Aspectes físics i químics del destintatge de paper revista mitjançant tensioactius catiònics

En una tesi anterior (Puig, 2004) es varen estudiar els aspectes mecànics vinculats al desfibratge i als consums energètics associats al procés de desintegració per acabar quantificant les forces implicades en el procés d'individualització dels components de diferents paperots. Aquest estudi, ha permès conèixer les condicions de desintegració que condueixen a un mínim consum energètic, aspecte complementari al reciclatge i destintatge del paperot però molt important per aconseguir un procés realment sostenible. Degut als requeriments del mercat, hi ha un altre aspecte o vessant realment important com és l'eliminació de tinta. Aquest procés, malgrat la complexitat industrial, es pot reduir o simplificar en dues etapes: la desintegració i la flotació. Ambdues, per raons d'eficàcia i condicionades pels agents químics que s'utilitzen, es realitzen en medi fortament alcalí (entorn d'un pH a 12). Aquest fet, genera una forta contaminació (DQO elevada) i per tant, és un procés poc respectuós amb el medi ambient. Els factors que condicionen treballar en medi alcalí són principalment, el despreniment de la tinta del suport, clarament accelerat en medi bàsic i fonamental per un bon destintatge i la utilització de tensioactius aniònics. Aquests tensioactius són sensibles al pH i la seva eficàcia disminueix en medi neutre o quasi neutre. Atès el que s'ha exposat, s'ha plantejat aquesta tesi que porta per títol "Aspectes Físics i Químics del Destintatge de Paper Revista mitjançant Tensioactius Catiònics", com un estudi del procés de destintatge de paper revista recuperat parant especial atenció a les variables físico-químiques i mecàniques del procés i a la seva influència en el despreniment i fragmentació de la tinta, així com en el procés d'eliminació de la tinta per flotació per tal d'avaluar la viabilitat d'un procés de destintatge en medi neutre enfront del destintatge alcalí convencional. S'ha utilitzat, com a paperot a destintar, el paper revista ja que aquest tipus de paper representa un percentatge elevat del paper recuperat a la Unió Europea. A més, aquest tipus de paper és utilitzat habitualment en les plantes de destintatge industrials per millorar les propietats de les suspensions destintades de paper de diari. La utilització de tensioactius catiònics és deguda a que la seva activitat no es veu afectada pel pH de la suspensió. Així, durant la comparació dels processos de destintatge en medi neutre i en medi alcalí, les eficàcies dels processos no es veuran influenciades pel grau d'ionització del tensioactiu. Donada l'absència d'estudis sobre la influència de les variables del procés en les mesures de concentració efectiva de tinta residual (ERIC) i ja que s'ha emprat aquest paràmetre per avaluar el despreniment i fragmentació de la tinta durant l'etapa de desintegració. En primer lloc, s'ha plantejat un estudi fonamental de la influència que poden tenir les variables del procés (granulometria, concentració de tinta i tipus de suport) en aquest paràmetre. Pel que fa a l'etapa de flotació, s'estudiarà l'efectivitat d'aquesta etapa, posant especial atenció a la capacitat del tensioactiu per eliminar tota la tinta despresa en l'etapa de desintegració. A més, donada la poca informació bibliogràfica referida als mecanismes de flotació amb tensioactius catiònics i la influència que té l'adsorció d'aquests agents per part de la suspensió paperera en l'etapa de flotació, s'ha dut a terme un estudi de l'adsorció dels tensioactius catiònics per part dels components d'una suspensió paperera. Per tant, la tesi realitzada té com a objectius:  Estudi fonamental de les mesures de ERIC (concentració efectiva de tinta residual) amb suports específics.  Estudi de la desintegració en medi neutre i comparació amb la desintegració clàssica.  Modelització del desfibratge de paperot a l'etapa de desintegració.  Estudi de l'eliminació de tinta per flotació en medi neutre i comparació amb la flotació clàssica.  Estudi del mecanisme d'adsorció de tensioactius en suspensions de cel·lulosa sintètica i de paperot.

