<p>Predmet istraživanja ove doktorske disertacije bio je ispitivanje adsorpcionog pona&scaron;anja As(III) i odabranih metala (Cu(II), Cd(II), Pb(II), Cr(VI)) na amino- funkcionalizovanim vi&scaron;eslojnim ugljeničnim nanocevima, MWCNT-NH₂, na četiri odabrane pH vrednosti (3; 4,5; 6 i 11) i pri različitim sastavima vodenog rastvora (prisustvo hlorida, nitrata, sulfata i fosfata), a u cilju ispitivanja mogućnosti primene MWCNT-NH₂ za uklanjanje arsena i jona metala iz vodenih rastvora u oblasti relativno niskih koncentracija (0,01-3 mg L ^-1 ). Fokus ove doktorske disertacije<br />je bio na utvrđivanju mehanizma procesa adsorpcije u ispitivanim uslovima.&nbsp;&nbsp; Adsorpciju arsena i metala na MWCNT-NH₂ najbolje je opisao reakcioni model pseudo-drugog reda &scaron;to&nbsp; znači da adsorpcija može biti pripisana uspostavljanju hemijskih interakcija između adsorbata i vezivnih grupa na povr&scaron;ini adsorbenta. Modelovanje brzine Weber Morris-ovim difuzionim modelom ukazalo je&nbsp; na to da unutarčestična difuzija, iako sporiji korak&nbsp; od eksterne difuzije, nije jedini ograničavajući korak u procesu adsorpcije, već su za to odgovorne i interakcije ispitivanih jona sa vezivnim mestima na povr&scaron;ini adsorbenta.&nbsp; U ravnotežnim uslovima, na različitim pH vrednostima, adsorpcija se mogla opisati&nbsp; Langmuir-ovim i Freundlich-ovim adsorpcionim modelima. Kapacitet i afinitet adsorbenta, kao i sam mehanizam adsorpcije, značajno su bili uslovljeni pH vredno&scaron;ću rastvora, kako zbog karakteristika povr&scaron;ine ispitivanog adsorbenta uslovljenih pH vredno&scaron;ću, tako i zbog uticaja pH vrednosti rastvora na pojavne hemijske oblike u kojima se arsen i metali nalaze. Ispitivanje uticaja anjona pokazalo je da je prisustvo hlorida povećalo afinitet povr&scaron;ine MWCNT-NH₂ka jonima arsena i svih metala u oblasti niskih<br />koncentracija, dok je prisustvo hlorida, nitrata, sulfata i fosfata pozitivno uticalo na afinitet povr&scaron;ine (od 2 do 8 puta veći u odnosu na dejonizovanu vodu) MWCNT-NH₂<br />ka Cu(II) u oblasti vi&scaron;ih koncentracija. Najmanji uticaj anjona na afinitet povr&scaron;ine ka vezivanju metala primećen je kod hroma. Pretpostavljeni&nbsp; mehanizmi uklanjanja arsena i odabranih metala u prisustvu anjona ukljuĉuju reakcije građenja različitih vrsta spolja&scaron;nje-&nbsp; i unutra&scaron;nje-sfernih kompleksa, jonske izmene, kao i&nbsp; elektrostatičke interakcije koje se ostvaruju između pozitivno naelektrisane povr&scaron;ine MWCNT-NH_{<span style="font-size: 8.33333px;">2</span>}&nbsp;i anjona, na pH vrednostima manjim od 6,4, a koje menjaju afinitet<br />povr&scaron;ine ka jonima arsena i metala. Rezultati ove doktorske disertacije pokazuju da se ispitivani adsorbent, MWCNT-NH₂,&nbsp; može koristiti za uklanjanje arsena i te&scaron;kih metala iz vode u prisustvu različitih anjona i da, svojim adsorpcionim karakteristikama, može konkurisati komercijalnim i&nbsp; ekonomski pristupačnim adsorbentima.</p> / <p>The subject of this doctoral thesis was the examination of the adsorption behaviour of As(III), and selected metals (Cu(II), Cd(II), Pb(II), Cr(VI)) on the amino-functionalized multiwalled carbon nanotubes, MWCNT-NH₂, at four pH values (3, 4.5, 6, and 11) with different compositions of aqueous solutions (in the presence of chlorides, nitrates, sulphates and phosphates), in order to examine the possibilities of applying MWCNT-NH₂ in removal of arsenic and metal ions from aqueous solutions in relatively low concentration (0,01- 3mg L^-1). The focus of this doctoral thesis was to establish the mechanism of adsorption process in given conditions. Arsenic and metal adsorption on MWCNT-NH₂ were best described with the pseudo-second order kinetic model, which assumes that adsorption can be attributed to the establishment of chemical reactions between the adsorbate, and the binding groups at the surface of adsorbent. The Weber - Morris