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Batteries play a pivotal role in the modern world, powering everything from portable electronics to electric vehicles, and are critical in the shift towards renewable energy sources by enabling efficient energy storage. This thesis presents new computational strategies to understand and predict surface degradation and stacking faults in battery cathodes, phenomena that have crucial impact on the battery lifetime. The starting point is a detailed first-principles analysis of LiNiO₂ surface degradation, assessing the thermodynamics of oxygen release and its impact on the surface integrity of this prospective cathode material. This research led to the development of a method for the automated enumeration of surface reconstructions and the development of a Python software package implementing the methodology, thereby greatly accelerating the computational surface characterization of electrode materials. The methodology made it feasible to extend the investigation to LiCoO₂ surfaces, comparing their oxygen retention and surface stability with LiNiO₂ and identifying the unique properties of the two transition metals that control their behavior during battery operation. In addition to surface phase changes, stacking faults are another important class of two-dimensional defects that can affect the properties of cathode materials. Combining information from first principles calculations with 17O nuclear magnetic resonance (NMR) spectroscopy provided by collaborators, we uncovered how stacking faults affect the capacity and cyclability of Li₂MnO₃ cathodes, a prototypical lithium-rich material with oxygen redox activity. Although automated first-principles calculations are, in principle, an ideal tool for understanding atomic-scale degradation phenomena in batteries, they are computationally demanding and, therefore, limited to materials with simple compositions. In the final chapter, we explore the application of machine learning for further accelerating computational battery degradation simulations by leveraging existing data first-principles calculations for predicting the stability of new surface reconstructions. This chapter points toward a new direction that should be further explored in the future. The research presented in this thesis not only advances the understanding of lithium-ion battery cathode materials but also introduces more-widely applicable computational methodologies that lay a foundation for the development of advanced materials for energy storage applications. This work demonstrates the benefits of integrating traditional computational methods with machine learning, contributing to ongoing progress in materials science and opening up new possibilities for advancements in energy technology and material engineering.

Thesis (DSc)--Stellenbosch University, 2012. / ENGLISH ABSTRACT: Examples of the use of NMR spectroscopy in the study of radical polymerization processes have been described. The studies presented have made a significant contribution to the understanding of the fundamental mechanistic processes in these polymerization systems. It is pointed out that NMR in conventional radical polymerization is of limited use due to the concurrent occurrence of all elementary reactions (initiation, propagation and termination). Conversely, for living radical polymerization, NMR has great value. In that case, the elementary reactions are somewhat more restricted to specific times of the polymerization process. This allows for example the detailed study of the early stages of chain growth in Reversible Addition-­‐Fragmentation Chain Transfer (RAFT) mediated polymerization. Two different studies are described. The first is related to the early stages of RAFT-­‐mediated polymerization. A process for which we coined the name initialization was studied via in situ 1H NMR spectroscopy. It is shown that in many cases, there is a selective reaction that converts the original RAFT agent into its single monomer adduct. A few different examples and their mechanistic interpretation are discussed. It is also shown that NMR spectroscopy can be a valuable tool for the assessment of a RAFT agent in conjunction with a specific monomer and polymerization conditions. In