Desenvolvimento de sistemas farmacêuticos emulsionados para veiculação gênica

Broadly speaking, the concept of gene therapy involves the transfer of a genetic material into a cell, tissue, or organ in order to cure a disease or at least improve the clinical status of a patient. Making it simple, gene therapy consists in the insertion of functional genes into cells containing defective genes by substituting, complementing or inhibiting them. The achievement of a foreigner DNA expression into a population of cells requires its transfer to the target. Therefore, it is a key issue to create systems able to transfer and protect the DNA until it reaches the target, the vectors. The disadvantages related to the use of viral vectors have encouraged efforts to develop emulsions as non-viral vectors. In fact, they are easily produced, present controllable stability and enable transfection. The aim of this work was to develop an emulsion for gene therapy and evaluate its ability to compact nucleic acids by the development of a complex with the plasmid pIRES2-EGFP. The first step was to determine the Hydrophilic Lipophilic Balance (HLB) of the Captex® 355 (oily internal phase of the emulsion) through long and short term stability assays. Based on the results, emulsions composed of Captex® 355, Tween 20® and Span 60® with 10.7 HLB were produced by three different methods: phase inversion, spontaneous emulsification and sonication. The results showed that the lowest diameter and best stability of the emulsions were achieved by the sonication method. The cationic emulsions were made by adding DOTAP to the basic emulsion. Its association with pIRES2-EGFP was evaluated by electrophoresis. Several rates of emulsion and DNA were evaluated and the results showed that 100% of the complex was formed when the rate DOTAP/DNA(nmol/µg) was 130. In conclusion, the overall results show the ability of the proposed emulsion to compact pIRES2-EGFP, which is a requirement to a successful transfection. Therefore, such formulation may be considered a promising candidate for gene therapy

Estudos das interações de quitosana/CTAB/C12E8

Surfactant-polymer interactions are widely used when required rheological properties for specific applications, such as the production of fluids for oil exploration. Studies of the interactions of chitosan with cationic surfactants has attracted attention by being able to cause changes in rheological parameters of the systems making room for new applications. The commercial chitosan represents an interesting alternative to these systems, since it is obtained from partial deacetylation of chitin: the residues sites acetylated can then be used for the polymer-surfactant interactions. Alkyl ethoxylated surfactants can be used in this system, since these non-ionic surfactants can interact with hydrophobic sites of chitosan, modifying the rheology of solutions or emulsions resultants, which depends on the relaxation phenomenon occurring in these systems. In this work, first, inverse emulsions were prepared from chitosan solution as the dispersed phase and cyclohexane as the continuous phase were, using CTAB as a surfactant. The rheological analysis of these emulsions showed pronounced pseudoplastic behavior. This behavior was attributed to interaction of "loops" of chitosan chains. Creep tests were also performed and gave further support to these discussions. Subsequently, in order to obtain more information about the interaction of chitosan with non-ionic surfactants, solutions of chitosan were mixed with C12E8 and and carried out rheological analysis and dynamic light scattering. The systems showed marked pseudoplastic behavior, which became less evident when the concentration of surfactant was increased. Arrhenius and KWW equations were used to obtain parameters of the apparent activation energy and relaxation rate distribution, respectively, to which were connected to the content of surfactant and temperature used in this work

Vesicle-to-micelle transition in dioctadecyldimethylammonium bromide and dioctadecyldimethylammonium chloride dispersions induced by octaethylene glycol n-dodecyl monoether. An isothermal titration calorimetry study

We have used isothermal titration calorimetry to investigate the vesicle-to-micelle transition in dioctadecyldimethylammonium bromide (DODAB) and chloride (DODAC) vesicle dispersions induced by the nonionic surfactant octaethylene glycol n-dodecyl monoether (C12E8) at room temperature. Small and giant unilamellar vesicles were prepared by sonication and without sonication, respectively, of the pure cationic surfactants at low concentrations in water. The titration of 1.0 mM DODAX (X = Cl- and Br-) by a concentrated micellar solution of C12E8 shows that the enthalpy of interaction (DeltaH(obs)) of C12E8 in micellar form with DODAX is always endothermic. The titration curves are understood on the basis of superposition of the enthalpies of partitioning of C12E8 into the bilayer, of micelle formation and of vesicle-to-micelle transformation. The enthalpy, DeltaH(obs), initially increases owing to the incorporation of C12E8 into the vesicle bilayer until the C12E8/DODAX saturation ratio (R-sat) is reached, then DeltaH(obs) decreases, in different ways for DODAB and DODAC, owing to degradation of vesicles and formation of mixed micelles and intermediary structures up to the C12E8/DODAX solubilization ratio, R-sol. Above R-sol only mixed micelles exist. The surfactant solubilization takes place in three stages. All the critical ratios are lower for DODAB than for DODAC, meaning that C12E8 solubilizes more strongly in DODAB for example, R-sat is 0.8 for DODAB and 1.2 for DODAC. Sonication has no significant effect on the transition.

