Synthesis of polyelectrolyte brushes on silica-based substrates through surface-initiated polymerization : brush characterization and responsiveness to variation in pH and ionic strength

Les brosses de polyélectrolytes font l’objet d’une attention particulière pour de nombreuses applications car elles présentent la capacité de changer de conformation et, par conséquent, de propriétés de surface en réponse aux conditions environnementales appliquées. Le contrôle des principaux paramètres de ces brosses telles que l'épaisseur, la composition et l'architecture macromoléculaire, est essentiel pour obtenir des polymères greffés bien définis. Ceci est possible avec la Polymérisation Radicalaire par Transfert d’Atomes - Initiée à partir de la Surface (PRTA-IS), qui permet la synthèse de brosses polymériques de manière contrôlée à partir d’une couche d'amorceurs immobilisés de manière covalente sur une surface. Le premier exemple d’une synthèse directe de brosses de poly(acide acrylique) (PAA) par polymérisation radicalaire dans l’eau a été démontré. Par greffage d’un marqueur fluorescent aux brosses de PAA et via l’utilisation de la microscopie de fluorescence par réflexion totale interne, le dégreffage du PAA en temps réel a pu être investigué. Des conditions environnementales de pH ≥ 9,5 en présence de sel, se sont avérées critiques pour la stabilité de la liaison substrat-amorceur, conduisant au dégreffage du polymère. Afin de protéger de l’hydrolyse cette liaison substrat-amorceur sensible et prévenir le dégreffage non souhaité du polymère, un espaceur hydrophobique de polystyrène (PS) a été inséré entre l'amorceur et le bloc de PAA stimuli-répondant. Les brosses de PS-PAA obtenues étaient stables pour des conditions extrêmes de pH et de force ionique. La réponse de ces brosses de copolymère bloc a été étudiée in situ par ellipsométrie, et le changement réversible de conformation collapsée à étirée, induit par les variations de pH a été démontré. De plus, des différences de conformation provenant des interactions du bloc de PAA avec des ions métalliques de valence variable ont été obtenues. Le copolymère bloc étudié semble donc prometteur pour la conception de matériaux répondant rapidement a divers stimuli. Par la suite, il a été démontré qu’un acide phosphonique pouvait être employé en tant qu’ amorceur PRTA-IS comme alternative aux organosilanes. Cet amorceur phosphonate a été greffé pour la première fois avec succès sur des substrats de silice et une PRTA-IS en milieux aqueux a permis la synthèse de brosses de PAA et de poly(sulfopropyl méthacrylate). La résistance accrue à l’hydrolyse de la liaison Sisubstrat-O- Pamorceur a été confirmée pour une large gamme de pH 7,5 à 10,5 et a permis l’étude des propriétés de friction des brosses de PAA sous différentes conditions expérimentales par mesure de forces de surface. Malgré la stabilité des brosses de PAA à haute charge appliquée, les études des propriétés de friction ne révèlent pas de changement significatif du coefficient de friction en fonction du pH et de la force ionique.

Electrostatic Interactions Between Glycosaminoglycan Molecules

The electrostatic interactions between nearest-neighbouring chondroitin sulfate glycosaminoglycan (CS-GAG) molecular chains are obtained on the bottle brush conformation of proteoglycan aggrecan based on an asymptotic solution of the Poisson-Boltzmann equation the CS-GAGs satisfy under the physiological conditions of articular cartilage. The present results show that the interactions are associated intimately with the minimum separation distance and mutual angle between the molecular chains themselves. Further analysis indicates that the electrostatic interactions are not only expressed to be purely exponential in separation distance and decrease with the increasing mutual angle but also dependent sensitively on the saline concentration in the electrolyte solution within the tissue, which is in agreement with the existed relevant conclusions.

