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It has been observed that in certain cases the exposure of dyed fibres to aging techniques results in the strengthening of fibres. This thesis explores the hypothesis that the strengthening is due to radical cross-coupling reactions that could be initiated through metal ion mediated photodecarboxylation. The approaches taken in this research include kinetic experiments (using flash photolysis), examination of possible cross-coupling experiments (using species of opposite charge), and the design and examination of small molecule model systems. A flash photolysis system was developed and used in attempts to determine the rates of photochemical product formation for cobalt(III) amino acid complexes. Lower limits have been established for the rate of product formation in these systems. The lower limits are: 2 x 10⁷ s⁻¹ for [Co(bpy)2(gly)]²⁺; 2 x 10⁷ s⁻¹ for [Co(tpa)(gly)]²⁺; and 5 x 10⁶ s⁻¹ for [Co(tpa)(aib)]²⁺, where bpy is 2,2'-bipyridine; gly is glycinate; tpa is tris(2-pyridylmethyl)amine; and aib is aminoisobutyrate. In past studies, the rates of a series of cobalt(III) amino acid complexes were reported as being the same, and much slower. It is thought that in these cases it may not be the rate of the formation of product that was being measured, but rather the response time of the electronics that was being observed. In this thesis the results obtained for the rate for the aib complex were somewhat lower than those of the gly complexes. This may imply, for the aib complex at least, the rate of the formation of the metallocycle is being observed (and not the response times of the electronics or other limitations of the instrumentation), but the data is poor and there is considerable doubt about this. The steady state photolysis of opposite charged species [Co(bpy)2(gly)]²⁺ and [Co(EDTA)]⁻ is reported. The reactions were carried out on a small scale in deuterated solvent for NMR spectrometry analysis and also on a large scale for the possible isolation and characterisation of the products. Evidence was found for a different reaction occurring when both complexes were present. The exact nature of the product remains elusive. A model system was designed in which a dinuclear ligand would bind to two metal centres and a fibre mimic would be later added. Eight ligands are discussed that could potentially bind two octahedral metal centres. They all had a xylene spacing group linking the two polydentate sites together. Five of the ligands have two bidentate binding sites. The other three had two tridentate sites. The binding sites in three of the bis(bidentate) ligands were based on ethane-1,2- diamine (en). Two of these ligands produced hypodentate monocobalt and sundentate dicobalt complexes. The other two bidentate ligands were based on 2- aminomethylpyridine (ampy). Both of these ligands degraded in the complexation reaction conditions. The binding sites in the tridentate ligands were all based on tacn. Once again, the principal products isolated were hypodentate systems in which only one metal ion was coordinated by the ligands. There is a distinct pattern observed in the xylene spaced ligands to form hypodentate complexes with cobalt(III) metal centred complexes. There is evidence of the di-nuclear species from a reaction with a charcoal catalyst in the bis(bidentate) system. ¹H NMR spectrometry, ¹³C NMR spectrometry, elemental analysis, X-ray crystallography and UV-vis spectroscopy were used to study and characterise the complexes and ligands that were prepared in this project.

A modular approach for the synthesis of highly ordered porous and chiral auxiliary (Evans auxiliary) decorated metal–organic frameworks is developed. Our synthesis strategy, which uses known porous structures as model materials for incorporation of chirality via linker modification, can provide access to a wide range of porous materials suitable for enantioselective separation and catalysis. Chiral analogues of UMCM-1 have been synthesized and investigated for the enantioseparation of chiral compounds in the liquid phase and first promising results are reported. / Dieser Beitrag ist mit Zustimmung des Rechteinhabers aufgrund einer (DFG-geförderten) Allianz- bzw. Nationallizenz frei zugänglich.

