University of Groningen
Polymeric surfactants based on the chemical modification of alternating aliphatic polyketones
Araya Hermosilla, Esteban Alejand
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Publication date: 2019
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Araya Hermosilla, E. A. (2019). Polymeric surfactants based on the chemical modification of alternating aliphatic polyketones. University of Groningen.
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Appendix
Appendix
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116 CHAPTER A
Summary
The fabrication of functional nanostructures can be accomplished through two ap-proaches: “top-down” and “bottom-up” nanofabrication. The latter rely strongly on the synthesis of functional molecules with specific dimensions, forms, and chemical characteristics, and on the principles of supramolecular chemistry. In this sense, self-assembly is a method where the molecules spontaneously form ordered aggregates; the interactions involved are non-covalent such as hydrogen bonding, electrostatic and aromatic interaction, hydrophobic, among others. In these self-assembled struc-tures, the intermolecular forces join the molecular building blocks in a reversible and controllable form. Thus, the combination of the individual component proper-ties and the reversibility of their interaction offer the possibility of creating stimuli-responsive supramolecular structures, which are of special interest in applications such as catalysis, chemical sensing, drug delivery, etc. During this thesis, we fo-cused on the synthesis of polymeric surfactant via the chemical modification of al-ternating aliphatic polyketones. In addition, these polymers bearing weak aromatic and non-aromatic electrolytes functional groups that provide them with pH-sensitive properties. They were used as building blocks together with active molecules for the fabrication of stimuli-responsive functional self-assembled structures using as approach the electrostatic self-assembly. Chapter 2 focused on the synthesis of a polymeric surfactant that bears imidazolium pendant groups. This polymer was used for the encapsulation of oxolinic acid and flumequine, which are commonly used in aquaculture as prophylactics, or chemotherapeutic agents to control dis-eases. In this context, we successfully encapsulated the two antibiotic in polymeric micelles in aqueous solution, not using any organic solvents. This is a valuable ac-complishment from a green chemistry perspective. Chapter 3 reports the utilization of surfactant polymers with different hydrophilic/hydrophobic balances to prevent the aggregation of 5,10,15,20-tetrakis-(sulfonatophenyl)porphyrine in acid aqueous environment. It was found that the polymer with a higher hydrophobicity (less in-corporation of pendant groups) could prevent the aggregation of the dye at lower values of pH in comparison to the rest of the polymers. Electrostatic interactions and preferential solvation of the dye by the polymer chain explains the stabilization found. Chapter 4 reports the preparation of micro- and nano-polymeric micellar ag-gregates using the electrostatic self-assembly strategy. The self-assembled structures are composed of pH-sensitive polymeric surfactants and the water-soluble porphyrin 5,10,15,20-tetrakis-(sulfonatophenyl)porphyrin (TPPS). The adjustment of the poly-mer/ porphyrin molar ratio and the solution pH, provide an interesting approach to the synthesis of supramolecular structures in aqueous solution. Chapter 5 shows the synthesis of pH-sensitive organic nanoparticles by the reduction of tetrazolium salt (TTC) to the corresponding red formazan (TF) stabilized by aromatic polyketones. In addition, the polyketones displayed the ability to undergo aromatic-aromatic inter-action with the redox-active precursor molecule TTC that is pivotal for the synthesis
of the redox nanoparticles. These structures are promising materials for the fabrica-tion of chemical sensors. Chapter 6 shows the versatility of the Paal-Knorr reacfabrica-tion in the synthesis of functional polymers via the chemical modification of aliphatic polyketones. Two promising applications are investigated: the synthesis of polymer support ionic liquids with thermoreversible properties for the synthesis of cyclic car-bonates; and the application of pH-sensitive polymeric surfactant for the formation of water in oil emulsions.
