Proefschrift Universiteit van Amsterdam. / Auteursnaam op omslag: Liesbeth Smits. Met lit. opg.-Met samenvatting in het Engels.

La tesi ripercorre il rapporto tra il cattolicesimo politico tedesco - coagulatosi attorno al partito del Zentrum nel 1870 - e la S. Sede durante i pontificati di Leone XIII e Pio X. / The thesis aims to describe the relationship between political catholicism, the Zentrumspartei, and the Holy See during the papacies of Leo XIII and Pius X.

For the first time, germania-based hybrid organic-inorganic sol-gel materials were developed for analytical sample preparation and chromatographic separation. Being an isostructural analog of silica (SiO2), germania (GeO2) is compatible with silica network. This structural similarity, which is reflected by the relative positions of germanium and silicon in the periodic table, stimulated our investigation on the development of germania-based sol-gel hybrid organic-inorganic coatings for analytical applications. Sol-gel sorbents and stationary phases reported to date are predominantly silica-based. Poor pH stability of silica-based materials is a major drawback. In this work, this problem was addressed through development of germania-based organic-inorganic hybrid sol-gel materials. For this, tetramethoxygermane (TMOG) and tetraethyoxygermane (TEOG) were used as precursors to create a sol-gel network via hydrolytic polycondensation reactions to provide the inorganic component (germania) of the organic-inorganic hybrid coating. The growing sol-gel germania network was simultaneously reacted with an organic ligand that contained sol-gel-active sites in its chemical structure. Hydroxy-terminated polydimethylsiloxane (PDMS) and 3-cyanopropyltriethoxysilane (CPTES) served as sources of nonpolar and polar organic components, respectively. The sol-gel reactions were performed within fused silica capillaries. The prepared sol-gel germania coatings were found to provide excellent pH and thermal stability. Their extraction characteristics remained practically unchanged after continuous rinsing of the sol-gel germania-PDMS capillary for 24 hours with highly basic (pH=13) and/or acidic (pH = 1.3) solution. They were very efficient in extracting non-polar and moderately polar analytes such as polycyclic aromatic hydrocarbons, aldehydes, ketones. Possessing the polar cyanopropyl moiety, sol-gel germania cyanopropyl-PDMS capillaries were found to effectively extract polar analytes such as alcohols, fatty acids, and phenols. Besides, they also showed superior thermal stability compared with commercial cyano-PDMS coatings thanks to the covalent attachment of the coating to capillary surface achieved through sol-gel technology. Their extraction characteristics remained unchanged up to 330°C which is significantly higher than the maximum operation temperature ( < 280 ºC) for commercial cyano-PDMS coatings. Low ng/L detection limits were achieved for both non-polar and polar test solutes. Our preliminary results also indicated that sol-gel hybrid germania coatings have the potential to offer great analytical performance as GC stationary phases.

This thesis involves a collaborative study of emic articulations and quotidian ways of ‘being German' and ‘being Paraguayan' in Nueva Germania, a rural municipality in Paraguay. An argument is made that the social categories focused upon during this thesis, were evoked according to different contexts. While many claimed that Germanness or Paraguayanness were key categories, essentialistic characteristics that defined them and others as people of a certain kind, in other situations these social divisions were disregarded or even contradicted. This leads me to the theoretical conclusion that social categories, and epistemic frameworks more broadly, should not be understood as universally relevant or as universally applicable, and should not be treated as such. The thesis therefore proposes to assume ‘contextual epistemic permissibility' as a key axiom for use within anthropology and in the wider social sciences. The possible theoretical and methodological consequences of such an assumption are elaborated upon. Different theories of self, social action, and agency are debated in the course of this thesis: it is asked which might best analytically accommodate the assumption of contextual epistemic permissibility. Furthermore, in order to reflect the multiplicity of emic epistemic frameworks, the thesis proposes that a notion of ‘analytical and representative complementarity' be introduced, rather than monistic theoretical models. Such complementarity is practised in the thesis through the use of different multiscalar analyses (for example, the use of different theories of nationalism), and through the simultaneous use of different forms of representation. The above theoretical divagations are intertwined and related to the individual stories of twelve people from Nueva Germania, and are presented with both textual and photographic means. The stories were created through a collaborative process. Each project participant was free to decide upon the subject of their account, and therefore the resulting stories are able to cover a variety of different themes, at the same time introducing the reader to individual histories, struggles, opinions, plans, and critiques. Some elements of these accounts directly relate to the theoretical debates focused upon within the thesis while other elements of the individual stories are left to speak for themselves, and for the reader to make sense of independently. The photographs and texts, in their intertextual presentation, allow for an embodiment of the argument concerning representational complementarity.

