Determinação do ponto de névoa em surfactantes não iônicos por espectroscopia de impedância elétrica

In this paper, we analyze the use of electrical impedance spectroscopy applied to determination of cloud point. The slope of admittance measured at 100 kHz is reduced to temperature above the critical value which characterizes the phase transition, in a strong indication that this process is activated during the clouding. Additionally to this study we explored the influence of parameters such as additives and temperature on the performance of phase separation of residues (silver nanoparticles) by cloud point extraction. The interaction with salt maximizes the separation of chemical residues in a progressively reduced temperature.

Electron paramagnetic resonance (EPR) spectral components of spin-labeled lipids in saturated phospholipid bilayers: effect of cholesterol

Electron paramagnetic resonance (EPR) spectroscopy was used to study the main structural accommodations of spin labels in bilayers of saturated phosphatidylcholines with acyl chain lengths ranging from 16 to 22 carbon atoms. EPR spectra allowed the identification of two distinct spectral components in thermodynamic equilibrium at temperatures below and above the main phase transition. An accurate analysis of EPR spectra, using two fitting programs, enabled determination of the thermodynamic profile for these major probe accommodations. Focusing the analysis on two-component EPR spectra of a spin-labeled lipid, the influence of 40 mol % cholesterol in DPPC was studied.

Influencia de variables de formulación en la viscosidad de emulsiones de surfactante aniónico-aceite-agua

Phase transition and viscosity behavior of emulsified systems were studied after modifying their physicochemical formulation. Effects of concentration and nature of salts and n-alcohols, and water/oil relation on the rheological properties of emulsions were also studied. Pre-equilibrated systems were emulsified according to an agitation procedure, and the viscosity (cP) was measured at different shear rates ranging from 1 to 300 s-1. The phase behavior, as well as the emulsion type based on electrolytic conductivity, was observed. Several interpretations of the flow and viscosity curves of emulsions were made through the estimation of rheological parameters such as consistency index "k" and behavior index "n".

Hitsausvirtalähteen ohjaus lämmöntuonnin ja jatkuvan jäähtymisen S-käyrän perusteella

Lämmöntuonnilla on oleellinen vaikutus hitsausliitoksen ominaisuuksiin, koska se vaikuttaa liitoksen jäähtymisnopeuteen, jolla on puolestaan suuri vaikutus jäähtymisessä syntyviin mikrorakenteisiin. Jatkuvan jäähtymisen S-käyrältä voidaan ennustaa hitsausliitokseen syntyvät mikrorakenteet. S-käyrät voidaan laatia hitsausolosuhteiden mukaisesti, jolloin faasimuutoskäyttäytyminen sularajalla saadaan selvitettyä. Tämän diplomityön tavoitteena oli kehittää hitsausvirtalähteen ohjaustapaa lämmöntuontiin ja jatkuvan jäähtymisen S-käyriin perustuen. Jatkuvan jäähtymisen S-käyrillä ja lämmöntuontiin perustuvalla hitsausparametrien säädöllä on yhteys. Työssä tutkittiin, miten haluttuun jäähtymisnopeuteen johtava lämmöntuonti voidaan määrittää S-käyrälle luotettavasti. Työssä perehdyttiin jatkuvan jäähtymisen S-käyriin ja eri jäähtymisnopeuksilla hitsausliitokseen syntyviin mikrorakenteisiin sekä hitsaus-inverttereiden ohjaus- ja säätötekniikkaan. Teoriaosuuden jälkeen tarkasteltiin eri vaihtoehtoja, miten hitsattavan materiaalin koostumusvaihtelut sekä lämmöntuontiin vaikuttavat tekijät voidaan ottaa huomioon virtalähteen ohjauksessa lämmöntuonnin perusteella. S-käyrältä määritettyjen lämmöntuonnin arvojen perusteella tehtiin kahdet koehitsaukset, joissa käytettiin kolmea eri aineenpaksuutta. Tulosten perusteella arvioitiin lämmöntuonnin arvojen toimivuutta käytännössä ja tutkittiin liitokseen syntyviä mikrorakenteita. Tutkimuksen pohjalta esitettiin jatkokehitystoimenpiteitä, joiden mukaan voidaan edetä lämmöntuontiin perustuvan säätöjärjestelmän kehitysprojektissa.

