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The circadian clock in animals and humans plays crucial roles in multiple physiological processes. Disruption of circadian homeostasis causes detrimental effects. Here, it is demonstrated that the disruption of the circadian rhythm by genetic deletion of mouse brain and muscle ARNT-like 1 (Bmal1) gene, coding for the key clock transcription factor, augments an exacerbated fibrotic phenotype in various tumors. Accretion of cancer-associated fibroblasts (CAFs), especially the alpha smooth muscle actin positive myoCAFs, accelerates tumor growth rates and metastatic potentials. Mechanistically, deletion of Bmal1 abrogates expression of its transcriptionally targeted plasminogen activator inhibitor-1 (PAI-1). Consequently, decreased levels of PAI-1 in the tumor microenvironment instigate plasmin activation through upregulation of tissue plasminogen activator and urokinase plasminogen activator. The activated plasmin converts latent TGF-beta into its activated form, which potently induces tumor fibrosis and the transition of CAFs into myoCAFs, the latter promoting cancer metastasis. Pharmacological inhibition of the TGF-beta signaling largely ablates the metastatic potentials of colorectal cancer, pancreatic ductal adenocarcinoma, and hepatocellular carcinoma. Together, these data provide novel mechanistic insights into disruption of the circadian clock in tumor growth and metastasis. It is reasonably speculated that normalization of the circadian rhythm in patients provides a novel paradigm for cancer therapy., Funding Agencies|European Research Council (ERC) advanced grant ANGIOFAT [250021]; Swedish Research Council; Swedish Cancer Foundation; Swedish Childrens Cancer Foundation; Strategic Research Areas (SFO)-Stem Cell and Regenerative Medicine Foundation; Karolinska Institute Foundation; Karolinska Institute distinguished professor award; Torsten Soderbergs Foundation; Maud and Birger Gustavsson Foundation; NOVO Nordisk Foundation-Advance grant; NOVO Nordisk Foundation; Knut and Alice Wallenbergs Foundation; Robert Lundberg Memorial Foundation [2021-00668]; National Key R & D Program of China [2020YFC0846600]; Volkswagen Stiftung

The interfacial energetics are known to play a crucial role in organic diodes, transistors, and sensors. Designing the metal-organic interface has been a tool to optimize the performance of organic (opto)electronic devices, but this is not reported for organic thermoelectrics. In this work, it is demonstrated that the electrical power of organic thermoelectric generators (OTEGs) is also strongly dependent on the metal-organic interfacial energetics. Without changing the thermoelectric figure of merit (ZT) of polythiophene-based conducting polymers, the generated power of an OTEG can vary by three orders of magnitude simply by tuning the work function of the metal contact to reach above 1000 mu W cm(-2). The effective Seebeck coefficient (S-eff) of a metal/polymer/metal single leg OTEG includes an interfacial contribution (V-inter/Delta T) in addition to the intrinsic bulk Seebeck coefficient of the polythiophenes, such that S-eff = S + V-inter/Delta T varies from 22.7 mu V K-1 [9.4 mu V K-1] with Al to 50.5 mu V K-1 [26.3 mu V K-1] with Pt for poly(3,4-ethylenedioxythiophene):p-toluenesulfonate [poly(3,4-ethylenedioxythiophene):poly(4-styrenesulfonate)]. Spectroscopic techniques are used to reveal a redox interfacial reaction affecting locally the doping level of the polymer at the vicinity of the metal-organic interface and conclude that the energetics at the metal-polymer interface provides a new strategy to enhance the performance of OTEGs., Funding Agencies|Knut and Alice Wallenberg Foundation; EU [ESR 955837_HORATES]; Swedish Research Council [2016-06146, 2016-03979]; Forsk [18-313]; Academy of Finland Postdoctoral Researcher [340103]; EU H2020 Marie Sklodowska-Curie [101022777]; Swedish Foundation for Strategic Research (SiOS); Swedish Government Strategic Research Area in Materials Science on Advanced Functional Materials at Linkoeping University [2009-00971]

Terahertz (THz) technologies provide opportunities ranging from calibration targets for satellites and telescopes to communication devices and biomedical imaging systems. A main component will be broadband THz absorbers with switchability. However, optically switchable materials in THz are scarce and their modulation is mostly available at narrow bandwidths. Realizing materials with large and broadband modulation in absorption or transmission forms a critical challenge. This study demonstrates that conducting polymer-cellulose aerogels can provide modulation of broadband THz light with large modulation range from approximate to 13% to 91% absolute transmission, while maintaining specular reflection loss < -30 dB. The exceptional THz modulation is associated with the anomalous optical conductivity peak of conducting polymers, which enhances the absorption in its oxidized state. The study also demonstrates the possibility to reduce the surface hydrophilicity by simple chemical modifications, and shows that broadband absorption of the aerogels at optical frequencies enables de-frosting by solar-induced heating. These low-cost, aqueous solution-processable, sustainable, and bio-friendly aerogels may find use in next-generation intelligent THz devices., Funding Agencies|Swedish Research Council(VR); Swedish Foundation for Strategic Research (SSF); Stellenbosch Institute for Advanced Study (STIAS); Swedish Foundation for International Cooperation in Research and Higher Education (STINT); Knut and Alice Wallenberg Foundation; Swedish Government Strategic Research Area in Materials Science on Functional Materials at Linkping University [61831012]; National Natural Science Foundation of China (NFSC) [62131006, 52003202, 2023YFB381130005, 2021JDTD0026, 2023JDGD0012]; National Key Research and Development Program of China [2019-252]; Sichuan Province Science and Technology Support Program [2020-00287, 2022-00211]; Guangdong Science and Technology Major Special Fund [2022-06214]; Wallenberg Wood Science Center; [2009 00971]; [62311530115]; [62235004]

The circadian clock in animals and humans plays crucial roles in multiple physiological processes. Disruption of circadian homeostasis causes detrimental effects. Here, it is demonstrated that the disruption of the circadian rhythm by genetic deletion of mouse brain and muscle ARNT-like 1 (Bmal1) gene, coding for the key clock transcription factor, augments an exacerbated fibrotic phenotype in various tumors. Accretion of cancer-associated fibroblasts (CAFs), especially the alpha smooth muscle actin positive myoCAFs, accelerates tumor growth rates and metastatic potentials. Mechanistically, deletion of Bmal1 abrogates expression of its transcriptionally targeted plasminogen activator inhibitor-1 (PAI-1). Consequently, decreased levels of PAI-1 in the tumor microenvironment instigate plasmin activation through upregulation of tissue plasminogen activator and urokinase plasminogen activator. The activated plasmin converts latent TGF-beta into its activated form, which potently induces tumor fibrosis and the transition of CAFs into myoCAFs, the latter promoting cancer metastasis. Pharmacological inhibition of the TGF-beta signaling largely ablates the metastatic potentials of colorectal cancer, pancreatic ductal adenocarcinoma, and hepatocellular carcinoma. Together, these data provide novel mechanistic insights into disruption of the circadian clock in tumor growth and metastasis. It is reasonably speculated that normalization of the circadian rhythm in patients provides a novel paradigm for cancer therapy., Funding Agencies|European Research Council (ERC) advanced grant ANGIOFAT [250021]; Swedish Research Council; Swedish Cancer Foundation; Swedish Childrens Cancer Foundation; Strategic Research Areas (SFO)-Stem Cell and Regenerative Medicine Foundation; Karolinska Institute Foundation; Karolinska Institute distinguished professor award; Torsten Soderbergs Foundation; Maud and Birger Gustavsson Foundation; NOVO Nordisk Foundation-Advance grant; NOVO Nordisk Foundation; Knut and Alice Wallenbergs Foundation; Robert Lundberg Memorial Foundation [2021-00668]; National Key R & D Program of China [2020YFC0846600]; Volkswagen Stiftung

The circadian clock in animals and humans plays crucial roles in multiple physiological processes. Disruption of circadian homeostasis causes detrimental effects. Here, it is demonstrated that the disruption of the circadian rhythm by genetic deletion of mouse brain and muscle ARNT-like 1 (Bmal1) gene, coding for the key clock transcription factor, augments an exacerbated fibrotic phenotype in various tumors. Accretion of cancer-associated fibroblasts (CAFs), especially the alpha smooth muscle actin positive myoCAFs, accelerates tumor growth rates and metastatic potentials. Mechanistically, deletion of Bmal1 abrogates expression of its transcriptionally targeted plasminogen activator inhibitor-1 (PAI-1). Consequently, decreased levels of PAI-1 in the tumor microenvironment instigate plasmin activation through upregulation of tissue plasminogen activator and urokinase plasminogen activator. The activated plasmin converts latent TGF-beta into its activated form, which potently induces tumor fibrosis and the transition of CAFs into myoCAFs, the latter promoting cancer metastasis. Pharmacological inhibition of the TGF-beta signaling largely ablates the metastatic potentials of colorectal cancer, pancreatic ductal adenocarcinoma, and hepatocellular carcinoma. Together, these data provide novel mechanistic insights into disruption of the circadian clock in tumor growth and metastasis. It is reasonably speculated that normalization of the circadian rhythm in patients provides a novel paradigm for cancer therapy., Funding Agencies|European Research Council (ERC) advanced grant ANGIOFAT [250021]; Swedish Research Council; Swedish Cancer Foundation; Swedish Childrens Cancer Foundation; Strategic Research Areas (SFO)-Stem Cell and Regenerative Medicine Foundation; Karolinska Institute Foundation; Karolinska Institute distinguished professor award; Torsten Soderbergs Foundation; Maud and Birger Gustavsson Foundation; NOVO Nordisk Foundation-Advance grant; NOVO Nordisk Foundation; Knut and Alice Wallenbergs Foundation; Robert Lundberg Memorial Foundation [2021-00668]; National Key R & D Program of China [2020YFC0846600]; Volkswagen Stiftung

