The efficiency of photoconversion systems such as organic photovoltaic cells and photocatalytic water-splitting cells is largely governed by the interfacial charge transfer processes. Understanding the structure-function relationship, specifically at the molecular thin film/transparent conducting oxide interface will allow for engineering these interfaces to promote charge transfer and reduce the rate of charge recombination. Important factors that are hypothesized to influence charge transfer are morphology, chemical characteristics, electronic properties and molecular orientation. As molecules are bound to a transparent conducting oxide or incorporated into a thin film, the local solid-state molecular environment greatly influences the excited state properties of the molecule. Pathways for quenching, radiative and nonradiative decay drastically limit the excited state lifetimes. In order to investigate the photoinduced kinetics of thin films and at interfaces a instrument was developed coupling transient absorbance spectroscopy to attenuated total reflectance spectroscopy. The photoinduced kinetics of a thin film of bacteriorhodopsin was used to evaluate the instrument performance, and it was determined that 1% of a close-packed monolayer could be detected with this geometry. The properties of a molecular thin film/transparent conducting oxide were investigated by tethering zinc porphyrin to ITO. The electrochemical properties were influenced by the functional group of the binding moiety. To improve our understanding of how the solid state molecular environment affects excited states lifetimes, zinc porphyrins were incorporated into mono- and multilayer thin films and measured with transient ATR spectroscopy. Finally, multilayer films related to photocatalytic water-splitting were investigated with the incorporation of inorganic nanosheets. The nanosheets helped to create a stratified assembly for multilayer films, spatially segregating electron donor (palladium porphyrin) and electron acceptor (poly(viologen)) molecules. The role of the nanosheets in the electron transfer between the donor and acceptor was studied by monitoring the triplet state lifetimes of a palladium porphyrin with transient ATR spectroscopy.

The vulnerability of the Arctic to climate change has been realized due to disproportionately large increases in surface air temperatures which are not uniformly distributed over the seasonal cycle. Effects of this temperature shift are widespread in the Arctic but likely include changes to the hydrological cycle and permafrost thaw, which have implications for the mobilization of organic carbon into rivers. The focus of this research was to describe the seasonal variability of the chemical composition of dissolved organic matter (DOM) in the six largest Arctic rivers (Yukon, Mackenzie, Ob, Yenisei, Lena and Kolyma) using optical properties (UV-Vis Absorbance and Fluorescence) and lignin phenol analysis. We also investigated differences between rivers and how watershed characteristics influence DOM composition. Dissolved organic carbon (DOC) concentrations followed the hydrograph with highest concentrations measured during peak river flow. The chemical composition of peak-flow DOM indicates a dominance of freshly leached material with elevated aromaticity, larger molecular weight, and elevated lignin yields relative to base-flow DOM. During peak flow, soils in the watershed are still frozen and snowmelt water follows a lateral flow path to the river channels. As the soils thaw, surface water penetrates deeper into the soil horizons leading to lower DOC concentrations and likely altered composition of DOM due to sorption and microbial degradation processes. The six rivers studied here shared a similar seasonal pattern and chemical composition. There were, however, large differences between rivers in terms of total carbon discharge reflecting the differences in watershed characteristics such as climate, catchment size, river discharge, soil types, and permafrost distribution. The large rivers (Lena, Yenisei), with a greater proportion of permafrost, exported the greatest amount of carbon. The Kolyma and Mackenzie exported the smallest amount of carbon annually, however, the discharge weighted mean DOC concentration was almost 2-fold higher in the Kolyma, again, indicating the importance of continuous permafrost. The quality and quantity of DOM mobilized into Arctic rivers appears to depend on the relative importance of surface run-off and extent of soil percolation. The relative importance of these is ultimately determined by watershed characteristics.

