Synthèse et caractérisation de nouveaux matériaux de type n pour applications en dispositifs photovoltaïques

Le PCBM (phenyl CÔI butyric methylester) est un dérivé très utilisé comme matériau de type n dans les piles solaires organiques (accepteur d'électrons). Avec les nombreuses recherches effectuées dans le domaine, il est désormais possible d'obtenir d'encourageants taux de conversion de l'énergie solaire en électricité (plus de 7 %). Bien que le PCBM donne de bons résultats, cet accepteur d'électrons n'est pas le composé optimal pour tous les polymères [Pi] -conjugués et une modulation du niveau énergétique de l'orbitale LUMO est souhaitable. L'objectif principal de ce projet est de synthétiser des dérivés solubles du C₆₀ dont l'orbitale LUMO se situe entre -3,7 et -4,0 eV (comparativement à -4,3 eV pour le PCBM) résultant en une augmentation de la valeur du Voc et conséquemment, de l'efficacité du dispositif. Quelques groupes de recherche se sont penchés sur la modulation de l'orbitale LUMO du C₆₀, mais les changements se sont avérés trop faibles pour avoir un impact significatif sur les performances des piles solaires. Cela peut s'expliquer par la faible communication électronique entre les groupements attachés au C₆₀ et le C₆₀ même. En effet, pour le PCBM, deux carbones sp³ lient le groupement au C₆₀, ce qui a comme effet d'empêcher une conduction directe des électrons au fullerène. Dans le cadre de ce projet, nous proposons d'utiliser une liaison conjuguée afin de lier des groupements électrodonneurs au C₆₀. Par cette liaison, seulement un carbone hybride sp est présent pour attacher le groupement. Ceci devrait donc permettre une meilleure conduction des électrons au C₆₀ et, par le fait même, permettre d'améliorer la modulation de l'orbitale LUMO de ce dernier. Nous avons donc effectué la synthèse de plusieurs dérivés contenant divers groupements électro-donneurs et électro-accepteurs pour étudier leur influence sur les niveaux énergétiques du fullerène. La synthèse de ces dérivés a été faite par la réaction d'éthynylation. Les composés obtenus ont été purifiés par chromatographie en phase liquide et complètement caractérisés par spectroscopie UV-visible et électrochimie. De plus, en utilisant la méthode DFT, nous avons comparé les niveaux énergétiques théoriques des nouveaux dérivés aux résultats expérimentaux

Building a Toolbox for Drug Delivery: Lipid-based Conjugated Polymer Nanoparticles

Conjugated polymer nanoparticles, or CPNs, are highly versatile nano-structured materials that have amassed great interest due to their straightforward synthesis, biocompatibility, and tunable properties.1 The properties of CPNs can be tuned by varying the composition of the surfactant conjugated to the polymer core of these nanoparticles, rendering them suitable for a variety of applications including many in the realm nanomedicine.1 This tunability is key for the design of new drug-delivery systems and therapeutics as the CPN size and structure directly impact important properties, such as the blood brain barrier (BBB) permeability and drug target selectivity.2 Similarly, lipids and lipid-based nanomaterials have been widely studied as nanocarriers transporting various therapeutics in drug delivery systems because of their non-toxic and biocompatible nature.3-5 In this work, the synthesis of an isoindigo - based CPN system is demonstrated with four different lipid surfactants; – DMPC (14:0), DMPS (14:0), DPPC (16:0) and DPPS (16:0). The size, morphology and fluorescence properties of the resulting nanoparticles have been characterized using dynamic light scattering (DLS), small angle neutron scattering (SANS), transmission electron microscopy (TEM), and fluorescence spectroscopy. The development of this lipid-containing CPN system places an emphasis on elucidating lipid – CPN structural relationships by harnessing the differences in the properties of lipids to control the shape and size of the CPNs produced. The resulting lipid-CPN systems and the new structure-relationships unraveled in this work contribute to the refinement of nanomedicine by unveiling novel design criteria in nanomaterials. This new knowledge will open new avenues for improved efficiency in treatments and consequently establish a novel family of nanomaterials as an alternative drug delivery system for cancer treatment. References: 1. Tuncel, D.; Demir, H. V., Conjugated polymer nanoparticles. Nanoscale 2010, 2 (4), 484-494. 2. Rizvi, S. A. A.; Saleh, A. M., Applications of nanoparticle systems in drug delivery technology. Saudi Pharm J 2018, 26 (1), 64-70. 3. Yingchoncharoen, P.; Kalinowski, D. S.; Richardson, D. R., Lipid-Based Drug Delivery Systems in Cancer Therapy: What Is Available and What Is Yet to Come. Pharmacol Rev 2016, 68 (3), 701-787. 4. Scioli Montoto, S.; Muraca, G.; Ruiz, M. E., Solid Lipid Nanoparticles for Drug Delivery: Pharmacological and Biopharmaceutical Aspects. Frontiers in Molecular Biosciences 2020, 7. 5. Bhalekar, M. R.; Madgulkar, A. R.; Desale, P. S.; Marium, G., Formulation of piperine solid lipid nanoparticles (SLN) for treatment of rheumatoid arthritis. Drug Development and Industrial Pharmacy 2017, 43 (6), 1003-1010