The interfacial energetics are known to play a crucial role in organic diodes, transistors, and sensors. Designing the metal-organic interface has been a tool to optimize the performance of organic (opto)electronic devices, but this is not reported for organic thermoelectrics. In this work, it is demonstrated that the electrical power of organic thermoelectric generators (OTEGs) is also strongly dependent on the metal-organic interfacial energetics. Without changing the thermoelectric figure of merit (ZT) of polythiophene-based conducting polymers, the generated power of an OTEG can vary by three orders of magnitude simply by tuning the work function of the metal contact to reach above 1000 mu W cm(-2). The effective Seebeck coefficient (S-eff) of a metal/polymer/metal single leg OTEG includes an interfacial contribution (V-inter/Delta T) in addition to the intrinsic bulk Seebeck coefficient of the polythiophenes, such that S-eff = S + V-inter/Delta T varies from 22.7 mu V K-1 [9.4 mu V K-1] with Al to 50.5 mu V K-1 [26.3 mu V K-1] with Pt for poly(3,4-ethylenedioxythiophene):p-toluenesulfonate [poly(3,4-ethylenedioxythiophene):poly(4-styrenesulfonate)]. Spectroscopic techniques are used to reveal a redox interfacial reaction affecting locally the doping level of the polymer at the vicinity of the metal-organic interface and conclude that the energetics at the metal-polymer interface provides a new strategy to enhance the performance of OTEGs., Funding Agencies|Knut and Alice Wallenberg Foundation; EU [ESR 955837_HORATES]; Swedish Research Council [2016-06146, 2016-03979]; Forsk [18-313]; Academy of Finland Postdoctoral Researcher [340103]; EU H2020 Marie Sklodowska-Curie [101022777]; Swedish Foundation for Strategic Research (SiOS); Swedish Government Strategic Research Area in Materials Science on Advanced Functional Materials at Linkoeping University [2009-00971]

Plant vasculature transports molecules that play a crucial role in plant signaling including systemic responses and acclimation to diverse environmental conditions. Targeted controlled delivery of molecules to the vascular tissue can be a biomimetic way to induce long distance responses, providing a new tool for the fundamental studies and engineering of stress-tolerant plants. Here, a flexible organic electronic ion pump, an electrophoretic delivery device, for controlled delivery of phytohormones directly in plant vascular tissue is developed. The c-OEIP is based on polyimide-coated glass capillaries that significantly enhance the mechanical robustness of these microscale devices while being minimally disruptive for the plant. The polyelectrolyte channel is based on low-cost and commercially available precursors that can be photocured with blue light, establishing much cheaper and safer system than the state-of-the-art. To trigger OEIP-induced plant response, the phytohormone abscisic acid (ABA) in the petiole of intact Arabidopsis plants is delivered. ABA is one of the main phytohormones involved in plant stress responses and induces stomata closure under drought conditions to reduce water loss and prevent wilting. The OEIP-mediated ABA delivery triggered fast and long-lasting stomata closure far away from the delivery point demonstrating systemic vascular transport of the delivered ABA, verified delivering deuterium-labeled ABA., Funding Agencies|European Union [800926 (FET-OPEN-HyPhOE)]; Swedish Foundation For Strategic Research; Swedish Foundation For Strategic Research [FFL18-0101]; Knut and Alice Wallenberg Foundation; Wallenberg Wood Science Center; Swedish Government Strategic Research Area in Materials Science on Advanced Functional Materials at Linkoeping University [2009-00971]; Swedish Research Council; Swedish Governmental Agency for Innovation Systems (VINNOVA)

Future brain-computer interfaces will require local and highly individualized signal processing of fully integrated electronic circuits within the nervous system and other living tissue. New devices will need to be developed that can receive data from a sensor array, process these data into meaningful information, and translate that information into a format that can be interpreted by living systems. Here, the first example of interfacing a hardware-based pattern classifier with a biological nerve is reported. The classifier implements the Widrow-Hoff learning algorithm on an array of evolvable organic electrochemical transistors (EOECTs). The EOECTs channel conductance is modulated in situ by electropolymerizing the semiconductor material within the channel, allowing for low voltage operation, high reproducibility, and an improvement in state retention by two orders of magnitude over state-of-the-art OECT devices. The organic classifier is interfaced with a biological nerve using an organic electrochemical spiking neuron to translate the classifiers output to a simulated action potential. The latter is then used to stimulate muscle contraction selectively based on the input pattern, thus paving the way for the development of adaptive neural interfaces for closed-loop therapeutic systems., Funding Agencies|Knut and Alice Wallenberg Foundation; Swedish Research Council [2018-06197, 2020-03243]; VINNOVA [2020-05223]; Swedish Foundation for Strategic Research [RMX18-0083]; European Research Council [834677]; European Commission [GA-964677]; Swedish Government Strategic Research Area in Materials Science on Functional Materials at Linkoping University [SFO-Mat-LiU 2009-00971]

Future brain-computer interfaces will require local and highly individualized signal processing of fully integrated electronic circuits within the nervous system and other living tissue. New devices will need to be developed that can receive data from a sensor array, process these data into meaningful information, and translate that information into a format that can be interpreted by living systems. Here, the first example of interfacing a hardware-based pattern classifier with a biological nerve is reported. The classifier implements the Widrow-Hoff learning algorithm on an array of evolvable organic electrochemical transistors (EOECTs). The EOECTs channel conductance is modulated in situ by electropolymerizing the semiconductor material within the channel, allowing for low voltage operation, high reproducibility, and an improvement in state retention by two orders of magnitude over state-of-the-art OECT devices. The organic classifier is interfaced with a biological nerve using an organic electrochemical spiking neuron to translate the classifiers output to a simulated action potential. The latter is then used to stimulate muscle contraction selectively based on the input pattern, thus paving the way for the development of adaptive neural interfaces for closed-loop therapeutic systems., Funding Agencies|Knut and Alice Wallenberg Foundation; Swedish Research Council [2018-06197, 2020-03243]; VINNOVA [2020-05223]; Swedish Foundation for Strategic Research [RMX18-0083]; European Research Council [834677]; European Commission [GA-964677]; Swedish Government Strategic Research Area in Materials Science on Functional Materials at Linkoping University [SFO-Mat-LiU 2009-00971]

Plant vasculature transports molecules that play a crucial role in plant signaling including systemic responses and acclimation to diverse environmental conditions. Targeted controlled delivery of molecules to the vascular tissue can be a biomimetic way to induce long distance responses, providing a new tool for the fundamental studies and engineering of stress-tolerant plants. Here, a flexible organic electronic ion pump, an electrophoretic delivery device, for controlled delivery of phytohormones directly in plant vascular tissue is developed. The c-OEIP is based on polyimide-coated glass capillaries that significantly enhance the mechanical robustness of these microscale devices while being minimally disruptive for the plant. The polyelectrolyte channel is based on low-cost and commercially available precursors that can be photocured with blue light, establishing much cheaper and safer system than the state-of-the-art. To trigger OEIP-induced plant response, the phytohormone abscisic acid (ABA) in the petiole of intact Arabidopsis plants is delivered. ABA is one of the main phytohormones involved in plant stress responses and induces stomata closure under drought conditions to reduce water loss and prevent wilting. The OEIP-mediated ABA delivery triggered fast and long-lasting stomata closure far away from the delivery point demonstrating systemic vascular transport of the delivered ABA, verified delivering deuterium-labeled ABA., Funding Agencies|European Union [800926 (FET-OPEN-HyPhOE)]; Swedish Foundation For Strategic Research; Swedish Foundation For Strategic Research [FFL18-0101]; Knut and Alice Wallenberg Foundation; Wallenberg Wood Science Center; Swedish Government Strategic Research Area in Materials Science on Advanced Functional Materials at Linkoeping University [2009-00971]; Swedish Research Council; Swedish Governmental Agency for Innovation Systems (VINNOVA)

Future brain-computer interfaces will require local and highly individualized signal processing of fully integrated electronic circuits within the nervous system and other living tissue. New devices will need to be developed that can receive data from a sensor array, process these data into meaningful information, and translate that information into a format that can be interpreted by living systems. Here, the first example of interfacing a hardware-based pattern classifier with a biological nerve is reported. The classifier implements the Widrow-Hoff learning algorithm on an array of evolvable organic electrochemical transistors (EOECTs). The EOECTs channel conductance is modulated in situ by electropolymerizing the semiconductor material within the channel, allowing for low voltage operation, high reproducibility, and an improvement in state retention by two orders of magnitude over state-of-the-art OECT devices. The organic classifier is interfaced with a biological nerve using an organic electrochemical spiking neuron to translate the classifiers output to a simulated action potential. The latter is then used to stimulate muscle contraction selectively based on the input pattern, thus paving the way for the development of adaptive neural interfaces for closed-loop therapeutic systems., Funding Agencies|Knut and Alice Wallenberg Foundation; Swedish Research Council [2018-06197, 2020-03243]; VINNOVA [2020-05223]; Swedish Foundation for Strategic Research [RMX18-0083]; European Research Council [834677]; European Commission [GA-964677]; Swedish Government Strategic Research Area in Materials Science on Functional Materials at Linkoping University [SFO-Mat-LiU 2009-00971]