diffusion model indicated that intercellular diffusion, although being a slower step than external diffusion, is not the only limiting step in the adsorption process, but also that the interactions of ions with the adsorbent surface binding sites, are responsible. In equilibrium, at different pH values, the adsorption could be described by the Langmuir and Freundlich adsorption models. The capacity and affinity of the adsorbent, and adsorption mechanism, were considerably determined by the pH value of the solution, either because of the characteristics of the surface of the investigated adsorbent depending on pH value, or the effect of the solution&rsquo;s pH value on the chemical forms of arsenic and other metals. Investigation of the influence of the anion showed that the presence of chloride increased affinity of the surface of MWCNT-NH₂ to arsenic ions and to all metals in low concentration ranges, while presence of chlorides, nitrates, sulphates and phosphates had a positive impact on the affinity of the surface (2 or 8 times greater than for deionized water) MWCNT-NH₂ for Cu(II) in high concentration ranges. The smallest impact of anions to affinity of the surface to bond metals was noticed for chromium. The assumed mechanisms of removing arsenic and selected metals in the presence of anions include reactions of forming various kinds of outer- and inner-spheric complexes, ionic exchange, as well as electrostatic interaction which occur between positively charged surface of MWCNT-NH₂ and anions, for pH &lt; 6.4, and which change affinity of the surface towards arsenic and metal ions. Results of this doctoral thesis show that the investigated adsorbent, MWCNT-NH₂, can be used for the removal of arsenic and heavy metals from water, in the presence of different anions, and that with its adsorbent characteristic it can compete with commercially, and economically more affordable adsorbents.</p>

Metal ions are a tempting tool for organisms thanks to the diversity of func- tions they have to offer, if they can be distinguished properly. Examining metal-ion selectivity computationally is challenging mainly due to complex- ity of electronic structure and solvation effects. A DFT-based protocol for predicting metal-ion selectivity of metal-binding systems was developed. The most essential part of the thesis is discussion of the magnitudes and sources of inherent errors, both for metal-ion complexes and small peptides. The thesis connects the work of four original papers. It includes computational and ex- perimental benchmarks, a case-study validating the computational protocol for obtaining energetic and structural insights, and attempts applying the protocol to peptidic systems. ii

Water quality is a crucial factor in determining the health of an environment, and in turn the health of all those living in the given environment. Early detection of potential hazards in source water used for drinking would help to avoid outbreaks of sickness and even death. Contaminants, found in contact and drinking water, having negative effects on human health may include pathogenic microorganisms, and metal ion pollutants such as lead or cadmium. Lead and cadmium were selected due to well-known electrochemical properties providing easy references for developing new detection devices. Current methods for detection of these contaminants are extremely expensive and time consuming. The focus of this project was to develop a single device that selectively detects multiple contaminants while maintaining sensitivity. This thesis provides an investigation into electrochemical techniques that can be used to develop cost effective, portable, and easy to use devices. A fabricated microelectrode array is proposed and tested that can be used for the detection of lead and cadmium ions, and also has the potential to incorporate detection of DNA sequences for specific species of pathogenic microorganisms.

