<p> Research in the field of sol-gel derived materials has evolved dramatically over the past forty years. The developments in the past decade, in the field of bioanalytical chemistry, have revolutionized this field. Early research, as well as that done by our group, has confirmed that the commonly used alkoxysilane precursors (tetraethylorthosilicate - TEOS or tetramethylorthosilicate - TMOS) are not ideal for entrapment of biomolecules. They produce materials that are brittle, often undergo cracking due to hydration stresses and in some cases, can block the accessibility of the analyte to the entrapped biomolecules. My research project therefore focuses on the development of new sol-gel processing methods through the use of an additive-glycerol, which will produce new "second generation" glasses. I have focused on obtaining a basic understanding of glycerol-doped sol-gel derived materials and the effect they have on the entrapped biomolecules. Glycerol-doped sol-gel materials display larger pore size, decreased shrinkage and cracking as compared to the TEOS-based materials. Biocatalysts entrapped in glycerol-doped materials showed significantly smaller decreases in activity over a period of one month relative to enzyme entrapped in TEOS. Also, to gain further insight into the effects of glycerol doping on the properties of entrapped proteins, both steady-state and time-resolved fluorescence of Trp 214 was used to examine the conformation, dynamics, accessibility, thermal/chemical stability and the degree of ligand binding of human serum albumin (HSA) in solution and after entrapment of the protein in glycerol-doped TEOS-based materials.</p> / Thesis / Master of Science (MSc)

Doping als psychosoziales Verhalten stellt mehr als die bloße Verletzung von Anti-Doping-Regeln dar. Doping betrifft sowohl den (Hoch-)Leistungs- als auch den Breiten- und Freizeitsport. Für die Vorhersage von Doping haben Einstellungen einen nachweislich großen Einfluss, jedoch konnte bisher kein zufriedenstellendes theoretisches Modell, welches sowohl Personen- und Situationsfaktoren ausreichend berücksichtigt, gefunden werden. Die erste Publikation konzentriert sich auf methodische Fragen zur Erfassung impliziter Dopingeinstellungen. Dieser Beitrag, der auf duale Einstellungstheorien (z.B., Fazio, 1990) basiert, diskutiert die indirekte Messung von Dopingeinstellungen mittels Impliziten Assoziationstest (Greenwald et al., 1998). Die zweite Publikation stützt sich auf ein erweitertes Dopingverständnis und untersucht den Schmerzmittelkonsum in Abhängigkeit von Situations- und Personenfaktoren anhand der Annahmen von Rational-Choice-Theorie und Routine-Activity-Ansatz (Clarke & Cornish, 1985; Cohen & Felson, 1979). Abschließend wird der Einfluss von moralischen Entscheidungen auf Doping diskutiert (z. B. Ntoumanis et al., 2014). Das Ethische Dilemmatraining (Elbe & Brand, 2016) stellt eine neue Methode dar, um die moralische Entscheidungsfähigkeit zu steigern und moralische Werte und Überzeugungen zu stärken. Als integrierender theoretischer Rahmen wird die Situational Action Theory (z. B., Wikström, 2014) vorgeschlagen, welche sowohl die Interaktion von Personen- und Situationsfaktoren als auch die moralische Entscheidungsfindung miteinander verbindet. Weiterführende Implikationen für die Dopingforschung und -prävention werden diskutiert.:List of Publications III List of Figures IV List of Tables VI Abstract VII Zusammenfassung VIII 1 Introduction 1 1.1 Historical Overview on Doping in Sports 1 1.2 Defining Doping - Strengths and Weaknesses 3 1.2.1 World Anti-Doping Code 4 1.2.2 Limitations of WADA Code 6 1.2.3 Doping as (Deviant) Social Behavior 7 2 A Review on Current Research on Doping 11 2.1 Prevalence of Doping Elite and Recreational Sport 11 2.2 Doping and Legal and Illegal Substance (Mis-)Use 15 2.3 Doping and Related Personal and Situational Factors 19 3 Modelling Doping - A Theoretical Overview 21 3.1 A Summary of Relevant Theories on Doping 21 3.1.1 Theory of Planned Behavior 21 3.1.2 Sport Drug Control Model 22 3.1.3 Life Cycle Model 24 3.1.4 Trans-contextual Model of Avoid Doping 25 3.2 A Dual-process Perspective on Doping 27 3.3 A Person-Situation Perspective - Impact of Situation and Context 31 3.4 A Gateway to Doping 34 3.5 Implication for Further Theoretical Discussion 37 4 Aim of Thesis and General Research Questions 39 5 Publications 43 5.1 Publication Manuscript 1 43 5.2 Publication Manuscript 2 51 5.3 Publication Manuscript 3 61 6 General Discussion and Conclusion 79 6.1 Future Perspectives on Research of Doping Attitudes 79 6.2 A Different Understanding of the Person-Situation Interaction 81 6.3 Bridging the Gap - An Integrative Model of Person and Situation 82 6.3.1 Situational Action Theory (SAT) 82 6.3.2 SAT - New Implications for Doping Research 90 6.4 Future Implications and Challenges for Doping Prevention 95 6.5 Conclusion 97 7 References 101 8 Appendix 130 8.1 Thesis Statement of Originality 130 8.2 Statement of Authorship 131 8.3 Curriculum Vitae 132 / Doping - as a psychosocial behavior - is more than simply violating anti-doping rules and laws. Doping has become a part of high-performance and recreational sports. Attitudes toward doping among athletes have been sufficiently proven as an important impact factor. However, theoretical consideration of the person-situation mode with other relevant factors (e.g., moral disengagement or situational factors) into an integrated understanding of doping is still needed. The first study presented in this thesis focusses on methodological issues and the assessment of implicit doping attitudes. Based on dual process theories of attitudes (e.g., Fazio, 1990), the first paper discusses the indirect measurement of doping attitudes via the Implicit