Synthetic scope and DFT analysis of the chiral binap-gold(I) complex-catalyzed 1,3-dipolar cycloaddition of azlactones with alkenes

he 1,3-dipolar cycloaddition between glycine-derived azlactones with maleimides is efficiently catalyzed by the dimeric chiral complex [(S-a)-Binap.AuTFA](2). The alanine-derived oxazolone only reacts with tert-butyl acrylate giving anomalous regiochemistry, which is explained and supported by Natural Resonance Theory and Nucleus Independent Chemical Shifts calculations. The origin of the high enantiodiscrimination observed with maleimides and tert-butyl acrylate is analyzed using DFT computed at M06/Lanl2dz//ONIOM(b3lyp/Lanl2dz:UFF) level. Several applications of these cycloadducts in the synthesis of new proline derivatives with a 2,5-trans-arrangement and in the preparation of complex fused polycyclic molecules are described.

The scope for biomanipulation in improving water quality

Biomanipulation is a form of biological engineering in which organisms are selectively removed or encouraged to alleviate the symptoms of eutrophication. Most examples involve fish and grazer zooplankton though mussels have also been used. The technique involves continuous management in many deeper lakes and is not a substitute for nutrient control. In some lakes, alterations to the lake environment have given longer-term positive effects. And in some shallow lakes, biomanipulation may be essential, alongside nutrient control, in re- establishing former aquatic-plant-dominated ecosystems which have been lost through severe eutrophication. The emergence of biomanipulation techniques emphasises that lake systems are not simply chemical reactors which respond simply to engineered chemical changes, but very complex and still very imperfectly understood ecosystems which require a yet profounder understanding before they can be restored with certainty.

Assessment of the impact of aquatic resources research by ICLARM: scope and methodologies

The importance of quantifying the economic returns to investments in aquatic resources research together with the social, environmental and institutional impacts of such investments is widely recognized among ICLARM's donors, trustees and beneficiaries. As with other Consultative Group on International Agricultural Research (CGIAR) centers, ICLARM is being asked to provide specific accounts of the outputs of its research and their impact on farms and on fisheries, including their socioeconomic impact. Such impact information has become a necessary, though not sufficient, basis for setting priorities and allocating resources for research for the CGIAR centers. This paper discusses the types and methods of impact assessment relevant to ICLARM's work. A three-pronged assessment approach is envisaged to capture the full range of impacts: 1) ex ante assessment for research priority setting; 2) assessment prior to dissemination or adoption along with monitoring and evaluation; and 3) ex post impact assessment. It also discusses the objectives and scope for operational impact assessment of ICLARM's research.

Recent advances and scope for sea farming in India

Although brackishwater prawn and fish culture was traditionally practiced for a long time in the country, efforts at sea farming are still in their infancy. During the past 15 years the Central Marine Fisheries Research Institute has developed various technologies for sea farming of mussels, pearl oysters, production of cultured pearls, edible oysters, clams, prawns, lobsters, seaweeds and more recently sea cucumbers and top shells. The paper outlines recent developments in these areas as well as in others like sea ranching of marine prawns and pearl oyster, and scope for enlarging sea farming activities including development of artificial reefs in India.

Scope for commercial culture of tilapia

The suitability of tilapia species for fish culture and the potential for the development of commercial culture operations in India are discussed. Sex regulation, monosex tilapia polyculture, chromosome manipulation and sex reversal, nutrition and feed formulation are examined in detail.

Present status and future scope of fisheries in the Andaman group of islands

The coastal area of approximately 2000 km and the water-bodies in between the Andaman and Nicobar islands are rich in fishery potential which range from 0.012-0.47 million tonnes. The fishery is dominated by catches of sardines, perches, carangids, mackerels, Leiognathus elasmobranchs, seerfish, mullets and tunas. About 2050 fishermen, with 1150 country craft, 113 mechanised boats and 1367 different kinds of nets and lines are engaged in active fishing in the island. Numerous bays, lagoons and creeks are available among the group of islands for mariculture activities. The mangroves of these islands provide feeding and nursery grounds for juveniles of penaeid prawns, crabs and finfishes.