Resorcinarenes are cyclic tetramers that are synthesized by the condensation of resorcinol and various aldehydes. The upper and lower rims can be modified with substituents that provide specific selectivity and other chemical features. In this work, resorcinarene-based macrocyclic ligands with specific selectivities have been designed, synthesized and applied to chiral amine discrimination and transition metal ion separations.These resorcinarenes fall into two categories. In the first type, the upper rims of resorcinarenes were modified with amino acid groups, including chiral alanine groups. The lower rims were modified with --CH3, or --C11H23 groups. The structures were studied by nuclear magnetic resonance (NMR), mass spectrometry (MS), dynamic light scattering (DLS), and sustained off-resonance irradiation collision induced dissociation (SORI-CID) techniques in Fourier transform ion cyclotron resonance mass spectrometry (FTICR-MS). The binding strength between the resorcinarenes with amines was studied by 1H NMR titration. Among these new resorcinarenes, the chiral alanine undecyl resorcinarenes acid (AUA) showed chiral discrimination among chiral secondary amines. The AUA ligands were adsorbed onto 55% cross-linked styrene-divinylbenzene resin and used as cation-exchangers in ion chromatography (IC) for transition metal ion separations. The AUA IC column showed selectivity for Cu2+ when no chelating eluent was used in the eluent, a selectivity which was not observed with a commercial column containing standard cation-exchangers. Six metal ions (Cu2+, Mn2+, Co2+, Ni2+, Cd2+, and Zn2+) were separated on the AUA column within a reasonable time with a simple oxalic acid gradient eluent. The second type of resorcinarene-based ligand, cyclenbowl, contains four cyclen units on the upper rim and four --C11H23 chains on the lower rim. The column packed with cyclenbowl adsorbed onto polystyrene showed selectivity for Cu2+ over five other transition metal ions including Mn2+, Co2+, Ni2+, Cd2+, and Zn2+ ions. The preconcentration of Cu2+ at the parts per billion level from a high concentration matrix of Mn2+, Co2+, Ni2+, Cd2+, and Zn2+ ions was achieved using HNO3 eluent. Recovery of Cu2+ was greater than 98%. Furthermore, the other five transition metal ions were well separated on the cyclenbowl column with an oxalic acid eluent gradient.

<p> A method for the simultaneous preconcentration by solvent extraction of a group of trace metal ions from natural waters has been developed. The procedure makes use of a proprietary "liquid cation-exchanger", Kelex 100, the primary component of which is an alkylated oxine (8-quinolinol) derivative, 7-(4-ethyl-1-methyloctyl)-8-quinolinol (HL). After purification of HL from the commercial mixture, the extraction of ten environmentally-significant trace metal ions from artificial seawater into toluene solution was studied as a function of pH. From these investigations, the optimal conditions for the extraction of Cd(II), Co(II), Cu(II), Mn(II), Ni(II), Pb(II) and Zn(II) from natural waters were established. The conditions for quantitative back-extraction of the metal ions were then investigated. With the exception of cobalt, the metal ions were quantitatively back-extracted into a small volume of nitric acid, simplifying the matrix and providing additional analyte enrichment. The optimized forward- and back-extraction technique was subsequently applied to the determination of total (soluble) Cd, Cu, Mn, Ni and Pb in a coastal seawater reference standard by graphite-furnace atomic absorption spectroscopy (GFAAS). The quantitative recovery of the analytes and the uncomplicated matrix of analysis enabled quantitation to be carried out by external calibration. Compared to the method of standard additions, external calibration has advantages in overall analysis time and sample consumption. Satisfactory agreement was obtained between the experimental and reference values, although Cu(II) blanks were high due to trace Cu(II) contamination of HL and the stability of the Cu(II)-HL chelate.</p> <p> The lipophilicity of HL and its metal chelates provided high metal chelate distribution ratios which, in turn, permitted preconcentration factors of up to 500 in a single batch-extraction. Additionally, studies on the recovery of radiotracer spikes from lakewater and seawater suggested that HL is an effective extractant for stripping metal ions from variously-bound forms from natural waters.</p> / Thesis / Master of Science (MSc)

<p>The copper-binding ability of the prion protein may be closely connected to its function. Identifying the exact function of the prion protein can clarify the underlying mechanism in prion diseases. In this work, the copper-binding octapeptide region in the human prion protein has been studied. The structural characteristics of the binding site are examined by quantum chemical structural optimization. The calculations aim at identifying a substitute for copper(II) to be used in NMR-spectroscopic studies of the copper-binding region. The dynamical and structural features of the peptide region are investigated in molecular dynamics simulations. Aspects of importance in the development of model systems in molecular dynamics simulation are addressed.</p>

Numerous enzymatic reactions are controlled by the chemistry of metallic ions. This dissertation investigates the electronic properties of three transition metal (copper, chromium, and nickel) complexes and describes modeling studies performed on glutathione synthetase. (1) Copper nitrene complexes were computationally characterized, as these complexes have yet to be experimentally isolated. (2) Multireference calculations were carried out on a symmetric C2v chromium dimer derived from the crystal structure of the [(tBu3SiO)Cr(µ-OSitBu3)]2 complex. (3) The T-shaped geometry of a three-coordinate β-diketiminate nickel(I) complex with a CO ligand was compared and contrasted with isoelectronic and isosteric copper(II) complexes. (4) Glutathione synthetase (GS), an enzyme that belongs to the ATP-grasp superfamily, catalyzes the (Mg, ATP)-dependent biosynthesis of glutathione (GSH) from γ-glutamylcysteine and glycine. The free and reactant forms of human GS (wild-type and glycine mutants) were modeled computationally by employing molecular dynamics simulations, as these currently have not been structurally characterized.

