Effects of Whole-Body Electromyostimulation on Physical Fitness and Health in Postmenopausal Women

La menopausa s’associa amb un deteriorament de la forma física juntament amb guanys de pes i massa grassa, que poden resultar de canvis hormonals relacionats amb la menopausa, malalties associades a l’envelliment i una disminució del temps d’activitat física. Aquesta situació adversa deixa a les dones postmenopàusiques un risc elevat de desenvolupar resultats adversos per a la salut que condueixen a una dependència en un futur proper i a una baixa qualitat de vida. S'ha establert que l'activitat física té un paper fonamental en la prevenció d'aquest deteriorament físic. Per tant, l’electromioestimulació del cos sencer (WB-EMS) podria ser una metodologia d’èxit com a entrenament per millorar la forma física i la salut en dones postmenopàusiques. L'objectiu d'aquesta tesi era: (1) Analitzar els resultats obtinguts de la investigació existent sobre WB-EMS i provar el nivell d'evidència de cadascun dels estudis per comprendre l'estat del problema i identificar possibles mètodes d'investigació en el futur. ; (2) Establir un protocol compatible amb una rigorosa metodologia científica per estudiar els efectes del WB-EMS. (3) Analitzar si el WB-EMS és adequat per a la prevenció i el tractament del deteriorament físic postmenopàusic. En conseqüència, aquesta tesi es presenta en un compendi de quatre publicacions, amb diferents dissenys i metodologies: la primera d’elles presenta una revisió sistemàtica dels efectes del WB-EMS sobre la salut i el rendiment. El segon presenta un disseny d’un protocol que permet avaluar, des d’una perspectiva àmplia i multivariable, la influència d’un programa d’entrenament WB-EMS de 10 setmanes sobre la condició física i la salut mitjançant un disseny de grup paral·lel de 2 braços amb seguiment. . Els dos restants, discuteixen els resultats d’una fase experimental on es va dur a terme l’esmentat protocol amb dones postmenopàusiques. Els resultats d’aquesta investigació suggereixen que hi ha una manca d’estudis controlats aleatoris i que els estudis existents presenten un nivell de risc de biaix moderat a elevat, cosa que fa necessària la realització d’assaigs de control que abordin aquesta qüestió des d’una perspectiva científica i rigorosa. A més, el WB-EMS mostra un efecte aïllat favorable en el desenvolupament de la força dinàmica de les cames, agilitat i resistència cardiovascular, però no en la força del braç dinàmic, la velocitat de la marxa, l’equilibri o la flexibilitat de les dones postmenopàusiques. La principal contribució d’aquest treball és l’evidència que, sota la supervisió d’un tècnic d’activitat física, el programa d’entrenament proposat basat en WB-EMS superposat podria ser adequat per a dones postmenopàusiques que tenen dificultats per realitzar exercici físic continu. Seria una metodologia adequada per desenvolupar la seva resistència aeròbica, així com la seva capacitat funcional. D’aquesta manera, a causa d’aquesta millora de la forma física, reduirien el risc de caigudes, el deteriorament cardiovascular i la dependència, cosa que milloraria la seva qualitat de vida.La menopausia se asocia con un deterioro de la condición física junto con el aumento de peso y masa grasa, que pueden derivarse de cambios hormonales relacionados con la menopausia, enfermedades asociadas al envejecimiento y disminución del tiempo de actividad física. Esta situación adversa deja a las mujeres posmenopáusicas en un mayor riesgo de desarrollar resultados de salud adversos, que conduzcan a una dependencia futura y una baja calidad de vida. Se ha establecido que la actividad física juega un papel fundamental en la prevención de este deterioro físico. Así, la electroestimulación de cuerpo entero (WB-EMS) podría ser una metodología exitosa como entrenamiento para mejorar la condición física y la salud en mujeres posmenopáusicas. Los objetivos de esta tesis fueron: (1) Analizar los resultados obtenidos de la investigación existente sobre WB-EMS y probar el nivel de evidencia de cada uno de los estudios para comprender el estado del tema e identificar posibles métodos de investigación en el futuro; (2) Establecer un protocolo compatible con una metodología científica rigurosa para estudiar los efectos de WB-EMS; (3) Analizar si WB-EMS es adecuada en la prevención y tratamiento del deterioro físico