Anionic polymerization and controlled radical polymerization enabled the synthesis of novel block copolymers with non-covalent interactions (electrostatic interaction and/or hydrogen bonding) to examine the relationships between mesoscale phenomenon and macroscopic physical properties. Non-covalent interactions offer extra intra- and inter-molecular interactions to achieve stimuli-responsive materials in various applications, such as artificial muscles, thermoplastic elastomers, and reversible biomacromolecule binding. The relationship between non-covalent interaction promoted mesoscale phenomenon (such as morphology) and consequent macroscopic physical properties is the key to optimize material design and improve end-use performance for emerging applications. Pendant hydrogen bonding in ABA block copolymers promoted microphase separation and delayed the order-disorder transition, resulting in tunable morphologies (through composition changes) and extended rubbery plateaus. Reversible addition-fragmentation chain transfer (RAFT) polymerization afforded a facile synthesis of ABA triblock copolymers with hydrogen bonding (urea sites) and electrostatic interactions (pyridinium groups). Pyridine groups facilitated hydrogen bonding through a preorganization effect, leading to highly ordered, long-range lamellar morphology and a significant increase of flow temperature (Tf) 80 °C above the hard block Tg. After quaternization of pyridine groups, electrostatic interaction, as a second physical crosslinking mechanism, disrupted ordered lamellar morphology and decreased Tf. Yet, extra physical crosslinking from electrostatic interactions pertained ordered hydrogen bonding at high temperature and exhibited improved stress-relaxation properties. Both conventional free radical polymerization and RAFT polymerization generated a library of poly(ionic liquid) (PIL) homopolymers with imidazolium groups as bond charge moieties. A long chain alkyl spacer between imidazolium groups and the polymer backbones ensured a low glass transition temperature (Tg), which is beneficial to ion conductivity. Four different counter anions enabled readily tunable Tgs all below room temperature and showed promising ion conductivities as high as 2.45 × 10⁻⁵ S/cm at 30 °C. For the first time, the influence of counter anions on radical polymerization kinetics was observed and investigated thoroughly using in situ FTIR, NMR diffusometry, and simulation. Monomer diffusion and aggregation barely contributed to the kinetic differences, and the Marcus theory was applied to explain the polymerization kinetic differences which showed promising simulation results. RAFT polymerization readily prepared AB diblock, ABA triblock and (AB)3 3-arm diblock copolymers using the ionic liquid (IL) monomers discussed above and deuterated/hydrogenated styrene. We demonstrated the first example of in situ morphology studies during an actuation process, and counter anions with varied electrostatic interactions showed different mesoscale mechanisms, which accounted for macroscopic actuation. The long chain alkyl spacer between imidazolium groups and polymer backbones decoupled ion dynamics and structural relaxation. For the first time, composition changes of block copolymers achieved tunable viscoelastic properties without altering ion conductivity, which provided an ideal example for actuation materials, solid electrolytes, and ion exchange membranes. / Ph. D. / My research focuses on the synthesis of novel soft materials with a special interest in responsive polymers. The incorporation of responsive chemistry, such as hydrogen bonding and ionic interactions, enables soft materials with complex responsive behavior were achieved. Polymers with ion pairs promise great potential as solid-state electrolytes (which transfer ions to generate current) to eliminate potential fire hazard in batteries, which has been an arising concern for modern cellphone and electric car industry. The introduction of strong dipoles into polymers allows the fabrication of actuators, which convert electric signals to physical movement. Under applied voltage, polymers bend within seconds while holding physical loads. Actuator studies in polymers paves the way towards artificial muscles as well as soft robotics. Temperature responsive hydrogen bonding in polymers offers drastically different viscoelastic properties at different temperature and serves as the key mechanism in holt-melt adhesives, controlled drug release, and high performance materials.