<p>Cilj ove doktorske disertacije je bio da se ispita mogućnost primene izluţenih rezanaca &scaron;ećerne repe i njihovih tretiranih oblika, nastalih u procesu proizvodnje bioetanola, kao biosorbenata za uklanjanje jona te&scaron;kih metala iz vode. U okviru eksperimenata, u laboratorijskim uslovima izvedeni su predtretman i hidroliza izluženih rezanaca kako bi se dobili tretirani oblici, a zatim je izvr&scaron;ena karakterizacija adsorbenata, ispitane njihove adsorpcione sposobnosti, utvrđeni najbolji uslovi za njihovu primenu i ispitana mogućnost njihove vi&scaron;estruke primene u obradi vode.<br />U okviru karakterizacije materijala određen je njihov sastav, specifiĉna povr&scaron;ina i poroznost, ispitana povr&scaron;ina primenom FTIR i EDS metode i kvantifikovana količina pojedinih funkcionalnih grupa prisutnih na povr&scaron;ini primenom Boehm-ove titracije. Na osnovu FTIR metode pre i posle adsoprcije utvrđeno je koje grupe učestvuju u vezivanju jona metala.<br />Ispitan je i uticaj razliĉitih parametara na adsorpciju (vreme kontakta adsorbenta i adsorbata, veličina čestice, pH, temperatura, primenjena doza adsorbenta, jonska jačina, su&scaron;enje) radi utvrđivanja najboljih uslova za maksimalnu efikasnost.<br />Kako bi se stekao bolji uvid u sam proces adsorpcije jona na povr&scaron;inu adsorbenata, na eksperimentalne podatke primenjeni su različiti modeli adsorpcionih izotermi, a mehanizam vezivanja je detaljnije razmotren primenom kinetiĉkih modela. Primenom termodinamičkih modela utvrđena je priroda procesa.<br />Radi vi&scaron;estruke primene ovih ekolo&scaron;kih biosorbenata ispitana je i mogućnost regeneracije materijala razliĉitim kiselinama kao desorbensima i utvrđeno optimalno vreme desorpcije. Ispitana je primena kroz vi&scaron;e uzastopnih ciklusa adsorpcija &ndash; desropcija. Rezultati su pokazali da ispitani materijali imaju zadovoljavajući adsorpcioni kapacitet, ali da se mogu primenjivati i vlažni, odmah nakon procesa ekstrakcije &scaron;ećera, depektinacije i hidrolize, bez utro&scaron;ka energije za su&scaron;enje. Pored toga, utvrđeno je da se mogu regenerisati i koristiti uspe&scaron;no vi&scaron;e puta, &scaron;to otvara mogućnost za njihovu primenu u praksi.</p> / <p>The aim of this PhD thesis was to investigate the possibility of usage of sugar beet shreds and their treated forms from the bioethanol production for removal of heavy metal ions from water. In the context of experiments, pretreatment and hydrolysis of sugar beet shreds were performed in order to obtain treated forms. The characterization of biosorbents was conducted and their adsorption capacity was investigated. Also, the optimal conditions for their implementation and the possibility of their multiple applications for water treatment were determined.<br />Within the characterization of materials their composition, specific surface area and porosity were determined. The surface of biosorbents was investigated by using FTIR and EDS methods. The amount of the functional groups present on the surface was quantified by Boehm&#39;s titration. On the basis of the FTIR method before and after adsorption it was determined which functional groups participate in the binding process.<br />The influence of various parameters on the adsorption (contact time of the adsorbent and adsorbate, particle size, pH, temperature, adsorbent dose, ionic strength, drying process) were examined in order to determine the best conditions for maximum efficiency.<br />For better insight into the process of adsorption of ions on the surface of the adsorbents, different models of adsorption isotherms were applied to experimental data. Mechanism of adsorption was determined by applying different kinetic models. The nature of the process was investigated by determining thermodynamic parameters.<br />The multiple applications of these eco-friendly biosorbents was examined by regeneration investigation. The optimal time of desorption was determined and different acids were used for regeneration study. The multiple cycles adsorption &ndash; desorption was also conducted.<br />The results showed that the investigated materials have a satisfactory adsorption capacity. They can also be applied wet, immediately after the process of sugar extraction, depectination and hydrolysis, without the energy consumption for drying. In addition, it was found that they can be regenerated and successfully used several times. This opens up the possibility for their practical application.</p>

