Rozprawy doktorskie na temat „Anionic Nanoparticles”

Anionic polymerisation techniques have been optimised to develop a “one-pot”, facile method to produce both linear and branched polystyrenes utilising the “Strathclyde” route to highly branched structures. ATRP was investigated as a possible method but anionic polymerisation was found to give much better control over the size and structure of polystyrenes produced. Using this anionic polymerisation relatively monodisperse linear polystyrenes were synthesised with dispersity values as low as 1.03 for a polystyrene chain with a targeted degree of polymerisation (DPn) of 100 monomer units. A number of different structures of branched polystyrene were synthesised, and their different physical properties examined by viscometry measurements and differential calorimetry scanning experiments. It has been found that very dense, highly branched materials (with approximations of 48 polymer chains branched together) can be synthesised with a targeted primary chain DPn = 10 monomer units. Weight average molecular weight (Mw) values as high as 992,000 gmol-1 for branched polystyrene can be synthesised with a primary chain length of DPn =50 monomer units. Functional polystyrenes were synthesised both by initiation with an amine containing compound and sec-BuLi, resulting in chain end functionalisation, and also post-functionalised by sulphonation of synthesised polystyrenes, resulting in a statistical distribution along the polymer chains pendant groups. The hydrophilicity could be manipulated by the percentage of sulphonation. At over 30% sulphonation of the pendant polystyrene groups, the polymers become water soluble. Polymer nanoparticles have been synthesised by a nanoprecipitation method from functionalised branched polystyrene synthesised by anionic polymerisation techniques. Nanoparticles synthesised from DPn10 branched sulphonated polystyrenes were analysed by dynamic light scattering and found to be approximately 60nm with dispersity values as low as 0.15. They were found to be stable after 6 months ambienmt storage, and some preliminary testing on the encapsulation of Oil red suggests that the nanoparticles may be capable of encapsulating hydrophobic drugs.

Silver colloids were synthesized in linear and branched anionic polymer matrices at different pH reducing by ascorbic acid. The template role of the host polymers in anionic form was studied at pH = 7 and pH = 12. Linear Polyacrylamide and star-like copolymers Dextran-graft-Polyacrylamide after alkaline hydrolysis were used as matrices. Silver colloids were studied by UV-Vis spectrophotometry just after synthesis and in 3 months. It is shown that branched polymer matrices are more efficient in comparison with linear one for in situ silver nanoparticle synthesis. The pH value affects the process of formation was investigated. When you are citing the document, use the following link http://essuir.sumdu.edu.ua/handle/123456789/35143

PONTIFÍCIA UNIVERSIDADE CATÓLICA DO RIO DE JANEIRO
CONSELHO NACIONAL DE DESENVOLVIMENTO CIENTÍFICO E TECNOLÓGICO
Atualmente a crescente demanda do uso de repelentes de insetos tem promovido a pesquisa de produtos mais eficazes e com uma maior durabilidade da ação repelente. O objetivo deste trabalho foi a obtenção de novas nanopartículas com propriedades interfaciais modificadas superficialmente com grupos funcionais catiônicos e polímeros aniônicos, com o intuito de melhorar a estabilidade de emulsões Pickering contendo um princípio ativo, N,N -dimetil-m-toluamida (DEET), comumente utilizado nos repelentes comerciais. A obtenção das nanopartículas incluiu a funcionalização inicial da superfície de nanopartículas de sílica comerciais com grupos amino secundários (R-NH2), seguido da introdução de grupos catiônicos de amônio quaternário (R-NR4 positivo) e posterior complexação eletrostática com polímeros aniônicos (poli(ácido acrílico), PAA, e poli(4-estireno sulfonato de sódio), PSS). As nanopartículas modificadas mostraram boa dispersabilidade em meio aquoso, favorecendo a estabilização de emulsões de tipo óleo em água (O/A). Os melhores resultados dos estudos de estabilidade no tempo das emulsões foram obtidos usando as nanopartículas catiônicas (SiNP-A,G) recobertas com PAA e com a mistura de polímeros (PAA mais PSS). As emulsões Pickering obtidas com as nanopartículas de sílica recobertas com PAA mostraram os melhores resultados na retardação da evaporação do DEET, com potencial uso para liberação lenta deste composto.
Currently the increasing demand for insect repellent use has promoted research into more effective products and a longer repellent action. The objective of this work was to obtain new nanoparticles by surface modification with cationic functional groups and anionic polymers, with the aim of improving the stability of Pickering emulsions containing an active ingredient, N,N -diethyl-m-toluamide (DEET) commonly used in commercial repellents. The preparation of the nanoparticles included initial surface functionalization of commercial silica nanoparticles with secondary amino groups (R-NH2), followed by the introduction of cationic quaternary ammonium groups (R-NR4 positive) and subsequent electrostatic complexation with anionic polymers (poly (acrylic acid), PAA, and poly(sodium 4-styrenesulfonate), PSS). The modified nanoparticles showed good dispersibility in aqueous medium, favoring the stabilization of emulsions oil-in-water (O/W). The best results of the emulsion time stability studies were obtained using cationic silica nanoparticles (SiNP-A,G) covered with PAA and with the polymer mixture (PA plus PSS). The Pickering emulsions obtained with the cationic silica nanoparticles coated with PAA showed the best results in retarding DEET evaporation, with potential use for slow release of this compound.

La surexploitation des ressources de la planète est aujourd’hui une problématique de premier ordre, et fait du remplacement des sources non renouvelables, d'énergie et de matières premières, l’un des défis majeurs du XXIe siècle. Dans cet objectif, les lignines, par leur disponibilité et leur biocompatibilité, apparaissent comme l’une des alternatives aux ressources fossiles. C’est dans ce contexte que le Laboratoire PEIRENE a décidé de mener ce travail de thèse portant sur le développement de nouveaux matériaux photosensibles à base de lignines modifiées. Dans ce but, trois lignines d’origines différentes ont été acétylées. Leur étude par spectroscopie RPE a révélé que le blocage de leurs fonctions antioxydantes augmente considérablement la quantité d’espèces réactives de l’oxygène qu’elles sont capables de générer sous irradiation lumineuse, permettant ainsi d’envisager l’utilisation de ce biopolymère modifié dans de nombreux domaines tels que le traitement photodynamique antimicrobien. Afin de les rendre hydrodispersibles et d’élargir ainsi leur champ d’applications, ces matériaux aux propriétés prometteuses ont été mis sous forme de nanoparticules puis, leur comportement photosensible a été lui aussi évalué par spectroscopie RPE. Il a ainsi été démontré qu’une fois dispersées dans l’eau sous la forme de nanoparticules, les lignines acétylées étaient toujours capables de produire de l’oxygène singulet sous irradiation lumineuse. Cette activité, qui n’a pas encore été reportée dans la littérature à notre connaissance, reste cependant assez restreinte et nécessite donc d’être améliorée. Afin d’élargir le domaine du spectre solaire permettant leur activation, un photosensibilisateur a par ailleurs été associé à ces nano-objets par encapsulation et par greffage covalent. L’ensemble des résultats découlant de ces travaux permettent d’envisager le développement de systèmes à base de nanoparticules de lignines acétylées dans de nombreux domaines, notamment pharmaceutique et phytosanitaire
The overexploitation of the planet's resources is nowadays a major problem and makes the replacement of non-renewable sources of energy and raw materials, one of the major challenges of the XXIe century. For this purpose, lignins, by their availability and their biocompatibility, appear as one of the alternatives to fossil resourcesIn this context, the PEIRENE Laboratory decided to carry out this PhD work on the development of new photosensitive materials based on modified lignins. For this purpose, three lignins from different origin were acetylated. Their study by EPR spectroscopy revealed that blocking their antioxidant functions considerably increases the quantity of reactive oxygen species they are able to generate under light irradiation. Thus it is possible to envisage the use of this modified biopolymer in many areas such as antimicrobial photodynamic therapy. In order to make them water-dispersible and thus to widen their field of applications, these materials with promising properties were put in the form of nanoparticles. Their photosensitive behavior has been also valuated by EPR spectroscopy. It has been demonstrated that once dispersed in water in the form of nanoparticles, the acetylated lignins were still capable of producing singlet oxygen under light irradiation. This activity, which has not yet been reported in the literature to our knowledge, however, remains quite limited and therefore needs to be improved. In order to widen the range of the solar spectrum allowing their activation, a photosensitizer has also been associated with these nano-objects by encapsulation and covalent grafting. The results of these studies make possible to envisage the development of systems based on acetylated lignins nanoparticles in in many field, in particular pharmaceutical and phytosanitary

The development of molecular receptors for anion recognition has become an important aspect of supramolecular chemistry. In this thesis, we focused our attention to the study of systems for fluoride recognition in water. Fluoride is indeed an anion of interest due to its implication in environmental and health related issues. Furthermore, its small size and high hydration energy make its recognition in water particularly challenging.

Most of the synthetic systems reported for fluoride recognition have been extensively studied in organic solvents (DMSO, acetonitrile) using tetrabutylammonium fluoride (TBAF) as the source of fluoride. In many cases, titra- tion behaviours are observed that cannot be ascribed to a classical 1:1 binding isotherm, deprotonation problems of Brønsted-Lowry acid type of receptors aside. In the first part of our thesis we investigated, using a uranyl-salophen re- ceptor which recognizes fluoride via Lewis Acide/Base interactions, the origin of the unusual titration behaviour. Via UV/vis, 19F and 1H NMR spectroscopies, we have been able to highlight that the equilibrium between the fluoride and the corresponding bihalide ion, HF−2 ,which is inevitably generated along with the hydroxide anion in situ due to trace amounts of water, can be at the ori- gin of this singular behaviour. Our results put to light that when undertaking titrations with fluoride in DMSO, the fluoride–bihalide equilibrium can affect the data and that the latter species can even be the dominating species at low TBAF concentrations. When varying the solvent from DMSO to acetonitrile, the s-shape titration curves observed by UV/vis are no longer observed for the uranyl-salophene receptor that we studied. The fluoride-bifluoride equilibrium is still present but both of the anions generated in this process are recognised by the uranyl-salophene receptor with similar affinity constants above 10^6 M−1.

The second part of our work was devoted to finding ways to solubilize anion receptors that are efficient in organic solvents, into an aqueous environment. Two approaches were investigated: (i) grafting of the receptors onto silica nanoparticles and (ii) the micellar incorporation of the receptors. For the first strategy, we developed two silylated urea-based receptors. These receptors were first studied in organic solvents (DMSO and/or acetonitrile) where they showed selectivity, among halides, towards fluoride. Once grafted on the silica nanoparticles, due to the fact that hydroxyl groups and solvent molecules are present in the silica matrix, fluoride recognition was not possible.

