Materials and Nanomaterials with Stimuli-Responsive Behaviour based on the Flexibility of the Copper-Halide Chain

Tesis Doctoral inédita leída en la Universidad Autónoma de Madrid, Facultad de Ciencias, Departamento de Química Inorgánica. Fecha de lectura: 22-11-2019The present PhD Thesis has been realized in the Inorganic Chemistry Department of the Autonomous University of Madrid (Universidad Autónoma de Madrid), under the supervision of Dr. Félix Zamora Abanades and Dr. Pilar Amo Ochoa of the Nanomaterials Research Group. To achieve the completion of this thesis, a series of materials based on coordination polymers (CPs) has been designed, synthesized and characterized. These compounds present electrical and luminescent properties which can be tuned by the presence of physical or chemical stimuli. These materials are commonly known to possess a dynamic or stimuli-responsive behavior. Apart from the experiments conducted in the presence of several stimuli, theoretical calculations have been used when necessary in order to rationalize the observed behaviors. This thesis will be divided into six chapters: an introduction to CPs and stimuli-responsive materials, accompanied by the purposes of the thesis (Chapter 1); three chapters where the results of the thesis and the subsequent discussion are detailed (Chapters 2-4); the conclusions (Chapter 5) and, finally, the experimental section (Chapter 6). The compounds described in chapter 2 share a common building block: copper(I) iodide and functionalized nitrogen-donor ligands. Aiming to obtain new materials based on one- and two-dimensional CPs with double zigzag Cu-I chains, this metal salt has been combined with the following organic ligands: methyl isonicotinate (MeIN), methyl 2-aminoisonicotinate (NH2-MeIN), aminopyrazine (Apyz) and 3-chloroisonicotinic acid (Cl-HIN). The obtained compounds have been characterized by means of infrared spectroscopy (IR), elemental analysis, single crystal X-ray diffraction (SCXRD) and powder X-ray diffraction (PXRD), and their electrical and luminescent properties have been evaluated. Afterwards, they have been prepared as nanostructures. Similarly, we have been able to obtain nanostructures of three previously described CPs, obtained by combining copper(I) iodide and isonicotinic acid (HIN), ethyl isonicotinate (EtIN) or 2-amino-5-nitropyridine (ANP). In chapter 3, a new compound based on a double Cu-I chain, where the terminal ligand is 3,5-dichloropyridine (Cl2-py), is described. This compound presents itself in two different forms depending on the synthetic method followed to achieve its preparation. In this chapter, the difference in the luminescent properties showed by the two forms of this compound will be explained, and it will be proven that these differences are caused by the presence of defects in one of them. Chapter 4 discloses the preparation of new composite materials based on two of the already outlined CPs and flexible organic matrices such as polyvinylidene difluoride (PVDF) and polylactic acid (PLA). The homogeneity and the luminescent and mechanical properties of these new materials will be studied, in order to present them as candidates for industrial or daily-life applications.Is worth to acknowledge that this thesis has been funded by the FPI-MINECO program of the Spanish Ministerio de Economía y Competitividad (and, therefore, the current Ministerio de Ciencia, Innovación y Universidades) with the grant BES-2015-071534, as well as projects MAT2016-77608-C3-1-P, MAT2016-75883-C2-2-P, MAT2016-75586-C4-4-P and CTQ2016-75816-C2-1P

Fast and efficient direct formation of size-controlled nanostructures of coordination polymers based on copper(i)-iodine bearing functional pyridine terminal ligands

We report on the direct formation of 1D nanostructures of two coordination polymers based on copper(i)-iodine double chains decorated with ethyl isonicotinate or 2-amino-5-nitropyridine as terminal ligands. The use of different reaction conditions, e.g. energy of the formation process, solvents, and/or concentration of reactants, has allowed the control of the size of the fibres and ribbons directly formed in this process going from micron- to submicron- up to nano-size. We show experiments that direct the formation of materials kinetically versus thermodynamically controlled, adjusting simple experimental parameters. Finally, a morphological study on the Cu(i)-iodine bearing 2-amino-5-nitropyridine nanofibres has confirmed their reversible molecular recognition ability towards acetic acid vapoursWe are grateful for financial support from the Spanish Ministerio de Economía y Competitividad (MAT2013-46502-C2-2P, MAT2016-75883-C2-2-P, BES-2015-071534) and also to the scientific computing center (CCC) of the Autónoma University of Madrid for their tim

