Catalytic Processes Mediated by Metal−Organic Frameworks : Reactivity and Mechanistic Studies

The present thesis describes the development of heterogeneous catalytic methodologies using metal−organic frameworks (MOFs) as porous matrices for supporting transition metal catalysts. A wide spectrum of chemical reactions is covered. Following the introductory section (Chapter 1), the results are divided between one descriptive part (Chapter 2) and four experimental parts (Chapters 3–6). Chapter 2 provides a detailed account of MOFs and their role in heterogeneous catalysis. Specific synthesis methods and characterization techniques that may be unfamiliar to organic chemists are illustrated based on examples from this work. Pd-catalyzed heterogeneous C−C coupling and C−H functionalization reactions are studied in Chapter 3, with focus on their practical utility. A vast functional group tolerance is reported, allowing access to substrates of relevance for the pharmaceutical industry. Issues concerning the recyclability of MOF-supported catalysts, leaching and operation under continuous flow are discussed in detail. The following chapter explores puzzling questions regarding the nature of the catalytically active species and the pathways of deactivation for Pd@MOF catalysts. These questions are addressed through detailed mechanistic investigations which include in situ XRD and XAS data acquisition. For this purpose a custom reaction cell is also described in Chapter 4. The scope of Pd@MOF-catalyzed reactions is expanded in Chapter 5. A strategy for boosting the thermal and chemical robustness of MOF crystals is presented. Pd@MOF catalysts are coated with a protecting SiO2 layer, which improves their mechanical properties without impeding diffusion. The resulting nanocomposite is better suited to withstand the harsh conditions of aerobic oxidation reactions. In this chapter, the influence of the nanoparticles’ geometry over the catalyst’s selectivity is also investigated. While Chapters 3–5 dealt with Pd-catalyzed processes, Chapter 6 introduces hybrid materials based on first-row transition metals. Their reactivity is explored towards light-driven water splitting. The heterogenization process leads to stabilized active sites, facilitating the spectroscopic probing of intermediates in the catalytic cycle.

Shape-based compliance control for snake robots

I serpenti robot sono una classe di meccanismi iper-ridondanti che appartiene alla robotica modulare. Grazie alla loro forma snella ed allungata e all'alto grado di ridondanza possono muoversi in ambienti complessi con elevata agilità. L'abilità di spostarsi, manipolare e adattarsi efficientemente ad una grande varietà di terreni li rende ideali per diverse applicazioni, come ad esempio attività di ricerca e soccorso, ispezione o ricognizione. I robot serpenti si muovono nello spazio modificando la propria forma, senza necessità di ulteriori dispositivi quali ruote od arti. Tali deformazioni, che consistono in movimenti ondulatori ciclici che generano uno spostamento dell'intero meccanismo, vengono definiti andature. La maggior parte di esse sono ispirate al mondo naturale, come lo strisciamento, il movimento laterale o il movimento a concertina, mentre altre sono create per applicazioni specifiche, come il rotolamento o l'arrampicamento. Un serpente robot con molti gradi di libertà deve essere capace di coordinare i propri giunti e reagire ad ostacoli in tempo reale per riuscire a muoversi efficacemente in ambienti complessi o non strutturati. Inoltre, aumentare la semplicità e ridurre il numero di controllori necessari alla locomozione alleggerise una struttura di controllo che potrebbe richiedere complessità per ulteriori attività specifiche. L'obiettivo di questa tesi è ottenere un comportamento autonomo cedevole che si adatti alla conformazione dell'ambiente in cui il robot si sta spostando, accrescendo le capacità di locomozione del serpente robot. Sfruttando la cedevolezza intrinseca del serpente robot utilizzato in questo lavoro, il SEA Snake, e utilizzando un controllo che combina cedevolezza attiva ad una struttura di coordinazione che ammette una decentralizzazione variabile del robot, si dimostra come tre andature possano essere modificate per ottenere una locomozione efficiente in ambienti complessi non noti a priori o non modellabili.