We explored it with different simple H-bond based urea receptors in the second srategy. With the cationic surfactants, cetyl trimethyl ammonium chloride and bromide, the counter-ions of the micelles interfere with the fluoride recognition. With the neutral surfactant triton X-100, the incorporation of the anion receptors proved to be difficult. Moreover, the variations observed in the UV/vis spectra upon titrations were too small to be able to make any conclusions about fluoride recognition.
Doctorat en Sciences de l'ingénieur
info:eu-repo/semantics/nonPublished

A range of novel host molecules with various degrees of pre-organisation for the supramolecular complexation of anionic guest species have been synthesized. Both organic core and nanoparticle-based derivatives of the ligands have been prepared and the properties of the new host ligands studied with particular reference to their anion binding behaviour. Two types of calix[4]arene derived cationic hosts for anions with, respectively, 1,3-altemate and cone conformations have been prepared. The affinity of the tetrasubstituted calix[4]arene hosts for a variety of anions has been probed with Ή NMR spectroscopic titration. The ԼՅ-alternate system binds dicarboxylate anions in a ditopic manner while the cone compounds have the highest affinity for bromide anion and are deprotonated by carboxylates. The potentially fluorescent 1,3-altemate calix[4]arene that contains a pyridinium functionality coupled via a methylene spacer to a pyrene group undergoes selective chloride-induced conformational change which results in strong increase in both monomer and excimer emission. Gold nanoparticles protected with 5-[l ,2]dithiolan-3yl-pentanoic acid pyridin-3-ylamide remain stable as colloidal solution in methanol and the UV aborption spectra demonstrate the nanoparticles' response to exposure of a variety of anions by red shift with concomitant decrease in intensity. Titration of the colloidal solution with silver tetrafluoroborate results in an increase in absorption indicating possible interaction of silver cations with the pyridyl nitrogen atoms

Les nanomatériaux carbonés (NMC) sont très utilisés dans le monde industriel et leurs applications, nombreuses, sont en plein développement. L’absence de réglementation pour leur préparation et leur emploi fait qu’il est nécessaire comme pour tous les nano-objets, de déterminer le risque qu’une exposition fait courir à l’Homme et d’adapter la législation en conséquence. Une meilleure connaissance de leur potentiel toxique est donc nécessaire. Les difficultés de plus en plus grandes pour utiliser les modèles animaux, rend nécessaire le développement d’études avec des lignées cellulaires au sein desquelles les macrophages ont une place prépondérante. Ces NMC sont très légers et forment facilement des aérosols et les modèles préférés sont les macrophages alvéolaires. Cependant il n’existe pas à l’heure actuelle de lignées de macrophages alvéolaires humains à la différence de cellules de rat. Le sujet de ma thèse porte sur l’étude de la réponse macrophagique aux NMC et la compréhension des effets de leurs caractéristiques physiques et chimiques sur leur transcriptome. Les NMC étudiés sont les nanotubes de carbone (NTC) multi feuillets, les NTC mono feuillets, le noir de carbone et l’oxyde de graphène. Nos résultats montrent que tous les NMC étudiés déclenchent une réaction inflammatoire dans les cellules NR8383 et les cellules THP-1 différenciées, et certains d’entre eux induisent une cytotoxicité importante. La taille, la fonctionnalisation et la forme contrôlent les mécanismes de toxicité induits par les NMC. Des NTC de tailles similaires altèrent des voies de signalisation identiques, une fonctionnalisation par des groupements amines produit un stress des lysosomes tandis que la fonctionnalisation par des groupements carboxyle entraine un stress du réticulum endoplasmique (RE). Les nanotubes induisent une désorganisation du cytosquelette plus importante que les nanoparticules sphériques. Nous avons également mis en évidence une accumulation de lipides chez les cellules NR8383 suite à un stress du RE induit par le Mitsui-7, un NTC multi feuillet. Le même NTC induit aussi une fusion de ces macrophages. La formation de ces cellules spumeuses et des cellules géantes à multi-noyaux sont des évènements clés entrainant la formation de granulomes. Les résultats obtenus présentent un support important pour la compréhension des effets des NMC montrant une certaine toxicité non négligeable de point de vue moléculaire. Cette toxicité est dépendante des caractéristiques physiques et chimiques de ces nanomatériaux. Ainsi, en se basant sur ce type de données, on pourra s’orienter vers une fabrication safe-by-design pour limiter les risques liés à leur exposition
Carbon nanomaterials (CNM) are widely used in the industrial world and they have many applications. The absence of legislation controlling their preparation and uses makes necessary, as for all nano-objects, the study of their toxicity in order to determine the risk of human exposure and to adapt legislation accordingly. Therefore, a better knowledge of their toxic potential is necessary. The increasing difficulties in using animal models make necessary the development of studies using cell lines especially macrophages that play a predominant role. These CNM are very light and form easily aerosols, reason why the preferred models for toxicity studies are alveolar macrophages. However, there are no human alveolar macrophage lines currently but rat cells exist. The subject of my thesis is to study macrophages response to CNM and the understanding of the effect of their physical and chemical characteristics on the transcriptome. The CNM studied are multiwall carbon nanotubes (CNT), single wall CNT, carbon black and graphene oxide. Our results show that all CNM studied trigger an inflammatory reaction in NR8383 and differentiated THP-1 cells, also some of them induce cytotoxicity. Size, functionalization and form control CNM toxicity mechanisms: CNT with similar size alter identical signaling pathways, amino group functionalization produces lysosomal stress, whereas functionalization with carboxyl groups causes reticulum endoplasmic (RE) stress, nanotubes induce cytoskeleton disorganization more than spherical nanoparticles. Otherwise, we identified lipid accumulation in NR8383 cells due to RE stress induced by Mitsui-7, a multiwall CNT. There was also a fusion of these macrophages. The formation of these foam cells and giant multi-nucleus cells are key events leading to granulomas formation. The results obtained are an important support for understanding CNM effects, showing some significant toxicity at molecular level. This toxicity is dependent on the physical and chemical characteristics of these nanomaterials. Thus, based on this type of data, we can move towards a safer manufacture to avoid the risks associated with their exposure

[EN] The PhD Thesis entitled "Silica nanoparticles as inorganic scaffolds for the preparation of hybrid materials for the optical detection of anions" deals with the combination of supramolecular and material chemistry concepts to prepare hybrid sensing materials with the ability to detect selected ions through color and emission changes. The first hybrid material prepared is based in the use of silica nanoparticles as inorganic scaffold functionalized with spirobenzopyrans (signaling unit) and with thiourea moieties (binding unit). In the final nanoparticles the spirobenzopyran signaling unit is in its open polar conformation (red color merocyanine structure). Coordination of long chain carboylates (octanoate, decanoate and dodecanoate) with the thiourea moieties induced the formation of a dense hydrophobic monolayer around the signaling unit. This non-polar monolayer induced a change in the conformation of the spirobenzopyran to the closed spirocyclic form with a subsequent color change. The second part of this PhD Thesis was related with the preparation of silica nanoparticles functionalized with anthracene, as signalling subunit, and two different thioureas, as anion binding sites. Acetonitrile suspensions of the bifunctionalized nanoparticles showed the typical structured emission band of the anthracene fluorophore. Addition of certain anions to acetonitrile suspensions of the nanoparticles induced an enhancement of the emission intensity (Cl-, Br-, H2PO4-, acetate and benzoate) or a marked quenching (F- and CN-). Finally, the last part of this PhD Thesis deals with the preparation of silica nanoparticles functionalized with terpyridine binding sites and sulforhodamine B as signaling subunit. Coordination of transition metal cations (Fe3+, Hg2+, Cu2+, Ni2+ and Pb2+) with the terpyridine bindind sites induced a marked quenching of the emsission intensity (ca. 95%) of the sulforhodamine B fluorophore. The prepared materials were used for the fluorogenic recognition of anions. At this respect, addition of H2PO4-, HSO4-, F-, Cl-, Br-, I- and NO3-anions induced different degrees of cation displacements with the subsequent enhancement of the emission intensity of the fluorophore. Principal component analysis (PCA) allowed the discrimination of all the anions tested. Besides, only H2PO4- anion was able to induce the displacement of Pb2+ cation with the subsequent emission enhancement.
[ES] La presente Tesis Doctoral titulada "Nanopartículas de sílice como soporte inorgánico para la preparación de materiales híbridos para la detección óptica de aniones" se basa en el empleo de conceptos de química supramolecular y de química de materiales para la preparación de sistemas sensores híbridos con capacidad para reconocer iones mediante cambios de color y de fluorescencia. El primer material sensor desarrollado esta basado en nanopartículas de sílice funcionalizadas con espirobenzopiranos (unidad indicadora) y con tioureas (unidad coordinante). En las nanopartículas bifuncionalizadas el espiropirano está en su forma polar abierta (merocianina de color rojo). Cuando coordinan las tioureas con carboxilatos de cadena larga (octanoato, decanoato y dodecanoato) se forma un entorno apolar alrededor de la unidad indicadora que favorece su transformación de la forma abierta a la apolar espirocíclica cerrada con el consiguiente cambio de color. En la segunda parte de la Tesis se han preparado nanoparticulas de sílice funcionalizadas con antraceno, como unidad indicadora, y con dos diferentes tioureas, como unidades coordinantes de aniones. Suspensiones de las nanopartículas bifuncionalizadas en acetonitrilo muestran la típica emisión estructurada del antraceno. Al añadir diferentes aniones a la suspensión de las nanoparticulas se obiene un aumento de fluorescencia (con Cl-, Br-, H2PO4-, acetato y benzoato) o una desactivación de la misma (F- y CN-). Por último se prepararon nanopartículas de sílice funcionalizadas con terpiridinas, como unidad coordinante, y con sulforodamina B, como unidad indicadora. La coordinación de cationes metálicos de transición (Fe3+, Hg2+, Cu2+, Ni2+ y Pb2+) con las terpiridinas dio lugar a una desactivación importante de la emisión de la sulforodamina B anclada (95% de la inicial). En un segundo paso se estudio la capacidad de ciertos aniones (H2PO4-, HSO4-, F-, Cl-, Br-, I- y NO3-) de desplazar al metal coordinado con la subsiguiente regeneración de la emisión de la sulforodamina. Aplicando el análisis de componentes principales (PCA) se consiguió la discriminación de todos los aniones empleados. Además, las nanopartículas tratadas con el catión Pb2+ dieron una respuesta selectiva con el anión H2PO4-.
[CAT] La present Tesi Doctoral titulada "Nanopartícules de sílice com a suport inorganic en la preparació de materials hibrids per a la detecció optica de anions" es basa en l'ús de conceptes de química supramolecular i de química de materials per a la preparació de sistemes sensors híbrids amb capacitat per a reconèixer ions mitjançant canvis de color i de fluorescència. El primer material sensor desenvolupat està basat en nanopartícules de sílice funcionalitzades amb espirobenzopirans (unitat indicadora) i amb tiourees (unitat coordinant). A les nanopartícules bifuncionalitzades l'espiropirà està en la seua forma polar oberta (merocianina de color vermell). Quan coordinen les tiourees amb carboxilats de cadena llarga (octanoat, decanoat i dodecanoat) es forma un entorn apolar al voltant de la unitat indicadora que afavoreix la seua transformació de la forma oberta a l'apolar espirocíclica tancada amb el conseqüent canvi de color. A la segona part de la Tesi s'han preparat nanoparticules de sílice funcionalitzades amb antracè, com a unitat indicadora, i amb dos tiourees diferents, com unitats coordinants d'anions. Suspensions de les nanopartícules bifuncionalitzades en acetonitril mostren la típica emissió estructurada del'antracè. En afegir diferents anions a la suspensió de les nanoparticules s'obté un augment de fluorescència (amb Cl-, Br-, H2PO4-, acetat i benzoat) o una desactivació de la mateixa (F- i CN-). Finalment es prepararen nanopartícules de sílicie funcionalitzades amb terpiridines, com a unitat coordinant, i amb sulforodamina B, com a unitat indicadora. La coordinació de cations metàl¿lics de transició (Fe3+, Hg2+, Cu2+, Ni2+ i Pb2+) amb les terpiridines va donar lloc a una desactivació important de l'emissió de la sulforodamina B unida covalentment al material (95% de la inicial). En un segon pas, es va estudiar la capacitat de certs anions (H2PO4-, HSO4-, F-, Cl-, Br-, I- i NO3-) de desplaçar al metall coordinat amb la subsegüent regeneració de l'emissió de la sulforodamina. Aplicant l'anàlisi de components principals (PCA) es va aconseguir la discriminació de tots els anions estudiats. A més, les nanopartícules tractades amb el catió Pb2+ van donar una resposta selectiva amb l'anió H2PO4-.
Calero Rodriguez, MP. (2016). Silica nanoparticles as inorganic scaffolds for the preparation of hybrid materials for the optical detection of anions [Tesis doctoral no publicada]. Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/63459
TESIS