L’évaluation de l’exposition aux composés organiques volatils (COV) recourt couramment à l’analyse des métabolites urinaires en assumant qu’aucune interaction ne survient entre les composés. Or, des études antérieures ont démontré qu’une inhibition de type compétitive survient entre le toluène (TOL), l’éthylbenzène (EBZ) et le m-xylène (XYL). Le chloroforme, qui est également un solvant métabolisé par le CYP2E1, se retrouve souvent en présence des autres COV dans les échantillons de biosurveillance. La présente étude visait donc à évaluer si le chloroforme (CHL) peut lui aussi interagir avec ces COV et évaluer ces interactions au niveau de l’excrétion des biomarqueurs urinaires associés, soit l’o-crésol, l’acide mandélique et l’acide m-méthylhippurique pour TOL, EBZ et XYL respectivement. Afin d’obtenir des données humaines, cinq volontaires ont été exposés par inhalation à différentes combinaisons de COV (seuls et mélanges binaires ou quaternaires) où la concentration de chacun des composés était égale à 1/4 ou 1/8 de la valeur limite d’exposition (VLE) pour une durée de 6h. Des échantillons d’air exhalé, de sang et d’urine ont été récoltés. Ces données ont ensuite été comparées aux modèles pharmacocinétiques à base physiologique (PCBP) existants afin de les ajuster pour l’excrétion urinaire. Certaines différences ont été observées entre les expositions aux solvants seuls et les coexpositions, mais celles-ci semblent majoritairement attribuables aux remplacements de participants à travers les différentes expositions. Les valeurs de Vmax pour EBZ et CHL ont été optimisées afin de mieux prédire les niveaux sanguins de ces COV. À l’exception du modèle pour EBZ, tous les paramètres pour l’excrétion urinaire ont été obtenus à partir de la littérature. Les modèles adaptés dans cette étude ont permis de simuler adéquatement les données expérimentales. / Evaluation of volatile organic compounds (VOC) exposure commonly resorts to urinary metabolite analyses, assuming that no interaction occur between coexposed chemicals. However, previous studies have reported competitive inhibition between toluene (TOL), ethylbenzene (EBZ) and m-xylene (XYL). Chloroform, which is also metabolized by CYP2E1, is also often found in human biomonitoring samples along with the mentioned VOCs. The goal of the present study was to evaluate if chloroform (CHL) can interact with previous VOC and to evaluate those interactions at the urinary biomarker excretion level for corresponding metabolites, namely o-cresol, mandelic acid and m-methylhippuric acid for TOL, EBZ and XYL respectively. To obtain human data, five male volunteers were exposed by inhalation to different VOC combinations (single and binary or quaternary mixtures) where concentration of each chemical was equal to 1/4 or 1/8 of the threshold limit value (TLV) for 6h. Exhaled air blood and urine samples were collected. These data were then compared with existing physiologically based pharmacokinetic (PBPK) model predictions for adjustment for urinary excretion. Some differences were observed between single and mixed exposures but they may be mainly related to volunteer replacements throughout experiments. Vmax values for EBZ and CHL were optimized to better fit blood data. Except for EBZ model, all urinary excretion parameters were taken from the literature. Models adapted in the present study adequately simulated experimental data.

Une approche synthétique a été développée pour préparer les phtalocyanines dimériques de fer azote ponté substituées par les substituants alkylesulfoniles attracteurs d’électrons. Six nouvelles phtalocyanines avec des petits substituants (méthylesulfonile, éthylesulfonile et hexylesulfonile) et des gros substituants (t-butylesulfonile, adamantylesulfonile et cyclohexylesulfonile) ont été préparées et caractérisées par ionisation électrospray (ESI-MS), UV-vis, FT-IR et RPE. Deux complexes (avec substituants hexylesulfoniles et t-butylesulfoniles) ont été caractérisés par spectroscopie Mössbauer, spectroscopie photoélectronique de rayons X (XPS) et par spectroscopie d’absorption des rayons X (XANES, EXAFS, spectroscopie d’émission Kβ haute résolution). Il a été montré que l’état électronique de fer de ces complexes dépend de la taille de substituants. Les phtalocyanines de fer à l’azote ponté avec les gros substituants (t-butylesulfonile, adamantylesulfonile et cyclohexylesulfonile) sont cationiques (PcFeIVNFeIVPc)+N3-, tandis que les complexes avec les substituants plus gros (t-butylesulfonyles, adamantylesulfonyles et cyclohexylesulfonyles) sont non-chargés, formellement PcFeIIINFeIVPc. Les propriétés catalytiques des six complexes ont été étudiées en utilisant du butyle hydroperoxyde comme oxydant en oxydation de toluène, de p-xylène et des alcools. Ce travail montre l’efficacité des phtalocyanines dimériques de fer azote ponté substituées par les groupements alkylesulfoniles attracteurs d’électrons comme catalyseurs pour oxydation dans les conditions favorables