Plant vasculature transports molecules that play a crucial role in plant signaling including systemic responses and acclimation to diverse environmental conditions. Targeted controlled delivery of molecules to the vascular tissue can be a biomimetic way to induce long distance responses, providing a new tool for the fundamental studies and engineering of stress-tolerant plants. Here, a flexible organic electronic ion pump, an electrophoretic delivery device, for controlled delivery of phytohormones directly in plant vascular tissue is developed. The c-OEIP is based on polyimide-coated glass capillaries that significantly enhance the mechanical robustness of these microscale devices while being minimally disruptive for the plant. The polyelectrolyte channel is based on low-cost and commercially available precursors that can be photocured with blue light, establishing much cheaper and safer system than the state-of-the-art. To trigger OEIP-induced plant response, the phytohormone abscisic acid (ABA) in the petiole of intact Arabidopsis plants is delivered. ABA is one of the main phytohormones involved in plant stress responses and induces stomata closure under drought conditions to reduce water loss and prevent wilting. The OEIP-mediated ABA delivery triggered fast and long-lasting stomata closure far away from the delivery point demonstrating systemic vascular transport of the delivered ABA, verified delivering deuterium-labeled ABA., Funding Agencies|European Union [800926 (FET-OPEN-HyPhOE)]; Swedish Foundation For Strategic Research; Swedish Foundation For Strategic Research [FFL18-0101]; Knut and Alice Wallenberg Foundation; Wallenberg Wood Science Center; Swedish Government Strategic Research Area in Materials Science on Advanced Functional Materials at Linkoeping University [2009-00971]; Swedish Research Council; Swedish Governmental Agency for Innovation Systems (VINNOVA)

Plant vasculature transports molecules that play a crucial role in plant signaling including systemic responses and acclimation to diverse environmental conditions. Targeted controlled delivery of molecules to the vascular tissue can be a biomimetic way to induce long distance responses, providing a new tool for the fundamental studies and engineering of stress-tolerant plants. Here, a flexible organic electronic ion pump, an electrophoretic delivery device, for controlled delivery of phytohormones directly in plant vascular tissue is developed. The c-OEIP is based on polyimide-coated glass capillaries that significantly enhance the mechanical robustness of these microscale devices while being minimally disruptive for the plant. The polyelectrolyte channel is based on low-cost and commercially available precursors that can be photocured with blue light, establishing much cheaper and safer system than the state-of-the-art. To trigger OEIP-induced plant response, the phytohormone abscisic acid (ABA) in the petiole of intact Arabidopsis plants is delivered. ABA is one of the main phytohormones involved in plant stress responses and induces stomata closure under drought conditions to reduce water loss and prevent wilting. The OEIP-mediated ABA delivery triggered fast and long-lasting stomata closure far away from the delivery point demonstrating systemic vascular transport of the delivered ABA, verified delivering deuterium-labeled ABA., Funding Agencies|European Union [800926 (FET-OPEN-HyPhOE)]; Swedish Foundation For Strategic Research; Swedish Foundation For Strategic Research [FFL18-0101]; Knut and Alice Wallenberg Foundation; Wallenberg Wood Science Center; Swedish Government Strategic Research Area in Materials Science on Advanced Functional Materials at Linkoeping University [2009-00971]; Swedish Research Council; Swedish Governmental Agency for Innovation Systems (VINNOVA)

Future brain-computer interfaces will require local and highly individualized signal processing of fully integrated electronic circuits within the nervous system and other living tissue. New devices will need to be developed that can receive data from a sensor array, process these data into meaningful information, and translate that information into a format that can be interpreted by living systems. Here, the first example of interfacing a hardware-based pattern classifier with a biological nerve is reported. The classifier implements the Widrow-Hoff learning algorithm on an array of evolvable organic electrochemical transistors (EOECTs). The EOECTs channel conductance is modulated in situ by electropolymerizing the semiconductor material within the channel, allowing for low voltage operation, high reproducibility, and an improvement in state retention by two orders of magnitude over state-of-the-art OECT devices. The organic classifier is interfaced with a biological nerve using an organic electrochemical spiking neuron to translate the classifiers output to a simulated action potential. The latter is then used to stimulate muscle contraction selectively based on the input pattern, thus paving the way for the development of adaptive neural interfaces for closed-loop therapeutic systems., Funding Agencies|Knut and Alice Wallenberg Foundation; Swedish Research Council [2018-06197, 2020-03243]; VINNOVA [2020-05223]; Swedish Foundation for Strategic Research [RMX18-0083]; European Research Council [834677]; European Commission [GA-964677]; Swedish Government Strategic Research Area in Materials Science on Functional Materials at Linkoping University [SFO-Mat-LiU 2009-00971]

The interfacial energetics are known to play a crucial role in organic diodes, transistors, and sensors. Designing the metal-organic interface has been a tool to optimize the performance of organic (opto)electronic devices, but this is not reported for organic thermoelectrics. In this work, it is demonstrated that the electrical power of organic thermoelectric generators (OTEGs) is also strongly dependent on the metal-organic interfacial energetics. Without changing the thermoelectric figure of merit (ZT) of polythiophene-based conducting polymers, the generated power of an OTEG can vary by three orders of magnitude simply by tuning the work function of the metal contact to reach above 1000 mu W cm(-2). The effective Seebeck coefficient (S-eff) of a metal/polymer/metal single leg OTEG includes an interfacial contribution (V-inter/Delta T) in addition to the intrinsic bulk Seebeck coefficient of the polythiophenes, such that S-eff = S + V-inter/Delta T varies from 22.7 mu V K-1 [9.4 mu V K-1] with Al to 50.5 mu V K-1 [26.3 mu V K-1] with Pt for poly(3,4-ethylenedioxythiophene):p-toluenesulfonate [poly(3,4-ethylenedioxythiophene):poly(4-styrenesulfonate)]. Spectroscopic techniques are used to reveal a redox interfacial reaction affecting locally the doping level of the polymer at the vicinity of the metal-organic interface and conclude that the energetics at the metal-polymer interface provides a new strategy to enhance the performance of OTEGs., Funding Agencies|Knut and Alice Wallenberg Foundation; EU [ESR 955837_HORATES]; Swedish Research Council [2016-06146, 2016-03979]; Forsk [18-313]; Academy of Finland Postdoctoral Researcher [340103]; EU H2020 Marie Sklodowska-Curie [101022777]; Swedish Foundation for Strategic Research (SiOS); Swedish Government Strategic Research Area in Materials Science on Advanced Functional Materials at Linkoeping University [2009-00971]

Plant vasculature transports molecules that play a crucial role in plant signaling including systemic responses and acclimation to diverse environmental conditions. Targeted controlled delivery of molecules to the vascular tissue can be a biomimetic way to induce long distance responses, providing a new tool for the fundamental studies and engineering of stress-tolerant plants. Here, a flexible organic electronic ion pump, an electrophoretic delivery device, for controlled delivery of phytohormones directly in plant vascular tissue is developed. The c-OEIP is based on polyimide-coated glass capillaries that significantly enhance the mechanical robustness of these microscale devices while being minimally disruptive for the plant. The polyelectrolyte channel is based on low-cost and commercially available precursors that can be photocured with blue light, establishing much cheaper and safer system than the state-of-the-art. To trigger OEIP-induced plant response, the phytohormone abscisic acid (ABA) in the petiole of intact Arabidopsis plants is delivered. ABA is one of the main phytohormones involved in plant stress responses and induces stomata closure under drought conditions to reduce water loss and prevent wilting. The OEIP-mediated ABA delivery triggered fast and long-lasting stomata closure far away from the delivery point demonstrating systemic vascular transport of the delivered ABA, verified delivering deuterium-labeled ABA., Funding Agencies|European Union [800926 (FET-OPEN-HyPhOE)]; Swedish Foundation For Strategic Research; Swedish Foundation For Strategic Research [FFL18-0101]; Knut and Alice Wallenberg Foundation; Wallenberg Wood Science Center; Swedish Government Strategic Research Area in Materials Science on Advanced Functional Materials at Linkoeping University [2009-00971]; Swedish Research Council; Swedish Governmental Agency for Innovation Systems (VINNOVA)