118 CHAPTER A
Samenvatting
De fabricage van functionele nanostructuren kan worden bereikt door middel van twee methoden: ”top-down” en ”bottom-up” nanofabricage. Laatstgenoemde meth-ode is gebaseerd op de synthese van functionele moleculen met specifieke afmetin-gen, vormen en chemische eigenschappen en op de principes van supramoleculaire scheikunde. Zodoende is zelfassemblage een methode waarbij de moleculen op spontane wijze geordende aggregaten vormen; hier zijn de interacties niet-covalent, zoals waterstofbindingen, elektrostatische- en aromatische interacties en hydrofobe, onder andere. In deze zelf-geassembleerde structuren voegen de intermoleculaire krachten de moleculaire bouwstenen samen op een reversibele en controleerbare manier. De combinatie van de individuele componenteigenschappen en de omkeer-baarheid van hun interactie biedt de mogelijkheid om stimuli-responsieve supramolec-ulaire structuren te creren, die van bijzonder belang zijn in toepassingen zoals katal-yse, chemische detectie, medicijnafgifte, etc. Tijdens dit proefschrift hebben we gefocust op de synthese van polymere oppervlakte-actieve stoffen via de chemische modificatie van alternerende alifatische polyketonen. Daarnaast dragen deze poly-meren zwak- of niet-aromatische functionele elektrolyt groepen die hen voorzien van pH-gevoelige eigenschappen. Ze werden gebruikt als bouwstenen in combi-natie met actieve moleculen voor de fabricage van stimuli-responsieve, functionele, zelf-geassembleerde structuren met elektrostatische zelf-assemblage als toegepaste methode.?Hoofdstuk 2 is gericht op de synthese van een polymere oppervlakte-actieve stof die imidazolium zijgroepen draagt. Dit polymeer werd gebruikt voor de inkapseling van oxolinezuur en flumequine, die veelvuldig worden gebruikt in de aquacultuur als profylactica, of chemotherapeutische middelen om ziekten on-der controle te houden. Hiermee hebben we met succes de twee antibiotica in-gekapseld in polymere micellen in een waterige oplossing zonder het gebruik van organische oplosmiddelen. Dit is een waardevolle prestatie vanuit het perspectief van groene chemie. Hoofdstuk 3 rapporteert het gebruik van polymere oppervlakte-actieve stoffen met verschillende hydrofiele / hydrofobe samenstellingen om de ag-gregatie van 5,10,15,20-tetrakis-(sulfonatofenyl)porfyrine in zure waterige omgevin-gen te voorkomen. Er is vastgesteld dat het polymeer met een hogere hydrofobiciteit (minder incorporatie van zijgroepen) de aggregatie van de kleurstof bij lagere pH-waarden in vergelijking met de rest van de polymeren kon voorkomen. Elektro-statische interacties en preferentile solvatatie van de kleurstof door de polymeer-keten verklaren de gevonden stabilisatie. Hoofdstuk 4 rapporteert de bereiding van micro- en nano-polymere micellaire aggregaten door middel van elektrostatische zelfassemblage-strategie. De zelf-geassembleerde structuren zijn samengesteld uit pH-gevoelige polymere oppervlakte-actieve stoffen en het in water oplosbare porfyrine 5,10,15,20-tetrakis-(sulfonatofenyl) porfyrine (TPPS). De aanpassing van de molaire
verhouding polymeer/ porfyrine en de pH van de oplossing verschaffen een
oplossing. In hoofdstuk 5 wordt de synthese van pH-gevoelige organische nanodeelt-jes beschreven door de reductie van tetrazoliumzout (TTC) naar de overeenkom-stige rode formazan (TF), gestabiliseerd door aromatische polyketonen. Daarnaast vertoonden de polyketonen het vermogen om aromatisch-aromatische interactie te ondergaan met het redox-actieve precursormolecuul-TTC, dat cruciaal is voor de synthese van de redox-nanodeeltjes. Deze structuren zijn veelbelovend voor de fab-ricage van chemische sensoren. Hoofdstuk 6 toont de veelzijdigheid van de Paal-Knorr-reactie in de synthese van functionele polymeren via de chemische modifi-catie van alifatische polyketonen. Twee veelbelovende toepassingen zijn onderzocht: de synthese van polymeer ondersteunde ionische vloeistoffen met thermoreversibele eigenschappen voor de synthese van cyclische karbonaten; en de toepassing van
pH-gevoelige polymere oppervlakte-actieve stoffen voor de vorming van emulsies van
120 CHAPTER A
Publication and Conferences
Publications
1. Esteban Araya-Hermosilla, Marnix Roscam-Abbing, Jos Cataln-Toledo, Francesco Picchioni, Felipe Oyarzn, Moreno-Villoslada Ignacio. Synthesis of Tuneable Amphiphilic-Modified Polyketone Polymers, their Complexes with 5,10,15,20-Tetrakis-(4-Sulfonatophenyl)porphyrin, and their Role in the Pho-tooxidation of 1,3,5-Triphenylformazan Confined in Polymeric Nanoparticles (2019). Polymer, 167, 215-223.
2. Esteban Araya-Hermosilla, Jos Cataln-Toledo, Fabin Muoz-Suescun, Felipe
Oyarzun-Ampuero, Patrizio Raffa, Lorenzo Massimo Polgar, Francesco
Pic-chioni, Ignacio Moreno-Villoslada. Totally organic redox-Active pH-sensitive nanoparticles stabilized by amphiphilic aromatic polyketones (2018). J. Phys. Chem. B, 122, 1747?1755.