Les phosphinines, analogues phosphorés des pyridines sont à la base de ce travail de thèse. La première partie de ce travail résume les différentes voies de synthèse de ces phosphinines, leurs propriétés électroniques ainsi que leurs diverses applications en catalyse. Différents ligands bidentates, tridentates et tétradentates ont pu être générés via l'attaque nucléophile d'organolithiens sur des phosphinines possédant des groupements ancillaires diphénylphosphine. De plus l'utilisation d'un complexe pinceur mono-anionique dérivé du diphénylphosphinométhane a été envisagée notamment dans le cadre de réactions ambitieuses telles que l'activation de liaisons C

Phosphinines, the phosphorus analogues of pyridines, are the common basis of the present thesis work here. In the first part, the various synthetic routes for the synthesis of phosphinines their electronic properties and their application in transition metal catalysis are summarized. Bidentate, tridentate and tetradentate ligands could be generated by the nucleophilic attack of organolithium reagents on phosphinines with pending diphenylphosphine groups. The use of monoanionic pincer complex derived from diphenylphosphinomethane ( dppm) was studied with special emphasis on the activation of poorly reactive moieties such as C-H bonds and on the dehydrogenation of borane adducts. The third part of this work, describes the synthesis of 3,5-substituted phosphinines via a desilylation method starting from the corresponding 2,6-(bistrimethylsilyl)phosphinines. The use of these 3,5-substituted phosphinines on the stabilization of metal(O)-transition metal (Au, Ni) nanoparticles was studied. In the last part of this work the use of phosphinines as precursors for the generation of bulky monodentate phosphines, the so called phosphabarrelens was studied. The electronic properties of these scarcely studied ligands was investigated experimentally and by the means of DFT calculations (CDA). The use of these ligands in coordination chemistry has allowed for the isolation of various coordination complexes of phosphabarrelenes with transition metals (Groups 9-11). Interestingly these ligands are sui table for the stabilization of highly unsaturated 14VE Pt(O) and Pd(O) complexes. These complexes could be successfully applied in cross-coupling and hydrosilylation reactions
Les phosphinines, analogues phosphorés des pyridines sont à la base de ce travail de thèse. La première partie de ce travail résume les différentes voies de synthèse de ces phosphinines, leurs propriétés électroniques ainsi que leurs diverses applications en catalyse. Différents ligands bidentates, tridentates et tétradentates ont pu être générés via l’attaque nucléophile d’organolithiens sur des phosphinines possédant des groupements ancillaires diphénylphosphine. De plus l’utilisation d’un complexe pinceur mono-anionique dérivé du diphénylphosphinométhane a été envisagée notamment dans le cadre de réactions ambitieuses telles que l’activation de liaisons C‒H peu réactives ou encore la déhydrogénation de boranes. La troisième partie de ce manuscrit décrit quant à elle la synthèse de phosphinines 3,5-substituées via désilylation à partir des 2,6-(bistriméthylsilyl)phosphinines correspondantes. L’utilisation de ces phosphinines 3,5-substituées pour la stabilisation de nanoparticules de métaux de transition (Au(0), Ni(0)) a elle aussi été étudiée. La dernière partie de ce travail est consacrée à la synthèse et à la caractérisation de phosphabarrélènes, ligands monodentates encombrés de type phosphine, obtenus à partir de phosphinines. Etant donné que les propriétés électroniques de ces ligands sont restées très peu décrites jusqu'à ce jour, des études expérimentales et théoriques ont été réalisées. Enfin, la chimie de coordination des phosphabarrélènes a été considérée et a permis de mettre en évidence divers complexes de métaux de transition (Groupes 9-11). De manière intéressante, ces ligands se sont montrés efficaces pour la stabilisation de complexes de Pt(0) ou Pd(0) hautement insaturés, ces derniers ayant été employés avec succès dans des réactions de couplage croisé ou d’hydrosilylation

The molecular electrostatic potential (MESP) distribution for 1-R-5-mercaptotetrazolium anions, as well as total energy of complexes of 1-R-5-mercaptotetrazoliums ions with silver and palladium particles has been calculated using DFT approach. Based on the results of quantum-chemical calculations, coordination mode of the ligands under their binding with surfaces of nanoparticles was proposed. When you are citing the document, use the following link http://essuir.sumdu.edu.ua/handle/123456789/35463

This thesis describes the synthesis and anion recognition properties of a variety of interlocked host receptors and the application of metal nanoparticles in the areas of catalysis and sensing. Chapter One introduces the field of anion supramolecular chemistry, with particular emphasis on areas relevant to the research discussed in later chapters. Following this, the synthesis and applications of metal nanoparticles are outlined. Chapter Two details the synthesis of a range of halo-triazolium based rotaxanes and explores the effects of altering both the halogen bond donor atom and degree of preorganisation on the anion recognition properties of the interlocked host system. A halogen bond containing catenane is also prepared and its anion binding properties investigated. Chapter Three initially reports the anion-templated synthesis of a series of neutral pyridine N-oxide axle containing rotaxanes before their ability to recognise anions in aqueous solvent mixtures is studied. Attempts to enhance anion binding through the incorporation of a positive charge into the macrocyclic component of the rotaxane structure are also explored. Chapter Four outlines the preparation of β-cyclodextrin functionalised metal nanoparticles and investigations of their catalytic and sensing properties. Chapter Five describes in detail the synthetic and analytical procedures discussed in chapters two to four. Chapter Six summarises the conclusions of this thesis.

Thesis (Ph. D.)--University of Maryland, College Park, 2004.
Thesis research directed by: Chemistry. Title from t.p. of PDF. Includes bibliographical references. Published by UMI Dissertation Services, Ann Arbor, Mich. Also available in paper.

Nous avons synthétisé trois types de dendrimères différents: des dendrimères à cœur colloi͏̈dal d'or (liaisons de coordination), des dendrimères "classiques" (liaisons covalentes) et des dendrimères supramoléculaires (liaisons hydrogène). Leur étude pour la reconnaissance d'oxoanions, principalement d'H2PO4- et de l'ATP2-, a montré quelques différences intéressantes. D'une part les nanoparticules d'or dendronisées peuvent être utilisées pour la préparation d'électrodes modifiées recyclables. D'autres part, les dendrimères possédant des fonctions ferrocényles perméthylées sont plus stables et permettent un titrage plus "propre" des anions. Enfin, les dendrimères formés par liaisons hydrogène possèdent des propriétés particulières de reconnaissance au cours du titrage des anions étudiés. Cette facilité d'accès à des objets moléculaires avec un grand nombre de fonctions périphériques, nous ouvre le champs à de nombreuses autres idées d'assemblages. Et la reconnaissance de l'ATP2- nous invite à tendre encore plus vers la biologie
We synthesized three different types of dendrimers: dendrimers with gold colloidal core (coordination bonds), " traditional " dendrimers (covalent bonds), supramolecular dendrimers (hydrogen bonds). Their study for the recognition of oxoanions, mainly of H2PO4 - and ATP2- showed some interesting differences. On the one hand, the dendronized gold nanoparticles can be used for the preparation of modified electrodes which can be recycled. On the other hand, the dendrimers with permethylated ferrocenyls functions are more stable and allow a " cleaner " titration of the anions. Moreover, the dendrimers formed by hydrogen bonds have particular properties of recognition during the titration of the investigated anions. The accessibility to molecular objects with a great number of peripheral functions, opens to us the fields with many other ideas of assemblies. And the recognition of the ATP2- invites us to tend even more towards biology