Yes / Amphiphilic diblock copolymers, poly(2-(diethylamino)ethyl methacrylate-co-2-(dimethylamino)ethyl methacrylate)-b-poly(2-(dimethylamino)ethyl methacrylate), P(DEAEMA-co-DMAEMA)-b-PDMAEMA with various amounts of DEAEMA have been synthesized by RAFT polymerization. Their micellization in water has been investigated by scattering measurements over a wide pH range. It appeared that the polymers self-assembled into pH sensitive star like micelles. For a given composition, when the pH is varied the extent of aggregation can be tuned reversibly by orders of magnitude. By varying the copolymer composition in the hydrophobic block, the onset and extent of aggregation were shifted with respect to pH. This class of diblock copolymer offers the possibility to select the range of stimuli-responsiveness that is useful for a given application, which can rarely be achieved with conventional diblock copolymers consisting of homopolymeric blocks. / European Science Foundation (ESF), Engineering and Physical Sciences Research Council (EPSRC), BP (Firm), Birmingham Science City, Advantage West Midlands (AWM), European Regional Development Fund (ERDF)

Yes / The synthesis and self-assembly of thymine-containing polymers were performed using RAFT dispersion polymerization. A combination of microscopy and scattering techniques was used to analyze the resultant complex morphologies. The primary observation from this study is that the obtained aggregates induced during the polymerization were well-defined despite the constituent copolymers possessing broad dispersities. Moreover, a variety of parameters, including the choice of polymerization solvent, the degree of polymerization of both blocks and the presence of an adenine-containing mediator, were observed to affect the resultant size and shape of the assembly. / University of Warwick, National Science Foundation (U.S.) (NSF), Engineering and Physical Sciences Research Council (EPSRC)

No description available.

Polyunsaturated fatty acids (PUFA) have been used with some success in the treatment of canine atopic dermatitis (CAD). Correspondent in vitro studies revealed that PUFA play a crucial role in the exocytosis of mast cells. n3 PUFA such as α-linolenic acid (LNA), eicosapentaenoic acid (EPA), docosahexaenoic acid (DHA), as well as the n6 PUFA linoleic acid (LA) have been shown to arrest the secretion of inflammatory mediators. Contrary, the n-6 PUFA arachidonic acid (AA) has been proven to promote the production of mast cell inflammatory mediators. However, we are still lacking a complete picture of the mode of action. The goal of this work was to further characterize the modulatory effects of PUFA supplementation on the plasma membrane lipid composition of mast cells. Furthermore the consequences of a membrane modulation of mast cells by PUFA on the localization and activity on of the membrane bound enzyme phospholipases D (PLD) were investigated. Canine mastocytoma cells (C2) were supplemented with one of the following PUFA: LNA, EPA, DHA, LA or AA. To investigate the influence of PUFA on the lipid composition of membrane microdomains, lipid rafts were separated from non-raft plasma membranes of mast cells for the first time using a detergent-free isolation technique. Results show that PUFA are significantly increased in rafts as well as in non-rafts microdomains (Publication 1). The incorporation of PUFA into the membrane goes along with an increase of the unsaturation status and the fluidity of the membrane. This rise in membrane fluidity may result in a reorganization of membrane signaling molecules and enzymes such as the PLD. To define the impact of a PUFA supplementation on PLD trafficking, C2 were transfected with green fluorescent protein (GFP) fusion plasmids encoding PLD1 or PLD2. Since the transfection ability of the suspension cell line C2 is limited, a special transfection protocol was established, suitable for non-adherent cell lines. Transfection succeeded using chicken egg white as coating material for the cell culture plates. The transfection efficiency rose to 50% versus 5% in uncoated plates. In addition to the obvious increase in the transfection efficiency, the new technique is simple and economic and might be suitable for a wide range of suspension cell lines (Publication 2). Using this optimized protocol the influence of PUFA on the trafficking of PLD isoforms was studied. LNA, EPA, DHA and LA but not AA prevented the stimulation-induced translocation of PLD1 to the plasma membrane. Since the translocation of PLD1 is important for mast cell exocytosis, LNA, EPA, DHA and LA do have an inhibiting effect on the stimulation-induced release of pro-inflammatory mediators. All PUFA tested boosted the total PLD activity. In order to rule out, which PLD isoform was affected by the PUFA, the mast cells were supplemented with DHA or AA in the presence of specific PLD isoform inhibitors. DHA completely abolished the inhibitiory effect of the PLD1 inhibitor