posmenopáusico. En consecuencia, esta tesis se presenta en un compendio de cuatro publicaciones, utilizando diferentes diseños y metodologías. La primera de ellas presenta una revisión sistemática sobre los efectos de WB-EMS en la salud y el desempeño. La segunda presenta el diseño de un protocolo que permite evaluar, desde una perspectiva amplia y multivariable, la influencia de un programa de entrenamiento WB-EMS de 10 semanas sobre la condición física y la salud, mediante un diseño de grupos paralelos de 2 brazos con seguimiento. Las dos restantes, discuten los resultados de una fase experimental donde se realizó el mencionado protocolo con mujeres posmenopáusicas. Los resultados de esta investigación sugieren que existe una falta de estudios controlados aleatorizados, y los estudios existentes exhiben un nivel de riesgo de sesgo de moderado a alto, lo que hace necesaria la realización de ensayos de control que aborden este tema desde una perspectiva científica y rigurosa. Además, WB-EMS muestra un efecto aislado favorable en el desarrollo de la fuerza dinámica de las piernas, la agilidad y la resistencia cardiovascular, pero no en la fuerza dinámica del brazo, la velocidad de la marcha, el equilibrio o la flexibilidad de las mujeres posmenopáusicas. El principal aporte de este trabajo es la evidencia de que, bajo la supervisión de un técnico de actividad física, el programa de entrenamiento propuesto basado en WB-EMS superpuesto podría ser adecuado para mujeres posmenopáusicas que tienen dificultades para realizar ejercicio físico continuo. Sería una metodología adecuada para desarrollar su resistencia aeróbica, así como su capacidad funcional. De esta forma, debido a esta mejora de la condición física, reducirían su riesgo de caídas, su deterioro cardiovascular y su dependencia, lo que mejoraría su calidad de vida.Menopause is associated with a deterioration of physical fitness along with weight and fat mass gains, which may result from menopause-related hormonal changes, aging-associated diseases, and decreased physical activity time. This adverse situation leaves postmenopausal women at a heightened risk for developing adverse health outcomes leading to a near future dependence and low quality of life. It has been established that physical activity plays a fundamental role in the prevention of this physical deterioration. Thus, whole-body electromyostimulation (WB-EMS) could be a successful methodology as a training to improve the physical fitness and health in postmenopausal women. The objectives of this thesis were: (1) To analyze the results obtained from the existing research on WB-EMS and testing the level of evidence of each of the studies to understand the status of the issue and identify possible methods of investigation in the future; (2) To establish a protocol compatible with a rigorous scientific methodology to study the effects of WB-EMS. (3) To analyze if WB-EMS is suitable in the prevention and treatment of postmenopausal physical deterioration. Accordingly, this thesis is presented in a compendium of four publications, using different designs and methodologies: the first of them presents a systematic review of the effects of WB-EMS on health and performance. The second presents a design of a protocol that allows the assessment, from a broad and multivariable perspective, the influence of a 10-week WB-EMS training program on the physical condition and health using a 2-arm parallel group design. The two remaining texts, discuss the results of an experimental phase where the mentioned protocol was carried out with postmenopausal women. Results of this research suggest that there is a lack of randomized controlled studies, and the existing studies exhibit a moderate to a high level of risk of bias, which makes necessary the realization of control trials approaching this issue from a scientific and rigorous perspective. Furthermore, WB-EMS shows a favorable isolated effect on the development of dynamic leg strength, agility, and cardiovascular endurance but did not in dynamic arm strength, gait speed, balance, or flexibility of postmenopausal women. The main contribution of this work is the evidence that, under the supervision of a physical activity technician, the proposed training program based on superimposed WB-EMS could be suitable for postmenopausal women who find it difficult to carry out continuous physical exercise. It would be an adequate methodology to develop their aerobic resistance, as well as its functional capacity. In this way, due to this physical fitness enhancement, they would reduce their risk of falls, their cardiovascular deterioration, and their dependence, what would improve their quality of life