The ability to probe molecular electronic and vibrational structures gives rise to optical absorption spectroscopy, which is a credible tool used in molecular quantification and classification with high sensitivity, low limit of detection (LoD), and immunity to electromagnetic noises. Spectra are sensitive to slight analyte variations, so they are often used to identify a sample’s components. This thesis proposes several methods for quick classification and quantification of analysts based on their absorbance spectra. functional Principal Component Analysis (fPCA) is employed for feature extraction and dimension reduction. For 1,000-pixel spectra data, fPCA can capture the majority variance with as few output scores as the number of expected analytes. This reduces the amount of calculation required for the following machine learning algorithms. Further, the output scores are fed into XGBoost and logistic regression for classification, and fed into XGBoost and linear regression for quantification. Our models were tested on both synthesized datasets and experimentally acquired dataset. Our models demonstrated similar performance compared to deep learning but with much faster processing speeds. For the synthesized 30 dB dataset, our model XGBoost with fPCA could reach a micro-averaged f1 score of 0.9551 ± 0.0008, while FNN-OT [1] could obtain 0.940±0.001. fPCA helped the algorithms extract the feature of each analyte; furthermore, the output scores nearly had a linear relationship with their concentrations. It was much easier for the algorithm to find the mapping function between the inputs and the outputs with fPCA, which shortened the training and testing time. / Graduate

Charles University Faculty of Pharmacy in Hradec Králové Department of Pharmacology & Toxicology Student: Monika Moravcová Supervisor: Assoc. Prof. Přemysl Mladěnka, Pharm.D., Ph.D. Title of thesis: Preparation of a Novel Method for Screening of Cobalt Chelators Cobalt as a structural part of the vitamin B12 is an essential microelement for living organisms including humans. However, its excess is associated with pathological conditions. Cobalt poisoning can be caused for example by exposure to cobalt metal dust during the production of hard metals or follow the corrosion of metal hip prosthesis. Patients intoxicated by cobalt can develop different manifestations including neurological impairment, hypothyroidism or cardiomyopathy. The aim of this work is to prepare a standardized, rapid, cheap but precise method for the screening of cobalt chelators. For this purpose, spectrophotometric detection using 1-nitroso-2-nafphhol-3,6-disulfonic acid disodium salt as the indicator was used. Firstly, it was found that the addition of cobalt ions led to a clear bathochromic shift of the maximum absorbance of the indicator. The relationship between the absorbance and cobalt concentration was highly linear from 470 to 560 nm at all 4 tested pH conditions (4.5, 5.5, 6.8 and 7.5). The sensitivity of the method...

Pesticides are a growing concern around the world as they are widely increasing in use and not as highly regulated as some health and environmental hazards. As agricultural, home, and other pesticide applications continue to rise, the need for analytical testing and removal of these pesticides from our rivers, streams, and other runoffs is becoming more and more significant. Glyphosate, an active ingredient in the herbicide Roundup, is an amine compound that has a maximum contamination level of 700 ppb. This work studied the use of water soluble Iron (II) tetrasolfophthalocyanine in amine detection that could be further applied to glyphosate. Also included in this study is a glimpse of removal possibilities combining phthalocyanines with traditional adsorption media for enhanced extraction and capacity.

No description available.

The stapedius muscle, which is located in the middle ear, goes into contraction when the ear is exposed to high sound intensities. This muscle activation is called ‘the acoustic reflex’. Measurement of the acoustic reflex is clinically of importance since it can reveal diagnostic information about the middle ear’s pathologies. Moreover, this muscle-activation alters the acoustic characteristics of the middle ear (i.e. the acoustic impedance and the power reflectance), which in turn, can significantly manipulate one’s perception of sounds. In the present study, these acoustic characteristics are measured in the ear canal by means of absorbance measures using equivalent Thevenin circuit theory. The quantities are then compared to form the shift responses between the baseline (before the activation) and the post-activator effect. This project investigates the shifts in power reflectance and admittance of the middle ear caused by the stapedius-muscle contraction. The wideband characterization (0.1- 8 kHz) of these acoustic reflex-induced shifts is achieved using chirp signals as a probe and through ipsilateral broadband noise activator. The data acquisition and signal processing of the project are carried out using MATLAB software. The hardware consists of National Instruments USB-6212 data acquisition interface and low noise microphone system Etymotic Research ER-10B+. A group of 10 adults including 5 males and 5 females are recruited as the participants for the project. The measurements of the reflectance shifts indicate that the most robust frequency region affected by the acoustic reflex is up to 4 kHz whereas for the admittance shifts, this region is up to 2 kHz. In addition, it is shown that the stapedius-muscle contraction leads to the attenuation of the lowfrequency transmission into the middle ear (less than 1 kHz) consistent with a stiffnesscontrolled system in this range of frequencies. In contrast, the results imply that the activation of the stapedius muscle leads to a slight enhancement of the frequency transmission in the range of 1-4 kHz (corresponding to the speech frequency band). These findings suggest a beneficial role for the stapedius-muscle contraction in the perception of speech during vocalization. Furthermore, the implemented methods in this project  can be useful in better understanding the effect of the stapedius-muscle contraction on the speech perception both in normal hearing and hearing impaired persons.