Optimizing the Optoelectronic Properties of Conjugated Polymers Through Metal-Ligand Coordination

From the phones at our fingertips to the solar panels on our roofs, humans are becoming increasingly dependent on electronics for information, entertainment, and to power their daily lives. Further advancements are paving the way for a new age of high-performance, flexible devices. Organic electronics made from conjugated semiconducting polymers are showing great potential as a softer and more processable material than brittle silicon used in today’s devices, while exhibiting comparable charge transport to silicon. However, one key challenge with these organic polymers is the difficulty to control their optical properties and charge transport in devices. Electronics must interact with and alter their lighting while efficiently conducting electricity. Therefore, the desired material must be tuneable to precisely control these important properties. In this research, a novel organic diketopyrrolopyrrole-based conjugated polymer is presented as a leading candidate for optoelectronics. This polymer uses noncovalent metal-ligand interactions, enabled by using specific terpyridine ligands, to fine-tune its ability to emit light and transport electrons. Various transition metal ions, including Fe2+, Co2+, Zn2+, and Mn2+, were introduced into the polymer to determine which species would coordinate most efficiently with the ligand, altering its optical nature. Results from fluorescence and absorption spectroscopies showed that the manganese ion coordinated the weakest to the ligand, while iron and cobalt ions bound the most efficiently and optimally altered emission intensity. Thus, iron and cobalt were identified as great candidates for metal-ligand coordination within the polymer for optimal optoelectronic capabilities. These findings contribute to the continued pursuit of creating efficient organic optoelectronics through the promising technique of metal-ligand interactions. Keywords: organic electronics, conjugated polymer, optoelectronics, metal-ligand interaction

Fabrication of an autonomously self-healing flexible thin-film capacitor by slot-die coating

Flexible pressure sensors with self-healing abilities for wearable electronics are being developed, but generally either lack autonomous self-healing properties or require sophisticated material processing methods. To address this challenge, we developed flexible, low-cost and autonomously self-healing capacitive sensors using a crosslinked poly(dimethylsiloxane) through metal-ligand interactions processed into thin films via slot-die coating. These films have excellent self-healing properties, approximately 1.34 × 105 μm3 per hour at room temperature and 2.87 × 105 μm3 per hour at body temperature (37 °C). Similarly, no significant change in capacitance under bending strain was observed on these flexible thin-films when assembled on poly(ethyleneterephthalate) (PET) substrates; capacitors showed good sensitivity at low pressure regimes. More importantly, the devices fully recovered their sensitivity after being damaged and healed, which is directly attributed to the rapid and autonomous self-healing of the dielectric materials

Photophysical and Optical Properties of Semiconducting Polymer Nanoparticles Prepared from Hyaluronic Acid and Polysorbate 80

Copyright © 2019 American Chemical Society. A nanoprecipitation procedure was utilized to prepare novel diketopyrrolopyrrole-based semiconducting polymer nanoparticles (SPNs) with hyaluronic acid (HA) and polysorbate 80. The nanoprecipitation led to the formation of spherical nanoparticles with average diameters ranging from 100 to 200 nm, and a careful control over the structure of the parent conjugated polymers was performed to probe the influence of π-conjugation on the final photophysical and thermal stability of the resulting SPNs. Upon generation of a series of novel SPNs, the optical and photophysical properties of the new nanomaterials were probed in solution using various techniques including transmission electron microscopy, dynamic light scattering, small-angle neutron scattering, transient absorption, and UV-vis spectroscopy. A careful comparison was performed between the different SPNs to evaluate their excited-state dynamics and photophysical properties, both before and after nanoprecipitation. Interestingly, although soluble in organic solution, the nanoparticles were found to exhibit aggregative behavior, resulting in SPNs that exhibit excited-state behaviors that are very similar to aggregated polymer solutions. Based on these findings, the formation of HA- and polysorbate 80-based nanoparticles does not influence the photophysical properties of the conjugated polymers, thus opening new opportunities for the design of bioimaging agents and nanomaterials for health-related applications

