This thesis deals with preparation of organic molecular thin film compounds and its properties like morphology and purity. The vapour deposition was used for thin films preparation, because used materials are very few soluble. Thin films properties were characterized with the infrared spectroscopy (FTIR) and scanning electron microscope. There are described basics of infrared spectroscopy, spectra measurement and interpretation in the theoretical part. Process of thin film preparation is also described in this part. In the experimental part are described used vacuum technology and measuring instruments, process of sample measurement and there is the list of studied materials. 12 derivates of diketopyrrolopyrrols (DPP) were studied in this thesis. Diketopyrrolopyrroles (DPP) and its derivates have interesting chemical and physical properties, expecting wide range of applications, especially in electronics industry.

Interaction of metallic structures with electromagnetic radiation is a living topic of near-field optics including plasmonics and nanophotonics. The field-matter interaction treated on the subwavelength scale opens the path to a wide range of applications, among others to different variants of the surface enhanced spectroscopy. In this thesis we theoretically describe how the near-field properties of the metallic structures can be accessed by a probe of near-field scanning optical microscope. Formation of the signal in the near-field microscopy utilizing weakly interacting probes is discussed. Further, we elucidate the mechanism of the surface enhanced infrared spectroscopy. We utilize a model example of linear dipole antennas interacting with sample structures. A close connection is found between the spectroscopic signal and signal of the scattering type near-field optical microscopy.

The dissertation thesis submitted deals with the study of dielectric properties of epoxy nanocomposites containing nanoparticles of inorganic oxides. These nanocomposites may have a promising technologic application for electric insulations in view of their higher resistance against partial discharges; yet information about their behavior in the course of ageing is not available. If at least a partial mass replacement of the currently used epoxy insulation with nanocomposite-based insulations is due to occur, the knowledge of the changes of their dielectric properties in the course of their operation will become indispensable. Within the framework of this dissertation, ensembles of samples of epoxy resins without fillers and with Al2O3, WO3, TiO2 and SiO2 fillers in the form of nanopowders, in concentrations up to 12 wt %, have been prepared. These ensembles have been measured prior to ageing and exposed to long-time (up to 5000 hours) ageing at increased temperatures 200, 250 and 300 °C and in a few cases also at 330 and 360 °C. Samples were measured in the course of ageing roughly in a logarithmic time series after 1, 2, 5, 10, 20, 50, 100, 200, 500, 1000, 2000 and 5000 hours. The measured quantities included complex permittivity , internal resistivity i and loss factor tan at temperatures ranging from -153 °C to +167 °C and in the frequency range 10-2 – 106 Hz. Changes in nanocomposites have been investigated using not just dielectric spectroscopy measurements, but other methods, too, namely Fourier-transformed infrared spectroscopy (FTIR), thermogravimetric analysis (TGA), differential scanning calorimetry (DSC) and scanning electron microscopy (SEM). The experiments have proved that materials with different fillers respond to the same concentrations of various fillers in different ways. The addition of nanoparticles, without the addition of microparticles, at a relatively low concentration (max 12 wt %), was not sufficient for reaching fundamental changes in dielectric spectrum; only smaller changes of dielectric strength and shifts of relaxations and in relaxation maps have occurred. Out of more pronounced changes, increase of concentration of the SiO2 filler in the epoxy matrix brings about a decrease of electrical conductivity in the resulting nanocomposite. The TiO2 filler had a different impact. Different TiO2 concentrations make their marked appearance in the region between the relaxation and relaxation. The TiO2-filled nanocomposites do not exhibit the unambiguous dependence of electrical conductivity on nanofiller concentration. It can be concluded that the mere addition of nanoparticles, without the addition of established microparticles, does not change the dielectric spectrum substantially. Generally, a serious problem was the production of the nanocomposite with a uniform distribution of nanoparticles. The preparation of such a nanocomposite was not trivial and, in industrial applications, this issue will require a specific focus, so as to avoid the formation of undesirable aggregates. Within the framework of this research, a methodology for the production of an epoxy nanocomposite has been developed with as high as possible uniformity of nanoparticle distribution.

