In dieser Doktorarbeit wurde gezeigt, dass die sehr begehrte J-Aggregation funktionaler Perylenbisimid-Chromophore durch geeignetes Design der monomeren Bausteine erreicht werden kann. Hierzu war einerseits die Selbstanordnung durch ein Zusammenwirken von Wasserstoffbrücken und Pi-Pi-Wechselwirkungen zu begünstigen, und andererseits eine Anordnung in kolumnaren Stapeln zu verhindern, was durch Kern-Verdrillung mittels sterisch anspruchsvollen Substituenten gelang. Desweiteren gaben Selbstanordnungsstudien neue Einblicke in den dynamischen Aggregationsprozess niedrigdimensionaler langgestreckter Aggregate mit stark exzitonisch gekoppelten Chromophoren. Die Beziehung zwischen bekannten Cyaninfarbstoffen, wie der von THIATS mit dem vorliegenden PBI 1a wurde durch Absorptions- und Fluoreszenzspektroskopie bei Tieftemperaturen von 5 K bis Raumtemperatur untersucht. Die vormals beispiellosen funktionalen Eigenschaften der PBI-Aggregate, welche aus der J-artigen exzitonischen Kopplung herrühren, sind vielversprechend für die Anwendung in optoelektronischen Bauteilen und für die Photovoltaik. / In conclusion, the present thesis demonstrates that the highly desired J-type aggregation of functional perylene bisimide chromophores can be achieved by proper design of monomeric building blocks that direct self-assemble by mutual effects of hydrogen bonding and pi-pi interaction, and on the other hand, are prevented to assemble in columnar stacks owing to their twisted pi-conjugated core and sterically demanding substituents. Furthermore, the self-assembly studies gave new insights into the dynamic aggregation process of low-dimensional extended assemblies with strongly excitonically coupled chromophores. The relationship between commonly known cyanine dye aggregates like that of THIATS and that of the present PBI 1a was investigated by absorption and fluorescence spectroscopy at low temperatures down to 5 K. The formerly unprecedented functional properties of PBI aggregates that are expressed in J-type excitonic coupling hold promise for application in optoelectronic and photovoltaic devices.

No description available.

Reactions of catalytic hydrogenations and polymerizations are widely used in industry for manufacture of fine chemicals, pharmaceuticals, and plastics. Homogeneous catalysts for the processes that have low stability and their separation is difficult. Therefore, the development of new highly active and stable catalysts for hydrogenations and polymerizations is a necessity. The objective of this research was the development of a strategy for immobilization of heterogeneous metallocene catalysts. First, a methodology of immobilization of bis-indenyl ligands on the surface of mesoporous silica gel was designed. Four bis-indenyl ligands containing functionalized tethers of various lengths with terminal alkene groups were synthesized. All bis-indenyl ligands were immobilized on the surface of mesoporous functionalized silica gel by two methods: hydrosilylation and thiol-ene coupling of the double bond. After comparing the results, the second strategy was chosen as more efficient. The materials can be used further as intermediates for synthesis of supported metallocene catalysts.

Age-related macular degeneration (AMD) is the leading cause of blindness in the United States of America. The pyridinium bis-retinoid A2-ethanolamine (A2E) has been implicated to play a role in AMD. We have observed novel pyridinium bis-retinoids through melanolipofuscin and human RPE extractions that may also play a role in the pathology of AMD. We have begun the construction of an amino-retinoid library in order to identify these ocular compounds. The compounds from the amino-retinoid library are also used in a targeted and triggered drug delivery system for treating cancer. Folic acid is coupled with the amino-retinoids to specifically target cancer cells. The first two amino-retinoids to be synthesized and characterized were A2-dopamine (A2D) and A2-cadaverine (A2C). Both pyridinium bis-retinoids were shown to generate cytotoxic oxidation products similar to A2E. Successful coupling of folic acid to A2C was achieved to form the folic acid-A2-cadaverine (FA-A2C) product. Preliminary irradiation results suggest that the FA-A2C product may be more photoreactive than initially anticipated. This could mean less drug and light exposure required to induce apoptosis and could eventually lead to a less invasive and toxic cancer treatment.