Sample preparation is the most time-consuming and error-prone step in chemical analysis. Miniaturization and automation of the sample preparation equipment eliminating or reducing the use of hazardous organic solvents, online hyphenation of sample preparation with analytical instruments in a cost-effective way are important factors that need to be considered to design and implement innovative sample preparation techniques and strategies. Solid-phase microextraction (SPME) is a simple, environmentally benign technique well suited for hyphenation with analytical instruments. However, poor coating stability is a significant drawback of SPME employing conventionally prepared coatings. This shortcoming arises from the lack of chemical bonding between the sorbent coating and the substrate. Introduction of sol-gel coatings in SPME greatly improved thermal stability and solvent stability in SPME, by providing direct chemical bonding between substrate and the sol-gel coating. In traditional fiber format of SPME (where the sorbent coating is placed on the outer surface of an end-segment of the fiber) the coating remains vulnerable to mechanical damage. Capillary microextraction (CME), the capillary format of SPME (also known as in-tube SPME), allows to overcome this shortcoming by securing the sorbent coating on inner walls of the capillary. This dissertation focuses on the development and systematic investigation of novel silica- and germania-based perfluorinated and non-fluorinated sol-gel sorbents in the form of CME surface coatings: their preparation, material characterization, CME performance evaluation, preconcentration and recovery of various analytes including environmental pollutants. This research established that germania-based sol-gel sorbents are characterized by superior microextraction performance than analogous silica-based sorbents. This enhanced performance provided by germania-based sol-gel sorbents may be explained based on thermogravimetric analysis suggests that higher carbon loading on germania-based sol-gel sorbents. Germania-based phenyl- (Ph), phenethyl- (PhE), octyl- (C8), octadecyl- (C18) and cyclohexenylethyl- (ChE) ligand-containing sol-gel sorbents were prepared and various pollutants with aromatic rings (such as aromatic ketones, aldehydes and polycyclicaromatic hydrocarbons) were extracted and analyzed by CME-GC and CME-HPLC. It was observed that sol-gel sorbents containing aromatic ligands (PhE and Ph) provided superior microextraction performance for the analytes with aromatic ring(s) in their structure, than the sorbents with aliphatic ligands (C8 and C18). Investigation of sol-gel sorbents containing hydrophobic perfluorooctyl (PF-C8) and perfluorododecyl (PF-C12) ligands revealed that PF-C8 and PF-C12 sol-gel sorbents provided ~ 3 times higher microextraction efficiency (measure in terms of specific extraction, SE) than corresponding non-fluorinated counterparts, C8- and C12-, respectively. The synthesis and design of silica- and germania-based dual ligands sol-gel sorbents simultaneously providing superhydrophobicity and π-π interactions with analytes represent a significant accomplishment of this research. Such sorbents contained a PF-C12 and PhE ligands incorporated in sorbent chemical structure. In this case, perfluoro- group provided enhanced hydrophobic interaction and PhE group provided π-π interaction with the analytes. Combination of such interactions proved to be quite effective in the microextraction of alkylbenzenes and related compounds. Dual-ligand sol-gel sorbents with both equimolar and non-equimolar ligand concentrations were prepared. Experimentally it was established that sorbents with higher perfluorinated alkyl ligand concentrations had higher affinity for aliphatic hydrocarbons; however; when PhE concentration was higher, the dual-ligand sorbent showed enhanced affinity for aromatic compounds. The prepared sol-gel sorbents were characterized by less than 5% run-to-run RSD values, and also less than 5% capillary-to-capillary RSD values, which indicate that the sol-gel technique used in sorbent preparation was highly reproducible. The prepared sol-gel sorbents also showed that their performance does not deteriorate under aqueous saline matrix; therefore, it could be useful in the microextraction of pollutants from ocean water.