The effect of chain length on the melting temperature and size of dialkyldimethylammonium bromide vesicles

Differential scanning calorimetry (DSc) and dynamic light scattering (DLS) were used to obtain the gel to liquid-crystalline phase transition temperature (T-m) and the apparent hydrodynamic radius (R-h) of spontaneously formed cationic vesicles of dialkyldimethylammonium bromide salts (CnH2n+1)(2)(CH3)(2)N+center dot Br-, with varying chain lengths. The preparation of cationic vesicles from aqueous solution of these surfactants, for n = 12, 14, 16 and 18 (DDAB, DTDAB, DHDAB and DODAB, respectively), requires the knowledge of the surfactant gel to liquid-crystalline phase transition temperature, or melting temperature (T-m) since below this temperature these surfactants are poorly or not soluble in water. That series of cationic surfactants has been widely investigated as vesicle-forming surfactants, although C-12 and C-18, DDAB and DODAB are by far the most investigated from this series. The dependence of T-m of these surfactants on the number n of carbons in the surfactant tails is reported. The T-m obtained by DSC increases non-linearly with n, and the vesicle apparent radius R-h is about the same for DHDAB and DODAB, but much smaller for DDAB. (c) 2006 Elsevier B.V.. All rights reserved.

Aggregation behaviour of hydrophobically modified poly(allylammonium) chloride

The behaviour of hydrophobically modified poly(allylammonium) chloride having octyl, decyl, dodecyl and hexadecyl side chains has been studied in aqueous solution using fluorescence emission techniques. Micropolarity studies using the I-1/I-3 ratio of the vibronic bands of pyrene show that the formation of hydrophobic microdomains depends on both the length of the side chain and the polymer concentration. The I-1/I-3 ratio of the polymers with low hydrophobe content (less than 5% mel) changes substantially when reaching a certain concentration. These changes are assigned to aggregation originating from interchain interactions. This behaviour is also confirmed by the behaviour of the monomer/excimer emission intensities of pyrene- dodecanoic acid used as a probe. For polymers having dodecyl side chains and hydrophobe contents higher than 10%, aggregates are formed independently of the polymer concentration. Anisotropy measurements show that microdomains resulting from the inter- and/or intramolecular interactions are similar to those observed for cationic surfactants. Viscosity measurements show that the coil dimensions are substantially decreased for the polymers having high hydrophobe contents, indicating intramolecular associations.

Ciclo reprodutivo de machos de Dendropsophus minutus (Anura, Hylidae)

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Arteroids: a poética do jogo e o jogo poético em redes digitais

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Interação de ácido algínico com surfactantes catiônicos em solução aquosa

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Interação de poli(etileno glicol) com brometo de dioctadecildimetilamônio e didodecilmetilamônio em dispersões aquosas

Pós-graduação em Biofísica Molecular - IBILCE

Counter-ion effect on surfactant-DNA gel particles as controlled DNA delivery systems

The ability to entrap drugs within vehicles and subsequently release them has led to new treatments for a number of diseases. Based on an associative phase separation and interfacial diffusion approach, we developed a way to prepare DNA gel particles without adding any kind of cross-linker or organic solvent. Among the various agents studied, cationic surfactants offered particularly efficient control for encapsulation and DNA release from these DNA gel particles. The driving force for this strong association is the electrostatic interaction between the two components, as induced by the entropic increase due to the release of the respective counter-ions. However, little is known about the influence of the respective counter-ions on this surfactant-DNA interaction. Here we examined the effect of different counter-ions on the formation and properties of the DNA gel particles by mixing DNA (either single-(ssDNA) or double-stranded (dsDNA)) with the single chain surfactant dodecyltrimethylammonium (DTA). In particular, we used as counter-ions of this surfactant the hydrogen sulfate and trifluoromethane sulfonate anions and the two halides, chloride and bromide. Effects on the morphology of the particles obtained, the encapsulation of DNA and its release, as well as the haemocompatibility of these particles are presented, using counter-ion structure and DNA conformation as controlling parameters. Analysis of the data indicates that the degree of counter-ion dissociation from the surfactant micelles and the polar/hydrophobic character of the counter-ion are important parameters in the final properties of the particles. The stronger interaction with amphiphiles for ssDNA than for dsDNA suggests the important role of hydrophobic interactions in DNA.