O monitoramento ambiental de forma contínua e em tempo real são desafios da realidade atual dos grandes centros urbanos, com a finalidade de prevenir desastres ambientais que possam pôr em perigo a saúde dos seres humanos e a existência de sistemas biológicos. Na presente tese foram propostos e desenvolvidos sistemas optoeletrônicos portáteis aplicados na detecção de O2, OD e íons de metais pesados, visando seu emprego no monitoramento de sistemas hidrológicos como mares, rios, lagos e lençóis freáticos. A definição final da estrutura do sistema portátil foi atingida após o desenvolvimento sistemático de diferentes ensaios experimentais. Primeiramente, foram estudadas e analisadas matrizes hospedeiras em estado sólido que fossem capazes de hospedar sistemas moleculares corantes sensíveis a certas substâncias específicas. A seguir, foi proposta e executada a integração direta dos filmes hospedeiros, dopados com moléculas corantes ativas, diretamente na superfície ativa de dispositivos fotodetectores para detecção de O2 e OD. Os resultados obtidos com estes sistemas que integram o detector e o filme ativo mostraram o mesmo nível de desempenho aos espectrômetros de bancada. Finalmente, de posse destes resultados, foi projetado e desenvolvido um sistema colorimétrico e fluorimétrico portátil e embarcado em uma placa de aquisição (myRIO-1900) da National Instruments, aplicado na detecção e classificação de íons metálicos. Destaque principal é outorgado à aplicação do colorímetro que, juntamente com o processamento de sinais e análises de padrões, utilizando o método de discriminante de Fisher, permitiu obter resultados excelentes na detecção e classificação dos íons de Pb2+, Cd2+, Zn2+, Cu2+, Fe3+ e Ni2+, com os mesmos níveis de desempenho que os obtidos a partir de espectrômetros de bancada de elevada resolução espectral. O sistema portátil desenvolvido sugere sua aplicação no controle ambiental in situ e em tempo real, podendo ser integrado em uma rede de sensores que possam fornecer dados de maneira contínua e receber comandos de centros de controle de monitoramento ambiental. No entanto, seria necessária a formulação de algoritmos eficientes no processo de mineração de dados da rede de sensores. / The continuous and in real time environmental monitoring are challenges of the current days of large urban centers, with the aim of preventing environmental disasters that could endanger human health and the existence of biological systems. In this thesis we have proposed and developed portable optoelectronic systems applied to the detection of O2, OD and heavy metal ions, aiming its use in monitoring hydrological systems such as oceans, rivers, lakes and groundwater. The final definition of the portable system structure was achieved after the systematic development of different experimental assays. First, host matrices were studied and analyzed in solid state which were able to host dye molecular systems sensitive to certain substances. Then, we proposed and executed the direct integration of the host film, doped with active dye molecules directly on the active surface of photodetector devices to the detection of O2 and OD. The results obtained with these systems that integrate the detector and the active film showed the same level of performance than those of benchtop spectrometers. Finally, with these results, we designed and developed a colorimetric and fluorimetric portable system with an embedded acquisition board (myRIO-1900) from National Instruments, applied to the detection and classification of metal ions. Main focus is given to the application of the colorimeter which, along with the signal processing and pattern analysis using the Fisher discriminant method, allowed to obtain excellent results in the detection and classification of Pb2+, Cd2+, Zn2+, Cu2+, Fe3+ and Ni2+ ions, with the same level of performance related to those obtained from high spectral resolution benchtop spectrometers. The portable system developed in the present thesis suggests its application in environmental control in situ and in real time, so that it can be integrated in a network of sensors that may provide continuous data and receive commands from environmental monitoring control center; nevertheless, requiring for that the development of efficient algorithms in data mining process of the sensor network.

