Desarrollo de interfaces de electrodos para la detección electroquímica de Bisfenol A: Estudio teórico

JAZMIN DELGADO AVILEZ (2023, [Tesis de maestría])

El bisfenol A (BPA), es un contaminante de origen industrial presente en efluentes y

aguas naturales, que representa un alto riesgo para el entorno ambiental y para la salud humana debido a su inherente toxicidad y su limitada capacidad de degradación. En este contexto, los sensores electroquímicos, generalmente basados en electrodos de carbono, son herramientas fundamentales con el propósito de detectar y cuantificar esta molécula. Sin embargo, estos dispositivos enfrentan desafíos sustanciales derivados de la inactivación electroquímica, un fenómeno atribuido a la formación de una capa aislante o polimerización durante el proceso de detección. La descripción de los mecanismos de reacción BPA/superficie del electrodo puede ser útil para identificar los sitios activos y contribuir a la elucidación del proceso de polimerización.

En esta investigación, se implementó un estudio teórico mediante Teoría de Funcionales de la Densidad (DFT) con el propósito de analizar con profundidad las interacciones entre el BPA en sus diversos estados de oxidación: oxidada (O), reducida (R) y monoprotonada (r*) y materiales de carbono. A tal efecto, se empleó el grafeno funcionalizado (plano basal, borde tipo silla y zigzag) como modelo representativo de la superficie del electrodo. Finalmente se evalúan las posibilidades de la dimerización del BPA o polimerización sobre varios grupos funcionales. El objetivo principal radica en la detección de grupos funcionales específicos que puedan inducir procesos secundarios, los cuales actúan como obstáculos para la eficaz detección electroquímica del BPA. La información resultante se instituye como un recurso valioso con miras al diseño y la optimización de sensores electroquímicos con un desempeño más robusto y sofisticado.

A continuación, se detalla la sinopsis general de este trabajo describiendo cada capítulo y las etapas involucradas en el estudio del modelo teórico de DFT para el sistema de reacción BPA/superficie del electrodo.

Capítulo 1. Estado del arte tanto de los usos industriales como las implicaciones

ambientales asociadas al Bisfenol A. Una de las problemáticas que se destacan es la necesidad de una detección precisa de esta molécula mediante sensores electroquímicos cuya limitación es la inactivación que presentan. También se describe la justificación del trabajo, así como el uso del modelo computacional, además de los objetivos y la hipótesis del mismo.

Capítulo 2. Descripción de los fundamentos teóricos basados en primeros principios, de la Teoría de Funcionales de la Densidad (DFT), con un enfoque especial en las aproximaciones para desarrollar modelos representativos que optimicen el tiempo de cálculo. Además, se detallan las características de la estructura y la superficie de los materiales de carbono considerados en el proceso de modelado.

Capítulo 3. Detalle del proceso de construcción del modelo de superficie para el estudio de las interacciones BPA/superficie del electrodo, donde se empleó el modelo del plano basal,así como los bordes tipo silla y zigzag del grafeno, con funcionalizaciones que incluyen COOH, OH, éter, epóxido, cetona y terminaciones de hidrógeno.

Bisphenol A (BPA) is a contaminant of industrial origin present in effluents and natural waters. It represents a high environmental and human health risk due to its inherent toxicity and limited degradation capacity. In this context, electrochemical sensors, generally based on carbon electrodes, are fundamental to detecting and quantifying this molecule. However, these devices face substantial challenges from electrochemical inactivation, a phenomenon attributed to forming an insulating layer or polymerization during the sensing process. The description of the BPA/electrode surface reaction mechanisms can be helpful to identify the active sites and contribute to the elucidation of the polymerization process.

In this research, a theoretical study was implemented using Density Functional Theory (DFT) to analyze in depth the interactions between BPA in its various oxidation states: oxidized (O), reduced (R), and monoprotonated (r*) and carbon materials. For this purpose, functionalized graphene (basal plane, saddle edge, and zigzag) was used as a representative model of the electrode surface. Finally, the possibilities of BPA dimerization or polymerization on various functional groups are evaluated. The main objective is detecting specific functional groups that can induce secondary processes, which act as obstacles to the effective electrochemical detection of BPA. The resulting information is a valuable resource for designing and optimizing electrochemical sensors with more robust and sophisticated performance.

