Dissertations / Theses on the topic 'Organic monolith'

This dissertation focuses on improving the chromatographic efficiency of polymeric organic monoliths by characterizing and optimizing the bed morphology. In-situ characterization techniques such as capillary flow porometry (CFP), 3-dimensional scanning electron microscopy (3D SEM) and conductivity measurements were developed and implemented to quantitatively characterize the morphology of poly(ethylene glycol) diacrylate (PEGDA) monoliths. The CFP measurements for monoliths prepared by the same procedure in capillaries with different diameters (i.e., 75, 150, and 250 μm) clearly showed a change in average through-pore size with capillary diameter, thus, certifying the need for in-situ measurement techniques. Serial sectioning and imaging of PEGDA monoliths using 3D SEM gave quantitative information about the average pore size, porosity, radial heterogeneity and tortuosity of the monolith. Chromatographic efficiency was better for a monolith with smaller average pore size (i.e., 5.23 μm), porosity (i.e., 0.49), radial heterogeneity (i.e., 0.20) and tortuosity (i.e., 1.50) compared to another monolith with values of 5.90 μm, 0.59, 0.50 and 2.34, respectively. Other than providing information about monolith morphology, these techniques also aided in identifying factors governing morphological changes, such as capillary diameter, polymerization method, physical/chemical properties of the pre-polymer constituents and weight proportion of the same. A statistical model was developed for optimizing the weight proportion of pre-polymer constituents from their physical/chemical properties for improved chromatographic efficiency. Fabricated PEGDA columns were used for liquid chromatography of small molecules such as phenols, hydroxyl benzoic acids, and alkyl parabens. The chromatographic retention mechanism was determined to be principally reversed-phase (RP) with additional hydrogen bonding between the polar groups of the analytes and the ethylene oxide groups embedded in the monolith structure. The chromatographic efficiency measured for a non-retained compound (uracil) was 186,000 plates/m when corrected for injector dead volume. High resolution gradient separations of selected pharmaceutical compounds and phenylurea herbicides were achieved in less than 18 min. Column preparation was highly reproducible, with relative standard deviation (RSD) values less than 2.1%, based on retention times of the phenol standards (3 different columns). A further improvement in chromatographic performance was achieved for monoliths fabricated using a different polymerization method, i.e., living free-radical polymerization (LFRP). The columns gave an unprecedented column performance of 238, 000 plates/m for a non-retained compound under RP conditions.

Abstract The harmful emissions of chlorinated volatile organic compounds (CVOCs) originate only from man-made sources. CVOCs are used in a variety of applications from pharmaceuticals production to decaffeination of coffee. Currently, CVOC emissions are limited by strict legislation. For these reasons, efficient CVOC abatement technologies are required. Catalytic oxidation is very promising option for this purpose, since catalysts can be tailored to each case to maximize the efficiency and minimize the formation of unwanted products, such as dioxins or Cl2. The goal of this thesis was to study the role of the physico-chemical properties of catalysts in dichloromethane (DCM) oxidation. To reach the aim, several catalytic materials were prepared and characterized, and their performance was tested in total oxidation of DCM. The catalytic materials used were powders of four single metal oxides (γ-Al2O3, TiO2, CeO2, MgO), three mixed oxides (Al2O3-xSiO2) washcoated on a cordierite monolith and four active phases (Pt, Cu, V, Mn). At first, support properties were studied. It was found that the DCM conversion and HCl production are dependent on support acidity when the studied single oxides are considered. The best DCM conversions and HCl yields were observed with the support having the highest total acidity (γ-Al2O3). Further, the quality of the by-products formed was dependent on the type of the acid sites present on the support surface. Secondly, the impregnation of the active compound was observed to improve the selectivity of the material. From the tested active phases, Pt presented the best performance, but also V2O5 and CuO showed almost equal performances. Especially CuO supported on γ-Al2O3, that had less formation of by-products and is less toxic than V-containing oxides, seems to be a promising alternative to Pt. Concerning stability, no deactivation was observed after 55h of testing of Pt/Al2O3. Furthermore, in the used reaction conditions, the formation of CuCl2 is not thermodynamically favoured. Finally, the good characteristics of the powder form catalysts were successfully transferred to the monolith. The performance of the Pt/90Al2O3-10SiO2 catalyst in DCM oxidation was improved when the channel density was increased due to an increase in geometric surface area and mechanical integrity factor, and a decrease in open fraction area and thermal integrity factor
Tiivistelmä Haitallisten kloorattujen orgaanisten yhdisteiden (CVOC) päästöt ovat ihmisten aiheuttamia. CVOC-yhdisteitä käytetään mm. liuottimina lääkeaineiden valmistuksessa ja kofeiinin poistossa. Nykyisin CVOC-päästöjä rajoitetaan tiukalla lainsäädännöllä. Näistä syistä tehokas CVOC-yhdisteiden käsittelymenetelmä on tarpeen. Katalyyttinen hapetus on hyvä vaihtoehto tähän tarkoitukseen, koska katalyytit voidaan räätälöidä niin, että puhdistuksen tehokkuus saadaan maksimoitua samalla kun ei-haluttujen tuotteiden, kuten dioksiinit ja kloorikaasu, muodostuminen voidaan minimoida. Tämän väitöskirjatyön tavoitteena oli selvittää katalyyttien fysikaalis-kemiallisten ominaisuuksien yhteyksiä dikloorimetaanin (DCM) hapetukseen. Tavoitteen saavuttamiseksi valmistettiin useita katalyyttejä, jotka karakterisoitiin ja testattiin DCM:n kokonaishapetuksessa. Työssä tutkittiin neljää jauhemaista metallioksidia (γ-Al2O3, TiO2, CeO2 ja MgO), kolmea metallioksidiseosta (Al2O3-xSiO2), jotka pinnoitettiin kordieriittimonoliitille, sekä neljää aktiivista ainetta: Pt, Cu, V and Mn. Aluksi työssä keskityttiin tukiaineiden ominaisuuksiin. Työn tulokset osoittivat, että DCM:n konversio ja HCl:n tuotanto ovat riippuvaisia tukiaineen happamuudesta. Paras tulos saavutettiin alumiinioksidilla, jolla oli korkein kokonaishappamuus. Lisäksi havaittiin, että sivutuotteiden laatu riippuu tukiaineen pinnalla olevien happopaikkojen tyypistä. Aktiivisen aineen impregnointi tukiaineeseen paransi materiaalin selektiivisyyttä. Tutkituista aineista Pt osoittautui parhaimmaksi, mutta myös V2O5 ja CuO olivat lähes yhtä hyviä. Erityisesti CuO-katalyytti, joka tuotti vähemmän sivutuotteita ja joka on materiaalina vähemmän haitallinen kuin V2O5, osoittautui lupaavaksi jalometallikatalyyttien korvaajaksi. Materiaalien stabiilisuuteen liittyen Pt/Al2O3-katalyytin toiminnassa ei havaittu muutoksia 55 tunnin testauksen jälkeen. Lisäksi CuCl2:n muodostuminen ei mallinnuksen mukaan ole termodynaamisesti todennäköistä tutkituissa reaktio-olosuhteissa. Jauhemaisen katalyytin hyvät ominaisuudet pystyttiin pinnoituksessa siirtämään monoliittirakenteiseen katalyyttiin. Pt/90Al2O3-10SiO2 -katalyytin aktiivisuus DCM:n hapetuksessa tehostui, kun monoliitin aukkoluku kasvoi aiheutuen suuremmasta geometrisestä pinta-alasta ja mekaanisesta eheystekijästä sekä pienemmästä avoimen pinnan osuudesta ja termisestä eheystekijästä