On the operation of small shrimp trawls in shallow waters-scope-ratio and size-depth relation

Studies on small trawls seem to be comparatively less. These trawls are generally operated in shallower waters, where due to the limitations in the length of warp that could be released, size restrictions have to be considered for their efficient functioning. An attempt has been made to assess the effective scope-ratio of length of warp required for the operation of trawls at shallower depth and to a judge the size of trawl suitable for use at lower depths.

A method for identifying scope and assumptions in developing and selecting methods and tools

This technical report describes a practical method consisting of a checklist and a supporting techniques for those planning or just starting to develop or select design tools and methods. The method helps to summarize and illustrate the envisaged tool or method by identifying its scope and the underlying assumptions. The resulting tool or method description clarifies the problem that is addressed, the approach and the possible implications, and can thus be used by a variety of people involved in assessing a tool or method in an early stage. For the developers themselves the method reveals how realistic the envisaged method or tool is, and whether the scope has to be narrowed.

Determining the Scope of English Quantifiers

How can one represent the meaning of English sentences in a formal logical notation such that the translation of English into this logical form is simple and general? This report answers this question for a particular kind of meaning, namely quantifier scope, and for a particular part of the translation, namely the syntactic influence on the translation. Rules are presented which predict, for example, that the sentence: Everyone in this room speaks at least two languages. has the quantifier scope AE in standard predicate calculus, while the sentence: At lease two languages are spoken by everyone in this room. has the quantifier scope EA. Three different logical forms are presented, and their translation rules are examined. One of the logical forms is predicate calculus. The translation rules for it were developed by Robert May (May 19 77). The other two logical forms are Skolem form and a simple computer programming language. The translation rules for these two logical forms are new. All three sets of translation rules are shown to be general, in the sense that the same rules express the constraints that syntax imposes on certain other linguistic phenomena. For example, the rules that constrain the translation into Skolem form are shown to constrain definite np anaphora as well. A large body of carefully collected data is presented, and used to assess the empirical accuracy of each of the theories. None of the three theories is vastly superior to the others. However, the report concludes by suggesting that a combination of the two newer theories would have the greatest generality and the highest empirical accuracy.

Synthesis and reactivity of α-diazo-β-keto sulfoxides: scope and synthetic potential

The research described in this thesis focuses on the design and synthesis of stable α-diazosulfoxides and investigation of their reactivity under a variety of conditions (transition-metal catalysis, thermal, photochemical and microwave) with a particular emphasis on the synthesis of novel heterocyclic compounds with potential biological activity. The exclusive reaction pathway for these α-diazosulfoxides was found to be hetero-Wolff rearrangement to give α-oxosulfine intermediates. In the first chapter, a literature review of sulfines is presented, including a discussion of naturally occurring sulfines, and an overview of the synthesis and reactivity of sulfines. The potential of sulfines in organic synthesis and recent developments in particular are highlighted. The second chapter discusses the synthesis and reactivity of α-diazosulfoxides, building on earlier results in this research group. The synthesis of lactone-based α-diazosulfoxides and, for the first time, ketone-based benzofused and monocyclic α-diazosulfoxides is described. The reactivity of these α-diazosulfoxides is then explored under a variety of conditions, such as transition-metal catalysis, photochemical and microwave, generating labile α-oxosulfine intermediates, which are trapped using amines and dienes, in addition to the spontaneous reaction pathways which occur with α-oxosulfines in the absence of a trap. A new reaction pathway was explored with the lactone based α-oxosulfines, involving reaction with amines to generate novel 3-aminofuran-2(5H)-ones via carbophilic attack, in very good yields. The reactivity of ketone-based α-diazosulfoxides was explored for the first time, and once again, pseudo-Wolff rearrangement to the α-oxosulfines was the exclusive reaction pathway observed. The intermediacy of the α-oxosulfines was confirmed by trapping as cycloadducts, with the stereochemical features dependant on the reaction conditions. In the absence of a diene trap, a number of reaction fates from the α-oxosulfines were observed, including complete sulfinyl extrusion to give indanones, sulfur extrusion to give indanediones, and, to a lesser extent, dimerisation. The indanediones were characterised by trapping as quinoxalines, to enable full characterisation. One of the overriding outcomes of this thesis was the provision of new insights into the behaviour of α-oxosulfines with different transition metal catalysts, and under thermal, microwave and photolysis conditions. A series of 3-aminofuran-2(5H)-ones and benzofused dihydro-2H-thiopyran S-oxides were submitted for anticancer screening at the U.S. National Cancer Institute. A number of these derivatives were identified as hit compounds, with excellent cell growth inhibition. One 3-aminofuran-2(5H)-one derivative has been chosen for further screening. The third chapter details the full experimental procedures, including spectroscopic and analytical data for the compounds prepared during this research. The data for the crystal structures are contained in the attached CD.