but had no effect on the inhibitory effect of PLD2 inhibitor. On the other hand, AA suppressed the inhibitory effect of both PLD1 and PLD2 inhibitor (Publication 3). Taking together, the studies provide a mechanistic base for the role of PUFA in the exocytosis processes of mast cells. PUFA of the n3 and the n6 families impact the lipid composition of membrane microdomains, which in turn lead to a modulation of the physiochemical properties of the membrane. LNA, EPA, DHA and LA suppress the release of inflammatory mediators through their inhibitory action on the stimulation-induced translocation of the PLD1. Contrariwise, AA permits the stimulation-induced migration of PLD1 to the plasma membrane and increases the activity of both PLD isoforms. Therefore, LNA, EPA, DHA and LA but not AA inhibit the release of mast cell inflammatory mediators upon stimulation. / Mehrfach ungesättigte Fettsäuren (PUFA) können mit einigem Erfolg zur Behandlung der caninen atopischen Dermatitis (CAD) eingesetzt werden. In vitro-Studien zeigten, dass PUFA eine entscheidende Rolle in der Exozytose von Mastzellen spielen. N-3-PUFA wie α-Linolensäure (LNA), Eicosapentaensäure (EPA), Docosahexaensäure (DHA) sowie die n-6-PUFA Linolsäure (LA) können die Sekretion von Entzündungsmediatoren vermindern. Arachidonsäure (AA) als n-6 mehrfach ungesättigte Fettsäure hingegen fördert die Entzündungsmediatoren-Freisetzung aus den Mastzellen. Eine vollständige Aufklärung der Wirkungsweise fehlt aber weiterhin. Das Ziel dieser Arbeit war eine weitergehende Charakterisierung der modulierenden Effekte einer PUFA-Supplementierung auf die Lipidzusammensetzung der Plasmamembran von Mastzellen. Darüber hinaus wurden die Auswirkungen von PUFA auf die Lokalisation und Aktivität des Membran-gebundenen Enzyms Phospholipase D (PLD) untersucht. Canine Mastozytom-Zellen (C2) wurden mit einer der folgenden PUFA kultiviert: LNA, EPA, DHA, LA oder AA. Um den Einfluss von PUFA auf die Lipidzusammensetzung der Membran-Mikrodomänen zu untersuchen, konnten sowohl Lipid Raft als auch Nicht-Raft Plasmamembran-Anteile von Mastzellen zum ersten Mal mittels einer Detergenzien-freien Isolationsmethode getrennt werden. Hervorzuheben ist, dass PUFA signifikant vermehrt in Raft- sowie in Nicht-Raft Membranmikrodomänen eingelagert werden (Publikation 1). Die Integration von PUFA in die Membran geht mit einer Steigerung der Doppelbindungsanzahl und der Fluidität der Membran einher. Diese Erhöhung der Membranfluidität kann zu einer Reorganisation von membranären Signalmolekülen und Enzymen wie der PLD führen. Um die Auswirkungen einer PUFA-Supplementierung auf den intrazellulären Transport der PLD in C2 zu bestimmen, wurden die Zellen mit PLD1- oder PLD2-codierenden grün fluoreszierenden Protein-(GFP-)Fusionsplasmiden transfiziert. Da die Transfektionsfähigkeit der Suspensions-Zelllinie C2 begrenzt ist, wurde ein für nicht-adhärente Zelllinien geeignetes Transfektionsprotokoll etabliert. Mit Hühnereiweiß als Beschichtungsmaterial für die Zellkultur-Platten stieg die Transfektionseffizienz auf 50% im Vergleich zu 5% bei unbeschichteten Platten. Neben der deutlichen Erhöhung der Transfektionseffizienz ist die neu etablierte Technik einfach durchzuführen sowie wirtschaftlich und kann für eine Vielzahl von Suspension-Zelllinien geeignet sein (Publikation 2). Unter Verwendung dieses optimierten Protokolls wurde der Einfluss von PUFA auf die Translokation der PLD-Isoformen untersucht. LNA, EPA, DHA und LA, nicht aber AA verhindern die stimulationsinduzierte Translokation der PLD1 an die Plasmamembran. Die Translokation der PLD1 ist wichtig für die Mastzell-Exozytose. LNA, EPA, DHA und LA haben hier eine hemmende Wirkung auf die stimulationsinduzierte Freisetzung von proinflammatorischen Mediatoren. Alle getesteten PUFA verstärken die Gesamt-PLD-Aktivität. Um zu unterscheiden, welche PLD-Isoform durch PUFA beeinflusst ist, wurden die Mastzellen mit DHA oder AA in Gegenwart von PLD-Isoform-Inhibitoren supplementiert. DHA hebt die inhibitorische Wirkung des PLD1-Inhibitors vollständig auf, zeigte aber keinen Einfluss auf die hemmende Wirkung des PLD2-Inhibitors. Andererseits unterdrückt AA die hemmende Wirkung des PLD1- als auch des PLD2-Inhibitors (Publikation 3). Zusammenfassend bietet die Studie eine mechanistische Basis für die Rolle von PUFA bei Exozytose-Prozessen von Mastzellen. PUFA der n-3- und n-6-Familie beeinflussen die Lipidzusammensetzung von membranären Mikrodomänen, was wiederum zu einer Modulation der physikalisch-chemischen Eigenschaften der Membran führt. LNA, EPA, DHA und LA verhindern die Freisetzung von Entzündungsmediatoren durch ihre hemmende Wirkung auf die stimulationsinduzierte Translokation der PLD1. Umgekehrt erlaubt AA eine stimulationsinduzierte Migration der PLD1 zur Plasmamembran und steigert die Aktivität der beiden Isoformen der PLD. Somit hemmen LNA, EPA, DHA und LA, aber nicht AA die Freisetzung von Mastzell-Entzündungsmediatoren nach Stimulation.

