| 1. |
- Abdel Aziz, Ilaria, et al.
(författare)
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Drug delivery via a 3D electro-swellable conjugated polymer hydrogel
- 2024
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Ingår i: Journal of materials chemistry. B. - : ROYAL SOC CHEMISTRY. - 2050-750X .- 2050-7518.
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Tidskriftsartikel (refereegranskat)abstract
- Spatiotemporal controlled drug delivery minimizes side-effects and enables therapies that require specific dosing patterns. Conjugated polymers (CP) can be used for electrically controlled drug delivery; however so far, most demonstrations were limited to molecules up to 500 Da. Larger molecules could be incorporated only during the CP polymerization and thus limited to a single delivery. This work harnesses the record volume changes of a glycolated polythiophene p(g3T2) for controlled drug delivery. p(g3T2) undergoes reversible volumetric changes of up to 300% during electrochemical doping, forming pores in the nm-size range, resulting in a conducting hydrogel. p(g3T2)-coated 3D carbon sponges enable controlled loading and release of molecules spanning molecular weights of 800-6000 Da, from simple dyes up to the hormone insulin. Molecules are loaded as a combination of electrostatic interactions with the charged polymer backbone and physical entrapment in the porous matrix. Smaller molecules leak out of the polymer while larger ones could not be loaded effectively. Finally, this work shows the temporally patterned release of molecules with molecular weight of 1300 Da and multiple reloading and release cycles without affecting the on/off ratio.
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| 2. |
- Abdel Aziz, Ilaria, et al.
(författare)
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Electrochemical modulation of mechanical properties of glycolated polythiophenes
- 2024
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Ingår i: Materials Horizons. - : ROYAL SOC CHEMISTRY. - 2051-6347 .- 2051-6355.
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Tidskriftsartikel (refereegranskat)abstract
- Electrochemical doping of organic mixed ionic-electronic conductors is key for modulating their conductivity, charge storage and volume enabling high performing bioelectronic devices such as recording and stimulating electrodes, transistors-based sensors and actuators. However, electrochemical doping has not been explored to the same extent for modulating the mechanical properties of OMIECs on demand. Here, we report a qualitative and quantitative study on how the mechanical properties of a glycolated polythiophene, p(g3T2), change in situ during electrochemical doping and de-doping. The Young's modulus of p(g3T2) changes from 69 MPa in the dry state to less than 10 MPa in the hydrated state and then further decreases down to 0.4 MPa when electrochemically doped. With electrochemical doping-dedoping the Young's modulus of p(g3T2) changes by more than one order of magnitude reversibly, representing the largest modulation reported for an OMIEC. Furthermore, we show that the electrolyte concentration affects the magnitude of the change, demonstrating that in less concentrated electrolytes more water is driven into the film due to osmosis and therefore the film becomes softer. Finally, we find that the oligo ethylene glycol side chain functionality, specifically the length and asymmetry, affects the extent of modulation. Our findings show that glycolated polythiophenes are promising materials for mechanical actuators with a tunable modulus similar to the range of biological tissues, thus opening a pathway for new mechanostimulation devices. This work investigates the changes in the mechanical properties of glycolated polythiophenes induced by electrochemical addressing and by electrolyte concentration, due to its ability to stabilize water.
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| 3. |
- Delavari, Najmeh, et al.
(författare)
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Water Intake and Ion Exchange in PEDOT:Tos Films upon Cyclic Voltammetry: Experimental and Molecular Dynamics Investigation
- 2021
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Ingår i: Macromolecules. - : AMER CHEMICAL SOC. - 0024-9297 .- 1520-5835. ; 54:13, s. 6552-6562
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Tidskriftsartikel (refereegranskat)abstract
- Conductive polymer PEDOT:Tos (3,4-ethylenedioxythiophene doped with molecular tosylate) gained considerable attention in various devices for bioelectronic applications, such as organic transistors and sensors. Many of these devices function upon oxidation/reduction processes in contact with aqueous electrolytes. So far, theoretical insight into morphological changes, ion injection, and water intake during these processes was rather limited. In the present work, we combined experiments and molecular dynamics simulations to study the water intake, swelling, and exchange of ions in the PEDOT:Tos film during cyclic voltammetry. We showed that the film underwent significant changes in morphology and mass during the redox processes. We observed both experimentally and in simulations that the film lost its mass during reduction, as tosylate and Na were expelled and gained mass during oxidation mainly due to the uptake of anions, i.e., tosylate and Cl. The results were in line with the UV-VIS-NIR absorption measurements and X-ray photoelectron spectroscopy (XPS) measurements, which revealed that during the redox process a portion of Tos was replaced by Cl- as the counterion for PEDOT. Also, the relative mass change between the most oxidized and reduced states was similar to 10 to 14% according to both experiments and simulations. We detected an overall material loss of the film during voltammetry cycles indicating that a portion of the material leaving the film during reduction did not return to the film during the consecutive oxidation. Our combined experimental/simulation study unraveled the underlying molecular processes in the PEDOT:Tos film upon the redox process, providing the essential understanding needed to improve and assess the performance of bioelectronic devices.