En la present tesi doctoral es descriu un procediment general per a l'obtenció de nanopartícules mesoporoses de sílice (MSNs) regioselectivament bifuncionalizades de forma ortogonal amb diferents grups funcionals. L'estratègia sintètica consisteix en la preparació de MSNs mitjançant co-condensació, seguit d'una posterior funcionalització covalent, mentre el tensioactiu es troba encara present en l'estructura de les MSNs. Seguint aquesta metodologia, s'han sintetitzat les nanopartícules bifuncionalizades amina-azida (MSN-(NH2)i(N3)o), amina-isotiocianat (MSN-(NH2)i(NCS)o) i amina-aldehid (MSN-(NH2)i(CHO)o), per al seu ús en aplicacions biomèdiques. En primer lloc, s'han sintetitzat i caracteritzat de forma homogènia i reproduïble les nanopartícules de referència (MSN-NH2) que permetran les successives funcionalitzacions. Aquestes nanopartícules aminades s'han fet servir posteriorment per a la síntesi de sensors de naftalimida. S'ha aconseguit desenvolupar un procediment general per a la introducció de 4-amino-1,8 naftalimides. Aquestes naftalimides han estat provades com a sensor i portes lògiques per a la detecció de H+ i F-. D'altra banda, s'ha descrit un protocol per preparar amino-azida-MSNs de forma regioselectiva. Aquestes MSNs han estat funcionalitzades per primera vegada amb foldàmers catiònics i la seva capacitat per creuar membranes citoplasmàtiques i viabilitat ha estat estudiada, així com l'ús d'aquests sistemes per a l'alliberament intracel·lular de Doxorubicina (DOX) de forma controlada. També s'ha realitzat un nou protocol per preparar MSNs amb isotiocianat en la seva estructura. La metodologia sintètica és general i es pot aplicar, en principi, a qualsevol MSNs aminada. L'eficiència de la funcionalització és comparable a la cicloaddició de coure (CuAAC) evitant els protocols d'aïllament i d'eliminació del metall. Seguint aquesta metodologia, s'han preparat unes noves amino-isotiocianat-MSNs per al disseny d'un nano-contenidor capaç d'alliberar el fàrmac Ataluren de forma controlada, per el seu us en la distròfia muscular de Duchenne (DMD). S'han aconseguit sintetitzar amina-aldehid-MSNs. Aquestes MSNs s'han aplicat com una nanoplataforma simple i versàtil capaç d'alliberar de forma dual una barreja CPT/DOX per al tractament del càncer, mitjançant l'ús d'estímuls de pH. Mentre un fàrmac és absorbit dins de la superfície interior, l'altre està unit covalentment a la superfície externa, actuant així, a la vegada, com a fàrmac i com agent bloquejant de porus. Aquest sistema respon als estímuls de pH i tots dos fàrmacs són només alliberats en un medi àcid.
En la presente tesis doctoral se describe un procedimiento general para la obtención de nanopartículas mesoporosas de sílice (MSNs) regioselectivamente bifuncionalizadas de forma ortogonal con distintos grupos funcionales. La estrategia sintética consiste en la preparación de MSNs mediande co-condensación, seguido de una posterior funcionalización covalente, mientras el tensioactivo se encuentra todavía presente en la estructura de las MSNs. Siguiendo esta metodología, se han sintetizado las nanopartículas bifuncionalizadas amina-azida (MSN-(NH2)i(N3)o), amina-isotiocianato (MSN-(NH2)i(NCS)o) y amina-aldehído (MSN-(NH2)i(CHO)o), para su uso en aplicaciones biomédicas. En primer lugar, se han sintetizado y caracterizado de forma homogénea y reproducible las nanopartículas aminadas de referencia (MSN-NH2) que permitirán las sucesivas funcionalizaciones, con un tamaño de 50 nm y 100 nm aproximadamente. Estas nanopartículas aminadas se han usado posteriormente para la síntesis de sensores de naftalimida. Se ha conseguido desarrollar un procedimiento general para la introducción de 4-amino-1,8 naftalimidas. Estas naftalimidas han sido probadas como sensores y puertas lógicas para la detección de H + y F-. Por otra parte, se ha descrito un protocolo para preparar amino-azida-MSNs de forma regioselectiva. Estas MSNs han sido funcionalizadas por primera vez con foldámeros catiónicos y su capacidad para cruzar membranas citoplasmáticas y viabilidad ha sido estudiada, así como el uso de estos sistemas para la liberación intracelular de doxorubicina (DOX) de forma controlada. También se ha realizado un nuevo protocolo para preparar MSNs con isotiocianato en su estructura. La metodología sintética es general y puede aplicarse, en principio, a todo tipo de MSNs aminadas. La eficiencia de la funcionalización es comparable a la cicloadición de cobre (CuAAC) evitando los protocolos de aislamiento y de eliminación del metal. Siguiendo esta metodología, se han preparado unas nuevas amino-isotiocianato-MSNs para el diseño de un nano-contenedor capaz de liberar el fármaco Ataluren de forma controlada. Se ha logrado sintetizar amina-aldehído-MSN. Estas MSNs se han aplicado como una nanoplataforma simple y versátil capaz de liberar de forma dual una mezcla CPT/DOX para el tratamiento del cáncer, mediante el uso de estímulos de pH. Mientras un fármaco es absorbido dentro de la superficie interior, el otro está unido covalentemente a la superficie externa, actuando así como fármaco y como agente bloqueante de poro. Este sistema responde a los estímulos de pH y ambos fármacos son solamente liberados en un medio ácido.
In this PhD dissertation, a general procedure for the obtaining of different regioselective orthogonal bifunctionalized mesoporous silica nanoparticles (MSNs) has been carried out. The strategy consists of a covalent functionalization of co-condensed monodispersed and uniform aminated-MSNs, where tensioactive is still present in its structure. Three bifunctionalized MSNs, amine-azide (MSN-(NH2)i(N3)o), amine-isothiocyanate (MSN-(NH2)i(NCS)o) and amine-aldehyde (MSN-(NH2)i(CHO)o), with efficient “click” reactions, have been synthetized for its use in biomedical applications. First, a well characterized batch of precursor aminated-MSNs (MSN-(NH2)) has been prepared. The best conditions for the synthesis of homogenous and reproducible MSN-(NH2) with a size between 50-100 nm have been studied. These aminated-MSNs have been used for the synthesis of naphthalimide sensors where a general procedure for the introduction of 4-amine-1,8-naphthalimides has been developed. These naphthalimides have been tested as potential logic gates for the detection of H+ and F-. A straightforward protocol to prepare amine-azide MSNs has been described. These MSNs have been functionalized with quinolin cationic foldamers for the first time. The ability of these foldamer-MSNs to cross cytoplasmic membranes and its viability has been studied. The penetrating capacity of foldamer-MSNs have been used for intracellular delivery of Doxorubicin (DOX). A new protocol to prepare isothiocyanate functionalized MSNs is described. The synthetic methodology is general and can be applied, in principle, to all type of aminated MSNs. The efficiency of the functionalization is comparable to the copper cycloaddition (CuAAC) avoiding isolation and copper removal protocols. Following this methodology, new amino-isothiocyanate-MSNs have been prepared for the design of a nano-container able to release the drug Ataluren in a controlled manner, for the treatment of Duchenne muscular dystrophy (DMD). Regioselective bifunctionalized amine-aldehyde-MSNs have been synthetized. These MSNs have been applied as a versatile nanoplatform able to release dual synergistic CPT/DOX mixture for cancer treatment only by using pH stimuli. While CPT is absorbed at the inner surface, DOX is covalently linked to the external surface acting both as an active and a capping agent (pH=4).

En este trabajo se han preparado tres nuevos complejos dinucleares de platino(II), [(dppp)Pt{-S(CH2)nNHC(=O)-NHR}]2(OTf)2 (n = 2, 3; R = Et, Ph), conteniendo ligandos tiolato-urea. Los complejos se han estudiado como receptores de aniones, mediante la determinación de las constantes de asociación por RMN de protón y mediante un ensayo de desplazamiento de indicador. También se han preparado nanopartículas magnéticas de cobalto y de magnetita y se han funcionalizado con macrociclos tipo éter corona, con -ciclodextrina y con organocatalizadores derivados de la L-hidroxiprolina. Las nanopartículas funcionalizadas con éteres corona se han utilizado como sistemas de extracción de Pb2+ de soluciones acuosas y orgánicas. Las nanopartículas conteniendo -ciclodextrina se han utilizado como sistemas de soporte de organocatalizadores, a través de interacciones de tipo host-guest. Estos sistemas se han estudiado a su vez como catalizadores reciclables en la reacción aldólica asimétrica en agua. Las nanopartículas funcionalizadas con organocatalizadores derivados de la L-hidroxiprolina, se utilizaron como catalizadores asimétricos en la reacción aldólica y en la adición de Michael.
In this work three new di-platinum(II) thiolato-bridged complexes [(dppp)Pt{-S(CH2)nNHC(=O)NHR}]2(OTf)2 (n = 2, 3; R = Et, Ph) have been synthesized, fully characterized and studied as synthetic receptors for anionic species. The binding of anions has been quantitatively determined by 1H NMR spectroscopy and in a qualitative fashion by an indicator displacement assays. These studies have shown the receptors to be selective for H2PO4-. Cobalt and magnetite magnetic nanoparticles have been prepared and functionalized with a wide range of structures, namely crown ether type macrocycles, organocatalysts and -cyclodextrin. The nanoparticles functionalized with crown ether were used in the extraction of Pb2+ from aqueous and organic solutions. -cyclodextrin functionalized nanoparticles were used as carriers of organocatalysts via non-covalent interactions, and were applied in the asymmetric version of the aldol reaction in aqueous media. Finally, L-hydroxyproline and (S)-α,α-diphenylprolinol trimethylsilyl ether functionalized nanoparticles were also prepared and investigated as catalysts in asymmetric aldol and Michael reactions respectively.

The study of ferritin includes a rich history of discoveries and scientific progress. Initially, the composition of ferritin was determined. Soon, it was shown that ferritin is a spherical, hollow protein. Eventually, over several decades of research, the structure and some function of this interesting protein was elucidated. However, the ferritin field was not completely satisfied. Today, for example, researchers are interested in refining the details of ferritin function, in discovering the role of ferritin in a variety of diseases, and in using ferritin for materials chemistry applications. The work presented in this dissertation highlights the progress that we have made in each of these three areas: 1) Mechanistic studies: The buffer used during horse spleen ferritin iron loading significantly influences the mineralization process and the quantity of iron deposited in ferritin. The ferrihydrite core of ferritin is crystalline and ordered when iron is loaded into ferritin in the presence of imidazole buffer. On the other hand, when iron is loaded into ferritin in the presence of MOPS buffer, the ferrihydrite core is less crystalline and less ordered, and a smaller amount of total iron is loaded in ferritin. We also show that iron can be released from the ferritin core in a non-reductive manner. The rate of Fe3+ release from horse spleen ferritin was measured using the Fe3+-specific chelator desferoxamine. We show that iron release occurs by three kinetic events. 2) Disease studies: In order to better understand iron disruption during disease states, we performed in vitro assays that mimicked chronic kidney disease. We tested the hypothesis that elevated levels of serum phosphate interrupted normal iron binding by transferrin and ferritin. Results show that phosphate competes for iron, forming an iron(III)-phosphate complex that is inaccessible to either transferrin or ferritin. Ferritin samples separated from the iron(III)-phosphate complex shows that as the phosphate concentration increases, iron loading into ferritin decreases. 3) Materials chemistry studies: Anion sequestration during ferritin core reduction was studied. When the core of horse spleen ferritin is fully reduced using formamidine sulfinic acid, a variety of anions, including halides and oxoanions, cross the protein shell and enter the ferritin interior. Efforts have been made to use ferritin to control the concentration of anions for reactions. In addition, the native ferrihydrite mineral core of ferritin is a semi-conductor capable of catalyzing oxidation/reduction reactions. Light can photo-reduce AuCl4- to form gold nanoparticles (AuNPs) with ferritin as a photocatalyst. The mechanism of AuNP formation using ferritin as a photocatalyst was examined. From this work, we propose that the ferrihydrite core of ferritin photo-reduces; the mineral core dissolves into a soluble iron(II) mineral. The iron(II) then re-oxidizes, and a new mineral forms that appears to be the new photocatalyst, as the lag phase is significantly decreased with this new mineral form of ferritin.

