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Internet-of-Everything (IoE) is defined as networked connections of things, people, data, and processes. IoE nodes, preferably shaped as printed flexible systems, serve as the frontier outpost of the Internet and comprise devices to record and regulate states and functions. To power distributed IoE nodes in an ecofriendly manner, a technology to scavenge energy from ambience and self-powered devices is developed. For this, piezoelectricity is regarded as a key property; however, the current technology typically based on polyvinylidene difluoride (PVDF) copolymers is expensive and produced via toxic protocols. We report piezoelectric characteristics of electrochemically poled cellulose nanofiber (CNF) thin films processed from water dispersions. Poling these films under humid conditions causes breaking and reorientation of CNF segments, which results in enhanced crystal alignment rendering the resulting material piezoelectric. Generators based on poled CNF show similar piezoelectric voltage and coefficient, here measured as d(33) = 46 pm V-1, to devices including PVDF copolymer layers of similar thickness. Our findings promise low-cost and printable ecofriendly piezoelectric-powered IoE nodes., Funding Agencies|Knut and Alice Wallenberg Foundation; Swedish Research Council [2016-06146, 2018- 04037, 2009-00971]; NCD- SWEET beamline of ALBA synchrotron in Barcelona, Spain; [VR 2016-05990]

Increasing plants photosynthetic efficienc y is a major challenge that must be addressed in order to cover the food demands of the growing population in the changing climate. Photosynthes i s 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 engineer-ing, 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 nanoparticl e s for enhancing the carbox-ylation 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 abi l i t y 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 t h a t can potentially increase photosynthetic efficiency and overall plants CO2 storage., Funding Agencies|European Union [800926, 101042148]; Swedish Research Council [VR-2017-04910]; Swedish Government Strategic Research Area in Materials Science on Advanced Functional Materials at Linkoping University [2009-00971]; MCIN/AEI [Ayuda RYC2021-031668-I]

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 NO3- more 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., Funding Agencies|University

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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., Funding Agencies|European UnionEuropean Commission [800926, 838171]; Swedish Research CouncilSwedish Research CouncilEuropean Commission [VR-2017-04910]; Knut and Alice Wallenberg FoundationKnut & Alice Wallenberg Foundation; Wallenberg Wood Science Center [KAW 2018.0452]; Swedish Government Strategic Research Area in Materials Science on Advanced Functional Materials at Linkoping University [2009-00971]; European Research Council (ERC)European Research Council (ERC)European Commission [834677]

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., The fulltext is published under a Creative Commons Attribution-NonCommercial 3.0 Unported Licence.https://creativecommons.org/licenses/by-nc/3.0

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., Funding Agencies|European UnionEuropean Union (EU) [800926]; MSCA-IF-2018 [838171]

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., European Union (EU); Horizon 2020; Research and Innovation Program; HyPhOE; MSCA-IF-2018; TEXTHIOL

We investigated the impact of singly occupied molecular orbital (SOMO) energy on the n-doping efficiency of benzimidazole derivatives. By designing and synthesizing a series of new air-stable benzimidazole-based dopants with different SOMO energy levels, we demonstrated that an increase of the dopant SOMO energy by only similar to 0.3 eV enhances the electrical conductivity of a benchmark electron-transporting naphthalenediimide-bithiophene polymer by more than 1 order of magnitude. By combining electrical, X-ray diffraction, and electron paramagnetic resonance measurements with density functional theory calculations and analytical transport simulations, we quantitatively characterized the conductivity, Seebeck coefficient, spin density, and crystallinity of the doped polymer as a function of the dopant SOMO energy. Our findings strongly indicate that charge and energy transport are dominated by the (relative) position of the SOMO level, whereas morphological differences appear to play a lesser role. These results set molecular-design guidelines for next-generation n-type dopants., Funding Agencies|Swedish Foundation for Strategic Research, VINNOVA [2015-04859]; Swedish Research CouncilSwedish Research Council [2016-03979]; AForsk [18-313]; Advanced Functional Materials Center at Linkoping University [2009-00971]; Regione LombardiaRegione Lombardia; Fondazione CariploFondazione Cariplo; SmartMatLab Centre project [2014-42639194]; Finnish Cultural FoundationFinnish Cultural Foundation; Universita degli Studi di Milano (Piano Sostegno alla Ricerca 2018 LINEA 2 Azione A-Giovani Ricercatori)