Missing data in randomized clinical trials for weight loss: scope of the problem, state of the field, and performance of statistical methods.

BACKGROUND: Dropouts and missing data are nearly-ubiquitous in obesity randomized controlled trails, threatening validity and generalizability of conclusions. Herein, we meta-analytically evaluate the extent of missing data, the frequency with which various analytic methods are employed to accommodate dropouts, and the performance of multiple statistical methods. METHODOLOGY/PRINCIPAL FINDINGS: We searched PubMed and Cochrane databases (2000-2006) for articles published in English and manually searched bibliographic references. Articles of pharmaceutical randomized controlled trials with weight loss or weight gain prevention as major endpoints were included. Two authors independently reviewed each publication for inclusion. 121 articles met the inclusion criteria. Two authors independently extracted treatment, sample size, drop-out rates, study duration, and statistical method used to handle missing data from all articles and resolved disagreements by consensus. In the meta-analysis, drop-out rates were substantial with the survival (non-dropout) rates being approximated by an exponential decay curve (e(-lambdat)) where lambda was estimated to be .0088 (95% bootstrap confidence interval: .0076 to .0100) and t represents time in weeks. The estimated drop-out rate at 1 year was 37%. Most studies used last observation carried forward as the primary analytic method to handle missing data. We also obtained 12 raw obesity randomized controlled trial datasets for empirical analyses. Analyses of raw randomized controlled trial data suggested that both mixed models and multiple imputation performed well, but that multiple imputation may be more robust when missing data are extensive. CONCLUSION/SIGNIFICANCE: Our analysis offers an equation for predictions of dropout rates useful for future study planning. Our raw data analyses suggests that multiple imputation is better than other methods for handling missing data in obesity randomized controlled trials, followed closely by mixed models. We suggest these methods supplant last observation carried forward as the primary method of analysis.

A New Approach to Media Cluster Research: Bringing the Human Factor back into Scope

This paper is part of a collaborative project being undertaken by the three leading universities of Brussels, VUB, ULB and USL-B supported by Innnoviris. The project called Media Clusters Brussels - MCB - started in October 2014 with the goal to analyze the development of a Media Park around the two public broadcasters at the site of Reyers in Brussels being host of a media cluster in the capital city. Not only policymakers but also many authors recognized in the last decade that the media industry is characterized from a geographical point of view by a heavy concentration to a limited number of large cities, where media clusters have emerged (Karlsson & Picard, 2011). The common assumption about media clusters is that locating inside a regional agglomeration of related actors brings advantages for these firms. Especially, the interrelations and interactions between the actors on a social level matter for the shape and efficiency of the agglomerations (Picard, 2008). However, even though the importance of the actors and their interrelations has been a common assumption, many authors solely focus on the macro-economical aspects of the clusters. Within this paper, we propose to realize a socio-economical analysis of media clusters to make informed decisions in the development and so, bring the social (human) factor back into scope. Therefore, this article focuses on the development of a novel valuable framework, the so-called 7P framework with a multilevel and interdisciplinary approach, which includes three aspects, which have been identified as emerging success-factors of media clusters: partnerships, (media) professionals and positive spillovers.