the second study, 15N NMR, 31P NMR and 1H NMR are used for two different types of experiments. The first is a conventional radical copolymerization in which the growing chains are trapped by a 15N labeled nitroxide to yield a stable product. In the second experiment, a similar copolymerization is conducted under nitroxide-­‐mediated conditions. The nitroxide of choice contains phosphorous, which enables the quantification of the terminal monomer in the dormant chains. Each of the experiments individually provides interesting information on conventional radical copolymerization and nitroxide-­‐mediated copolymerization, respectively. Combination of the experimental data reveals an interesting discrepancy in the ratio of terminal monomer units in active chains and dormant chains. Although not unexpected, this result is interesting and useful from a mechanistic as well as a synthetic point of view. In terms of future perspectives, it is expected that the advanced analytical techniques as described here will remain crucial in polymer science. Present developments in radical polymerization, such as investigations into monomer sequence control, rely on accurate knowledge of kinetic and mechanistic details of elementary reactions. It is expected that such detailed studies will be a main challenge for the next decade of polymer research. / AFRIKAANSE OPSOMMING: Voorbeelde van die gebruik van KMR-­‐spektroskopie in die studie van radikaalpolimerisasies word beskryf. Hierdie studies het ʼn beduidende bydrae gelewer tot die verstaan van die fundamentele meganistiese prosesse in hierdie polimerisasiesisteme. Dit het daarop gewys dat KMR beperkte gebruike het in konvensionele radikaalpolimerisasies as gevolg van die gelyktydige voorkoms van alle basiese reaksies (afsetting, voortsetting en beëindiging). Aan die anderkant het KMR groot waarde vir lewende radikaalpolimerisasie. In hierdie geval is die elementêre reaksies ietwat meer beperk tot spesifieke tye van die polimerisasieproses. Gedetailleerde studies kan byvoorbeeld van die vroeë stadiums van die kettinggroei in Omkeerbare Addisie-­‐Fragmentasie-­‐ KettingOordrag (OAFO)-­‐bemiddelde polimerisasie gedoen word. Twee verskillende studies is beskryf. Die eerste het betrekking op die vroeë stadiums van die OAFO-­‐bemiddelde polimerisasie. 'n Proses wat “inisialisering” genoem is, is bestudeer deur middel van in situ 1H KMR-­‐spektroskopie. Dit is bewys dat daar in baie gevalle 'n selektiewe reaksie is wat die oorspronklike OAFO-­‐agent in sy enkelmonomeeradduk verander voor polimerisasie. 'n Paar ander voorbeelde en hul meganistiese interpretasie is bespreek. Dit is ook bewys dat KMR-­‐spektroskopie 'n waardevolle hulpmiddel kan wees vir die assessering van 'n OAFO-­‐agent in samewerking met 'n spesifieke monomeer en polimerisasie toestande. In die tweede studie is 15N KMR, 31P KMR en 1H KMR gebruik vir twee verskillende tipes van die eksperiment. Die eerste is 'n konvensionele radikaalkopolimerisasie waarin die groeiende kettings vasgevang word deur 'n 15N-­‐gemerkte nitroksied om 'n stabiele produk te lewer. In die tweede eksperiment is 'n soortgelyke kopolimerisasie gedoen onder nitroksied-­‐ bemiddelde toestande. Die gekose nitroksied bevat fosfor wat die kwantifisering van die terminale monomeer in die dormante kettings moontlik maak. Elkeen van die individuele eksperimente lewer interessante inligting oor konvensionele radikale kopolimerisasie en nitroksied-­‐bemiddelde kopolimerisasie, onderskeidelik. ʼn Kombinasie van die eksperimentele data toon 'n interessante verskil aan in die verhouding van die terminale monomeereenhede in die aktiewe en sluimerende kettings. Alhoewel dit nie onverwags is nie, is die resultate interessant en van waarde vanuit 'n meganistiese-­‐ sowel as 'n sintetiese oogpunt. In terme van toekomstige perspektiewe word daar verwag dat gevorderde analitiese tegnieke soos hier beskryf, belangrik sal bly in polimeerwetenskap. Huidige ontwikkelinge in radikaalpolimerisasie, soos ondersoeke na die beheer van monomeervolgorde, maak staat op akkurate kennis van kinetiese en meganistiese besonderhede van die basiese reaksies. Daar word verwag dat sulke gedetailleerde studies ʼn uitdaging sal bied vir die volgende dekade van polimeernavorsing.

