Neste trabalho foi avaliada a degradação de alquilbenzeno linear sulfonado (LAS) de água residuária de lavanderia comercial (ARLC) em reator anaeróbio de leito fluidificado (RALF) utilizando areia como material suporte, lodo oriundo de UASB empregado no tratamento de resíduos de suinocultura como inóculo e tempo de detenção hidráulica de 18 horas. O período de 330 dias de operação foi divido em quatro etapas: (a) etapa I, com adaptação da biomassa ao substrato sintético contendo etanol e sacarose (1:1 DQO); (b) etapa II, com adição de ARLC (18,2 ± 11,5mgLAS.L-1) ao substrato sintético mais etanol e sacarose (1:1 DQO); (c) etapa III, com adição de ARLC (25,4 ± 8,8 mgLAS.L-1) ao substrato sintético mais etanol e (d) etapa IV, com adição de ARLC (20,4 ± 5,8 mgLAS.L-1) ao substrato sintético, sem adição de fonte suplementar de carbono. Equilíbrio reacional ao longo das etapas de operação foi verificado em função da baixa concentração de ácidos orgânicos voláteis e sólidos suspensos voláteis efluente. Na etapa I, verificou-se 82,9 ± 13,6% de remoção de DQO para 683,9 ± 110,4 mgDQO.L-1 afluente. Para todas as etapas de operação, observou-se a manutenção dessa eficiência sempre superior a 88%. Verificou-se aumento da eficiência de remoção do surfactante de 51,7 ± 23,9% na etapa II na presença de etanol e sacarose (1:1 DQO) (872,3 ± 141,8 mgDQO.L-1 afluente), para 72,9 ± 18,8% na etapa III, somente com etanol (705,0 ± 155,8 mgDQO.L-1 afluente), e de 76,8 ± 16,9% na etapa IV, após a retirada das fontes suplementares de carbono (633,4 ± 156,88 mgDQO.L-1 afluente). A substituição de sacarose e etanol por somente etanol foi extremamente favorável para a remoção do LAS, isto porque foram identificadas alterações das populações microbianas de acordo com a modificação da fonte suplementar de carbono relacionadas, principalmente, ao nível taxonômico de família. Na etapa II, observou-se predomínio de representantes da família Comamonadaceae (abundância relativa de 47% no biofilme). Também para o biofilme das etapas III e IV, verificou-se decréscimo para menos de 4% da abundância relativa de representantes pertencentes à família Comamonadaceae. Todavia, verificou-se aumento da abundância relativa de representantes da família Rhodocyclaceae (18%, 88% e 77% no biofilme das etapas II, III e IV, respectivamente). O principal gênero da família Comamonadaceae identificado na etapa II foi Curvibacter, cujo crescimento pode estar associado a açúcares (abundância relativa de 28% no biofilme). Verificou-se decréscimo da abundância relativa deste gênero inferior a 0,9% nas etapas III e IV. Para os representantes da família Rhodocyclaceae foram identificados gêneros possivelmente relacionados à degradação do LAS: Dechloromonas, Georgfuchsia e Zoogloea (78%, 67% e 98% dos gêneros pertencentes à família Rhodocyclaceae identificados no biofilme das etapas II, III e IV, respectivamente). Por meio do sequenciamento massivo, 37 gêneros possivelmente relacionados à degradação do LAS foram identificados. Quarenta compostos xenobióticos, alguns tóxicos à biota aquática, foram detectados no efluente via cromatografia gasosa/espectrometria de massas. Verificou-se, por meio do índice de Bray-Curtis, maior similaridade entre a biomassa do biofilme e do separador de fases de uma mesma etapa do que entre amostras de biomassa de etapas de operação distintas, evidenciando que houve diferenciação das populações de acordo com a fonte de carbono empregada. Por meio do balanço de massa global, observou-se que somente 0,81% do LAS removido ficou adsorvido. / In the present study, the degradation of linear alkylbenzene sulfonate (LAS) from laundry wastewater (LW) was investigated by using an anaerobic fluidized bed reactor (AFBR) with sand as support material, inoculum coming from a UASB reactor used in the treatment of swine manure, and hydraulic retention time of 18 hours. The operation time was divided into four stages: (a) stage I composed by the adaptation of the biomass in the presence of synthetic substrate containing sucrose and ethanol (1:1 COD); (b) stage II with addition of LW (18.2 ± 11.5mgLAS.L-1) plus synthetic substrate containing sucrose and ethanol (1:1 COD); (c) stage III with LW (25.4 ± 8.8 mgLAS.L-1) plus synthetic substrate containing ethanol; (d) stage IV with addition of LW (20.4 ± 5.8 mgLAS.L-1) plus synthetic substrate without supplementary carbon source. Low concentration of volatile organic acids and volatile suspended solids were observed in the reactor effluent indicating the system exhibited good stability. The COD removal efficiency was 82.9 ± 13.6% during the biomass adaptation in stage I (683.9 ± 110.4 mg.L-1 of COD influent). That removal efficiency was high throughout the operational time, exceeding 88%. The surfactant removal efficiency increased from 51.7 ± 23.9% in stage II with the presence of ethanol and sucrose (872.3 ± 141.8 mgCOD.L-1 influent) to 72.9 ± 18.8% in stage III, with only ethanol (705.0 ± 155.8 mgCOD.L-1 influent). In the stage IV, after the withdrawal of additional carbon sources, the removal efficiency was 76.8 ± 16.9% (633.4 ± 156.88 mgCOD.L-1 influent). The replacement of sucrose and ethanol by only ethanol favored the LAS efficiency removal due to the microbial community change according to the additional carbon source modification, what was mainly detected at family level. In stage II there was a predominance of representatives of Comamonadaceae family (relative abundance of 47% in the biofilm). That relative abundance decreased to less than 4% in stages III and IV. However, there was an increase in relative abundance of representatives of the Rhodocyclaceae family (18%, 88% and 77% of the biofilm in stages II, III and IV, respectively). The main genus of Comamonadaceae family identified in stage II was Curvibacter whose growth may be associated with sugars (relative abundance of 28% in the biofilm). That relative abundance was decreased to less than 0.9% in stages III and IV. For representatives of Rhodocyclaceae family, some genera possibly related to the degradation of LAS were identified: Dechloromonas, Georgfuchsia and Zoogloea (78%, 67% and 98% of the genera of the Rhodocyclaceae family identified in the biofilm from stages II, III and IV, respectively). By means of massive sequencing, 37 genera possibly related to degradation of LAS were identified. Forty xenobiotic compounds, some of them toxic to aquatic biota, were detected in the reactor effluent through gas chromatography/ mass spectrometry. According to the Bray-Curtis similarity, the samples collected in the same operation stage showed higher similarity coefficients than those collected in the same sampling site (biofilm from support material or phase separator). That result confirms the microbial community differentiation according to the carbon source employed. Through the overall mass balance, it was found that only 0.81% of LAS added was removed by adsorption.

