-catch in Kalpitiya, Sri Lanka

The by-catch from the shrimp trawl fishery in Kalpitiya is mainly used for the production of dried fish, which provides an additional source of income for fishermen in the area. It has been observed that current handling practices along the value addition chain are responsible for the poor quality and low price of the end product. This study was aimed at identifying the shortcomings in such handling practices by fishermen and dried fish producers and assessing the quality of shrimp fishery by-catch along the processing chain in order to recommend more efficient utilization methods that will improve the quality of the end product. Fresh fish, dried fish and harbour water samples were tested for total coli forms, faecal coliforms, E. coli and Salmonella in order to assess their microbial quality: In addition, standard plate counts (SPC) of fish samples were also carried out. A survey was carried out from July-October 2006 at Kalpitiya, using a pre-tested questionnaire to collect information from individuals who have been engaged in dried fish processing. Average values obtained for freshly landed and dried fish respectively, were, SPC 9.88x10 super(5) CFU/g and 30.43x10 super(5) CFU/g, total coliforms 23.05 and 24.23 MPN/g and fecal coliforms 8.28 and 9.00 MPN/g. These values exceed the recommendations in the SL standards. A quarter of the landed fresh fish and 38% of dried fish from the producers were positive for E. coli and thus failed to show required end product quality. SPC of harbour water was 14.35x10 super(6) CFU/ml and all samples were found to be contaminated with E. coli. None of the fishermen and dried fish producers were satisfied with the quality of the end product. The reasons for poor quality as indicated by them were: limited availability of ice (75%), lack of infrastructure facilities (65%), uncertainty of markets (52%), lack of emphasis on quality (47%) and poor access to available technologies (41%). Respondents to the questionnaire also identified: unavailability of potable water, insulated boxes, good landing jetty, racks for drying fish, poor cold storage facilities and limitations in dried fish storage facilities, as further factors leading to the loss of quality in their products. Results demonstrate that improvements to the infrastructure facilities and conducting of proper awareness programmes on handling practices could lead for improvements in the quality of value added products prepared from the shrimp fishery by-catch at Kalpitiya.

Ecological limits of high-density milkfish farming

In the Philippines at present, milkfish farming in ponds includes a wide range of intensities, systems and practices. To make aquaculture possible, ecosystems are used as sources of energy and resources and as sinks for wastes. The growth of aquaculture is limited by the life-support functions of the ecosystem, and sustainability depends on matching the farming techniques with the processes and functions of the ecosystems, for example, by recycling some degraded resources. The fish farm has many interactions with the external environment. Serious environmental problems may be avoided if high-intensity farms are properly planned in the first place, at the farm level and at the level of the coastal zone where it can be integrated with other uses by other sectors. It is believed that the key to immediate success in the mass production of milkfish for local consumption and for export of value-added forms may be in semi-intensive farming at target yields of 3 tons per ha per year, double the current national average. Intensive milkfish farming will be limited by environmental, resource and market constraints. Integrated intensive farming systems are the appropriate long-term response to the triple needs of the next century: more food, more income, and more jobs for more people, all from less land, less resources, and less non-renewable energy.

基于CAN总线的分布式数据采集与控制系统

随着电子技术和计算机技术的不断发展，工业生产过程的控制系统正在向着智能化、数字化和网络化的方向发展。传统的集散控制方式和计算机分层控制方式已经开始让位于智能终端与网络结合的总线网络控制方式。当今，在工厂中过程控制环境下的分布式自动化系统变得越来越复杂，尤其系统内部的各设备之间需要快速交换大量的信息，以便实现对被控系统更为精确的控制和提供一些辅助的评价函数。这就意味着要不断增加带宽和提高通信速率以满足网络通信的需要。在现有的多种可利用网络设备中，CAN总线以其清晰的定义、极高的可靠性及其独特的设计，被认为是最能有效地解决这一问题的途径之一。而且市场上基于通信技术的产品中，就实时性考虑，由于CAN总线采用的非表意性的通信方式，因此其结构更为简单，实时性更好。基于此背景，我们以CAN总线作为通信媒介，将分布于各控制现场的传感器、执行器和控制器有序地连接起来，构成了一个基于CAN总线的分布式局域网络控制系统。本文首先介绍了基于CAN总线的分布式数据采集与控制系统的总体结构。然后从硬件方面描述了基于CAN总线的通信协议转换单元、数据采集单元和输出控制单元的功能、硬件配置及各单元功能的具体实现过程，给出了各单元的性能指标。软件方面，以C语言作为平台，开发了基于CAN总线的上位计算机管理与监控软件，实现了对整个网络设备的系统管理和系统控制功能。对于该总线系统，作者运用了PID控制和模糊控制算法实现了对水箱液位的控制，达到了理想的效果。基于CAN总线的控制系统很好地解决了集散控制系统难以解决的难题，模糊控制的应用能很好地把总线控制系统应用到具有非线性、大时滞和难于获得精确模型的控制系统中。

Mercados diferenciados de hortaliças.