Abstract : Normal aging is accompanied by several metabolic and structural changes in the brain and a heightened risk of cognitive decline. These brain changes may increase the chances of later developing Alzheimer’s disease. The first major objective of the present work was to quantify, through positron emission tomography (PET) and volumetric magnetic resonance (MR) imaging techniques, the effects of normal aging on brain metabolism and structure. Our results indicate that brain glucose hypometabolism can be present in older individuals who remain cognitively normal. Cognitive status was assessed using age-normalised neuropsychological tests. Brain glucose hypometabolism was quite specific and affected primarily the prefrontal cortex and the caudate nucleus. Due to the high variation in plasma ketones, brain ketone hypometabolism per se was not present in older persons (≥65 years old). However, a lower rate constant for brain ketone uptake was fairly widespread in our healthy older group. Lower regional brain volume during normal aging was widespread throughout the cortex and was more apparent than cortical thickness loss. The second major objective was to characterize brain ketone and glucose metabolism in the context of mild Alzheimer’s disease. Glucose hypometabolism in Alzheimer’s disease was present in the temporoparietal cortex when compared with cognitively normal older adults. However, no significant differences in brain ketone metabolism or rate constant were found between the two groups. Alternative energy sources to glucose may therefore be beneficial to the Alzheimer’s disease brain, at least early in the disease process, in order to maintain neuronal capacity and limit synaptic loss and decline in memory and cognition. // Résumé : Au cours du vieillissement normal, le cerveau va subir plusieurs changements métaboliques et structuraux qui vont accroitre le risque de déclin cognitif et du fait même augmenter le risque de développer la maladie d’Alzheimer. Les objectifs du présent travail étaient de : 1) quantifier l’effet du vieillissement normal sur la structure et le métabolisme du cerveau, grâce aux techniquesd’imagerie tomographie par émission de positons et l’imagerie par résonance magnétique ; 2) caractériser le métabolisme cérébral des deux substrats énergétiques du cerveau, le glucose et les cétones, dans un contexte de la maladie d’Alzheimer. Nos résultats indiquent qu’un hypométabolisme du glucose est présent chez des personnes âgées (65 ans et plus) qui démontrent pourtant une cognition normale. Cette diminution du métabolisme cérébral du glucose est observée spécifiquement au niveau des régions du cortex préfrontal et du noyau caudé. Du fait d’une grande variabilité au niveau des concentrations plasmatiques en cétones, aucune diminution du métabolisme des cétones n’a été constatée chez les personnes âgées. En revanche, la constante de transfert des cétones au cerveau était globalement diminuée. En ce qui concerne l’atrophie cérébrale au cours du vieillissement normal, nous avons observé qu’elle était globale, qu’elle concerne l’ensemble du cerveau et qu’elle était plus marquée que la diminution de l’épaisseur corticale. En comparant des personnes âgées en bonne santé à des personnes ayant la maladie d’Alzheimer, nous avons également confirmé que chez ces dernières, le métabolisme du glucose est diminué spécifiquement au niveau du cortex temporopariétal. Cependant, aucune différence entre les deux groupes de personnes n’a été observée en ce qui concerne le métabolisme cérébral des cétones. Ainsi en fournissant des substrats énergétiques autres que le glucose, il serait donc possible de maintenir les capacités neuronales, limiter la perte synaptique et ralentir le déclin cognitif. Ceci pourrait constituer une stratégie prometteuse dans la prévention et le traitement complémentaire au début de la maladie d’Alzheimer.