Future brain-computer interfaces will require local and highly individualized signal processing of fully integrated electronic circuits within the nervous system and other living tissue. New devices will need to be developed that can receive data from a sensor array, process these data into meaningful information, and translate that information into a format that can be interpreted by living systems. Here, the first example of interfacing a hardware-based pattern classifier with a biological nerve is reported. The classifier implements the Widrow-Hoff learning algorithm on an array of evolvable organic electrochemical transistors (EOECTs). The EOECTs channel conductance is modulated in situ by electropolymerizing the semiconductor material within the channel, allowing for low voltage operation, high reproducibility, and an improvement in state retention by two orders of magnitude over state-of-the-art OECT devices. The organic classifier is interfaced with a biological nerve using an organic electrochemical spiking neuron to translate the classifiers output to a simulated action potential. The latter is then used to stimulate muscle contraction selectively based on the input pattern, thus paving the way for the development of adaptive neural interfaces for closed-loop therapeutic systems., Funding Agencies|Knut and Alice Wallenberg Foundation; Swedish Research Council [2018-06197, 2020-03243]; VINNOVA [2020-05223]; Swedish Foundation for Strategic Research [RMX18-0083]; European Research Council [834677]; European Commission [GA-964677]; Swedish Government Strategic Research Area in Materials Science on Functional Materials at Linkoping University [SFO-Mat-LiU 2009-00971]

Cellulose opens for sustainable materials suitable for radiative cooling thanks to inherent high thermal emissivity combined with low solar absorptance. When desired, solar absorptance can be introduced by additives such as carbon black. However, such materials still shows high thermal emissivity and therefore performs radiative cooling that counteracts the heating process if exposed to the sky. Here, this is addressed by a cellulose-carbon black composite with low mid-infrared (MIR) emissivity and corresponding suppressed radiative cooling thanks to a transparent IR-reflecting indium tin oxide coating. The resulting solar heater provides opposite optical properties in both the solar and thermal ranges compared to the cooler material in the form of solar-reflecting electrospun cellulose. Owing to these differences, exposing the two materials to the sky generated spontaneous temperature differences, as used to power an ionic thermoelectric device in both daytime and nighttime. The study characterizes these effects in detail using solar and sky simulators and through outdoor measurements. Using the concept to power ionic thermoelectric devices shows thermovoltages of >60 mV and 10 degrees C temperature differences already at moderate solar irradiance of approximate to 400 W m(-2)., Funding Agencies|Wallenberg Wood Science Center; Swedish Government Strategic Research Area in Materials Science on Functional Materials at Linkoping University [2009 00971]; Swedish Research Council [2018-04037, 2020-00287]; Knut and Alice Wallenberg Foundation; Linkoeping University

Cellulose opens for sustainable materials suitable for radiative cooling thanks to inherent high thermal emissivity combined with low solar absorptance. When desired, solar absorptance can be introduced by additives such as carbon black. However, such materials still shows high thermal emissivity and therefore performs radiative cooling that counteracts the heating process if exposed to the sky. Here, this is addressed by a cellulose-carbon black composite with low mid-infrared (MIR) emissivity and corresponding suppressed radiative cooling thanks to a transparent IR-reflecting indium tin oxide coating. The resulting solar heater provides opposite optical properties in both the solar and thermal ranges compared to the cooler material in the form of solar-reflecting electrospun cellulose. Owing to these differences, exposing the two materials to the sky generated spontaneous temperature differences, as used to power an ionic thermoelectric device in both daytime and nighttime. The study characterizes these effects in detail using solar and sky simulators and through outdoor measurements. Using the concept to power ionic thermoelectric devices shows thermovoltages of >60 mV and 10 degrees C temperature differences already at moderate solar irradiance of approximate to 400 W m(-2)., Funding Agencies|Wallenberg Wood Science Center; Swedish Government Strategic Research Area in Materials Science on Functional Materials at Linkoping University [2009 00971]; Swedish Research Council [2018-04037, 2020-00287]; Knut and Alice Wallenberg Foundation; Linkoeping University

Cellulose opens for sustainable materials suitable for radiative cooling thanks to inherent high thermal emissivity combined with low solar absorptance. When desired, solar absorptance can be introduced by additives such as carbon black. However, such materials still shows high thermal emissivity and therefore performs radiative cooling that counteracts the heating process if exposed to the sky. Here, this is addressed by a cellulose-carbon black composite with low mid-infrared (MIR) emissivity and corresponding suppressed radiative cooling thanks to a transparent IR-reflecting indium tin oxide coating. The resulting solar heater provides opposite optical properties in both the solar and thermal ranges compared to the cooler material in the form of solar-reflecting electrospun cellulose. Owing to these differences, exposing the two materials to the sky generated spontaneous temperature differences, as used to power an ionic thermoelectric device in both daytime and nighttime. The study characterizes these effects in detail using solar and sky simulators and through outdoor measurements. Using the concept to power ionic thermoelectric devices shows thermovoltages of >60 mV and 10 degrees C temperature differences already at moderate solar irradiance of approximate to 400 W m(-2)., Funding Agencies|Wallenberg Wood Science Center; Swedish Government Strategic Research Area in Materials Science on Functional Materials at Linkoping University [2009 00971]; Swedish Research Council [2018-04037, 2020-00287]; Knut and Alice Wallenberg Foundation; Linkoeping University

Cellulose opens for sustainable materials suitable for radiative cooling thanks to inherent high thermal emissivity combined with low solar absorptance. When desired, solar absorptance can be introduced by additives such as carbon black. However, such materials still shows high thermal emissivity and therefore performs radiative cooling that counteracts the heating process if exposed to the sky. Here, this is addressed by a cellulose-carbon black composite with low mid-infrared (MIR) emissivity and corresponding suppressed radiative cooling thanks to a transparent IR-reflecting indium tin oxide coating. The resulting solar heater provides opposite optical properties in both the solar and thermal ranges compared to the cooler material in the form of solar-reflecting electrospun cellulose. Owing to these differences, exposing the two materials to the sky generated spontaneous temperature differences, as used to power an ionic thermoelectric device in both daytime and nighttime. The study characterizes these effects in detail using solar and sky simulators and through outdoor measurements. Using the concept to power ionic thermoelectric devices shows thermovoltages of >60 mV and 10 degrees C temperature differences already at moderate solar irradiance of approximate to 400 W m(-2)., Funding Agencies|Wallenberg Wood Science Center; Swedish Government Strategic Research Area in Materials Science on Functional Materials at Linkoping University [2009 00971]; Swedish Research Council [2018-04037, 2020-00287]; Knut and Alice Wallenberg Foundation; Linkoeping University

Cellulose opens for sustainable materials suitable for radiative cooling thanks to inherent high thermal emissivity combined with low solar absorptance. When desired, solar absorptance can be introduced by additives such as carbon black. However, such materials still shows high thermal emissivity and therefore performs radiative cooling that counteracts the heating process if exposed to the sky. Here, this is addressed by a cellulose-carbon black composite with low mid-infrared (MIR) emissivity and corresponding suppressed radiative cooling thanks to a transparent IR-reflecting indium tin oxide coating. The resulting solar heater provides opposite optical properties in both the solar and thermal ranges compared to the cooler material in the form of solar-reflecting electrospun cellulose. Owing to these differences, exposing the two materials to the sky generated spontaneous temperature differences, as used to power an ionic thermoelectric device in both daytime and nighttime. The study characterizes these effects in detail using solar and sky simulators and through outdoor measurements. Using the concept to power ionic thermoelectric devices shows thermovoltages of >60 mV and 10 degrees C temperature differences already at moderate solar irradiance of approximate to 400 W m(-2)., Funding Agencies|Wallenberg Wood Science Center; Swedish Government Strategic Research Area in Materials Science on Functional Materials at Linkoping University [2009 00971]; Swedish Research Council [2018-04037, 2020-00287]; Knut and Alice Wallenberg Foundation; Linkoeping University

Electrochemical valorization of biomass waste (e.g., glycerol) for production of value-added products (such as formic acid) in parallel with hydrogen production holds great potential for developing renewable and clean energy sources. Here, a synergistic effort between theoretical calculations at the atomic level and experiments to predict and validate a promising oxide catalyst for the glycerol oxidation reaction (GOR) are reported, providing a good example of designing novel, cost-effective, and highly efficient electrocatalysts for producing value-added products at the anode and high-purity hydrogen at the cathode. The predicted CoMoO4 catalyst is experimentally validated as a suitable catalyst for GOR and found to perform best among the investigated metal (Mn, Co, Ni) molybdate counterparts. The potential required to reach 10 mA cm(-2) is 1.105 V at 60 degrees C in an electrolyte of 1.0 m KOH with 0.1 m glycerol, which is 314 mV lower than for oxygen evolution. The GOR reaction pathway and mechanism based on this CoMoO4 catalyst are revealed by high-performance liquid chromatography and in situ Raman analysis. The coupled quantitative analysis indicates that the CoMoO4 catalyst is highly active toward C-C cleavage, thus presenting a high selectivity (92%) and Faradaic efficiency (90%) for formate production.