This thesis is divided into two parts.Part I describes the organic extraction, separation, and liquid chromatographic-mass spectrometric analysis of chromophores from human and bovine retinal pigment epithelium. Flurorophores in the retinal pigment epithelium have been implicated in age related macular degeneration. In addition, the synthesis and characterization of a number of bis-retinoid type compounds that may potentially be found in such extracts, or that may be used for insight into pyridinium bis-retinoid reactivity, was accomplished.Part II describes a study of pyridinium bis-retinoid-folic acid coupling with respect to linker type, linker length, and nature of the linkage. Folic acid has been used as a targeting compound for a variety of cancer types. Development of HPLC and UV-Vis conditions suitable for the analysis of this new type of macromolecule was performed.

This thesis presents an evaluation of various graphical user interface (GUI) technologies for use in the supervision software of CERN’s Beam Interlock System (BIS). The evaluation is necessary because the current GUItechnology used by the supervision software, JavaFX, is no longer supported by Oracle. It also relies on aninternal library that is no longer maintained. Furthermore, a second version of the BIS is being developed, anda GUI is needed that works with BIS and BIS2 in parallel.Which technology is most suitable for the next version of the BIS supervision GUI?This question was answered by gathering user stories from users and experts. Simple proof of concepts weredeveloped for each technology, in order to identify technical limitations and register the development time. Theuser stories relevant to the choice of technology were listed, and each technology received points depending onwhether they were able to fulfill the requirement or not.Furthermore, in order to evaluate the ease of use, wireframes were created based on some of the user stories.These were qualitatively evaluated with stakeholders, which produced feedback that may be used for furtherdevelopment.Out of the four technologies evaluated, PyQt scored 6, ACW scored 4, WRAP scored 6 and Grafana scored3. WRAP and Grafana were discarded as viable options, since they were not able to fulfill hard requirements.ACW scored lower because it is web based and comes with a bigger maintenance overhead. / <p>This thesis was done as a part of a technical studentship at CERN.</p>

No description available.

No description available.