O metaboloma é definido como a coleção qualitativa e quantitativa de todos os metabólitos de baixa massa molecular presentes nas células, os quais participam de reações bioquímicas necessárias para a manutenção, crescimento e fisiologia celular. A avaliação metabolômica permite o delineamento do processo bioquímico de sistemas a fim de ampliar o entendimento de como as patologias se manifestam. A Espectroscopia de Ressonância Magnética Nuclear (RMN) é usada para investigar uma variedade de processos biológicos em diversos sistemas. A magnética aplicada a células e biópsias de tecido intacto de melanoma murino B16F10 contribuiu para a caracterização bioquímica de biomarcadores das diferentes fases de progressão tumoral do melanoma murino B16F10. Os resultados obtidos neste estudo permitiram a identificação de 33 metabólitos possíveis, envolvidos na carga lipídica e no metabolismo secundário da via glicolítica, que favorecem o crescimento e a progressão tumoral. A presença da taurina, prolina, serina, fenilalanina, que aumentaram quantitativamente, são possíveis marcadores da invasão, progressão e metastatização. A análise quantitativa desses metabólitos mostrou diferença significativa em 11 compostos, dos quais 9 estão diretamente envolvidos na expressão das respostas proliferativas, de morte celular e angiogênese, nos diferentes períodos de crescimento do melanoma B16F10, avaliados neste estudo. Desta forma, os achados obtidos neste estudo, quando associados no futuro a outros fatores, poderão ser úteis no diagnóstico e auxiliar na escolha terapêutica alvo com maior especificidade e menores efeitos colaterais. RMN pode ter um importante impacto na monitorização de metabólitos em células e tecidos tumorais, possibilitando a detecção mais precoce de tumores malignos, em suma, através da combinação de métodos de ressonância magnética. / The metabolome is defined as the qualitative and quantitative collection of all low weight molecular metabolites in cells that participate in biochemical reactions necessary for the maintenance, growth and physiology of cell. The metabolomic evaluation allows the design of systems of biochemical process in order to broaden the understanding of how diseases manifest. The Nuclear Magnetic Resonance Spectroscopy (NMR) is used for investigating a variety of biological processes in several systems. The magnetics applied to cell and tissue biopsies intact murine melanoma B16F10 contributed to the biochemical characterization of biomarkers of different stages of tumor progression of murine melanoma B16F10. The results obtained in this study allowed the identification of 33 potential metabolites involved in lipid content in the secondary metabolism of the glycolytic pathway, which promote growth and tumor progression. The presence of taurine, proline, serine, phenylalanine, which quantitatively increased, is possibly markers of invasion and metastasis progression. Quantitative analysis of these metabolites showed a significant difference in 11 compounds, of which 9 are directly involved in the expression of proliferative responses, cell death and angiogenesis in different periods of growth of B16F10 melanoma, evaluated in this study. Thus, the findings from this study, when associated in the future with other factors, may be useful in the diagnosis and may assist in choosing therapeutic target with greater specificity and fewer side effects. NMR may have a significant impact on monitoring metabolites in tumor cells and tissues, allowing for earlier detection of malignant tumors; in short, by combining MRI methods.

A evolução da planície costeira do Estado de São Paulo foi influenciada por eventos de transgressões e regressões do mar durante o Quaternário e suas características resultam da interação da dinâmica dos processos geológicogeomorfológicos que agiram continuamente durante esses eventos. Os solos de maior ocorrência nesse ambiente, genericamente chamado de restinga, são os Espodossolos, caracterizados pela presença de horizonte espódico (Bh ou Bhm). São poucos os estudos científicos relacionadas à gênese destes solos em regiões tropicais, assim como há poucos estudos detalhados avaliando as características e a composição química da matéria orgânica (MO) presente