Desalination by capacitive deionization (CDI) is a promising technique to combine desalination and energy storage. The efficiency of charge storage process, which is equivalent to the desalination process, depends strongly on the presence of Faradic side reactions on the electrode. Herein, the performance of a new low-cost designed flow-through electrode with porous carbon nanoparticles (CP) coating on carbon-fiber paper (CFP) is evaluated. The CP layer enables high capacitance while the CFP core makes fluid dynamics along and across the electrode. The electrodes are evaluated by studying the effective operational CDI parameters, such as operational voltage, degassing of electrolyte, and salt concentration. The Faradic side reaction and its effect on charge efficiency (CE) are evaluated which are estimated to decrease to 46% by liquid flow bringing dissolved oxygen from the air-electrolyte interface to the electrode. The CE enhances to 59% with a salt concentration of 1 m. By purging N-2 gas, CE is much higher (>85%) with a maximum efficiency of 97% at 0.6 V. Three regimes of the complex kinetic of side reactions are found involving various species such as O-2, H2O2, H-2, and carbon oxidation and the implication of those regimes for real applications are discussed., Funding Agencies|Swedish Research Council [VR 2016-05990]; Knut and Alice Wallenberg Foundation [KAW 2018.0058]; Swedish Energy Agency [P52023-1]; Swedish Government Strategic Research Area in Materials Science on Advanced Functional Materials at Linkoeping University [2009-00971]

Perovskite solar cells (PSCs) suffer from significant nonradiative recombination at perovskite/charge transport layer heterojunction, seriously limiting their power conversion efficiencies. Herein, solution-processed chromium multioxide (CrOx) is judiciously selected to construct a MAPbI(3)/CrOx/Spiro-OMeTAD hole-selective heterojunction. It is demonstrated that the inserted CrOx not only effectively reduces defect sites via redox shuttle at perovskite contact, but also decreases valence band maximum (VBM)-HOMO offset between perovskite and Spiro-OMeTAD. This will diminish thermionic losses for collecting holes and thus promote charge transport across the heterojunction, suppressing both defect-assisted recombination and interface carrier recombination. As a result, a remarkable improvement of 21.21% efficiency with excellent device stability is achieved compared to 18.46% of the control device, which is among the highest efficiencies for polycrystalline MAPbI(3) based n-i-p planar PSCs reported to date. These findings of this work provide new insights into novel charge-selective heterojunctions for further enhancing efficiency and stability of PSCs., Funding Agencies|National Science Foundation of China [21875067]; Shanghai Science and Technology Innovation Action Plan [22ZR1418900]; Fundamental Research Funds for the Central Universities; Shanghai Rising-Star [19QA1403100]; East China Normal University (ECNU) Multifunctional Platform for Innovation; open research fund of Songshan Lake Materials Laboratory [2021SLABFK02]; National Key Research and Development Program of China [2017YFA0206600]; National Natural Science Foundation of China [51922032, 21961160720]

The drawbacks of current state-of-the-art selective membranes, such as poor barrier properties, high cost, and poor recyclability, limit the large-scale deployment of electrochemical energy devices such as redox flow batteries (RFBs) and fuel cells. In recent years, cellulosic nanomaterials have been proposed as a low-cost and green raw material for such membranes, but their performance in RFBs and fuel cells is typically poorer than that of the sulfonated fluoropolymer ionomer membranes such as Nafion. Herein, sulfonated cellulose nanofibrils densely cross-linked to form a compact sulfonated cellulose membrane with limited swelling and good stability in water are used. The membranes possess low porosity and excellent ionic transport properties. A model aqueous organic redox flow battery (AORFB) with alizarin red S as negolyte and tiron as posolyte is assembled with the sulfonated cellulose membrane. The performance of the nanocellulose-based battery is superior in terms of cyclability in comparison to that displayed by the battery assembled with commercially available Nafion 115 due to the mitigation of crossover of the redox-active components. This finding paves the way to new green organic materials for fully sustainable AORFB solutions., Funding Agencies|VINNOVA (Digital Cellulose Center); BillerudKorsnas; Knut and Alice Wallenberg foundation [KAW 2019.0604, KAW 2021.0195]; Swedish Energy Agency [52023-1]; Vetenskapradet [2016-05990]

Solid-state precipitation can be used to tailor material properties, ranging from ferromagnets and catalysts to mechanical strengthening and energy storage. Thermoelectric properties can be modified by precipitation to enhance phonon scattering while retaining charge-carrier transmission. Here, unconventional Janus-type nanoprecipitates are uncovered in Mg3Sb1.5Bi0.5 formed by side-by-side Bi- and Ge-rich appendages, in contrast to separate nanoprecipitate formation. These Janus nanoprecipitates result from local comelting of Bi and Ge during sintering, enabling an amorphous-like lattice thermal conductivity. A precipitate size effect on phonon scattering is observed due to the balance between alloy-disorder and nanoprecipitate scattering. The thermoelectric figure-of-merit ZT reaches 0.6 near room temperature and 1.6 at 773 K. The Janus nanoprecipitation can be introduced into other materials and may act as a general property-tailoring mechanism., Funding Agencies|National Key Research and Development Program of China [2018YFB0703600]; National Natural Science Foundation of China [51872133]; Guangdong Innovative and Entrepreneurial Research Team Program [2016ZT06G587]; Guangdong Provincial Key Laboratory Program from the Department of Science and Technology of Guangdong Province [2021B1212040001]; Tencent Foundation through the XPLORER PRIZE; Swedish Government Strategic Research Area in Materials Science on Functional Materials at Linkoping University (Faculty Grant SFO-Mat-LiU) [2009 00971]; Knut and Alice Wallenberg foundation through the Wallenberg Academy Fellows program [KAW-2020.0196]; Swedish Foundation for Strategic Research (SSF) [RIF 14-0074]; German Science Foundation (DFG) [SFB 917]

On-surface synthesis has recently emerged as a powerful strategy to design conjugated polymers previously precluded in conventional solution chemistry. Here, an N-containing pentacene-based precursor (tetraazapentacene) is ex-professo synthesized endowed with terminal dibromomethylene (:CBr2) groups to steer homocoupling via dehalogenation on metallic supports. Combined scanning probe microscopy investigations complemented by theoretical calculations reveal how the substrate selection drives different reaction mechanisms. On Ag(111) the dissociation of bromine atoms at room temperature triggers the homocoupling of tetraazapentacene units together with the binding of silver adatoms to the nitrogen atoms of the monomers giving rise to a N-containing conjugated coordination polymer (P1). Subsequently, P1 undergoes ladderization at 200 degrees C, affording a pyrrolopyrrole-bridged conjugated polymer (P2). On Au(111) the formation of the intermediate polymer P1 is not observed and, instead, after annealing at 100 degrees C, the conjugated ladder polymer P2 is obtained, revealing the crucial role of metal adatoms on Ag(111) as compared to Au(111). Finally, on Ag(100) the loss of :CBr2 groups affords the formation of tetraazapentacene monomers, which coexist with polymer P1. Our results contribute to introduce protocols for the synthesis of N-containing conjugated polymers, illustrating the selective role of the metallic support in the underlying reaction mechanisms., Funding Agencies|European Research Council (ERC CoG ELECNANO) [766555]; Comunidad de Madrid [project QUIMTRONIC-CM] [Y2018/NMT-4783]; Ministerio de Ciencia e Innovacion [PID2019-108532GB-I00]; "Severo Ochoa" Programme for Centers of Excellence in RD (MINECO) [SEV-2016-0686]; European Unions Horizon 2020 research and innovation programme under the Marie Skodowska-Curie grant [886314]; Swedish Research Council; Swedish Government Strategic Research Area in Materials Science on Functional Materials at Linkoping University (Faculty Grant SFO-Mat-LiU) [2009 00971]

Optical nanoantennas provide control of light at the nanoscale, which makes them important for diverse areas ranging from photocatalysis and flat metaoptics to sensors and biomolecular tweezing. They have traditionally been limited to metallic and dielectric nanostructures that sustain plasmonic and Mie resonances, respectively. More recently, nanostructures of organic J-aggregate excitonic materials have been proposed capable of also supporting nanooptical resonances, although their advance has been hampered from difficulty in nanostructuring. Here, the authors present the realization of organic J-aggregate excitonic nanostructures, using nanocylinder arrays as model system. Extinction spectra show that they can sustain both plasmon-like resonances and dielectric resonances, owing to the material providing negative and large positive permittivity regions at the different sides of its exciton resonance. Furthermore, it is found that the material is highly anisotropic, leading to hyperbolic and elliptic permittivity regions. Nearfield analysis using optical simulation reveals that the nanostructures therefore support hyperbolic localized surface exciton resonances and elliptic Mie resonances, neither of which has been previously demonstrated for this type of material. The anisotropic nanostructures form a new type of optical nanoantennas, which combined with the presented fabrication process opens up for applications such as fully organic excitonic metasurfaces., Funding Agencies|AngstromForsk Foundation; Knut and Alice Wallenberg Foundation; Swedish Research Council (VR); Swedish Foundation for Strategic Research (SSF); Swedish Government Strategic Research Area in Materials Science on Functional Materials at Linkoping University [2009 00971]; National Research Foundation of Korea (NRF) [2020R1A2C1102558]; Commercializations Promotion Agency for R&D Outcomes Grant (2022, Research Equipment Technician Training Program) - Korea government (MSIT) [2018R1A6A9056986]; Regional Innovation Strategy (RIS) - Ministry of Education (MOE) [2021RIS-001]; Korea Evaluation Institute of Industrial Technology (KEIT) [20015764]; Korea government (MOTIE) [20005750]

