Thesis (Ph. D.)--Institute of Paper Chemistry, 1959. / Includes bibliographical references (p. 142-143).

A series of cis- and trans-bis(ethynyl)platinum complexes containing dimethyldihydropyrene (DHP) photochromic compounds were synthesized from RDHPCCH (R = H, CH3CO, PhCO, 1-naphthoyl and benzo[e]) and platinum chloride with appropriate ancillary ligands (PEt3, PPh3, dppe, bipy and phen). The complexes were studied using mass spectrometry, NMR spectroscopy (1H, 13C, 31P and 195Pt) and IR. The X-ray structural information for bis(DHP-ethynyl) platinum complexes 44, 45, 47, 49, and 52 revealed that the Pt complexes possessed a square planar geometry at the metal centers. These platinum complexes are T type photochromic compounds. The BDHP-derived platinum complexes 48, 49, and 52 open completely when irradiated by visible light (λ > 590 nm). The photoopening rates for the platinum complexes are about 4 times slower than the corresponding DHP-alkynes. All the alkynyl platinum complexes close thermally faster than the corresponding free alkynes, and the closing rate is not affected substantially by changing the ancillary phosphine ligands. The BDHP-ethynyl platinum complexes with PEt3, PPh3 and dppe ligands have similar thermal closing half lives at 25°C of τ1/2 = 42 h, 38 h and 33 h, respectively, in contrast to the half life τ1/2 = 62 h of the BDHP-ethyne 40. The first cyclobutadienyl cobalt substituted dihydropyrenes were prepared by CpCo(CO)2 cyclization of a series of dihydropyrenyl ethynes. When the other alkyne substituent was small (methyl or carboxyethyl) only cis (head-to-head) isomers were obtained, but with larger sized groups, mixed head-to-head and head-to-tail isomers were obtained. The crystal structure of complex 21 indicated some unusually short bond distances were present. By comparison of the NMR and bond length data for complexes 21 or 69 with those for phenyl-DHP 60, the aromaticity of the cyclobutadienyl cobalt fragment was estimated quantitatively to be at least as large as that of benzene. The organometallic fragment [Cbd-Co-Cp] substantially slowed the DHP photoopening reaction of complex 72 relative to precursors 67 or 35. DHP[e]tropone, 17, DHP[e]tropylium cation, 18 and DHP[e]cyclooctatetraene dianion, 20 were synthesized to study the relative bond localizing abilities of COT dianion 80 (105 % relative to benzene), tropylium cation 15 (55 % relative to benzene), tropone 79 (13 % relative to benzene) using DHP as the NMR probe. The internal methyl protons of DHP resonated at δ -3.56 for 17, δ -2.61 for 18 and δ -1.38 for 20. Cycloheptatrienyl anions 111, 112 and 19 were made from cyclohepta-2,4,6-triene (CHT) isomers 107 and 108 (for two anions, 112 and 19). The internal methyl protons of their DHP resonated at δ -2.52, 2.67 for 111, δ -0.80, -0.84 for 112 and δ +2.10 for 19. The anion 19 was best taken as a 20π electron paratropic system. The homo-aromaticity of the CHT isomers 107, 108 and 117 was estimated based on the NMR data and X-ray structural data. Obvious anisotropic effects existed and the bond localization ability of the CHT (24% based on NMR data for 108) may have a large error. The ring inversion barriers of the COT 82 and CHT 77 were measured using variable temperature NMR spectroscopy as 13.9 and 8.7 kcal/mol, respectively. Five X-ray crystallography structures were obtained for 99B, 17, 108, 117 and 125 and the information was used in estimating the bond localization abilities and in establishing absolute stereochemistry / Graduate

Thesis (M.Sc.)--University of Alberta, 2010. / A thesis submitted to the Faculty of Graduate Studies and Research in partial fulfillment of the requirements for the degree of Department of Physiology. Title from pdf file main screen (viewed on March 20, 2010). Includes bibliographical references.

Thesis (Ph. D.)--Colorado State University, 2004. / Includes bibliographical references.