Association Test (Greenwald et al., 1998) as a tool to overcome limitations of self-reported attitudes. The second study presented here uses a broader understanding of doping and focuses on the parallelism of doping and doping-like behavior. The study analyzes the use of NSAID (non-steroidal anti-inflammatory drugs) in different intake situations. The influence of situation and person factors is tested by using the assumption of high- and low-cost situations from the Rational Choice Theory and Routine Activity Approach (e.g., Clarke & Cornish, 1985; Cohen & Felson, 1979). Finally, research has shown that moral decision-making has an impact on doping behavior (e.g., Ntoumanis et al., 2014). Ethical dilemma training (e.g., Elbe & Brand, 2016) may be employed as a new method to increase moral decision-making ability and to strengthen moral values and beliefs. Accordingly, the third research paper presented discusses this as a new approach to doping prevention. Overall, this thesis introduces Situational Action Theory ( e.g., Wikström, 2014) as an integrative theoretical approach, focussing on the person-situation interaction, as well as on moral decision-making. Further implications for doping research and for prevention are discussed.:List of Publications III List of Figures IV List of Tables VI Abstract VII Zusammenfassung VIII 1 Introduction 1 1.1 Historical Overview on Doping in Sports 1 1.2 Defining Doping - Strengths and Weaknesses 3 1.2.1 World Anti-Doping Code 4 1.2.2 Limitations of WADA Code 6 1.2.3 Doping as (Deviant) Social Behavior 7 2 A Review on Current Research on Doping 11 2.1 Prevalence of Doping Elite and Recreational Sport 11 2.2 Doping and Legal and Illegal Substance (Mis-)Use 15 2.3 Doping and Related Personal and Situational Factors 19 3 Modelling Doping - A Theoretical Overview 21 3.1 A Summary of Relevant Theories on Doping 21 3.1.1 Theory of Planned Behavior 21 3.1.2 Sport Drug Control Model 22 3.1.3 Life Cycle Model 24 3.1.4 Trans-contextual Model of Avoid Doping 25 3.2 A Dual-process Perspective on Doping 27 3.3 A Person-Situation Perspective - Impact of Situation and Context 31 3.4 A Gateway to Doping 34 3.5 Implication for Further Theoretical Discussion 37 4 Aim of Thesis and General Research Questions 39 5 Publications 43 5.1 Publication Manuscript 1 43 5.2 Publication Manuscript 2 51 5.3 Publication Manuscript 3 61 6 General Discussion and Conclusion 79 6.1 Future Perspectives on Research of Doping Attitudes 79 6.2 A Different Understanding of the Person-Situation Interaction 81 6.3 Bridging the Gap - An Integrative Model of Person and Situation 82 6.3.1 Situational Action Theory (SAT) 82 6.3.2 SAT - New Implications for Doping Research 90 6.4 Future Implications and Challenges for Doping Prevention 95 6.5 Conclusion 97 7 References 101 8 Appendix 130 8.1 Thesis Statement of Originality 130 8.2 Statement of Authorship 131 8.3 Curriculum Vitae 132

L’objectif de ce travail de thèse est de tester l'efficacité du paradigme de la communication engageante appliqué à la prévention des conduites dopantes. Les conduites dopantes sont la consommation de substances (principalement des drogues licites ou illicites) afin d’améliorer les performances physiques et psychologiques. Dans le sport, certaines de ces substances sont interdites et les conduites dopantes sont simplement appelées "dopage". Les conduites dopantes, et bien plus encore dans le sport, sont souvent considérées comme problématiques car elles peuvent générer des risques pour la santé et également de la tricherie. Trois recherches-actions sont réalisées. La première, auprès de 52 sportifs de haut niveau volontaires, montre que l'engagement semble produire un effet allant dans le sens d’une meilleure prévention du dopage. La deuxième étude teste un dispositif de communication engageante avec 111 athlètes d’élite volontaires : les résultats montrent une diminution de la consommation des compléments alimentaires, excitants et substances contre la douleur, en condition libre choix et actes publics. La troisième recherche se déroulait dans le contexte réel d’une prévention. Les résultats des 760 élèves montrent une diminution de la consommation de tabac et de cannabis après l'action de communication engageante, et une augmentation de l'affirmation de soi. Une réflexion sur l’application et la faisabilité du paradigme de la communication engageante appliquée au domaine de la prévention est proposée en fin de thèse. / The aim of this work is to test the effectiveness of the binding communication paradigm applied to doping behavior prevention. A doping behavior is the use of a substance (mainly a licit or an illicit drug) with the aim to enhance physical or psychological performance. In sports, some of these substances are prohibited, and doping behaviors are simply named "doping". Doping behaviors, and much more doping in sport, are often regarded as problematic, because they may generate health hazards, and cheating as well. Three studies are conducted. The first one, among 52 top-level volunteers athletes, shows that commitment seems to produce an effect which is in line with a better doping prevention. The second study tests a "committing communication" device with 111 elite volunteers athletes: results show a decrease in consumption of dietary supplements, stimulating products and substances against pain, with conditions of free choice and public acts. The third search occurs in the real context of a prevention. The 760 pupils' results show a decrease of tobacco and cannabis consumption after "committing communication" action, and increasing self-affirmation. A reflexion on the application and feasibility of the binding communication paradigm applied to the field of prevention is proposed at the end of the thesis.