pour les applications industrielles propres / The synthetic approach was developed for the preparation of N-bridged diiron phthalocyanines substituted by different electron-withdrawing alkylsulfonyl substituents. Six novel phthalocyanines bearing small (methylsulfonyl, ethylsulfonyl and hexylsulfonyl) and bulky (t-butylsulfonyl, adamantylsulfonyl and cyclohexylsulfonyl) substituents have been prepared and characterized by electrospray ionization mass spectrometry (ESI-MS), UV-Vis, FT-IR and EPR. Two complexes (with hexylsulfonyl and t-butylsulfonyl substituents) were characterized in addition by Mössbauer techniques, X-ray photoelectron spectroscopy (XPS) and Fe K-edge X-ray absorption spectroscopy (XANES, EXAFS, high resolution Kβ emission spectroscopy). It has been evidenced that the electronic state of iron in these complexes depends on the size of the substituents. While N-bridged diiron phthalocyanines having methylsulfonyl, ethylsulfonyl and hexylsulfonyl substituents are cationic (PcFeIVNFeIVPc)+N3- complexes, N-bridged diiron phthalocyanines with bulkier t-butylsulfonyl, adamantylsulfonyl and cyclohexylsulfonyl substituents are formally neutral PcFeIIINFeIVPc species. The catalytic properties of six N-bridged diiron phthalocyanines have been studied, using tert-butyl hydroperoxide (tBuOOH) as the oxidant in the oxidation of toluene, p-xylene as well as in the oxidation of various alcohols. This thesis demonstrates the efficiency of N-bridged diiron phthalocyanines substituted by electron-withdrawing alkylsulfonyl groups as oxidation catalysts, in conditions required by environmental and industrial preoccupations

Afin de répondre aux demandes des industriels de nouveaux matériaux poreux sont testés pour de nouvelles applications ou pour améliorer les procédés existants. Les adsorbants de types Metal Organic Frameworks(MOFs) ont des structures construites à partir d'unités inorganiques reliées entre elles par des ligands organiques. La possibilité de varier ces deux entités, offre une grande diversité de structures avec des cavités de tailles contrôlées. L'objectif de cette thèse a été d'évaluer les performances des MOFs pour l'adsorption de composés organiques et de comprendre les mécanismes d'adsorption. Les deux problématiques sélectionnées sont d'intérêt pour l'industrie pétrochimique. La séparation du para-xylène des autres isomères du xylène et de l'éthylbenzene, permets de répondre à la demande de matière première pour la synthèse du polytéréphtalate d'éthylène. L'adsorption des composés azotés et soufrés (teneur fixée par des législations), permets la purification de carburants. Notre étude thermodynamique est basée sur la réalisation d'isothermes d'adsorption et la détermination d'enthalpies d'adsorption par microcalorimétrie en phase liquide. L'adsorption des vapeurs des xylènes purs a été étudiée pour comprendre l'effet du solvant. Une grande variété de comportement a été observée selon les structures des MOFs. Nous avons par exemple mis en évidence l'effet de l'empilement moléculaire des isomères du xylène sur la sélectivité des MOFs. Nous avons démontré que la flexibilité des MOFs intervient sur les interactions au cours de l'adsorption des xylènes. Nous avons mis en évidence une sélectivité des MOFs possédant un centre métallique insaturé en faveur des composés azotés / In order to meet the industrials requirements, new porous materials are tested for new applications or to improve existing processes. The Metal Organic Frameworks (MOFs) are hybrids crystalline compounds made up of clusters (or chains) of metal ions coordinated by organic linkers to form three dimensional structures. The ability to vary these two entities offers to MOFs a wide variety of organized structure with pore sizes controlled. The aim of this thesis was to evaluate the MOF performances for the adsorption of organic compounds and also understand the related adsorption mechanism. The two selected issues are of interest for the petrochemical industry. The para-xylène separation from the other xylene isomers (ortho, meta) and ethylbenzene, allows to meet the demand for raw materials in the polyethylene terephthalate (PET) synthesis. The nitrogen and sulphur compounds adsorption allows the purification of fuels (sulphur content set by legislation). We present a thermodynamic study of adsorption from solution based on the determination of adsorption isotherms by depletion method and adsorption enthalpies by microcalorimetry. The pure xylenes vapour adsorption was also studied to understand the solvent effect. A wide variety of behaviour has been observed depending on MOF structures. For example we demonstrated the effect of xylene isomers molecular packing on MOF selectivity. Furthermore we have shown that the MOF structure flexibility influence the interactions involved during xylene isomers adsorption. We also demonstrated that MOF with unsaturated metallic centres present selectivity for nitrogen compounds (Lewis acid/base).