The content of this thesis The agricultural management impact on matter losses in the model catchment of the Stropnice river was to observe the quality of surface water and matter losses in five small catchments of Stropnice river. The samples from physico-chemical analysis were medium values from 2001 to 2011. There were observed pH, conductivity and concentrations of main ions and carbon in the surface waters. The results were analysed with multivariate Measures Anova - Tukey HSD post- hoc analyse. For the selected parameters a correlation analysis of the closeness of relationships was performed. There were differences between in sulphates surface water chemism in the upper parts of five streams. In the lower parts of five streams were significant differences between arable soils and meadows. The results confirmed that occurs a positive relation between the chemism of surface water and land use.

à bem sabido que o aumento da produÃÃo de resÃduos particularmente os agroindustriais torna o destino final um problema ambiental Recentemente estudos com o uso de resÃduos agroindustriais na remoÃÃo de poluentes inorgÃnicos presentes em efluente tÃm-se tornado atraentes por serem baratos simples e eficientes Neste trabalho onde utiliza o pà da casca de coco verde modificado quimicamente na remoÃÃo de Ãnions de efluente em processo batelada AtravÃs de experimento fatorial o material foi modificado quimicamente com sal quaternÃrio de amÃnio (cloreto de 3-cloro-2-hidroxipropiltrimetilamÃnio) O material modificado obtido foi caracterizado (quÃmica e fÃsica) para comprovar o aumento da eficiÃncia pela modificaÃÃo quÃmica realizada. Os parÃmetros pH, concentraÃÃo inicial dosagem de adsorbente cinÃtica e isoterma de adsorÃÃo com Ãnions nitrato sulfato e fosfato foram investigados neste estudo no material modificado Os resultados com planejamento fatorial mostraram que a temperatura e pressÃo sÃo parÃmetros que mais influenciaram no processo de modificaÃÃo quÃmica do material adsorbente A cinÃtica de adsorÃÃo foi examinada em termos de modelos de pseudo-primeira ordem pseudo-segunda ordem e difusÃo intraparticular O modelo de Pseudo-segunda ordem mostrou as maiores concordÃncias com os dados experimentais Dados de equilÃbrio analisados pelos modelos nÃo linear e linear de Langmuir Freundlich SIPS Redlich-Peterson Toth e Tempkin indicaram que os dados experimentais sÃo melhor descritos pelas equaÃÃes de Freundilich e Langmuir A caracterizaÃÃo do bagaÃo de coco modificado foi realizada pelas tÃcnicas FTIR MEV, analise elementar BET e DifraÃÃo de RaiosâX A anÃlise de FTIR indicou que o grupo NH2 do sal de amina interage com grupos quÃmicos do bagaÃo de coco e os resultados indicaram que o bagaÃo de coco modificado exibiu potencial para a sua aplicaÃÃo na remoÃÃo de nitrato, sulfato e fosfato de soluÃÃo aquosa / Its very known that the increase from residues production particularly the agricultural waste becomes an environmental problem of final destiny of this material In recent years the use of agricultural by-products for the removal of inorganic polutant from wastewater has attracted so many researchers because they are cheap simple and of low cost as sorbents natural for wastewater treatment In this work the powder of the peel of green coconut was modified chemically for the removal anions from aqueous effluent by batch process The preparation of the material modified with quaternary salt of ammonium (2-hidroxypropyltrimethyl ammonium chloride) it was accomplished through factorial experiment The chemical and physical characterization of the raw material and modified was carried out to prove the accomplished chemical modification