Synthèse de brosses de polyélectrolytes par polymérisation initiée depuis une surface de mica et étude de leur réponse en fonction du pH et de la force ionique

Cette thèse rapporte le greffage chimique de brosses de polymères neutres de poly(acrylate de tert-butyle) (PtBA) et de brosses chargées d’acide polyacrylique (PAA) sur des substrats de mica afin d’étudier leur conformation en fonction de la densité de greffage, du pH et de la force ionique. Le greffage est réalisé par polymérisation contrôlée par transfert d’atome (ATRP) initiée depuis la surface de mica afin de contrôler la croissance du polymère et sa densité de greffage. L’étude de la conformation des brosses de PtBA et de PAA a été menée avec la technique AFM en mesurant les épaisseurs des films à sec et gonflés sous différentes conditions de solvant, de pH et de force ionique. Une monocouche d’amorceurs est tout d’abord greffée sur du mica porteur de groupes hydroxyles créés par plasma (Ar/H2O). Cette couche a été caractérisée par des mesures d’angle de contact et par la technique TOF-SIMS. L’amorceur greffé a ensuite permis d’initier l’ATRP directement depuis la surface pour former des brosses neutres de PtBA liés de façon covalente au mica. La croissance linéaire de l’épaisseur du film avec la masse molaire du polymère en solution et le taux de conversion montre que la polymérisation est contrôlée. De plus, la ré-initiation des chaînes greffées atteste du caractère vivant de la polymérisation. L’hydrolyse des brosses de PtBA, confirmée par des mesures d’angle de contact, d’épaisseur et par FT-IR, conduit à des brosses de PAA. Les différentes couches greffées sont stables à l’air, en milieu organique et en milieu aqueux et leur gonflement est réversible. Le degreffage de la couche de PAA est observé suite à une longue exposition à pH basique. Cette étude représente le premier exemple de brosses greffées chimiquement sur du mica par polymérisation initiée depuis la surface. La variation des paramètres de la réaction de greffage de l’amorceur, tels que la concentration et la durée de réaction, a permis de contrôler le taux de recouvrement de l’amorceur et la densité de greffage du polymère. Une grande gamme de taux de recouvrement de l’amorceur est accessible et se traduit par un intervalle de densités de greffage allant de faibles à élevées (e.g. 0,04 chaîne/nm2 à 0,5 chaîne/nm2). L’étude de la conformation des chaînes de PtBA dans le DMF montre que cet intervalle de densités recouvre le régime crêpe au régime brosse. Le gonflement de brosses de PAA et la variation de la hauteur de la brosse L ont été étudiés en fonction de la densité de greffage, du pH et du sel ajouté cs (NaCl). Une transition brusque de collapsée à étirée est observée avec l’augmentation du pH, indépendamment de la densité de greffage. A pH neutre, les brosses sont collapsées et se comportent comme des brosses neutres en mauvais solvant. A pH basique, les brosses sont gonflées et chargées et se trouvent dans un régime de Pincus caractéristique des polyélectrolytes forts. En présence de sel, les charges sont partiellement écrantées et les répulsions électrostatiques dominent toujours dans la brosse. Cette étude contribue à une meilleure compréhension du comportement complexe des brosses de polyélectrolytes faibles et apporte un soutien expérimental à la théorie sur le comportement de ces brosses.

Differences between Tethered Polyelectrolyte Chains on Bare Mica and Hydrophobically Modified Mica

This study investigates the structures of layers of amphiphilic diblock copolymers of poly(t-butyl styrene)-poly- (styrene sulfonate) (PtBS-PSS) adsorbed on both the bare mica surface (hydrophilic) and an octadecyltriethoxysilane (OTE)-modified mica surface (hydrophobic). When the surface is rendered hydrophobic, the nonsoluble block exhibits stronger interaction with the surface and higher adsorbed masses are achieved. Interaction forces between two such adsorbed layers on both substrates were measured using the surface forces apparatus. The effect of salt concentration (Cs) and molecular weight (N) on the height of the self-assembled layers (L0) was examined in each case. The resulting scaling relationship is in good agreement with predictions of the brush model, L0 ∞ N1.0 in the low-salt limit and L0N-1 ∞ (Cs/σ)-0.32 in the salted regime, when adsorption takes place onto the hydrophobized mica surface. For adsorption on the bare mica surface, L0N-0.7 ∞ Cs -0.17 agrees with the scaling prediction of the sparse tethering model. The results suggest that, on the hydrophilic bare mica surface, the adsorbed amount is not high enough to form a brush structure and only very little intermolecular stretching of the tethered chains occurs; in contrast, the presence of the hydrophobic OTE layer increases the tethering density such that the polyelectrolyte chains adopt a brush conformation.

