Random Copolymers with 2,2′-Dioxy-1,1′-biphenyl-phosphazene and Chiral 2,2′-dioxy-1,1′-binaphthylphosphazene Units Functionalized in the 6,6′-Positions with PPh<Subscript>2</Subscript> Groups as Precursors for Ru(arene) Catalysts

The chiral phosphazene copolymers {[NP(O₂C₁₂H₈)]_0.9[NP(O₂C₂₀H₁₂)]_0.1} (1) and {[NP(O₂C₁₂H₈)]_0.9[NP(O₂C₂₀H₁₀Br₂)]_0.1} _n (2) [(O₂C₁₂H₈) = 2,2′-dioxy-1,1′-biphenyl; (O₂C₂₀H₁₂) = R-2,2′-dioxy-1,1′-binaphthyl and (O₂C₂₀H₁₀Br₂) = R-6,6′-dibromo-2,2′-dioxy-1,1′-binaphthyl] were prepared by sequential substitution from [NPCl₂] _n and the corresponding dihydroxy-biphenyl or binaphthyl reagents in the presence of Cs₂CO₃ and K₂CO₃. The reaction of (2) with ^tBuLi in THF, followed by addition of PPh₂Cl and a treatment with SiHCl₃/PPh₃ to eliminate any oxidized OC₆H₄P(O)Ph₂ groups, gave the phosphine containing copolymer {[NP(O₂C₁₂H₈)]_0.9[NP(O₂C₂₀H₁₀[PPh₂]₂)]_0.1} _n (3), that was used as a chiral ligand to support [Ru(p-cymene)Cl] complexes. The resulting catalyst was active for hydrogen transfer from isopropyl alcohol to acetophenone but the placement of the Ru centers in the 6,6′-positions of the binaphthoxyphosphazene units induced no enantioselectivity. Dedicated to Professor Christopher Allen.     

Classifying unlabeled short texts using a fuzzy declarative approach

Web 2.0 provides user-friendly tools that allow persons to create and publish content online. User generated content often takes the form of short texts (e.g., blog posts, news feeds, snippets, etc). This has motivated an increasing interest on the analysis of short texts and, specifically, on their categorisation. Text categorisation is the task of classifying documents into a certain number of predefined categories. Traditional text classification techniques are mainly based on word frequency statistical analysis and have been proved inadequate for the classification of short texts where word occurrence is too small. On the other hand, the classic approach to text categorization is based on a learning process that requires a large number of labeled training texts to achieve an accurate performance. However labeled documents might not be available, when unlabeled documents can be easily collected. This paper presents an approach to text categorisation which does not need a pre-classified set of training documents. The proposed method only requires the category names as user input. Each one of these categories is defined by means of an ontology of terms modelled by a set of what we call proximity equations. Hence, our method is not category occurrence frequency based, but highly depends on the definition of that category and how the text fits that definition. Therefore, the proposed approach is an appropriate method for short text classification where the frequency of occurrence of a category is very small or even zero. Another feature of our method is that the classification process is based on the ability of an extension of the standard Prolog language, named Bousi~Prolog , for flexible matching and knowledge representation. This declarative approach provides a text classifier which is quick and easy to build, and a classification process which is easy for the user to understand. The results of experiments showed that the proposed method achieved a reasonably useful performance.     

An autonomous educational mobile robot mediator

So far, most of the applications of robotic technology to education have mainly focused on supporting the teaching of subjects that are closely related to the Robotics field, such as robot programming, robot construction, or mechatronics. Moreover, most of the applications have used the robot as an end or a passive tool of the learning activity, where the robot has been constructed or programmed. In this paper, we present a novel application of robotic technologies to education, where we use the real world situatedness of a robot to teach non-robotic related subjects, such as math and physics. Furthermore, we also provide the robot with a suitable degree of autonomy to actively guide and mediate in the development of the educational activity. We present our approach as an educational framework based on a collaborative and constructivist learning environment, where the robot is able to act as an interaction mediator capable of managing the interactions occurring among the working students. We illustrate the use of this framework by a 4-step methodology that is used to implement two educational activities. These activities were tested at local schools with encouraging results. Accordingly, the main contributions of this work are: i) A novel use of a mobile robot to illustrate and teach relevant concepts and properties of the real world; ii) A novel use of robots as mediators that autonomously guide an educational activity using a collaborative and constructivist learning approach; iii) The implementation and testing of these ideas in a real scenario, working with students at local schools.

IEEE 802.21: Media independence beyond handover

The IEEE 802.21 standard facilitates media independent handovers by providing higher layer mobility management functions with common service primitives for all technologies. Right after the base specification was published, several voices rose up in the working group advocating to broaden the scope of IEEE 802.21 beyond handovers. This paper aims at updating the reader with the main challenges and functionalities required to create a Media Independence Service Layer, through the analysis of scenarios which are being discussed within the working group: 1) Wireless Coexistence, and 2) Heterogeneous Wireless Multihop Backhaul Networks.     

Using Similarity Analyses to Scale Out Research Findings Across Andean Watershed Basins

Abstract

Strategic research in agriculture and natural resources carried out by international research centers is deemed a public good and should, sooner or later, be put into the hands of development, governmental and non-governmental organizations. However, this research is usually done at specific pilot sites; there is a greater need to know how representative those sites are in relation to the diversity of contexts in other locations. Such is the case with the Challenge Program on Water and Food (CPWF), a global initiative in water research promoted by the Consultative Group on International Agricultural Research (CGIAR), which is developing and implementing strategic research in nine basins located in the tropics of Africa, Asia and South America. Given that resources are not available to collect data from the whole of the region, pilot sites are needed. It is hoped that research outputs obtained in the selected pilot sites can be the basis for scaling out solutions to similar situations in neighbouring or adjacent areas in same or different basins.