Synthesis and characterization of structurally well-defined polymer-layered silicate nanocomposites

Zusammenfassung Nanokomposite aus Polymeren und Schichtsilikaten werden zumeist auf der Basis natürlicher Tone wie Montmorillonit hergestellt. Für NMR- und EPR-Untersuchungen der Tensidschicht, die das Silikat mit dem Polymer kompatibilisiert, ist der Eisengehalt natürlicher Tone jedoch abträglich, weil er zu einer Verkürzung der Relaxationszeiten und zu einer Linienverbreiterung in den Spektren führt. Dieses Problem konnte überwunden werden, indem als Silikatkomponente eisenfreies, strukturell wohldefiniertes Magadiit hydrothermal synthetisiert und für die Kompositbildung eingesetzt wurde. Die Morphologie des Magadiits wurde durch Rasterelektronenmikroskopie charakterisiert und der Interkalationsgrad von schmelzinterkalierten Polymer-Nanokompositen wurde durch Weitwinkelröntgenstreuung bestimmt. Polymere mit Carbonylgruppen scheinen leichter zu interkalieren als solche ohne Carbonylgruppen. Polycaprolacton interkalierte sowohl in Oragnomagadiite auf der Basis von Ammoniumtensiden als auch in solche auf der Basis von Phosphoniumtensiden. Die Dynamik auf einer Nanosekundenzeitskala und die Struktur der Tensidschicht wurden mittels ortsspezifisch spinmarkierter Tensidsonden unter Nutzung von Dauerstrich- (CW) und Puls-Methoden der elektronenparamagnetischen Resonanzspektroskopie (EPR) untersucht. Zusätzlich wurde die statische 2H-Kernmagnetresonanz (NMR) an spezifisch deuterierten Tensiden angewendet, um die Tensiddynamik auf einer komplementären Zeitskala zwischen Mikrosekunden und Millisekunden zu erfassen. Sowohl die CW-EPR- als auch die 2H-NMR-Ergebnisse zeigen eine Beschleunigung der Tensiddynamik durch Interkalation von Polycaprolacton auf, während sich in den nichtinterkalierten Mikrokompositen mit Polystyrol die Tensiddynamik verlangsamt. Die Rotationskorrelationszeiten und Aktivierungsenergien offenbaren verschiedene Regime der Tensiddynamik. In Polystyrol-Mikrokompositen entspricht die Übergangstemperatur zwischen den Regimen der Glasübergangstemperatur von Polystyrol, während sie in Polycaprolacton-Nanokompositen bei der Schmelztemperatur von Polycaprolacton liegt. Durch die erhebliche Verlängerung der Elektronenspin-Relaxationszeiten bei Verwendung von eisenfreiem Magadiit können Messdaten hoher Qualität mit Puls-EPR-Experimenten erhalten werden. Insebsondere wurden die Vier-Puls-Elektron-Elektron-Doppelresonanz (DEER), die Elektronenspinechoenveloppenmodulation (ESEEM) und die Elektronen-Kern-Doppelresonanz (ENDOR) an spinmarkierten sowie spezifisch deuterierten Tensiden angewandt. Die ENDOR-Ergebnisse legen ein Model der Tensidschicht nahe, in dem zusätzlich zu den Oberflächenlagen auf dem Silikat eine wohldefinierte mittlere Lage existiert. Dieses Modell erklärt auch Verdünnungseffekte durch das Polymer in Kompositen mit Polycaprolacton und Polystyrol. Die umfangreiche Information aus den Magnetresonanztechniken ergänzt die Information aus konventionellen Charakterisierungstechniken wie Röntgendiffraktion und Transmissionselektronenmikroskopie und führt so zu einem detaillierteren Bild der Struktur und Dynamik der Tensidschicht in Nanokompositen aus Polymeren und Schichtsilikaten.

