Spectroscopic and synthetic studies relating to a dirhodium hydroformylation catalyst

The main goal of this dissertation research was to further study and characterize our bimetallic hydroformylation catalyst, rac-[Rh2(nbd)2(et,ph-P4)](BF4)2, and to fully identify the catalytically inactive mono- and dirhodium complexes formed upon fragmentation of the catalyst under hydroformylation conditions. Various in situ NMR methods such as 1D 1H and 31P, and 2D COSY, HMBC, and HMQC were employed and indicated the formation of the key catalyst, [rac-Rh2H2(μ-CO)2(CO)4(et,ph-P4)]2+, 4, and a number of other Rh-phosphine species on and off the catalytic cycle. Detailed spectroscopic data was used to propose the structures of these catalytically inactive fragmentation complexes, namely [RhH2(η4-et,ph-P4)]+, 10, and [rac,rac-Rh(η4-et,ph-P4)2RhH2]2+, 11. Mono- and bimetallic rhodium tetraphosphine compounds, RhCl2(η4-et,ph-P4)BF4, 12, Rh(Cl)(CH2Cl)(η4-et,ph-P4)BF4, 13, and [Rh2(η4-et,ph-P4)2](BF4)2, 14 were synthesized, characterized, and their NMR spectroscopic data was obtained. The 31P analyses of these compounds were correlated with the spectroscopic data obtained from the in situ NMR studies of [Rh2(nbd)2(et,ph-P4)](BF4)2 catalyst precursor and indicated that none of these three complexes are present during hydroformylation catalysis. The above compounds were studied to help us expand our knowledge about the bimetallic catalyst and the possible mechanism of the fragmentation process occurring during hydroformylation. In addition, me,ph-P4 ligand, a variation of the et,ph-P4, and dirhodium me,ph-P4 catalyst were synthesized. Separation of meso and racemic diastereomers of this ligand was also achieved. Research in this area involved the synthesis of dimethylchlorophosphine, Me2PCl, and the halogenated methylene bridged bisphosphine, Cl2PCH2PCl2

Le choix de la proximité pour un jardin collectif face aux défis sociaux et environnementaux

International audienceUrban agriculture structures, like many other organizations of the French Social and Solidarity Economy, offer innovative solutions to improve biodiversity and social diversity in some urban areas. In this paper, we want to correlate these progresses with different dynamics of convergence implemented by these structures in their developing economic networks. On the basis of data gathered during a long-term participatory observation fieldwork in a collective and associative community garden in Grenoble, we will show the correlation between the institutional and organizational proximity links that the structure develops and its social and natural impacts. Then we will highlight the opportunities and risks encountered by this kind of structure during these convergence processes.Les structures d’agriculture urbaine, comme de nombreuses autres organisations d’économie sociale et solidaire, proposent des solutions innovantes pour améliorer la biodiversité et la diversité sociale dans certains espaces urbains. Dans cette communication, nous souhaitons mettre en relation ces avancées avec les dynamiques de convergence que ces structures développent dans leurs réseaux. En prenant appui sur les informations récoltées durant un travail d’observation participative dans un jardin collectif et associatif du territoire grenoblois, nous montrerons les effets et retombées de l’activité de la structure sur un plan social et environnemental. Nous mettrons particulièrement en avant les différentes formes de proximité permettant de développer ou valoriser ces effets positifs permis par l’introduction d’espaces naturels et agricoles en ville. Nous mettrons ensuite en exergue les opportunités et les risques associés à la construction de ces partenariats

Green Public-Private Partnerships (PPPs) as an Instrument for Sustainable Development

The purpose of this paper is to analyse green Public-Private Partnerships (PPPs) as an instrument to contribute to sustainable development. The research of the green PPPs in their international context and the innovative mechanisms for their financial support and implementation is made through a review of their role in the global sustainable development agenda and the policy of the European Union as well as a survey of several case studies. The conceptual framework contains the theoretical background of green PPPs as innovative investment solutions, and the discussion of the results is presented afterwards. The author gives recommendations for overcoming the challenges of the green economy, especially the perception of the collaboration between the private and public sectors in accomplishing the Sustainable Development Goals (SDGs). Particular attention is paid to the new dimensions of cooperation as one of the key factors for achieving better socio-economic and environmental conditions.     CITE THIS PAPER: Vassileva, Antoaneta G. (2022). "Green Public-Private Partnerships (PPPs) as an Instrument for Sustainable Development" Journal of World Economy: Transformations & Transitions (JOWETT) 2(05):22. DOI: https://doi.org/10.52459/jowett25221122

Mass-elite dimensions of support for the EU in Bulgaria (1989-2007)

