Convergence of products from Povarov and von Miller reactions: approaches to helquinoline

Yttrium triflate or triflic acid catalysed Povarov reaction of methyl anthranilate with ethyl vinyl ether, both as aldehyde surrogate and as alkene, gave the desired 2-methyl-4-ethoxytetrahydroquinoline diastereoisomers as the major products along with four component coupling von Miller adducts. A proton NMR-study, using yttrium triflate as catalyst, revealed that the cis-diastereoisomers were the initial major products in both the Povarov and von Miller reactions but that these isomerised to the trans-diastereoisomers under the reaction conditions. Two distinct pathways for forming von Miller adducts were uncovered with the initial Povarov products being converted to von Miller adducts under the reaction conditions. Replacement of the 4-ethoxy with a 4-methoxy group under acidic conditions gave predominantly the trans-diastereoisomer, which was subsequently converted to a cis/trans mixture of the tetrahydroquinoline antibiotic helquinoline. It was also possible to convert the von Miller products to Povarov products under acidic conditions

Cinchona alkaloids and BINOL derivatives as privileged catalysts or ligands in asymmetric synthesis

During the last fifteen years organocatalysis emerged as a powerful tool for the enantioselective functionalization of the most different organic molecules. Both C-C and C-heteroatom bonds can be formed in an enantioselective fashion using many types of catalyst and the field is always growing. Many kind of chiral catalysts have emerged as privileged, but among them Proline, cinchona alkaloids, BINOL, and their derivatives showed to be particularly useful chiral scaffolds. This thesis, after a short presentation of many organocatalysts and activation modes, focuses mainly on cinchona alkaloid derived primary amines and BINOL derived chiral Brønsted acids, describing their properties and applications. Then, in the experimental part, these compounds are used for the catalysis of new transformations. The enantioselective Friedel-Crafts alkylation of cyclic enones with naphthols using cinchona alkaloid derived primary amines as catalysts is presented and discussed. The results of this work were very good and this resulted also in a publication. The same catalysts are then used to accomplish the enantioselective addition of indoles to cyclic enones. Many catalysts in combination with many acids as co-catalysts were tried and the reaction was fully studied. Selective N-alkylation was obtained in many cases, in combination with quite good to good enantioselectivities. Also other kind of catalysis were tried for this reaction, with interesting results. Another aza-Michael reaction between OH-free hydroxylamines and nitrostyrene using cinchona alkaloid derived thioureas is briefly discussed. Then our attention focused on Brønsted acid catalyzed transformations. With this regard, the Prins cyclization, a reaction never accomplished in an enantioselective fashion until now, is presented and developed. The results obtained are promising. In the last part of this thesis the work carried out abroad is presented. In Prof. Rueping laboratories, an enantioselective Nazarov cyclization using cooperative catalysis and the enantioselective desymmetrization of meso-hydrobenzoin catalyzed by Brønsted acid were studied.

Cooperative RNA Polymerase Molecules Behavior on a Stochastic Sequence-Dependent Model for Transcription Elongation

The transcription process is crucial to life and the enzyme RNA polymerase (RNAP) is the major component of the transcription machinery. The development of single-molecule techniques, such as magnetic and optical tweezers, atomic-force microscopy and single-molecule fluorescence, increased our understanding of the transcription process and complements traditional biochemical studies. Based on these studies, theoretical models have been proposed to explain and predict the kinetics of the RNAP during the polymerization, highlighting the results achieved by models based on the thermodynamic stability of the transcription elongation complex. However, experiments showed that if more than one RNAP initiates from the same promoter, the transcription behavior slightly changes and new phenomenona are observed. We proposed and implemented a theoretical model that considers collisions between RNAPs and predicts their cooperative behavior during multi-round transcription generalizing the Bai et al. stochastic sequence-dependent model. In our approach, collisions between elongating enzymes modify their transcription rate values. We performed the simulations in Mathematica® and compared the results of the single and the multiple-molecule transcription with experimental results and other theoretical models. Our multi-round approach can recover several expected behaviors, showing that the transcription process for the studied sequences can be accelerated up to 48% when collisions are allowed: the dwell times on pause sites are reduced as well as the distance that the RNAPs backtracked from backtracking sites. © 2013 Costa et al.