A remoção do surfactante Alquilbenzeno Linear Sulfonado (LAS) de água residuária de lavanderia comercial foi estudada em EGSB (Expanded granular sludge bed). Essa água residuária foi diluída em esgoto sanitário. O volume útil do reator era de 1,8 L. Toda a operação ocorreu em condições mesofílicas, para TDH (tempo de detenção hidráulica) de 36 horas, velocidade ascensional de 4 m/h e vazão de recirculação de 8,5 L/h. A água residuária de lavanderia era diluída até que se atingisse aproximadamente 20 mg/L de LAS na alimentação do reator. O sistema foi operado em três fases. Na primeira fase de operação usou-se água de abastecimento para diluir a água residuária de lavanderia; na segunda fase utilizou-se uma mistura de água de abastecimento e esgoto sanitário para diluição da água residuária de lavanderia, sendo que 50 % da composição era esgoto sanitário; e, por fim, na última fase de operação utilizou-se apenas esgoto sanitário como diluente da água residuária. Na primeira fase foi necessária adição de bicarbonato de sódio como agente tamponante. Em todas as fases aplicou-se DQO (demanda química de oxigênio) e LAS afluente de 341 ± 216 mg/L e 18,8 ± 7,3 mg/L, respectivamente. A adição do esgoto sanitário afetou a remoção do surfactante, o que na fase inicial (Fase I) representou 77,2 ± 14,9 % e na fase final (Fase III) passou a ser 55,3 ± 18,4 % de remoção de LAS. No entanto, ao passo que a remoção de LAS diminuiu, a remoção de DQO aumentou de 57 ± 16 % para 65 ± 10 %, respectivamente, para a Fase I e Fase III. Além disso, devido a adição de esgoto sanitário verificou-se aumento do tamanho dos grânulos, de 3,67 ± 1,83 mm (Fase I) para 4,97 ± 1,99 mm (Fase II); e também da concentração de sólidos totais no reator, de 5,79 g/L (Etapa I) para 9,50 g/L (Fase III). Por meio do balanço de massa de LAS verificou-se remoção de 69 % de LAS, sendo que 67 % foram removidos por degradação e 2 % por adsorção do mesmo na biomassa. Por fim, por meio das análises por CG/EM (Cromatografia gasosa acoplada a espectrometria de massas) observou-se 17 substâncias no afluente e apenas 4 no efluente, tais como, mercaptanas, hidrocarbonetos, aminas e amidas. A maioria delas são tóxicas aos organismos aquáticos e estão presentes em produtos de limpeza e higiene pessoal. / The removal of the surfactant Linear Alkylbenzene Sulfonate (LAS) of wastewater of a commercial laundry was studied in an EGSB (Expanded granular sludge bed). This wastewater was diluted in sewage. The useful volume of the reactor was of 1,8 L. The whole operation occurred on mesophilic conditions, to HRT (Hydraulic Retention Time) was 36 hours, the upflow speed of 4 m/h and recirculation flow of 8,5 L/h. The laundry waste water was diluted until achieve 20 mg/L of LAS on the reactor feed. The system was operated in three stages. In the first operation stage water supply was used to dilute the wastewater laundry; in the second stage used a mixture of water supply and sewage for dilution of wastewater laundry and 50 % of the composition was sewage; and finally, in the last stage of operation is only used sewage as a diluent of wastewater. In the first stage was required addition of sodium bicarbonate as buffering agent. All the stages was applied COD (Chemical oxygen demand) and LAS influent 341 ± 216 mg/L and 18,8 ± 7,3 mg/L, respectively. The addition of sewage affected the surfactant removal, which on the first stage (Stage I) represented 77,2 ± 14,9 % and on the final stage (Stage III) became 55,3 ± 18,4 % of LAS removal. However, while removing of LAS decreased the COD removal increased from 57 ± 16 % to 65 ± 10 %, respectively, to Stage I and Stage III . Furthermore, due to the addition of sewage was checked an increased on the size of the grain from 3,67 ± 1,83 mm (Stage I) to 4,97 ± 1,99 mm (Stage II); and also the concentration of total solids into the reactor, from 5,79 g/L (Stage I) to 9,50 g/L (Stage III). By mass balance LAS was found a remove of 69 % of LAS, wherein 67 % were removed by degradation and 2 % by adsorption of the surfactant in the biomass. Finally, through analysis by GC/MS (gas chromatograph/mass spectrometry) 17 substances were observed in the influent and only 4 in the effluent, such as, mercaptans, hydrocarbons, amines and amides. Most of them are toxic to aquatic organisms and are present in cleaning products and personal hygiene.