To date, there has been little research into the role of microbial community structure in the functioning of the soil ecosystem and on the links between microbial biomass size, microbial activity and key soil processes that drive nutrient availability. The maintenance of structural and functional diversity of the soil microbial community is essential to ensure the sustainability of agricultural production systems. Soils of the same type with similar fertility that had been under long-term organic and conventional crop management in Canterbury, New Zealand, were selected to investigate relationships between microbial community composition, function and potential environmental impacts. The effects of different fertilisation strategies on soil biology and nitrogen (N) dynamics were investigated under field (farm site comparison), semi-controlled (lysimeter study) and controlled (incubation experiments) conditions by determining soil microbial biomass carbon (C) and N, enzyme activities (dehydrogenase, arginine deaminase, fluorescein diacetate hydrolysis), microbial community structure (denaturing gradient gel electrophoresis following PCR amplification of 16S and 18S rDNA fragments using selected primer sets) and N dynamics (mineralisation and leaching). The farm site comparison revealed distinct differences between the soils in microbial community structure, microbial biomass C (conventional > organic) and arginine deaminase activity (organic > conventional). In the lysimeter study, the soils were subjected to the same crop rotation (barley (Hordeum vulgare L.), maize (Zea mays L.), rape (Brassica napus L. ssp. oleifera (Moench)) plus a lupin green manure (Lupinus angustifolius L.) and two fertiliser regimes (following common organic and conventional practice). Soil biological properties, microbial community structure and mineral N leaching losses were determined over 2½ years. Differences in mineral leaching losses were not significant between treatments (total organic management: 24.2 kg N per ha; conventional management: 28.6 kg N per ha). Crop rotation and plant type had a larger influence on the microbial biomass, activity and community structure than fertilisation. Initial differences between soils decreased over time for most biological soil properties, while they persisted for the enzyme activities (e.g. dehydrogenase activity: 4.0 and 2.9 µg per g and h for organic and conventional management history, respectively). A lack of consistent positive links between enzyme activities and microbial biomass size indicated that similarly sized and structured microbial communities can express varying rates of activity. In two successive incubation experiments, the soils were amended with different rates of a lupin green manure (4 or 8t dry matter per ha), and different forms of N at 100 kg per ha (urea and lupin) and incubated for 3 months. Samples were taken periodically, and in addition to soil biological properties and community structure, gross N mineralisation was determined. The form of N had a strong effect on microbial soil properties. Organic amendment resulted in a 2 to 5-fold increase in microbial biomass and enzyme activities, while microbial community structure was influenced by the addition or lack of C or N substrate. Correlation analyses suggested treatment-related differences in nutrient availability, microbial structural diversity (species richness or evenness) and physiological properties of the microbial community. The findings of this thesis showed that using green manures and crop rotations improved soil biology in both production systems, that no relationships existed between microbial structure, enzyme activities and N mineralisation, and that enzyme activities and microbial community structure are more closely associated with inherent soil and environmental factors, which makes them less useful as early indicators of changes in soil quality.

L'intérêt grandissant porté au cours de ces dix dernières années aux monolithes organiques pour des applications électroséparatives se justifie en partie par leur préparation aisée au sein de systèmes miniaturisés, le large choix des monomères précurseurs disponibles, ainsi que la possibilité d'ajuster les paramètres structuraux du matériau final par un contrôle judicieux des conditions opératoires. Au cours de ce travail, la synthèse de nouvelles phases monolithiques a été mise au point selon une stratégie en deux étapes. Dans une première étape, la copolymérisation radicalaire photo-initiée du Nacryloxysuccinimide avec le diméthacrylate d'éthylène glycol réalisée en présence de toluène, a permis l'élaboration de monolithes macroporeux réactifs et hautement perméables. La présence d'esters de succinimide dans la structure chimique du monolithe polymère a été mise à profit pour fonctionnaliser la surface du monolithe par des greffons de nature variée par réaction de substitution nucléophile faisant intervenir des dérivés aminés. Le choix judicieux des greffons a permis la mise au point rapide de phases stationnaires présentant des propriétés électrochromatographiques ciblées. Ainsi, le contrôle du caractère hydrophobe des supports obtenus par greffage d'alkylamines de taille variable a été mis en évidence par la séparation de dérivés benzéniques selon un mécanisme à polarité de phase inversée avec de très bonnes efficacités (200000 plateaux par mètre). L'utilisation de phases stationnaires monolithiques greffées par des sélecteurs aromatiques a été proposée comme alternative aux monolithes aliphatiques hydrophobes. La synthèse de monolithes organiques hydrophiles a été possible par la fonctionnalisation du support réactif par des alkyldiamines. La préparation d'une phase stationnaire chirale a été réalisée selon une approche originale de chimie click consistant à immobiliser un dérivé de cyclodextrine. Dans le but d'étendre l'application des monolithes à base de NAS au greffage de biomacromolécules, une nouvelle matrice monolithique incorporant dans sa structure chimique un co-monomère hydrophile a été élaborée. Les résultats préliminaires ont montré que l'augmentation du caractère hydrophile du squelette monolithique permet d'accroître sensiblement la réactivité des esters de Nhydroxysuccinimide en milieu aqueux

As part of the ongoing research efforts to discover alternative support materials to polymer beads for use in polymer-supported synthesis, particularly under flow-through, this project involved the synthesis of PolyHIPE (High Internal Phase Emulsion) polymer monoliths. PolyHIPEs containing high loadings of chloromethyl groups were efficiently prepared by the direct copolymerisation of 4-vinylbenzyl chloride and divinylbenzene monomers. As revealed by characterisation of the materials obtained, the VBC monomer hydrolysed to an extent during the polymerisation, replacing a small amount of the chloromethyl functionalities with hydroxymethyl groups. Functionalisation of the PolyHIPEs, in batch and flow-through reactions, produced supports with aminomethyl and hydroxymethyl linkers attached. Conversions were often higher as a result of the flow-through modifications. Capacities were increased further with the introduction of trisaminomethyl and trishydroxymethyl linkers, which showed potential as supports for polymer assisted solution phase (PASP) synthesis and solid phase organic synthesis (SPOS), respectively. Chloromethyl PolyHIPE was shown to be an excellent support for batch and flow-through Suzuki cross-coupling reactions. A remarkably high yield of pure biaryl product was obtained using PolyHIPE in cubic form and an electron-rich boronic acid. In comparison to polymer beads, PolyHIPE was found to be a much more efficient support in both batch and continuous flow modes. PolyHIPE converted a greater amount of chloromethyl groups into biaryl product under identical reaction conditions. Under flow, the channelling effect observed with the beads was completely eliminated with PolyHIPE monoliths. The utility of hydroxymethyl- fianctionalised PolyHIPEs (Wang and tris-OH) in Suzuki coupling reactions was investigated and both showed promise as supports in this application.