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| 4. |
- Gladisch, Johannes, et al.
(författare)
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An Electroactive Filter with Tunable Porosity Based on Glycolated Polythiophene
- 2022
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Ingår i: Small Science. - : Wiley. - 2688-4046. ; 2:4
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Tidskriftsartikel (refereegranskat)abstract
- The porosity of filters is typically fixed; thus, complex purification processes require application of multiple specialized filters. In contrast, smart filters with controllable and tunable properties enable dynamic separation in a single setup. Herein, an electroactive filter with controllable pore size is demonstrated. The electroactive filter is based on a metal mesh coated with a polythiophene polymer with ethylene glycol sidechains (p(g3T2)) that exhibit unprecedented voltage-driven volume changes. By optimizing the polymer coating on the mesh, controllable porosity during electrochemical addressing is achieved. The pores reversibly open and close, with a dynamic range of more than 95%, corresponding to over 30 mu m change of pores widths. Furthermore, the pores widths could be defined by applied potential with a 10 mu m resolution. From among hundreds of pores from different samples, about 90% of the pores could be closed completely, while only less than 1% are inactive. Finally, the electroactive filter is used to control the flow of a dye, highlighting the potential for flow control and smart filtration applications.
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| 5. |
- Gladisch, Johannes, 1987-
(författare)
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Investigating volume change and ion transport in conjugated polymers
- 2021
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Doktorsavhandling (övrigt vetenskapligt/konstnärligt)abstract
- Volume changes are the foundation for a wide range of phenomena and applications, ranging from the movement of plants to valves and drug delivery devices. Therefore, it does not come as a surprise that controlled volume changes are an interesting topic of research. In this thesis, volume changes in polymers are the object of investigation. Polymers are a class of macromolecules that comprise repetitive units. Owing to the wide variety of such units, polymers can exhibit manifold properties, including but not limited to strong water attraction and electrical conductivity. The former is the defining property in polymer hydrogels while the latter is a core property of conducting polymers. Both the water attracting properties and conductivity are closely linked to transport events on a molecular level. In the case of hydrogels, it is predominantly water uptake, while in the case of conducting polymers it is a complex interplay between charges, ionic charge balancing entities and water. However, in either case the transport events lead to volume changes. Despite the similarities, the properties of the materials differ greatly. On the one hand volume changes in hydrogels are very large but hard to control. On the other hand, volume changes in conducting polymers are much smaller than in hydrogels, but the control is easier due to the electronic addressing. P(gXTX) polymers combine a conducting polymer backbone with hydrogel sidechains. As described in publication 1, this combination of molecular entities was found to enabled unique properties of an electrically controllable giant volume change and concomitant solid-gel transition. In the second publication, the effect of the side chain lengths on the volume change properties of the polymers were explored. The knowledge acquired from these studies helped us to develop an electroactive filter based on p(gXTX) polymers which enabled electrochemical modulation of flow (publication 3). The aim of the fourth publication was to study the complex electronic-ionic transport processes and volume changes in a model conducting polymer, PEDOT:Tos. The understanding of fundamental processes and properties of controllable volume changes may pave the way for advances in various applications, including electroactive meshes, actuators and drug delivery devices.
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| 6. |
- Gladisch, Johannes, et al.
(författare)
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Reversible Electronic Solid-Gel Switching of a Conjugated Polymer
- 2020
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Ingår i: ADVANCED SCIENCE. - : WILEY. - 2198-3844. ; 7:2
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Tidskriftsartikel (refereegranskat)abstract
- Conjugated polymers exhibit electrically driven volume changes when included in electrochemical devices via the exchange of ions and solvent. So far, this volumetric change is limited to 40% and 100% for reversible and irreversible systems, respectively, thus restricting potential applications of this technology. A conjugated polymer that reversibly expands by about 300% upon addressing, relative to its previous contracted state, while the first irreversible actuation can achieve values ranging from 1000-10 000%, depending on the voltage applied is reported. From experimental and theoretical studies, it is found that this large and reversible volumetric switching is due to reorganization of the polymer during swelling as it transforms between a solid-state phase and a gel, while maintaining percolation for conductivity. The polymer is utilized as an electroactive cladding to reduce the void sizes of a porous carbon filter electrode by 85%.
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| 7. |
- Han, Shaobo, et al.