L’objectif premier de ce travail a été de trouver une méthode de synthèse permettant depréparer des terpolymères ABC linéaires et en étoile en gardant la masse molaire des blocs A et B(PS et P2VP) constantes, tout en faisant varier la masse molaire du bloc C (PI) de sorte à avoiraccès à différentes morphologies. Le deuxième objectif consistait en l’auto-assemblage desterpolymères synthétisés sous forme de films minces.Afin de répondre au premier objectif de cette thèse, une voie de synthèse, combinant lapolymérisation anionique avec une méthode de couplage, a été mise au point. La polymérisationanionique séquentielle des blocs PS et P2VP a donné lieu à des chaînes PS-b-P2VPfonctionnalisées qui ont été ensuite couplées à différents blocs PI via une estérification de Steglich.Cette méthode de synthèse s’est révélée pertinente car des terpolymères ABC linéaires et en étoiletrès bien définis (c-à-d ayant une dispersité inférieure à 1.1) ont pu être synthétisés. De plus, laméthode de couplage, ayant un rendement proche de 100%, ne met pas en jeu l’utilisation de métalen tant que catalyseur.Dans un deuxième temps, l’auto-organisation des terpolymères a permis d’obtenir denouvelles morphologies sous forme de films minces. Un recuit par vapeur de solvant a été utilisépour apporter de la mobilité aux chaînes terpolymères. Ainsi, nous avons montré que l’autoorganisationde chaînes terpolymères linéaires (PS-b-P2VP-b-PI) permettait la formation d’unephase double gyroid coeur-écorce en film mince. De plus, l’auto-organisation des terpolymères enétoile (3 μ-ISP) a permis d’obtenir un pavage d’Archimède de type (4.6.12) pour la première foisen film mince. Dans ce cas, nous avons aussi montré que varier la masse molaire du bloc PI ainsique la nature du solvant de recuit permettait une rotation des domaines au sein la structure.Typiquement le coeur de la structure peut être occupé soit par le PI ou bien le PS. / The first objective of this work was to develop a synthesis method enabling the preparationof linear and star ABC terpolymers. The molecular weights of the A and B (PS and P2VP) blockswere kept constant while the size of the C (PI) block was varied to achieve different morphologies.The second objective of this work was devoted to the study of the self-assembly of linear and starABC terpolymer thin films. A synthesis route combining the anionic polymerization with acoupling method was developed. The PS and P2VP blocks were synthesized by a sequential anionicpolymerization. The PI block separately synthesized by anionic polymerization was then coupledto the PS-b-P2VP diblock via a Steglich esterification. This method revealed to be efficient sinceit is a catalyst metal-free reaction enabling to achieve well-defined terpolymers with a dispersitybelow 1.1The study of star and linear ABC terpolymer self-assembly led to new morphologies in thinfilm. A solvent vapor annealing treatment was used to promote the mobility of the polymericchains. A core-shell double gyroid structure was produced from the self-assembly of linear PS-b-P2VP-b-PI thin films. Four different crystallographic planes were observed depending on the filmthickness. Moreover, the self-assembly of star ABC terpolymer chains into a thin film (4.6.12)Archimedean tilling pattern was demonstrated for the first time. Here, the PS and PI blocksoccupied different places within the (4.6.12) tiling pattern depending on the PI volume ratio andthe solvent selected to swell the film.