Suite à la première thèse sur le greffage et l’adsorption physique successives de sélecteurs chiraux dans des tubes ouverts en électrochromatographie capillaire (ECC ou CEC) chirale, menée par le Dr Guillaume Pédéhontaa-Hiaa au sein de l’équipe du laboratoire COBRA (IUT d’Evreux), nous avons développé des phases stationnaires chirales covalentes (CSPs) à base de cyclodextrines (CDs) en tubes ouverts et des CSPs sur supports monolithiques pour l’emploi en CEC. Nous avons ainsi évalué les paramètres électrochromatographiques et la stabilité de ces CSPs en séparant une variété de racémiques neutres et chargés. L’influence de la température d’analyse, le potentiel appliqué ainsi que la nature et le pH des électrolytes sur la qualité des électrochromatogrammes ont été étudié en CEC chirale. Cette étude se divise en deux grandes parties. La première concerne les CSPs élaborées sur colonnes à tubes ouverts pour l’OT-CEC. Il s’agit initialement de graver la surface interne d’un capillaire de silice de 50 μm de diamètre interne à l’aide d’une solution de bifluorure d’ammonium dans le but premier d’augmenter considérablement sa surface spécifique et d’immobiliser en surface une grande quantité de sélecteurs chiraux à base de β-CD. Nous avons alors décrit des greffages covalents de CDs anioniques (Scc-β-CD et CM-β-CD) et d’un polymère anionique de CDs (p-CM-β-CD-) en surface de capillaire de gel de silice gravée et modifiée chimiquement par l’aminopropyltriéthoxysilane (APTEOS). Les greffages des sélecteurs ont été reproduits dans les mêmes conditions que dans la thèse rapportée précédemment en électrophorèse. L’originalité de la construction de ces CSPs réside dans la rapidité et la simplicité du couplage dit péptidique à température ambiante, des sélecteurs carboxylés sur des colonnes préalablement gravées. Ce greffage nécessite des agents de couplage peptidique solubles dans l’eau tels que 1-Ethyl-3-(diméthylaminopropyl)carbodiimide (EDC) et le N-Hydroxysuccinimide (NHS). Il peut aussi être obtenu de manière moins efficace avec d’autres agents solubles en milieu organique tels que le O-(Benzotriazol-1-yl)-N,N,N’,N’-tétraméthyluronium tétrafluoroborate et la triéthylamine (TBTU/TEA). Chaque étape menant aux CSPs a été caractérisée par une étude de flux électroosmotique (FEO) en OT-CEC. Des analyses en AFM et en MEB nous renseignent d’avantage sur le succès du procédé « etching » de nos capillaires. La deuxième grande partie de cette étude traite de la synthèse in-situ de CSPs sur des colonnes de type polymères monolithes organiques et un monolithe hybride à base de sol gel. Des post modifications de surface de ces supports monolithiques nous ont permis d’immobiliser de façon covalente et non covalente des sélecteurs de β-CD en surface des volumes macroporeux. Deux collaborations ont vu le jour pour atteindre ces objectifs. La première eut lieu avec le Dr Thuy Tran et le Pr Myriam Taverna de la Faculté de Pharmacie de Chatenay Malabry (UMR 8612), durant laquelle nous avons reproduit une colonne monolithe organique de type méthacrylate, porteuse de groupements phosphate dans l’optique d’adsorber physiquement en surface le polymère cationique de CDs (p-CD+) que nous a transféré le Pr Benjamin Carbonnier et d’évaluer les capacités de discrimination chirale de cette nouvelle CSP en m-CEC. La seconde collaboration a eu lieu avec le Dr Mohamed Guerrouache et le Pr Benjamin Carbonnier au sein du laboratoire ICMPE de Thiais, où nous avons synthétisé des colonnes monolithiques organiques à base d’acrylates dans le but de greffer en surface de façon covalente et non covalente les CDs et polymères de CDs et d’évaluer ces nouvelles CSPs en m-CEC. La troisième phase stationnaire monolithique employée est celle décrite par le Dr Huihui Yang qui décrit un monolithe hybride porteur de groupements sulfonates nous permettant par la suite d’immobiliser électrostatiquement le p-CD+ sur le réseau poreux et d’évaluer cette nouvelle CSP en m-CEC
New chiral stationary phases have been prepared for Open Tubular and monolithic columns used in electrochromatography capillary. In order to separate racemic mixtures such as flavonoïd, Hidantoïn derivatives, Binaphtalene-2, 2-hydrogenophosphate and others chiral solutes, we use the β-cyclodextrin forms as chiral selector. Besides, β-cyclodextrin seems to be the most efficient chiral selector in chromatography since it is able to complex and dissolve optical organic isomers in an aqueous media, this chiral selector is able to dissolve even lipophilic molecule with high weight. The complexation is based on interactions with β-cyclodextrin. This study aims to elaborate new chiral stationary phase for CEC using β-cyclodextrin polymers and β-cyclodextrin derivatives. Two approaches were used: Firstly, covalent stationary phases coating with carboxymethyl-β-cyclodextrin polymers and oligomers containing carboxyl’s group had been experimented for open tubular and monolithic column in CEC. Then a non-covalent coating cationic polymer of β-cyclodextrin’s derivatives was immobilized (polytrimethyl ammonium β-CD) on continuous organic monoliths bearing anionic’s group. Prior to the covalent coating of the CD’s chiral selector for OT-CEC and m-CEC, we needed to modify the silicate surface and the monolithic surface with a primary amine silicate1,2 (aminopropyltriethoxysilane) and EDA, an amino-organic moiety (Ethylene diamine). The stability of the bonded organic moiety (APTEOS, EDA) were studied by CEC at different pH with constant ionic strength’s buffer. In this way, graft of carboxymethyl-β-cyclodextrin polymer on silica inner surface modified by APTEOS and on NAS-co-EDMA surface modified by EDA succeeded in activating and covalently coupling reagent as EDC and NHS (1-ethyl-3(-3-dimethtylaminopropyl) carbodiimide and N-hydroxysuccinimide, respectively3) with carboxymethyl’s group of carboxymethyl-β-cyclodextrin . The resultant stationary phase lead to stable chiral stationary phases, easier to prepare starting by coupling the selector to the amine’s group using EDC and NHS. In order to optimize enantio-separations by increasing the specific surface of open tubular columns, we reproduce the etching process to bared capillaries with ammonium bifluoride solution, referred to Pesek’s process4. By this mean, we increase dramatically the specific surface of bared capillaries before anchoring CDs polymers to silicate surfaces modified by APTEOS. Finally due to etching process, we obtain a covalent bonded Chiral Stationary Phase (CSP) which led to more efficient and resolvent enantio-separations by CEC. To describe, in another way, the non-covalent coating of CSP, we immobilised a cationic polymer (polytrimethyl ammonium β-CD+) on two kind of continuous organic and silica hybrid monoliths bearing sulfonate5 and phosphate’s groups. Based on precedent results for OT-CEC enantio-separation with LbL stationary phase7, using successive layers charged polymers to separate racemic mixture in CEC, we decided to adsorb a polycationic polymer hydrosoluble onto the silica hybrid monolith column to form chiral stationary phase (CSP) polytrimethyl ammonium β-cyclodextrin. This way of modification for monolithic surface by chiral selectors is nowadays highly efficient and attractive for CEC. The effect of the matrix and the coating’s nature are discussed by comparing the chromatographic parameters

The research described in this thesis is to develop and validate a process system model for an electrothermal swing adsorption (ESA) process that incorporates novel activated carbon monoliths (ACMs) for the recovery of volatile organic compounds (VOCs). The process system comprises two columns one dedicated for adsorption and the other for desorption and works in a cyclic mode of operation. Two mathematical models have been developed to describe the process system, namely in one dimension (1D) and in three dimensions (3D). The developed models have been validated using experimental data at the bench and the pilot scale, at different operating conditions and for two VOCs. It has been concluded that the 1D model was sufficient to represent the experimental data of the current study without going through the trouble of using the 3D model which was more demanding in terms of formulation and computation. The linear driving force approximation (LDF) approximation adequately predicted the concentration of VOCs in the gas phase with no need for a fundamental diffusion study within the solid of the ACMs. The kinetics of adsorption and desorption was governed by the mass transfer coefficient which was found by parameter estimation and was directly related to the internal mass transfer coefficient controlled mainly by molecular diffusion inside the pore structure of the ACMs.

Du fait du coût élevé de certains matériaux adsorbants d’intérêt pour le traitement de la micropollution organique, l’étude a porté sur la régénération de matériaux adsorbants de type zéolithes hydrophobes et monolithe de carbone dans le cas de l’adsorption du bisphénol A et du diclofénac comme micropolluants réfractaires. Des procédés d’oxydation avancée impliquant des espèces radicalaires HO• (réaction de Fenton, électro-Fenton) et SO₄• – (activation de persulfate par voie thermique) ont été utilisés pour assurer la régénération des matériaux par désorption et dégradation oxydative des polluants fixés. La production de radicaux HO• au sein de la phase aqueuse circulant au niveau de l’adsorbant n’est pas suffisamment efficace pour sa régénération. Il a donc été envisagé de générer les radicaux au plus près des molécules adsorbées. Au cours de ce travail, une méthode sensible d’analyse par polarographie de H₂O₂ a été développée et validée pour le suivi des expériences avec les procédés mettant en jeu la réaction de Fenton. Pour différentes zéolithes, le catalyseur de la réaction de Fenton à base de fer a été incorporé préalablement dans la zéolithe. Pour le monolithe de carbone, les propriétés de conduction du matériau ont été mises à profit en l’utilisant comme cathode pour l’application du procédé électro-Fenton permettant de produire les radicaux HO• directement au sein du matériau. Cela a conduit à améliorer les performances de la régénération avec toutefois une diminution de son efficacité au cours de cycles successifs adsorption/régénération
The elimination of organic micropollutants often requires the use of adsorption processes among the water treatments. The aim of our study is to regenerate two expensive materials (hydrophobic zeolites and carbon monoliths) to increase their life expectancy and decrease their investing cost. Two organic contaminants were targeted : diclofenac and bisphenol A, which are refractory pollutants. Advanced oxidation processes involve radical species, HO• (Fenton and electro-Fenton reactions) and SO₄• – (thermal activation of persulfate ion). These oxidants were used to decompose the adsorbed pollutants and thus regenerate the adsorbents. The HO• production, within the core of aqueous phase, did not reach satisfactory regeneration, and a loss of adsorption capacity was observed. Furthermore, during this study, a sensitive polarographic analytical method was developed and validated for the quantification of H₂O₂ in the aqueous phase. This method was used to follow in situ the Fenton reaction. The location of the catalyst in a closer vicinity of the adsorbed species was then optimized and the iron catalyst was impregnated in the host, prior to the adsorption, on different types of hydrophobic zeolites. Concerning carbon monolith, the electro-Fenton process was carried out using the material as the cathode thanks to its electrical conductivity. Consequently, HO• are produced in the porosity of monolith. This latter property enhanced the degradation of adsorbed solutes. The overall performances were increased compared to the homogeneous Fenton process. Nonetheless, a decrease of the adsorption capacities with adsorption-regeneration cycles was observed