Non-Markovian dynamics and quantum information probes

This Thesis discusses the phenomenology of the dynamics of open quantum systems marked by non-Markovian memory effects. Non-Markovian open quantum systems are the focal point of a flurry of recent research aiming to answer, e.g., the following questions: What is the characteristic trait of non-Markovian dynamical processes that discriminates it from forgetful Markovian dynamics? What is the microscopic origin of memory in quantum dynamics, and how can it be controlled? Does the existence of memory effects open new avenues and enable accomplishments that cannot be achieved with Markovian processes? These questions are addressed in the publications forming the core of this Thesis with case studies of both prototypical and more exotic models of open quantum systems. In the first part of the Thesis several ways of characterizing and quantifying non-Markovian phenomena are introduced. Their differences are then explored using a driven, dissipative qubit model. The second part of the Thesis focuses on the dynamics of a purely dephasing qubit model, which is used to unveil the origin of non-Markovianity for a wide class of dynamical models. The emergence of memory is shown to be strongly intertwined with the structure of the spectral density function, as further demonstrated in a physical realization of the dephasing model using ultracold quantum gases. Finally, as an application of memory effects, it is shown that non- Markovian dynamical processes facilitate a novel phenomenon of timeinvariant discord, where the total quantum correlations of a system are frozen to their initial value. Non-Markovianity can also be exploited in the detection of phase transitions using quantum information probes, as shown using the physically interesting models of the Ising chain in a transverse field and a Coulomb chain undergoing a structural phase transition.

How does yeast respond to pressure?

The brewing and baking yeast Saccharomyces cerevisiae has been used as a model for stress response studies of eukaryotic cells. In this review we focus on the effect of high hydrostatic pressure (HHP) on S. cerevisiae. HHP exerts a broad effect on yeast cells characteristic of common stresses, mainly associated with protein alteration and lipid bilayer phase transition. Like most stresses, pressure induces cell cycle arrest. Below 50 MPa (500 atm) yeast cell morphology is unaffected whereas above 220 MPa wild-type cells are killed. S. cerevisiae cells can acquire barotolerance if they are pretreated with a sublethal stress due to temperature, ethanol, hydrogen peroxide, or pressure. Nevertheless, pressure only leads to protection against severe stress if, after pressure pretreatment, the cells are also re-incubated at room pressure. We attribute this effect to the inhibition of the protein synthesis apparatus under HHP. The global genome expression analysis of S. cerevisiae cells submitted to HHP revealed a stress response profile. The majority of the up-regulated genes are involved in stress defense and carbohydrate metabolism while most repressed genes belong to the cell cycle progression and protein synthesis categories. However, the signaling pathway involved in the pressure response is still to be elucidated. Nitric oxide, a signaling molecule involved in the regulation of a large number of cellular functions, confers baroprotection. Furthermore, S. cerevisiae cells in the early exponential phase submitted to 50-MPa pressure show induction of the expression level of the nitric oxide synthase inducible isoform. As pressure becomes an important biotechnological tool, studies concerning this kind of stress in microorganisms are imperative.