[EN] Abstract The present PhD thesis entitled "Supramolecular Chemistry: New chemodosimeters and hybrid materials for the chromo-fluorogenic detection of anions and neutral molecules" is based on the application of supramolecular chemistry and material science principles for the development of optical chemosensors for anions and neutral molecules detection. The second chapter of this PhD thesis is devoted to the preparation of chemodosimeters for the chromo-fluorogenic detection of fluoride, diisopropyl fluorophosphates (DFP) and hydrogen sulfide. The optical detection of fluoride anion was achieved by using a pyridine derivative containing a t-butyldimethylsilyl ether group. Aqueous solutions of the chemodosimeter were colorless but turned yellow upon addition of fluoride anion. Also a remarkable enhancement in emission was observed only upon the addition of fluoride. The optical changes were ascribed to a fluoride-induced hydrolysis of the silyl ether moiety. Also a chemodosimeter for the optical recognition of DFP, a nerve agent simulant, was prepared. In this case, the chemodosimeter was based on a stilbene pyridinium derivative functionalized with hydroxyl and silyl ether moieties. Aqueous solutions of the chemodosimeter were colorless changing to yellow upon DFP addition. The optical changes were ascribed to a hydroxyl phosphorylation followed by a fluoride-induced hydrolysis of the silyl ether group. Besides, that probe was implemented in test strips and DFP detection in gas phase was accomplished. Finally, the fluorogenic recognition of hydrogen sulfide anion was explored. For this purpose different fluorophores were selected and fucntionalized with 2,4-dinitrophenyl ether groups. The prepared probes were neraly non-emissive but remarkable emission enhancements upon addition of hydrogen sulfide were observed. The emission enhancements observed were due to a selective sulfide-induced hydrolysis of the 2,4-dinitrophenyl ether moiety that yielded the free fluorophores. Another set of chemodosimeters equipped with azide and sulfonylazide moieties were prepared. Again these probes were non-fluorescent but upon addition of hydrogen sulfide an important enhancement in emission was found. The selective response was ascribed to a reduction of the azide and sulfonylazide moieties to amine and sulfonylamide induced by hydrogen sulfide anion. Besides, the viability assays showed that these dosimeters were essentially non-toxic and real-time fluorescence imaging measurements confirmed their ability to detect intracellular hydrogen sulfide at micromolar concentrations. The third chapter of this PhD thesis was devoted to the preparation of nanoscopic gated materials and their use in sensing protocols. In a first step a gated material for the optical detection of glutathione (GSH) was prepared. For this purpose MCM-41 mesoporous silca nanoparticles were selected as inorganic scaffold. The pores were loaded with safranine O and the external surface was functionalized with disulfide-containing oligo(ethylene glycol) moieties. Dye delivery from aqueous suspensions of the sensory material was only observed in the presence of GSH. The signalling paradigm was ascribed to the selective reduction of the disulfide bond by GSH which induced pore opening and dye release. Also capped organic-inorganic hybrid materials for the selective detection of hydrogen sulfide were prepared and characterized. In this case the same MCM-41 support was used and charged with [Ru(bipy)3]2+ dye. Then, the external surface was functionalized with Cu(II)-macorcyclic complexes and finally, the pores were capped by the addition of the bulky anion hexametaphosphate. Aqueous suspensions of this material showed negligible dye release whereas in the presence of hydrogen sulfide anion a remarkable colour change was observed. This optical response was ascribed to a demetallation process of the Cu(II) complex induced by hydrogen sulfide.
[ES] Resumen La presente tesis doctoral titulada "Química supramolecular: Nuevos dosímetros químicos y materiales híbridos para la detección cromo-fluorogénica de aniones y moléculas neutras." está basada en la aplicación de principios básicos de la química supramolecular y de la ciencia de materiales en el desarrollo de sensores ópticos para aniones y moléculas neutras. El segundo capítulo de esta tesis doctoral está dedicado a la preparación de dosímetros químicos para la detección cromo-fluorogénica de fluoruro, diisopropil fluorofosfato (DFP) y sulfuro de hidrógeno. Para la detección óptica del anión fluoruro se sintetizó un derivado de piridina funcionalizado con un t-butildimetilsilil éter. En este capítulo también se describe la preparación de un dosímetro químico para la detección de DFP, que es un simulante de agentes nerviosos. Este dosímetro está basado en un estilbeno funcionalizado con una sal de piridinio que contiene grupos hidroxilo y silil éter en su estructura. Finalmente se prepararon dos familias de sensores para la detección óptica de hidrógeno sulfuro. La primera familia de sensores consiste en fluoróforos comunes funcionalizados con 2,4-dinitrofenil éteres. Los sensores preparados no presentaron una emisión de fluorescencia importante mientras que, en presencia del anión hidrógeno sulfuro, se observó un aumento significativo. La segunda familia de dosímetros también estaba compuesta por ciertos fluorofóros pero, en este caso, funcionalizados con grupos azida y sulfonilazida. Los dosimétros preparados, siguiendo esta segunda aproximación, tampoco dieron una fluorescencia significativa observándose un aumento de la misma al añadir el anión hidrógeno sulfuro. El tercer capítulo de esta tesis doctoral está dedicado a la preparación de materiales híbridos nanoscópicos funcionalizados con puertas moleculares y su aplicación en protocolos de reconocimiento. En primer lugar se preparó un material para la detección óptica de glutatión (GSH). Para ello se emplearon nanopartículas de MCM-41 mesoporosas como soporte inorgánico. Los poros del soporte fueron cargados con el colorante safranina O y la superficie externa funcionalizada con oligo(etilenglicol) conteniendo enlaces disulfuro. También se prepararon y caracterizaron varios materiales híbridos para la detección selectiva del anión hidrógeno sulfuro. En este caso también se empleó, como soporte inorgánico, sílice mesoporosa MCM-41. Los poros del soporte inorgánico fueron cargados con [Ru(bipy)3]2+ y la superficie externa funcionalizada con varios complejos macrocíclicos de Cu(II). El material sensor final fue obtenido al añadir el anion hexametafosfato, que compleja con los complejos de Cu(II), produciendo un bloqueo de los poros.
[CAT] Resum La present tesi doctoral titulada "Química supramolecular: Nous dosímetres químics i materials híbrids per a la detecció cromo-fluorogènica d'anions i molècules neutres." està basada en l'aplicació dels principis bàsics de la química supramolecular i de la ciència dels materials en el desenvolupament de sensors òptics per a anions i molècules neutres. El segon capítol d'aquesta tesi doctoral està dedicat a la preparació de dosímetres químics per a la detecció cromo-fluorogènica de fluorur, diisopropil fluorofosfat (DFP) i sulfur d'hidrogen. Per a la detecció òptica de l'anió fluorur es va sintetitzar un derivat de piridina funcionalitzat amb un t-dibutildimetilsilil èter. En aquest capítol també es descriu la preparació d'un dosímetre químic per a la detecció de DFP, que és un simulant d'agents nerviosos. Aquest dosímetre està basat en un estilbè funcionalitzat amb una sal de piridina que conté grups hidroxil i silis èter en la seua estructura. Finalment varen ser preparades dues famílies de sensors per a la detecció òptica de sulfur d'hidrogen. La primera família consisteix en fluoròfors comuns funcionalitzats amb 2,4-dinitrofenil èters. Els sensors preparats no presentaren una emissió de fluorescència significativa mentre que, en presencia de l'anió hidrogen sulfur, es va observar un augment significatiu. La segona família de dosímetres també estava composada per certs fluròfors però, en aquest cas, funcionalitzats amb grups azida i sulfonilazida. Els dosímetres preparats, seguint aquesta segona aproximació, tampoc donaren una fluorescència significativa observant-se un augment de la mateixa al afegir l'anió hidrogen sulfur. El tercer capítol d'aquesta tesi doctoral està dedicat a la preparació de materials híbrids nanoscòpics funcionalitzats amb portes moleculars i la seua aplicació en protocols de reconeixement. En primer lloc es va preparar un material per a la detecció òptica de glutatió (GSH). Per a aquest propòsit es varen emprar nanopartícules MCM-41 mesoporoses com a suport inorgànic. Els porus del suport varen ser carregats amb el colorant safranina O i la superfície externa funcionalitzada amb oligo(etilenglicol) que contenia enllaços disulfurs. També varen ser preparats i caracteritzats diversos materials híbrids per a la detecció selectiva de l'anió hidrogen sulfur. En aquest cas també es va emprar, com a suport inorgànic, sílice mesoporosa MCM-41. Els porus del suport inorgànic varen ser carregats amb [Ru(bipy)3]2+ i la superfície externa funcionalitzada amb diversos complexos macrocíclics de Cu(II). El material sensor final es va obtindre al afegir l'anió hexametafosfat, que es complexa amb macrocicles de Cu(II), produint un bloqueig dels porus.
El Sayed Shehata Nasr, S. (2015). Supramolecular Chemistry: New chemodosimeters and hybrid materials for the chromo-fluorogenic detection of anions and neutral molecules [Tesis doctoral no publicada]. Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/52598
TESIS

Des poly(liquides ioniques) (PILs) arrangés sous la forme de copolymères statistiques,de nanoparticules à chaine unique ou bien sous la forme de copolymères à blocs autoassemblés ont été employés comme précurseurs de carbènes N-hétérocycliques (NHC)s à des fins de catalyses organiques ou organométalliques. L’introduction d’anions acétate dans des unités PIL dérivés d’imidazolium permet la génération in situ de NHCs actifs en catalyse. Les nanoparticules composées d’une chaine unique polymère repliée sur elle-même (SCNP) ont été spécialement conçues selon deux stratégies impliquant, d’une part, une réaction d’autoquaternisation entre groupements fonctionnels antagonistes portés par la chaine et, d’autre part, une réaction de complexation organométallique à l’aide d’un sel de palladium. Dans lesdeux cas, les chaines polymères ont été obtenues par polymérisation contrôlée (méthode RAFT). Les copolymères à blocs amphiphiles comportant un bloc PIL fonctionnalisé par du palladium ont été synthétisés par polymérisation RAFT et auto-assemblés dans l’eau sous forme de micelles.Un effet de confinement des sites catalytiques a clairement été démontré à travers des réactions de catalyse pour les couplages de Suzuki et de Heck dans l’eau, avec un gain cinétique très net par rapport à des homologues non micellisés, en plus d’une grande facilité de recyclage de ces supports micellaires.Enfin, des copolymères à blocs à base de PIL-benzimidazolium à contre anion bis(trifluoromethane)-sulfonylimide de lithium ont été développés comme agents dopants conducteurs ioniques de matrices structurantes PS-b-PEO. Des mélanges configurés en films minces avec une quantité minimale d’agent dopant ont conduit dans certaines conditions à des valeurs optimales de conductivité ionique grâce à une nano structuration des films à longue distance
Poly(ionic liquid)s (PILs) in the form of random copolymers, single chain nanoparticles(SCNPs), or self assembled block copolymers have been used as N-heterocyclic carbenes(NHCs) precursors for the purpose of organic and organometallic catalysis. Introducing acetate derivative counter anion in imidazolium based PIL units enable in situ generation of catalyticallyactive NHC. SCNPs have been specially designed along two strategies including, firstly, a self quaternization reaction involving two antagonists groups supported on to the polymer chain and,secondly, an organometallic complexation featuring palladium salt. Both polymeric precursors were obtained using RAFT as controlled polymerization method. Amphiphilic block copolymers composed of a PIL block functionalized by palladium have been synthesized by RAFT and self-assembled in water, leading to micellar structures. Confinement effect has been demonstrated through Suzuki and Heck coupling in water showing kinetic gain compared to molecular homologue in addition to an easier recycling method.Finally, PIL-benzimidazolium based block copolymers with lithium bis(trifluoromethane)-sulfonylimide anion have been developed as ionic conductor doping agent for PS-PEO matrix. Thin films blends with minimum doping agent amount led to optimum ionic conductivity owing tolong range order