[EN] The present PhD thesis is centred in the design (using concepts of supramolecular chemistry), synthesis and characterization of different hybrid organic-inorganic materials for boron removal from aqueous media. The interaction between boron and organic groups, polyols, used in the development of these new adsorbents is also studied. In the first part of the thesis it is presented a brief review of supramolecular chemistry concepts, chemistry of boron and also the main methods for boron removal (first chapter) and, also, the objectives of this thesis (second chapter). The third chapter exposes the results obtained by using a ceramic foam as macroscopic support for active materials for boron removal. This support is previously "impregnated" with an inorganic silica mesoporous material (UVM-7) and, in a second step, it is functionalized with an organic group with high boron affinity (gluconamide). This organic group, which works as an adsorbent, remains anchored to a macroscopic support, which will facilitate the use of these materials in industrial applications. Once the material is synthetized their boron adsorption and elimination abailability in aqueous media is studied and its ulterior reutilization. The fourth chapter of the PhD thesis is focused on the preparation of low cost materials for boron adsorption from water. In first place, it is used, as inorganic scaffolding, UVM-7 material, a mesoporous silica phase with a bimodal pore system. This material has a high boron adsorption capacity after its functionalization with the polyalcohol (as it is shown in the previous chapter) nevertheless, the reagents used in the synthesis tetraethylorthosilicate, as silica source, and hexadecyltrimethylammonium bromide, as templating agent are so expensive that they induce a high cost of final materials. In this chapter is presented as an alternative another materials which are able to perform as inorganic scaffolds: UVM-11 (surfactant-free mesoporous material), two silica xerogels with pores within the mesoporous range and comercial high surface area silica fume were prepared. Once all the materials are synthetized they are functionalized with gluconamides which are the active compounds for boron adsorption. Finally, a comparative study of the boron adsorption capacities in water is carried out. Low cost materials present comparable boron removal to those of higher cost and comercially abailable materials. Finally, in the fith chapter of this PhD thesis, the adsorption mechanism of boron on the active materials (based on UVM-7 as inorganic support) is studied using solid Nuclear Magnetic Resonance measures of 11B and 13C and using techniques as Magic Angle Sppining, crossed polarization and heteronuclear polarization disacoplament. To do that, a hybrid material composed by UVM-7 matrix grafted with gluconamide is prepared and then the solid is put in contact with different boron quantities. Final solids are characterized through 13C and 11B NMR, showing the formation of boronesters between gluconamide diol groups and boron adsorbed. When low boron concentration is used, bisquelate complexes are formed (B:glucosa = 1:2), however with higher concentrations monoquelate complexes are formed (B:glucosa = 1:1). This work was carried out in collaboration with the research group of "sol-gel materials and NMR", appertaining to the center of "Chimie de la matière condensée de Paris" of the "Université Pierre et Marie Curie".
[ES] La presente tesis doctoral está dedicada al diseño (empleando conceptos de química supramolecular), síntesis y caracterización de diferentes materiales híbridos orgánico-inorgánicos para la eliminación de boro en medios acuosos. También se ha procedido a estudiar detalladamente la interacción del boro con las agrupaciones orgánicas, polialcoholes, empleadas en el desarrollo de estos nuevos adsorbentes. En la primera parte de la tesis de presenta una introducción en la que se revisa los conceptos de química supramolecular, química del boro y los principales métodos de eliminación de boro (primer capítulo) y, también, se exponen los objetivos de la tesis (segundo capítulo). Ya en el tercer capítulo se exponen los resultados obtenidos empleando una esponja cerámica como soporte macroscópico para los materiales activos frente a la eliminación de boro. Este soporte se "impregnan" previamente con un material inorgánico silíceo mesoporoso (UVM-7) y, en una fase posterior, se funcionaliza con un grupo orgánico con alta afinidad hacia el boro (gluconamida). El grupo orgánico que funcionará como adsorbente queda así anclado a un soporte de tamaño macroscópico que facilitará la aplicación de estos materiales a gran escala. Una vez preparado y caracterizado se estudió la capacidad del material para adsorber y eliminar boro de medios acuosos y su posterior reutilización. En el cuarto capítulo de la tesis doctoral se aborda la preparación de materiales adsorbentes de bajo coste económico para la eliminación de boro en medios acuosos. En primer lugar se emplea, como soporte inorgánico, UVM-7 una sílice mesoporosa con un sistema bimodal de poros. Este material tiene una capacidad de adsorción de boro muy elevada una vez funcionalizado con el correspondiente polialcohol (tal y como se expone en el capítulo anterior) sin embargo los reactivos para su síntesis tetraetilortosilicato como fuente de sílice y bromuro de cetiltrimetilamonio como agente director de estructura son muy caros con lo que el material final presenta un elevado coste. En este capítulo se presenta como alternativa otros materiales que puedan actuar como soportes inorgánicos: UVM-11, material mesoporoso que no requiere de agente director de estructura en su síntesis, dos xerogeles con poros en el rango meso y una sílice comercial nanoparticulada de elevada superficie específica. Una vez sintetizados y caracterizados los cinco soportes se funcionalizaron con gluconamidas, que son los componentes activos frente a la adsorción de boro. Finalmente, se realiza un estudio comparativo de la capacidad de eliminación de boro de los cinco materiales preparados. Los materiales de bajo coste estudiados presentan una capacidad de eliminación de boro comparable a los materiales de mayor coste y a los materiales comercialmente disponibles. Por último, en el capítulo cinco de esta tesis doctoral, se aborda el estudio del mecanismo de adsorción del boro en los materiales activos preparados (basados en UVM-7 como soporte inorgánico) mediante medidas de resonancia magnética nuclear de sólidos, tanto de 13C como de 11B empleando las técnicas de rotación en ángulo mágico, polarización cruzada, y el desacoplamiento dipolar heteronuclear. Para ello se prepara un material híbrido formado por una matriz de UVM-7 funcionalizada con gluconamidas y este sólido se pone en contacto con diferentes cantidades de boro. Los sólidos finales se caracterizan mediante RMN de 13C y de 11B, observándose la formación de boroesteres entre los grupos diol de las gluconamidas ancladas y el boro adsorbido. Cuando la concentración de boro empleada es baja se forman complejos bisquelados (B:glucosa = 1:2) mientras que a concentraciones altas empiezan a formarse complejos monoquelados (B:glucosa = 1:1). Este trabajo se llevó a cabo en colaboración con el grupo de investigación de "Materiales sol-gel y RMN", perteneciente al centro "Chimie de la matiè
[CAT] La present tesi doctoral està dedicada al disseny (empleant conceptes de química supramolecular), síntesi i caracterització de diferents materials híbrids orgànico-inorgànics per a la el¿liminació de bor en medi aquòs. També s'ha precedit a estudiar detalladament la interacció del bor amb les agrupacions orgàniques, polialcohols, empreats en el desenvolupament d'aquestos nous adsorbents. En la primera part de la tesi es presenta una introducció en la que es revisen els conceptes de química supramolecular, química del bor i els principals mètodes de el¿liminació de bor (primer capítol) i, també, s'exposen els objectius de la tesi (segon capítol). Ja en el tercer capítol s'exposen els resultats obtinguts empreant una esponja ceràmica com a suport macroscòpic per als materials actius front a l'el¿liminació del bor. Aquest suport s'impregna prèviament amb un material inorgànic de sílice mesoporós (UVM-7) i, en una següent fase, es funcionalitza amb un grup orgànic amb alta afinitat cap al bor (gluconamida). El grup orgànic que funcionarà com a adsorbent queda aixina anclat a un suport de tamany macroscòpic que facil¿litarà l'aplicació d'aquestos materials a gran escala. Una vegada preparat i caracteritzat s'estudia la capacitat del material per a adsorber i el¿liminar bor en medi aquós i la seua posterior reutilització. Al quart capítol de la tesi doctoral s'aborda la preparació de materials adsorbents de baix cost econòmic per a l'eliminació de bor en medi aquòs. En primer lloc, s'empra, com a suport inorgànic, UVM-7 una sílice mesoporosa amb un sistema bimodal de porus. Aquest material té una capacitat d'adsorció molt elevadadeprés de la seua funcionalització amb el corresponent polialcohol (tal i com s'exposa al capítol anterior), no obstant això els reactius que s'utilitzen per a la seua síntesi tetraetilortosilicat com a font de sílice i bromur de cetiltrimetilamoni com agent director d'estructura són molt cars, per tant el material final presenta un elevat cost. En aquest capítol es presenta com alternativa altres materials que puguen actuar com a suports inorgànics: UVM-11, material mesoporòs que no requereix d'agent director d'estructura durant la seua síntesi, dos xerogels en porus en el rang meso i una sílice comercial nanoparticulada amb elevada superficie específica. Una vegada sintetitzats i caracteritzats els cinc suports es funcionalitzen en gluconamides, que són els components actius front a la adsorció de bor. Finalment, es realitza un estudi comparatiu de la capacitat d'el¿liminació de bor dels cinc materials preparats. Els materials de baix cost estudiats presenten una capacitat de eliminació de bor semblant als materials de major cost i als materials comercialment disponibles. Per últim, al capítol cinc d'aquesta tesi doctoral, s'aborda l'estudi del mecanisme d'adsorció de bor als materials actius preparats (basats en UVM-7 com a suport inorgànic) mitjançant medides de resonància magnética nuclear de sólids, tant de 13C com de 11B emprant tècniques de rotació en àngul màgic, polarització creuada, i el desacoplament dipolar heteronuclear. Per a ell es prepara un material híbrid format per una matriu de UVM-7 funcionalitzada amb gluconamides i aquest sòlid es posa en contacte amb diferents quantitats de bor. Els sòlids finals es caracteritzen mitjançant RMN de 13C i de 11B observant-se la formació de borésters entre els grups diol de les gluconamides anclades i el bor adsorbit. Quan la concentració de bor emprada és baixa es formen complexos bisquelats (B:glucosa = 1:2) mentre que a concentracions més altes comencen a formar-se complexos monoquelats (B:glucosa = 1:1). Aquest treball és va realitzar ne col¿laboració amb el grup d'investigació de "Materials sol-gel i RMN", perteneixent al centre "Chimie de la matière condensée de Paris" de la "Université Pierre et Marie Curie".
Sanfeliu Cano, C. (2016). Organic-inorganic hybrid materials for boron removal from aqueous media [Tesis doctoral no publicada]. Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/63277
TESIS

