Orientador: Jarbas José Rodrigues Rohwedder / Tese (doutorado) - Universidade Estadual de Campinas, Instituto de Química / Made available in DSpace on 2018-08-27T15:32:58Z (GMT). No. of bitstreams: 1 Santos_LiviaMartinsdos_D.pdf: 6212654 bytes, checksum: f20eb97ce2aae510654340b401468dd2 (MD5) Previous issue date: 2015 / Resumo: A contaminação de solos oriundos de derrames de compostos derivados do petróleo é um problema que representa riscos ao meio ambiente e a população. Dentre os constituintes do petróleo, os BTEX são os mais tóxicos. O uso da espectroscopia no infravermelho próximo (NIR) foi empregado como uma ferramenta analítica visando a determinação de BTEX em amostras de solo. À um espectrofotômetro construído no laboratório foi adaptado uma célula de medida, uma célula de amostra e uma válvula esfera responsável pela conexão entre essas duas células. Uma bomba de vácuo foi adaptada ao instrumento visando facilitar o enriquecimento da fase vapor dos hidrocarbonetos voláteis na célula de medida, a qual operou com uma pressão de 29,0 inHg abaixo da pressão do laboratório (APL). Os espectros obtidos da fase vapor contendo os hidrocarbonetos aromáticos apresentaram sobreposição de bandas de absorção. Desta forma, foi necessária a construção de modelos de calibração multivariados empregando Regressão por Mínimos Quadrados Parciais (PLS). Os resultados do melhor modelo de regressão obtidos a melhores condições experimentais mostraram que os valores de RMSECV foram de 12,4 mg kg-1, 47,3 mg kg-1, 72,4 mg kg-1 e 58,6 mg kg-1, respectivamente, para benzeno, tolueno, etilbenzeno e xilenos. Esses valores estão de acordo com os valores orientadores para solo da CETESB de 2005, com exceção para o benzeno que encontra-se acima do valor permitido. Para cada tipo de solo é necessário a construção de modelos de calibração, pois a composição do solo influencia na determinação dos hidrocarbonetos / Abstract: The contamination of soils due to petroleum compounds spills is a problem that represents risks to environment and population. Among petroleum constituents, the volatile aromatic hydrocarbons known as BTEX are toxic. This study aims to evaluate the use of near infrared spectroscopy as an analytical tool for determination of volatile hydrocarbons in soil samples. Spectra were obtained in a spectrophotometer built in the laboratory. It is also part of the instrument, a measuring cell with 540 mm of optical path, a sample cell and a valve which allows connection between the two cells. A vacuum pump was adapted to the instrument in order to facilitate enrichment of the vapor phase of the volatile hydrocarbons in the measuring cell, which operated at a pressure of 29.0 inHg below of the laboratory pressure (BLP). Spectra of the vapor phase containing aromatic hydrocarbons exhibited overlapping of absorption bands. Thus, it was necessary to construct multivariate calibration models using Partial Least Squares Regression (PLS). The results obtained for the calibration model provided values of RMSECV of 12.4 mg Kg¬-1, 47.3 mg Kg¬-1, 72.4 mg Kg¬-1 and 58.6 mg Kg¬-1 for benzene, toluene, ethylbenzene and xylenes, respectively. These values are in agreement with the 2005 CETESB guiding values for soil, except for benzene that is above the allowed value. For each type of soil, it was needed to build calibration models because soil composition affects the determination of hydrocarbons. The developed method is promising and may be used as a screening method to determine the occurrence of contamination in soils by BTEX / Doutorado / Quimica Analitica / Doutora em Ciências

Orientador: Ivo Milton Raimundo Júnior / Tese (doutorado) - Universidade Estadual de Campinas, Instituto de Química / Made available in DSpace on 2018-08-27T23:35:46Z (GMT). No. of bitstreams: 1 Fontes_LaianedeMoura_D.pdf: 2914385 bytes, checksum: 3a68971b696f9f31967f1132ab348427 (MD5) Previous issue date: 2015 / Resumo: Este trabalho descreve o desenvolvimento de diferentes fases extratoras para a determinação de hidrocarbonetos aromáticos e de íons metálicos em água. Para o desenvolvimento das fases extratoras de polidimetilsiloxano e nanotubos de carbono (PDMS-NTC), os nanotubos foram tratados com ácido nítrico, octadecilamina e hipoclorito de sódio. Este último produziu grupos carboxílicos na superfície do nanomaterial, aumentando sua afinidade por hidrocarbonetos aromáticos. A fase extratora foi preparada pela dispersão dos NTC no PDMS e, depois