This research studies mass-elite dimensions of support for the EU in Bulgaria. The scope is to fill a missing gap in the existing literatures on public opinion and party positions on European integration providing an in-depth study on a specific case of Central and Eastern Europe before accession. In order to present the most comprehensive study, the research employs quantitative and qualitative research methodologies in the form of cross tabulations of public opinion surveys, contents and discourse analysis of election programmes, parliamentary debates and elite interviews. The main research question is what the level of support was for the EU at mass and elite levels in Bulgaria during the accession process, and what the relationship between them was. The results are likely to be valid well beyond the specific interest of the research in all current member states and candidate countries. The main conclusions drawn from this project are that in Bulgaria the utilitarian and proxy models of support explain well the high degree of public support for EU membership before accession and in that respect Bulgaria conforms to the analysis of past academic contributions on public opinion in Central and Eastern Europe. At elite level European integration was perceived positively and debated in broad terms until the Copenhagen criteria for accession were formulated. In the latter part of the transition EU membership was established as a valence issue in Bulgarian party politics but the parties differed in their visions of the EU according to ideology, their coalition potential and positions in the party system. Moreover, the level of support for the EU in Bulgaria was influenced by internal (domestic) and external (EU related) factors associated with European integration. Chapters 2 and 3 of the thesis provide a contextual framework for the empirical chapters by describing the environment in which support for the EU in Bulgaria was formed and developed. Chapters 4, 5 and 6 analyse the public and elite debates on European integration. The concluding Chapter 7 builds upon the thesis’ findings by suggesting new avenues for research

Implementation of the EM Algorithm for Maximum Likelihood Estimation of a Random Effects Model for One Longitudinal Ordinal Outcome

2010 Mathematics Subject Classification: 62J99.Longitudinal data arise when we have repeated measures on subjects over time. The correlated probit model is frequently used for ordered longitudinal data since it allows to seamlessly incorporate different correlation structures. The estimation of the probit model parameters based on direct maximization of the limited information maximum likelihood is a numerically intensive procedure especially when we have repeated measures on subjects. We propose an extension of the EM algorithm for obtaining maximum likelihood estimates for one ordinal longitudinal outcome. The algorithm is implemented in the free software environment for statistical computing and graphics R. We use simulations to examine the performance of the developed algorithm and apply the model to data from the Health and Retirement Study (HRS). We apply a bootstrap approach for standard error approximation. Advantages of the presented algorithm include the potential of dealing with high-dimensional random effects and of extending the algorithm to combinations of ordinal and continuous longitudinal outcomes

The EU\u27s Impact on Managing Levels of Corruption in the Post-Communist World

This study examines the role of the European Union (EU) in the process of managing corruption in the post-communist world. Throughout the post-communist transitions, which began in 1989, the EU has been consistent in putting a strong emphasis on the problem of corruption. As part of the transitions, there were many attempts at abating corruption domestically, most of which were expressed in the creation of institutions and legislation. Yet such attempts had varying effectiveness, and outcomes were not always expected nor predicted by scholars and policy-makers. Internationally, the EU expected that conditionality, which offered EU membership in exchange for compliance with EU- promoted anti-corruption norms, to be an effective mechanism to address high levels of corruption in the post-communist world. Yet, evidence demonstrates that membership incentive did not always correlate with strong performance. Countries such as Georgia, without the prospect of membership, often outperformed countries that had a membership incentive in addition to strong sanctions and conditions. This study sets out to explain these puzzles and to identify the conditions under which the EU had the most leverage over domestic anti-corruption reforms. Based on a comparison of EU\u27s efforts of three countries - Bulgaria, Georgia, and Montenegro - and employing a combination of qualitative and quantitative data gathering techniques, the study makes two arguments. First, anti-corruption institutions were more successful in managing corruption where civil society was included in the process of institution-building, and later in the process of monitoring and reforming these institutions. Second, the study argues that the EU had more leverage over domestic anti-corruption reforms where it engaged non-state actors (non-governmental agencies) in a political dialogue and where a process of social learning started before membership conditionality. When this condition was present, the EU created a like-minded domestic partner capable of championing EU-promoted norms and supplying the EU with feedback and knowledge necessary to adapt conditions, incentives, and sanction to the local context and better address domestic corruption. The study contributes to our broader knowledge of post-communist transitions, Europeanization, and the scope and limits of international organizations\u27 impact on domestic politics. In examining the development of civil society, it explains the role that civil society played in post-communist transitions. In examining the interaction of domestic civil society and international organizations, it contributes to the general understanding of the mechanisms and extent to which external actors can impact complex domestic issues

Em Algorithm for MLE of a Probit Model for Multiple Ordinal Outcomes

The correlated probit model is frequently used for multiple ordered data since it allows to incorporate seamlessly different correlation structures. The estimation of the probit model parameters based on direct maximization of the limited information maximum likelihood is a numerically intensive procedure. We propose an extension of the EM algorithm for obtaining maximum likelihood estimates for a correlated probit model for multiple ordinal outcomes. The algorithm is implemented in the free software environment for statistical computing and graphics R. We present two simulation studies to examine the performance of the developed algorithm. We apply the model to data on 121 women with cervical or endometrial cancer. Patients developed normal tissue reactions as a result of post-operative external beam pelvic radiotherapy. In this work we focused on modeling the effects of a genetic factor on early skin and early urogenital tissue reactions and on assessing the strength of association between the two types of reactions. We established that there was an association between skin reactions and polymorphism XRCC3 codon 241 (C>T) (rs861539) and that skin and urogenital reactions were positively correlated. ACM Computing Classification System (1998): G.3