Perovskite solar cells (PSCs) suffer from significant nonradiative recombination at perovskite/charge transport layer heterojunction, seriously limiting their power conversion efficiencies. Herein, solution-processed chromium multioxide (CrOx) is judiciously selected to construct a MAPbI(3)/CrOx/Spiro-OMeTAD hole-selective heterojunction. It is demonstrated that the inserted CrOx not only effectively reduces defect sites via redox shuttle at perovskite contact, but also decreases valence band maximum (VBM)-HOMO offset between perovskite and Spiro-OMeTAD. This will diminish thermionic losses for collecting holes and thus promote charge transport across the heterojunction, suppressing both defect-assisted recombination and interface carrier recombination. As a result, a remarkable improvement of 21.21% efficiency with excellent device stability is achieved compared to 18.46% of the control device, which is among the highest efficiencies for polycrystalline MAPbI(3) based n-i-p planar PSCs reported to date. These findings of this work provide new insights into novel charge-selective heterojunctions for further enhancing efficiency and stability of PSCs., Funding Agencies|National Science Foundation of China [21875067]; Shanghai Science and Technology Innovation Action Plan [22ZR1418900]; Fundamental Research Funds for the Central Universities; Shanghai Rising-Star [19QA1403100]; East China Normal University (ECNU) Multifunctional Platform for Innovation; open research fund of Songshan Lake Materials Laboratory [2021SLABFK02]; National Key Research and Development Program of China [2017YFA0206600]; National Natural Science Foundation of China [51922032, 21961160720]

Perovskite solar cells (PSCs) suffer from significant nonradiative recombination at perovskite/charge transport layer heterojunction, seriously limiting their power conversion efficiencies. Herein, solution-processed chromium multioxide (CrOx) is judiciously selected to construct a MAPbI(3)/CrOx/Spiro-OMeTAD hole-selective heterojunction. It is demonstrated that the inserted CrOx not only effectively reduces defect sites via redox shuttle at perovskite contact, but also decreases valence band maximum (VBM)-HOMO offset between perovskite and Spiro-OMeTAD. This will diminish thermionic losses for collecting holes and thus promote charge transport across the heterojunction, suppressing both defect-assisted recombination and interface carrier recombination. As a result, a remarkable improvement of 21.21% efficiency with excellent device stability is achieved compared to 18.46% of the control device, which is among the highest efficiencies for polycrystalline MAPbI(3) based n-i-p planar PSCs reported to date. These findings of this work provide new insights into novel charge-selective heterojunctions for further enhancing efficiency and stability of PSCs., Funding Agencies|National Science Foundation of China [21875067]; Shanghai Science and Technology Innovation Action Plan [22ZR1418900]; Fundamental Research Funds for the Central Universities; Shanghai Rising-Star [19QA1403100]; East China Normal University (ECNU) Multifunctional Platform for Innovation; open research fund of Songshan Lake Materials Laboratory [2021SLABFK02]; National Key Research and Development Program of China [2017YFA0206600]; National Natural Science Foundation of China [51922032, 21961160720]

Electrochemical valorization of biomass waste (e.g., glycerol) for production of value-added products (such as formic acid) in parallel with hydrogen production holds great potential for developing renewable and clean energy sources. Here, a synergistic effort between theoretical calculations at the atomic level and experiments to predict and validate a promising oxide catalyst for the glycerol oxidation reaction (GOR) are reported, providing a good example of designing novel, cost-effective, and highly efficient electrocatalysts for producing value-added products at the anode and high-purity hydrogen at the cathode. The predicted CoMoO4 catalyst is experimentally validated as a suitable catalyst for GOR and found to perform best among the investigated metal (Mn, Co, Ni) molybdate counterparts. The potential required to reach 10 mA cm(-2) is 1.105 V at 60 degrees C in an electrolyte of 1.0 m KOH with 0.1 m glycerol, which is 314 mV lower than for oxygen evolution. The GOR reaction pathway and mechanism based on this CoMoO4 catalyst are revealed by high-performance liquid chromatography and in situ Raman analysis. The coupled quantitative analysis indicates that the CoMoO4 catalyst is highly active toward C-C cleavage, thus presenting a high selectivity (92%) and Faradaic efficiency (90%) for formate production.

The drawbacks of current state-of-the-art selective membranes, such as poor barrier properties, high cost, and poor recyclability, limit the large-scale deployment of electrochemical energy devices such as redox flow batteries (RFBs) and fuel cells. In recent years, cellulosic nanomaterials have been proposed as a low-cost and green raw material for such membranes, but their performance in RFBs and fuel cells is typically poorer than that of the sulfonated fluoropolymer ionomer membranes such as Nafion. Herein, sulfonated cellulose nanofibrils densely cross-linked to form a compact sulfonated cellulose membrane with limited swelling and good stability in water are used. The membranes possess low porosity and excellent ionic transport properties. A model aqueous organic redox flow battery (AORFB) with alizarin red S as negolyte and tiron as posolyte is assembled with the sulfonated cellulose membrane. The performance of the nanocellulose-based battery is superior in terms of cyclability in comparison to that displayed by the battery assembled with commercially available Nafion 115 due to the mitigation of crossover of the redox-active components. This finding paves the way to new green organic materials for fully sustainable AORFB solutions., Funding Agencies|VINNOVA (Digital Cellulose Center); BillerudKorsnas; Knut and Alice Wallenberg foundation [KAW 2019.0604, KAW 2021.0195]; Swedish Energy Agency [52023-1]; Vetenskapradet [2016-05990]

Solid-state precipitation can be used to tailor material properties, ranging from ferromagnets and catalysts to mechanical strengthening and energy storage. Thermoelectric properties can be modified by precipitation to enhance phonon scattering while retaining charge-carrier transmission. Here, unconventional Janus-type nanoprecipitates are uncovered in Mg3Sb1.5Bi0.5 formed by side-by-side Bi- and Ge-rich appendages, in contrast to separate nanoprecipitate formation. These Janus nanoprecipitates result from local comelting of Bi and Ge during sintering, enabling an amorphous-like lattice thermal conductivity. A precipitate size effect on phonon scattering is observed due to the balance between alloy-disorder and nanoprecipitate scattering. The thermoelectric figure-of-merit ZT reaches 0.6 near room temperature and 1.6 at 773 K. The Janus nanoprecipitation can be introduced into other materials and may act as a general property-tailoring mechanism., Funding Agencies|National Key Research and Development Program of China [2018YFB0703600]; National Natural Science Foundation of China [51872133]; Guangdong Innovative and Entrepreneurial Research Team Program [2016ZT06G587]; Guangdong Provincial Key Laboratory Program from the Department of Science and Technology of Guangdong Province [2021B1212040001]; Tencent Foundation through the XPLORER PRIZE; Swedish Government Strategic Research Area in Materials Science on Functional Materials at Linkoping University (Faculty Grant SFO-Mat-LiU) [2009 00971]; Knut and Alice Wallenberg foundation through the Wallenberg Academy Fellows program [KAW-2020.0196]; Swedish Foundation for Strategic Research (SSF) [RIF 14-0074]; German Science Foundation (DFG) [SFB 917]

Optical nanoantennas provide control of light at the nanoscale, which makes them important for diverse areas ranging from photocatalysis and flat metaoptics to sensors and biomolecular tweezing. They have traditionally been limited to metallic and dielectric nanostructures that sustain plasmonic and Mie resonances, respectively. More recently, nanostructures of organic J-aggregate excitonic materials have been proposed capable of also supporting nanooptical resonances, although their advance has been hampered from difficulty in nanostructuring. Here, the authors present the realization of organic J-aggregate excitonic nanostructures, using nanocylinder arrays as model system. Extinction spectra show that they can sustain both plasmon-like resonances and dielectric resonances, owing to the material providing negative and large positive permittivity regions at the different sides of its exciton resonance. Furthermore, it is found that the material is highly anisotropic, leading to hyperbolic and elliptic permittivity regions. Nearfield analysis using optical simulation reveals that the nanostructures therefore support hyperbolic localized surface exciton resonances and elliptic Mie resonances, neither of which has been previously demonstrated for this type of material. The anisotropic nanostructures form a new type of optical nanoantennas, which combined with the presented fabrication process opens up for applications such as fully organic excitonic metasurfaces., Funding Agencies|AngstromForsk Foundation; Knut and Alice Wallenberg Foundation; Swedish Research Council (VR); Swedish Foundation for Strategic Research (SSF); Swedish Government Strategic Research Area in Materials Science on Functional Materials at Linkoping University [2009 00971]; National Research Foundation of Korea (NRF) [2020R1A2C1102558]; Commercializations Promotion Agency for R&D Outcomes Grant (2022, Research Equipment Technician Training Program) - Korea government (MSIT) [2018R1A6A9056986]; Regional Innovation Strategy (RIS) - Ministry of Education (MOE) [2021RIS-001]; Korea Evaluation Institute of Industrial Technology (KEIT) [20015764]; Korea government (MOTIE) [20005750]