To date, there has been little research into the role of microbial community structure in the functioning of the soil ecosystem and on the links between microbial biomass size, microbial activity and key soil processes that drive nutrient availability. The maintenance of structural and functional diversity of the soil microbial community is essential to ensure the sustainability of agricultural production systems. Soils of the same type with similar fertility that had been under long-term organic and conventional crop management in Canterbury, New Zealand, were selected to investigate relationships between microbial community composition, function and potential environmental impacts. The effects of different fertilisation strategies on soil biology and nitrogen (N) dynamics were investigated under field (farm site comparison), semi-controlled (lysimeter study) and controlled (incubation experiments) conditions by determining soil microbial biomass carbon (C) and N, enzyme activities (dehydrogenase, arginine deaminase, fluorescein diacetate hydrolysis), microbial community structure (denaturing gradient gel electrophoresis following PCR amplification of 16S and 18S rDNA fragments using selected primer sets) and N dynamics (mineralisation and leaching). The farm site comparison revealed distinct differences between the soils in microbial community structure, microbial biomass C (conventional>organic) and arginine deaminase activity (organic>conventional). In the lysimeter study, the soils were subjected to the same crop rotation (barley (Hordeum vulgare L.), maize (Zea mais L.), rape (Brassica napus L. ssp. oleifera (Moench)) plus a lupin green manure (Lupinus angustifolius L.) and two fertiliser regimes (following common organic and conventional practice). Soil biological properties, microbial community structure and mineral N leaching losses were determined over 2½ years. Differences in mineral leaching losses were not significant between treatments (total organic management: 24.2 kg N ha⁻¹; conventional management: 28.6 kg N ha⁻¹). Crop rotation and plant type had a larger influence on the microbial biomass, activity and community structure than fertilisation. Initial differences between soils decreased over time for most biological soil properties, while they persisted for the enzyme activities (e.g. dehydrogenase activity: 4.0 and 2.9 µg g⁻¹ h⁻¹ for organic and conventional management history, respectively). A lack of consistent positive links between enzyme activities and microbial biomass size indicated that similarly sized and structured microbial communities can express varying rates of activity. In two successive incubation experiments, the soils were amended with different rates of a lupin green manure (4 or 8t dry matter ha⁻¹), and different forms of N at 100 kg ha⁻¹ (urea and lupin) and incubated for 3 months. Samples were taken periodically, and in addition to soil biological properties and community structure, gross N mineralisation was determined. The form of N had a strong effect on microbial soil properties. Organic amendment resulted in a 2 to 5-fold increase in microbial biomass and enzyme activities, while microbial community structure was influenced by the addition or lack of C or N substrate. Correlation analyses suggested treatment-related differences in nutrient availability, microbial structural diversity (species richness or evenness) and physiological properties of the microbial community. The findings of this thesis showed that using green manures and crop rotations improved soil biology in both production systems, that no relationships existed between microbial structure, enzyme activities and N mineralisation, and that enzyme activities and microbial community structure are more closely associated with inherent soil and environmental factors, which makes them less useful as early indicators of changes in soil quality.

A simple capillary flow porometer (CFP) was assembled for pore structure characterization of monolithic capillary liquid chromatography columns based on ASTM standard F316-86. Determination of differential pressures and flow rates through dry and wet samples provided the necessary information to determine the through-pore throat diameter, bubble point pore diameter, mean flow pore diameter, and pore distribution. Unlike measurements in bulk using traditional techniques to provide indirect information about the pore properties of monolithic columns, monoliths can be characterized in their original chromatographic forms with this system. The performance of the new CFP was first evaluated by characterizing the pore size distributions of capillary columns packed with 3, 5, and 7 µm spherical silica particles. The mean through-pore diameters of the three packed columns were measured to be 0.5, 1.0 and 1.4 µm, which are all smaller than the pore diameters calculated from a close-packed arrangement (i.e., 0.7, 1.1 and 1.6 µm), with distributions ranging from 0.1 - 0.7, 0.3 - 1.1 and 0.4 - 2.6 µm, respectively. This is reasonable, since visual inspection of SEM images of the particles showed relatively large fractions of smaller than specified particles in the samples. Typical silica monoliths were fabricated via phase separation by polymerization of tetramethoxysilane (TMOS) in the presence of poly(ethylene glycol) (PEG). The mean pore diameter and pore size distribution measured using the CFP system verified that a greater number of pores with small throat diameters were prepared in columns with higher PEG content in the prepolymer mixture. SEM images also showed that the pore diameters of monoliths fabricated in bulk were found to be smaller than those in monoliths synthesized by the same procedure, but confined in capillary tubes. The CFP system was also used to study the effects of column inner diameter and length on pore properties of polymeric monoliths. Typical monoliths based on butyl methacrylate (BMA) and poly(ethylene glycol) diacrylate (PEGDA) in capillary columns with different inner diameters (i.e., 50 to 250 µm) and lengths (i.e., 1.5 to 3.0 cm) were characterized. The mean pore diameters and the pore size distributions indicated that varying the inner diameter and/or the length of the column affected little the pore properties. The latter finding is especially important to substantiate the use of CFP for determination of monolithic pore structures in capillaries. The results indicate that the through-pores are highly interconnected and, therefore, pore structure determinations by CFP are independent of capillary length. A negatively charged polymer monolith based on BMA, ethylene glycol dimethacrylate (EDMA) and 2-acryloylamido-2-methylpropanesulfonic acid monomer (AMPS), was successfully prepared in silica sacrificial layer, planar (SLP) microchannels. Extraction of FITC (fluorescein 5-isothiocyanate) labeled phenylalanine and capillary electrochromatography (CEC) of FITC labeled glycine using this monolithic stationary phase were demonstrated.