The sources of real agency: Kant on the metaphysics of freedom and life

The role of Kant’s Critique of Judgment in his overall theory of freedom has been largely confined to making room for the possibility of the realization of our ultimate moral goals in the world. While this is a central task Kant endeavoured to address with the third Critique, that work had a more overreaching impact in his general metaphysical picture of nature, which is instrumental in making sense of the core tenets of his theory of freedom. In this dissertation, I argue that Kant’s solution to what I term the real agency problem, namely, how actions that are determined by the laws of nature can be nevertheless said to be freely caused by agents, is riddled with problems unless we incorporate the requirements brought by the power of judgment into it. I argue that, according to Kant, judgment compels us to posit a purposive ground of nature that accounts for the necessity of empirical laws, and in such a way that the causality of organisms can be made possible. By doing so, we gain a warrant to judge human beings as intelligibly grounded. Insofar as humans exhibit rational behaviour, this opens a space to our judging them as having an intelligible character which grounds actions as freely caused. Thus, the new insights provided by the third Critique are instrumental in understanding Kant’s metaphysics of freedom

Design of a windmill for a Romanian countriside home

El principal objetivo de este proyecto es diseñar un pequeño aerogenerador que proporcione suficiente suministro eléctrico para una familia. El proyecto está desarrollado en Rumania (Iasi) concretamente para una zona de población rural dentro de esta provincia, donde se puede encontrar a personas de avanzada edad con problemas en el suministro eléctrico o para favorecer el desarrollo de esta zona, dando acceso a personas sin recursos a algo tan básico como la electricidad. Incluso se puede encontrar en esta zona problemas con el suministro eléctrico, así lo asegura la unión europea, en un informe sobre las infraestructuras de este país, en el que asegura que no ha entrado aun en el nivel de la media Europa. Nos encontramos en una zona con mucho viento para instalar un pequeño aerogenerador conectado fuera de la red pública, que nos pueda solventar los problemas de suministro para poder desarrollar otras actividades, o en este caso vivir, lo cual nos haría resolver el problema energético. Hoy en día el coste de este aerogenerador no es muy caro y podría ser asumido por cualquier familia, como se demostrará en este proyecto. Para asegurarnos el funcionamiento y la estructura del aerogenerador, se ha realizado un exhaustivo análisis con ANSYS del eje, estructura, escaleras, y mecanismo del aerogenerador, asegurando que pueden resistir incluso en las peores condiciones de viento en Iasi, siguiendo datos del mapa de viento que proporciona en tiempo real la Unión Europea. Todo el modelo 3D de este aerogenerador así como los planos se ha realizado con CATIA V5 R20 dando la posibilidad, para que en el futuro se puedan mejorar componentes, materiales, en general el diseño, y incluso hacer un proyecto más rentable para el desarrollo de la sociedad. Como se podrá ver en el desarrollo del trabajo se encuentran multitud de problemas que se intentan solucionar eligiendo diversos materiales para cada parte del proyecto.En cualquier caso se asegura al menos una vida estimada de 18 años. Al final del proyecto se presenta un apartado económico muy importante hoy en dia, y unas conclusiones a tomar en cuenta.Departamento de Ciencias de los Materiales e Ingeniería Metalúrgica, Expresión Gráfica en la Ingeniería, Ingeniería Cartográfica, Geodesia y Fotogrametría, Ingeniería Mecánica e Ingeniería de los Procesos de FabricaciónGrado en Ingeniería Mecánic

Computational studies of electronic and thermal properties of low dimensional materials