This thesis deals with a summary of individual method for determining of hyaluronan concentration, especially in aqueous solutions. Selected methods were compared to their functionality in university workplace. Any functional methods may be used for many purposes in university workplace in research of materials based on hyaluronan. It has been studied usability to assess residual content of hyaluronan in supernatant of gel formed from hyaluronan and surfuctant, in this thesis. We choosed sptectrophotometric methods, especially with UV spectroscopy and IR spectroscopy. Two precipitation methods using alcian blue were also tested. As the most reliable, the least demanding and specific method seems to be the method using IR spectroscopy, thanks to it we are able to determine the concentration of HA from 0.01 %. With this method, it has been found, that if there will be located some amount of HA in supernatant, it will be below the detection limit of assay. The remanining methods were modified to help determine the concentrations of HA, but works only in aqueous solutions. A possible variation for determination of very low concentrations of HA may be the method using ELISA kits. However their cost is higher than the above-mentioned methods.

Cell penetrating peptides (CPPs) are short sequences of amino acids that excel in crossing the cellular membrane without inducing cytotoxicity Interest in these peptides stem from their ability to be attached, and grant their penetrating properties to, a variety of cargo In this work we have combined the application of Confocal Raman Microscopy (CRM) and Atomic Force Microscopy for the first time to examine the interactions of unlabeled Transportan (TP), one of the most well studied CPPs, with mammalian cells CRM’s capability to discriminate control and treated cell groups was verified by principal component analysis (PCA) and linear discriminant analysis (LDA) and was 93-100% accurate We’ve determined that at a concentration of 20 μM TP enters cells through a non-endocytotic mechanism, has a high affinity for the cytoplasm and membranes, and results in a significant increase in cellular stiffness Our work provides the first direct evidence of this cell-stiffening phenomenon SFTI-1, the smallest member of a bicyclic, cysteine rich class of CPPs, was examined by CRM to determine the potential role of cyclic structure on cellular uptake The peptide, along with monocyclic and linear analogs was heavy isotope labeled and incubated with mammalian cells at numerous concentrations and timespans Our work is the first SFTI-1 uptake study forgoing the use of fluorophore conjugates, which have been linked to artificial cellular uptake We demonstrate herein the absence of any CRM detectable uptake, providing the first evidence that SFTI-1 may not be a CPP Finally, CRM was applied to the discrimination of normal and basal cell carcinoma cells obtained from the same donor The use of patient matched cells avoids the normal biochemical variations that exist among individuals, ensuring that discrimination is based solely on the cell’s diseased state CRM spectra, analyzed by PCA and LDA, were capable of spectral discrimination with 100% accuracy Major differences in the cancerous cells were an increase in lipids and nucleic acids, and an overall decrease in protein We also demonstrate an enhancement in Raman signal through the use of an aluminum foil substrate, providing a practical approach for measuring cells with thin morphologies / Includes bibliography / Dissertation (PhD)--Florida Atlantic University, 2016 / FAU Electronic Theses and Dissertations Collection

Ce travail s’intéresse à l’étude de l’adsorption sélective du phénol dans des solutions d’hydrocarbures pour la purification des biocarburants issus de la biomasse de la 2ème génération. L’objectif de ce travail est de proposer, à l’aide d’une approche expérimentale et théorique, un adsorbant présentant à la fois une grande capacité d’adsorption du phénol, une sélectivité envers le phénol même en présence d’autres composés aromatiques ainsi qu’un bon pouvoir régénératif dans des conditions douces.Plusieurs familles d’adsorbants sont étudiées : des zéolithes Y et USY avec différents cations de compensation de charge (H+ et Na+) et différentes proportions de la surface micro et de mésoporeuse, des solides siliciques ayant des variables teneurs en groupement silanols et du charbon actif comme solide de référence. Les résultats d’adsorption montrent que dans les micropores des zéolithes, le phénol « interne » peut s’adsorber au nombre de 2 à 4 molécules par supercage, sans pouvoir entrer dans les cages sodalites. Dans la surface mésoporeuse des zéolithes USY et des solides siliciques, la quantité de phénol « externe » adsorbée dépend de la densité des silanols. En présence de toluène dans le mélange, les sites acides montrent une sélectivité importante envers l’adsorption du phénol, cette sélectivité est justifiée par une énergie d’interaction du phénol supérieure à celle du toluène sur ces sites. En revanche, l’adsorption du phénol sur le Na+ et les groupements silanols est affectée respectivement par la présence de faibles et de hautes teneurs en toluène. L’étude de la capacité de régénération des adsorbants met en évidence que les espèces phénoliques fortement liées sont formées sur les sites acides des zéolithes Y (H+Y, Na+Y et USY).Le meilleur compromis en termes de capacité d’adsorption de phénol, de sélectivité et de pouvoir régénératif est obtenu sur la zéolithe H+Y présentant un rapport Si/Al de 2,9. / This work focuses on the study of the selective adsorption of phenol from hydrocarbon solutions for the purification of 2nd generation biofuels. The objective of this work is to propose, using experimental and theoretical approaches, an adsorbent that can gather a good adsorption capacity of phenol, a selectivity towards phenol even in the presence of other aromatic compounds as well as good regeneration capacity under mild conditions.Several adsorbents were studied: Y and USY zeolites with different cations (H+ and Na+) and different proportions of micro and mesoporous surfaces, silica based solids presenting variable amount of silanol group and charcoal as a reference. The adsorption results show that, in the microporous of zeolites, the "internal" phenol can be adsorb to the number of 2 to 4 molecules per supercage, without being able to enter in the sodalite cages. In the mesoporous surface of the USY zeolites and the silica based solids, the amount of adsorbed "external" phenol depends on the density of the silanol groups. In the presence of toluene in the mixture, the acidic sites show a high selectivity towards phenol adsorption, this selectivity is justified by a higher interaction energy of phenol than toluene over these sites. Whereas, the adsorption of phenol over Na+ cation and over the silanol groups was respectively affected at low and high toluene levels. The study of the regeneration capacity of the adsorbents shows that the strongly bounded phenolic species are formed on the acidic sites of Y zeolites (H+Y, Na+Y and USY).The best compromise in terms of phenol adsorption capacity, selectivity and regeneration ability was obtained over the H+Y zeolite presenting a Si/Al ratio of 2.9.

