| 1. |
- Franco Gonzalez, Juan Felipe, et al.
(författare)
-
Morphology of a self-doped conducting oligomer for green energy applications
- 2017
-
Ingår i: Nanoscale. - : Royal Society of Chemistry. - 2040-3364 .- 2040-3372. ; 9:36, s. 13717-13724
-
Tidskriftsartikel (refereegranskat)abstract
- A recently synthesized self-doped conducting oligomer, salt of bis[3,4-ethylenedioxythiophene]3thiophene butyric acid, ETE-S, is a novel promising material for green energy applications. Recently, it has been demonstrated that it can polymerize in vivo, in plant systems, leading to a formation of long-range conducting wires, charge storage and supercapacitive behaviour of living plants. Here we investigate the morphology of ETE-S combining the experimental characterisation using Grazing Incidence Wide Angle X-ray Scattering (GIWAXS) and atomistic molecular dynamics (MD) simulations. The GIWAXS measurements reveal a formation of small crystallites consisting of π–π stacked oligomers (with the staking distance 3.5 Å) that are further organized in h00 lamellae. These experimental results are confirmed by MD calculations, where we calculated the X-ray diffraction pattern and the radial distribution function for the distance between ETE-S chains. Our MD simulations also demonstrate the formation of the percolative paths for charge carriers that extend throughout the whole structure, despite the fact that the oligomers are short (6–9 rings) and crystallites are thin along the π–π stacking direction, consisting of only two or three π–π stacked oligomers. The existence of the percolative paths explains the previously observed high conductivity in in vivo polymerized ETE-S. We also explored the geometrical conformation of ETE-S oligomers and the bending of their aliphatic chains as a function of the oligomer lengths.
|
|
| 2. |
- Mantione, Daniele, et al.
(författare)
-
Thiophene-Based Trimers for In Vivo Electronic Functionalization of Tissues
- 2020
-
Ingår i: ACS APPLIED ELECTRONIC MATERIALS. - : AMER CHEMICAL SOC. - 2637-6113. ; 2:12, s. 4065-4071
-
Tidskriftsartikel (refereegranskat)abstract
- Electronic materials that can self-organize in vivo and form functional components along the tissue of interest can result in a seamless integration of the bioelectronic interface. Previously, we presented in vivo polymerization of the conjugated oligomer ETE-S in plants, forming conductors along the plant structure. The EDOT-thiophene-EDOT trimer with a sulfonate side group polymerized due to the native enzymatic activity of the plant and integrated within the plant cell wall. Here, we present the synthesis of three different conjugated trimers based on thiophene and EDOT or purely EDOT trimers that are able to polymerize enzymatically in physiological pH in vitro as well as in vivo along the roots of living plants. We show that by modulating the backbone and the side chain, we can tune the electronic properties of the resulting polymers as well as their localization and penetration within the root. Our work paves the way for the rational design of electronic materials that can self-organize in vivo for spatially controlled electronic functionalization of living tissue.
|
|
| 3. |
- Oikonomou, Vasileios, et al.
(författare)
-
eSoil : A low-power bioelectronic growth scaffold that enhances crop seedling growth
- 2024
-
Ingår i: Proceedings of the National Academy of Sciences of the United States of America. - : NATL ACAD SCIENCES. - 0027-8424 .- 1091-6490. ; 121:2
-
Tidskriftsartikel (refereegranskat)abstract
- Active hydroponic substrates that stimulate on demand the plant growth have not been demonstrated so far. Here, we developed the eSoil, a low-power bioelectronic growth scaffold that can provide electrical stimulation to the plants' root system and growth environment in hydroponics settings. eSoil's active material is an organic mixed ionic electronic conductor while its main structural component is cellulose, the most abundant biopolymer. We demonstrate that barley seedlings that are widely used for fodder grow within the eSoil with the root system integrated within its porous matrix. Simply by polarizing the eSoil, seedling growth is accelerated resulting in increase of dry weight on average by 50% after 15 d of growth. The effect is evident both on root and shoot development and occurs during the growth period after the stimulation. The stimulated plants reduce and assimilate NO-3more efficiently than controls, a finding that may have implications on minimizing fertilizer use. However, more studies are required to provide a mechanistic understanding of the physical and biological processes involved. eSoil opens the pathway for the development of active hydroponic scaffolds that may increase crop yield in a sustainable manner.
|
|
| 4. |
- Parker, Daniela, et al.