The “social” aspect of social-ecological systems: a critique of analytical frameworks and findings from a multisite study of coastal sustainability

We evaluate whether society can adequately be conceptualized as a component of social-ecological systems, given social theory and the current outputs of systems-based research. A mounting critique from the social sciences posits that resilience theory has undertheorized social entities with the concept of social-ecological systems. We trace the way that use of the term has evolved, relating to social science theory. Scientometic and network analysis provide a wide range of empirical data about the origin, growth, and use of this term in academic literature. A content analysis of papers in Ecology and Society demonstrates a marked emphasis in research on institutions, economic incentives, land use, population, social networks, and social learning. These findings are supported by a review of systems science in 18 coastal assessments. This reveals that a systems-based conceptualization tends to limit the kinds of social science research favoring quantitative couplings of social and ecological components and downplaying interpretive traditions of social research. However, the concept of social-ecological systems remains relevant because of the central insights concerning the dynamic coupling between humans and the environment, and its salient critique about the need for multidisciplinary approaches to solve real world problems, drawing on heuristic devices. The findings of this study should lead to more circumspection about whether a systems approach warrants such claims to comprehensiveness. Further methodological advances are required for interdisciplinarity. Yet there is evidence that systems approaches remain highly productive and useful for considering certain social components such as land use and hybrid ecological networks. We clarify advantages and restrictions of utilizing such a concept, and propose a reformulation that supports engagement with wider traditions of research in the social sciences.

Remolding a company through a compliance program : the case of Siemens

Abstract : Since at least the 1980's, a growing number of companies have set up an ethics or a compliance program within their organization. However, in the field of study of business management, there is a paucity of research studies concerning these management systems. This observation warranted the present investigation of one company's compliance program. Compliance programs are set up so that individuals working within an organization observe the laws and regulations which pertain to their work. This study used a constructivist grounded theory methodology to examine the process by which a specific compliance program, that of Siemens Canada Limited, was implemented throughout its organization. In conformity with this methodology, instead of proceeding with the investigation in accordance to a particular theoretical framework, the study established a number of theoretical constructs used strictly as reference points. The study's research question was stated as: what are the characteristics of the process by which Siemens' compliance program integrated itself into the existing organizational structure and gained employee acceptance? Data consisted of documents produced by the company and of interviews done with twenty-four managers working for Siemens Canada Limited. The researcher used QSR-Nvivo computer assisted software to code transcripts and to help with analyzing interviews and documents. Triangulation was done by using a number of analysis techniques and by constantly comparing findings with extant theory. A descriptive model of the implementation process grounded in the experience of participants and in the contents of the documents emerged from the data. The process was called "Remolding"; remolding being the core category having emerged. This main process consisted of two sub-processes identified as "embedding" and "appraising." The investigation was able to provide a detailed account of the appraising process. It identified that employees appraised the compliance program according to three facets: the impact of the program on the employee's daily activities, the relationship employees have with the local compliance organization, and the relationship employees have with the corporate ethics identity. The study suggests that a company who is entertaining the idea of implementing a compliance program should consider all three facets. In particular, it suggests that any company interested in designing and implementing a compliance program should pay particular attention to its corporate ethics identity. This is because employee's acceptance of the program is influenced by their comparison of the company's ethics identity to their local ethics identity. Implications of the study suggest that personnel responsible for the development and organizational support of a compliance program should understand the appraisal process by which employees build their relationship with the program. The originality of this study is that it points emphatically that companies must pay special attention in developing a corporate ethics identify which is coherent, well documented and well explained.

Ensuring Mobile Device Security and Compliance at the Workplace

End users urgently request using mobile devices at their workplace. They know these devices from their private life and appreciate functionality and usability, and want to benefit from these advantages at work as well. Limitations and restrictions would not be accepted by them. On the contrary, companies are obliged to employ substantial organizational and technical measures to ensure data security and compliance when allowing to use mobile devices at the workplace. So far, only individual arrangements have been presented addressing single issues in ensuring data security and compliance. However, companies need to follow a comprehensive set of measures addressing all relevant aspects of data security and compliance in order to play it safe. Thus, in this paper at first technical architectures for using mobile devices in enterprise IT are reviewed. Thereafter a set of compliance rules is presented and, as major contribution, technical measures are explained that enable a company to integrate mobile devices into enterprise IT while still complying with these rules comprehensively. Depending on the company context, one or more of the technical architectures have to be chosen impacting the specific technical measures for compliance as elaborated in this paper. Altogether this paper, for the first time, correlates technical architectures for using mobile devices at the workplace with technical measures to assure data security and compliance according to a comprehensive set of rules.

State of Iowa Public Drinking Water Program 2015 Annual Compliance Report, June 2016

This report contains information about Iowa's public drinking water program for the calendar year 2015. Included in the report are descriptions of Iowa's systems, monitoring and reporting requirements of the systems, and violations incurred during the year. This report meets the federal Safe Drinking Water Act's requirement of an annual report on violations of national primary drinking water regulations by public water supply systems in Iowa.