O tolueno e o xileno são substâncias presentes, ao lado de outras, em vários produtos, entre eles as tintas, tíneres e colas, provocando exposição combinada dos trabalhadores a diversas substâncias químicas. Assim, foi objetivo deste trabalho desenvolver um método simples, rápido e confiável de cromatografia em fase gasosa que permitisse análise simultânea do ácido hipúrico (AH) e ácido metil-hipúrico (AMH) em urina, bioindicadores de dose interna utilizados na monitorização da exposição ocupacional ao tolueno e xileno respectivamente. Após extração líquido-líquido e derivação com trimetilfenilamôneo, foi realizada análise cromatográfica em coluna capilar 100% polidimetilsiloxano, usando-se o ácido heptadecanóico como padrão interno. Foram avaliados 69 trabalhadores que manipulavam tintas em atividades de repintura de veículos e 31 trabalhadores não-expostos (controle). O método mostrou-se linear entre 0,1 (limite de quantificação) e 5,0 g/L para o AH e 0,2 (limite de quantificação) e 5 g/L para o AMH. A recuperação média foi de 81 % e a inexatidão de aproximadamente - 8,0% (bias) para ambos os analitos. Os coeficientes de variação médios para as concentrações de 0,5; 2,0 e 4,0 g/L foram, para a precisão intra-ensaio, de 3,5% para o AH e de 3,7% para o AMH, e para a interensaio, de 10,5% para o AH e de 10,7% para o AMH. Os analitos permaneceram estáveis em até 3 ciclos de congelamento/descongelamento das amostras de urina. O valor médio obtido nas amostras de trabalhadores expostos foi de 0,55 g/g de creatinina (mediana = 0,36 g/g de creatinina). Apesar de diferença estatisticamente significativa (teste t Student, p ≤ 0,05) ter sido observada entre os valores médios de AH nos trabalhadores expostos e nos do grupo controle, esta diferença não foi detectada quando analisou-se as medianas. O hábito de fumar e de ingerir bebidas alcoólicas também não mostrou alterar significativamente a excreção dos bioindicadores no grupo avaliado. / Toluene and the xylene, among others substances, are solvents used in several products, such as inks, thiners and glues, and are responsible for mixed exposure in workers. Thus, the aim of this work was to develop a simple, fast and reliable gas chromatographic method to allow the simultaneous detection and quantitation of hippuric acid (HA) and methylhippuric acid (MHA) in urine, which are internai dose bioindicators in the monitoring of occupational exposure to toluene and the xylene, respectively. After liquid-liquid extraction and derivation with trimethylphenylammonium, the chromatographic analysis was accomplished using capillary column 100% methylsiloxane, and heptadecanoic acid as internai standard. 69 workers exposed to inks in activities such as vehicles painting and 31 nonexposed workers were evaluated. The method showed linearity range between 0,1 (quantitation limit) and 5,0 g/L for HA and 0,2 (quantitation limit) and 5 g/L for MHA. The recovery was 81 % and the inaccuracy of approximately - 8,0% (bias) for both analytes. The mean variation . coefficients for the concentrations of 0,5; 2,0 and 4,0 g/L were, for the intraassay precision, of 3,5% for HA and of 3,7% for MHA, and for the inter assay, 10,5% for HA and 10,7% for MHA. The analytes were stable for 3 freezing cycles of the urine samples. The medium value obtained in the exposed workers\' samples was of 0,55 creatinina g/g (medium = 0,36 creatinina g/g). In spite of the observed statistical significant differences (test t Student, p ≤ 0,05) among the medium values of HA in the exposed workers and the control groups, this difference was not detected when it was analyzed the respective median values. Smoking and drinking alcoholic beverages habits did not significantly alter the excretion of these bioindicators in the studied group.