(författare)
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Cellulose-Conducting Polymer Aerogels for Efficient Solar Steam Generation
- 2020
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Ingår i: Advanced Sustainable Systems. - : Wiley-VCH Verlag. - 2366-7486. ; 4:7, s. 2000004-
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Tidskriftsartikel (refereegranskat)abstract
- Seawater desalination and wastewater purification technologies are the main strategies against the global fresh water shortage. Among these technologies, solar-driven evaporation is effective in extracting fresh water by efficiently exploiting solar energy. However, building a sustainable and low-cost solar steam generator with high conversion efficiency is still a challenge. Here, pure organic aerogels comprising a cellulose scaffold decorated with an organic conducting polymer absorbing in the infrared are employed to establish a high performance solar steam generator. The low density of the aerogel ensures minimal material requirements, while simultaneously satisfying efficient water transport. To localize the absorbed solar energy and make the system floatable, a porous floating and thermal-insulating foam is placed between the water and the aerogel. Thanks to the high absorbance of the aerogel and the thermal-localization performance of the foam, the system exhibits a high water evaporation rate of 1.61 kg m−2 h−1 at 1 kW m−2 under 1 sun irradiation, which is higher than most reported solar steam generation devices.
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| 8. |
- Huss, Jessica C., et al.
(författare)
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Climate-Dependent Heat-Triggered Opening Mechanism of Banksia Seed Pods
- 2018
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Ingår i: Advanced Science. - : Wiley. - 2198-3844. ; 5:1
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Tidskriftsartikel (refereegranskat)abstract
- Heat-triggered fruit opening and delayed release of mature seeds are widespread among plants in fire-prone ecosystems. Here, the material characteristics of the seed-containing follicles of Banksia attenuata (Proteaceae), which open in response to heat frequently caused by fire, are investigated. Material analysis reveals that long-term dimensional stability and opening temperatures of follicles collected across an environmental gradient increase as habitats become drier, hotter, and more fire prone. A gradual increase in the biaxial curvature of the hygroscopic valves provides the follicles in the driest region with the highest flexural rigidity. The irreversible deformation of the valves for opening is enabled via a temperature-dependent reduction of the elastic modulus of the innermost tissue layer, which then allows releasing the stresses previously generated by shrinkage of the fiber bundles in the adjacent layer during follicle drying. These findings illustrate the level of sophistication by which this species optimizes its fruit opening mechanism over a large distribution range with varying environmental conditions, and may not only have great relevance for developing biomimetic actuators, but also for elucidating the species' capacity to cope with climatic changes.
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| 9. |
- Kumar, Divyaratan, et al.
(författare)
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Water-in-Polymer Salt Electrolyte for Long-Life Rechargeable Aqueous Zinc-Lignin Battery
- 2024
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Ingår i: Energy and Environmental Materials. - : WILEY. - 2575-0356 .- 2575-0348. ; In Press
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Tidskriftsartikel (refereegranskat)abstract
- Zinc metal batteries (ZnBs) are poised as the next-generation energy storage solution, complementing lithium-ion batteries, thanks to their cost-effectiveness and safety advantages. These benefits originate from the abundance of zinc and its compatibility with non-flammable aqueous electrolytes. However, the inherent instability of zinc in aqueous environments, manifested through hydrogen evolution reactions (HER) and dendritic growth, has hindered commercialization due to poor cycling stability. Enter potassium polyacrylate (PAAK)-based water-in-polymer salt electrolyte (WiPSE), a novel variant of water-in-salt electrolytes (WiSE), designed to mitigate side reactions associated with water redox processes, thereby enhancing the cyclic stability of ZnBs. In this study, WiPSE was employed in ZnBs featuring lignin and carbon composites as cathode materials. Our research highlights the crucial function of acrylate groups from WiPSE in stabilizing the ionic flux on the surface of the Zn electrode. This stabilization promotes the parallel deposition of Zn along the (002) plane, resulting in a significant reduction in dendritic growth. Notably, our sustainable Zn-lignin battery showcases remarkable cyclic stability, retaining 80% of its initial capacity after 8000 cycles at a high current rate (1 A g−1) and maintaining over 75% capacity retention up to 2000 cycles at a low current rate (0.2 A g−1). This study showcases the practical application of WiPSE for the development of low-cost, dendrite-free, and scalable ZnBs.
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| 10. |
- Kumar, Divyaratan, et al.
(författare)
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Water-in-Polymer Salt Electrolyte for Long-Life Rechargeable Aqueous Zinc-Lignin Battery
- 2024
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Ingår i: Energy & Environmental Materials. - : John Wiley & Sons. - 2575-0356 .- 2575-0348.