nestes solos, bem como as suas relações com a transcorrência do tempo e as condições de drenagem. Os municípios paulistas de Cananéia e Bertioga foram selecionados para o desenvolvimento desta pesquisa devido à presença de diferentes unidades sedimentares e de vegetação remanescente. A caracterização dos ácidos húmicos (AH) extraídos dos horizontes dos diferentes perfis de Espodossolos com o emprego de técnicas espectroscópicas como Ressonância Magnética Nuclear (RMN) de 13C, Espectroscopia de Infravermelho com Transformada de Fourier (FTIR) e Fluorescência, bem como o fracionamento quantitativo das substâncias húmicas (SH), foram realizadas com o objetivo de se conseguir um maior detalhamento da matéria orgânica (MO) presente nesses solos e, a partir daí, relacionar os resultados com a estabilidade do carbono e o tempo de residência médio (TRM) da MO. A principal hipótese testada foi a de que os perfis com a MO com maior TRM teriam os maiores conteúdos de compostos mais recalcitrantes e as condições de drenagem dos perfis poderia interferir nas concentrações e características desses compostos. Neste âmbito, os principais resultados relacionados com os objetivos foram: (a) independente do perfil, os espectros de RMN de 13C dos AH apresentaram uma tendência de diminuição das porcentagens de alquil C e O-alifáticos e aumento de aromáticos, carboxílicos e carbonílicos em profundidade; (b) os perfis mais antigos foram os que apresentaram as maiores concentrações de compostos mais recalcitrantes, principalmente nos horizontes subsuperficiais (Bh e Bhm), essa inferência pode indicar que com a transcorrência do tempo a MO presente tende a sofrer alterações na sua composição e se tornar mais recalcitrante; (c) as condições de drenagem e a presença ou não de horizonte cimentado (Bhm) pode, de certa forma, estabelecer uma diferenciação na distribuição das frações húmicas ao longo dos perfis. / The evolution of the coastal plain of São Paulo State was influenced by transgressions and regressions events of the sea during the Quaternary and their characteristics result from the interaction of the dynamics of geologicalgeomorphological processes that acted continuously during these events. The soils of higher occurrence in this environment, generically called restinga, are Espodossolos, have characterized by the presence of spodic horizon (Bh or Bhm). Few scientific studies related to the genesis of these soils in tropical regions, as there are few detailed studies assessing the characteristics and chemical composition of organic matter (OM) present in these soils and their relations with the transcurrent time and conditions drainage. The municipalities of Cananéia and Bertioga were selected for this research due to the presence of different sedimentary units and the remaining vegetation. The characterization of humic acids (HA) extracted from different horizons of Espodossolos profiles with the use of spectroscopic techniques as Nuclear Magnetic Resonance (NMR) of 13C spectroscopy, Fourier Transform Infrared (FTIR) and Fluorescence, as well as the quantitative fractionation humic substance (HS) were conducted with the aim of achieving a greater detail of organic matter (OM) present in these soils and, thereafter, to relate the results with the stable carbon and the mean residence time (MRT) of OM. The main hypothesis tested was that the profiles with the OM with higher MRT would have the higher content of recalcitrant compounds and the drainage of the profiles could influence the concentrations and characteristics of these compounds. In this context, the main results related to the aims were: (a) regardless of the profile, the 13C NMR spectra of the HA showed a tendency to decrease the percentage of alkyl C and O-aliphatic and increased aromatic, carboxyl and carbonyl in depth; (b) older profiles showed the highest concentrations of the more recalcitrant compounds, especially in the subsurface horizons (Bh and Bhm), this inference may indicate that with the transcurrent time the OM tends to change in its composition and becomes more recalcitrant; (c) the drainage and the presence or absence of cemented horizon (Bhm) can somehow make a difference in the distribution of humic fractions along the profiles.