Hydrogen Sensor Application of Anodic Titanium Oxide Nanostructures

Hydrogen (H2) fuel cells have been considered a promising renewable energy source. The recent growth of H2 economy has required highly sensitive, micro-sized and cost-effective H2 sensor for monitoring concentrations and alerting to leakages due to the flammability and explosiveness of H2 Titanium dioxide (TiO2) made by electrochemical anodic oxidation has shown great potential as a H2 sensing material. The aim of this thesis is to develop highly sensitive H2 sensor using anodized TiO2. The sensor enables mass production and integration with microelectronics by preparing the oxide layer on suitable substrate. Morphology, elemental composition, crystal phase, electrical properties and H2 sensing properties of TiO2 nanostructures prepared on Ti foil, Si and SiO2/Si substrates were characterized. Initially, vertically oriented TiO2 nanotubes as the sensing material were obtained by anodizing Ti foil. The morphological properties of tubes could be tailored by varying the applied voltages of the anodization. The transparent oxide layer creates an interference color phenomena with white light illumination on the oxide surface. This coloration effect can be used to predict the morphological properties of the TiO2 nanostructures. The crystal phase transition from amorphous to anatase or rutile, or the mixture of anatase and rutile was observed with varying heat treatment temperatures. However, the H2 sensing properties of TiO2 nanotubes at room temperature were insufficient. H2 sensors using TiO2 nanostructures formed on Si and SiO2/Si substrates were demonstrated. In both cases, a Ti layer deposited on the substrates by a DC magnetron sputtering method was successfully anodized. A mesoporous TiO2 layer obtained on Si by anodization in an aqueous electrolyte at 5°C showed diode behavior, which was influenced by the work function difference of Pt metal electrodes and the oxide layer. The sensor enabled the detection of H2 (20-1000 ppm) at low operating temperatures (50–140°C) in ambient air. A Pd decorated tubular TiO2 layer was prepared on metal electrodes patterned SiO2/Si wafer by anodization in an organic electrolyte at 5°C. The sensor showed significantly enhanced H2 sensing properties, and detected hydrogen in the range of a few ppm with fast response/recovery time. The metal electrodes placed under the oxide layer also enhanced the mechanical tolerance of the sensor. The concept of TiO2 nanostructures on alternative substrates could be a prospect for microelectronic applications and mass production of gas sensors. The gas sensor properties can be further improved by modifying material morphologies and decorating it with catalytic materials.

Optical properties of organic superconductor K-(BETS)2FeBr4 /

K-(BETS)2FeBr4 is a quasi-2D charge transfer organic metal with interesting electronic and magnetic properties. It undergoes a transition to an antiferromagnetic (AF) state at ambient pressure at the Neel temperature (T^^) = 2.5 K, as well as to a superconducting (SC) state at 1.1 K [1]. The temperature dependence of the electrical resistivity shows a small decrease at T;v indicating the resistivity drops as a result of the onset of the ordering of Fe'*''" spins. A sharp drop in the resistivity at 1.1 K is due to its superconducting transition. The temperature dependence of the susceptibility indicates an antiferromagnetic spin structure with the easy axis parallel to the a-axis. The specific heat at zero-field shows a large peak at about 2.4 K, which corresponds to the antiferromagnetic transition temperature (Tat) and no anomaly is observed around the superconducting transition temperature (1.1 K) demonstrating that the magnetically ordered state is not destroyed by the appearance of another phase transition (the superconducting transition) in the 7r-electron layers [1], [2]. This work presents an investigation of how the low frequency electromagnetic response is affected by the antiferromagnetic and superconducting states, as well as the onset of strong correlation. The location of the easy axis of three samples was determined and polarized thermal reflectance measurements of these «-(BETS)2FeBr4 samples oriented with their vertical axis along the a- and c axes were then carried out using a *He refrigerator cryostat and a Martin-Puplett type polarizing interferometer at various temperatures (T = 0.5 K, 1.4 K. 1.9 K, 2.8 K) above and below the superconducting state and/or antiferromagnetic state. Comparison of the SC state to the normal state along the o- and c-axes indicates a rising thermal reflectance at low frequencies (below 10 cm"' ) which may be a manifestation of the superconducting energy gap. A dip-Hke feature is detected at low frequencies (below 15 cm"') in the thermal reflectance plots which probe the antiferromagnetic state along the two axes, and may be due to the opening of a gap in the excitation spectrum as a result of the antiferromagnetism. In another set of experiments, thermal reflectance measurements carried out along the a- and c-axes at higher temperatures (10 K-80 K) show that the reflectivity decreases with increasing temperature to 60 K (the coherence temperature) above which it increases again. Comparison of the thermal reflectance plots along the a- and c-axes at higher temperatures reveals an anisotropy between these two axes. The Hagen-Rubens thermal reflectance plots corresponding to an average over the ac-plane were calculated using experimental hterature resistivity values. Comparison of the Hagen-Rubens plots with the experimental thermal reflectance along the a- and c-axes indicates that both exhibit the general trend of a decrease in thermal reflectance with increasing frequency, however the calculated Hagen-Rubens thermal reflectance at different temperatures is much lower than the experimental curves.