Die Verbindung von hoch entwickelten Nanomaterialien mit fluoreszenzbasierten Technologien hat sich zu einem aufstrebenden Forschungsbereich entwickelt. Nichtsdestotrotz ist bis heute der Schritt von einem organischen Indikatormolekül zum anwendbaren Sensorsystem ein komplexer Prozess. Diese Arbeit zielte darauf ab, sensorische Materialien verschiedener chemischer Natur für diverse Analyten zu entwickeln, zu charakterisieren und zu etablieren. Hierbei wurden zunächst pH sensitive Fluoreszenzfarbstoffe entwickelt und in dünnen Membranen immobilisiert. Der Teststreifen ermöglicht die Beurteilung von pH-Änderungen mit dem Auge. Darüber hinaus wurde gezeigt, wie diese Farbstoffe auch in eine wasserlösliche Form überführt werden können. Damit konnten lokale pH-Änderungen an der Wachstumsfront von Silikat-Biomorphs detektiert werden. Auch partikuläre Systeme stellten sich als geeignete Materialien heraus. Es konnte gezeigt werden, wie die Silikat-Matrix von Partikeln zu verbesserten Eigenschaften für Farbstoffe führt. Mittels farbstoffbeladener Partikel konnte in einem Lateral-Flow-Assay ein schneller Nachweis von TATP etabliert werden. Ein anderer Ansatz verfolgte das Ziel des sensitiven Nachweises von Quecksilberionen in Wasser. In einem anderen System konnten Silikat-Nanopartikeln so funktionalisiert werden, dass ein sensitiver und selektiver Nachweis von Schwermetallionen und Anionen über ein Quencher-Displacement-Assay gelang. Zusätzlich wurde die einzigartige Oberfläche von Zellulosepartikeln mithilfe eines neu entwickelten Fluoreszenzfarbstoffs untersucht. Die untersuchten Materialien und Strategien zeigen, wie leicht innovative Moleküle für potentielle sensorische Systeme im wässrigen Medium auf Basis von fluoreszierenden Partikeln und dünnen Schichten geschaffen werden können. Das Verhalten der hergestellten Materialien wurde über spektroskopische Methoden evaluiert und dabei, wenn möglich, die Parameter Sensitivität, Selektivität und Ansprechzeit beurteilt.
The combination of fluorescence and nanomaterials has developed into an emerging research area. Nonetheless until now the step from an organic sensory molecule to a final sensor format is a complex endeavor. This thesis aimed at the preparation of particulate and thin-film based platforms for various analytes through combining the features of an appropriate host material with outstanding properties of dyes concomitant with sensitive fluorescence detection techniques. In particular, pH sensitive fluorescent probes were sterically immobilized into a thin membrane. The dip-stick allows the assessment upon change in pH with the eye. Especially a probe working at high basic pH range was converted into a water-soluble analogue and was directly applied at the growth front of silica biomorphs to detect local pH changes. But also particulate structures are suitable host materials. It is shown how the silica matrix of nanoparticles lead to improved optical properties for embedded dyes. The interactions of silica and fluorescent dyes within the pores of mesoporous particles were exploited to develop an actual sensor format based detection of TATP. In another approach it was possible to detect mercury ions in water. Heavy metal ions were also successfully detected in a quencher displacement assay involving receptor-dye functionalized silica nanoparticles. The impact of the unique surface properties of cellulose microparticles was shown by a fluorescent dye which allows an assessment of the surface functional groups and microenvironment through the reactivity and its changes in the optical properties. The performance of the prepared materials were evaluated mostly by spectroscopic methods and if possible assessed in terms of sensitivity, selectivity and response time. The newly developed and investigated materials based on fluorescent particulate and thin-films show the facile application of innovative sensor probes for potentially sensing devices.

碩士
國立中正大學
化學工程所
93
The aim of this work is to prepare the polystyrene with thiol terminal group (PS-SH) and use this functionalized polystyrene to stabilize and control the size of gold nanoparticles. The PS-SH was first synthesized via an anionic polymerization. Then, PS-SH was mixed with HAuCl4·3H2O in THF solvent in the presence of a reducing agent, super hydride. Upon the reduction of Au+ to Au atoms, the thiol groups of the polymer molecules were bonded onto the gold surface and a polymeric nanocomposite with well-distribute nanogold particles material was thus formed. Depending on the molar ratio of thiol to Au+ and the molecular weight of the polymer, the particle size was controlled within a range of 3~30nm with little aggregation. 1H-NMR、13C-NMR、TEM、XPS、TGA、DSC and UV-VIS were used to investigate the physical properties of the nanocomposite.

碩士
國立中正大學
化學工程所
96
The aim of this work is to prepare vis anionic polymerization a PS-b-PI block copolymer containing chemically bonded gold nanoparticles. The block copolymer is first functionalized with thiol terminal group (PS-b-PI-SH) and then bonded onto the in-situ formed gold nanoparticles, resulting in (PS-b-PI)-AuNPs. We have discovered: first, the size of gold nanoparticles depends on the polymer molecular weight, structure, shape, and the thiol group to Au ratio control; second, in a fixed amount of polymer the size of the in-situ formed gold nanoparticles varies with the total gold amount changed. Third, from microphase separation of the block compolymer, the TEM image indicates that, the gold nanoparticles were confined or in the proximity of PI domains. In addition, GPC、NMR、XPS、TGA、UV、TEM、SEM and AFM were utilized to investigate thoroughly the physical and thermal properties of (PS-b-PI)-AuNPs material.

Nanoparticles promise many interesting applications because of their exceptional chemical and physical properties. Therefore nanoparticles offer a pathway for the fabrication of new functional, smart materials. Since the primary particle strongly tends to strong agglomeration, and since the surface of nanoparticles is often not compatible with polymers, it is not possible to disperse single particles homogeneously in a polymer melt. Formations of agglomerates are responsible for strong differences in concentration of the nanoparticles in the material matrix and therefore impede a homogeneous property profile. Furthermore properties of compounds are not only determined by single components, but considerably by the interface between these single components. Hence, a strong chemical and physical adhesion between the constituents is required. Thus, surface modification of nanoparticles is a crucial issue. This work focuses on the control of the particle/polymer interface in composite materials which has a thickness of some nanometers. This interface regulates the compatibility of the surface of the nanoparticles and their environment. This interface is also the place where the transmission of energy between nanoparticle and polymer occurs. The interlayer of this boundary surface should be occupied with functional “primer”-macromolecules that provide at least two types of functional groups: one species of functional group should assure the bonding of the primer to the surface of the nanoparticle, and the second type enables the compatibilizing to the matrix, and when indicated also the covalent adhesion to the ambient polymer system. The macromolecular scaffold of the primer permits the selective adjustment of important interface properties as elasticity, durability and the surface energy of the particle – matrix interface. Within this thesis hyperbranched polyethylene (PEI) imine was used as starting platform for “Quat-Primer Polymers” bearing a multitude of functional moieties in form of primary, secondary and tertiary amino groups. Chapter 2 gives a literature – review on hyperbranched polymers – with focus on PEI, stabilization of colloids by polymers, as well as polymer – “nanocomposites”. In Chapter 3 the reaction of PEI with glycidyltrimethylammonium chloride will be described to obtain hyperbranched polymers that consist of (i) the hyperbranched PEI scaffold, (ii) primary, secondary and tertiary amino groups that can be used for further modification reactions with amino-reactive compounds, and (iii) ammonium moieties that can adsorb to negatively charged surfaces. It will be shown that these Quat-Primer polymers have the ability to stabilize several nanoparticles in water to form aqueous dispersions and that they are capable to partially deagglomerate nanoparticles leading to smaller diameters of the particles in the dispersion. Additionally the reaction of hyperbranched polyethylene imine with glycidol will be described displaying a possibility to change the reactivity of the functional groups and exhibiting that also the generated hydroxyl groups generated by the ring-opening reaction of epoxides with PEI react with epoxide rings to form ether linkages. In Chapter 4 the synthesis of several amino-reactive ATRP initiators will be described and two methods to graft PMMA arms to “Quat-Primer polymers” presented in the previous chapter including the “grafting from” and the “grafting to” technique. These synthesized Quat-Primer polymers bearing ammonium moieties, as well as PMMA arms can be used to fabricate PMMA nanocomposites with homogeneously distributed nanoparticles. The developed method allow for grafting monomers that can be used in ATRP polymerization, including acrylates, acrylonitriles and styrenes, to hyperbranched polyethylene imine. Chapter 5 will display pathways to graft caprolactam derivatives to hyperbranched polyethylene imine to generate Quat-Primer polymers bearing ammonium moieties, as well as caprolactam rings. These quat-primer polymers can be used for the fabrication of PA-6 nanocomposites by dispersing nanoparticles in presence of these Quat-Primer polymers and subsequent polymerization.

碩士
國立中正大學
化學工程研究所
101
This work mainly takes advantage of anionic polymerization to synthesize SCH3-polystyrene and SCH3-polystyrene-SH. Basically speaking，we use n-butyllithium to activate one side of dimethyl sulfide to form activated complex ion. Then we add styrene monomers to proceed polymerization. Finally, we use ethylene sulfide as end-functionalization agent to quench the polymer chain. Most importantly, we make use of the sulfur atom to form gold nanoparticle/ polystyrene nanocomposite with the addition and reduction of gold solution. We observe the effect on the size of gold nanoparticles of not only the amount of polymer but also the type of functional group. The composite is analyzed by GPC、1H-NMR、13C-NMR、EDS、TEM、UV-Vis、TGA and DSC for details.