in English This master thesis is focused on verifying the possibility of optimizing FTIR spectrometric analysis of terpenic resins using derivatized (fluorinated) samples using XtalFluor-E in combination with triethylamine trihydrofluoride as an agent. Terpenic resins have very similar FTIR spectra, so for their better differentiation, they need to be derivatized to minimize the influence of overlapping spectral bands in FTIR spectra. This work aimed to create a methodology for derivatization of samples of natural polymers for the National Technical Museum in Prague, where the work was performed. Samples of terpenic resins were measured non-fluorinated by the ATR crystal method and by transmission, after fluorination, only the ATR crystal method was used. Different fluorination conditions, different times (2, 4, 6, 24 and 96 hours), the effect of sample rinsing (diethyl ether, ethylene tetrachloride) and the effect of matrix on the sample (KBr pellet) were tested. Fluorination has shown to be effective. Four hours of fluorination and the need to rinse the sample with diethyl ether were chosen as the optimal fluorination conditions. After testing the resins themselves, fluorinated samples of violin varnishes and samples of historical varnishes from harp and piano were analyzed. Their spectra before...

The idea of terahertz-time-domain spectroscopy (THz-TDS) is to exploit a single cycle, spectrally broad THz radiation pulse to gain insight into the response of matter. Photoconductive devices and nonlinear crystals are utilized in both the generation as well as the coherent detection of THz radiation. The relatively high cost and the complexity of commonly used titanium-sapphire lasers hinder a more widespread use of pulsed THz systems for commercial applications. Er-doped femtosecond fiber lasers operating at 1.55 μm could offer a viable alternative. In this thesis nonlinear crystals and photoconductive emitters are discussed for excitation in the near infrared (NIR) window of between 800 nm to 1550 nm. The main focus of this thesis is a detailed study of substrate materials for an interdigitated photoconductive antenna. Photoconductive antennas with microstructured electrodes provide high electric acceleration fields at moderate voltages because of small electrode separations. The scalability of these devices allows for large active areas in the mm^2 range, which are sufficient for excitation at large optical powers. In comparison with conventional emitter structures, these antennas have more favourable characteristics regarding THz power, spectral properties, and ease of handling. Depending on the utilized substrate material, photoconductive antennas can then be operated using different excitation wavelengths. By employing substrates with short carrier trapping times these antennas can be operated as THz-detectors. Moreover the design of electrode structures for generating radially and azimuthally polarized THz waves are presented. A second topic deals with the signal analysis and signal interpretation of THz pulses transmitted through several material systems. These experiments show the potential for tomographic and spectroscopic applications. The third part deals with THz emission by frequency mixing in nonlinear organic and inorganic crystals. Hereby the focus is on polaritonic phase matching in GaAs. Furthermore, indications of THz tunability by the excitation wavelength were found by utilizing waveguide structures. However, the observed tuning range is much lower then theoretically predicted. Specific reasons for this are discussed.

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.