Monte Carlo study of the XY-model on quasi-periodic lattices

Monte Carlo Simulations were carried out using a nearest neighbour ferromagnetic XYmodel, on both 2-D and 3-D quasi-periodic lattices. In the case of 2-D, both the unfrustrated and frustrated XV-model were studied. For the unfrustrated 2-D XV-model, we have examined the magnetization, specific heat, linear susceptibility, helicity modulus and the derivative of the helicity modulus with respect to inverse temperature. The behaviour of all these quatities point to a Kosterlitz-Thouless transition occuring in temperature range Te == (1.0 -1.05) JlkB and with critical exponents that are consistent with previous results (obtained for crystalline lattices) . However, in the frustrated case, analysis of the spin glass susceptibility and EdwardsAnderson order parameter, in addition to the magnetization, specific heat and linear susceptibility, support a spin glass transition. In the case where the 'thin' rhombus is fully frustrated, a freezing transition occurs at Tf == 0.137 JlkB , which contradicts previous work suggesting the critical dimension of spin glasses to be de > 2 . In the 3-D systems, examination of the magnetization, specific heat and linear susceptibility reveal a conventional second order phase transition. Through a cumulant analysis and finite size scaling, a critical temperature of Te == (2.292 ± 0.003) JI kB and critical exponents of 0:' == 0.03 ± 0.03, f3 == 0.30 ± 0.01 and I == 1.31 ± 0.02 have been obtained.

The design of a reflectance spectrometer and its calibration using SrTiO3 /

A new Ultra-High Vacuum (UHV) reflectance spectrometer was successfully designed, making use of a Janis Industries ST-400 sample cryostat, IR Labs bolometer, and Briiker IFS 66 v/S spectrometer. Two of the noteworthy features include an in situ gold evaporator and internal reference path, both of which allow for the experiment to progress with a completely undisturbed sample position. As tested, the system was designed to operate between 4.2 K and 325 K over a frequency range of 60 - 670 cm~^. This frequency range can easily be extended through the addition of appUcable detectors. Tests were performed on SrTiOa, a highly ionic incipient ferroelectric insulator with a well known reflectance. The presence and temperatmre dependence of the lowest frequency "soft" mode were measured, as was the presence of the other two infrared modes. During the structural phase transition from cubic to tetragonal perovskite, the splitting of the second phonon mode was also observed. All of the collected data indicate good agreement with previous measurements, with a minor discrepency between the actual and recorded sample temperatures.

Elucidation of a mechanism of cell lysis by chorhexidine : a biophysical approach

Chlorhexidine is an effective antiseptic used widely in disinfecting products (hand soap), oral products (mouthwash), and is known to have potential applications in the textile industry. Chlorhexidine has been studied extensively through a biological and biochemical lens, showing evidence that it attacks the semipermeable membrane in bacterial cells. Although extremely lethal to bacterial cells, the present understanding of the exact mode of action of chlorhexidine is incomplete. A biophysical approach has been taken to investigate the potential location of chlorhexidine in the lipid bilayer. Deuterium nuclear magnetic resonance was used to characterize the molecular arrangement of mixed phospholipid/drug formulations. Powder spectra were analyzed using the de-Pake-ing technique, a method capable of extracting both the orientation distribution and the anisotropy distribution functions simultaneously. The results from samples of protonated phospholipids mixed with deuterium-labelled chlorhexidine are compared to those from samples of deuterated phospholipids and protonated chlorhexidine to determine its location in the lipid bilayer. A series of neutron scattering experiments were also conducted to study the biophysical interaction of chlorhexidine with a model phospholipid membrane of DMPC, a common saturated lipid found in bacterial cell membranes. The results found the hexamethylene linker to be located at the depth of the glycerol/phosphate region of the lipid bilayer. As drug concentration was increased in samples, a dramatic decrease in bilayer thickness was observed. Differential scanning calorimetry experiments have revealed a depression of the DMPC bilayer gel-to-lamellar phase transition temperature with an increasing drug concentration. The enthalpy of the transition remained the same for all drug concentrations, indicating a strictly drug/headgroup interaction, thus supporting the proposed location of chlorhexidine. In combination, these results lead to the hypothesis that the drug is folded approximately in half on its hexamethylene linker, with the hydrophobic linker at the depth of the glycerol/phosphate region of the lipid bilayer and the hydrophilic chlorophenyl groups located at the lipid headgroup. This arrangement seems to suggest that the drug molecule acts as a wedge to disrupt the bilayer. In vivo, this should make the cell membrane leaky, which is in agreement with a wide range of bacteriological observations.