de pronta, inserida num frasco preenchido com as soluções aquosas dos analitos. Após 60 minutos sob agitação, a fase extratora foi removida da solução, seca e inserida em um sistema de medidas, empregando-se um espectrofotômetro FT-NIR. A fase extratora com NTC oxidados com NaOCl possibilitou um aumento da capacidade de extração de 40% e 20% para tolueno e benzeno, respectivamente. No segundo momento, foram desenvolvidas membranas poliméricas plastificadas utilizando os reagentes complexantes Br-PADAP e TAN para a determinação de cobre e chumbo em água por espectroscopia de emissão óptica com plasma induzido por laser (LIBS). As membranas de PVC não forneceram resultados satisfatórios como fase extratora, pois a homogeneidade e estabilidade da superfície das membranas não puderam ser estabelecidas de maneira satisfatória. Papel de filtro analítico foi utilizado como fase extratora para a pré-concentração de íons cobre e chumbo em meio aquoso de forma eficiente, superando as desvantagens das medidas diretas de líquidos por LIBS. A capacidade de adsorção do papel de filtro foi favorecida pela utilização de soluções básicas, principalmente, entre pH 8,0 e 9,0. O tempo de extração foi de 30 minutos para cobre e 60 minutos para chumbo. Os limites de detecção encontrados foram de 0,22 e 0,53 mg L-1 para cobre e chumbo, respectivamente. Não foi observada interferência dos íons Ni (II), Zn (II), Cd (II) e Fe(III), tampouco influência da força iônica. O método proposto foi utilizado para a determinação de cobre e chumbo em amostra de água de torneira enriquecida em três níveis de concentrações. Recuperações na faixa de 98,8% - 114,3% foram obtidas indicando que a determinação direta de íons cobre e chumbo em amostras aquosas pela técnica LIBS utilizando papel de filtro como fase extratora apresenta potencial para a análise de amostras reais / Abstract: This work describes the development of extraction phases for determination of aromatic hydrocarbons and metal ions in water. For development of the phase based on polydimethilsiloxane and carbon nanotubes (PDMS-NTC), carbon nanotubes were previously functionalized with nitric acid, octadecylamine and sodium hypochlorite. The latter oxidizing agent produced carboxyl groups on the surface of the nanomaterial, increasing its affinity for aromatic hydrocarbons. The extraction phase was prepared by dispersing the functionalized NTC in PDMS, which was polymerized to form cylindrical monoliths. Extractions were performed by immersing the monolith in a flask filled with the aqueous solutions of analytes, containing 2.0 mol L-1 NaCl. After an extraction time of 60 min under constant stirring, the monolith was removed from the flask, dried and inserted in the measuring cell of the FT-NIR spectrophotometer. The extraction phase containing NTC oxidized by sodium hypochlorite allow an increase of the sensitivity of 40% and 20% for toluene and benzene, respectively. In the second part, plasticized polymeric membranes containing Br-PADAP or TAN as complexing reagents were developed for determination of lead and copper in water by laser induced breakdown spectroscopy (LIBS). The PVC membranes did not provide satisfactory results, as the homogeneity and the stability of the membrane could not be attained. Analytical filter paper was then employed as an extraction phase to efficiently pre-concentrate lead and copper ions from aqueous solution, circumventing the disadvantages of direct measurements of liquid phase by LIBS. The sorption capacity of the filter paper was enhanced in basic solutions, mainly within pH 8.0 and 9.0. The ideal extraction time for Cu(II) was 30 minutes and 60 minutes for Pb(II). The detection limits were estimated as 0.22 and 0.53 mg L-1 for Cu(II) and Pb(II), respectively. Interference of Ni (II), Zn (II), Cd (II) and Fe(II) ions were not observed, as well as the influence of the ionic strength. The proposed method was employed for determination of cooper and lead in tap water fortified at three concentrations levels. Recoveries in the range from 98.8% to 114.3% were obtained, indicating that direct determination of these ions in aqueous samples by the LIBS using filter paper as an extraction phase has a potential for analysis of aqueous samples / Doutorado / Quimica Analitica / Doutora em Ciências