Cooperative effects of H+ and H- hydrido carbonyl ruthenium derivatives; role of homogeneous and heterogeneous protonic and lewis acids in catalytic hydrocarbonylation reactions

The role played by H+ hydrido iodocarbonyl and H- hydrido carbonyl ruthenium catalysts in the different catalytic steps of hydroformylation and hydroesterification of olefins, and in the homologation of alcohols has been investigated. The H- hydrido carbonyl species are mainly involved in the activation of olefins and in the hydrogenation of the acyl intermediates to aldehydes and alcohols, whereas the H+ hydrido iodocarbonyl derivatives are involved in the activation of alcohols and other oxygenated substrates, and in their carbonylation to esters. The cooperation between the two species, possible under particular reaction conditions, results in an improvement of the selectivity towards homologation (carbonylation plus hydrogenation) products. Heterogeneous Lewis acid promoters, easily recyclable from the reaction mixture, have also been successfully used in the hydrocarbonylation of alcohols, resulting in an increase of the carbonylation and homologation products. A reaction pathway in agreement with the experimental results is discussed. © 1989.

Cooperative binding of effectors by an allosteric ribozyme

An allosteric ribozyme that requires two different effectors to induce catalysis was created using modular rational design. This ribozyme construct comprises five conjoined RNA modules that operate in concert as an obligate FMN- and theophylline-dependent molecular switch. When both effectors are present, this ‘binary’ RNA switch self-cleaves with a rate enhancement of ∼300-fold over the rate observed in the absence of effectors. Kinetic and structural studies implicate a switching mechanism wherein FMN binding induces formation of the active ribozyme conformation. However, the binding site for FMN is rendered inactive unless theophylline first binds to its corresponding site and reorganizes the RNA structure. This example of cooperative binding between allosteric effectors reveals a level of structural and functional complexity for RNA that is similar to that observed with allosteric proteins.

Submission to the House of Representatives Standing Committee on Environment and Heritage : Inquiry into a Sustainability Charter by the Cooperative Research Centre for Construction Innovation

The Cooperative Research Centre for Construction Innovation1 (hereafter called Construction Innovation) supports the notion of the establishment of a Sustainability Charter for Australia and is interested in working collaboratively to achieve this outcome. A number of challenges need to be addressed to develop this Charter. This submission outlines these challenges and possible responses to them by a Sustainability Commission.

Improvements in sustainable energy and water practice in the food processing industry : an in depth analysis of the manufacture of Ghee at the Butter Producers' Cooperative Federation Limited, Brisbane

This thesis is a documented energy audit and long term study of energy and water reduction in a ghee factory. Global production of ghee exceeds 4 million tonnes annually. The factory in this study refines dairy products by non-traditional centrifugal separation and produces 99.9% pure, canned, crystallised Anhydrous Milk Fat (Ghee). Ghee is traditionally made by batch processing methods. The traditional method is less efficient, than centrifugal separation. An in depth systematic investigation was conducted of each item of major equipment including; ammonia refrigeration, a steam boiler, canning equipment, pumps, heat exchangers and compressed air were all fine-tuned. Continuous monitoring of electrical usage showed that not every initiative worked, others had pay back periods of less than a year. In 1994-95 energy consumption was 6,582GJ and in 2003-04 it was 5,552GJ down 16% for a similar output. A significant reduction in water usage was achieved by reducing the airflow in the refrigeration evaporative condensers to match the refrigeration load. Water usage has fallen 68% from18ML in 1994-95 to 5.78ML in 2003-04. The methods reported in this thesis could be applied to other industries, which have similar equipment, and other ghee manufacturers.

Collaboration using BIM : results of cooperative research centre for construction innovation projects

This paper discusses the issues with sharing information between different disciplines in collaborative projects. The focus is on the information itself rather than the wider issues of collaboration. A range of projects carried out by the Cooperative Research Centre for Construction Innovation (CRC CI) in Australia is used to illustrate the issues.

Articulating cooperative systems and driver behaviour theories

There has been increased research interest in Co-operative Vehicle Infrastructure Systems (CVIS) from the eld of Intelligent Transport Systems (ITS). However most of the research have focused on the engineering aspects and overlooked their relevance to the drivers' behaviour. This paper argues that the priority for cooperative systems is the need to improve drivers decision making and reduce drivers' crash risk exposure to improve road safety. Therefore any engineering solutions need to be considered in conjuction with traffic psychology theories on driver behaviour. This paper explores the advantages and limitations of existing systems and emphasizes various theoretical issues that arise in articulating cooperative systems' capabilities and drivers' behaviour.