The control of low dimensional materials holds potential for revolutionizing the electronic, thermal, and thermoelectric materials engineering. Through strategic manipulation and optimization of these materials, unique properties can be uncover which enable more efficient and effective materials development. Towards the determination of nanoscale strategies to improve the electronic and phononic devices, computational simulations of modified low dimensional materials have been carried in this research. First, the electronic properties of chemically func tionalized phosphorene monolayers are evaluated with spin-polarized Density Functional Theory, as a potential method to tune their electronic properties. The functionalization not only leads to formation of additional states within the semiconducting gap, but also to the emergence of local magnetism. The magnetic ground state and electronic structure are investigated in dependence of molecular coverage, lattice direction of the molecular adsorption and molecule type functionalization. Furthermore, the physical and transport properties of phosphorene grain boundaries under uniaxial strain are evaluated by the use of Density Functional based Tight Binding method in combination with Landauer theory. In both grain boundary types, the electronic bandgap decreases under strain, however, the respective thermal conductance is only weakly affected, despite rather strong changes in the frequency-resolved phonon transmission. The combination of both effects results in an enhancement in the thermoelectric figure of merit in the phosphorene grain boundary systems. Finally, the thermoelectric properties of carbon nanotubes peapod heterostructures are studied and compared to pristine nanotubes using also the Density Functional based Tight Binding method and Landauer theory. It is found that the fullerene encapsulation modifies the electron and phonon transport properties, causing the formation of electronic channels and the suppression of vibrational modes that lead to an improvement of the thermoelectric figure of merit. The results of this thesis highlight the potential of strategic manipulation and optimization of low dimensional materials in improving their unique electronic and thermal properties, revealing promising avenues for improving electronic and phononic devices.:ABSTRACT i ZUSAMMENFASSUNG ii ACKNOWLEDGEMENT iv LIST OF FIGURES ix LIST OF TERMS AND ABBREVIATIONS xviii 1 Introduction 1 1.1 Motivation 1 1.2 Objectives and outline 6 2 Computational Methods 8 2.1 Density Functional Theory 8 2.1.1 The Many-Body System Hamiltonian and the Born-Oppenheimer approximation 9 2.1.2 Thomas-Fermi-Dirac approximation model 10 2.1.3 The Hohenberg-Kohn theorems 12 2.1.4 The Kohn-Sham orbitals equations 13 2.1.5 Exchange-correlation functionals 15 2.2 Density Functional Based Tight Binding method 16 2.2.1 Tight-binding formalism 17 2.2.2 From DFT to DFTB 20 2.2.3 Parametrization 22 2.3 Atomistic Green’s functions 23 2.3.1 Non-Equilibrium Green’s functions for modeling electronic transmission 23 2.3.2 Non-equilibrium Green’s function for modeling thermal transmission 27 3 Tuning the electronic and magnetic properties through chemical functionalization 3.1 Introduction 33 3.1.1 Black phosphorus as a 2D material 33 3.1.2 Chemical Functionalization of low dimensional systems 35 3.1.3 Bipolar Magnetic Semiconductors 36 3.2 Computational approach 38 3.3 Interface effects in phosphorene by OH functionalization 39 3.3.1 Single molecule functionalization 39 3.3.2 Lattice selection 43 3.3.3 Coverage 45 3.4 Chiral functionalization effect in phosphorene 48 3.5 Functionalizing phosphorene towards BMS 51 3.6 Summary 53 4 Tuning transport properties through strain and grain bound-aries 4.1 Introduction 54 4.1.1 Strain in low dimensional materials 54 4.1.2 Grain boundaries 56 4.2 Computational approach 58 4.2.1 Molecular systems 58 4.2.2 Electron and phonon transport and thermoelectric figure of merit 58 4.3 Structural modification by strain in GB systems 60 4.4 Electronic structure modification by strain in GB systems 63 4.5 Thermal transport modification by strain in GB systems 65 4.6 Thermoelectric figure of merit of strained GB systems 68 4.7 Summary 71 5 Tuning transport properties through hybrid nanomaterials: CNT peapods 73 5.1 Introduction 73 5.1.1 Carbon-based nanostructures 73 5.1.2 CNT peapods as hybrid nanomaterials 76 5.2. Computational details 77 5.2.1 CNT peapod model 77 5.2.2 Quantum transport methodology 78 5.3 Structural properties of