The postural control-cognition dual-task literature has demonstrated greater postural stability through the examination of multiple kinetic and kinematic measures. Recently, sample entropy (SampEn) and wavelet discrete transform have supported the claim of automaticity, as higher SampEn values and a shift toward higher contribution from automatic sensory systems have been demonstrated in dual-task settings. In order to understand the cortical component of postural control, functional near-infrared spectroscopy (fNIRS) has been used to identify cortical activation under postural control conditions. However, the neural correlates of automatic postural behaviour have yet to be fully investigated. Therefore, the purpose of this study is to confirm the presence of automatic postural control through static and dynamic measurements, and to investigate the prefrontal cortex activation (PFC) when concurrently performing quiet standing and auditory cognitive tasks. Eighteen healthy young adults (21,4 ± 3,96yo), 12 females and 6 males, with no balance deficits were recruited. Participants were instructed to either quietly stand on a force platform (SM), perform three cognitive tasks while seated (SC) and perform a combination of SM and SC concurrently (DT). Results revealed automatic postural control as evidenced by lower area and standard deviation of center-of-pressure in DT conditions. As for SampEn and the wavelet analysis, greater values and a shift from vision to the cerebellum contribution were demonstrated in DT conditions. For the DNS task, a trend toward significantly lower right hemisphere PFC activation compared to left hemisphere activation in DT was evidenced, which potentially reiterate the presence of automaticity. Therefore, as demonstrated by this experiment, the simultaneous performance of a difficult cognitive task and posture yields automatic postural behaviour, and provides insight into the neural correlates of automaticity.

京都大学 / 新制・課程博士 / 博士(情報学) / 甲第23543号 / 情博第773号 / 新制||情||132(附属図書館) / 京都大学大学院情報学研究科知能情報学専攻 / (主査)准教授 延原 章平, 教授 西野 恒, 教授 西田 眞也, 教授 佐藤 いまり(国立情報学研究所) / 学位規則第4条第1項該当 / Doctor of Informatics / Kyoto University / DFAM

Patients with atrial fibrillation (AF) require modification of ectopic electrical activity to avoid potentially fatal health complications. Catheter ablation therapy is a minimally invasive procedure to create tissue necrosis, called lesion, in areas of abnormal electrical activity. However, significant proportion of patients require repeat treatment from AF recurrences in part by electrical reconnection from incomplete lesions and conduction recovery. Current therapeutic approaches are limited by reliable methods to assess AF structural substrates and validate lesion sufficiency during procedures. In recent years, development of near-infrared optical spectroscopy has provided a non-invasive method to evaluate biological tissue. Near infrared spectroscopy (NIRS) is an optical technique that enables direct characterization of pathological tissue based on the absorption of major chromophores and light scattering. In this thesis, we explore the use of near-infrared optical spectroscopy to identify AF substrates and quantify lesion formation to improve treatment efficacy. First, we developed a near-infrared multispectral imaging system and present a model to assess lesion adequacy by direct visualization of cardiac lesions through an endoscope-integrated probe. Then, a custom single fiber integrated radiofrequency (RF) ablation catheter was fabricated to track irrigated lesion progression real-time on ex vivo swine hearts. A machine learning model was introduced to predict lesion size and transmurality. Additionally, we assess the feasibility of near-infrared spectroscopy by fabricating a NIRS-integrated open-irrigation RF ablation catheter and an algorithm to assess lesion dimensions based on key features derived from NIRS measurements. Using this model, we demonstrate real-time tracking of irrigated lesion delivery in both ex vivo and in vivo swine model. Lastly, we show left atrial endocardial mapping with NIRS-integrated RF mapping catheter to assess AF structural substrates. We present a classification algorithm for important AF structural substrates, such as pulmonary vein sleeve, normal myocardium, ablated tissue, and fibrosis, and a regression model to validate lesion adequacy. A near-infrared spectroscopy-based techniques to localize structural complexities and validate lesion sufficiency at the catheter tip could enhance the understanding of underlying AF substrates and improve treatment efficacy.