Made available in DSpace on 2016-08-10T10:55:51Z (GMT). No. of bitstreams: 1 MARIA PAULA THEES PERILLO RODRIGUES.pdf: 616615 bytes, checksum: ff241c7f4362c3709564d808bc919f92 (MD5) Previous issue date: 2005-06-17 / Xylene is an aromatic hydrocarbon of oily consistency, practically insoluble in water, inflammable and toxic. Its contamination is persistent and bioaccumulative and can damage health and environment. Due to increasing amounts of work-related injuries, mainly those caused by chemical intoxication, health and safety programs have been implemented. Regulatory rules were created aiming workers’ integrity and health, such as the NR7 that established biological parameters to occupational exposure to chemicals and NR15 that determined the allowed tolerance limit in an occupational setting. This study aimed evaluating hematological and immunological parameters of technicians in histological laboratories exposed to xylene and non-exposed individuals. The urine methylhippuric acid level was measured by high performance liquid chromatography. The hematological indices were evaluated in technicians exposed to xylene and non-exposed controls. The T lymphocytes (CD3+) and subpopulations (CD4+ and CD8+), NK cells (CD56+) and B cells (CD19+) were evaluated by flow cytometry. Phagocytic index was assessed in peripheral blood neutrophiles in technicians and normal controls using Saccharomyces cerevisiae yeast sensitized or not with serum. Methylhippuric acid levels present in the urine of technicians and controlled groups were within the allowed tolerance limits. No significant quantitative alterations of hematological indices were shown in technicians when compared to normal controls. However, peripheral blood neutrophils phagocytic index in technicians was significantly higher than in normal controls. Data shows that xylene use in this occupational activity does not imply in quantitative hematological and immunological alterations. Nonetheless, increased phagocytic capacity of the peripheral blood neutrophils of technicians suggest hyperactivation of these cells. / O xilol é um hidrocarboneto aromático de consistência líquida oleosa, praticamente insolúvel em água, inflamável e tóxico. Sua contaminação é persistente e bioacumulativa podendo causar danos à saúde e ao meio ambiente. Devido ao aumento de ocorrências de doenças profissionais principalmente as provocadas por intoxicação de produtos químicos, programas de saúde e segurança foram implementados. Foram criadas normas regulamentadoras que visam a saúde e integridade do trabalhador, como a NR7 que estabeleceu parâmetros biológicos à exposição ocupacional a produtos químicos, o utilizado para o xilol é o ácido metilhipúrico; e a NR15 que determinou o limite de tolerância permitido no ambiente ocupacional. O presente trabalho objetivou avaliar parâmetros hematológicos e imunológicos em histotécnicos de laboratório de anatomia patológica expostos ao xilol e indivíduos não expostos. A metodologia utilizada para a quantificação do ácido metilhipúrico na urina foi a cromatografia líquida de alta perfomance. Através do hemograma automatizado foram demonstrados os índices hematimétricos, leucocitário e plaquetário do sangue periférico de histotécnicos e controles não expostos ao xilol. A imunofenotipagem de linfócitos T totais ( CD3+) e subpopulações (CD4+, CD8+), células NK (CD56+) e células B (CD19+) foi avaliada por citometria de fluxo. O índice fagocitário foi avaliado em neutrófilos do sangue periférico de histotécnicos e controles normais utilizando leveduras de Saccharomyces cerevisiae sensibilizadas ou não. Os níveis de ácido metilhipúrico na urina dos histotécnicos e controles se apresentaram dentro dos limites de tolerância permitidos. Não foram demonstradas alterações quantitativas significativas dos índices hematimétricos, leucocitário e plaquetário de histotécnicos quando comparadas ao controles normais. Entretanto, o índice fagocitário de neutrófilos do sangue periférico de histotécnicos foi significativamente maior do que o de controles normais. Nossos dados indicam que a utilização do xilol nesta atividade ocupacional não induz alterações quantitativas hematológicas e imunológicas. Entretanto foram observadas alterações na atividade fagocitária de neutrófilos do sangue periférico sugerindo a hiperativação destas células.