The general synopsis of this work is detailed below, describing each chapter and the

stages involved in the study of the theoretical DFT model for the BPA/electrode surface reaction system.

Chapter 1. State of the art of industrial uses and the environmental implications associated with Bisphenol A. One of the problems that stands out is the need for precise detection of this molecule using electrochemical sensors, whose limitation is the inactivation they present. The justification of the work is also described, as well as the use of the computational model, in addition to its objectives and hypothesis.

Chapter 2. Description of the theoretical foundations based on first principles of Density Functional Theory (DFT), focusing on approaches to develop representative models that optimize calculation time. Additionally, the structure and surface characteristics of the carbon materials considered in the modeling process are detailed.

Chapter 3. Detail of the construction process of the surface model for the study of BPA/electrode surface interactions, where the basal plane model was used, as well as the chair- type and zigzag edges of graphene, with functionalizations that include COOH, OH, ether, epoxide, ketone, and hydrogen endings.

INGENIERÍA Y TECNOLOGÍA CIENCIAS TECNOLÓGICAS Oxidación de fenoles, Teoría de funcionales de la densidad (DFT), electrodos de carbono, desactivación electroquímica, Bisfenol A (BPA). Phenol oxidation, Density Functional Theory (DFT), carbon electrodes, electrochemical deactivation, Bisphenol A (BPA).

Diluted density. Urban planning in the Monterrey Metropolitan Area

Sheila Ferniza Quiroz Jesús Manuel Fitch Osuna (2021, [Artículo, Artículo])

The Monterrey Metropolitan Area (mma) in Northern Mexico has had an expansive and dispersed growth in recent decades. In 35 years, the city doubled its population and grew 8 times in territory (Secretariat for Sustainable Development, 2020). As a mitigation measure and with the objective of repopulating the areas within the city, urban regulations have been promoted that allow higher density and building potentials in some municipalities; however, the efforts are isolated and without metropolitan coordination. What are the urban regulation guidelines in the municipalities of the mma? How dense are its municipalities? Where are located the densest areas of the city? The objective of this research is to establish the current state of local regulation regarding urban development and to map the housing density to identify the locations with the lowest and highest density at the mma. The gross density at the Ageb scale is mapped for the 18 municipalities of the mma through the QGis software; data from the Inegi 2020 National Population and Housing Census is used. It is found that the peripheral municipalities of recent incorporation to the mma, unlike those of greater urbanization, lack urban development plans, and that most of the municipalities do not have updated regulations based on the current laws. The areas with the highest density are located in the peripheral municipalities, associated with the construction of low-income mass housing, and those with the lowest density in interior municipalities in areas of higher socioeconomic status, diluting the small efforts of densification in the city.

density urban sprawl urban planning densidad expansión urbana planeación urbana HUMANIDADES Y CIENCIAS DE LA CONDUCTA HUMANIDADES Y CIENCIAS DE LA CONDUCTA

Monitoreo con drones en gráficas con viento dinámico

Jovanni Manuel López Elisea (2024, [Tesis de maestría])

108 páginas. Maestría en Optimización.

Dada una gráfica completa no dirigida, se desea recorrer un subconjunto de sus aristas usando una flotilla de drones. Los drones tienen baterías limitadas que pueden recargarse al regresar a la base y, en principio, el tiempo para recorrer una arista está en función de la distancia entre sus vértices. Sin embargo, ante la presencia de viento el tiempo de recorrer una arista puede depender del sentido en el que se haga. La dificultad del problema aumenta si además la intensidad del viento puede variar de un instante a otro. En esta tesis se aborda el problema anteriormente descrito para el caso particular en el que los vértices son puntos en el plano, el impacto del viento en los tiempos de recorrido de las aristas está relativamente acotado y el subconjunto de las aristas a recorrer inducen un árbol que abarca todos los vértices excepto la base de los drones. Dado que los drones operan simultáneamente y pueden recorrer distintas partes de la gráfica de manera independiente, se desea minimizar el tiempo que emplea el dron con el recorrido más tardado. Esta tesis presenta un modelo matemático para resolver el problema de manera exacta, así como tres heurísticas diferentes para obtener buenas soluciones factibles. La primera de estas heurísticas transforma una solución sin viento y sin batería en una solución con viento y batería. La segunda heurística es un algoritmo glotón sin comunicación entre los drones y la última heurística también es un algoritmo glotón, pero con comunicación entre los drones. Aunque el problema abordado resulta ser lo suficientemente difícil como para que su resolución exacta sea inviable en la práctica, las heurísticas diseñadas son fáciles de implementar y obtuvieron resultados razonables en un tiempo corto de cómputo.