The Effects of Annealing URu2Si2 on the Resistivity and Meissner Effect

The enigmatic heavy fermion URu2Si2, which is the subject of this thesis, has attracted intensive theoretical and experimental research since 1984 when it was firstly reported by Schlabitz et al. at a conference [1]. The previous bulk property measurements clearly showed that one second order phase transition occurs at the Hidden Order temperature THO ≈ 17.5 K and another second order phase transition, the superconducting transition, occurs at Tc ≈ 1 K. Though twenty eight years have passed, the mechanisms behind these two phase transitions are still not clear to researchers. Perfect crystals do not exist. Different kinds of crystal defects can have considerable effects on the crystalline properties. Some of these defects can be eliminated, and hence the crystalline quality improved, by annealing. Previous publications showed that some bulk properties of URu2Si2 exhibited significant differences between as-grown samples and annealed samples. The present study shows that the annealing of URu2Si2 has some considerable effects on the resistivity and the DC magnetization. The effects of annealing on the resistivity are characterized by examining how the Residual Resistivity Ratio (RRR), the fitting parameters to an expression for the temperature dependence of the resistivity, the temperatures of the local maximum and local minimum of the resistivity at the Hidden Order phase transition and the Hidden Order Transition Width ∆THO change after annealing. The plots of one key fitting parameter, the onset temperature of the Hidden Order transition and ∆THO vs RRR are compared with those of Matsuda et al. [2]. Different media used to mount samples have some impact on how effectively the samples are cooled because the media have different thermal conductivity. The DC magnetization around the superconducting transition is presented for one unannealed sample under fields of 25 Oe and 50 Oe and one annealed sample under fields of 0 Oe and 25 Oe. The DC field dependent magnetization of the annealed Sample1-1 shows a typical field dependence of a Type-II superconductor. The lower critical field Hc1 is relatively high, which may be due to flux pinning by the crystal defects.

Investigation of Frustrated Quasi-One-Dimensional Quantum Spin-Chain Materials

Copper arsenite CuAs2O4 and Copper antimonite CuSb2O4 are S=1/2 (Cu2+ 3d9 electronic configuration) quasi-one-dimensional quantum spin-chain compounds. Both compounds crystallize with tetragonal structures containing edge sharing CuO6 octahedra chains which experience Jahn-Teller distortions. The basal planes of the octahedra link together to form CuO2 ribbon-chains which harbor Cu2+ spin-chains. These compounds are magnetically frustrated with competing nearest-neighbour and next-nearest-neighbour intrachain spin-exchange interactions. Despite the similarities between CuAs2O4 and CuSb2O4, they exhibit very different magnetic properties. In this thesis work, the physical properties of CuAs2O4 and CuSb2O4 are investigated using a variety of experimental techniques which include x-ray diffraction, magnetic susceptibility measurements, heat capacity measurements, Raman spectroscopy, electron paramagnetic resonance, neutron diffraction, and dielectric capacitance measurements. CuAs2O4 exhibits dominant ferromagnetic nearest-neighbour and weaker antiferromagnetic next-nearest-neighbour intrachain spin-exchange interactions. The ratio of the intrachain interactions amounts to Jnn/Jnnn = -4.1. CuAs2O4 was found to order with a ferromagnetic groundstate below TC = 7.4 K. An extensive physical characterization of the magnetic and structural properties of CuAs2O4 was carried out. Under the effect of hydrostatic pressure, CuAs2O4 was found to undergo a structural phase transition at 9 GPa to a new spin-chain structure. The structural phase transition is accompanied by a severe alteration of the magnetic properties. The high-pressure phase exhibits dominant ferromagnetic next-nearest-neighbour spin-exchange interactions and weaker ferromagnetic nearest-neighbour interactions. The ratio of the intrachain interactions in the high-pressure phase was found to be Jnn/Jnnn = 0.3. Structural and magnetic characterizations under hydrostatic pressure are reported and a relationship between the structural and magnetic properties was established. CuSb2O4 orders antiferromagnetically below TN = 1.8 K with an incommensurate helicoidal magnetic structure. CuSb2O4 is characterized by ferromagnetic nearest-neighbour and antiferromagnetic next-nearest-neighbour spin-exchange interactions with Jnn/Jnnn = -1.8. A (H, T) magnetic phase diagram was constructed using low-temperature magnetization and heat capacity measurements. The resulting phase diagram contains multiple phases as a consequence of the strong intrachain magnetic frustration. Indications of ferroelectricity were observed in the incommensurate antiferromagnetic phase.