Decomposition of two types of electric wires considering the effect of the metal in the production of pollutants

Combustion runs at 700 °C in a horizontal laboratory furnace were carried out on two different electric wires (PVC and halogen-free wire). Tests were performed in the presence and in the absence of the metal conductor of the wires. The analyses of the polycyclic aromatic hydrocarbons (PAHs), chlorobenzenes (CBzs), chlorophenols (CPhs), mono- to octa-chlorodibenzo-p-dioxin and dibenzofurans (PCDD/Fs), and dioxin-like PCBs are shown. Regarding semivolatile compounds, PAHs production decreases in the presence of metal, while a higher amount of chlorinated compounds are emitted. Respect to the PCDD/Fs, the PVC wire in the presence of metal presents the highest emission, with a much more emission of furans than dioxins. The maximum emission is with 2 or 3 chlorine atom PCDD/Fs. PCBs emission correlates with PCDD/F production and represents 3–4% of total toxicity, determined by using WHO2005 factors.Support for this work was provided by the Generalitat Valenciana (Spain) with Projects PROMETEO/2009/043/FEDER, and by the Spanish MCT CTQ2008-05520

Pollutant Formation During the Thermal Decomposition of Electrical and Electronic Wastes

Paper submitted to the 7th International Symposium on Feedstock Recycling of Polymeric Materials (7th ISFR 2013), New Delhi, India, 23-26 October 2013.In this contribution we present the results of the research done at the University of Alicante in the last four years [1-7] about the thermal decomposition of waste electrical and electronic equipment (WEEE). Several materials have been studied, including PVC and halogen-free wires, printed circuit boards and casing from mobile phones, as well as brominated flame reatardants used in the EEE preparation such as TBBPA (tetra-bromo-bisphenol-A). Several experiments were performed in a nitrogen atmosphere (pyrolysis runs) and also in an oxidative atmosphere with different oxygen concentrations. Thermogravimetric runs were used to characterize samples, and a horizontal laboratory reactor was used to study the formation and destruction of pollutants during the thermal decomposition of these samples. More than 150 compounds, including carbon oxides, light hydrocarbons, polycyclic aromatic hydrocarbons (PAHs), chlorophenols (ClPhs), chlorobenzenes (ClBzs) and bromophenols (BrPhs) have been identified and quantified. Furthermore, polychlorodibenzo-p-dioxin and polychlorodibenzofurans (PCDD/Fs), polybromodibenzo-p-dioxin and polybromodibenzofurans (PBDD/Fs), and dioxin-like PCBs produced were analyzed.Generalitat Valenciana: PROMETEO/2009/043/FEDER. Ministerio de Educación y Ciencia: CTQ2008-05520

Thermogravimetric study of the decomposition of printed circuit boards from mobile phones

Thermal decomposition of printed circuits boards (PCB) is studied, using thermogravimetric analysis to compare the thermal behavior of PCB of mobile phones before and after the removal of the metallic fraction by acid washing. Several dynamic and dynamic + isothermal runs have been carried out at different heating rates (5, 10 and 20 K min−1), from room temperature to more than 1100 K. Also runs in the presence and in the absence of oxygen were performed (combustion and pyrolysis runs). Moreover, TG–MS experiments were performed (both in inert and oxidizing atmosphere) in order to better understand the thermal decomposition of these wastes and identify some compounds emitted during the controlled heating of these materials. Different reaction models are proposed, one for pyrolysis and one for combustion of the two kinds of wastes studied, which proved to simulate appropriately the experimental results at all the heating rates simultaneously.Support for this work was provided by the Generalitat Valenciana (Spain), research project Prometeo/2009/043/FEDER, and by the Spanish MCT, research project CTQ2008-05520