Algae can be used to treat wastewater and manure while producing a feedstock for renewable energy. Algae require nutrients to achieve their maximum growth and manure could provide those nutrients, thereby reducing the cost of algae production and the impact of manure treatment. Algae concentration during cultivation is a critical variable that is difficult to measure due to the high concentration of suspended solids present in manure. This dissertation addresses methods to measure algae concentration in the presence of manure solids. Quantifying the algae concentration gravimetrically or by optical density was unreliable due to manure solids interfering with the measurement. Cell counting to determine algae concentration was accurate but time consuming, subjective, required dilution of concentrated samples and only small sample volumes could be measured. Chlorophyll extraction was a consistent method to determine algae concentration in manure based media, but the model had to be adjusted to account for solids interference. The proposed equation predicted chlorophyll concentration from Chlorella vulgaris in dairy manure better than the reference equation. Different algae strains (Chlorella vulgaris, Cylindrocystis sp, and Scenedesmus sp.) and manure sources (dairy, beef, swine, and sheep) were used to validate the proposed equation and all combinations had a linear relationship between actual and predicted chlorophyll concentration, but not all comparisons followed a 1:1 reference line. Even with chlorophyll extraction the manure solids interfered with the chlorophyll measurement and calibrations had to be developed based on manure type. A method based on spectral deconvolution was used to quantify algae concentration in the presence of manure without chlorophyll extraction. Various manure-algae mixtures were scanned with a spectrophotometer. Algae concentration was accurately determined with the four manure sources. Measuring algae concentration required absorbance spectra from 600 to 700 nm and manure solids concentration between 280 and 350 nm. Spectral deconvolution was able to differentiate algae concentration and manure solids concentration with a Pearson coefficient of 95.3% and 99.8% respectively. This method proved to be an accurate and efficient method for estimating algae and manure solids content in unprocessed samples. A critical factor was utilizing appropriate reference spectra.

No description available.

The optical frequency comb is a coherent light source whose spectrum consists of hundreds of thousands perfectly equidistant narrow frequency components and precisely expressed in just two radio frequencies. Even though optical frequency combs were developed 25 years ago, that led to the Nobel Prize in Physics 2005, only recently there was a significant progress in generating broadband optical frequency combs in the mid-infrared. These achievements became possible due to the development of new types of robust fiber and solid-state lasers and the efficient downconverting of their frequencies through different techniques based on advanced nonlinear crystals. In this dissertation, I study the techniques of producing ultra-broadband frequency combs in the challenging mid-infrared and terahertz regions of the electromagnetic spectrum. These combs find applications in high-precision molecular spectroscopy, atmosphere monitoring, reaction kinetics, and ultrasensitive trace gas detection to name a few. In addition, I investigate their application in the dual-comb spectroscopy, which is a tool involving two combs with slightly different comb line spacings that are interfered on a photodetector generating a radiofrequency comb. So, effectively high optical frequency is mapped to radiofrequency that can be easily recorded with available digital electronics. This method has a list of advantages over traditional spectrometers, namely broadband coverage combined with superior spectral resolution, high acquisition speed, high precision, and the absence of moving parts. Moreover, in the context of the experimental results, my spectroscopy investigations with low-pressure gases led to reliving a massive amount of spectroscopic data that had never been explored before, and some of which was already included into a global database. The results presented in this dissertation paves the way for creating highly accurate molecular spectroscopic databases and have the potential for real-time medical diagnostics through multi-species exhaled breath analysis.