Inner speech has been implicated in Vygotsky´s theory of cognitive development. Converging evidence suggests that language skills as well as self-directed speech, in particular inner speech, is important for cognitive functions. However, the role of self-directed speech (including inner speech) in the relation between language skills and cognition have remained unclear. Despite a growing body of studies on the neural substrate of inner and overt speech, evidences of the neural differences between inner and overt speech have remained diffuse. The present dissertation aimed at filling the gap by investigating inner speech and its process of internalization with behavioral and neuroscientific methods. One study addressed the role of self-directed speech in the interplay between language skills and cognition by using the Tower of London task in children. Two studies addressed the neural correlates of the differences between inner and overt speech in adults and children during a picture-naming task by simultaneously applying the electroencephalography and functional near-infrared spectroscopy. The results of the first study confirmed that the internalization of speech is related to children´s cognition although it cannot explain the relation between language skills and problem-solving. The second study showed that inner speech is not overt speech without articulation, even more it is that prior phonological processes are downregulated. Moreover, the study showed that the brain differentiates between inner and overt speech even when no linguistic and motoric process is necessary. The results of the third study showed less differences between inner and overt speech in children indicating that inner speech is not yet adult-like. Even more it seems that inner speech represents linguistically the same like overt speech in the children´s brain.:Table of Content Danksagung VIII Bibliographische Darstellung X Zusammenfassung XI Summary XVI Theoretical Part 1 1 Introduction and Overview 2 1.1 Introduction 2 1.2 Theoretical Background 4 1.3 Development of Inner Speech 15 1.4 Behavioral Significance of Inner Speech 17 1.4.1 The Link between Inner Speech and Cognition 18 1.4.2 The Link between Inner Speech and Language 22 1.4.3 The Link between Language Skills and Cognition 23 1.5 Psycholinguistic and Biological Significance of Inner Speech 25 1.5.1 Speech Production Model 27 1.5.2 Differences between Inner and Overt Speech in the Brain 32 1.6 Overview of the Goals and Research Questions 42 2 Study Designs and Methodologies 46 2.1 Behavioral Methods 46 2.1.1 Tower of London 46 2.2 Neuroscientific Methods 51 2.2.1 Electroencephalography 52 2.2.1.1 Physiological Principles of the EEG 52 2.2.1.2 Technical Principles of the EEG 55 2.2.1.3 EEG Frequency Bands 57 2.2.1.4 Event-related Brain Potentials (ERPs) 58 2.2.2 Functional Near-Infrared Spectroscopy 59 2.2.2.1 Physical Principles of the fNIRS 59 2.2.2.2 Physiological Principles of the fNIRS 65 2.2.2.3 Technical Principles of the fNIRS - Measurement Setup 66 Empirical Part 68 Preliminary Note 69 3 Study 1 - The role of self-directed speech in problem-solving 70 3.1 Introduction 70 3.1.1 The Association between Language Skills and Executive Functions 71 3.1.2 The association between language skills and use of self-directed speech 72 3.1.3 The role of self-directed speech in Executive Functions 73 3.1.3.1 Quantitative and qualitative analysis of self-directed speech 73 3.1.3.2 Dual-task method 74 3.1.3.3 Triggering self-directed speech 75 3.2 The present study 76 3.3 Material and Method 78 3.3.1 Participants 78 3.3.2 General procedure 79 3.3.3 Measures 79 3.3.3.1 Language Skills 79 3.3.3.2 Receptive and Expressive Vocabulary 79 3.3.3.3 Expressive Grammar 80 3.3.3.4 Receptive Grammar 80 3.3.3.5 Non-verbal intelligence (IQ) 81 3.3.3.6 Complex EF (problem-solving ability) 81 3.3.4 Coding speech 84 3.3.4.1 Quantity 85 3.3.4.2 Quality: Internalization 85 3.3.4.3 Quality: Spatial language 86 3.3.4.4 Quality: Planning function 86 3.3.4.5 Quality: Grammatical completeness 87 3.3.4.6 Interrater reliability 87 3.4 Results 88 3.4.1 Preliminary analyses 88 3.4.1.1 Factor analysis 88 3.4.1.2 Bivariate Correlations between all study measures 88 3.4.2 Main analyses 90 3.4.2.1 H1: Relation between language skills and problem-solving 90 3.4.2.2 RQ: Role of self-directed speech 91 3.4.2.2.1 RQ1: Mediation effect of self-directed speech 91 3.4.2.2.2 RQ2: Susceptibility to articulatory suppression 95 3.4.2.2.3 RQ3: Prompting self-directed speech 96 3.5 Discussion 