The parameters such as pH initial anion concentration adsorbent dosage adsorption kinetic and isotherm adsorption with modified material were investigated in this study Adsorption kinetic was also examined in terms of three kinetic models ie pseudo-first-order pseudo-second-order and intraparticle diffusion model Pseudo-second-order kinetic model showed a good agreement with the experimental data. Equilibrium data were evaluated by using nonlinear and linear models of Langmuir Freundlich SIPS Redlich-Peterson Toth e Tempkin equations It was obtained that experimental data conforms to the Langmuir and Freundlich equations In order to characterize synthesized material were measurement performed of FTIR elemental analysis SEM and X-ray From FTIR analysis observed that coconut shells species may interact with NH2 groups coconut shells and the results indicated that coconut shells exhibited potential for application in removal of nitrate sulfate and phosphate from aqueous solutions

Submitted by Erika Demachki (erikademachki@gmail.com) on 2014-11-03T16:02:19Z No. of bitstreams: 2 Dissertação - Wolney Arruda de Lima - 2013.pdf: 8969401 bytes, checksum: 67628ca83f7e7b88a59b09ef9dcfd500 (MD5) license_rdf: 23148 bytes, checksum: 9da0b6dfac957114c6a7714714b86306 (MD5) / Approved for entry into archive by Erika Demachki (erikademachki@gmail.com) on 2014-11-03T16:03:42Z (GMT) No. of bitstreams: 2 Dissertação - Wolney Arruda de Lima - 2013.pdf: 8969401 bytes, checksum: 67628ca83f7e7b88a59b09ef9dcfd500 (MD5) license_rdf: 23148 bytes, checksum: 9da0b6dfac957114c6a7714714b86306 (MD5) / Made available in DSpace on 2014-11-03T16:03:42Z (GMT). No. of bitstreams: 2 Dissertação - Wolney Arruda de Lima - 2013.pdf: 8969401 bytes, checksum: 67628ca83f7e7b88a59b09ef9dcfd500 (MD5) license_rdf: 23148 bytes, checksum: 9da0b6dfac957114c6a7714714b86306 (MD5) Previous issue date: 2013-07-31 / In this work were prepared and characterized polyaniline/poly(styrene-co-divinylbenzene) composites by in situ oxidative polymerization of aniline in the pores of styrene-divinylbenzene copolymers. The aim was to obtain composites with high specific surface areas and total pore volumes for use as adsorbents of complex anions [SnCl4]2-. The copolymers with 29 and 84 % of divinylbenzene (DVB) were called PStyDVB 29 and PStyDVB 84, respectively. They were synthesized by suspension polymerization in the presence of inert diluents like toluene and heptane to obtain mesoporous beads with sizes in the range of 400 to 800 μm. Before the oxidative polymerization, the copolymers were swelled with aniline and ethanol mixture at volumetric ratio 20:80. The oxidative polymerization of aniline in the copolymers was carried out using benzoyl peroxide as an oxidant in the presence of hydrochloric or nitric acid as dopant at 25°C in three polymerization cycles. The materials were characterized by infrared spectroscopy with Fourier transform (FTIR), elemental analysis (CNHS), X ray diffraction, thermogravimetry, nitrogen adsorption (specific surface area and pore volume), Scanning Electron Microscopy and Atomic Absorption spectrophotometry. Elemental analysis indicated that the composite doped with HCl adsorb higher amounts of polyaniline (PANI) than using HNO3. The FTIR spectra and X-ray diffraction patterns of the composites were similar to the ones of the copolymers due the low amounts of PANI incorporated. The copolymers had lower thermal stability than composites, and the copolymer PStyDVB 84 had higher thermal stability due to a higher crosslinking degree. The specific surface areas (SBET) and pore volume (Vp) of the composites showed a decrease compared to the respective