The present thesis is focused on the synthesis and environmental applications of polyaniline and its nanocomposites. It is organized in six chapters and brief discussions of the contents of the individual chapters are given below. Chapter 1 reviews two important water purification methods: adsorption and photocatalysis, which are widely discussed in literature. A general introduction to conducting polymers has been given and their photocatalytic activity has been described. Chapter 2 reports the application of polyaniline emeraldine salt for the removal of anionic dyes from aqueous solutions by adsorption. A possible mechanism for the anionic dye adsorption by PANI emeraldine salt has been proposed. The electrostatic interaction between the positively charged PANI backbone and dye anions is responsible for significant dye adsorption. The kinetic parameters for the adsorption of anionic dyes on PANI have also been determined. In Chapter 3, we investigate the adsorption and desorption of anionic dyes from aqueous solution by PANI doped with different protonic acids. PANI with three dopants, namely p-toluene sulfonic acid (PTSA), camphor sulfonic acid (CSA) and dodecyl benzene sulfonic acid (DBSA) were used to adsorb various dyes. The adsorbed dyes were desorbed from the polymer by using a basic aqueous solution. It was found that the adsorption of dye is dependent on the size and nature of the dopant acids. The influence of different dopants on the adsorption and desorption kinetic parameters was also examined. In chapter 4, the inherent property of PANI to adsorb dyes has been explored for the detection of dyes by electrochemical method. The changes in the CV of PANI film coated on Pt electrodes on addition of dye have been employed for detection of dye in aqueous solution. Furthermore, PANI coated stainless steel (SS) electrodes show a change in current intensity of Fe2+/Fe3+ redox peaks due to addition of dye in the electrolyte solution. Chapter 5 describes the synthesis and characterization of polyaniline-grafted-chitosan (CPANI) with different grafting ratios. The mechanical properties and the crystallinity of CPANI were investigated by means of nanoindentation and X-ray diffraction experiments, respectively. CPANI has been further self-assembled into multilayer thin film via versatile and simple layer-by-layer (LbL) approach. Negatively charged hyaluronic acid (HUA) was used as complementary polyelectrolyte for the self-assembly. LbL growth of the multilayer thin films has been monitored with UV-vis spectral analysis as well as by AFM. The formation of thin film has been further characterized by SEM. The pH responsive behavior of CPANI/HUA multilayer thin film has been investigated. Reusability of this thin film has been investigated by repeating the pH responsive experiments for 10 cycles. Chapter 6 is focused on the preparation of nanocomposite thin films of CPANI/PSS/TiO2 via LbL approach. LbL growth of this self-assembly was monitored by UV-vis spectral analysis and porous nature was observed from SEM images. Poly (styrene sulfonate) (PSS) was used as bridging layer between TiO2 nanoparticles and CPANI for the multilayer self-assembly. Incorporation of CPANI within this LbL self-assembly enhanced the dye degradation ability of the thin film by increasing the availability of dye molecules around the TiO2 nanoparticles. Furthermore, CPANI may act as a sensitizer to enhance the photocatalytic activity of TiO2. The effects of surface area of the multilayer thin film and amount of catalysts (TiO2 nanoparticles) incorporated in the self-assembly were described based on the kinetics of the dye degradation reactions. The same multilayer thin film can be efficiently used for dye degradation several times. The work presented in this thesis utilizes unique dye adsorption properties of PANI and its copolymers. The change in conductivity of PANI after dye adsorption and the electrochemical dye detection in aqueous medium promise the potential of PANI as a dye sensing material in waste water at very low concentration. The nanocomposites of CPANI/PSS/TiO2 present a novel material for photocatalysis.

The present thesis is focused on the synthesis and environmental applications of polyaniline and its nanocomposites. It is organized in six chapters and brief discussions of the contents of the individual chapters are given below. Chapter 1 reviews two important water purification methods: adsorption and photocatalysis, which are widely discussed in literature. A general introduction to conducting polymers has been given and their photocatalytic activity has been described. Chapter 2 reports the application of polyaniline emeraldine salt for the removal of anionic dyes from aqueous solutions by adsorption. A possible mechanism for the anionic dye adsorption by PANI emeraldine salt has been proposed. The electrostatic interaction between the positively charged PANI backbone and dye anions is responsible for significant dye adsorption. The kinetic parameters for the adsorption of anionic dyes on PANI have also been determined. In Chapter 3, we investigate the adsorption and desorption of anionic dyes from aqueous solution by PANI doped with different protonic acids. PANI with three dopants, namely p-toluene sulfonic acid (PTSA), camphor sulfonic acid (CSA) and dodecyl benzene sulfonic acid (DBSA) were used to adsorb various dyes. The adsorbed dyes were desorbed from the polymer by using a basic aqueous solution. It was found that the adsorption of dye is dependent on the size and nature of the dopant acids. The influence of different dopants on the adsorption and desorption kinetic parameters was also examined. In chapter 4, the inherent property of PANI to adsorb dyes has been explored for the detection of dyes by electrochemical method. The changes in the CV of PANI film coated on Pt electrodes on addition of dye have been employed for detection of dye in aqueous solution. Furthermore, PANI coated stainless steel (SS) electrodes show a change in current intensity of Fe2+/Fe3+ redox peaks due to addition of dye in the electrolyte solution. Chapter 5 describes the synthesis and characterization of polyaniline-grafted-chitosan (CPANI) with different grafting ratios. The mechanical properties and the crystallinity of CPANI were investigated by means of nanoindentation and X-ray diffraction experiments, respectively. CPANI has been further self-assembled into multilayer thin film via versatile and simple layer-by-layer (LbL) approach. Negatively charged hyaluronic acid (HUA) was used as complementary polyelectrolyte for the self-assembly. LbL growth of the multilayer thin films has been monitored with UV-vis spectral analysis as well as by AFM. The formation of thin film has been further characterized by SEM. The pH responsive behavior of CPANI/HUA multilayer thin film has been investigated. Reusability of this thin film has been investigated by repeating the pH responsive experiments for 10 cycles. Chapter 6 is focused on the preparation of nanocomposite thin films of CPANI/PSS/TiO2 via LbL approach. LbL growth of this self-assembly was monitored by UV-vis spectral analysis and porous nature was observed from SEM images. Poly (styrene sulfonate) (PSS) was used as bridging layer between TiO2 nanoparticles and CPANI for the multilayer self-assembly. Incorporation of CPANI within this LbL self-assembly enhanced the dye degradation ability of the thin film by increasing the availability of dye molecules around the TiO2 nanoparticles. Furthermore, CPANI may act as a sensitizer to enhance the photocatalytic activity of TiO2. The effects of surface area of the multilayer thin film and amount of catalysts (TiO2 nanoparticles) incorporated in the self-assembly were described based on the kinetics of the dye degradation reactions. The same multilayer thin film can be efficiently used for dye degradation several times. The work presented in this thesis utilizes unique dye adsorption properties of PANI and its copolymers. The change in conductivity of PANI after dye adsorption and the electrochemical dye detection in aqueous medium promise the potential of PANI as a dye sensing material in waste water at very low concentration. The nanocomposites of CPANI/PSS/TiO2 present a novel material for photocatalysis.

碩士
國立中正大學
化學工程研究所
92
The work is mainly to combine the anionic polymerization technique and gold nanoparticle for synthesizing gold nanoparticle/poly p-methylstyrene nanocomposite. The way is to prepare poly p-methylstyrene containing sulfide group and use this sulfide group for chemisorption of gold nanoparticl. The steps are: first, polymerization of p-methylstyrene. Second, chlorination by sodium hypochlorite and phase transfer catalyst of the polymer to produce CH2Cl group. Third, lithiation of dimethyl sulfide by n-butyllithium and capping with the chlorinated polymer. The feature of the study is that functionalization of polymer occurs on side-chains rather than main-chain ends. Therefore more bonding points are available for reaction. Finally, the composite is analyzed using TEM,UV-VIS,TGA,EDS and XPS.

Διερευνήθηκε η δέσμευση/αποδέσμευση ιόντων Cu(II) ή/και αντίθετα φορτισμένων επιφανειοδραστικών ενώσεων από συμπολυμερή τύπου κτένας. Ο κεντρικός σκελετός ήταν το πολυ(ακρυλικό νάτριο), PANa, ενώ οι πλευρικές αλυσίδες ήταν το Πολυ(Ν,Ν-διμεθυλακρυλαμίδιο) και το πολυ(Ν-Ισοπροπυλακρυλαμίδιο). Η συμπλοκοποίηση των συμπολυμερών με τα ιόντα Cu(II)σε υδατικό περιβάλλον διερευνήθηκε με θολομετρία, ιξωδομετρία, φασματοφωτομετρία UV-Vis, δυναμική σκέδαση φωτός, ιχνηθέτηση με φθορίζοντες ιχνηθέτες και προσδιορισμό του ζ-δυναμικού. Σε επόμενο στάδιο διερευνήθηκε η δυνατότητα σχηματισμού τριμερών συμπλόκων ΡAΝa/Cu(II)/επιφανειοδραστικής ένωσης σε υδατικό περιβάλλον. Από τη φυσικοχημική μελέτη των συστημάτων σε συνάρτηση του pΗ, ελήφθησαν σημαντικές πληροφορίες σχετικά με τον ανταγωνισμό των δύο ειδών (ιόντα Cu(II)ή ιόντα επιφανειοδραστικής ένωσης) να σχηματίσουν σύμπλοκα με το PANa. Ως τελικό στάδιο, παρασκευάστηκαν αδιάλυτα στο νερό υβριδικά υλικά πολυμερούς/Cu(II)ή πολυμερούς/Cu(II)/επιφανειοδραστικής ένωσης. Έπειτα από διερεύνηση της συμβατότητας/αναμιξιμότητάς τους με εμπορικές μήτρες που χρησιμοποιούνται συνήθως στη βιομηχανία χρωμάτων, ορισμένα από αυτά ενσωματώθηκαν σε πραγματικά χρώματα.
The binding/release of Cu(II) ions or/and surfactants from comb-type copolymers was studied. The backbone was poly(sodium acrylate), PANa, whereas the side chains were poly(N, N-Dimethylacrylamide) and Poly9N-Isopropylacrylamide). The complexation of these copolymers with Cu(II) ions in water, was studied by turbidimetry, viscometry, UV-Vis fasmatophotometry, dynamic light scattering, fluorescense probing and ζ-potential. As a next step, the possible formation of ternary PANa/Cu(II)/surfactant complexes in water was studied. From the physiocochemical studies with pH, important information was taken as far as the competition of the two species (Cu(II) ions and surfactant) to form complexes with PANa is concerned. As a next step, water-insoluble hybrid polymer/Cu(II) or polymer/Cu(II)/surfactant materials were produced. After studies upon the compatibility/mischibility of the hybrid materials with matrices that are usually used in paints, some of the materials were incorporated to paints.