Cooperative learning in Thailand : professional development to enhance primary education

The overall purpose of this study was to develop a model to inform the design of professional development programs and the implementation of cooperative learning within Thai primary school mathematics classrooms. Action research design, with interviews, surveys and observations, was used for this study. Survey questionnaires and classroom observations investigated the factors that influence the implementation of cooperative learning strategies and academic achievement in Thai primary school mathematics classrooms. The teachers’ interviews and classroom observation also examined the factors that need to be addressed in teacher professional development programs in order to facilitate cooperative learning in Thai mathematics classrooms. The outcome of this study was a model consisting of two sets of criteria to inform the successful implementation of cooperative learning in Thai primary schools. The first set of criteria was for proposers and developers of professional development programs. This set consists of macro- and micro-level criteria. The macro-level criteria focus on the overall structure of professional development programs and how and when the professional development programs should be implemented. The micro-level criteria focused on the specific topics that need to be included in professional development programs. The second set of criteria was for Thai principals and teachers to facilitate the introduction of cooperative learning in their classrooms. The research outcome also indicated that the attainment of these cooperative learning strategies and skills had a positive impact on the students’ learning of mathematics.

Multi-vehicles interaction graph model for cooperative collision warning system

Cooperative collision warning system for road vehicles, enabled by recent advances in positioning systems and wireless communication technologies, can potentially reduce traffic accident significantly. To improve the system, we propose a graph model to represent interactions between multiple road vehicles in a specific region and at a specific time. Given a list of vehicles in vicinity, we can generate the interaction graph using several rules that consider vehicle's properties such as position, speed, heading, etc. Safety applications can use the model to improve emergency warning accuracy and optimize wireless channel usage. The model allows us to develop some congestion control strategies for an efficient multi-hop broadcast protocol.

Crash Risk Assessment with Cooperative Systems

Crash risk is the statistical probability of a crash. Its assessment can be performed through ex post statistical analysis or in real-time with on-vehicle systems. These systems can be cooperative. Cooperative Vehicle-Infrastructure Systems (CVIS) are a developing research avenue in the automotive industry worldwide. This paper provides a survey of existing CVIS systems and methods to assess crash risk with them. It describes the advantages of cooperative systems versus non-cooperative systems. A sample of cooperative crash risk assessment systems is analysed to extract vulnerabilities according to three criteria: market penetration, over-reliance on GPS and broadcasting issues. It shows that cooperative risk assessment systems are still in their infancy and requires further development to provide their full benefits to road users.

Two Thai teachers' perceptions of cooperative learning

Over the past decade, the need for educational reform in Thailand has become increasingly apparent. The strong tradition of teacher-directed instruction has been the major teaching and learning style in Thai education. Recent policy changes have focused on expanding education opportunities, the implementation of compulsory education and also on more student-centered pedagogies (Carter, 2006). A suggested way of bringing about the changes necessary to improve the standard of education in primary schools and retention rates is to incorporate cooperative learning into Thai primary school classrooms. The action research in this study proceeded in four stages. There were pre-implementation interviews of teachers, teacher preparation, implementation of program, and post-implementation evaluation. This study focused on the two Thai teachers' perceptions about the benefits of cooperative learning and the roles of the teachers in cooperative learning classroom. The study found that the two teachers had constructed different levels of perceptions about the benefits of cooperative learning and the roles of the teacher. These findings indicated that Thai teachers who are relatively inexperienced, lacking in confidence and with little or no experience with group work strategies such as peer tutoring need alternative, less intense professional development programs conducted over a period of a semester than the professional development program implemented in this study. In addition to being conducted over a longer period of time, the findings also indicate that alternative teacher professional programs need to provide additional workshops to improve their understanding of cooperative learning and the teachers' roles.

Thai students' engagement with cooperative learning in mathematics classrooms

Over the past decade, Thai schools have been encouraged by the Thai Ministry of Education to introduce more student-centred pedagogies such as cooperative learning into their classrooms (Carter, 2006). However, prior research has indicated that the implementation of cooperative learning into Thai schools has been confounded by cultural traditions endemic within Thai schools (Deveney, 2005). The purpose of the study was to investigate how 32 Grade 3 and 32 Grade 4 students enrolled in a Thai school engaged with cooperative learning in mathematics classrooms after they had been taught cooperative learning strategies and skills. These strategies and skills were derived from a conceptual framework that was the outcome of an analysis and synthesis of social learning, behaviourist and socio-cognitive theories found in the research literature. The intervention began with a two week program during which the students were introduced to and engaged in practicing a set of cooperative learning strategies and skills (3 times a week). Then during the next four weeks (3 times a week), these cooperative learning strategies and skills were applied in the contexts of two units of mathematics lessons. A survey of student attitudes with respect to their engagement in cooperative learning was conducted at the conclusion of the six-week intervention. The results from the analysis of the survey data were triangulated with the results derived from the analysis of data from classroom observations and teacher interviews. The analysis of data identified four complementary processes that need to be considered by Thai teachers attempting to implement cooperative learning into their mathematics classrooms. The paper concludes with a set of criteria derived from the results of the study to guide Thai teachers intending to implement cooperative learning strategies and skills in their classrooms.