Made available in DSpace on 2014-12-17T15:41:48Z (GMT). No. of bitstreams: 1 SyllosSS_DISSERT.pdf: 3274284 bytes, checksum: efc9ef709dfd1e06b4170ed41eedf3fb (MD5) Previous issue date: 2010-02-22 / The generation of wastes in most industrial process is inevitable. In the petroleum industry, one of the greatest problems for the environment is the huge amount of produced water generated in the oil fields. This wastewater is a complex mixture and present great amounts. These effluents can be hazardous to the environmental without adequate treatment. This research is focused in the analysis of the efficiencies of the flotation and photo-oxidation processes to remove and decompose the organic compounds present in the produced water. A series of surfactants derivated from the laurilic alcohol was utilized in the flotation to promote the separation. The experiments have been performed with a synthetic wastewater, carefully prepared with xylene. The experimental data obtained using flotation presented a first order kinetic, identified by the quality of the linear data fitting. The best conditions were found at 0.029 g.L-1 for the surfactant EO 7, 0.05 g.L-1 for EO 8, 0.07 g.L-1 for EO 9, 0.045 g.L-1 for EO 10 and 0.08 g.L-1 for EO 23 with the following estimated kinetic constants: 0.1765, 0.1325, 0.1210, 0.1531 and 0.1699 min-1, respectively. For the series studied, the most suitablesurfactant was the EO 7 due to the lower reagent consumption, higher separation rate constant and higher removal efficiency of xylene in the aqueous phase (98%). Similarly to the flotation, the photo-Fenton process shows to be efficient for degradation of xylene and promoting the mineralization of the organic charge around 90% and 100% in 90 min / A gera??o de res?duos na maioria dos processos industriais ? quase que inevit?vel. Na ind?stria do petr?leo, um dos grandes vil?es para o meio ambiente ? o enorme volume de ?guas produzidas nos campos de petr?leo. Este efluente apresenta composi??o complexa e aliado ao grande volume envolvido pode-se tornar bastante danoso ao meio ambiente quando descartado de forma inadequada. Esta pesquisa est? centrada na an?lise das efici?ncias dos processos de flota??o em coluna e oxida??o avan?ada por processo foto-Fenton para remo??o/degrada??o de org?nicos presentes na ?gua produzida. Uma s?rie de tensoativos derivados de ?lcool laur?lico foi utilizada na flota??o para promover a melhoria da cin?tica e efici?ncia de separa??o. Os experimentos foram realizados com efluente sint?tico contendo xileno como poluente modelo. Os dados experimentais obtidos da flota??o apresentaram cin?tica de 1? ordem, identificada pela qualidade dos ajustes lineares. As melhores condi??es encontradas foram 0,029 g.L-1 para o EO 7, 0,05 g.L-1 para o EO 8, 0,07 g.L-1 para o EO 9, 0,045 g.L-1 para o EO 10 e 0,08 g.L-1 para o EO 23 com as seguintes constantes de velocidade iguais a 0,1765, 0,1325, 0,1210, 0,1531, 0,1699 min-1, respectivamente. Para a s?rie estudada, o tensoativo mais adequado foi o EO 7 devido o menor consumo de reagente, maior constante cin?tica de separa??o e maior efici?ncia de remo??o do xileno da fase aquosa (98%). De forma similar a flota??o, o processo foto-Fenton demonstrou ser eficiente para degrada??o do xileno alcan?ando efici?ncia de mineraliza??o da carga org?nica entre 90% e 100% em 90 min

L'objectif de cette thèse était d’évaluer quelques Metal-Organic Frameworks (MOFs), choisis en fonction de leur taille de pores, de leur volume poreux et de leur stabilité thermique, en adsorption et séparation des hydrocarbures. Pour étudier le comportement général des MOFs nous avons choisi des MOFs avec des centres métalliques insaturés, des MOFs à charpente anionique et des ZIFs neutres et avons étudié leur sélectivité en séparation de trois familles d'hydrocarbures, à savoir alcanes, alcènes, aromatiques. Les MOFs à centre métallique insaturé se comportent généralement comme des zéolithes polaires, les ZIFs comme des zéolithes apolaires et/ou comme des tamis moléculaires. Les adsorbants les plus prometteurs sont testés sur des séparations d’intérêt industriel telles que la séparation des isomères de xylène, la séparation des paraffines linéaires, monobranchées et di-branchées et l’adsorption sélective du thiophène en vu de l’évaluation de ces adsorbants en désulfuration des essences. / The aim of this thesis was to evaluate several Metal Organic Frameworks (MOFs), selected based on criteria of pore size, pore volume and thermal stability, in adsorption and separation of hydrocarbons. For studying the general behavior of MOFs in hydrocarbon adsorption, we have chosen MOFs with open metal sites, MOFs with anionic frameworks and neutral ZIFs. The MOFs with open metal sites behave similar to polar zeolites, the ZIFs behave like apolar zeolites and/or like molecular sieves. Finally we selected the most interesting MOFs and tested them in several separations with industrial interest: xylene isomers, paraffin isomers and selective adsorption of thiophene for the purpose of fuel desulfuration.