Structure et dynamique des communautés multi-espèces : le rôle de l’espace

Cette thèse porte sur le rôle de l’espace dans l’organisation et dans la dynamique des communautés écologiques multi-espèces. Deux carences peuvent être identifiées dans les études théoriques actuelles portant sur la dimension spatiale des communautés écologiques : l’insuffisance de modèles multi-espèces représentant la dimension spatiale explicitement, et le manque d’attention portée aux interactions positives, tel le mutualisme, en dépit de la reconnaissance de leur ubiquité dans les systèmes écologiques. Cette thèse explore cette problématique propre à l’écologie des communautés, en utilisant une approche théorique s’inspirant de la théorie des systèmes complexes et de la mécanique statistique. Selon cette approche, les communautés d’espèces sont considérées comme des systèmes complexes dont les propriétés globales émergent des interactions locales entre les organismes qui les composent, et des interactions locales entre ces organismes et leur environnement. Le premier objectif de cette thèse est de développer un modèle de métacommunauté multi-espèces, explicitement spatial, orienté à l’échelle des individus et basé sur un réseau d’interactions interspécifiques générales comprenant à la fois des interactions d’exploitation, de compétition et de mutualisme. Dans ce modèle, les communautés locales sont formées par un processus d’assemblage des espèces à partir d’un réservoir régional. La croissance des populations est restreinte par une capacité limite et leur dynamique évolue suivant des mécanismes simples de reproduction et de dispersion des individus. Ces mécanismes sont dépendants des conditions biotiques et abiotiques des communautés locales et leur effet varie en fonction des espèces, du temps et de l’espace. Dans un deuxième temps, cette thèse a pour objectif de déterminer l’impact d’une connectivité spatiale croissante sur la dynamique spatiotemporelle et sur les propriétés structurelles et fonctionnelles de cette métacommunauté. Plus précisément, nous évaluons différentes propriétés des communautés en fonction du niveau de dispersion des espèces : i) la similarité dans la composition des communautés locales et ses patrons de corrélations spatiales; ii) la biodiversité locale et régionale, et la distribution locale de l’abondance des espèces; iii) la biomasse, la productivité et la stabilité dynamique aux échelles locale et régionale; et iv) la structure locale des interactions entre les espèces. Ces propriétés sont examinées selon deux schémas spatiaux. D’abord nous employons un environnement homogène et ensuite nous employons un environnement hétérogène où la capacité limite des communautés locales évoluent suivant un gradient. De façon générale, nos résultats révèlent que les communautés écologiques spatialement distribuées sont extrêmement sensibles aux modes et aux niveaux de dispersion des organismes. Leur dynamique spatiotemporelle et leurs propriétés structurelles et fonctionnelles peuvent subir des changements profonds sous forme de transitions significatives suivant une faible variation du niveau de dispersion. Ces changements apparaissent aussi par l’émergence de patrons spatiotemporels dans la distribution spatiale des populations qui sont typiques des transitions de phases observées généralement dans les systèmes physiques. La dynamique de la métacommunauté présente deux régimes. Dans le premier régime, correspondant aux niveaux faibles de dispersion des espèces, la dynamique d’assemblage favorise l’émergence de communautés stables, peu diverses et formées d’espèces abondantes et fortement mutualistes. La métacommunauté possède une forte diversité régionale puisque les communautés locales sont faiblement connectées et que leur composition demeure ainsi distincte. Par ailleurs dans le second régime, correspondant aux niveaux élevés de dispersion, la diversité régionale diminue au profit d’une augmentation de la diversité locale. Les communautés locales sont plus productives mais leur stabilité dynamique est réduite suite à la migration importante d’individus. Ce régime est aussi caractérisé par des assemblages incluant une plus grande diversité d’interactions interspécifiques. Ces résultats suggèrent qu’une augmentation du niveau de dispersion des organismes permet de coupler les communautés locales entre elles ce qui accroît la coexistence locale et favorise la formation de communautés écologiques plus riches et plus complexes. Finalement, notre étude suggère que le mutualisme est fondamentale à l’organisation et au maintient des communautés écologiques. Les espèces mutualistes dominent dans les habitats caractérisés par une capacité limite restreinte et servent d’ingénieurs écologiques en facilitant l’établissement de compétiteurs, prédateurs et opportunistes qui bénéficient de leur présence.