Thermal Decomposition of Mobile Phones

Paper submitted to the 31st International Symposium on Halogenated Persistent Organic Compounds (Dioxin 2011), Brussels, Belgium, 21-25 August 2011.Mobile phones are used for a variety of purposes, including keeping in touch with family members, conducting business, and having access to a telephone in the event of an emergency. Some people carry more than one cell phone for different purposes. In 2006 more than one billion mobile phones were shipped worldwide, 22.5 % more than the quantity shipped in 2005. By 2008 the number of mobile phone users around the world was predicted to reach two billion.Support for this work was provided by the Generalitat Valenciana (Spain) with projects Prometeo/2009/043/FEDER and ACOMP2011/224, and by the Spanish MCT CTQ2008-05520

Micro and nano smart composite films based on copper-iodine coordination polymer as thermochromic biocompatible sensors

Herein is presented the preparation and characterization of a composite material obtained by the combination of nanosheets of a coordination polymer (CP) based on the copper(I)-I double chain with response to temperature and pressure with polylactic acid (PLA) as biodegradable organic matrix. The new films of composite materials are generated using a simple and low-cost method and can be created with long lateral dimensions and thicknesses ranging from a few microns to a few nanometers. Studies show that the new material maintains the optical response versus the temperature, while the elasticity and flexibility of the PLA totally quenches the response to pressure previously observed for the CP. This new material can act as a reversible sensor at low temperatures, thanks to the flexibility of the copper(I)-iodine chain that conforms the CP. The addition of CP to the PLA matrix reduces the elastic modulus and ultimate elongation of the organic matrix, although it does not reduce its tensile strengthThis article has been funded by the Spanish Ministerio de Economía y Competitividad (and the current Ministerio de Ciencia, Innovación y Universidades) (MAT2016-77608-C3-1-P, MAT2016-75883-C2-2-P, MAT2016-75586-C4-4-P, CTQ2016-75816-C2-1P). J.C.-E. acknowledges the financial support by the “FPI-MINECO” Program of MINECO (Grant BES-2015-071534

Micro and nano smart composite films based on copper-iodine coordination polymer as thermochromic biocompatible sensors

Herein is presented the preparation and characterization of a composite material obtained by the combination of nanosheets of a coordination polymer (CP) based on the copper(I)-I double chain with response to temperature and pressure with polylactic acid (PLA) as biodegradable organic matrix. The new films of composite materials are generated using a simple and low-cost method and can be created with long lateral dimensions and thicknesses ranging from a few microns to a few nanometers. Studies show that the new material maintains the optical response versus the temperature, while the elasticity and flexibility of the PLA totally quenches the response to pressure previously observed for the CP. This new material can act as a reversible sensor at low temperatures, thanks to the flexibility of the copper(I)-iodine chain that conforms the CP. The addition of CP to the PLA matrix reduces the elastic modulus and ultimate elongation of the organic matrix, although it does not reduce its tensile strength

Valoración de distintos tiempos de espera previos al sacrificio en corderos lechales sobre su comportamiento y varios parámetros sanguíneos indicadores de estrés

En 18 corderos lechales machos de 11-13 Kg de peso vivo de raza Lacaune, se han estudiado las repercusiones que tienen los tiempos de espera en matadero de 0, 3 y 6 horas sobre los parámetros de comportamiento indicadores del bienestar animal (de pie quieto o en movimiento, tumbado y número de veces que beben) y los parámetros plasmáticos indicadores de deshidratación (proteinas totales), de estrés físico (lactato) y de estrés psicológico (cortisol). Los corderos que permanecieron en la sala de espera (3 y 6 h) presentaron niveles significativamente más elevados (P < 0,01) de lactato que los sacrificados inmediatamente (0 h), como consecuencia de un mayor gasto energético. En relación a los parámetros de comportamiento los corderos estuvieron tumbados más tiempo en la sala de espera en las tres primeras horas que en las tres últimas (P< 0,001), sin diferencias significativas entre los lotes de 3 y 6 horas. Los resultados de este trabajo indican que el bienestar de los corderos lechales puede verse afectado por el tiempo de espera en el matadero, que debería ser mínimo.18 male suckling lambs 11-13 kg live weight of Lacaune breed have been studied in order to evaluate the impact of lairage time of 0, 3 and 6 hours at slaughterhouse: on the behavioural indicators of animal welfare (standing or moving, lying and number time of drinking) and plasma parameters of physical stress (lactate) and psychological stress (total protein and cortisol). Lambs housed in the lairage had significantly higher levels of lactate (