(författare)
-
Biohybrid plants with electronic roots via in vivo polymerization of conjugated oligomers
- 2021
-
Ingår i: Materials Horizons. - : Royal Society of Chemistry. - 2051-6347 .- 2051-6355. ; 8:12, s. 3295-3305
-
Tidskriftsartikel (refereegranskat)abstract
- Plant processes, ranging from photosynthesis through production of biomaterials to environmental sensing and adaptation, can be used in technology via integration of functional materials and devices. Previously, plants with integrated organic electronic devices and circuits distributed in their vascular tissue and organs have been demonstrated. To circumvent biological barriers, and thereby access the internal tissue, plant cuttings were used, which resulted in biohybrids with limited lifetime and use. Here, we report intact plants with electronic functionality that continue to grow and develop enabling plant-biohybrid systems that fully maintain their biological processes. The biocatalytic machinery of the plant cell wall was leveraged to seamlessly integrate conductors with mixed ionic-electronic conductivity along the root system of the plants. Cell wall peroxidases catalyzed ETE-S polymerization while the plant tissue served as the template, organizing the polymer in a favorable manner. The conductivity of the resulting p(ETE-S) roots reached the order of 10 S cm(-1) and remained stable over the course of 4 weeks while the roots continued to grow. The p(ETE-S) roots were used to build supercapacitors that outperform previous plant-biohybrid charge storage demonstrations. Plants were not affected by the electronic functionalization but adapted to this new hybrid state by developing a more complex root system. Biohybrid plants with electronic roots pave the way for autonomous systems with potential applications in energy, sensing and robotics.
|
|
| 5. |
|
|
| 6. |
- Routier, Cyril, et al.
(författare)
-
Chitosan-modified polyethyleneimine nanoparticles for enhancing the carboxylation reaction and plants' CO2 uptake
- 2023
-
Ingår i: ACS Nano. - : American Chemical Society (ACS). - 1936-0851 .- 1936-086X. ; 17:4, s. 3430-3441
-
Tidskriftsartikel (refereegranskat)abstract
- Increasing plants' photosynthetic efficiency is a major challenge that must be addressed in order to cover the food demands of the growing population in the changing climate. Photosynthesis is greatly limited at the initial carboxylation reaction, where CO2 is converted to the organic acid 3-PGA, catalyzed by the RuBisCO enzyme. RuBisCO has poor affinity for CO2, but also the CO2 concentration at the RuBisCO site is limited by the diffusion of atmospheric CO2 through the various leaf compartments to the reaction site. Beyond genetic engineering, nanotechnology can offer a materials-based approach for enhancing photosynthesis, and yet, it has mostly been explored for the light-dependent reactions. In this work, we developed polyethyleneimine-based nanoparticles for enhancing the carboxylation reaction. We demonstrate that the nanoparticles can capture CO2 in the form of bicarbonate and increase the CO2 that reacts with the RuBisCO enzyme, enhancing the 3-PGA production in in vitro assays by 20%. The nanoparticles can be introduced to the plant via leaf infiltration and, because of the functionalization with chitosan oligomers, they do not induce any toxic effect to the plant. In the leaves, the nanoparticles localize in the apoplastic space but also spontaneously reach the chloroplasts where photosynthetic activity takes place. Their CO2 loading-dependent fluorescence verifies that, in vivo, they maintain their ability to capture CO2 and can be therefore reloaded with atmospheric CO2 while in planta. Our results contribute to the development of a nanomaterials-based CO2-concentrating mechanism in plants that can potentially increase photosynthetic efficiency and overall plants' CO2 storage.
|
|
| 7. |
- Brooke, Robert, et al.
(författare)
-
Vapor phase synthesized poly(3,4-ethylenedioxy-thiophene)-trifluoromethanesulfonate as a transparent conductor material
- 2018
-
Ingår i: Journal of Materials Chemistry A. - : ROYAL SOC CHEMISTRY. - 2050-7488 .- 2050-7496. ; 6:43, s. 21304-21312
-
Tidskriftsartikel (refereegranskat)abstract
- Inorganic transparent conductive oxides have dominated the market as transparent electrodes due to their high conductivity and transparency. Here, we report the fabrication and optimization of the synthesis of poly(3,4-ethylenedioxythiophene) trifluoromethanesulfonate via vapor phase polymerization for the potential replacement of such inorganic materials. The parameters and conditions of the polymerization were investigated and an electrical conductivity of 3800 S cm(-1) and 4500 S cm(-1) after acid treatment were obtained while maintaining an absorbance similar to that of commercial indium tin oxide. This increase in electrical conductivity was rationalized experimentally and theoretically to an increase in the oxidation level and a higher order of crystallinity which does not disrupt the pi-pi stacking of PEDOT chains.
|
|
| 8. |
- Chen, Shangzhi, et al.