The International <IR> Framework’s impact on the social and relationship disclosures in the healthcare industry

Abstract Background and Problem: The altering business world and the growing requests from stakeholders have resulted in the establishment of new reports. These are among others Sustainability reports and Integrated Reporting. On the contrary, traditional financial reports do not consider the significance of intangible assets in modern entities. The social and relationship capital has further shown to be important for firms, especially healthcare companies and pharmaceuticals, but is not as developed as other capitals within the <IR> framework and therefore not always included in annual reports. However too few disclosures within this area could lead to high liabilities. The IIRC launched the <IR> framework year 2013 as a solution, as it gives a more comprehensive view of the reporting entity. Within this framework there are six capitals: manufactured, human, financial, natural, intellectual and social and relationship.   Purpose: The purpose of this thesis is to find out how the International <IR> Framework has influenced the reporting of the social and relationship disclosures within the healthcare industry, to compare the reporting of the six medical firms chosen and to examine how the social concerns have been developed over time. Delimitations: This study is conducted over a period of three years, from year 2012 to year 2014. It only examines healthcare companies which use the International <IR> framework and it has solely focus on the social and relationship capital. All other capitals within the <IR> framework are excluded from the study. Method: This study has a qualitative research strategy and is based on information collected from published documents in form of annual reports. The annual reports from year 2010, 2011 and 2012 are used to find social and relationship disclosures and a disclosure scoreboard is used to find similarities, differences and patterns. Empirical Results and Conclusion: It has been found that the aggregated social and relationship disclosures have been reduced over time. The year followed by the release of the <IR> framework was seen to have the least disclosures and therefore conclusion was drawn that the <IR> framework had a negative influence on the social and relationship disclosures. There were also differences among the companies studied both in extent and content. The former could be linked to factors such as size and nationality and the latter could be linked to reputation preservation and legitimacy interests.

Comply-or-explain in Sweden : A study on the quality of non-compliance explanations

Purpose: The purpose of this study is to examine the effectiveness of the comply-or-explain principle in Sweden to determine if the flexible approach is functioning as in-tended. Research design: This paper scrutinizes the quality of the explanations with respect to the Swedish Corporate Governance Code. A quantitative research with a cross-sectional design has been performed and the data collection covers 241 companies listed on Nasdaq OMX Stockholm for the fiscal year of 2014. The secondary data has been gathered from corporate governance reports of the researched companies and analysed by using a tax-onomy of explanations. Findings: The report demonstrates that the comply-or-explain principle in Sweden is effective. A clear majority of the explanations, 71,8%, were deemed as informative, mean-ing that a large proportion of the Swedish firms are utilizing the flexible approach in an effective manner. However, one out of four explanations were classified as insufficient and we have thus provided recommendations in order for the code to become even more effective. Contribution: Our findings provide insights on how the comply-or-explain principle works in a country that is supposed to be a leading example of how the comply-or-explain approach should be implemented. This study should be of significance for policy makers considering that we have outlined how the principle works and provided recommenda-tions on how the Swedish Corporate Governance Code can be improved. Value: Our findings demonstrate that companies listed on Nasdaq OMX Stockholm pro-vide high quality explanations that can serve as an inspiration for companies listed in other countries. Furthermore, the results indicate that managers are likely to act within ethically desired norm. Considering the social implications, as Swedish firms are informative in terms of explanations, it minimizes the risk of firms acting dishonestly.

Product quality and compliance in the pharmaceutical industry

This thesis aims to highlight the importance of a Product Quality & Compliance department in a Pharmaceutical Industry, on the good performance of company's activities and the achievement of their goals and mission. Despite the wide activities performed by this Department, the purpose of this work will be completed by describing only some of their reponsibilities. The tasks described are specifically the ones I have been performing throughout my professional experience at Bluepharma - Pharmaceutical Industry, SA, initiated in June 2012 in the Quality Assurance Department until today in the currently named Product Quality & Compliance department. This thesis is structured into 4 parts. The first chapter is an introduction to this thesis, and includes its context and objectives, followed by a brief overview of the state-of-the art in the pharmaceutical industry, including the market environment, the regulatory environment and quality requirements. A small presentation of the company and the department where were and still are developed my professional activity is also made in this chapter. In the following chapter are described the main tasks performed, the complementary activities and key skills acquired throughout this professional experience. A discussion and conclusion is presented at the end, including an analysis of the reported activities, main difficulties encountered its role and importance in the company performance as well as the skills acquired during this work experience.