99 3.5.1 Limitations and Next Steps 105 3.5.2 Conclusion 107 4 Study 2 - Differences between inner and overt speech in adults 108 4.1 Introduction 108 4.2 Material and Method 114 4.2.1 Participants 114 4.2.2 Material 114 4.2.3 Tasks and Procedure 115 4.3 NIRS/EEG Data Recordings 117 4.3.1 fNIRS Data Recording 117 4.3.2 EEG Data Recording 118 4.4 Data analyses 119 4.4.1 fNIRS Data Analyses 119 4.4.2 EEG Data Analyses 120 4.5 Results 121 4.5.1 fNIRS results 121 4.5.2 EEG results 122 4.6 Discussion 127 4.7 Conclusions 131 5 Study 3 - Differences between inner and overt speech in children 133 5.1 Introduction 133 5.2 Material and Method 138 5.2.1 Participants 138 5.2.2 Material 139 5.2.3 Tasks and Procedure 139 5.3 NIRS/EEG Data Recordings 141 5.3.1 fNIRS Data Recording 141 5.3.2 EEG Data Recording 143 5.4 Data analyses 143 5.4.1 fNIRS Data: Analyses 143 5.4.2 EEG Data Analyses 144 5.5 Results 145 5.5.1 fNIRS results 145 5.5.2 EEG results 146 5.6 Discussion 146 5.7 Conclusion 150 6 General Discussion 151 6.1 What role does self-directed and inner speech play in the relation between language and cognition in children? 152 6.1.1 Quantitative and qualitative analyses of self-directed speech 152 6.1.2 Articulatory suppression of self-directed speech 155 6.1.3 Triggering self-directed speech 158 6.1.4 Conclusion 159 6.2 What distinguishes inner speech from external (overt) speech in adults? 160 6.2.1 Preparation phase 161 6.2.2 Execution phase 162 6.2.3 Conclusion 164 6.3 What distinguishes inner speech from external (overt) speech in children? 164 6.3.1 Preparation phase 165 6.3.2 Execution phase 167 6.3.3 Conclusion 169 6.4 Limitations and Future Research 169 6.5 Conclusion 176 7 References 179 Appendices 212 Coding Manual of Self-Directed Speech 213 Coding scheme 213 Coding Speech 214 Quantity of Private Speech 214 Quality of Private Speech 216 Speech Structure 216 Content Functions 218 Syntactic Features 221 Publications and Conference Contributions 222 Selbstständigkeitserklärung 225

Breast cancer is fast becoming the leading cause of mortality in women worldwide. As of this year, there are more than 3.1 million women with a history of breast cancer in the U.S., and about 41,760 women are expected to die from this disease. Neoadjuvant chemotherapy (NAC) has become a well-established therapy in the treatment of patients with locally advanced or primarily inoperable breast cancer. It consists of 3-9 months of drug treatment to shrink the tumor size before surgical removal of any remaining mass. A pathological complete response (pCR) is defined as complete disappearance of the tumor before surgery and correlates with 5-year overall survival of the treated patient. However, only 15-40% of subjects who undergo NAC will achieve a pCR, while the remaining patients do not benefit from a therapy that has considerable side effects. In this Ph.D. thesis, I explore the potential of diffuse optical tomography (DOT) for breast cancer imaging and NAC monitoring. The overall objective is two-fold. First, I seek to identify breast cancer patients who will not respond to NAC shortly after the initiation of a 5-9 months therapy regimen. Identifying these patients early will allow a switch to a more promising therapy and avoiding months of ineffective therapy with a drug regimen that has considerable side effects. Second, I use the optical data simultaneously obtained from the contralateral, non-tumor bearing breast to better understand the factors that modulate breast density and the source of its contrast in DOT. This work analyzed DOT data from 105 patients with stage II-III breast cancer under NAC regimen. Data processing and image analysis protocols were developed to more effectively evaluate static tissue contrast and dynamic functional imaging of the breast. Notably, we observed that there are differences in the time evolution of DOT features between pCR and non-pCR tumors under NAC, and DOT features can contribute to the successful prediction of pCR status from pretreatment imaging. Lastly, our analysis demonstrated a positive correlation between DOT feature and mammographic density classification, which could lead to research on the potential use of DOT as a predictor of breast cancer as well as an assessment tool to longitudinally evaluate the efficacy of chemoprevention strategies. These findings represent important steps towards the translation of DOT into current clinical workflow to contribute to better-personalized breast cancer therapies and breast cancer risk management.