1999

Compilation and analysis of integrated regional input-output tables for NUTS 2 regions in Ireland

In 1966, Roy Geary, Director of the ESRI, noted “the absence of any kind of import and export statistics for regions is a grave lacuna” and further noted that if regional analyses were to be developed then regional Input-Output Tables must be put on the “regular statistical assembly line”. Forty-five years later, the lacuna lamented by Geary still exists and remains the most significant challenge to the construction of regional Input-Output Tables in Ireland. The continued paucity of sufficient regional data to compile effective regional Supply and Use and Input-Output Tables has retarded the capacity to construct sound regional economic models and provide a robust evidence base with which to formulate and assess regional policy. This study makes a first step towards addressing this gap by presenting the first set of fully integrated, symmetric, Supply and Use and domestic Input-Output Tables compiled for the NUTS 2 regions in Ireland: The Border, Midland and Western region and the Southern & Eastern region. These tables are general purpose in nature and are consistent fully with the official national Supply & Use and Input-Output Tables, and the regional accounts. The tables are constructed using a survey-based or bottom-up approach rather than employing modelling techniques, yielding more robust and credible tables. These tables are used to present a descriptive statistical analysis of the two administrative NUTS 2 regions in Ireland, drawing particular attention to the underlying structural differences of regional trade balances and composition of Gross Value Added in those regions. By deriving regional employment multipliers, Domestic Demand Employment matrices are constructed to quantify and illustrate the supply chain impact on employment. In the final part of the study, the predictive capability of the Input-Output framework is tested over two time periods. For both periods, the static Leontief production function assumptions are relaxed to allow for labour productivity. Comparative results from this experiment are presented.

Cost-effectiveness analysis of the diagnosis of meniscus tears.

BACKGROUND: Diagnostic imaging represents the fastest growing segment of costs in the US health system. This study investigated the cost-effectiveness of alternative diagnostic approaches to meniscus tears of the knee, a highly prevalent disease that traditionally relies on MRI as part of the diagnostic strategy. PURPOSE: To identify the most efficient strategy for the diagnosis of meniscus tears. STUDY DESIGN: Economic and decision analysis; Level of evidence, 1. METHODS: A simple-decision model run as a cost-utility analysis was constructed to assess the value added by MRI in various combinations with patient history and physical examination (H&P). The model examined traumatic and degenerative tears in 2 distinct settings: primary care and orthopaedic sports medicine clinic. Strategies were compared using the incremental cost-effectiveness ratio (ICER). RESULTS: In both practice settings, H&P alone was widely preferred for degenerative meniscus tears. Performing MRI to confirm a positive H&P was preferred for traumatic tears in both practice settings, with a willingness to pay of less than US$50,000 per quality-adjusted life-year. Performing an MRI for all patients was not preferred in any reasonable clinical scenario. The prevalence of a meniscus tear in a clinician's patient population was influential. For traumatic tears, MRI to confirm a positive H&P was preferred when prevalence was less than 46.7%, with H&P preferred above that. For degenerative tears, H&P was preferred until the prevalence reaches 74.2%, and then MRI to confirm a negative was the preferred strategy. In both settings, MRI to confirm positive physical examination led to more than a 10-fold lower rate of unnecessary surgeries than did any other strategy, while MRI to confirm negative physical examination led to a 2.08 and 2.26 higher rate than H&P alone in primary care and orthopaedic clinics, respectively. CONCLUSION: For all practitioners, H&P is the preferred strategy for the suspected degenerative meniscus tear. An MRI to confirm a positive H&P is preferred for traumatic tears for all practitioners. Consideration should be given to implementing alternative diagnostic strategies as well as enhancing provider education in physical examination skills to improve the reliability of H&P as a diagnostic test. CLINICAL RELEVANCE: Alternative diagnostic strategies that do not include the use of MRI may result in decreased health care costs without harm to the patient and could possibly reduce unnecessary procedures.

NAFTA and the apparel commodity chain: Corporate strategies, interfirm networks, and industrial upgrading

The apparel industry is one of the oldest and largest export industries in the world, with global trade and production networks that connect firms and workers in countries at all levels of economic development. This chapter examines the impact of the North American Free Trade Agreement (NAFTA) as one of the most recent and significant developments to affect patterns of international trade and production in the apparel and textile industries. Tr ade policies are changing the institutional environment in which firms in this industry operate, and companies are responding to these changes with new strategies designed to increase their profitability and strengthen their control over the apparel commodity chain. Our hypothesis is that lead firms are establishing qualitatively different kinds of regional production networks in North America from those that existed prior to NAFTA, and that these networks have important consequences for industrial upgrading in the Mexican textile and apparel industries. Post-NAFTA crossborder production arrangements include full-package networks that link lead firms in the United States with apparel and textile manufacturers, contractors, and suppliers in Mexico. Full-package production is increasing the local value added provided by the apparel commodity chain in Mexico and creating new opportunities for Mexican firms and workers. The chapter is divided into four main sections. The first section uses trade and production data to analyze shifts in global apparel flows, highlighting the emergence and consolidation of a regional trade bloc in North America. The second section discusses the process of industrial upgrading in the apparel industry and introduces a distinction between assembly and full-package production networks. The third section includes case studies based on published industry sources and strategic interviews with several lead companies whose strategies are largely responsible for the shifting trade patterns and NAFTA-inspired cross-border production networks discussed in the previous section. The fourth section considers the implications of these changes for employment in the North American apparel industry. © 2009 by Temple University Press. All rights reserved.