Proteins and DNA are essential to life as we know it and understanding their function is understanding their structure and dynamics. The importance of the latter is being appreciated more in recent years and has led to the development of novel interdisciplinary techniques and approaches to studying protein function. Three techniques to study protein structure and dynamics have been used and combined in different ways in the context of this thesis and have led to a better understanding of the three systems described herein. X-ray crystallography is the oldest and still arguably most popular technique to study macromolecular structures. Nuclear magnetic resonance (NMR) spectroscopy is a not much younger technique that is a powerful tool not only to probe molecular structure but also dynamics. The last technique described herein are molecular dynamics (MD) simulations, which are only just growing out of their infancy. MD simulations are computer simulations of macromolecules based on structures solved by X-ray crystallography or NMR spectroscopy, that can give mechanistic insight into dynamic processes of macromolecules whose amplitudes can be estimated by the former two techniques. MD simulations of the model protein GB3 (B3 immunoglobulin-binding domain of streptococcal protein G) were conducted to identify origins of discrepancies between order parameters derived from different sets of MD simulations and NMR relaxation experiments.The results highlight the importance of time scales as well as sampling when comparing MD simulations to NMR experiments. Discrepancies are seen for unstructured regions like loops and termini and often correspond to nanosecond time scale transitions between conformational substates that are either over- or undersampled in simulation. Sampling biases can be somewhat remedied by running longer (microsecond time scale) simulations. However, some discrepancies persist over even very long trajectories. We show that these discrepancies can be due to the choice of the starting structure and more specifically even differences in protonation procedures. A test for convergence on the nanosecond time scale is shown to be able to correct for many of the observed discrepancies. Next, MD simulations were used to predict in vitro thermostability of members of the bacterial Ribonuclease HI (RNase H) family of endonucleases. Thermodynamic stability is a central requirement for protein function and a goal of protein engineering is improvement of stability, particularly for applications in biotechnology. The temperature dependence of the generalized order parameter, S, for four RNase H homologs, from psychrotrophic, mesophilic and thermophilic organisms, is highly correlated with experimentally determined melting temperatures and with calculated free energies of folding at the midpoint temperature of the simulations. This study provides an approach for in silico mutational screens to improve thermostability of biologically and industrially relevant enzymes. Lastly, we used a combination of X-ray crystallography, NMR spectroscopy and MD simulations to study specificity of the interaction between Drosophila Hox proteins and their DNA target sites. Hox proteins are transcription factors specifying segment identity during embryogenesis of bilaterian animals. The DNA binding homeodomains have been shown to confer specificity to the different Hox paralogs, while being very similar in sequence and structure. Our results underline earlier findings about the importance of the N-terminal arm and linker region of Hox homeodomains, the cofactor Exd, as well as DNA shape, for specificity. A comparison of predicted DNA shapes based on sequence alone with the shapes observed for different DNA target sequences in four crystal structures when in complex with the Drosophila Hox protein AbdB and the cofactor Exd, shows that a combined ”induced fit”/”conformational selection” mechanism is the most likely mechanism by which Hox homeodomains recognize DNA shape and achieve specificity. The minor groove widths for all sequences is close to identical for all ternary complexes found in the different crystal structures, whereas predicted shapes vary between the different DNA sequences. The sequences that have shown higher affinity to AbdB in vitro have a predicted DNA shape that matches the observed DNA shape in the ternary complexes more closely than the sequences that show low in vitro affinity to AbdB. This strongly suggests that the AbdB-Exd complex selects DNA sequences with a higher propensity to adopt the final shape in their unbound form, leading to higher affinity. An additional AbdB monomer binding site with a strongly preformed binding competent shape is observed for one of the oligomers in the reverse complement strand of one of the canonical (weak) Hox-Exd complex binding site. The shape preference seems strong enough for AbdB monomer binding to compete with AbdB-Exd dimer binding to that same oligomer, suggested by the presence of both binding modes in the same crystal. The monomer binding site is essentially able to compete with the dimer binding site, even though binding with the cofactor is not possible, because its shape is very close to the ideal shape. A comparison of different crystal structures solved herein and in the literature as well as a set of molecular dynamics simulations was performed and led to insights about the importance of residues in the Hox N-terminal arm for the preference of certain Hox paralogs to certain DNA shapes. Taken together all these insights contribute to our understanding of Hox specificity in particular as well as protein-DNA interactions in general.