3. R. Araya-Hermosilla, A. Pucci, E. Araya-Hermosilla, P. P. Pescarmona, P.
Raffa, L. M. Polgar, I. Moreno-Villoslada, M. Flores, G. Fortunato, A. A.
Broekhuis and F. Picchioni. An easy synthetic way to exfoliate and stabilize MWCNTs in a thermoplastic pyrrole-containing matrix assisted by hydrogen bonds (2016). RSC Advances, 6, 85829-85837.
4. Esteban Araya-Hermosilla, Sandra orellana, Claudio Toncelli, Francesco Picchioni, Ignacio Moreno-Villoslada. Novel polyketones with pendant im-idazolium groups as nanodispersants of hydrophobic antibiotics (2015). Jour-nal of Applied Polymer Science, 132, 42363.
5. Esteban Araya-Hermosilla, Daniel Munoz, Sandra Orellana, Lejandro Yanez, Andres F. Olea, Felipe Ayarzun-Ampuero, Alejandro Yaez, Ignacio Moreno-Villoslada. Immobilization of rhodamine 6G in calcium alginate microcap-sules base on aromatic-aromatic interactions with poly
(sodium 4-styrenesulfonate) (2014). Reactive & Functional Polymers 81, 14-21.
6. R. Araya-Hermosilla, E. Araya-Hermosilla, C. Torres-Gallegos, C. Alarcn-Alarcn, Hiroyuki Nishide, I. Moreno-Villoslada. Sensing Cu2+by controlling
the aggregation properties of the fluorescent dye rhodamine 6G with the aid of polyelectrolytes bearing different linear aromatic density (2013). Reactive and Functional Polymers, 73, 11, 1455-1463.
Manuscripts in preparation
7. Esteban Araya-Hermosilla, Patrizio Raffa, Ignacio Moreno-Villoslada,
5,10,15,20-Tetrakis-(4-sulfonatophenyl)porphyrin. Manuscript in progress (2019).
Contribution to international conferences
1. Esteban Araya-Hermosilla, Patrizio Raffa, Ignacio Moreno-Villoslada,
Francesco Picchioni (4-9 Decembre 2016). Formazan nanoprecipitates con-trolled by the use of a polyanion derived from polyketone. American Ad-vanced Materials Congress. Miami, USA. Oral presentation
2. Esteban Araya-Hermosilla, Patrizio Raffa, Ignacio Moreno-Villoslada,
Francesco Picchioni (23-27 October 2016). pH-responsive polymers based on the chemical modification of polyketones. XV Simposio Latinoamericano de Polimeros, XIII Congreso Iberoamericano de Polimeros. Cancun-Rivera Maya, Mexico. Oral presentation
3. Esteban Araya-Hermosilla, Patrizio Raffa, Ignacio Moreno-Villoslada,
Francesco Picchioni (30 August - 2 September 2015). Polymeric surfactants based on the chemical modification of polyketones. International Symposium on Amphiphilic Polymers, Networks, Gels and Membranes. Budapest, Hun-gary. Poster
122 CHAPTER A
Acknowledgements
I would like to thanks deeply to my family for the support during these years of study. My special gratitude to my parents Mercedes and Valdemar who sacrificed their entirely life to give me everything that a human being deserves, love, human values, support, and education. I express gratitude to my brother Rodrigo for inspiring me to follow other routes in life: university studies instead of professional football player (best decision of my life!!!). My biggest thankfulness to my fiance Maria Cristina for endure stoically my difficult personality, for all the support in the last year of my PhD studies, and for helping me to believe in my capacities every day. I would like to thank the reading committee: Prof. Mark Kobrak, Prof. Ren Rossi and Prof. G.J.W. Euverink for their insightful comments and corrections. I express my most sincere gratitude to my supervisor Prof. dr. Francesco Picchioni for his support during these years, for his friendship and understanding in the difficult moments. I thank Francesco for believing in my abilities and for help me to grow as a scientist. I would like to thanks to my external co-supervisor Ignacio Moreno-Villoslada for his guidance and for help me to publish the papers. I would like to thanks to my daily supervisor in the two first years of my PhD Patrizio Raffa for his friendship, guidance, especially for his patience, and for help me to writing the papers and thesis. I would like to thanks Paolo Pescarmona for his friendship, wise corridor con-versations in Spanish, guidance in the last project of this thesis, and for help me to write this thesis. I would like to thanks again to Mark Kobrak for his friendship, wise corridor and lunch conversations, guidance during the last months of my PhD, and for help me to write this thesis. My big gratitude to my Chilean friends who help me to endure the difficult moment of this journey, for host me in their houses, for introduce the love of my life, for drinking and laughing with me. Finally, I would like to all people who worked or working in the Product Technology Department, PhD and maters students, technicians, professors, and secretariats.