L’objectif de cette étude est de synthétiser de nouveaux polymères aux propriétés spécifiques, en utilisant pour la première fois comme monomère un aldocétène : l’éthylcétène. La synthèse de l’éthylcétène a été entreprise en utilisant deux procédés distincts :d’une part la méthode de McCarney, qui a permis de le préparer dans un solvant par entraînement à la vapeur, et d’autre part le craquage de l’anhydride butyrique à 575°C sous 40mbar.La polymérisation ionique de l’éthylcétène a ensuite été réalisée, dans différentes conditions de solvant, de température et avec plusieurs amorceurs. La polymérisation anionique a abouti uniquement à la formation d’un polyester amorphe, tandis que la polymérisation cationique a conduit exclusivement à un polymère de structure polycétone,d’une grande stéréorégularité avec une cristallinité moyenne de 0,34. Une caractérisation fine de ces polymères a été effectuée par IRTF-ATR, RMN, TGA, DSC, GPC et diffraction desRX. / The aim of this study is to synthesize new polymers with specific properties, using for the first time an aldoketene as monomer, namely ethylketene.The synthesis of ethylketene was carried out by using two distinct processes: on the one hand the method of McCarney, which led to its synthesis in a solvent by co-distillation, and on the other hand the pyrolysis of butyric anhydride at 575°C under 40 mbar.The ionic polymerization of ethylketene was then carried out, using different solvents, temperatures and initiators. The anionic polymerization gave only amorphous polyesters,while the cationic polymerization led exclusively to a polyketonic polymer, highly stereoregular with an average cristallinity of 0.34. A precise characterization of thesepolymers was undertaken by FTIR-ATR, NMR, TGA, DSC, GPC and X-ray diffraction.

京都大学 / 0048 / 新制・課程博士 / 博士(人間・環境学) / 甲第22549号 / 人博第952号 / 新制||人||226(附属図書館) / 2019||人博||952(吉田南総合図書館) / 京都大学大学院人間・環境学研究科相関環境学専攻 / (主査)教授 内本 喜晴, 教授 吉田 寿雄, 准教授 戸﨑 充男 / 学位規則第4条第1項該当 / Doctor of Human and Environmental Studies / Kyoto University / DFAM

Surfactants are surface-active agents decreasing surface tension to simplify removing dirt. Surfactants can be divided into four basic classes: anionic, cationic, non-ionic and amfolytic. In Czech Republic there are mostly used anionic surfactants nowadays which get into waste water through detergents. The thesis deals with the spectrophotometric determination of anionic surfactants and the study of interferences to this method.

The biopharmaceutical industry is constantly developing biological drugs, resulting in increased levels of product related impurities having similar characteristics as the target. The aim of the ligand project was to address future challenging purifications by developing new ligands for future resins for the biopharmaceutical industry. The purpose of this study was to develop a high-throughput screening method and use it to compare 15 novel multimodal anionic exchange ligand analogues with two reference ligands, for future polishing steps in the downstream process. The protein binding behavior of the ligands were studied with alkaline phosphatase, human serum albumin, α-chymotrypsinogen A and a monoclonal antibody as model proteins, at various pH values and salt concentrations. The selection process of the model proteins was based on stability studies, a study of their adsorption to the 96 well plate, and their binding behavior on three of the ligand analogues and one reference ligand. The percent protein bound to the ligands at the various conditions was calculated and presented in plots in order to study their binding behaviors. The calculated values were also used in order to evaluate the results in principal component analysis, creating chromatographic diversity maps. The maps were used to get an overview of the differences and similarities of the ligand analogues compared to the reference resins, which can be used for selecting ligands for future research and biomanufacturing. Four analogues and one reference ligand were also studied in a column format where different gradients were used, which confirmed the obtained results in the plate experiments.

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

京都大学 / 0048 / 新制・課程博士 / 博士(工学) / 甲第19895号 / 工博第4211号 / 新制||工||1651(附属図書館) / 32972 / 京都大学大学院工学研究科合成・生物化学専攻 / (主査)教授 吉田 潤一, 教授 松田 建児, 教授 松原 誠二郎 / 学位規則第4条第1項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DFAM

No description available.