Drone aircraft--Control systems. Drone aircraft--Mathematical models. Mathematical optimization. Heuristic programming. Dynamical systems. Graph theory. Micro vehículos aéreos. Optimización matemática. Programación heurística. Teoría de grafos. TL589.4 CIENCIAS FÍSICO MATEMÁTICAS Y CIENCIAS DE LA TIERRA MATEMÁTICAS INVESTIGACIÓN OPERATIVA DISTRIBUCIÓN Y TRANSPORTE

Optimizing nitrogen fertilizer and planting density levels for maize production under current climate conditions in Northwest Ethiopian midlands

Kindie Tesfaye Dereje Ademe Enyew Adgo (2023, [Artículo])

This study determined the most effective plating density (PD) and nitrogen (N) fertilizer rate for well-adapted BH540 medium-maturing maize cultivars for current climate condition in north west Ethiopia midlands. The Decision Support System for Agrotechnology Transfer (DSSAT)-Crop Environment Resource Synthesis (CERES)-Maize model has been utilized to determine the appropriate PD and N-fertilizer rate. An experimental study of PD (55,555, 62500, and 76,900 plants ha−1) and N (138, 207, and 276 kg N ha−1) levels was conducted for 3 years at 4 distinct sites. The DSSAT-CERES-Maize model was calibrated using climate data from 1987 to 2018, physicochemical soil profiling data (wilting point, field capacity, saturation, saturated hydraulic conductivity, root growth factor, bulk density, soil texture, organic carbon, total nitrogen; and soil pH), and agronomic management data from the experiment. After calibration, the DSSAT-CERES-Maize model was able to simulate the phenology and growth parameters of maize in the evaluation data set. The results from analysis of variance revealed that the maximum observed and simulated grain yield, biomass, and leaf area index were recorded from 276 kg N ha−1 and 76,900 plants ha−1 for the BH540 maize variety under the current climate condition. The application of 76,900 plants ha−1 combined with 276 kg N ha−1 significantly increased observed and simulated yield by 25% and 15%, respectively, compared with recommendation. Finally, future research on different N and PD levels in various agroecological zones with different varieties of mature maize types could be conducted for the current and future climate periods.

Maize Model Planting Density CIENCIAS AGROPECUARIAS Y BIOTECNOLOGÍA MAIZE MODELS SPACING NITROGEN FERTILIZERS YIELDS

Abduction according to Peirce: reflections from the south on the crisis of representation brought on by COVID-19

Paulina Aroch (2023, [Artículo, Artículo])

In this article, I reflect on the importance of abductive thinking for processes of material and conceptual reinvention in the context of the current public health crisis. Inseparable from the climate change engulfing the planet, this crisis provides the basis for a semiotic revolution. Therefore, I interrogate Peirce’s work without losing sight of my own time and place of interlocution. COVID-19 has brought with it a crisis of representation which, in contrast to that unleashed by the Holocaust and World War II, and to which the Frankfurt School responded, demands responses from the Global South. Beginning from Dussel’s call to defend life as a matter of ethical urgency in the face of its irresponsible objectification within colonial capitalist modernity –which arguably triggered the pandemic–, I trace a “nocturnal map” that registers the present meaning-making crisis, and allows for a reimagining and remaking of the world from elsewhere.