Dusty plasmas are plasmas that contain solid particles of nano- or micrometer size. They are widespread in the cosmic environment and act as precursors in the formation of planets and stars. Such plasmas are also used in laboratories for the synthesis of nanocomposites, which have wide technological and medical applications. While a large scientific effort has been invested in the study and control of such plasmas, the initial growth mechanism of powders (i.e. before they reach several tens of nanometers) remains poorly known. This work contributes primarily to expand the fundamental knowledge in the field of dusty plasmas. Our goal is to understand the physical chemistry of high-frequency plasmas magnetically confined in chemically reactive gases. In addition, we aim by examining the kinetics of the precursors in the plasma to understand the mechanisms of nanoparticle formation in the volume and to control their characteristics in a magnetically confined low pressure Ar/C2H2 plasma. This contribution has a direct impact on science and plasma applications. Among the applications related directly to this research, we mention the synthesis of carbon-based nanocomposites for their integration in solar cells and biomaterials. By examining the plasma characteristics (plasma temperature and density, cation and anion density) and correlating them to those of the dust particles, we found that the magnetic field changes the process of the formation of these particles in the discharge at very low pressure. Specifically, it stimulates the nucleation of carbon nanoparticles through several channels, i.e. through the anions and cations. These nanoparticles include two different phases, an amorphous carbon layer and a porous core formed of grains aggregate. These grains are formed of graphite nanocrystals coated with an amorphous layer. Moreover, the radius of the dust particles increases with the magnetic field, which is related to the enhancement of their residence time in the plasma volume.
Les plasmas poudreux sont des plasmas qui contiennent des particules solides de taille nano- ou même micrométrique. Ils sont répandus dans l'environnement cosmique et jouent le rôle de précurseurs dans la formation des planètes et des étoiles. Ce type de plasma est également utilisé dans les laboratoires pour la synthèse des nanocomposites possédant de vastes applications dans le monde technologique et médical. Tandis qu’un grand effort scientifique a été investi dans l’étude et le contrôle de ce type de plasmas, les mécanismes initiaux de formation des poudres (i.e. avant qu’elles atteignent quelques dizaines de nanomètres) demeurent très peu connus. On sait toutefois que des réactions physico-chimiques sont à l’origine de précurseurs des poudres qui déclenchent la nucléation. Ce travail contribue en premier lieu à accroître les connaissances fondamentales dans le domaine des plasmas poudreux en général. Il s’agit en particulier de comprendre la physico-chimie des plasmas de haute fréquence de très basse pression soumis à un confinement magnétique dans des gaz chimiquement réactifs. Plus spécifiquement, l’objectif de ce travail est d’examiner la cinétique des précurseurs produits dans le plasma afin de comprendre les mécanismes de formation de nanoparticules en volume et le contrôle de leurs caractéristiques dans des mélanges d’Ar/C2H2 de très basse pression confinés magnétiquement. Cet apport a des retombées directes en science et applications des plasmas. Parmi les applications directement visées par cette recherche, notons la synthèse de nanomatériaux composites à base de carbone pour leur intégration dans les cellules solaires et les biomatériaux. En examinant les caractéristiques du plasma (température et densité du plasma, densité des cations et des anions) et en les corrélant à celles des particules de poudre, on constate que le champ magnétique modifie le processus de la formation des particules poudreuses dans la décharge à très basse pression. Plus précisément, il favorise la nucléation des nanoparticules de carbone à travers plusieurs voies impliquant les anions et les cations. Ces nanoparticules comprennent deux phases différentes, une couche de carbone amorphe et un noyau poreux formé d'un agrégat de grains eux-mêmes constitués de nanocristaux de graphite revêtus d'une couche amorphe. On constate que le rayon moyen des particules de poudre augmente avec le champ magnétique, ce qui est lié à l’amélioration de leur temps de résidence dans le volume du plasma.

abstract: Biofuel from microbial biomass is a viable alternative to current energy production practices that could mitigate greenhouse gas levels and reduce dependency on fossil fuels. Sustainable production of microbial biomass requires efficient utilization of nutrients like phosphorus (P). P is a limited resource which is vital for global food security. This paper seeks to understand the fate of P through biofuel production and proposes a proof-of-concept process to recover P from microbial biomass. The photosynthetic cyanobacterium Synechocystis sp. PCC 6803 is found to contain 1.4% P by dry weight. After the crude lipids are extracted for biofuel processing, 92% of the intercellular P is found within the residual biomass. Most intercellular P is associated with nucleic acids which remain within the cell after lipids are extracted. Phospholipids comprise a small percentage of cellular P. A wet chemical advanced oxidation process of adding 30% hydrogen peroxide followed by 10 min of microwave heating converts 92% of the total cellular P from organic-P and polyphosphate into orthophosphate. P was then isolated and concentrated from the complex digested matrix by use of resins. An anion exchange resin impregnated with iron nanoparticles demonstrates high affinity for P by sorbing 98% of the influent P through 20 bed volumes, but only was able to release 23% of it when regenerated. A strong base anion exchange resin sorbed 87% of the influent P through 20 bed volumes then released 50% of it upon regeneration. The overall P recovery process was able to recover 48% of the starting intercellular P into a pure and concentrated nutrient solution available for reuse. Further optimization of elution could improve P recovery, but this provides a proof-of-concept for converting residual biomass after lipid extraction to a beneficial P source.
Dissertation/Thesis
M.S. Civil and Environmental Engineering 2012

abstract: Ion exchange sorbents embedded with metal oxide nanoparticles can have high affinity and high capacity to simultaneously remove multiple oxygenated anion contaminants from drinking water. This research pursued answering the question, “Can synthesis methods of nano-composite sorbents be improved to increase sustainability and feasibility to remove hexavalent chromium and arsenic simultaneously from groundwater compared to existing sorbents?” Preliminary nano-composite sorbents outperformed existing sorbents in equilibrium tests, but struggled in packed bed applications and at low influent concentrations. The synthesis process was then tailored for weak base anion exchange (WBAX) while comparing titanium dioxide against iron hydroxide nanoparticles (Ti-WBAX and Fe-WBAX, respectively). Increasing metal precursor concentration increased the metal content of the created sorbents, but pollutant removal performance and usable surface area declined due to pore blockage and nanoparticle agglomeration. An acid-post rinse was required for Fe-WBAX to restore chromium removal capacity. Anticipatory life cycle assessment identified critical design constraints to improve environmental and human health performance like minimizing oven heating time, improving pollutant removal capacity, and efficiently reusing metal precursor solution. The life cycle environmental impact of Ti-WBAX was lower than Fe-WBAX as well as a mixed bed of WBAX and granular ferric hydroxide for all studied categories. A separate life cycle assessment found the total number of cancer and non-cancer cases prevented by drinking safer water outweighed those created by manufacture and use of water treatment materials and energy. However, treatment relocated who bore the health risk, concentrated it in a sub-population, and changed the primary manifestation from cancer to non-cancer disease. This tradeoff was partially mitigated by avoiding use of pH control chemicals. When properly synthesized, Fe-WBAX and Ti-WBAX sorbents maintained chromium removal capacity while significantly increasing arsenic removal capacity compared to the parent resin. The hybrid sorbent performance was demonstrated in packed beds using a challenging water matrix and low pollutant influent conditions. Breakthrough curves hint that the hexavalent chromium is removed by anion exchange and the arsenic is removed by metal oxide sorption. Overall, the hybrid nano-sorbent synthesis methods increased sustainability, improved sorbent characteristics, and increased simultaneous removal of chromium and arsenic for drinking water.
Dissertation/Thesis
Doctoral Dissertation Civil and Environmental Engineering 2016

The aim of this thesis is to obtain new optical sensors for ions, especially sensors using metallic nanostructures. Metal cations and inorganic anions were selected as the analytes, since they are widespread chemical species. They play various roles in our surroundings: as fundamental electrolytes in bodies of living organisms (e.g. sodium or potassium cations, chloride anions), food additives (nitrates, carbonates) and even pollutants (heavy metal cations, sulphates, phosphates). Detection of ions is essential in, just to name a few: quality control of food products, testing environmental samples, industrial waste monitoring, as well as rapid detection of diseases. Due to the presence of ion in so many areas, lots of effort is put into development of diverse sensors. Apart from well-known electrochemical sensors, optical sensors gain popularity. In principle, information about the environment is in this case carried by a light beam. The analyte has an influence on interactions between the light and the reporter molecule (a molecule sensitive to the presence of a detected substance). Fluorescence spectroscopy, UV-Vis absorption spectroscopy and techniques based on oscillation spectroscopy are the main techniques employed for the optical detection. We live in a world driven by miniaturization: it comes as no surprise that analytical methods reach out to nanotechnology. This trend stimulates development of nanosensors based on surface enhanced Raman scattering (SERS). In SERS spectroscopy, intrinsically weak inelastic light scattering (Raman scattering) – is enhanced due to a giant increase of electromagnetic field intensity near the surface of metallic nanostructures. When placed in this area, a molecule is exposed to electric field of extremely high amplitude, which gives rise to a strong SERS signal – with sensitivity reaching down to a single molecule (so called single molecule SERS). More details on SERS spectroscopy, as well as PM-IRRAS spectroscopy, which accompanied SERS in research on anion detection, can be found in Chapter 1. Nanometric size of such systems lets the researchers reach such unattainable places as the inside of a cell and its compartments. What is more, confinement of the SERS phenomenon to the direct vicinity of a metal nanoparticle gives promise to obtaining resolution much higher than diffraction limit, as it would be determined solely by the size of the nanoparticle (NP) itself. All these features, as well as optical character of work and, consequently, non-invasive way of passing information about the surroundings, make such sensors particularly useful in biological applications. However, while there are many known systems based on SERS spectroscopy which are sensitive to such biological parameters as pH value or redox potential, efficient ion determination in live cells with SERS still poses a challenge. Although this issue has seemingly been examined: equilibrium concentrations of inorganic ions are already commonly known, their distribution inside the cell, transport and accumulation mechanisms inside organelles have yet to be elucidated. Research on fabrication of such sensors will contribute to development of analytical methods already in use, as well as will open up new perspectives for detection of ions, and in consequence, of disorders in their metabolism paths as well as diseases caused by them. Chapter 2 contains current state of the art in the subject of optical nanosensors. It is worth pointing out that metal cations, as one-atom species, are undetectable by vibrational spectroscopies. As they have no vibrational fingerprint, their detection must be made indirectly by observation of the impact they have on the signal of a reporter molecule. Changes may concern total intensities of the spectrum, relative intensities of some bands or the energy shift of bands. In the thesis, 2-mercaptoethanesulphonate anion (MES) is selected as a Raman reporter molecule. Two components of the SO3- symmetric stretching vibrations are chosen to be marker bands – bands, whose changes are related to the presence of the analyte. Their intensity ratio is used to determine a cation concentration, while the energy shift of one of these two bands makes differentiation between cations possible. Chapter 3 presents the effort to use MES molecules adsorbed on silver nanoparticles as Ag-MES nanosensor. Its sensitivity towards heavy metal cations and more biologically relevant cations of alkali and alkaline earth metals is described there. In Chapter 4, tests of performance of the Ag-MES nanosensor in biological systems can be found. Cells incubated in a cell medium containing the nanoprobes are proved to absorb Ag-MES NPs and the distribution of internal potassium concentration is deduced based on SERS mapping. Well studied system of Ag-MES NPs was employed in the further research on permeation of cations through a thick silica shell. Discussion on these results collected for silica covered Ag-MES nanosensors: Ag-MES@SiO2 is given in Chapter 5. Synthesis of other types of biocompatible nanoparticles based on gold nanostars: i) Janus nanoparticles of gold nanostars and Fe3O4 and ii) gold nanostars encapsulated in mesoporous silica – both types additionally covered with a thin layer of silver – are included in Chapter 6. In case of Janus NPs, the effect of magnetic field on the intensity of SERS spectra is examined. Chapter 7 refers to anion detection with use of brand new type of carbazole derivatives deposited on metal surfaces. Surface-attached diamidocarbazoles are proved to be able to bind sulphates from the solution. The scope of the thesis has already been published in two original articles (Sensors and Actuators B: Chemical and Journal of Physical Chemistry C) and one chapter in a book (Optical Spectroscopy and Computational Methods in Biology and Medicine, publ. Springer Netherlands); another article is being prepared for a prompt submission.