On-surface synthesis has recently emerged as a powerful strategy to design conjugated polymers previously precluded in conventional solution chemistry. Here, an N-containing pentacene-based precursor (tetraazapentacene) is ex-professo synthesized endowed with terminal dibromomethylene (:CBr2) groups to steer homocoupling via dehalogenation on metallic supports. Combined scanning probe microscopy investigations complemented by theoretical calculations reveal how the substrate selection drives different reaction mechanisms. On Ag(111) the dissociation of bromine atoms at room temperature triggers the homocoupling of tetraazapentacene units together with the binding of silver adatoms to the nitrogen atoms of the monomers giving rise to a N-containing conjugated coordination polymer (P1). Subsequently, P1 undergoes ladderization at 200 degrees C, affording a pyrrolopyrrole-bridged conjugated polymer (P2). On Au(111) the formation of the intermediate polymer P1 is not observed and, instead, after annealing at 100 degrees C, the conjugated ladder polymer P2 is obtained, revealing the crucial role of metal adatoms on Ag(111) as compared to Au(111). Finally, on Ag(100) the loss of :CBr2 groups affords the formation of tetraazapentacene monomers, which coexist with polymer P1. Our results contribute to introduce protocols for the synthesis of N-containing conjugated polymers, illustrating the selective role of the metallic support in the underlying reaction mechanisms., Funding Agencies|European Research Council (ERC CoG ELECNANO) [766555]; Comunidad de Madrid [project QUIMTRONIC-CM] [Y2018/NMT-4783]; Ministerio de Ciencia e Innovacion [PID2019-108532GB-I00]; "Severo Ochoa" Programme for Centers of Excellence in RD (MINECO) [SEV-2016-0686]; European Unions Horizon 2020 research and innovation programme under the Marie Skodowska-Curie grant [886314]; Swedish Research Council; Swedish Government Strategic Research Area in Materials Science on Functional Materials at Linkoping University (Faculty Grant SFO-Mat-LiU) [2009 00971]

Electrochemical valorization of biomass waste (e.g., glycerol) for production of value-added products (such as formic acid) in parallel with hydrogen production holds great potential for developing renewable and clean energy sources. Here, a synergistic effort between theoretical calculations at the atomic level and experiments to predict and validate a promising oxide catalyst for the glycerol oxidation reaction (GOR) are reported, providing a good example of designing novel, cost-effective, and highly efficient electrocatalysts for producing value-added products at the anode and high-purity hydrogen at the cathode. The predicted CoMoO4 catalyst is experimentally validated as a suitable catalyst for GOR and found to perform best among the investigated metal (Mn, Co, Ni) molybdate counterparts. The potential required to reach 10 mA cm(-2) is 1.105 V at 60 degrees C in an electrolyte of 1.0 m KOH with 0.1 m glycerol, which is 314 mV lower than for oxygen evolution. The GOR reaction pathway and mechanism based on this CoMoO4 catalyst are revealed by high-performance liquid chromatography and in situ Raman analysis. The coupled quantitative analysis indicates that the CoMoO4 catalyst is highly active toward C-C cleavage, thus presenting a high selectivity (92%) and Faradaic efficiency (90%) for formate production.

Electrochemical valorization of biomass waste (e.g., glycerol) for production of value-added products (such as formic acid) in parallel with hydrogen production holds great potential for developing renewable and clean energy sources. Here, a synergistic effort between theoretical calculations at the atomic level and experiments to predict and validate a promising oxide catalyst for the glycerol oxidation reaction (GOR) are reported, providing a good example of designing novel, cost-effective, and highly efficient electrocatalysts for producing value-added products at the anode and high-purity hydrogen at the cathode. The predicted CoMoO4 catalyst is experimentally validated as a suitable catalyst for GOR and found to perform best among the investigated metal (Mn, Co, Ni) molybdate counterparts. The potential required to reach 10 mA cm(-2) is 1.105 V at 60 degrees C in an electrolyte of 1.0 m KOH with 0.1 m glycerol, which is 314 mV lower than for oxygen evolution. The GOR reaction pathway and mechanism based on this CoMoO4 catalyst are revealed by high-performance liquid chromatography and in situ Raman analysis. The coupled quantitative analysis indicates that the CoMoO4 catalyst is highly active toward C-C cleavage, thus presenting a high selectivity (92%) and Faradaic efficiency (90%) for formate production.

Perovskite solar cells (PSCs) suffer from significant nonradiative recombination at perovskite/charge transport layer heterojunction, seriously limiting their power conversion efficiencies. Herein, solution-processed chromium multioxide (CrOx) is judiciously selected to construct a MAPbI(3)/CrOx/Spiro-OMeTAD hole-selective heterojunction. It is demonstrated that the inserted CrOx not only effectively reduces defect sites via redox shuttle at perovskite contact, but also decreases valence band maximum (VBM)-HOMO offset between perovskite and Spiro-OMeTAD. This will diminish thermionic losses for collecting holes and thus promote charge transport across the heterojunction, suppressing both defect-assisted recombination and interface carrier recombination. As a result, a remarkable improvement of 21.21% efficiency with excellent device stability is achieved compared to 18.46% of the control device, which is among the highest efficiencies for polycrystalline MAPbI(3) based n-i-p planar PSCs reported to date. These findings of this work provide new insights into novel charge-selective heterojunctions for further enhancing efficiency and stability of PSCs., Funding Agencies|National Science Foundation of China [21875067]; Shanghai Science and Technology Innovation Action Plan [22ZR1418900]; Fundamental Research Funds for the Central Universities; Shanghai Rising-Star [19QA1403100]; East China Normal University (ECNU) Multifunctional Platform for Innovation; open research fund of Songshan Lake Materials Laboratory [2021SLABFK02]; National Key Research and Development Program of China [2017YFA0206600]; National Natural Science Foundation of China [51922032, 21961160720]

Electrochemical valorization of biomass waste (e.g., glycerol) for production of value-added products (such as formic acid) in parallel with hydrogen production holds great potential for developing renewable and clean energy sources. Here, a synergistic effort between theoretical calculations at the atomic level and experiments to predict and validate a promising oxide catalyst for the glycerol oxidation reaction (GOR) are reported, providing a good example of designing novel, cost-effective, and highly efficient electrocatalysts for producing value-added products at the anode and high-purity hydrogen at the cathode. The predicted CoMoO4 catalyst is experimentally validated as a suitable catalyst for GOR and found to perform best among the investigated metal (Mn, Co, Ni) molybdate counterparts. The potential required to reach 10 mA cm(-2) is 1.105 V at 60 degrees C in an electrolyte of 1.0 m KOH with 0.1 m glycerol, which is 314 mV lower than for oxygen evolution. The GOR reaction pathway and mechanism based on this CoMoO4 catalyst are revealed by high-performance liquid chromatography and in situ Raman analysis. The coupled quantitative analysis indicates that the CoMoO4 catalyst is highly active toward C-C cleavage, thus presenting a high selectivity (92%) and Faradaic efficiency (90%) for formate production.

The drawbacks of current state-of-the-art selective membranes, such as poor barrier properties, high cost, and poor recyclability, limit the large-scale deployment of electrochemical energy devices such as redox flow batteries (RFBs) and fuel cells. In recent years, cellulosic nanomaterials have been proposed as a low-cost and green raw material for such membranes, but their performance in RFBs and fuel cells is typically poorer than that of the sulfonated fluoropolymer ionomer membranes such as Nafion. Herein, sulfonated cellulose nanofibrils densely cross-linked to form a compact sulfonated cellulose membrane with limited swelling and good stability in water are used. The membranes possess low porosity and excellent ionic transport properties. A model aqueous organic redox flow battery (AORFB) with alizarin red S as negolyte and tiron as posolyte is assembled with the sulfonated cellulose membrane. The performance of the nanocellulose-based battery is superior in terms of cyclability in comparison to that displayed by the battery assembled with commercially available Nafion 115 due to the mitigation of crossover of the redox-active components. This finding paves the way to new green organic materials for fully sustainable AORFB solutions., Funding Agencies|VINNOVA (Digital Cellulose Center); BillerudKorsnas; Knut and Alice Wallenberg foundation [KAW 2019.0604, KAW 2021.0195]; Swedish Energy Agency [52023-1]; Vetenskapradet [2016-05990]

Solid-state precipitation can be used to tailor material properties, ranging from ferromagnets and catalysts to mechanical strengthening and energy storage. Thermoelectric properties can be modified by precipitation to enhance phonon scattering while retaining charge-carrier transmission. Here, unconventional Janus-type nanoprecipitates are uncovered in Mg3Sb1.5Bi0.5 formed by side-by-side Bi- and Ge-rich appendages, in contrast to separate nanoprecipitate formation. These Janus nanoprecipitates result from local comelting of Bi and Ge during sintering, enabling an amorphous-like lattice thermal conductivity. A precipitate size effect on phonon scattering is observed due to the balance between alloy-disorder and nanoprecipitate scattering. The thermoelectric figure-of-merit ZT reaches 0.6 near room temperature and 1.6 at 773 K. The Janus nanoprecipitation can be introduced into other materials and may act as a general property-tailoring mechanism., Funding Agencies|National Key Research and Development Program of China [2018YFB0703600]; National Natural Science Foundation of China [51872133]; Guangdong Innovative and Entrepreneurial Research Team Program [2016ZT06G587]; Guangdong Provincial Key Laboratory Program from the Department of Science and Technology of Guangdong Province [2021B1212040001]; Tencent Foundation through the XPLORER PRIZE; Swedish Government Strategic Research Area in Materials Science on Functional Materials at Linkoping University (Faculty Grant SFO-Mat-LiU) [2009 00971]; Knut and Alice Wallenberg foundation through the Wallenberg Academy Fellows program [KAW-2020.0196]; Swedish Foundation for Strategic Research (SSF) [RIF 14-0074]; German Science Foundation (DFG) [SFB 917]