estudios de la comunicación semiótica crítica Sur Global crisis de representación COVID-19 HUMANIDADES Y CIENCIAS DE LA CONDUCTA HUMANIDADES Y CIENCIAS DE LA CONDUCTA Critical theory interdisciplinarity Global South crisis of representation

Comparison of sequencing-based and array-based genotyping platforms for genomic prediction of maize hybrid performance

XUECAI ZHANG Zefeng Yang Yang Xu (2022, [Artículo])

Genotyping by Sequencing Genomic Selection SNP Array Marker Density CIENCIAS AGROPECUARIAS Y BIOTECNOLOGÍA MARKER-ASSISTED SELECTION MAIZE SINGLE NUCLEOTIDE POLYMORPHISM HYBRIDS

Accumulation of wheat phenolic acids under different nitrogen rates and growing environments

Wenfei Tian Yong Zhang Zhonghu He (2022, [Artículo])

Functional Wheat Trans-Ferulic Acid Nitrogen Management Environment Interaction CIENCIAS AGROPECUARIAS Y BIOTECNOLOGÍA WHEAT PHENOLIC ACIDS NITROGEN ENVIRONMENT ANTIOXIDANTS

Bacterial communities in the rhizosphere at different growth stages of maize cultivated in soil under conventional and conservation agricultural practices

Yendi Navarro-Noya Bram Govaerts Nele Verhulst Luc Dendooven (2022, [Artículo])

Farmers in Mexico till soil intensively, remove crop residues for fodder and grow maize often in monoculture. Conservation agriculture (CA), including minimal tillage, crop residue retention and crop diversification, is proposed as a more sustainable alternative. In this study, we determined the effect of agricultural practices and the developing maize rhizosphere on soil bacterial communities. Bulk and maize (Zea mays L.) rhizosphere soil under conventional practices (CP) and CA were sampled during the vegetative, flowering and grain filling stage, and 16S rRNA metabarcoding was used to assess bacterial diversity and community structure. The functional diversity was inferred from the bacterial taxa using PICRUSt. Conservation agriculture positively affected taxonomic and functional diversity compared to CP. The agricultural practice was the most important factor in defining the structure of bacterial communities, even more so than rhizosphere and plant growth stage. The rhizosphere enriched fast growing copiotrophic bacteria, such as Rhizobiales, Sphingomonadales, Xanthomonadales, and Burkholderiales, while in the bulk soil of CP other copiotrophs were enriched, e.g., Halomonas and Bacillus. The bacterial community in the maize bulk soil resembled each other more than in the rhizosphere of CA and CP. The bacterial community structure, and taxonomic and functional diversity in the maize rhizosphere changed with maize development and the differences between the bulk soil and the rhizosphere were more accentuated when the plant aged. Although agricultural practices did not alter the effect of the rhizosphere on the soil bacterial communities in the flowering and grain filling stage, they did in the vegetative stage.

Community Assembly Functional Diversity Intensive Agricultural Practices Plant Microbiome CIENCIAS AGROPECUARIAS Y BIOTECNOLOGÍA SUSTAINABLE AGRICULTURE TILLAGE SOIL BACTERIA MAIZE

Multi-trait, multi-environment deep learning modeling for genomic-enabled prediction of plant traits

Osval Antonio Montesinos-Lopez Jose Crossa Francisco Javier Martin Vallejo (2018, [Artículo])

Deep Learning Genomic Prediction Bayesian Modeling Shared Data Resources CIENCIAS AGROPECUARIAS Y BIOTECNOLOGÍA BAYESIAN THEORY RESOURCES DATA BREEDING PROGRAMMES

Efficacy of pre- and post-emergence herbicide combinations on weed control in no-till mechanically transplanted rice

PRATEEK MADHAB BHATTACHARYA Apurba Chowdhury Tapamay Dhar Md. Saiful Islam Alison Laing Mahesh Gathala (2022, [Artículo])

Mechanized Transplanted Rice Weed Biomass Weed Density Weed Control Efficiency CIENCIAS AGROPECUARIAS Y BIOTECNOLOGÍA HERBICIDES WEED CONTROL RICE ZERO TILLAGE MECHANIZATION