Three-dimensional self-assembly of brush block copolymers to photonic crystals

The development of Ring Opening Metathesis Polymerization has allowed the world of block copolymers to expand into brush block copolymers. Brush block copolymers consist of a polymer backbone with polymeric side chains, forcing the backbone to hold a stretched conformation and giving it a worm-like shape. These brush block copolymers have a number of advantages over tradition block copolymers, including faster self-assembly behavior, larger domain sizes, and much less entanglement. This makes them an ideal candidate in the development of a bottom-up approach to forming photonic crystals. Photonic crystals are periodic nanostructures that transmit and reflect only certain wavelengths of light, forming a band gap. These are used in a number of coatings and other optical uses. One and two dimensional photonic crystals are commercially available, though are often expensive and difficult to manufacture. Previous work has focused on the creation of one dimensional photonic crystals from brush block copolymers. In this thesis, I will focus on the synthesis and characterization of asymmetric brush block copolymers for self-assembly into two and three dimensional photonic crystals. Three series of brush block copolymers were made and characterized by Gel Permeation Chromatography and Nuclear Magnetic Resonance spectroscopy. They were then made into films through compressive thermal annealing and characterized by UV-Vis Spectroscopy and Scanning Electron Microscopy. Evidence of non-lamellar structures were seen, indicating the first reported creation of two or three dimensional photonic crystals from brush block copolymers.

How useful is expert opinion for predicting the distribution of a species within and beyond the region of expertise? A case study using brush-tailed rock-wallabiesPetrogale penicillata

1. Species' distribution modelling relies on adequate data sets to build reliable statistical models with high predictive ability. However, the money spent collecting empirical data might be better spent on management. A less expensive source of species' distribution information is expert opinion. This study evaluates expert knowledge and its source. In particular, we determine whether models built on expert knowledge apply over multiple regions or only within the region where the knowledge was derived. 2. The case study focuses on the distribution of the brush-tailed rock-wallaby Petrogale penicillata in eastern Australia. We brought together from two biogeographically different regions substantial and well-designed field data and knowledge from nine experts. We used a novel elicitation tool within a geographical information system to systematically collect expert opinions. The tool utilized an indirect approach to elicitation, asking experts simpler questions about observable rather than abstract quantities, with measures in place to identify uncertainty and offer feedback. Bayesian analysis was used to combine field data and expert knowledge in each region to determine: (i) how expert opinion affected models based on field data and (ii) how similar expert-informed models were within regions and across regions. 3. The elicitation tool effectively captured the experts' opinions and their uncertainties. Experts were comfortable with the map-based elicitation approach used, especially with graphical feedback. Experts tended to predict lower values of species occurrence compared with field data. 4. Across experts, consensus on effect sizes occurred for several habitat variables. Expert opinion generally influenced predictions from field data. However, south-east Queensland and north-east New South Wales experts had different opinions on the influence of elevation and geology, with these differences attributable to geological differences between these regions. 5. Synthesis and applications. When formulated as priors in Bayesian analysis, expert opinion is useful for modifying or strengthening patterns exhibited by empirical data sets that are limited in size or scope. Nevertheless, the ability of an expert to extrapolate beyond their region of knowledge may be poor. Hence there is significant merit in obtaining information from local experts when compiling species' distribution models across several regions.

A brush with the real world : the future of inertial motion capture in live performance

3D Motion capture is a medium that plots motion, typically human motion, converting it into a form that can be represented digitally. It is a fast evolving field and recent inertial technology may provide new artistic possibilities for its use in live performance. Although not often used in this context, motion capture has a combination of attributes that can provide unique forms of collaboration with performance arts. The inertial motion capture suit used for this study has orientation sensors placed at strategic points on the body to map body motion. Its portability, real-time performance, ease of use, and its immunity from line-of-sight problems inherent in optical systems suggest it would work well as a live performance technology. Many animation techniques can be used in real-time. This research examines a broad cross-section of these techniques using four practice-led cases to assess the suitability of inertial motion capture to live performance. Although each case explores different visual possibilities, all make use of the performativity of the medium, using either an improvisational format or interactivity among stage, audience and screen that would be difficult to emulate any other way. A real-time environment is not capable of reproducing the depth and sophistication of animation people have come to expect through media. These environments take many hours to render. In time the combination of what can be produced in real-time and the tools available in a 3D environment will no doubt create their own tree of aesthetic directions in live performance. The case study looks at the potential of interactivity that this technology offers.