Die Assemblierung von Influenzaviren erfolgt an Rafts der apikalen Wirtszellplasmamembran mit denen das Hämagglutinin (HA) über Acylierungen im C-Terminus und hydrophobe Aminosäuren seiner Transmembrandomäne (TMD) interagiert. M2 besitzt eine cytoplasmatische amphiphile Helix (AH), die ebenso potenzielle Raft-Motive aufweist: Eine Acylierung und Cholesterol-Bindemotive. In dieser Arbeit wurde per Konfokalmikroskopie an polarisierten Zellen, die fluoreszenzmarkierte M2-Varianten exprimierten, gezeigt, dass diese M2-Motive nicht für den apikalen Transport, der vermutlich durch Raft-ähnliche Vesikel erfolgt, benötigt werden. Messungen des Förster-Resonanzenergietransfers über Fluoreszenz-Lebenszeit-Mikroskopie (FLIM-FRET) in der Plasmamembran lebender Zellen, die fluoreszenzmarkiertes HA und M2 koexprimierten, ergaben, dass diese Motive auch nicht für die Interaktion mit den durch HA, in Abhängigkeit von dessen Raft-Motiven, stabilisierten Raft-Domänen notwendig sind. Mittels reverser Genetik konnten infektiöse WSN-Viren mit fehlender Acylierung am Ende der HA-TMD, nicht jedoch Viren ohne die zwei cytoplasmatischen Acylierungen hergestellt werden. Weiterhin ergaben Wachstumsanalysen, dass die Acylierung von HA und M2 für den gleichen Schritt des viralen Replikationszyklus von Bedeutung sind. Für die M2-AH wurde postuliert, dass sie die Membrankrümmung detektiert und durch Insertion in die Wirtszellmembran die Virusabschnürung bewirkt. Infektiöse Viren ohne M2 oder ohne die AH konnten ebenso wie Viren mit M2 mit einer Helix mit reduzierter Amphiphilität in dieser Arbeit nicht hergestellt werden. Allerdings führte die Substitution der AH durch typische krümmungsdetektierende oder modulierende Helices zu Viren, deren Wachstum um zwei bis vier Titerstufen im Vergleich zum Wildtyp reduziert war. Die Helix-Amphiphilität scheint wichtig zu sein, aber auch die Sequenz oder bestimmte Aminosäuren sind offenbar für eine effiziente Virusreplikation notwendig. / The assembly of influenza virus particles occurs at the apical plasma membrane of the host cell at membrane rafts which the hemagglutinin (HA) interacts with via acylations in its C-terminal region and via hydrophobic amino acids in the transmembrane domain (TMD). M2 possesses a cytoplasmic amphiphilic helix (AH) that also contains potential raft motifs: an acylation and cholesterol-binding motifs. In this work, confocal microscopy of polarised cells, which were expressing fluorescently labelled M2-variants, demonstrated that these motifs of M2 are not required for apical transport, which is assumed to be mediated by raft-like vesicles. Furthermore, FLIM-FRET (Förster resonance energy transfer measured via fluorescence lifetime imaging microscopy) analyses, performed in the plasma membrane of living cells coexpressing fluorescently labelled HA and M2, revealed that these M2-motifs are not required for association with the large coalesced raft phase organised by HA. In contrast, deleting HA’s raft-targeting features clearly reduced clustering with M2. While the removal of the two cytoplasmic acylations prevented the rescue of infectious virus by reverse genetics, a mutant virus without acylation in the HA-TMD could be rescued. Moreover, growth analyses revealed that the acylations of HA and M2 are important for the same step in the viral replication cycle. It has been postulated that the M2-AH detects membrane curvature and accomplishes membrane scission by inserting into the host cell membrane. Viruses without M2, without the M2-AH or with M2 containing a helix with reduced amphiphilicity could not be produced in this work. However, substituting the AH by typical curvature-sensing or -generating helices led to viruses with two to four orders of magnitude reduced growth as compared to wildtype virus. The amphiphilicity of the helix seems to be important, but also the sequence or specific amino acids appear to be necessary for an efficient virus replication.