copolymers, due to the incorporation of polyaniline by homogeneously distributed inside and outside surfaces. The increasing of DVB content in the composites and copolymers favored the formation of high specific surface areas and pore volumes. The adsorption of anion complex [SnCl4]2- by the composites occurred by ion exchange of ions Cl- or NO3-. The results showed that the complex anions [SnCl4]2- adsorption increased with the increasing of hydrochloric acid and tin ion (II) concentrations. The complex anions [SnCl4]2- adsorbed more on the composite PANI/PStyDVB 84 HNO3, although it showed the lowest PANI content, the highest specific surface area and pore volume compared to the other composites. It can be concluded that the anion complex [SnCl4]2- adsorption depends on the number of binding sites and on the porous structure of the composites. / Neste trabalho, foram preparados e caracterizados compósitos Polianilina/Poli(estireno-co-divinilbenzeno), através da polimerização oxidativa in situ da anilina nos poros dos copolímeros estireno e divinilbenzeno. O objetivo foi obter compósitos com altas áreas superficiais específicas e volume de poros totais, para utilização como adsorventes de ânions complexo [SnCl4]2-. Os copolímeros com 29 e 84 % de divinilbenzeno (DVB) foram denominados PStyDVB 29 e PStyDVB 84, respectivamente, e sintetizados através de polimerização em suspensão, na presença de diluentes inertes tolueno e heptano para obtenção de pérolas com estrutura mesoporosa e tamanhos na faixa de 400 e 800 μm. Antes da polimerização oxidativa, os copolímeros foram intumescidos com mistura de anilina e etanol, na razão volumétrica 20:80. A polimerização oxidativa da anilina nos copolímeros foi realizada com peróxido de benzoíla, como oxidante, na presença de ácido clorídrico ou nítrico como dopante a 25°C, em três ciclos de polimerização. Os materiais foram caracterizados por espectroscopia de Infravermelho com Transformada de Fourier, Análise Elementar (CNHS), Difratometria de Raios X, Termogravimetria, Adsorção Física de Nitrogênio (área específica e volume de poros), Microscopia Eletrônica de Varredura e espectrofotometria de Absorção Atômica. A análise elementar indicou que os compósitos dopados com HCl, adsorveram maiores quantidades de Polianilina (PANI) do que com o uso de HNO3. Os espectros de FTIR e difratogramas de Raios X dos compósitos assemelharam-se aos dos copolímeros, pela baixa quantidade de PANI incorporada. Os copolímeros apresentaram menor estabilidade térmica que os compósitos, sendo que o copolímero PStyDVB 84 apresentou maior estabilidade térmica, devido a um maior número de ligações cruzadas. As medidas de áreas superficiais específicas (SBET) e o volume de poros (Vp) dos compósitos apresentaram diminuição em relação aos respectivos copolímeros, devido à incorporação da Polianilina distribuída homogeneamente pela superfície interna e externa. O copolímero PStyDVB 84 e seus compósitos apresentaram altas áreas superficiais específicas e volumes de poros devido ao maior teor de DVB. A adsorção de ânions complexo de [SnCl4]2- pelos compósitos ocorreu pelo processo de troca iônica de íons Cl- ou NO3-. Os ânions complexo [SnCl4]2- foram mais adsorvidos com a elevação das concentrações do ácido clorídrico e do íon estanho (II) em solução. Os ânions complexos [SnCl4]2- adsorveram mais no compósito PANI/PStyDVB 84 HNO3, sendo que ele apresentou o menor teor de PANI, a maior área superficial específica e o maior volume de poros em comparação com os demais compósitos. Pode ser concluído que a adsorção dos ânios complexo [SnCl4]2- depende do número de sítios ligantes e da estrutura porosa do compósito.