High-performance liquid chromatography (HPLC) is the most widely used analysis technique. However, its sensitivity is limited. Sample preconcentration methods, such as fiber-based solid-phase microextraction (SPME) and in-tube SPME (capillary microextraction) offer improved detection limits. It is, however, difficult to couple fiber SPME on-line with HPLC due to the need for complicated desorption devices. Such coupling is further complicated due to the limited solvent stability of the extracting phase both in the fiber and in-tube formats of SPME. In this research, surface-bonded sol-gel sorbents were developed to provide the solvent stability required for effective on-line hyphenation of capillary microextraction (CME) with HPLC. These sol-gel sorbents were prepared using (1) silica-based, (2) titania-based, and (3) germania-based sol-gel precursors. Sol-gel reactions were performed within fused silica capillaries to create a number of organic-inorganic hybrid sorbents in the form of surface-bonded coatings: (1) alkyl (methyl, octyl, octadecyl), (2) polydimethyldiphenylsiloxane, (3) titania poly(tetrahydrofuran), and (4) germania tri-block polymer. The sol-gel coated microextraction capillaries were capable of efficiently extracting a wide variety of analytes, including polycyclic aromatic hydrocarbons, ketones, aldehydes, aromatic compounds, amines, alcohols, and phenols with ng/L to pg/L detection limits. The sol-gel methyl coating demonstrated a counterintuitive ability to extract polar analytes. Sol-gel polydimethyldiphenylsiloxane coatings were found to be resistant to high temperature solvent exposure (150°C and 200°C), making them suitable for use in high-temperature liquid phase separations. To better understand how extraction takes place, effects of alkyl chain length and sol-gel precursor concentration were evaluated in the study on sol-gel alkyl coatings. The sol-gel titania poly(tetrahydrofuran) coating was also capable of extracting underivatized aromatic acids and polypeptides at pHs near their respective isolectric points. The sol-gel titania poly(tetrahydrofuran) coatings and the sol-gel germania tri-block polymer coatings demonstrated impressive resistance to extreme pH conditions, surviving prolonged exposure to 1.0 M HCl (pH approx. 0.0) and 1.0 M NaOH (pH approx. 14.0) with virtually no change in extraction behavior. Sol-gel germania tri-block polymer coatings were also stable under high temperature solvent conditions (200°C). In addition, for the first time, the analyte distribution constants between a sol-gel germania coating and the aqueous samples (Kcs) were determined.

Die Herstellung von ultradünnen Germaniumdioxidfilmen auf Metallsubstraten ist erstmals erfolgreich gelungen. Die Filmstruktur konnte mittels oberflächensensitiven Techniken mit atomarer Präzision und chemischer Sensitivität aufgelöst werden. Zur Untersuchung werden STM-Bilder analysiert und durch niederenergetische Elektronenbeugung (LEED), eine dynamischen LEED-Studie und extern ausgeführte Dichtefunktionaltheorieberechnungen (DFT) ergänzt. In dieser Arbeit werden atomar aufgelöste Rastertunnelmikroskopiebilder (STM) von ultradünnen Germaniumdioxid- und Siliziumdioxidfilmen direkt verglichen. Ziel der Analyse ist es, den Einfluss des Metallsubstrats auf die Struktur von Oxidfilmen zu untersuchen. Zu diesem Zweck werden ultradünne Germaniumdioxid-Filme auf Ru(0001), Pt(111) und Au(111) abgeschieden und mit Siliziumdioxid-Filmen auf verschiedenen Substraten verglichen, die in früheren Studien untersucht wurden. Germaniumdioxid und Siliziumdioxid sind eng miteinader verknüpft. Hierbei sind Struktur und chemische Eigenschaften als äquivalent anzusehen. Es wurden drei verschiedene Netzwerkstrukturen aufgeklärt: Monolagen-, Zickzack- und Bilagenfilme. Die einzelnen Bausteine in diesen Filmsystemen bestehen aus verzerrten Tetraedern, in denen ein Germaniumatom von vier Sauerstoffatomen umgeben ist. Benachbarte Tetraeder sind durch Ge-O-Ge-Bindungen miteinander verknüpft und binden im Fall der Monolagenfilme an das darunterliegende Metallsubstrat. In Bilagenfilmen hingegen gibt es keine chemischen Bindungen zum Substrat, wodurch die Filmstruktur flexibler wird. Durch Variation der Herstellungsbedingungen kann man rein kristalline, amorphe oder Phasen mittlerer Ordnung erhalten. Es ist wichtig hervorzuheben, dass der amorphe Germaniumdioxid-Bilagenfilm ein neues amorphes zweidimensionales Material darstellt. / The preparation of metal-supported ultrathin films of germanium dioxide, termed also germania, has been successfully achieved for the first time. The structure of the films is elucidated with atomic precision and chemical sensitivity using surface science techniques. The investigation is performed by analyzing STM images and is complemented by low-energy electron diffraction (LEED) patterns, a dynamical LEED study, and external support from density functional theory (DFT) calculations. In this work, we compare side-by-side atomically-resolved scanning tunneling microscopy (STM) images of ultrathin films of germania and silica. The analysis aims to investigate the impact of the metal support on the structure of oxide films. For that purpose, ultrathin germania films are grown on Ru(0001), Pt(111) and Au(111), and compared with previously reported silica ultrathin films supported on different substrates. Germania has been widely associated with silica since they are considered to be structural and chemical equivalent materials. Three main network structures have been characterized: monolayer, zigzag and bilayer films. In all systems, the building block consists of a distorted tetrahedron with a germanium atom surrounded by four oxygen atoms. Adjacent tetrahedra connect to each other through Ge-O-Ge bonds and, in the case of the monolayer films, they also bind to the metal support. Conversely, in bilayer films there are no chemical bonds to the metal substrate, thus providing more flexibility to the film structure. Through a meticulous control of the preparation conditions one can obtain a purely crystalline phase, an amorphous one, or one with intermediate order. It is important to highlight that the amorphous germania bilayer film represents a new 2-dimensional amorphous material.