[pt] O comportamento de radiers estaqueados submetidos a carregamento vertical é estudado nesse trabalho. O método de análise é baseado no método dos elementos finitos, através da utilização do programa ABAQUS. Estimativas de valores de recalque ao longo de três seções distintas e distribuição de forças nos topos das estacas são obtidas para diversas configurações de radiers estaqueados em meio homogêneo com diferentes quantidades e arranjos de estacas, para os quais são adotados diferentes comprimentos relativos das estacas L/d, coeficientes de Poisson do solo Vs e espessuras do radier. A maior parte do recalque ocorre imediatamente após a construção, sendo que os recalques por adensamento se apresentam maiores no centro do que na borda do radier. Uma considerável parcela da carga aplicada é transferida diretamente ao solo através do radier, especialmente sob condições não-drenadas. Para condições drenadas essa proporção é reduzida, mostrando que o efeito do coeficiente de Poisson do solo na distribuição de cargas é bastante significativo. A posição das estacas no radier afetam diretamente a proporção da carga transmitida diretamente do radier para o solo, sendo este efeito mais representativo à medida que aumentam o comprimento relativo das estacas e a rigidez do radier. Análises de capacidade de carga são realizadas em condições não-drenadas para todas as configurações avaliadas, mostrando que o aumento na rigidez do radier contribui significativamente para o aumento dos coeficientes de segurança das estacas. / [en] The behaviour of vertically loaded piled rafts is studied in this research. The main objective of this thesis is to analyse the behaviour of a piled raft foundation system acting on a homogeneous half-space subjected to vertical loading. The analysis is based on finite element method by using of the computational program ABAQUS. The evaluation of settlements along three main sections and the load distribution on pile top were obtained for several piled raft configurations in single layered soil profile with different pile number and position, considering different values of pile slenderness ratio, soil Poisson s ratio and also of raft thickness. It has been shown that the major component of the total settlement takes place immediately after the loading application and the component of the consolidation settlement are bigger close to the raft centre than values at the raft edge. A big part of the total applied load is directly transferred to the subsoil by the raft, which becomes more significant under undrained conditions. For drained conditions this ratio decreases, which have shown that the soil Poisson s ratio influence at the load distribution is significant. The pile position under the raft influences the percentage of the load transferred directly to the subsoil by the raft. This influence becomes more significant with the increase of the pile slenderness ratio and of the raft stiffness. The bearing capacity of the piled raft configurations for undrained conditions was evaluated, which have indicated that the increase of the raft stiffness contributes to the increase of the pile safety factors.

No description available.

No description available.