Em tempos nos quais a sociedade se volta a reflexões sobre questões climáticas e energéticas, células a combustível surgem como uma alternativa promissora no âmbito das políticas que visam o desenvolvimento sustentável. Nesse sentido, há ainda desafios a serem superados nas esferas fundamental e aplicada. Entender o papel das espécies presentes no eletrólito de suporte é fundamental em tal descrição. Especificamente no caso de ânions dissolvidos no eletrólito, o papel mais comumente atribuído é o de inibir o processo eletrocatalítico de interesse, por meio do bloqueio de sítios superficiais. No entanto, atribui-se recentemente ao ânion BF4- um efeito diverso; o aumento dos valores de corrente de eletro-oxidação em baixos potenciais. Apresenta-se na presente dissertação, um estudo sistemático deste processo, empregando a técnica da nanobalança eletroquímica a cristal de quartzo (NECQ), em conjunto com técnicas eletroquímicas tradicionais. Tal estudo revelou a ocorrência de diferenças notáveis nos perfis voltamassométricos do sistema eletroquímico quando da adição de pequenas quantidades do reagente HBF4. Tais diferenças têm caráter bastante especial, uma vez que nos perfis voltamétricos não são observadas diferenças marcantes nos valores de corrente entre o sistema eletroquímico com a adição de pequenas quantidades do reagente HBF4 e o sistema eletroquímico sem a adição desse reagente. À partir dos métodos utilizados e das evidências experimentais observadas, é possível inferir que o comportamento peculiar até então atribuído ao HBF4 na verdade resulta de uma contaminação com o semimetal arsênio, apesar de o rótulo do fabricante não informar sobre a possibilidade da ocorrência de traços do semimetal. / In times where the society turns its reflections on climate and energy questions, fuel cells appear as a promising alternative for the policies aimed at sustainable development. In this sense, there are still challenges to overcome in fundamental and applied levels. Understand the role of species in the supporting electrolyte is crucial in such a description. Specifically in the case of anions dissolved in the electrolyte, the most commonly assigned role is to inhibit the electrocatalytic process of interest, through blockade of surface sites. However, to the anion BF4- is recently attributed a diverse effect, the increase of the current values of electro-oxidation at low potentials. It is presented in this dissertation, a systematic study of this process, using the technique of the electrochemical quartz crystal nanobalança (EQCN), combined with traditional electrochemical techniques. This study revealed the occurrence of remarkable differences in the voltamassometric profiles of the electrochemical system when adding small amounts of reagent HBF4. Such differences are special features, since in the voltammetric profiles marked differences are not observed in current values between the electrochemical system with or without the addition of small amounts of reagent HBF4. On the basis of methods utilized and the experimental evidence observed, it is possible to infer that the peculiar behavior previously attributed to HBF4 actually results from a semimetal contamination with arsenic, although the manufacturer\'s label gives no information about the occurrence of traces of the semimetal.

Orientador: Matthieu Tubino / Tese (doutorado) - Universidade Estadual de Campinas, Instituto de Química / Made available in DSpace on 2018-08-21T09:33:03Z (GMT). No. of bitstreams: 1 Silveira_EvaLuciaCardoso_D.pdf: 1544784 bytes, checksum: 21e0e9cae43209115424068ca5568476 (MD5) Previous issue date: 2012 / Resumo: Um método de baixo custo é proposto neste trabalho para a análise quantitativa do álcool residual em biodiesel através da determinação do ponto de fulgor. Foram analisados ésteres metílicos obtidos de óleos de soja, milho, girassol e de sebo bovino. Os ésteres etílicos foram obtidos de óleo de soja. Em todos os casos ficou evidente que há uma correlação entre o ponto de fulgor e o teor de álcool residual no biodiesel. Assim, o parâmetro ponto de fulgor pode ser usado diretamente para determinar o teor de álcool residual do biodiesel. Foi proposto também um método para a determinação de fósforo em biodiesel por espectrofotometria de absorção molecular UV-Vis. As amostras de biodiesel são mineralizadas por calcinação a 550 °C seguindo dissolução do resíduo em H2SO4 1,0 mol L. O