Monolithic columns are continuous interconnected networks with large through-pore channels. This structure results in a decrease in the diffusion path and affords high permeability, which result in obtaining good separation efficiency. Ideally, the structure of monoliths should be bi-model consisting of meso-pores and macro-pores responsible for retention time and flow of mobile phase respectively. The structure also enhances the mechanical strength, and the large through-pore channels afford very low flow resistance. This combination therefore results in the ability of smaller diameter monolithic columns to be employed under high flow rates, increasing both sensitivity and throughput simultaneously. Additionally, the unique structure of monoliths improves permeability and mass transfer leading to a decrease in band broadening. The first stage of the project was focused on the fabrication and characterisation of an organic monolithic column namely poly (SMA-co-EDMA) followed by quantification of caffeine in Arabic coffee. Since the efficiency of the above monolith was low due to the low number of mesopores (low surface area), the second stage was centered on improving the efficiency of organic monoliths via the use of a longer crosslinker namely 1,6-HEDA. This novel monolith column poly (HMA-co-1,6-HEDA) afforded high efficiency, good porosity, high permeability and excellent reproducibility. Next, this monolith was applied to several applications namely separation of neutral non-polar analytes, weak acids, and strong bases, followed by a quantification of amitriptyline in commercial pharmaceutical tablets. Since the results obtained for this novel monolith using capillary liquid chromatography were encouraging, the third stage was investigating the possibilities of coupling narrow fused silica capillaries with mass spectrometry (MS). In this stage, the novel monolith (HMA-co-1,6- HEDA) lacked stability under high pressure due to either the low concentration of the crosslinker (1,6-HEDA) in the polymerisation mixture or the ratio between the monomer mixture (HMA and 1,6-HEDA) and porogen system (1-propanol and 1,4-butanediol). Hence, a move towards using nano-flow to couple narrow fused silica capillaries to the MS was utilised and was successful in separating two basic drugs (amitriptyline and nortriptyline). Finally, in order to widen the application of reversed- phase monoliths, a new monolithic material namely poly (GMA-co-EDMA) was synthesised followed by incorporation of high purity Congo red (CR) which contains several functional groups including SO3H, and then evaluating by separation of some reversed phase and HILIC mixtures.

L’oxygène et l’eau présents dans l’atmosphère sont des acteurs important dans la dégradationdes matériaux contenus dans les dispositifs opto-électroniques organiques. Dans le but d’améliorerla stabilité et la durée de vie de ces dispositifs, ces dispositifs sont encapsulés avec desmatériaux barrière aux gaz par lamination ou par l’utilisation de couches minces. Cette dernière,notamment utilisée pour les OLED, permet de fournir des barrières aux gaz performantes parle dépôt de couches inorganiques denses directement sur les dispositifs. Cependant, elles sontassujetties aux défauts des surfaces sur lesquelles elle sont déposées.L’objectif de ces travaux est de développer une couche de planarisation afin d’homogénéiserla surface des dispositifs photovoltaïques organiques (OPV) et de réduire la rugosité dans lebut d’obtenir une protection barrières aux gaz améliorée, conférée par le dépôt subséquent decouches denses inorganiques selon divers moyens (voie liquide et gazeuse).Dans un premier temps, des couches de planarisation ont été développées à partir de 6 copolymèresp(VDF-HFP). Ces derniers ont été caractérisés afin d’améliorer nos connaissances sur cesmatériaux.Grâce à une étude de solubilité, des encres à différentes concentrations dans l’acétate d’éthyleont été réalisées. Ces dernières ont été étudiées par des mesures rhéologiques et de tension desurface permettant de mieux appréhender leur étalement, et les états de surface obtenus sur dessubstrats PET et sur les dispositifs OPV. Ces recherches ont été complétées par un contrôlede la topographie et par conséquent de la planarisation des dispositifs OPV par microscopieconfocale.Pour finir, l’étude des performances barrière des structures d’encapsulations hybrides (organiqueinorganique)ont dévoilé une bonne compatibilité lorsque la rugosité de la couche de planarisationest très faible. Ces résultats sont confirmés par des mesures barrières aux gaz et des tests devieillissement accélérés des dispositifs OPV encapsulés en enceinte climatique qui permettentd’illustrer l’intérêt de l’encre planarisante développée.Ce travail a été réalisé au laboratoire LMPO au CEA/LITEN en collaboration avec l’industrielArkema dans le but de fournir des technologies d’encapsulations performantes
Oxygen and water present in the atmosphere are important actors of the degradation of materialscontained in optoelectronic devices. In order to increase the stability and the lifetime ofOPV, the devices are encapsulated with gas-barrier materials by lamination encapsulation orthin film encapsulation. These latter, espacially used in OLED technology, provides high performancegas barriers by depositing dense inorganic layers directly onto the devices. However,they are subject to the defects of the surfaces on which they are deposited.The purpose of this study is to develop a planarinzing layer in order to homogenize the surfaceof organic photovoltaic devices (OPV) and to reduce the roughness with the aim to obtain animproved gas barrier protection, conferred by the subsequent deposition of dense inorganic layersby various ways (liquid and gaseous routes).In a first step, the planarization layers were developed from six p(VDF-HFP) co-polymers. Thesehave been characterized to improve our knowledge on those materials.Through a solubility study, inks at different concentrations in ethyl acetate were made. Thelatter were studied by rheological measurements and surface tension to understand better theirspread, and the surface conditions obtained on PET substrates and OPV devices. Those researchswere completed with a topography control and consequently the planarization of OPVdevices by confocal microscopy.Finally, the study of the barrier performance of hybrid encapsulation structures (organic-inorganic)revealed a good compatibility when the rugosity of the planarization layer is very low. Theseresults are confirmed by permeation measurements and accelerated aging tests of OPV devicesencapsulated in climatic chambers that illustrate the interest of the planarized ink developed.This work has been performed in the LMPO Laboratory at CEA/LITEN in collaboration withthe chemical company Arkema in order to be able to provide performant encapsulation technologies

El desenvolupament de diferents materials per a les tècniques d’extracció mitjançant processos de sorció és una àrea en continua expansió; no obstant, l’extracció d’anàlits polars encara és un tema que requereix més investigació. En aquesta Tesi s’han desenvolupa nous materials que reuneixen de selectivitat i/o capacitat característiques per a extreure contaminants orgànics polars en mostres aquoses. La primera part descriu el desenvolupament de nous materials polimèrics que milloren la capacitat i selectivitat de l’extracció en fase solida, i hi inclau els polímers altament entrecreuats amb caràcter hidrofílic, els sorbents altament entrecreuats d’intercanvi iònic de mode-mixte i els líquids iònics suportots en fases polimèriques; així com la seva avaluació com a nous sorbents per a la extracció de contaminats polars en diferents mostres aquoses mediambientals seguit de l’anàlisi per LC. La segona part está centrada en la preparació de noves barres agitadores amb recobriments monolítics polars i la seva posterior aplicació per l’extracció d’analits polars en diferents aigües de procedéncia mediambiental.
The development of different materials for sorptive extraction techniques is a continuously evolving field of research. Although there have been significant developments in this area, the extraction of polar analytes is still considered the bottleneck of the extraction process. The efforts have been undertaken to improve capacity and selectivity. For this reason, one of the main objectives of this Thesis is to develop new materials to extract polar organic contaminants from water samples. The first part reports on the development of new polymeric materials for solid-phase extraction including hypercrosslinked polymers with hydrophilic character, mixed-mode ion-exchange hypercrosslinked sorbents and supported ionic liquid polymeric phases and their evaluation as SPE sorbents for the extraction of polar contaminants, followed by LC analysis. The second part is focused on the preparation of new stir bars with polar monolithic coatings and their application to stir bar sorptive extract polar analytes from environmental water samples.