A evolução da planície costeira do Estado de São Paulo foi influenciada por eventos de transgressões e regressões do mar durante o Quaternário e suas características resultam da interação da dinâmica dos processos geológicogeomorfológicos que agiram continuamente durante esses eventos. Os solos de maior ocorrência nesse ambiente, genericamente chamado de restinga, são os Espodossolos, caracterizados pela presença de horizonte espódico (Bh ou Bhm). São poucos os estudos científicos relacionadas à gênese destes solos em regiões tropicais, assim como há poucos estudos detalhados avaliando as características e a composição química da matéria orgânica (MO) presente nestes solos, bem como as suas relações com a transcorrência do tempo e as condições de drenagem. Os municípios paulistas de Cananéia e Bertioga foram selecionados para o desenvolvimento desta pesquisa devido à presença de diferentes unidades sedimentares e de vegetação remanescente. A caracterização dos ácidos húmicos (AH) extraídos dos horizontes dos diferentes perfis de Espodossolos com o emprego de técnicas espectroscópicas como Ressonância Magnética Nuclear (RMN) de 13C, Espectroscopia de Infravermelho com Transformada de Fourier (FTIR) e Fluorescência, bem como o fracionamento quantitativo das substâncias húmicas (SH), foram realizadas com o objetivo de se conseguir um maior detalhamento da matéria orgânica (MO) presente nesses solos e, a partir daí, relacionar os resultados com a estabilidade do carbono e o tempo de residência médio (TRM) da MO. A principal hipótese testada foi a de que os perfis com a MO com maior TRM teriam os maiores conteúdos de compostos mais recalcitrantes e as condições de drenagem dos perfis poderia interferir nas concentrações e características desses compostos. Neste âmbito, os principais resultados relacionados com os objetivos foram: (a) independente do perfil, os espectros de RMN de 13C dos AH apresentaram uma tendência de diminuição das porcentagens de alquil C e O-alifáticos e aumento de aromáticos, carboxílicos e carbonílicos em profundidade; (b) os perfis mais antigos foram os que apresentaram as maiores concentrações de compostos mais recalcitrantes, principalmente nos horizontes subsuperficiais (Bh e Bhm), essa inferência pode indicar que com a transcorrência do tempo a MO presente tende a sofrer alterações na sua composição e se tornar mais recalcitrante; (c) as condições de drenagem e a presença ou não de horizonte cimentado (Bhm) pode, de certa forma, estabelecer uma diferenciação na distribuição das frações húmicas ao longo dos perfis. / The evolution of the coastal plain of São Paulo State was influenced by transgressions and regressions events of the sea during the Quaternary and their characteristics result from the interaction of the dynamics of geologicalgeomorphological processes that acted continuously during these events. The soils of higher occurrence in this environment, generically called restinga, are Espodossolos, have characterized by the presence of spodic horizon (Bh or Bhm). Few scientific studies related to the genesis of these soils in tropical regions, as there are few detailed studies assessing the characteristics and chemical composition of organic matter (OM) present in these soils and their relations with the transcurrent time and conditions drainage. The municipalities of Cananéia and Bertioga were selected for this research due to the presence of different sedimentary units and the remaining vegetation. The characterization of humic acids (HA) extracted from different horizons of Espodossolos profiles with the use of spectroscopic techniques as Nuclear Magnetic Resonance (NMR) of 13C spectroscopy, Fourier Transform Infrared (FTIR) and Fluorescence, as well as the quantitative fractionation humic substance (HS) were conducted with the aim of achieving a greater detail of organic matter (OM) present in these soils and, thereafter, to relate the results with the stable carbon and the mean residence time (MRT) of OM. The main hypothesis tested was that the profiles with the OM with higher MRT would have the higher content of recalcitrant compounds and the drainage of the profiles could influence the concentrations and characteristics of these compounds. In this context, the main results related to the aims were: (a) regardless of the profile, the 13C NMR spectra of the HA showed a tendency to decrease the percentage of alkyl C and O-aliphatic and increased aromatic, carboxyl and carbonyl in depth; (b) older profiles showed the highest concentrations of the more recalcitrant compounds, especially in the subsurface horizons (Bh and Bhm), this inference may indicate that with the transcurrent time the OM tends to change in its composition and becomes more recalcitrant; (c) the drainage and the presence or absence of cemented horizon (Bhm) can somehow make a difference in the distribution of humic fractions along the profiles.