procedimento analítico é baseado na formação do complexo azul de molibdênio. Empregou-se o ácido 1-amino-2-naftol-4-sulfônico como agente redutor. O método foi aplicado para amostras de biodiesel de soja, canola, girassol e de sebo bovino. Os limites de detecção e quantificação obtidos para fósforo foram de 0,57 mg kg e 1,71 mg kg, respectivamente. O desvio padrão relativo médio obtido foi cerca de 5 %. A simplicidade do procedimento adicionado à precisão, exatidão e o baixo custo indicam que é uma excelente opção para a determinação de fósforo em biodiesel. Um terceiro método, neste caso, para a determinação de ânions em biodiesel baseado na extração com água assistida por ultrassom também foi desenvolvido neste trabalho. Os extratos obtidos das amostras de biodiesel foram analisados por cromatografia de íons. Os limites de quantificação foram 0,97; 4,10; 0,30; 2,47 e 0,26 mg kg para acetato, formiato, cloreto, fosfato e sulfato, respectivamente. A técnica de cromatografia de íons mostrou-se viável para a separação e quantificação de ânions orgânicos e inorgânicos em biodiesel simultaneamente diminuindo assim o tempo de análise / Abstract: A low cost method is proposed in this work for the quantitative analysis of residual alcohol in biodiesel through determination of the flash point. We analyzed methyl esters obtained from oils such as soy, corn, sunflower and of bovine fat. The ethyl esters were obtained from soy oil. In all cases it became very evident that there is a correlation between the flash point and the residual alcohol content in the biodiesel. Therefore the parameter flash point can be used to directly determine the residual alcohol content of biodiesel. A method has been proposed for the determination of phosphorus in biodiesel by UV-vis molecular absorption spectrophotometry. The biodiesel samples are mineralized using an ashing procedure at 550 °C following dissolution of the residue in 1.0 mol L H2SO4. The analytical procedure is based on the formation of a blue molybdenum complex. 1-amino-2naphthol-4-sulfonic acid is used as reducing agent. The method was applied to biodiesel samples of soy, canola and sunflower oils and of bovine fat. The limits of detection and quantification are 0.57 mg kg and 1.71 mg kg, respectively. The average standard deviation obtained was about 5 %. The simplicity of the procedure added to its precision, accuracy and low cost indicate that it is an excellent option for the determination of phosphorus in biodiesel. A third method, in this case, for the determination of anions in biodiesel based on extraction with ultrasound assisted water has also been developed in this study. The extracts of biodiesel samples were analyzed by ion chromatography. The limits of quantification obtained were 0.97, 4.10, 0.30, 2.47 and 0.26 mg kg for acetate, formate, chloride, phosphate and sulfate, respectively. The technique of ion chromatography proved to be feasible for the simultaneously separation and quantification of organic anions in biodiesel, thereby reducing analysis time / Doutorado / Quimica Analitica / Doutora em Ciências

La presente tesis doctoral titulada "Sondas moleculares y complejos de rutenio (II) y osmio (II) para la detección cromo-fluorogénica de especies cargadas y monóxido de carbono" se centra en el desarrollo de sensores químicos moleculares. El trabajo realizado se puede dividir en dos partes: (i) síntesis y caracterización de sondas moleculares multifuncionales para la detección óptica de aniones y cationes metálicos y, (ii) preparación de complejos de rutenio (II) y osmio (II) para la detección cromo-fluorogénica de monóxido de carbono. La primera familia de sondas moleculares, a la cual se hace referencia en el capítulo 2, se basa en el uso de imidazoantraquinonas como subunidad indicadora. Empleando este fragmento molecular se prepararon y caracterizaron cuatro sondas (2a-2d). De todos los aniones que se ensayaron, sólo el fluoruro es capaz de inducir la aparición de una banda de absorción (lo cual se refleja en diferentes cambios de color) y bandas de emisión desplazadas hacia el rojo. Estos cambios se atribuyen a la desprotonación del grupo N-H del anillo de imidazol inducida por el fluoruro. También los cationes Fe3+, Al3+ y Cr3+ son capaces de producir desplazamientos moderados hacia el azul de las bandas de absorción de los cuatro receptores, así como una desactivación marcada de la emisión a causa de