In order to contribute to the scaling-out process, different classification methodologies were applied to determine how specific watershed basins are representative of larger areas. The Andean eco-region served as a case study but the methods can easily be applied in other regions. The spatial diversity of biophysical and social conditions across the Andes requires careful site selection. Two methods, a combination of Weight of Evidence (WofE) and Logistic Regression (LR) methods and Fast Cluster analysis, were used to determine the similarity of selected sites with those excluded. A 1-km study resolution covering most of the Andes eco-region included annual rainfall, elevation, length of growing period, land cover, roads and population density as the key variables. Results showed complementarities between the two methods in presenting a probability surface of similarity across the Andes and a clustering of similar sites inside and outside the pilot basins. The output information forms a strong basis for devising plans to scale out research findings from the pilot basins to the whole region.     

Cell formation in group technology using constraint programming and Boolean satisfiability

Cell formation consists in organizing a plant as a set of cells, each of them containing machines that process similar types or families of parts. The idea is to minimize the part flow among cells in order to reduce costs and increase productivity. The literature presents different approaches devoted to solve this problem, which are mainly based on mathematical programming and on evolutionary computing. Mathematical programming can guarantee a global optimal solution, however at a higher computational cost than an evolutionary algorithm, which can assure a good enough optimum in a fixed amount of time. In this paper, we model and solve this problem by using state-of-the-art constraint programming (CP) techniques and Boolean satisfiability (SAT) technology. We present different experimental results that demonstrate the efficiency of the proposed optimization models. Indeed, CP and SAT implementations are able to reach the global optima in all tested instances and in competitive runtime.     

Poly(L‐lactic acid) with added α‐tocopherol and resveratrol: optical,physical, thermal and mechanical properties

Poly(L ‐lactic acid) (PLLA) films containing various concentrations of two natural antioxidants, α‐tocopherol and resveratrol, were fabricated by a melt compounding and compression molding process. The influence of the antioxidants on the optical properties such as color and UV‐visible light transmission was analyzed. The thermal, mechanical, rheological and physical properties of PLLA films with added antioxidants were assessed. PLLA films with added α‐tocopherol and resveratrol showed a yellowish brown color and the lightness was influenced by the presence of the antioxidants. The glass transition and melting temperatures were significantly reduced with the addition of antioxidants while enhanced thermal stability was observed, which could be a benefit and important for processing and production. PLLA films with added antioxidants were slightly more hydrophobic than neat PLLA. The combination effect of plasticizing and enhancement of the elastic modulus with differing concentrations of two antioxidants played a critical role in the mechanical and thermomechanical properties of PLLA films. The melt viscosity of the PLLA films with added antioxidants was substantially higher than that of neat PLLA. The higher melt viscosity and G′(ω) could be an indication of formation of entanglement between PLLA and the two antioxidants. Copyright © 2012 Society of Chemical Industry     

Preparation and characterization of β‐cyclodextrin‐linked chitosan microparticles

Hydrophobically modified chitosan containing β‐cyclodextrin (CD) units was synthesized by using tosylated β‐CD. The final product was characterized by Fourier transform infrared (FTIR) spectroscopy, elemental analysis and TGA, and rheometry. The polymer bearing β‐CD moieties was used to obtain crosslinked microparticles by spray‐drying which could then be used in a controlled release system for drugs. FTIR confirmed the formation of an amide linkage between cyclodextrin and chitosan. As fluorescence spectroscopy demonstrated, hydrophobic microenvironments were formed by chitosan bearing cyclodextrin in solution at lower concentrations than for chitosan. Rheometry and FTIR showed the crosslinking of the new polymer using genipin, a molecule of natural origin. Microspheres (MS) obtained by spray‐drying showed narrow size distribution when β‐CD was grafted onto chitosan and ξ‐potential of MS was slightly lower although it remained positive. In conclusion, β‐CD linked chitosan polymer can be considered as a very promising controlled drug delivery system for drugs. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Synthesis and Biological Activity of New Brassinosteroid Analogs of Type 24-Nor-5β-Cholane and 23-Benzoate Function in the Side Chain

Brassinosteroids are polyhydroxysteroids that are involved in different plants’ biological functions, such as growth, development and resistance to biotic and external stresses. Because of its low abundance in plants, much effort has been dedicated to the synthesis and characterization of brassinosteroids analogs. Herein, we report the synthesis of brassinosteroid 24-nor-5β-cholane type analogs with 23-benzoate function and 22,23-benzoate groups. The synthesis was accomplished with high reaction yields in a four-step synthesis route and using hyodeoxycholic acid as starting material. All synthesized analogs were tested using the rice lamina inclination test to assess their growth-promoting activity and compare it with those obtained for brassinolide, which was used as a positive control. The results indicate that the diasteroisomeric mixture of monobenzoylated derivatives exhibit the highest activity at the lowest tested concentrations (1 × 10⁻⁸ and 1 × 10⁻⁷ M), being even more active than brassinolide. Therefore, a simple synthetic procedure with high reaction yields that use a very accessible starting material provides brassinosteroid synthetic analogs with promising effects on plant growth. This exploratory study suggests that brassinosteroid analogs with similar chemical structures could be a good alternative to natural brassinosteroids.