Les polymères sensibles à des stimuli ont été largement étudiés ces dernières années notamment en vue d’applications biomédicales. Ceux-ci ont la capacité de changer leurs propriétés de solubilité face à des variations de pH ou de température. Le but de cette thèse concerne la synthèse et l’étude de nouveaux diblocs composés de deux copolymères aléatoires. Les polymères ont été obtenus par polymérisation radicalaire contrôlée du type RAFT (reversible addition-fragmentation chain-transfer). Les polymères à bloc sont formés de monomères de méthacrylates et/ou d’acrylamides dont les polymères sont reconnus comme thermosensibles et sensible au pH. Premièrement, les copolymères à bloc aléatoires du type AnBm-b-ApBq ont été synthétisés à partir de N-n-propylacrylamide (nPA) et de N-ethylacrylamide (EA), respectivement A et B, par polymérisation RAFT. La cinétique de copolymérisation des poly(nPAx-co-EA1-x)-block-poly(nPAy-co-EA1-y) et leur composition ont été étudiées afin de caractériser et évaluer les propriétés physico-chimiques des copolymères à bloc aléatoires avec un faible indice de polydispersité . Leurs caractères thermosensibles ont été étudiés en solution aqueuse par spectroscopie UV-Vis, turbidimétrie et analyse de la diffusion dynamique de la lumière (DLS). Les points de trouble (CP) observés des blocs individuels et des copolymères formés démontrent des phases de transitions bien définies lors de la chauffe. Un grand nombre de macromolécules naturels démontrent des réponses aux stimuli externes tels que le pH et la température. Aussi, un troisième monomère, 2-diethylaminoethyl methacrylate (DEAEMA), a été ajouté à la synthèse pour former des copolymères à bloc , sous la forme AnBm-b-ApCq , et qui offre une double réponse (pH et température), modulable en solution. Ce type de polymère, aux multiples stimuli, de la forme poly(nPAx-co-DEAEMA1-x)-block-poly(nPAy-co-EA1-y), a lui aussi été synthétisé par polymérisation RAFT. Les résultats indiquent des copolymères à bloc aléatoires aux propriétés physico-chimiques différentes des premiers diblocs, notamment leur solubilité face aux variations de pH et de température. Enfin, le changement d’hydrophobie des copolymères a été étudié en faisant varier la longueur des séquences des blocs. Il est reconnu que la longueur relative des blocs affecte les mécanismes d’agrégation d’un copolymère amphiphile. Ainsi avec différents stimuli de pH et/ou de température, les expériences effectuées sur des copolymères à blocaléatoires de différentes longueurs montrent des comportements d’agrégation intéressants, évoluant sous différentes formes micellaires, d’agrégats et de vésicules. / Stimuli-responsive polymers and their use in biomedical applications have been widely investigated in recent years. These polymers change their physical properties such as water-solubility, when subjected to certain stimuli, for example change in temperature or pH. The main purpose of this work is to study new diblock copolymers consisting of two random copolymers, i.e., diblock random copolymers. Polymers with well-defined structures and tunable properties have been made using reversible addition−fragmentation chain-transfer (RAFT) polymerization, one of the controlled radical polymerization techniques. The blocks are made of acrylamide- and/or methacrylate-based monomers, which commonly show thermo-responsiveness and hence, double stimuli-responsive behavior is shown. First, a diblock random copolymer in the form of AnBm-b-ApBq was synthesized with N-n-propylacrylamide (nPA) and N-ethylacrylamide (EA) as A and B using RAFT polymerization. Kinetic study of the copolymerization process confirmed the controlled character of the copolymerization. The diblock random copolymers with the compositions of poly(nPAx-co-EA1-x)-block-poly(nPAy-co-EA1-y) and low polydispersity were obtained. With UV-visible spectroscopy and dynamic light scattering (DLS) we investigate their thermoresponsive characteristics in aqueous solutions. Individual blocks showed tunable cloud points, and the diblock copolymer exhibited a well-separated two-step phase transition upon heating. Macromolecules in nature can often respond to a combination of external stimuli, most commonly temperature and pH, rather than a single stimulus. Therefore, a second type of diblock random copolymer in the form of AnBm-b-ApCq was synthesized by combining a pH- and temperature-responsive block with another, only temperature-responsive block, producing responsiveness to multiple stimuli. This polymer with the composition of poly(nPAx-co-DEAEMA1-x)-block-poly(nPAy-co-EA1-y) where DEAEMA stands for 2-diethylaminoethyl methacrylate with well-defined structure and tunable properties has also been made using sequential RAFT polymerization. The resulting diblock random copolymer changes its physico-chemical properties, such as water-solubility, in a quite controlled manner when subjected to the changes in temperature or pH. What happens when blocks of different lengths change their relative hydrophilicity? It is known that the relative length of the blocks in amphiphilic diblock copolymers affects the aggregation mechanism. We compared three diblock copolymers with different block and chain lengths in aqueous solution when they change their relative hydrophilicity due to the change in the external stimuli. The variation of the length and chemical composition of the blocks allows the tuning of the responsiveness of the block copolymers toward both pH and temperature and determines the formation of either micelles or vesicles during the aggregation.