su coordinación (con los átomos de oxígeno y nitrógeno del cromóforo imidazoantraquinona). El segundo capítulo también está dedicado al estudio del comportamiento de coordinación frente a aniones y cationes de una segunda familia de sondas (3a-3d) basadas en derivados de imidazoquinolina. Nuevamente el anión fluoruro promueve la desprotonación de estos compuestos, lo cual se refleja en la aparición de bandas de absorción y de emisión desplazadas hacia el rojo. En cuanto a la respuesta óptica en presencia de cationes metálicos es muy poco selectiva, observándose cambios en las bandas UV-visible y una desactivación de las bandas de emisión en presencia de Hg2+, Cu2+, Co2+, Fe3+, Fe2+, Zn2+, Pb2+, Cd2+, Cr3+ y Al3+. A lo largo del capítulo 3 se presenta la síntesis, caracterización y comportamiento cromo-fluorogénico frente al monóxido de carbono de dos conjuntos de complejos de rutenio (II) y osmio (II) que tienen en su esfera de coordinación los fluróforos 2,1,3-benzotiadiazol (BTD) y 5-(3-tienil)-2,1,3-benzotiadiazol (TBTD). En la primera parte de este capítulo se prepararon ocho compuestos con el ligando BTD (1-8). Al burburjearles CO, las disoluciones de cloroformo de dichos complejos mostraron notables cambios de color. Además, su emisión se vio incrementada debido a la coordinación de los complejos con el CO y el desplazamiento del fluoróforo BTD. Por otro lado, la adsorción de los complejos en sílice dio lugar a sólidos que presentaron importantes cambios de color permitiendo la detección de CO en fase gas a simple vista y con alta selectividad y sensitividad. El segundo conjunto de complejos de rutenio (II) y osmio (II) contiene el fluróforo TBTD (3-7). Éstos también son capaces de detectar CO cuando se encuentran disueltos en cloroformo y adsorbidos en sílice a través de cambios de color y fluorescencia. Por otra parte, se prepararon dos nuevos complejos (8 y 9) funcionalizados con una cadena de polietilenglicol. Ambos complejos son solubles en agua y permiten la detección de CO en este disolvente altamente competitivo. Además, los compuestos 8 y 9 no son tóxicos y se emplearon con éxito en la detección de CO en células HeLa. / The present PhD thesis entitled "Molecular probes and ruthenium (II) and osmium (II) complexes for the chromo-fluorogenic sensing of charged species and carbon monoxide" is focused on the development of molecular chemosensors. More in detail, the work carried out is clearly divided into two independent parts: (i) the synthesis and characterization of multifunctional molecular probes for the optical detection of anions and metal cations and, (ii) the preparation of ruthenium (II) and osmium (II) complexes for the chromo-fluorogenic sensing of carbon monoxide. The first family of molecular probes, reported in chapter 2, is based on the use of imidazoanthraquinone as signaling subunit. Using this molecular fragment four probes (2a-2d) are prepared and characterized. Of all the anions tested, only fluoride is able to induce the appearance of red-shifted absorption (reflected in marked color changes) and emission bands. These changes are ascribed to a fluoride-induced deprotonation of the N-H moiety of the imidazole ring. Also Fe3+, Al3+ and Cr3+ were able to induce moderate blue-shifts of the absorption bands of the four receptors upon coordination (with the oxygen and nitrogen atoms of the imidazoanthraquinone chromophore) and marked emission quenching. The second chapter is also devoted to study the coordination behavior toward anions and cations of a second family of probes (3a-3d) containing imidazoquinoline derivatives. Again, fluoride anion promoted the deprotonation on the probes that are reflected in the apperacence of red-shifted absorption and emission bands. The optical response in the presence of metal cations is quite unselective and UV-visible shifts and emission quenchings are observed in the presence of Hg2+, Cu2+, Co2+, Fe3+, Fe2+, Zn2+, Pb2+, Cd2+, Cr3+ and Al3+. Chapter 3 presents the synthesis, characterization and chromo-fluorogenic behavior toward of carbon monoxide of two set of ruthenium (II) and osmium (II) complexes bearing 2,1,3-benzothiadiazole (BTD) and 5-(3-thienyl)-2,1,3-benzothiadiazole (TBTD) fluorophores. Eight complexes functionalized with BTD ligand (1-8) are prepared in the first part of this chapter. Chloroform solutions of the complexes underwent remarkable color changes when CO is bubbled. Also, significative