The importance of ecological scale for wildlife conservation in naturally fragmented environments: A case study of the Brush-Tailed Rock-Wallaby (Petrogale Penicillata)

Determining the ecologically relevant spatial scales for predicting species occurrences is an important concept when determining species–environment relationships. Therefore species distribution modelling should consider all ecologically relevant spatial scales. While several recent studies have addressed this problem in artificially fragmented landscapes, few studies have researched relevant ecological scales for organisms that also live in naturally fragmented landscapes. This situation is exemplified by the Australian rock-wallabies’ preference for rugged terrain and we addressed the issue of scale using the threatened brush-tailed rock-wallaby (Petrogale penicillata) in eastern Australia. We surveyed for brush-tailed rock-wallabies at 200 sites in southeast Queensland, collecting potentially influential site level and landscape level variables. We applied classification trees at either scale to capture a hierarchy of relationships between the explanatory variables and brush-tailed rock-wallaby presence/absence. Habitat complexity at the site level and geology at the landscape level were the best predictors of where we observed brush-tailed rock-wallabies. Our study showed that the distribution of the species is affected by both site scale and landscape scale factors, reinforcing the need for a multi-scale approach to understanding the relationship between a species and its environment. We demonstrate that careful design of data collection, using coarse scale spatial datasets and finer scale field data, can provide useful information for identifying the ecologically relevant scales for studying species–environment relationships. Our study highlights the need to determine patterns of environmental influence at multiple scales to conserve specialist species such as the brush-tailed rock-wallaby in naturally fragmented landscapes.

Comparison of three expert elicitation methods for logistic regression on predicting the presence of the threatened brush-tailed rock-wallaby petrogale penicillata

Numerous expert elicitation methods have been suggested for generalised linear models (GLMs). This paper compares three relatively new approaches to eliciting expert knowledge in a form suitable for Bayesian logistic regression. These methods were trialled on two experts in order to model the habitat suitability of the threatened Australian brush-tailed rock-wallaby (Petrogale penicillata). The first elicitation approach is a geographically assisted indirect predictive method with a geographic information system (GIS) interface. The second approach is a predictive indirect method which uses an interactive graphical tool. The third method uses a questionnaire to elicit expert knowledge directly about the impact of a habitat variable on the response. Two variables (slope and aspect) are used to examine prior and posterior distributions of the three methods. The results indicate that there are some similarities and dissimilarities between the expert informed priors of the two experts formulated from the different approaches. The choice of elicitation method depends on the statistical knowledge of the expert, their mapping skills, time constraints, accessibility to experts and funding available. This trial reveals that expert knowledge can be important when modelling rare event data, such as threatened species, because experts can provide additional information that may not be represented in the dataset. However care must be taken with the way in which this information is elicited and formulated.

Magnetic nanoparticles boosting the osmotic efficiency of a polymeric FO draw agent: Effect of polymer conformation

Poly sodium acrylate (PSA)-coated Magnetic Nanoparticles (PSA-MNPs) were synthesized as smart osmotic draw agent (SMDA) for water desalination by forward osmosis (FO) process. The PSA-coated MNPs demonstrated significantly higher osmotic pressure (~ 30 fold) as well as high FO water flux (~ 2–3 fold) when compared to their polymer (polyelectrolyte) counterpart, even at a very low concentration of ~ 0.13 wt.% in the draw solution. The PSA polymer chain conformation – coiled to extended – demonstrates a significant impact on the availability of the polymer hydrophilic groups in solution which is the driving force to attain higher osmotic pressure and water flux. When an optimum concentration of the polymer was anchored to a NP surface, the polymer chains assume an extended open conformation making the functional hydrophilic groups available to attract water molecules. This in turn boosts the osmotic pressure and FO water flux of the PSA-MNP draw agents. The low concentration of the PSA-MNP osmotic agent and the associated high water flux enhances the cost-effectiveness of our proposed SMDA system. In addition, easier magnetic separation and regeneration of the SMDA also improves its usability making it efficient, cost-effective and environment-friendly.