(författare)
-
Unraveling vertical inhomogeneity in vapour phase polymerized PEDOT:Tos films
- 2020
-
Ingår i: Journal of Materials Chemistry A. - : Royal Society of Chemistry. - 2050-7488 .- 2050-7496. ; 8, s. 18726-18734
-
Tidskriftsartikel (refereegranskat)abstract
- The conducting polymer poly(3,4-ethylenedioxythiophene) (PEDOT) forms a promising alternative to conventional inorganic conductors, where deposition of thin films via vapour phase polymerization (VPP) has gained particular interest owing to high electrical conductivity within the plane of the film. The conductivity perpendicular to the film is typically much lower, which may be related not only to preferential alignment of PEDOT crystallites but also to vertical stratification across the film. In this study, we reveal non-linear vertical microstructural variations across VPP PEDOT:Tos thin films, as well as significant differences in doping level between the top and bottom surfaces. The results are consistent with a VPP mechanism based on diffusion-limited transport of polymerization precursors. Conducting polymer films with vertical inhomogeneity may find applications in gradient-index optics, functionally graded thermoelectrics, and optoelectronic devices requiring gradient doping.
|
|
| 9. |
- Chen, Shangzhi, et al.
(författare)
-
Unraveling vertical inhomogeneity in vapour phase polymerized PEDOT:Tos films
- 2020
-
Ingår i: Journal of Materials Chemistry A. - : Royal Society of Chemistry. - 2050-7488 .- 2050-7496. ; 8:36, s. 18726-18734
-
Tidskriftsartikel (refereegranskat)abstract
- The conducting polymer poly(3,4-ethylenedioxythiophene) (PEDOT) forms a promising alternative to conventional inorganic conductors, where deposition of thin filmsviavapour phase polymerization (VPP) has gained particular interest owing to high electrical conductivity within the plane of the film. The conductivity perpendicular to the film is typically much lower, which may be related not only to preferential alignment of PEDOT crystallites but also to vertical stratification across the film. In this study, we reveal non-linear vertical microstructural variations across VPP PEDOT:Tos thin films, as well as significant differences in doping level between the top and bottom surfaces. The results are consistent with a VPP mechanism based on diffusion-limited transport of polymerization precursors. Conducting polymer films with vertical inhomogeneity may find applications in gradient-index optics, functionally graded thermoelectrics, and optoelectronic devices requiring gradient doping.
|
|
| 10. |
- Deribew, Dargie, et al.
(författare)
-
Crystallization-Driven Enhancement in Photovoltaic Performance through Block Copolymer Incorporation into P3HT:PCBM Blends
- 2013
-
Ingår i: Macromolecules. - : American Chemical Society (ACS). - 0024-9297 .- 1520-5835. ; 46:8, s. 3015-3024
-
Tidskriftsartikel (refereegranskat)abstract
- We report the increased crystallization of poly(3-hexylthiophene)(P3HT) in the donor−acceptor mixture of [6,6]-phenyl-C61-butyric acid methylester (PCBM) with P3HT by the addition of a block copolymer, P3HT-b-PI, where PI refers to polyisoprene. The photovoltaic performance of devices created using this blendis markedly improved by the addition of the diblock copolymer. We have characterizedthe structure of thin films of the P3HT-b-PI containing mixtures using opticalmicroscopy, scanning force microscopy, UV−vis absorption spectroscopy, neutronreflectometry, and grazing incidence X-ray diffraction (GIXD). The GIXD data providethe information on the crystallinity of the films, the absorption data were used toconfirm that the addition of the diblock was responsible for the increase in crystallization, neutron reflectometry data reveal a PCBM-rich region near the hole injection layer, and the two microscopy techniques revealed the structural effect of the crystallization at the surface of the films.
|
|