Synthese und Charakterisierung von multivalenten kationischen Tensiden und Polymeren

Der Einsatz von den Polyelektrolytkomplexen von DNA / RNA mit Polykationen oder Lipiden in der Gen-Therapie ist für Wissenschaftler von besonderem Interesse, da sie als Träger für den Transport von genetischem Material in lebende Zellen fungieren können. Interessant ist auch die Komplexbildung aus Gadolinium und Polykation, hier können die stabil gebildeten Aggregate als Kontrastmittel zur Anwendung in der Magnetresonanztomographie eingeführt werden. Ziel der vorliegenden Arbeit war es, strukturdefinierte, positiv geladene, polyvalente sperminanaloge Polymere zu synthetisieren. Durch die polyelektrolytische Natur erlauben solche Polymere die Komplexierung von mehr Gadolinium-Polyoxometalaten und wären deshalb sehr gut als Kontrastmittel geeignet. Aufbauend auf den Vorarbeiten, wurde insbesondere die Komplexbildung von kationischem Polymer mit der Green Fluorescent Protein DNA in physiologischem Salzgehalt untersucht. Die Beschreibung der Synthese im Rahmen dieser Arbeit zeigt, dass es mit dem entwickelten Syntheseprinzip, also unter Einsatz von orthogonaler Schutzgruppenchemie und funktionaler Transformation gelungen ist, durch einfache nukleophile Substitution die Kopplung der Elementareinheiten zu komplexeren, auch ionischen Tensiden durchzuführen. Die Komplexierung von Gadolinium-Polyoxometalat mit kationisch geladenem Polymer in reinem Wasser und in physiologischem Salzgehalt hat gezeigt, dass bei einem Ladungsverhältnis von ungefähr 2:1 stabile sphärische Komplexe gebildet werden. HeLa-Zellen zeigen keine hohe Empfindlichkeit gegenüber Polykation-POM-Komplexen, da deren toxische Wirkung nur einen Anteil toter Zellen von maximal 24 % zur Folge hatte. Die Bildqualität einer MRT-Aufnahme der gebildeten Polykation-POM-Komplexe wurde im Vergleich zu den reinen Gadolinium-Polyoxometalat-Lösungen erheblich verbessert. Die Komplexierung von DNA mit dem im Überschuss vorliegenden kationisch geladenen Polymer wurde mittels Rasterkraftmikroskopie, statischer sowie dynamischer Lichtstreuung untersucht. Die Molmasse und Größe der Polykation-DNA-Komplexe geben eindeutige Hinweise darauf, dass sich in physiologischer Salzlösung Multi-Ketten-Komplexe bilden. Neben der Untersuchung der Polymer-Komplexe wurde eine Reihe neuartiger multivalenter kationischer Tenside hergestellt, wobei ihre Eigenschaften beispielsweise mit Tensid B (C12N4), Tensid C (EG8N4) und Tensid F (EG8C12N4) in wässriger Lösung bei verschiedener Salzkonzentration im Vordergrund stehen.

Mesostructured zeolites: bridging the gap between zeolites and MCM-41

Surfactant-templating is one of the most versatile and useful techniques to implement mesoporous systems into solid materials. Various strategies based on various interactions between surfactants and solid precursors have been explored to produce new structures. Zeolites are invaluable as size- and shape-selective solid acid catalysts. Nevertheless, their micropores impose limitations on the mass transport of bulky feed and/or product molecules. Many studies have attempted to address this by utilizing surfactant-assisting technology to alleviate the diffusion constraints. However, most efforts have failed due to micro/mesopore phase separation. Recently, a new technique combining the uses of cationic surfactants and mild basic solutions was introduced to synthesise mesostructured zeolites. These materials sustain the unique characteristics of zeolites (i.e., strong acidity, crystallinity, microporosity, and hydrothermal stability), including tunable mesopore sizes and degrees of mesoporosity. The mesostructured zeolites are now commercially available through Rive Technology, and show superior performance in VGO cracking. This feature article provides an overview of recent explorations in the introduction of mesoporosity into zeolites using surfactant-templating techniques. Various porous materials, preparation methods, physical and catalytic properties of mesostructured zeolites will be discussed.

The interlayer swelling and molecular packing in organoclays

Understanding the interlayer swelling and molecular packing in organoclays is important to the formation and design of polymer nanocomposites. This paper presents recent experimental and molecular simulation studies on a variety of organoclays that show a linear relationship between the increase of d-spacing and the mass ratio between organic and clay. A denser molecular packing is observed in organoclays containing surfactants with hydroxyl-ethyl units. Moreover, our simulation results show that the head (nitrogen) groups are essentially tethered to the clay surface while the long hydrocarbon chains tend to adopt a layering structure with disordered conformation, which contrasts with the previous assumptions of either the chains lying parallel to the clay surface or being tilted at rather precise angles. (c) 2005 Elsevier Inc. All rights reserved.