United abominations: Density functional studies of heavy metal chemistry

The present work consists of chapters that are either in press, in preparation for submission, or previously unpublished. Chapter 2 is a study of carbonyl and nitrile addition to uranyl (UO22+). Chapter 3 investigates the competition between nitrile and water ligands in the formation of uranyl complexes. Chapter 4 examines the possibility of hypercoordinated uranyl with acetone ligands. Chapter 5 is a study of uranyl with diactone alcohol ligands as a means to explain the apparent hypercoordinated uranyl. A Discussion of the formation of mesityl oxide ligands is also included in chapter 5. Chapter 6 is a joint theory/experimental study of reactions of zwitterionic boratoiridium(I) complexes with oxazoline-based scorpionate ligands. Chapter 7 is a computational study of the catalytic hydroamination/cyclization of aminoalkenes with zirconium-based catalysts. Chapter 8 is a survey of techniques for programming for graphical processing units (GPUs) using Fortran. Chapter 9 is a discussion of the general conclusions drawn from the work presented in this dissertation

Theoretical Investigations on Adsorption of NO on Copper Exchanged Zeolites (Cu-ZSM-5)

Articlehttp://deepblue.lib.umich.edu/bitstream/2027.42/96967/1/UMURF-Issue03_2006-GSchoendorff.pd

The acceptance and commitment therapy matrix mobile app: A pilot randomized trial on health behaviors

Mobile apps provide a promising format for delivering acceptance and commitment therapy (ACT) to improve diet/exercise. This pilot trial evaluated a novel ACT-based app for health behaviors based on the matrix approach. A sample of 23 community adults were randomly assigned to use the app for two weeks or to a waitlist condition. Findings indicated a high degree of satisfaction with the app and acceptable adherence. Although the intent-to-treat sample indicated few intervention effects, when focusing on program engagers only, health behaviors significantly improved in the app condition relative to waitlist. There were no differences between conditions on valued action or experiential avoidance. However, the rate of valued actions increased over days using the app. This was moderated by baseline values and experiential avoidance, suggesting those more psychologically flexible benefit more from the matrix app. An ACT matrix app appears promising for improving health behaviors, but additional revisions and research is needed

Density Functional Studies on the Complexation and Spectroscopy of Uranyl Ligated with Acetonitrile and Acetone Derivatives

The coordination of nitrile (acetonitrile, propionitrile, and benzonitrile) and carbonyl (formaldehyde, acetaldehyde, and acetone) ligands to the uranyl dication (UO22+) has been examined using density functional theory (DFT) utilizing relativistic effective core potentials (RECPs). Complexes containing up to six ligands have been modeled in the gas phase for all ligands except formaldehyde, for which no minimum could be found. A comparison of relative binding energies indicates that 5-coordinate complexes are predominant, while 6-coordinate complexes involving propionitrile and acetone ligands might be possible. Additionally, the relative binding energy and the weakening of the uranyl bond is related to the size of the ligand, and in general, nitriles bind more strongly to uranyl than carbonyls