O monitoramento ambiental de forma contínua e em tempo real são desafios da realidade atual dos grandes centros urbanos, com a finalidade de prevenir desastres ambientais que possam pôr em perigo a saúde dos seres humanos e a existência de sistemas biológicos. Na presente tese foram propostos e desenvolvidos sistemas optoeletrônicos portáteis aplicados na detecção de O2, OD e íons de metais pesados, visando seu emprego no monitoramento de sistemas hidrológicos como mares, rios, lagos e lençóis freáticos. A definição final da estrutura do sistema portátil foi atingida após o desenvolvimento sistemático de diferentes ensaios experimentais. Primeiramente, foram estudadas e analisadas matrizes hospedeiras em estado sólido que fossem capazes de hospedar sistemas moleculares corantes sensíveis a certas substâncias específicas. A seguir, foi proposta e executada a integração direta dos filmes hospedeiros, dopados com moléculas corantes ativas, diretamente na superfície ativa de dispositivos fotodetectores para detecção de O2 e OD. Os resultados obtidos com estes sistemas que integram o detector e o filme ativo mostraram o mesmo nível de desempenho aos espectrômetros de bancada. Finalmente, de posse destes resultados, foi projetado e desenvolvido um sistema colorimétrico e fluorimétrico portátil e embarcado em uma placa de aquisição (myRIO-1900) da National Instruments, aplicado na detecção e classificação de íons metálicos. Destaque principal é outorgado à aplicação do colorímetro que, juntamente com o processamento de sinais e análises de padrões, utilizando o método de discriminante de Fisher, permitiu obter resultados excelentes na detecção e classificação dos íons de Pb2+, Cd2+, Zn2+, Cu2+, Fe3+ e Ni2+, com os mesmos níveis de desempenho que os obtidos a partir de espectrômetros de bancada de elevada resolução espectral. O sistema portátil desenvolvido sugere sua aplicação no controle ambiental in situ e em tempo real, podendo ser integrado em uma rede de sensores que possam fornecer dados de maneira contínua e receber comandos de centros de controle de monitoramento ambiental. No entanto, seria necessária a formulação de algoritmos eficientes no processo de mineração de dados da rede de sensores. / The continuous and in real time environmental monitoring are challenges of the current days of large urban centers, with the aim of preventing environmental disasters that could endanger human health and the existence of biological systems. In this thesis we have proposed and developed portable optoelectronic systems applied to the detection of O2, OD and heavy metal ions, aiming its use in monitoring hydrological systems such as oceans, rivers, lakes and groundwater. The final definition of the portable system structure was achieved after the systematic development of different experimental assays. First, host matrices were studied and analyzed in solid state which were able to host dye molecular systems sensitive to certain substances. Then, we proposed and executed the direct integration of the host film, doped with active dye molecules directly on the active surface of photodetector devices to the detection of O2 and OD. The results obtained with these systems that integrate the detector and the active film showed the same level of performance than those of benchtop spectrometers. Finally, with these results, we designed and developed a colorimetric and fluorimetric portable system with an embedded acquisition board (myRIO-1900) from National Instruments, applied to the detection and classification of metal ions. Main focus is given to the application of the colorimeter which, along with the signal processing and pattern analysis using the Fisher discriminant method, allowed to obtain excellent results in the detection and classification of Pb2+, Cd2+, Zn2+, Cu2+, Fe3+ and Ni2+ ions, with the same level of performance related to those obtained from high spectral resolution benchtop spectrometers. The portable system developed in the present thesis suggests its application in environmental control in situ and in real time, so that it can be integrated in a network of sensors that may provide continuous data and receive commands from environmental monitoring control center; nevertheless, requiring for that the development of efficient algorithms in data mining process of the sensor network.