emission enhancements are obserbed due to coordination of CO and displacement of BTD fluorophore. Besides, the adsorption of the complexes on silica yielded solids that presented remarkable color changes that allowed a naked eye detection of CO in gas phase. The second set of ruthenium (II) and osmium (II) complexes contains TBTD fluorophore (3-7). Also these complexes are able to detect CO in chloroform solution and in gas phase when adsorbed on silica through color and fluorescence changes. Moreover, two new complexes (8 and 9) containing a poly(ethylene) glycol chain are prepared. Both complexes are water soluble and allowed CO detection in this highly competitive solvent. Besides, 8 and 9 are non-toxic and are successfully used for CO detection in HeLa cells. / La present tesi doctoral titulada "Sondas moleculars i complexos de ruteni (II) i osmi (II) per a la detecció cromo-fluorogènica d'espècies carregades i monòxid de carboni" es centra en el desenvolupament de sensors químics moleculars. El treball realizat es pot dividir en dues parts: (i) síntesi i caracterització de sondes moleculars multifuncionals per a la detecció òptica d'anions i cations metàli·lics i, (ii) preparació de complexos de ruteni (II) i osmi (II) per a la detecció cromo-fluorogènica de monòxid de carboni. La primera família de sondes moleculars, a la qual es fa referència en el capítol 2, es basa en l'ús d'imidazoantraquinones com a subunitat indicadora. Emprant aquest fragment molecular es van preparar i caracteritzar quatre sondes (2a-2d). De tots els anions que es van assajar, només el fluorur és capaç d'induir l'aparició d'una banda d'absorció (la qual cosa es reflecteix en diferents canvis de color) i bandes d'emissió desplaçades cap al roig. Aquestos canvis s'atribuïxen a la desprotonació del grup NH de l'anell d'imidazol induïda pel fluorur. També els cations Fe3+, Al3+ i Cr3+ són capaços de produir desplaçaments moderats cap al blau de les bandes d'adsorció dels quatre receptors, així com una desactivació marcada de l'emissió a causa de la seua coordinació (amb els àtoms d'oxigen i nitrogen del cromòfor imidazoantraquinona). El segon capítol també està dedicat a l'estudi del comportament de coordinació en presència d'anions i cations d'una segona família de sondes (3a-3d) basades en derivats d'imidazoquinolina. Novament l'anió fluorur promou la desprotonació d'aquestos compostos, la qual cosa es reflecteix en l'aparició de bandes d'absorció i d'emissió desplaçades cap al roig. Quant a la resposta òptica en presència de cations metàl·lics és molt poc selectiva, observant-se canvis en les bandes UV-visible i una desactivació de les bandes d'emissió en presència de Hg2+, Cu2+, Co2+, Fe3+, Fe2+, Zn2+, Pb2+, Cd2+, Cr3+ i Al3+. Al capítol 3 es presenta la síntesi, caracterització i comportament cromo-fluorogènic en presència de monòxid de carboni de dos conjunts de complexos de ruteni (II) i osmi (II) que tenen a la seua esfera de coordinació els fluoròfors 2,1,3-benzotiadiazol (BTD) i 5-(3-tienil)-1,2,3-benzotiadiazol (TBTD). A la primera part d'aquest capítol es van preparar huit compostos amb el lligant BTD (1-8). Al bambollejar-les CO, les dissolucions de cloroform d'aquestos complexos van mostrar notables canvis de color. A més, la seua emissió es va veure incrementada a causa de la coordinació dels complexos amb el CO i el desplaçament del fluoròfor BTD. D'altra banda, l'adsorció dels complexos en sílice va donar lloc a sòlids que van presentar importants canvis de color premetent la detecció de CO en fase gas a simple vista i amb alta selectivitat i sensitivitat. El segon conjunt de complexos de ruteni (II) i osmi (II) conté el fluoròfor TBTD (3-7). Aquestos també són capaços de detectar CO quan es troben dissolts en cloroform i adsorbits en sílice a través de canvis de color i fluorescència. D'altra banda, es van preparar dos nous complexos (8 i 9) funcionalitzats amb una cadena de polietilenglicol. Ambdós complexos són solubles en aigua i permeten la detecció de CO en aquest dissolvent altament competitiu. A més, els compostos 8 i 9 no són tòxics i es van emprar amb èxit en la detecció de CO en cèl·lules HeLa. / Marín Hernández, C. (2017). Molecular probes and ruthenium (II) and osmium(II) complexes for the chromofluorogenic sensing of charged species and carbon monoxide [Tesis doctoral no publicada]. Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/95407 / TESIS