Electrospinning and characterization of self-assembled inclusion complexies

L’électrofilage est une technique permettant de fabriquer des fibres polymériques dont le diamètre varie entre quelques nanomètres et quelques microns. Ces fibres ont donc un rapport surface/volume très élevé. Les fibres électrofilées pourraient trouver des applications dans le relargage de médicaments et le génie tissulaire, comme membranes et capteurs chimiques, ou dans les nanocomposites et dispositifs électroniques. L’électrofilage était initialement utilisé pour préparer des toiles de fibres désordonnées, mais il est maintenant possible d’aligner les fibres par l’usage de collecteurs spéciaux. Cependant, il est important de contrôler non seulement l’alignement macroscopique des fibres mais aussi leur orientation au niveau moléculaire puisque l’orientation influence les propriétés mécaniques, optiques et électriques des polymères. Les complexes moléculaires apparaissent comme une cible de choix pour produire des nanofibres fortement orientées. Dans les complexes d’inclusion d’urée, les chaînes polymères sont empilées dans des canaux unidimensionnels construits à partir d’un réseau tridimensionnel de molécules d’urée liées par des ponts hydrogène. Ainsi, les chaînes polymère sonts très allongées à l’échelle moléculaire. Des nanofibres du complexe PEO-urée ont été préparées pour la première fois par électrofilage de suspensions et de solutions. Tel qu’attendu, une orientation moléculaire inhabituellement élevée a été observée dans ces fibres. De tels complexes orientés pourraient être utilisés à la fois dans des études fondamentales et dans la préparation de matériaux hiérarchiquement structurés. La méthode d’électrofilage peut parfois aussi être utilisée pour préparer des matériaux polymériques métastables qui ne peuvent pas être préparés par des méthodes conventionnelles. Ici, l’électrofilage a été utilisé pour préparer des fibres des complexes stables (α) et "métastables" (β) entre le PEO et l’urée. La caractérisation du complexe β, qui était mal connu, révèle un rapport PEO:urée de 12:8 appartenant au système orthorhombique avec a = 1.907 nm, b = 0.862 nm et c = 0.773 nm. Les chaînes de PEO sont orientées selon l’axe de la fibre. Leur conformation est significativement affectée par les ponts hydrogène. Une structure en couches a été suggérée pour la forme β, plutôt que la structure conventionnelle en canaux adoptée par la forme α. Nos résultats indiquent que le complexe β est thermodynamiquement stable avant sa fonte et peut se transformer en forme α et en PEO liquide par un processus de fonte et recristallisation à 89 ºC. Ceci va dans le sens contraire aux observations faites avec le complexe β obtenu par trempe du complexe α fondu. En effet, le complexe β ainsi obtenu est métastable et contient des cristaux d’urée. Il peut subir une transition de phases cinétique solide-solide pour produire du complexe α dans une vaste gamme de températures. Cette transition est induite par un changement de conformation du PEO et par la formation de ponts hydrogène intermoléculaires entre l’urée et le PEO. Le diagramme de phases du système PEO-urée a été tracé sur toute la gamme de compositions, ce qui a permis d’interpréter la formation de plusieurs mélanges qui ne sont pas à l’équilibre mais qui sont été observés expérimentalement. La structure et le diagramme de phases du complexe PEO-thiourée, qui est aussi un complexe très mal connu, ont été étudiés en détail. Un rapport molaire PEO :thiourée de 3:2 a été déduit pour le complexe, et une cellule monoclinique avec a = 0.915 nm, b = 1.888 nm, c = 0.825 nm et β = 92.35º a été déterminée. Comme pour le complexe PEO-urée de forme β, une structure en couches a été suggérée pour le complexe PEO-thiourée, dans laquelle les molécules de thiourée seraient disposées en rubans intercalés entre deux couches de PEO. Cette structure en couches pourrait expliquer la température de fusion beaucoup plus faible des complexes PEO-thiourée (110 ºC) et PEO-urée de forme β (89 ºC) en comparaison aux structures en canaux du complexe PEO-urée de forme α (143 ºC).