Tacky Elastomers to Enable Tear-Resistant and Autonomous Self-Healing Semiconductor Composites

Mechanical failure of π-conjugated polymer thin films is unavoidable under cyclic loading conditions, due to intrinsic defects and poor resistance to crack propagation. Here, the first tear-resistant and room-temperature self-healable semiconducting composite is presented, consisting of conjugated polymers and butyl rubber elastomers. This new composite displays both a record-low elastic modulus

Tacky Elastomers to Enable Tear-Resistant and Autonomous Self-Healing Semiconductor Composites

Mechanical failure of π-conjugated polymer thin films is unavoidable under cyclic loading conditions, due to intrinsic defects and poor resistance to crack propagation. Here, the first tear-resistant and room-temperature self-healable semiconducting composite is presented, consisting of conjugated polymers and butyl rubber elastomers. This new composite displays both a record-low elastic modulus

Polymérisation topochimique de macrocycles rigides : nouvelle stratégie pour l'obtention de nanotubes organiques

Les travaux présentés dans cette thèse concernent principalement la mise en place d’une stratégie visant à obtenir de nouvelles nano-architectures moléculaires à partir de composés ayant une réactivité et une structure bien définies. Ainsi, par l’utilisation de macrocycles rigides de type phénylacétylène, il a été possible d’obtenir des nanotubes entièrement organiques, et ce, de façon plus rapide et contrôlée. Dans le chapitre 1, une revue de la littérature scientifique actuelle sera présentée en mettant l’accent particulièrement sur l’obtention de nano-objets à partir de précurseurs moléculaires bien définis. Par la suite, dans le chapitre 2, une étude détaillée sur l’empilement supramoléculaire des macrocycles rigides de type phénylacétylène à l’état gel sera présentée en mettant en lumière l’influence des différents paramètres structuraux sur la réactivité de ces précurseurs. Dans le troisième chapitre, il sera question de la photopolymérisation topochimique à l’état gel des unités diynes contenuesy dans les macrocycles de type phénylacètylene vers l’obtention de nanobâtonnets rigides. Une caractérisation détaillée par spectroscopie Raman et par microscopie électronique sera présentée dans le but de confirmer les structures attendues. Dans le chapitre 4, il sera question de la photopolymérisation topochimique de macrocycles plus larges de type phénylènebutadiynylène dans le but de contrôler la largeur de la cavité interne des nouvelles nano-architectures tubulaires. L’utilisation de ces précurseurs montrant la polyvalence de notre approche hybride pour le contrôle des nanostructures finales. Le chapitre 5 comprendra une étude de la pyrolyse des nanotubes décrits dans les chapitres précédents dans le but d’aller vers des nanotubes riches en carbone. L’obtention de tels matériaux est particulièrement intéressante vu l’utilisation des plus en plus répandue des nanotubes de carbone, souvent difficile d’obtention avec de bonnes puretés. Dans le chapitre 6, il sera question de nos récentes tentatives afin d’augmenter la réactivité des macrocycles à la réaction de polymérisation topochimique par la modification des chaînes périphériques. Finalement, une conclusion et une synthèse des résultats ainsi qu’une mise en contexte des travaux futurs seront présentées dans le chapitre 7.The work presented in this thesis mainly concerns the establishment of a novel strategy to obtain new molecular nanoarchitectures from molecular precursors having a precise reactivity and a well-defined structure. Thus, by the use of shape-persistent phenylacetylene macrocycles, it has been possible to obtain discrete organic nanotubes in a more rapid and controlled fashion. In chapter 1, a review of the recent literature will be presented focusing particularly on synthesis of nanomaterials from well-defined molecular precursors. Subsequently, in the second chapter, a detailed study on the supramolecular stacking of rigid phenylacetylene macrocycles in a gel state will be presented highlighting the influence of different structural parameters on the reactivity of these precursors. In the third chapter, the topochemical photopolymerization in the gel state of diynes containing phenylacetylene macrocycles to obtain well-defined organic nanorods will be presented. A detailed characterization by Raman spectroscopy and electron microscopy will be presented in order to confirm the expected structures. The chapter 4 will present the topochemical photopolymerization of larger phenylenebutadiynylene macrocycles in order to control the width of the inner cavity of the new tubular nanoarchitectures. By using these precursors, the versatility of our approach by a hybrid method will be discussed to exemplify the control over the final nanostructures. Chapter 5 will present a study on the pyrolysis of the previously obtained organic nanorods toward carbon-rich nanotubes. The production of such materials is particularly interesting given the large use of carbon nanotubes, often difficult to obtain with good purities. Chapter 6 will present our recent strategy to improve the reactivity of the macrocycles toward topochemical polymerization by side-chains modification. Finally, chapter 7 will present a conclusion and future work