Compiuta un'ampia digressione di carattere interdisciplinare in tema di suicidio tale da abbracciare considerazioni di natura sociologica, letteraria, filosofica, storica e giuridica, si è proceduto ad una valutazione delle forme di repressione concepite in passato per rispondere a condotte agevolatrici di tale gesto, giungendosi da ultimo a ponderare il dibattito sorto in seno alle scuole penalistiche dell'epoca, le soluzioni adottate dai Codici Zanardelli e Rocco nonché i rilievi dottrinali da esse immediatamente stimolati. Tale premessa si è rivelata imprescindibile per un'approfondita analisi del procedimento a carico di Marco Cappato, attingendo da esso interessanti spunti di riflessione riguardanti, prima ancora che le disposizioni penali in materia di fine vita, i principi costituzionali e i valori tatti da simili scelte terminali. La riflessione sulla dignità, così come quella inerente i confini dell'autodeterminazione in materia sanitaria, ha condotto a soppesare la possibilità di disciplinare trattamenti di eutanasia attiva diretta, confrontandosi con i numerosi ostacoli opposti e chiamando in causa la nozione di “diritto a morire”. Il terzo capitolo, riservando alcune considerazioni preliminari al rapporto fra Diritto e morale e alle funzioni tradizionalmente assolte dalla sanzione penale, propone l'elaborazione di una scriminante procedurale tale da riconoscere il carattere di liceità di pratiche di “aiuto medico a morire”. L'analisi dei suoi requisiti operativi è affiancata ad alcune riflessioni in tema di omicidio pietatis causa, seguite dall'annosa questione relativa all'esercizio dell'obiezione di coscienza da parte del personale sanitario e da alcuni profili di responsabilità del medico coinvolto in procedure di nuova concezione. Infine, l'esigenza di un'indagine attenta al metodo comparatistico ha reso ineludibile il riferimento a due recenti stimoli legislativo e giurisprudenziale, rispettivamente rappresentati dalla proposta di Ley Orgánica presentata al Congreso spagnolo (approvata in via definitiva il 18 marzo 2021) e dalla sentenza con cui il Bundesverfassungsgericht ha dichiarato l'illegittimità costituzionale del § 217 StGB in materia di agevolazione al suicidio prestata in forma commerciale.

