The effect of thiol substitution in radical thiol–ene reactions has been studied by using model, monofunctional thiols as well as multifunctional thiol monomers along with the assessment of their subsequent polymerization reactions and polymer mechanical behavior. FT-IR was used to monitor the polymerization rate and quantify the overall conversion. While the total conversion was observed to range from 70% to 100%, the polymerization rate was found to decrease by as much as 10-fold as the thiol substitution was changed from primary to tertiary. Analogous multi-thiol monomers of similar structure but varying substitution were synthesized to observe the effect of substitution type on polymerization kinetics and polymer behavior. Methylation at the α-carbon was varied from primary to tertiary to observe these differences. Mechanical properties were assessed by using dynamic mechanical analysis and water sorption experiments, where the glass transition temperatures were found to be within 1–2 °C as thiol substitution varied. Furthermore, primary thiol films absorbed 1–3% more water than secondary thiol films. Resin shelf stability experiments were performed by using rheometry to measure storage time-dependent viscosity changes, and it was found that secondary thiol films remained relatively stable for up to 100 times longer than their primary counterparts. It was concluded that while there are differences under relatively slow initiation conditions, at typical initiation rates all three thiol substitutions may be made to react at similar rates for both monofunctional and polymeric systems.
La normalidad constitucional consiste en la aplicación habitual y general de una serie de reglas jurídicas preestablecidas, ello con el objetivo de ordenar la pacífica convivencia ciudadana. Sin embargo, existen situaciones de peligro extraordinario en las que deberá estar justificado que las reglas habituales cedan en gran medida, ello con el objetivo de lograr una pronta restauración de la normalidad político-constitucional. Aunque anticipar todas las circunstancias excepcionales susceptibles de producirse es tarea del todo imposible, va en beneficio de la seguridad jurídica la previsión de, al menos, las amenazas más comunes. En esa regulación consiste lo que la doctrina española mayoritaria conviene en denominar estado de excepción o derecho de excepción, entendidos en sentido amplio.Este trabajo rehúye la anterior concepción terminológica, y lo hace en el marco de una nueva propuesta taxonómica aplicable al ámbito de la anormalidad constitucional. Así, partiendo de la diferenciación entre situaciones de emergencia constitucional reglada y no reglada, defendemos que la verdadera situación jurídica de excepción se manifiesta cuando, no existiendo regulación aplicable frente a la amenaza concreta, la reacción estatal no encuentra más límites que el respeto al principio de proporcionalidad en la defensa de los valores democráticos consagrados en la Constitución. Es esto, además, lo que impide afirmar la suspensión total del derecho frente al hecho excepcional no regulado, perteneciendo todas estas premisas jurídicas a lo que nosotros entendemos que es el derecho de emergencia constitucional.
Resumen:El año 2017 fue testigo de importantes acontecimientos en relación con el fenómeno de la ideología de ultra derecha en Alemania. Si en enero, el Tribunal Constitucional Federal fallaba en contra de la prohibición del NPD pese a reconocer el carácter antidemocrático de sus objetivos, en julio entraba en vigor una reforma constitucional para excluir de la financiación estatal a formaciones políticas que, siendo contrarias al orden democrático, no sean objeto de prohibición al carecer del potencial necesario para alcanzar sus objetivos. A modo de colofón, septiembre finalizaba con la celebración de elecciones federales y la entrada de la AfD en el Bundestag como tercera fuerza política. A la luz de todo ello, en el presente trabajo se apuesta por el análisis de las principales implicaciones jurídicas derivadas de dichos hechos, ello con el ánimo de ofrecer al lector una visión actualizada sobre el control jurídico aplicable a la ideología de los partidos políticos en Alemania.Summary1. Introduction. 2. The right of every democratic system to its self-defence. 2.1. Theoretical approach. 2.2. Express intangibility clauses and ideological control. 3. The defense of democracy and political parties in the German legal system. 3.1. The German concept of militant democracy. 3.2. Legal regime applicable to anti-democratic political parties. 3.2.1. Constitutional framework. 3.2.2. Basic legislative framework. 4. The German jurisprudential adaptation to the ECHR conventionality control: the NPD case. 4.1. The necessity test according to the ECHR jurisprudence. 4.2. Potentiality as a substitute for the principle of proportionality. 4.3. Anti-democratic but constitutional. 5. Main observations after the recent constitutional reform. 6. Conclusions. Bibliography.Abstract:2017 witnessed important events in relation to the phenomenon of the right-wing ideology in Germany. First, in January, the Federal Constitutional Court ruled against the prohibition of the NPD, despite recognizing the anti-democratic nature of its objectives; then, in July, a constitutional reform came into effect to exclude from the state funding those political formations that, contravening the democratic order, are not prohibited as they lack the necessary potential to achieve their objectives. To conclude, September ended with the holding of federal elections and the entry of the AfD into the Bundestag, as the country’s third largest force. In light of all this, the present work is committed to the analysis of the main legal implications derived from these events, this with the aim to offer the reader an updated view on the legal control applicable to theideology of political parties in Germany.
LABURPENA: 2020ko martxoaren 14a, larunbata. COVID-19aren pandemiari aurre egiteko, Espainiako Gobernuak alarma-egoera erabiltzea erabaki du. Neurri murriztaile batzuk orokortzea dakar, denetan garrantzitsuena, etxeko konfinamendu zorrotza. Ikusi egin beharko da ea konstituzio-ordenak nola eusten dion. Alarma-egoerak muga guztiak gainditu eta apurtu izanik, konstituzioaren kontra gertatu diren okerkeriak erakusten ditu artikulu honek, horixe jazo baita, oinarrizko eskubideak orokorrean etenda utzi zirenetik Konstituzioak horretarako eskatzen duen bermerik gabe. ABSTRACT: Saturday, March 14, 2020. The Spanish government has decided to use the state of alert to tackle the pandemic caused by COVID-19, which involves the generalisation of a series of restrictive measures that will test out the strength of the established constitutional order. With strict home confinement as the most important of these actions, this article shows the unconstitutionality of a state of alarm that has gone completely beyond its limits, since it imposes a general suspension of fundamental rights without the corresponding constitutional guarantees required for this purpose. RESUMEN: Sábado, 14 de marzo de 2020. El Gobierno de España decide recurrir al estado de alarma para hacer frente a la pandemia provocada por el COVID-19, en lo que supone la generalización de una serie de medidas restrictivas que pondrán a prueba la fortaleza del orden constitucional establecido. Siendo el estricto confinamiento domiciliario la más importante de todas ellas, este artículo pone de manifiesto los vicios de inconstitucionalidad en que ha incurrido un estado de alarma claramente extralimitado, ello desde el momento en que impone la suspensión general de derechos fundamentales sin las correspondientes garantías constitucionales exigidas para ello.
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