Conformation-activity correlations for chemotactic tripeptide analogs incorporating dialkyl residues with linear and cyclic alkyl sidechains at position 2

Five stereochemically constrained analogs of the chemotactic tripeptide incorporating 1-aminocycloalkane-1-carboxylic acid (Ac(n)c) and alpha,alpha-dialkylglycines (Deg, diethylglycine; Dpg, n,n-dipropylglycine and Dbg, n,n-dibutylglycine) at position 2 have been synthesized. NMR studies of peptides For-Met-Xxx-Phe-OMe (Xxx = Ac(7)c, I; Ac(8)c, II; Deg, III; Dpg, IV and Dbg, V; For, formyl) establish that peptides with cycloalkyl residues, I and II, adopt folded beta-turn conformations in CDCl3 and (CD3)(2)SO. In contrast, analogs with linear alkyl sidechains, III-V, favour fully extended (C-5) conformations in solution. Peptides I-V exhibit high activity in inducing beta-glucosaminidase release from rabbit neutrophils, with ED(50) values ranging from 1.4-8.0 x 10(-11)M. In human neutrophils the Dxg peptides III-V have ED(50) values ranging from 2.3 x 10(-8) to 5.9 x 10(-10) M, with the activity order being V > IV > III. While peptides I-IV are less active than the parent. For-Met-Leu-Phe-OH, in stimulating histamine release from human basophils, the Dbg peptide V is appreciably more potent, suggesting its potential utility as a probe for formyl peptide receptors.

1H and 13C NMR spectra of some unsymmetric N,N-dipyridyl ureas: spectral assignments and molecular conformation

Abstract: The H-1 NMR spectra of N-(2-pyridyl), N'-(3-pyridyl)ureas and N-(2-pyridyl), N'-(4-pyridyl)ureas in CDCl3 and (CD3)(2)CO have been assigned with the aid of COSY and NOE experiments and chemical shift and coupling constant correlations, The C-13 NMR spectra in CDCl3 were analysed utilizing the HETCOR and proton coupled spectra, The H-1 NMR spectra, NOE effects and MINDO/3 calculations have been utilized to show that the molecular conformation of these compounds has the 2-pyridyl ring coplanar with the urea plane with the N-H group hydrogen bonded to the nitrogen of the 2-pyridyl group on the other urea nitrogen while the 3/4-pyridyl group rotates rapidly about the N-C-3/N-C-4 bond.

Determination of beta-turn conformation by laser Raman spectroscopy

To correlate the Raman frequencies of the amide I and III bands to beta-turn structures, three peptides shown to contain beta-turn structure by x-ray diffraction and NMR were examined. The compounds examined were tertiary (formula: see text). The amide I band of these compounds is seen at 1,668, 1,665, and 1,677 cm-1, and the amide III band appears at 1,267, 1,265, and 1,286 cm-1, respectively. Thus, it is concluded that the amide I band for type III beta-turn structure appears in the range between 1,665 and 1,677 cm-1 and the amide III band between 1,265 and 1,286 cm-1.

pi-conjugation and conformation in a semiconducting polymer: small angle x-ray scattering study

Small angle x-ray scattering (SAXS) in a poly[2-methoxy-5-(2'-ethyl-hexyloxy)-1,4-phenylene vinylene] (MEH-PPV) solution has shown the important role of pi-electron conjugation in controlling the chain conformation and assembly. By increasing the extent of conjugation from 30 to 100%, the persistence length (l(p)) increases from 20 to 66 angstrom. Moreover, a pronounced second peak in the pair distribution function has been observed in a fully conjugated chain, at larger length scales. This feature indicates that the chain segments tend to self-assemble as the conjugation along the chain increases. Xylene enhances the rigidity of the PPV backbone to yield extended structures, while tetrahydrofuran solvates the side groups to form compact coils in which the lp is much shorter.

Molecular-Conformation of 1,3-Pyridylphenylureas by H-1 and C-13 NMR-study

1H and 13C NMR spectra are reported for several 1,3-pyridylphenyl ureas. Analysis of the spectra yielded the chemical shifts. The variations in the chemical shifts have been discussed in terms of the molecular conformations.