博士
中原大學
化學研究所
101
This study comprises two parts. The first part presents the use of metal-organic frameworks (MOFs) for proteomics study and the second part studies the organic polymer monolith chromatographic stationary phase for proteomics. Here, we show a new approach to biofunctionalization on metal-organic framework (MOF) via a 30 min vortex-assisted host-guest interaction without the necessity of chemical modification on the MOF surface. A fluorescein isothiocyanate (FITC) dye, whose molecular dimension is similar to the MOF’s channel pore size and can be reacted with trypsin by nucleophile attack then carried trypsin onto MOFs that creates a novel biocatalyst “trypsin-FITC@CYCU-4” with exemplary biocatalytic performance in bovine serum albumin (BSA) digestion. When a new MOF, CYCU-4 (Al), was functionalized with a conjugated trypsin-FITC catalyst, its structure obtained both micro- and mesopores permitting trypsin to reside on the surface with great stability. With this properties and the new synthesis strategy, a specific host-guest interaction combined with a space confinement effect was provided by the MOF. Furthermore, FITC was replaced with 4-Chloro-7-nitrobenzofurazan (NBD) whose size is smaller than FITC which is more suitable to be anchored into most MOFs and the specific fluorescent feature could be used to calculate directly the loading capacity. In addition, the protein digestion efficiency of trypsin-NBD@MOF is as good as trypsin-FITC@CYCU-4 and this biocatalyst maintained its crystalline nature even after trypsin-NBD treatment. Therefore, preparation of the proposed MOF biocatalyst is faster, easier and the digestion efficiency is exceptionally high even when reused many times. However, before checking the performance of MOF-based biocatalyst, a protein identification method needs to be developed. Herein, a poly(stearyl methacrylate-divinylbenzene) (poly(SMA-DVB)) was synthesized and tested its performance in small molecules, penicillin antibiotics, on CEC system. First, the penicillin separation effect with different charged monomer was discussed. Results indicated that poly(SMA-DVB-VBTA) monolithic column provided reproducible performance, while the negatively charged poly(SMA-DVB-VBSA) column produced unstable separation. To enhance the sensitivity, on-line concentration steps of step-gradient elution combined with anion selective injection (ASEI) coupled with CEC-MS system was used for penicillin detection. Sensitivities were further improved to 0.05-0.2 µg/L. Then, this CEC-MS method was applied to trace penicillin analyses in milk samples. In addition, the proposed monolith with little monomer ratio adjustment was used to identify BSA digests in nano LC- MS2. The sequence coverage was 72 % which was as good as conventional C18 packing column, and the sequence coverage was still 76 % even when reused after one month, which demonstrated that poly(SMA-DVB) is very stable and suitable to evaluate the performance of MOF-based biocatalyst.

碩士
國立臺灣大學
環境工程學研究所
100
Photocatalytic oxidation (PCO) was used to control α-pinene in indoor environment in this research. Effecient use the space for the photocatalystreaction with indoor VOCs is important. The objective of coating the photocatalyst on honeycomb support is to make the best of space by addition the area of reaction. The honeycomb support needs to be operated with optical fiber for UV light. In the experiment, Degussa P25 TiO2 was chosen as catalyst. The UV lamp is 254nm and 8W. The key factors including α-pinene concentration, relative humidity, gas flow rate and the experiment conducted twice for average. In the experiment, the effect of gas-phase transfer could be negligible when gas flow rate exceeded 1500ml/min. Therefore the rate-determaining step was related with the surface reaction of catalyst for photocatalysis. The gas flow rate is fixed at 1500ml/min to conduct the following experiment. The inlet concentration was from 400ppb to 2400ppb, the conversion of photocatalyst was maintained between 90% to 95% regardless of the relative humidity which is from 30% to 70%. PCO rate is increased with the inlet concentration. PCO rate at the relative humidity 50% is more than it at the relative humidity 30% and 70%. Therefore, the moderate relative humidity (50%) is helpful to PCO rate, others were not. At the relative humidity 70%, the conversion of photocatalyst and the residual intermediate were decrease with the inlet concentration. To fit the reaction rate of photocatalyst, it is to use the Langmuir-Hinshelwood model for bimolecular competitive adsorption form. The Langmuir adsorption constants of α-pinene and water at relative humidity 30% is 0.168 and 1×10-2 ppm-1. And the reaction rate constants of α-pinene at relative humidity 30% is 0.82 μmole/m2-s; The Langmuir adsorption constants of α-pinene and water at relative humidity 50% is 0.56 and 5.4×10-3 ppm-1. And the reaction rate constants of α-pinene at relative humidity 50% is 0.24 μmole/m2-s; The Langmuir adsorption constants of α-pinene and water at relative humidity 70% is 1.74 and 9.6×10-3 ppm-1. And the reaction rate constants of α-pinene at relative humidity 70% is 0.18 μmole/m2-s. Relative humidity may affect the production of hydroxyl radicals and the competitive adsorption in photocatalytic reaction. Results indicated that the increase of relative humidity could decrease the intermediates by about 8%. However, the increase of relative humidity had slightly effect on the conversion of photocatalyst. Consequently, relative humidity had an enhancement effect on production of the hydroxyl radicals in the experiment.

碩士
輔仁大學
化學系
106
Part.Ⅰ Polymer monolith microextraction (PMME) based on capillary monolithic column is an effective and useful technique to preconcentrate trace analytes from environmental and biological samples. A wide variety of household, medical systems and industrial waste waters have been discharged into groundwater, rivers and oceans without sewage treatment. Many organic compounds that have adverse effects on the human body have been detected such as non-steroidal anti-inflammatory drugs and endocrine disrupting compounds are collectively called environmental pollutant. The sample preparation methods was developed with environmental pollutant, including Naproxen (Na), 2,4-diclorophenol (2,4-DCP), Diclofenac (Di), Estradiol (E2), Ibuprofen (Ibu), Phenothiazine (Ptz), and Mefenamic acid (Me) by UPLC-DAD ( Ultra performance liquid chromatography- Diode array detection，UPLC-DAD). The PMME optimal parameters, silanized with MSMA about 5 hr, polymerized about 1 hr, loading speed for the PMME was 0.9 mL/hr and the elute solvent was 200 μL 25 mM ammonium acetate pH 5.0: MeOH (4:6,v/v). The coefficients of correlation (r2) for the UPLC-DAD calibration curves were greater than 0.9997. The limits of detection (LOD) and limits of quantificantion LOQ) were determined within 0.20 to 2.12 ng/mL and 0.68 to 7.07 ng/mL. The recovery of environmental pollutant in spike urine were 40.0 % to 102.0 %. Though the recovery was't very well, it could effectively reduce the matrix effect. These results shown this capillary monolithic column could be used for extraction environmental pollutant from human urine sample or reduce the matrix effect such as sorbent. Part.Ⅱ Acetaminophen (AC), is a medicine used to treat pain and fever. It is typically used for mild to moderate pain relief. However, long-term exposure or excessive use of acetaminophen causes accumulation of toxic metabolites, which leads to kidney and liver disease thus precise determination and quantitation is important. Development of highly sensitive and selective electrochemical sensors using chitosan (CHS) and metal-organic frameworks (MOFs) modified glassy carbon electrode (GCE) is creating fast and simple method for determination of acetaminophen in environmental water Development of highly sensitive and selective electrochemical sensors using chitosan (CHS) and metal-organic frameworks (MOFs) modified glassy carbon electrode (GCE) is creating fast and simple method for determination of acetaminophen in environmental water . In this optimal conditions, the results shown the modified GCE have properties of excellent electron transfer characteristics, low electron transfer resistance and increase the oxidation current by differential pulse voltammetry (DPV) and electrochemical impedance analysis (EIS). In the other hand the bare electrode and modified electrode were characterized by scanning electron microscope (SEM), energy dispersive spectrometer (EDS) and powder X - ray diffraction (PXRD), which confirmed that chitosan/ metal-organic frameworks modified electrode can be successfully prepared . The chitosan/metal-organic frameworks modified electrode shown a linear response for acetaminophen in the concentration range of 0.1 to 50 μM with detection limit of 30 nM at S/N = 3, respectively. In addition, the reproducibility and stability of this chitosan/ metal-organic frameworks modified electrode were discussed. Its relative standard deviation (RSD) of intra day and inter day were less than 4.74 % and 3.12 %, respectively. Stability still remanined above 100.84 % during one week. These results have confirmed that this modified electrode have satisfactory reproducbility and stability. Finally, this chitosan/ metal-organic frameworks modified electrode was successfully applied in the determination of acetaminophen in environmental water. The recovery was between 98.47 to 112.66 %. These results have confirmed that this modified electrode have good accuracy.