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Tidskriftsartikel (refereegranskat)abstract
- Zinc metal batteries (ZnBs) are poised as the next-generation energy storage solution, complementing lithium-ion batteries, thanks to their cost-effectiveness and safety advantages. These benefits originate from the abundance of zinc and its compatibility with non-flammable aqueous electrolytes. However, the inherent instability of zinc in aqueous environments, manifested through hydrogen evolution reactions (HER) and dendritic growth, has hindered commercialization due to poor cycling stability. Enter potassium polyacrylate (PAAK)-based water-in-polymer salt electrolyte (WiPSE), a novel variant of water-in-salt electrolytes (WiSE), designed to mitigate side reactions associated with water redox processes, thereby enhancing the cyclic stability of ZnBs. In this study, WiPSE was employed in ZnBs featuring lignin and carbon composites as cathode materials. Our research highlights the crucial function of acrylate groups from WiPSE in stabilizing the ionic flux on the surface of the Zn electrode. This stabilization promotes the parallel deposition of Zn along the (002) plane, resulting in a significant reduction in dendritic growth. Notably, our sustainable Zn-lignin battery showcases remarkable cyclic stability, retaining 80% of its initial capacity after 8000 cycles at a high current rate (1 A g-1) and maintaining over 75% capacity retention up to 2000 cycles at a low current rate (0.2 A g-1). This study showcases the practical application of WiPSE for the development of low-cost, dendrite-free, and scalable ZnBs. A dendrite-free and long-life cycle Zn-lignin battery was demonstrated using water-in-polymer salt electrolyte.
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| 11. |
- Moser, Maximilian, et al.
(författare)
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Controlling Electrochemically Induced Volume Changes in Conjugated Polymers by Chemical Design : from Theory to Devices
- 2021
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Ingår i: Advanced Functional Materials. - : Wiley. - 1616-301X .- 1616-3028. ; n/a:n/a
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Tidskriftsartikel (refereegranskat)abstract
- Electrochemically induced volume changes in organic mixed ionic-electronic conductors (OMIECs) are particularly important for their use in dynamic microfiltration systems, biomedical machinery, and electronic devices. Although significant advances have been made to maximize the dimensional changes that can be accomplished by OMIECs, there is currently limited understanding of how changes in their molecular structures impact their underpinning fundamental processes and their performance in electronic devices. Herein, a series of ethylene glycol functionalized conjugated polymers is synthesized, and their electromechanical properties are evaluated through a combined approach of experimental measurements and molecular dynamics simulations. As demonstrated, alterations in the molecular structure of OMIECs impact numerous processes occurring during their electrochemical swelling, with sidechain length shortening decreasing the number of incorporated water molecules, reducing the generated void volumes and promoting the OMIECs to undergo different phase transitions. Ultimately, the impact of these combined molecular processes is assessed in organic electrochemical transistors, revealing that careful balancing of these phenomena is required to maximize device performance.
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| 12. |
- Moser, Maximilian, et al.
(författare)
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Side Chain Redistribution as a Strategy to Boost Organic Electrochemical Transistor Performance and Stability
- 2020
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Ingår i: Advanced Materials. - : WILEY-V C H VERLAG GMBH. - 0935-9648 .- 1521-4095. ; 32
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Tidskriftsartikel (refereegranskat)abstract
- A series of glycolated polythiophenes for use in organic electrochemical transistors (OECTs) is designed and synthesized, differing in the distribution of their ethylene glycol chains that are tethered to the conjugated backbone. While side chain redistribution does not have a significant impact on the optoelectronic properties of the polymers, this molecular engineering strategy strongly impacts the water uptake achieved in the polymers. By careful optimization of the water uptake in the polymer films, OECTs with unprecedented steady-state performances in terms of [mu C*] and current retentions up to 98% over 700 electrochemical switching cycles are developed.
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| 13. |
- Zokaei, Sepideh, 1991, et al.
(författare)
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Toughening of a Soft Polar Polythiophene through Copolymerization with Hard Urethane Segments
- 2021
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Ingår i: Advanced Science. - : Wiley. - 2198-3844. ; 8:2
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Tidskriftsartikel (refereegranskat)abstract
- Polar polythiophenes with oligoethylene glycol side chains are exceedingly soft materials. A low glass transition temperature and low degree of crystallinity prevents their use as a bulk material. The synthesis of a copolymer comprising 1) soft polythiophene blocks with tetraethylene glycol side chains, and 2) hard urethane segments is reported. The molecular design is contrary to that of other semiconductor-insulator copolymers, which typically combine a soft nonconjugated spacer with hard conjugated segments. Copolymerization of polar polythiophenes and urethane segments results in a ductile material that can be used as a free-standing solid. The copolymer displays a storage modulus of 25 MPa at room temperature, elongation at break of 95%, and a reduced degree of swelling due to hydrogen bonding. Both chemical doping and electrochemical oxidation reveal that the introduction of urethane segments does not unduly reduce the hole charge-carrier mobility and ability to take up charge. Further, stable operation is observed when the copolymer is used as the active layer of organic electrochemical transistors.
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