La ricerca indaga qual sia stato il ruolo regionale della Germania nel periodo che va dalla crisi economica del 2008 al 2015 basandosi su tre elementi in particolare: 1)Tipologia/stile di potere regionale. Il potere esercitato dalla Germania a livello regionale di tipo egemonico coercitivo o benevolente e multilaterale. 2)Guida/conduzione della regione. L'efficacia complessiva della guida/conduzione regionale della Germania nel periodo post-crisi. 3)Influenza complessiva. L’influenza complessiva del potere della Germania a livello regionale tra il 2008 ed il 2015. La ricerca sostiene che la Germania, successivamente alla crisi economica globale, abbia disposto nell’arco temporale 2008-2015 di un potere molto efficace, sia a livello deliberato che non-intenzionale, sviluppando un ruolo regionale non sempre ben definito, esibendo tuttavia tratti caratteristici più assimilabili alla leadership in senso stretto e dimostrandosi spesso molto capace nel condurre la regione europea attraverso situazioni critiche. / The research investigates what has been the particular role of Germany in the period from the 2008 economic crisis up to 2015, based on three elements in particular: 1) Type/style of regional power. The power exercised by Germany, on a continuum from a regional hegemonic type to a benevolent and multilateral leadership. 2) Guide/conduct of region. The overall effectiveness of Germany's regional guide role in the post-crisis period. 3) Overall influence or "power over outcomes". The influence excercised by Germany at the regional level between 2008 and 2015. The research supports eventually that Germany, following the global economic crisis, has disposed during the period 2008-2015 of a very effective power (both intentional and non-intentional) developing a particular regional role not always in a clear and defined way, exhibiting indeed traits similar to a leadership and being often capable of leading the European region through critical situations.

Avec ma thèse de doctorat, j’ai pour objectif d’étudier la place et l’influence des commerçants et des transporteurs de la société des provinces gauloises et germaniques du Haut Empire Romain ainsi que les relations existant entre eux et d’autres agents sociaux comme les notables locaux. En développant mes recherches précédentes à propos des relations entre les notables locaux et les commerçants gaulois comme des relations parmi ces derniers et en élargissant le champ de recherche, j’ai l’intention de répondre à la question suivante : - Comment les milieux relatifs aux activités économiques, y compris les transporteurs et les propriétaires fonciers, participaient-ils au commerce ? Certes, nous avons connaissance de plusieurs recherches traitant des marchands dans les provinces du nord-ouest. Cependant nous ferons deux remarques. D’une part, on donne surtout de l’importance aux problèmes les concernant en tant que groupe social plutôt qu’aux rapports entre milieux différents, soit les rapports entre commerçants, soit ceux entre ces derniers et d’autres agents sociaux. D’autre part, certains chercheurs, en incluant dans le champ de recherche les provinces gauloises, nous semblent engager un débat basé sur des sources provenant notamment de grands centres commerciaux comme Ostie et Lyon. Mais on peut se demander s’il est toujours possible de généraliser les résultats obtenus à ces points importants du commerce en raison de leur caractère très singulier et de leur documentation. Dans cette situation de recherche et dans le contexte provincial, mon étude a pour but de mieux comprendre la nature et la fonction sociale des participants aux actions commerciales, mais également les particularités de la société des provinces du nord-ouest. Plus concrètement, tout en continuant à examiner les rapports entre les hommes de métier et les élites, j’analyse les relations parmi les hommes de métier eux-mêmes. Dans ce but, je dépouille des inscriptions concernant les milieux commerciaux ou les transporteurs dans les provinces gauloises et germaniques, tout en tenant compte des données archéologiques. / With my dissertation, I aim to examine the role and influence of merchants and transporters in the society of Gallic and Germanic provinces of the Early Roman Empire and the relationships between them and other social agents like local notables. Developing my previous researches about rapports between local élite and Gallic merchants as well as relationships among the latter, and broadening the scope of research, I intend to reply to following question: - How did those who were related to economic activities, including transporters and landowners, participate in trade? Certainly, we are aware of many studies on merchants in the northwestern provinces. However, we can make two remarks. On the one hand, certain scholars give particular importance to the issues related to traders as a social group rather than to relationships between different people, either relationships among merchants or those between them and other social agents. On the other hand, some researchers, who include the Gallic provinces in their scopes of research, seem to engage in discussions based on sources mainly from commercial centers like Ostia and Lyon. But one may wonder if it is always possible to generalize the results got at these important commercial hubs because of their singular character and their documentation. In this research situation and in the provincial context, my study aims to better understand the social nature and function of participants in commercial activities, but also the characteristics of the society of the northwest provinces. More specifically, while continuing to examine the relationships between skilled people and élite, I analyze the rapports among the skilled themselves. For this purpose, I study in detail inscriptions concerned with merchants or transporters in the provinces of Gaul and Germania, taking into account archaeological sources.