碩士
中原大學
化學研究所
100
In this study, the monolithic columns were used for the capillary electrochromatographic (CEC) separation of basic compounds. CEC method coupled either with UV or mass spectrometric detection was developed for the detection of melamine and its derivatives (ammeline, ammelide, and cyanuric acid). A series of poly(alkene-divinylbenzene-VBTA) monolithic columns, such as 1-octene, 1-dodecene or 1-octadecene, were used as separation columns with vinylbenzyl trimethylammonium chloride (VBTA) as the positive charged monomer and EOF provider. Optimization of the polymerization conditions (monomer level and ratio of charge-monomer) and mobile phase conditions (ACN content, pH value and concentration of electrolyte) were conducted. The poly(1-dodecene-DVB-VBTA) monolith was chosen as the optimal chromatographic material because it provided a better separation of the four melamine derivatives, which was completed within 5 min. Detection limit was in the range of 0.6-2.18 mg L−1 by the optimal CEC-UV mode, and was reduced from 2.2 to 19.4μg L−1 by the optimal CEC-MS mode. Finally, the proposed CEC methods successfully determined melamine contaminations (0.1 mg L−1 per analyte) in milk powder with analyte recovery range of up to 70%, with even better detection ability than previous GC–MS, CE–MS, as well as LC–MS methods.

博士
中原大學
化學研究所
102
In this dissertation, novel monolithic columns were developed and were applied as stationary phases for capillary electrochromatography (CEC), nano liquid chromatography (nano-LC) and sorbents for solid phase microextraction (SPME). In the first part, triallyl isocyanurate (TAIC), ethylene dimethacrylate (EDMA), stearyl methacrylate (SMA) and 2-acrylamido-2-methylpropanesulfonic acid (AMPS) were polymerized to produce poly(TAIC-EDMA-AMPS) monolithic column and applied in nano-LC for the separation of phenolic acids. The phenolic acids were successfully separated using gradient elution for 90 min. The column efficiency was determined by using the van Deemter curve and results indicated that the plate heights was lower than 20 μm at linear flow rate of 0.1-1.0 μL/min. In comparison with the common hydrophilic monolithic column, the poly(TAIC-EDMA-AMPS) revealed more efficient in separating the phenolic acids. In the second part, metal-organic framework (MOF) (MIL-101(Cr)) was studied as chromatographic stationary phases. At first, the MIL-101(Cr) was packed into capillary and applied in CEC system. However, due to high back pressure of MIL-101(Cr) column, attempts in applying for nano-LC system was deemed impossible. Thus, in this case, novel MOF-polymer monolith was successfully developed with improved effectiveness against high back pressure problems caused by packing. For the preparation of MOF-polymer, MIL-101(Cr), butyl methacrylate (BMA) and EDMA were homogeneously mixed in [C6mim][BF4] ionic liquid solvent via microwave assisted heating. In comparison with MOF packed column, the permeability of MOF-polymer was increased approximately to 20-fold. The MOF-polymer monoliths were characterized by scanning electron microscope (SEM), powder x-ray diffraction (PXRD), surface area analyzer and fourier transform infrared spectroscopy (FTIR). The novel MOF-polymer monolithic columns were successfully applied for CEC, and nano-LC for several aromatic compounds, and revealed a good column efficiency and column reproducibility, respectively. Moreover, MIL-101(Cr)-polymer monolithic column was also applied in peptides analyses, the result showed that 46 peptides were identified with sequence coverage of 64 % from tryptic digest of Bovine Serum Albumin (BSA). For the last part, MOF-polymer monoliths were applied to SPME technique for penicillins extraction, and quantitatively analyzed by CEC method to determine extraction efficiency. Using 25 wt% MOF, the desorption solvent and volume, condition solution volume, washing solution type, sample flow rate, and sample pH were optimized in the extraction of penicillin using MIL-101(Cr)-polymer as sorbent. The maximun penicillins adsorption for MIL-101(Cr) were 9.1 - 11.1 μg/mg obtained from breathrough curve. At 25 wt%, different MOFs (cage and tunnel type) were also used to expore their extraction efficiencies. The result revealed that the recovery for cage type MIL-101(Cr) was 63.0 % - 96.2 %, while with the same cage structure MIL-100(M), the recoveries for MIL-100(Cr), MIL-100(Fe) and MIL-100(Al) were 23.9 % - 78.4 %, 7.0 % - 22.5 % and 15.6 % - 81.5 %, respectively. Meanwhile, for the tunnel type MOF, the recovery for MIL-53(Al) was 54.7 % - 67.7 %. With the results, it suggests that MIL-101(Cr) and MIL-53(Al) have greater adsorption capacities in extracting the penicillin. Further studies have conducted on MIL-101(Cr) and MIL-53(Al) by increasing the MOF wt% to 37.5. Based on the results, the recovery for MIL-53(Al) further increased to 76.4 % - 94.0 % and was comparable to MIL-101(Cr). For MIL-101(Cr)-polymer SPME, the fabricated method exhibited a good linearity (with R2 between 0.9982 and 0.9993) from 0.01 - 1.0 μg/mL, low limits of detection (1.2 - 4.5 ng/mL), and limit of quantification (4.0 - 14.8 ng/mL). The MOF-polymer SPME was applied in river sample and the recovery ranges from 67.9 % - 91.2 % and 62.5 % - 90.8 % at spiked 0.05 μg/mL and 0.10 μg/mL concentration, respectively. Finally, the MIL-101(Cr)-polymer can be re-used at least 45 times which shows high column life-time. With these results, it showed the potential application of MOF-polymer SPME.

碩士
中原大學
化學研究所
102
In this study, metal-organic framework–polymeric monolith (MOF-polymer) were used as adsorbent for solid-phase microextraction (SPME) of sulfonamides and non-steroidal anti-inflammatory drugs (NSAIDs). For the first part in this dissertation, MOF-polymers were applied for SPME technology for sulfonamides extraction and analyzed by using microemulsion electrokinetic chromatography (MEEKC) method to determine the extraction efficiency. Considering the extraction efficiency of sulfonamides, different type of MOFs and extraction conditions were optimized. The results show that 50 weight percent MOF amount, sample matrix at pH 5, 5 cm of extraction column lengths, 0.125 mL/min of extraction flow rate and 1 mL methanol as eluting solvent for optimized conditions. Based on the optimized results, the recoveries and relative standard deviation (RSD) for intra-day were ranged from 40.6% - 93.0% and <4.8%, respectively. For inter-day, the recoveries were ranged from 40.6% - 91.2%, and RSD < 6.4 %. In addition, the recoveries of column-to-column were ranged from 41.9% - 89.7% and RSD < 5.3%, demonstrated MIL-53(Al)-polymer column was high reproducibility. Furthermore, the MIL-53(Al)-polymer column can be re-used at least 30 times. For the second part in this dissertation, MOF-polymers were applied for SPME technology for NSAIDs extraction. The results show that 33 weight percent MOF amount, 0.125 mL/min of extraction flow rate for optimized conditions. Based on the optimized results, the extraction recoveries by using MIL-101(Cr)-polymer were ranged from 84.0 % - 104.5 % and RSD < 5.7%.Comparison with different type of MOF for NSAIDs extraction, the extraction recoveries by using DUT-5-polymer were ranged from 91.0% - 106.6% and RSD < 8.7 %. The extraction recoveries by using MIL-100(Fe)-polymer were ranged from 52.1% - 79.6% and RSD < 10.5%. The extraction recoveries by using UIO-66-polymer were ranged from 46.7% - 69.9% and RSD < 10.4%.Finally, the results showed that the MOF-polymer were successfully applied for SPME application in the extraction of NASIDs.

碩士
中原大學
化學研究所
105
In the present study, the porous carbon material derived from metal-organic gels (cMOGs) was defined as cAl-BDC-NH2, which embedded with polymer monolithic column for solid-phase microextraction (SPME) of catecholamine. In this experiment, cAl-BDC-NH2-poly(butyl methacrylate-ethylene dimethacrylate) (cAl-BDC-NH2-poly(BMA-EDMA)) was used to optimize the extraction parameters, and the results of the extraction steps were detected by micellar electrokinetic capillary chromatography (MEKC). Finally, the compare of the catecholamine extraction effect with metal-organic gels (Al-BDC-NH2-poly(BMA-EDMA)), different metal centers (cCr-BDC-NH2-poly(BMA-EDMA)) and embedded with different integrally formed polymers (cAl-BDC-NH2-poly(Sty-DVB)). The results showed that the optimum conditions were 36% cAl-BDC-NH2-poly(BMA-EDMA), 5 cm column length, 5 mM phosphate sample matrix at pH 7, ACN as washing solvent and 40 mM phosphate buffer in 30% methanol at pH 2 as the desorption solvent, the recovery was 50.3% to 97.2%. In this study, cMOGs-polymer extraction column were successfully prepared and applied to SPME of catecholamines compounds, which were highly polar biological analytes.