L'influenza del diritto sovranazionale, l'ampliamento del concetto di “materia penale” e la prospettiva “integrata” della legalità hanno portato ad una progressiva ridefinizione del perimetro applicativo delle garanzie intertemporali. In particolare, le norme della legge sull’esecuzione della pena, comprese quelle sui benefici penitenziari e sulle misure alternative, sono state sempre considerate di natura processuale, con la conseguente applicazione del canone del tempus regit actum, nonostante si sia sottolineata l'opportunità di evitare modifiche peggiorative di tali norme rispetto al momento in cui si stringe il "patto rieducativo" con il condannato. Il criterio formalistico, che distingue i diversi regimi di efficacia nel tempo in base alla “natura” delle norme o degli istituti, presenta mai superati limiti: come distinguere le norme di “natura” sostanziale da quelle di “natura” processuale, se si possa parlare realmente di “natura” processuale o sostanziale e soprattutto se tutta la categoria delle norme processuali si sottragga al divieto di retroattività in peius, sono domande a cui non si sono date risposte univoche. Tali latenti problematiche sono recentemente (ri)emerse con l’emanazione della c.d. legge “Spazzacorrotti”, che ha inserito molti dei delitti contro la p.a. nell’elenco di quelli ostativi alla concessione dei benefici e delle misure alternative previste dalla legge sull’Ordinamento penitenziario. La Consulta, con la sentenza n. 32/2020, ricorrendo al criterio dell’incidenza qualitativa sulla libertà personale, ha ritenuto illegittimo il diritto vivente consolidato, secondo cui le modifiche peggiorative in materia di misure alternative e la sospensione dell’ordine di carcerazione ex art. 656 c.p.p. potrebbero essere applicate anche per fatti commessi prima della loro entrata in vigore. L'obiettivo del lavoro è stato quello di condurre una riflessione in merito all'estensione dell'ambito operativo del principio di irretroattività della legge penale sfavorevole, evidenziandone le antiche e fondamentali istanze garantistiche, per verificare se -ed in quali termini- possa trovare applicazione in materia di esecuzione della pena alla luce dei principi enunciati nella Cedu ed evidenziati dalla Corte di Strasburgo e dalla Consulta. Il lavoro si propone di indagare gli effetti dell'approccio sostanzialistico della Corte Edu, che sembra aver dato l'impulso per riconsiderare la formalistica distinzione tra norme sostanziali e processuali, nell'ottica di estendere il divieto di retroattività in malam partem alle modifiche legislative incidenti in via diretta sulla qualità e sulla durata della pena. Inoltre, l’impostazione sovranazionale, secondo cui la disciplina prevista per la successione di leggi può riferirsi anche ai mutamenti giurisprudenziali in ossequio ad una prospettiva "integrata" delle diverse concezioni della legalità, ha dischiuso da tempo un orizzonte di nuove riflessioni in materia di irretroattività. Nel presente lavoro, in particolare, si vogliono analizzare gli effetti del revirement sfavorevole compiuto da Strasburgo nella sentenza Mursic c. Croazia, in punto di spazio minimo vitale per il detenuto e computo del mobilio, sull’applicazione dell’art. 35-ter o.p., che rinvia all’art. 3 Cedu come interpretato dalla giurisprudenza della Corte Edu. Si è voluta condurre un'analisi idonea a cogliere i punti di arrivo e di ripartenza, valorizzando il costante lavoro compiuto dalla Corte costituzionale, sempre più coraggiosa nell’affermare la forza dei principi costituzionali e convenzionali anche in materia di esecuzione della pena.

Con objeto de encontrar nuevas aplicaciones catalíticas para el oro e incluso de mejorar los resultados alcanzados con catalizadores de este metal, se sintetizaron tres catalizadores de oro (III) partiendo de la sal NaAuCl4.2H2O y diversos ligandos quirales derivados de oxazolina. En las condiciones de síntesis, uno de los ligandos experimentó una apertura completa de ambos anillos de oxazolina, mientras que en los otros dos casos esta apertura fue parcial, perdiendo de esta forma la simetría C-2. Por otro lado, se prepararon catalizadores de oro heterogéneos basados en nanopartículas de oro soportadas sobre el biopolímero quitosán, el cual fue depositado a su vez sobre sílice, obteniéndose dos catalizadores de oro con distinta relación biopolímero/sílice. La actividad catalítica de los catalizadores sintetizados, homogéneos y heterogéneos, fue estudiada en la hidroaminación intermolecular de alquinos, así como en la epoxidación y ciclopropanación asimétrica de olefinas. En la hidroaminación intermolecular de alquinos los catalizadores de oro fueron activos en ausencia de promotores, necesarios con el empleo de otros metales de transición. Los catalizadores basados en sílice-quitosán-oro no solo fueron más activos que otros catalizadores de oro conocidos, sino además los más estables pudiendo ser usados hasta seis veces sin pérdida de actividad. En la epoxidación asimétrica de olefinas, los catalizadores de oro mostraron actividad con oxidantes clásicos como NaOCl y PhIO pero la velocidad de la reacción aumentó considerablemente cuando se incorporaba oxígeno molecular en el medio de reacción. Estudios mecanísticos pusieron de manifiesto un posible mecanismo dual para la reacción de transferencia de oxígeno. Se obtuvieron moderados valores de enantioselectividad. Los catalizadores heterogéneos pudieron ser utilizados cuatro veces sin pérdida de actividad. Por último, en la ciclopropanación asimétrica de olefinas, el empleo de los catalizadores de oro condujo a / Domínguez Pérez, I. (2007). Catalizadores de oro y sus aplicaciones en reacciones de formación de enlaces C-C, C-N y C-O [Tesis doctoral]. Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/1983