The technological interest in developing novel functional nano-objects that exhibit new properties arising from their nanoscopic nature is undoubtful. Although bulk ZnO is considered to be non-ferroelectric, herein, the ferroelectric behavior of undoped and self-standing ZnO nanoparticles is reported for the first time. The nanoparticles (NPs) under study are synthesized by an organometallic approach. When dispersed in a PMMA dielectric matrix, clear polarization loops and antisymmetric switching currents are recorded for the NPs with the larger volume, in coherence with the significant polar response of these NPs in solution, measured by polarization-resolved second harmonic scattering experiments. Structural characterizations reveal that ferroelectricity is related to the appearance of a new hexagonal crystalline phase, its unit cell being swelled with respect to the well-known wurtzite ZnO cell. The volume fraction of this new phase, the polar SHS response, and the amount of ferroelectric polarization response are all linearly linked, underlining the consistency between these complementary physical characterizations.

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., Funding Agencies|Knut and Alice Wallenberg Foundation; Swedish Energy Agency [38332-1]

Room temperature flexible heat harvesters based on conducting polymers are ideally suited to cover the energy demands of the modern nomadic society. The optimization of their thermoelectric efficiency is usually sought by tuning the oxidation levels of the conducting polymers, even if such methodology is detrimental to the Seebeck coefficient (S) as both the Seebeck coefficient and the electrical conductivity (sigma) are antagonistically related to the carrier concentration. Here we report a concurrent increase of S and sigma and we experimentally derive the dependence of Seebeck coefficient on charge carrier mobility for the first time in organic electronics. Through specific control of the conducting polymer synthesis, we enabled the formation of a denser percolation network that facilitated the charge transport and the thermodiffusion of the charge carriers inside the conducting polymer layer, while the material shifted from a Fermi glass towards a semi-metal, as its crystallinity increased. This work sheds light upon the origin of the thermoelectric properties of conducting polymers, but also underlines the importance of enhanced charge carrier mobility for the design of efficient thermoelectric polymers., Funding Agencies|Arkema; Region Aquitaine; Industrial Chair (Arkema/ANR) [AC-2013-365]; Region Aquitaine [20111101004]; Equipex ELORPrintTec [ANR-10-EQPX-28-01]; Labex AMADEUS [ANR-10-LABEX-0042-AMADEUS]; French state Initiative dExcellence IdEx [ANR-10-IDEX-003-02]

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., Funding agencies: Swedish Energy Agency [38332-1]; Knut and Alice Wallenberg Foundation; Marie Sklodowska Curie Individual Fellowship (MSCA-IF-EF-ST) [702641]

The response of sand stabilised with colloidal silica aqueous gel is examined in the laboratory, under direct shear, triaxial and normal compression loading, in comparison to that of untreated sand of similar density to evaluate the effect of stabilisation on subsequent sand response. The behaviour of the treated sand differs in important respects from the behaviour of the untreated sand: a significant increase in the angle of shearing resistance is observed at lower stress levels, diminishing with increasing stress level; the peak strength envelope is curved at low stresses for the treated sand only, while at ultimate strength, the envelopes coincide for treated and untreated sands. However, at all stress levels, extreme dilation is associated with the treated sand at peak and ultimate strength conditions. Under normal compression, the treated sand is easily densified, exhibiting higher compressibility than that of sand of similar density. It appears that depending on loading conditions, the aqueous gel alters its structure and has the capacity to absorb or discharge free water; it is of paramount importance to measure volume change and/or pore water pressure change during stabilised sand testing.