Polyethylene and Semiconducting Polymer Blends for the Fabrication of Organic Field-Effect Transistors: Balancing Charge Transport and Stretchability

Polyethylene is amongst the most used polymers, finding a plethora of applications in our lives owing to its high impact resistance, non-corrosive nature, light weight, cost effectiveness, and easy processing into various shapes from different sizes. Despite these outstanding features, the commodity polymer has been underexplored in the field of organic electronics. This work focuses on the development of new polymer blends based on a low molecular weight linear polyethylene (LPE) derivative with a high-performance diketopyrrolopyrrole-based semiconducting polymer. Physical blending of the polyethylene with semiconducting polymers was performed at ratios varying from 0 to 75 wt.%, and the resulting blends were carefully characterized to reveal their electronic and solid-state properties. The new polymer blends were also characterized to reveal the influence of polyethylene on the mechanical robustness and stretchability of the semiconducting polymer. Overall, the introduction of LPE was shown to have little to no effect on the solid-state properties of the materials, despite some influence on solid-state morphology through phase separation. Organic field-effect transistors prepared from the new blends showed good device characteristics, even at higher ratios of polyethylene, with an average mobility of 0.151 cm2 V−1 s−1 at a 25 wt.% blend ratio. The addition of polyethylene was shown to have a plasticizing effect on the semiconducting polymers, helping to reduce crack width upon strain and contributing to devices accommodating more strain without suffering from decreased performance. The new blends presented in this work provide a novel platform from which to access more mechanically robust organic electronics and show promising features for the utilization of polyethylene for the solution processing of advanced semiconducting materials toward novel soft electronics and sensors

Polyethylene and Semiconducting Polymer Blends for the Fabrication of Organic Field-Effect Transistors: Balancing Charge Transport and Stretchability

Polyethylene is amongst the most used polymers, finding a plethora of applications in our lives owing to its high impact resistance, non-corrosive nature, light weight, cost effectiveness, and easy processing into various shapes from different sizes. Despite these outstanding features, the commodity polymer has been underexplored in the field of organic electronics. This work focuses on the development of new polymer blends based on a low molecular weight linear polyethylene (LPE) derivative with a high-performance diketopyrrolopyrrole-based semiconducting polymer. Physical blending of the polyethylene with semiconducting polymers was performed at ratios varying from 0 to 75 wt.%, and the resulting blends were carefully characterized to reveal their electronic and solid-state properties. The new polymer blends were also characterized to reveal the influence of polyethylene on the mechanical robustness and stretchability of the semiconducting polymer. Overall, the introduction of LPE was shown to have little to no effect on the solid-state properties of the materials, despite some influence on solid-state morphology through phase separation. Organic field-effect transistors prepared from the new blends showed good device characteristics, even at higher ratios of polyethylene, with an average mobility of 0.151 cm2 V−1 s−1 at a 25 wt.% blend ratio. The addition of polyethylene was shown to have a plasticizing effect on the semiconducting polymers, helping to reduce crack width upon strain and contributing to devices accommodating more strain without suffering from decreased performance. The new blends presented in this work provide a novel platform from which to access more mechanically robust organic electronics and show promising features for the utilization of polyethylene for the solution processing of advanced semiconducting materials toward novel soft electronics and sensors