Stereo vision is one of the most active research areas in computer vision. While hundreds of stereo reconstruction algorithms have been developed, little work has been done on the evaluation of such algorithms and almost none on evaluation on Near-Infrared (NIR) images. Of almost a hundred examined, we selected a set of 15 stereo algorithms, mostly with real-time performance, which were then categorized and evaluated on several NIR image datasets, including single stereo pair and stream datasets. The accuracy and run time of each algorithm are measured and compared, giving an insight into which categories of algorithms perform best on NIR images and which algorithms may be candidates for real-time applications. Our comparison indicates that adaptive support-weight and belief propagation algorithms have the highest accuracy of all fast methods, but also longer run times (2-3 seconds). On the other hand, faster algorithms (that achieve 30 or more fps on a single thread) usually perform an order of magnitude worse when measuring the per-centage of incorrectly computed pixels.

Photobiomodulation (PBM) therapy involves the irradiation of tissues with red to near- infrared (NIR) light at low power densities to stimulate healing, reduce inflammation, and promote optimal cellular functioning. These beneficial effects are thought to occur due to the absorption of NIR light by the chromophore, and terminal enzyme in the mitochondrial electron transport chain, cytochrome c oxidase (CCO). It is hypothesized that increased oxygen consumption due to the photostimulation of CCO, as well as photodissociation of the vasodilator nitric oxide from its binding site in the binuclear center of CCO, contribute to improved tissue healing by increasing blood flow to the irradiated region. Applied to the brain, PBM therapy has the potential to improve many neurological injuries and diseases for which reduced cerebral blood flow (CBF) is a common finding. This study examines whether cortical irradiation with NIR light has an impact on CBF in mice. Mice were administered brain PBM via 810nm, 190mW LED for 18 minutes. CBF was measured before, during, and after treatment using Doppler Optical Coherence Tomography. Results from 16 trials demonstrated a significant, 40% increase in CBF during NIR treatment. This CBF increase was not observed during control trials. Additionally, irradiation with a 730nm LED did not increase CBF, indicating that the blood flow increase observed with 810nm irradiation was not simply due to tissue heating. These findings provide support for the value of PBM therapy for the treatment of neurological conditions. / 2023-05-14T00:00:00Z

Background: Near-IR fluorescence (NIRF) imaging is becoming a promising approach in preclinical tumor detection and clinical image-guided oncological surgery. While heptamethine cyanine dye IR780 has excellent tumor targeting and imaging potential, its hydrophobic property limits its clinical use. In this study, we developed nanoparticle formulations to facilitate the use of IR780 for fluorescent imaging of malignant brain tumor. Methods: Self-assembled IR780-liposomes and IR780-phospholipid micelles were prepared and their NIRF properties were characterized. The intracellular accumulation of IR780-nanoparticles in glioma cells were determined using confocal microscopy. The in vivo brain tumor targeting and NIRF imaging capacity of IR780-nanoparticles were evaluated using U87MG glioma ectopic and orthotopic xenograft models and a spontaneous glioma mouse model driven by RAS/RTK activation. Results: The loading of IR780 into liposomes or phospholipid micelles was efficient. The particle diameter of IR780-liposomes and IR780-phospholipid micelles were 95 and 26nm, respectively. While stock solutions of each preparation were maintained at ready-to-use condition, the IR780-phospholipid micelles were more stable. In tissue culture cells, IR780-nanoparticles prepared by either method accumulated in mitochondria, however, in animals the IR780-phospholipid micelles showed enhanced intra-tumoral accumulation in U87MG ectopic tumors. Moreover, IR780-phospholipid micelles also showed preferred intracranial tumor accumulation and potent NIRF signal intensity in glioma orthotopic models at a real-time, non-invasive manner. Conclusion: The IR780-phospholipid micelles demonstrated tumor-specific NIRF imaging capacity in glioma preclinical mouse models, providing great potential for clinical imaging and image-guided surgery of brain tumors.