Actualización del tratamiento de la dermatitis atópica

Introducción. La dermatitis atópica (DA) es una enfermedad inflamatoria de la piel que se caracteriza por un intenso picor y apariciones de lesiones eczematosas. Aunque a menudo comienza en la infancia y puede afectar hasta tres de cada diez niños, es también una enfermedad que resulta frecuente en adultos. Existen diferentes clasificaciones según la severidad de las lesiones; a pesar de que en el mayor número de los casos la enfermedad es autorresolutiva, hay casos que no consiguen esta mejoría y alcanzan niveles de severidad que comprometen seriamente la calidad de vida del paciente. Objetivos. El objetivo principal del trabajo es llevar a cabo una revisión bibliográfica actualizada del tratamiento farmacológico al que se acude según las diferentes formas clínicas de la DA, profundizando en los mecanismos de acción, indicaciones, contraindicaciones y principales reacciones adversas de los fármacos que la integran, además de revisar otras medidas no farmacológicas. Metodología. Las bases de datos científicas empleadas fueron: PubMed, Fisterra, ClinicalTrials y diversas guías y páginas web de interés especializadas. Resultados. El tratamiento establecido para la DA se presenta de forma escalada dependiendo de la severidad y respuesta del eczema ante éste. Los principales fundamentos en los que se va a basar el tratamiento en casos leves de la enfermedad son la reparación continua de la barrera epidérmica con emolientes, la evitación de factores desencadenantes y la terapia antiinflamatoria con corticosteroides tópicos o inhibidores tópicos de la calcineurina (ITC). En casos severos, se puede llegar a indicar fototerapia o acudir a una terapia sistémica a base de fármacos inmunosupresores, corticosteroides orales y retinoides. El tratamiento sintomático del prurito y el control de las posibles infecciones también resultan claves para el manejo de la enfermedad, además de la introducción de medidas higiénico-dietéticas saludables. Conclusiones. A pesar de que existen alternativas terapéuticas que permiten mejorar los síntomas y lograr cierto control a largo plazo de la enfermedad, la DA en la actualidad carece de cura. La búsqueda de prometedores fármacos más selectivos, potentes, sencillos de usar y con mínimos o nulos efectos adversos resulta de gran interés ya que podrían cambiar completamente el panorama actual de la enfermedad.Universidad de Sevilla. Grado en Farmaci

El Dr. Carlos María Cortezo y su obra (1850-1933)

Fac. de MedicinaTRUEProQuestpu

A Randomized Controlled Trial of Multiple Versions of an Acceptance and Commitment Therapy Matrix App for Well-Being

Mobile apps may be useful in teaching psychological skills in a high-frequency, low-intensity intervention. The Acceptance and Commitment Therapy (ACT) matrix is a visual tool to help develop psychological flexibility by categorizing moment-to-moment experience and is well suited to a mobile app. This pilot study tested the effects of a simple and complex version of a novel app using the ACT matrix in two distinct samples: help-seeking individuals (n = 35) and students receiving SONA credit (n = 63). Findings indicated no differences between app conditions and a waitlist condition in the SONA credit sample. However, in the help-seeking sample improvements were found on well-being and valued action in participants who used the app, with greater improvements and app adoption for those using a complex version with additional skills. A mobile app based on the ACT matrix has benefits for help-seeking individuals, but supplementary features may be necessary to support consistent use and benefits

Gas Phase Computational Studies on the Competition between Nitrile and Water Ligands in Uranyl Complexes

The gas phase formation of uranyl dicationic complexes containing water and nitrile (acetonitrile, propionitrile, and benzonitrile) ligands, [UO2(H2O)m(RCN)n]2+, has been studied using density functional theory with a relativistic effective core potential to account for scalar relativistic effects on uranium. It is shown that nitrile addition is favored over the addition of water ligands. Decomposition of these complexes to [UO2OH(H2O)m(RCN)n]+ by the loss of either H3O+ or (RCN + H)+ is also examined. It is found that this reaction is competitive with the ligand addition when the coordination sphere of uranyl is unsaturated. Additionally, this reaction is influenced by the size of the nitrile ligand with reactions involving acetonitrile being the most prevalent. Finally, ligand addition to the monocation shows trends similar to that of the dication with energetic differences being smaller for the addition to the monocation

Quasi-Atomic Bond Analyses in the Sixth Period: I. Relativistic Accurate Atomic Minimal Basis Sets for the Elements Cesium to Radon

Full-valence relativistic accurate atomic minimal basis set (AAMBS) orbitals are developed for the sixth-row elements from cesium to radon, including the lanthanides. Saturated primitive atomic basis sets are developed and subsequently used to form the AAMBS orbitals. By virtue of the use of a saturated basis, properties computed based on the AAMBS orbitals are basis set independent. In molecules, the AAMBS orbitals can be used to construct valence virtual orbitals (VVOs) that provide chemically meaningful abinitio lowest unoccupied molecular orbitals (LUMOs) with basis set independent orbital energies. The optimized occupied molecular orbitals complemented with the VVOs form a set of full-valence molecular orbitals. They can be transformed into a set of oriented quasi-atomic orbitals (QUAOs) that provide information on intramolecular bonding via an intrinsic density analysis. In the present work, the development of the AAMBS for the sixth row is presented