Influence of pharmacotherapy complexity on compliance with the therapeutic objectives for HIV+ patients on antiretroviral treatment concomitant with therapy for dyslipidemia: INCOFAR Project

Objectives: To analyze the relationship between pharmacotherapeutical complexity and compliance of therapeutic objectives in HIV+ patients on antiretroviral treatment and concomitant dyslipidemia therapy. Materials and methods: A retrospective observational study including HIV patients on stable antiretroviral treatment during the past 6 months, and dyslipidemia treatment between January and December, 2013. The complexity index was calculated with the tool developed by McDonald et al. Other variables analyzed were: age, gender, risk factor of HIV, smoking, alcoholism and drugs, psychiatric disorders, adherence to antiretroviral treatment and lipid lowering drugs, and clinical parameters (HIV viral load, CD4 count, plasma levels of total cholesterol, LDL, HDL, and triglycerides). In order to determine the predictive factors associated with the compliance of therapeutic objectives, univariate analysis was conducted through logistical regression, followed by a multivariate analysis. Results: The study included 89 patients; 56.8% of them met the therapeutic objectives for dyslipidemia. The complexity index was significantly higher (p = 0.02) in those patients who did not reach the objective values (median 51.8 vs. 38.9). Adherence to lipid lowering treatment was significantly associated with compliance of the therapeutic objectives established for dyslipidemia treatment. A 67.0% of patients met the objectives for their antiretroviral treatment; however, the complexity index was not significantly higher (p = 0.06) in those patients who did not meet said objectives. Conclusions: Pharmacotherapeutical complexity represents a key factor in terms of achieving health objectives in HIV+ patients on treatment for dyslipidemia.

Monitoring Compliance with Open Access policies

In the last few years, academic communities have seen an increase in the number of Open Access (OA) policies being adopted at the institutional and funder levels. In parallel to policy implementation, institutions and funders have also been engaged in developing mechanisms to monitor academics and researchers compliance with the existing OA policies. This study highlights a few of the cases where compliance is being effectively monitored by institutions and funders. In the first section, Open Access is briefly overviewed and the rationale for monitoring OA policy compliance is explained. The second section looks at best practices in monitoring policy compliance with OA policies by funders and institutions. The case studies reflect on compliance with the UK Funding Councils and the USA National Institutes of Health OA policies. The third section makes recommendations on what processes and procedures universities and funders should adopt to monitor compliance with their OA policies. The final section recapitulates some of the key ideas related to monitoring policy compliance.

FRAMEWORK SYNTHESIS FOR SYMBOLIC EXECUTION OF EVENT-DRIVEN FRAMEWORKS

Symbolic execution is a powerful program analysis technique, but it is very challenging to apply to programs built using event-driven frameworks, such as Android. The main reason is that the framework code itself is too complex to symbolically execute. The standard solution is to manually create a framework model that is simpler and more amenable to symbolic execution. However, developing and maintaining such a model by hand is difficult and error-prone. We claim that we can leverage program synthesis to introduce a high-degree of automation to the process of framework modeling. To support this thesis, we present three pieces of work. First, we introduced SymDroid, a symbolic executor for Android. While Android apps are written in Java, they are compiled to Dalvik bytecode format. Instead of analyzing an app’s Java source, which may not be available, or decompiling from Dalvik back to Java, which requires significant engineering effort and introduces yet another source of potential bugs in an analysis, SymDroid works directly on Dalvik bytecode. Second, we introduced Pasket, a new system that takes a first step toward automatically generating Java framework models to support symbolic execution. Pasket takes as input the framework API and tutorial programs that exercise the framework. From these artifacts and Pasket's internal knowledge of design patterns, Pasket synthesizes an executable framework model by instantiating design patterns, such that the behavior of a synthesized model on the tutorial programs matches that of the original framework. Lastly, in order to scale program synthesis to framework models, we devised adaptive concretization, a novel program synthesis algorithm that combines the best of the two major synthesis strategies: symbolic search, i.e., using SAT or SMT solvers, and explicit search, e.g., stochastic enumeration of possible solutions. Adaptive concretization parallelizes multiple sub-synthesis problems by partially concretizing highly influential unknowns in the original synthesis problem. Thanks to adaptive concretization, Pasket can generate a large-scale model, e.g., thousands lines of code. In addition, we have used an Android model synthesized by Pasket and found that the model is sufficient to allow SymDroid to execute a range of apps.