CNT peapods 79 5.4 Electronic properties of CNT peapods 80 5.5 Thermal properties of CNT peapods 83 5.6 Thermoelectronic properties of CNT peapods 85 5.7 Summary 88 6 Conclusions and outlook 91 Appendices Appendix A Supplementary information to phosphorene functionalization A.1 Spin resolved density of states of 1-OH system 96 A.2 Spin valve model 97 Appendix B Supplementary information to phosphorene grain boundaries 98 B.1 Projected Phonon Density of States in GB1 98 B.2 Thermoelectric transport properties of GB2 99 Appendix C Supplementary information to CNT peapods 101 C.1 Geometry optimization of CNT peapods with larger CNT diameter 101 C.2 Additional analysis of electron transport properties 102 C.3 Phonon band structure of different CNT structures 104 C.4 Additional analysis of thermoelectric performance 105 REFERENCES 105 LIST OF PUBLICATIONS 131 PRESENTATIONS 132Die Kontrolle niedrigdimensionaler Materialien birgt das Potenzial für eine Revolutionierung der elektronischen, thermischen und thermoelektrischen Technologien. Durch strategische Manipulation und Optimierung dieser Materialien können einzigartige Eigenschaften aufgedeckt werden, die eine effizientere und effektivere Materialentwicklung ermöglichen. Um Strategien im Nanobereich zur Verbesserung elektronischer und phononischer Bauelemente zu ermitteln, wurden in dieser Forschungsarbeit rechnerische Simulationen modifizierter niedrigdimensionaler Materialien durchgeführt. Zunächst werden die elektronischen Eigenschaften von chemisch funktionalisierten Phosphoren-Monoschichten mit Hilfe der spinpolarisierten Dichtefunktionaltheorie als potenzielle Methode zur Abstimmung ihrer elektronischen Eigenschaften bewertet. Die Funktionalisierung führt nicht nur zur Bildung zusätzlicher Zustände innerhalb der halbleitenden Lücke, sondern auch zum Auftreten von lokalem Magnetismus. Der magnetische Grundzustand und die elektronische Struktur werden in Abhängigkeit von der molekularen Bedeckung, der Gitterrichtung der molekularen Adsorption und der Funktionalisierung des Moleküls untersucht. Darüber hinaus werden die Transporteigenschaften von Phosphoren-Korngrenzen unter uniaxialer Belastung mit Hilfe der auf Dichtefunktionen basierenden Tight-Binding-Methode in Kombination mit der Landauer-Theorie untersucht. In beiden Korngrenzentypen nimmt die elektronische Bandlücke unter Dehnung ab, die jeweilige Wärmeleitfähigkeit wird jedoch nur schwach beeinflusst, trotz ziemlich starker Änderungen in der frequenzaufgelösten Phononentransmission. Die Kombination bei der Effekte führt zu einer Erhöhung der thermoelektrischen Leistungszahl in den Phosphorkorngrenzensystemen. Schließlich werden die thermoelektrischen Eigenschaften von Kohlenstoffnanoröhren-Peapod-Heterostrukturen untersucht und mit denen von reinen Nanoröhren verglichen, wobei auch die auf Dichtefunktionen basierende Tight-Binding-Methode und die Landauer-Theorie verwendet werden. Es wird festgestellt, dass die Fullereneinkapselung die Elektronen- und Phononentransporteigenschaften modifiziert und die Bildung von elektronischen Kanälen und die Unterdrückung von Schwingungsmoden bewirkt, was zu einer Verbesserung der thermoelektrischen Leistungszahl führt. Die Ergebnisse dieser Arbeit verdeutlichen das Potenzial der strategischen Manipulation und Optimierung niedrigdimensionaler Materialien zur Verbesserung ihrer einzigartigen elektronischen und thermischen Eigenschaften und zeigen vielversprechende Wege zur Verbesserung elektronischer und phononischer Bauteile auf.:ABSTRACT i ZUSAMMENFASSUNG ii ACKNOWLEDGEMENT iv LIST OF FIGURES ix LIST OF TERMS AND ABBREVIATIONS xviii 1 Introduction 1 1.1 Motivation 1 1.2 Objectives and outline 6 2 Computational Methods 8 2.1 Density Functional Theory 8 2.1.1 The Many-Body System Hamiltonian and the Born-Oppenheimer approximation 9 2.1.2 Thomas-Fermi-Dirac approximation model 10 2.1.3 The Hohenberg-Kohn theorems 12 2.1.4 The Kohn-Sham orbitals equations 13 2.1.5 Exchange-correlation functionals 15 2.2 Density Functional Based Tight Binding method 16 2.2.1 Tight-binding formalism 17 2.2.2 From DFT to DFTB 20 2.2.3 Parametrization 22 2.3 Atomistic Green’s functions 23 2.3.1 Non-Equilibrium Green’s functions for modeling electronic transmission 23 2.3.2 Non-equilibrium Green’s function for modeling thermal transmission 27 3 Tuning the electronic and magnetic properties through