Prevalence of physical activity in European adults — Compliance with the World Health Organization's physical activity guidelines

Background. Adults are recommended to engage in at least 150 min/week of moderate-to-vigorous physical activity (PA). Purpose. This study aimed to examine the level of compliance with PA recommendations among European adults. Methods. Using data from European Social Survey round 6, PA self-report data was collected from 52,936 European adults from 29 countries in 2012. Meeting PA guidelines was assessed usingWorld Health Organization criteria. Results. 61.47% (60.77% male, 62.05% female) of European adults reported to be engaged in moderate to vigorous PA at least 30 min on 5 or more days per week. The likelihood of achieving the PA recommended levels was higher among respondents older than 18–24. For those aged 45–64 years the likelihood increased 65% (OR = 1.65, 95% CI: 1.51–1.82, p b 0.001) and 112% (OR = 2.12, 95% CI: 1.94–2.32, p b 0.001) for males and females, respectively. Those who were high school graduates were more likely to report achieving the recommended PA levels than those with less than high school education (males: OR = 1.19, 95% CI: 1.12–1.27, p b 0.001; females: OR = 1.13, 95% CI: 1.06–1.20, p b 0.001). Conclusion. Although about 60% of European adults reported achieving the recommended levels of PA, there is much room for improvement among European adults, particularly among relatively inactive subgroups.

Synthesis and structural stability of metal-organic frameworks

Metal-organic frameworks (MOFs) have attracted significant attention during the past decade due to their high porosity, tunable structures, and controllable surface functionalities. Therefore many applications have been proposed for MOFs. All of them however are still in their infancy stage and have not yet been brought into the market place. In this thesis, the background of the MOF area is first briefly introduced. The main components and the motifs of designing MOFs are summarized, followed by their synthesis and postsynthetic modification methods. Several promising application areas of MOFs including gas storage and separation, catalysis and sensing are reviewed. The current status of commercialization of MOFs as new chemical products is also summarized. Examples of the design and synthesis of two new MOF structures Eu(4,4′,4′′,4′′′-(porphine-5,10,15,20-tetrayl)tetrakis(benzoic acid))·2H2O∙xDMF and Zn4O(azobenzene-4,4’-dicarboxylic acid)3∙xNMP are described. The first one contains free-base porphyrin centers and the second one has azobenzene components. Although the structures were synthesized as designed, unfortunately they did not possess the expected properties. The research idea to use MOFs as template materials to synthesize porous polymers is introduced. Several methods are discussed to grow PMMA into IRMOF-1 (Zn4O(benzene-1,4-dicarboxylate)3, IR stands for isoreticular) structure. High concentration of the monomers resulted in PMMA shell after MOF digestion while with low concentration of monomers no PMMA was left after digestion due to the small iii molecular weight. During the study of this chapter, Kitagawa and co-workers published several papers on the same topic, so this part of the research was terminated thereafter. Many MOFs are reported to be unstable in air due to the water molecules in air which greatly limited their applications. By incorporating a number of water repelling functional groups such as trifluoromethoxy group and methyl groups in the frameworks, the water stability of MOFs are shown to be significantly enhanced. Several MOFs inculding Banasorb-22 (Zn4O(2-trifluoromethoxybenzene-1,4-dicarboxylate)3), Banasorb-24 (Zn4O(2, 5-dimethylbenzene-1,4-dicarboxylate)3) and Banasorb-30 (Zn4O(2-methylbenzene-1,4-dicarboxylate)3) were synthesized and proved to have isostructures with IRMOF-1. Banasorb-22 was stable in boiling water steam for one week and Banasorb-30’s shelf life was over 10 months under ambient condition. For comparison, IRMOF-1’s structure collapses in air after a few hours to several days. Although MOF is a very popular research area nowadays, only a few studies have been reported on the mechanical properties of MOFs. Many of MOF’s applications involve high pressure conditions, so it is important to understand the behavior of MOFs under elivated pressures. The mechanical properties of IRMOF-1 and a new MOF structure Eu2(C12N2O4H6)3(DEF)0.87(H2O)2.13 were studied using diamond anvil cells at Advanced Photon Source. IRMOF-1 experienced an irriversible phase transtion to a nonporous phase followed by amorphization under high pressure. Eu2(C12N2O4H6)3(DEF)0.87(H2O)2.13 showed reversible compression under pressure up to 9.08GPa.