chemical functionalization 3.1 Introduction 33 3.1.1 Black phosphorus as a 2D material 33 3.1.2 Chemical Functionalization of low dimensional systems 35 3.1.3 Bipolar Magnetic Semiconductors 36 3.2 Computational approach 38 3.3 Interface effects in phosphorene by OH functionalization 39 3.3.1 Single molecule functionalization 39 3.3.2 Lattice selection 43 3.3.3 Coverage 45 3.4 Chiral functionalization effect in phosphorene 48 3.5 Functionalizing phosphorene towards BMS 51 3.6 Summary 53 4 Tuning transport properties through strain and grain bound-aries 4.1 Introduction 54 4.1.1 Strain in low dimensional materials 54 4.1.2 Grain boundaries 56 4.2 Computational approach 58 4.2.1 Molecular systems 58 4.2.2 Electron and phonon transport and thermoelectric figure of merit 58 4.3 Structural modification by strain in GB systems 60 4.4 Electronic structure modification by strain in GB systems 63 4.5 Thermal transport modification by strain in GB systems 65 4.6 Thermoelectric figure of merit of strained GB systems 68 4.7 Summary 71 5 Tuning transport properties through hybrid nanomaterials: CNT peapods 73 5.1 Introduction 73 5.1.1 Carbon-based nanostructures 73 5.1.2 CNT peapods as hybrid nanomaterials 76 5.2. Computational details 77 5.2.1 CNT peapod model 77 5.2.2 Quantum transport methodology 78 5.3 Structural properties of CNT peapods 79 5.4 Electronic properties of CNT peapods 80 5.5 Thermal properties of CNT peapods 83 5.6 Thermoelectronic properties of CNT peapods 85 5.7 Summary 88 6 Conclusions and outlook 91 Appendices Appendix A Supplementary information to phosphorene functionalization A.1 Spin resolved density of states of 1-OH system 96 A.2 Spin valve model 97 Appendix B Supplementary information to phosphorene grain boundaries 98 B.1 Projected Phonon Density of States in GB1 98 B.2 Thermoelectric transport properties of GB2 99 Appendix C Supplementary information to CNT peapods 101 C.1 Geometry optimization of CNT peapods with larger CNT diameter 101 C.2 Additional analysis of electron transport properties 102 C.3 Phonon band structure of different CNT structures 104 C.4 Additional analysis of thermoelectric performance 105 REFERENCES 105 LIST OF PUBLICATIONS 131 PRESENTATIONS 13

Visible light assisted organosilane assembly on mesoporous silicon films and particles

Porous silicon (PSi) is a versatile matrix with tailorable surface reactivity, which allows the processing of a range of multifunctional films and particles. The biomedical applications of PSi often require a surface capping with organic functionalities. This work shows that visible light can be used to catalyze the assembly of organosilanes on the PSi, as demonstrated with two organosilanes: aminopropyl-triethoxy-silane and perfluorodecyl-triethoxy-silane. We studied the process related to PSi films (PSiFs), which were characterized by X-ray photoelectron spectroscopy (XPS), time of flight secondary ion mass spectroscopy (ToF-SIMS) and field emission scanning electron microscopy (FESEM) before and after a plasma patterning process. The analyses confirmed the surface oxidation and the anchorage of the organosilane backbone. We further highlighted the surface analytical potential of 13 C, 19 F and 29 Si solid-state NMR (SS-NMR) as compared to Fourier transformed infrared spectroscopy (FTIR) in the characterization of functionalized PSi particles (PSiPs). The reduced invasiveness of the organosilanization regarding the PSiPs morphology was confirmed using transmission electron microscopy (TEM) and FESEM. Relevantly, the results obtained on PSiPs complemented those obtained on PSiFs. SS-NMR suggests a number of siloxane bonds between the organosilane and the PSiPs, which does not reach levels of maximum heterogeneous condensation, while ToF-SIMS suggested a certain degree of organosilane polymerization. Additionally, differences among the carbons in the organic (non-hydrolyzable) functionalizing groups are identified, especially in the case of the perfluorodecyl group. The spectroscopic characterization was used to propose a mechanism for the visible light activation of the organosilane assembly, which is based on the initial photoactivated oxidation of the PSi matrixWe acknowledge MSC funding provided by the European Commission through FP7 grant THINFACE (ITN GA 607232) and by Ministerio de Economía y Competitividad through grant NANOPROST (RTC-2016-4776-1