On-surface synthesis has recently emerged as a powerful strategy to design conjugated polymers previously precluded in conventional solution chemistry. Here, an N-containing pentacene-based precursor (tetraazapentacene) is ex-professo synthesized endowed with terminal dibromomethylene (:CBr2) groups to steer homocoupling via dehalogenation on metallic supports. Combined scanning probe microscopy investigations complemented by theoretical calculations reveal how the substrate selection drives different reaction mechanisms. On Ag(111) the dissociation of bromine atoms at room temperature triggers the homocoupling of tetraazapentacene units together with the binding of silver adatoms to the nitrogen atoms of the monomers giving rise to a N-containing conjugated coordination polymer (P1). Subsequently, P1 undergoes ladderization at 200 degrees C, affording a pyrrolopyrrole-bridged conjugated polymer (P2). On Au(111) the formation of the intermediate polymer P1 is not observed and, instead, after annealing at 100 degrees C, the conjugated ladder polymer P2 is obtained, revealing the crucial role of metal adatoms on Ag(111) as compared to Au(111). Finally, on Ag(100) the loss of :CBr2 groups affords the formation of tetraazapentacene monomers, which coexist with polymer P1. Our results contribute to introduce protocols for the synthesis of N-containing conjugated polymers, illustrating the selective role of the metallic support in the underlying reaction mechanisms., Funding Agencies|European Research Council (ERC CoG ELECNANO) [766555]; Comunidad de Madrid [project QUIMTRONIC-CM] [Y2018/NMT-4783]; Ministerio de Ciencia e Innovacion [PID2019-108532GB-I00]; "Severo Ochoa" Programme for Centers of Excellence in RD (MINECO) [SEV-2016-0686]; European Unions Horizon 2020 research and innovation programme under the Marie Skodowska-Curie grant [886314]; Swedish Research Council; Swedish Government Strategic Research Area in Materials Science on Functional Materials at Linkoping University (Faculty Grant SFO-Mat-LiU) [2009 00971]

Optical nanoantennas provide control of light at the nanoscale, which makes them important for diverse areas ranging from photocatalysis and flat metaoptics to sensors and biomolecular tweezing. They have traditionally been limited to metallic and dielectric nanostructures that sustain plasmonic and Mie resonances, respectively. More recently, nanostructures of organic J-aggregate excitonic materials have been proposed capable of also supporting nanooptical resonances, although their advance has been hampered from difficulty in nanostructuring. Here, the authors present the realization of organic J-aggregate excitonic nanostructures, using nanocylinder arrays as model system. Extinction spectra show that they can sustain both plasmon-like resonances and dielectric resonances, owing to the material providing negative and large positive permittivity regions at the different sides of its exciton resonance. Furthermore, it is found that the material is highly anisotropic, leading to hyperbolic and elliptic permittivity regions. Nearfield analysis using optical simulation reveals that the nanostructures therefore support hyperbolic localized surface exciton resonances and elliptic Mie resonances, neither of which has been previously demonstrated for this type of material. The anisotropic nanostructures form a new type of optical nanoantennas, which combined with the presented fabrication process opens up for applications such as fully organic excitonic metasurfaces., Funding Agencies|AngstromForsk Foundation; Knut and Alice Wallenberg Foundation; Swedish Research Council (VR); Swedish Foundation for Strategic Research (SSF); Swedish Government Strategic Research Area in Materials Science on Functional Materials at Linkoping University [2009 00971]; National Research Foundation of Korea (NRF) [2020R1A2C1102558]; Commercializations Promotion Agency for R&D Outcomes Grant (2022, Research Equipment Technician Training Program) - Korea government (MSIT) [2018R1A6A9056986]; Regional Innovation Strategy (RIS) - Ministry of Education (MOE) [2021RIS-001]; Korea Evaluation Institute of Industrial Technology (KEIT) [20015764]; Korea government (MOTIE) [20005750]

Perovskite solar cells (PSCs) suffer from significant nonradiative recombination at perovskite/charge transport layer heterojunction, seriously limiting their power conversion efficiencies. Herein, solution-processed chromium multioxide (CrOx) is judiciously selected to construct a MAPbI(3)/CrOx/Spiro-OMeTAD hole-selective heterojunction. It is demonstrated that the inserted CrOx not only effectively reduces defect sites via redox shuttle at perovskite contact, but also decreases valence band maximum (VBM)-HOMO offset between perovskite and Spiro-OMeTAD. This will diminish thermionic losses for collecting holes and thus promote charge transport across the heterojunction, suppressing both defect-assisted recombination and interface carrier recombination. As a result, a remarkable improvement of 21.21% efficiency with excellent device stability is achieved compared to 18.46% of the control device, which is among the highest efficiencies for polycrystalline MAPbI(3) based n-i-p planar PSCs reported to date. These findings of this work provide new insights into novel charge-selective heterojunctions for further enhancing efficiency and stability of PSCs., Funding Agencies|National Science Foundation of China [21875067]; Shanghai Science and Technology Innovation Action Plan [22ZR1418900]; Fundamental Research Funds for the Central Universities; Shanghai Rising-Star [19QA1403100]; East China Normal University (ECNU) Multifunctional Platform for Innovation; open research fund of Songshan Lake Materials Laboratory [2021SLABFK02]; National Key Research and Development Program of China [2017YFA0206600]; National Natural Science Foundation of China [51922032, 21961160720]

On-surface synthesis has recently emerged as a powerful strategy to design conjugated polymers previously precluded in conventional solution chemistry. Here, an N-containing pentacene-based precursor (tetraazapentacene) is ex-professo synthesized endowed with terminal dibromomethylene (:CBr2) groups to steer homocoupling via dehalogenation on metallic supports. Combined scanning probe microscopy investigations complemented by theoretical calculations reveal how the substrate selection drives different reaction mechanisms. On Ag(111) the dissociation of bromine atoms at room temperature triggers the homocoupling of tetraazapentacene units together with the binding of silver adatoms to the nitrogen atoms of the monomers giving rise to a N-containing conjugated coordination polymer (P1). Subsequently, P1 undergoes ladderization at 200 degrees C, affording a pyrrolopyrrole-bridged conjugated polymer (P2). On Au(111) the formation of the intermediate polymer P1 is not observed and, instead, after annealing at 100 degrees C, the conjugated ladder polymer P2 is obtained, revealing the crucial role of metal adatoms on Ag(111) as compared to Au(111). Finally, on Ag(100) the loss of :CBr2 groups affords the formation of tetraazapentacene monomers, which coexist with polymer P1. Our results contribute to introduce protocols for the synthesis of N-containing conjugated polymers, illustrating the selective role of the metallic support in the underlying reaction mechanisms., Funding Agencies|European Research Council (ERC CoG ELECNANO) [766555]; Comunidad de Madrid [project QUIMTRONIC-CM] [Y2018/NMT-4783]; Ministerio de Ciencia e Innovacion [PID2019-108532GB-I00]; "Severo Ochoa" Programme for Centers of Excellence in RD (MINECO) [SEV-2016-0686]; European Unions Horizon 2020 research and innovation programme under the Marie Skodowska-Curie grant [886314]; Swedish Research Council; Swedish Government Strategic Research Area in Materials Science on Functional Materials at Linkoping University (Faculty Grant SFO-Mat-LiU) [2009 00971]

The drawbacks of current state-of-the-art selective membranes, such as poor barrier properties, high cost, and poor recyclability, limit the large-scale deployment of electrochemical energy devices such as redox flow batteries (RFBs) and fuel cells. In recent years, cellulosic nanomaterials have been proposed as a low-cost and green raw material for such membranes, but their performance in RFBs and fuel cells is typically poorer than that of the sulfonated fluoropolymer ionomer membranes such as Nafion. Herein, sulfonated cellulose nanofibrils densely cross-linked to form a compact sulfonated cellulose membrane with limited swelling and good stability in water are used. The membranes possess low porosity and excellent ionic transport properties. A model aqueous organic redox flow battery (AORFB) with alizarin red S as negolyte and tiron as posolyte is assembled with the sulfonated cellulose membrane. The performance of the nanocellulose-based battery is superior in terms of cyclability in comparison to that displayed by the battery assembled with commercially available Nafion 115 due to the mitigation of crossover of the redox-active components. This finding paves the way to new green organic materials for fully sustainable AORFB solutions., Funding Agencies|VINNOVA (Digital Cellulose Center); BillerudKorsnas; Knut and Alice Wallenberg foundation [KAW 2019.0604, KAW 2021.0195]; Swedish Energy Agency [52023-1]; Vetenskapradet [2016-05990]

Solid-state precipitation can be used to tailor material properties, ranging from ferromagnets and catalysts to mechanical strengthening and energy storage. Thermoelectric properties can be modified by precipitation to enhance phonon scattering while retaining charge-carrier transmission. Here, unconventional Janus-type nanoprecipitates are uncovered in Mg3Sb1.5Bi0.5 formed by side-by-side Bi- and Ge-rich appendages, in contrast to separate nanoprecipitate formation. These Janus nanoprecipitates result from local comelting of Bi and Ge during sintering, enabling an amorphous-like lattice thermal conductivity. A precipitate size effect on phonon scattering is observed due to the balance between alloy-disorder and nanoprecipitate scattering. The thermoelectric figure-of-merit ZT reaches 0.6 near room temperature and 1.6 at 773 K. The Janus nanoprecipitation can be introduced into other materials and may act as a general property-tailoring mechanism., Funding Agencies|National Key Research and Development Program of China [2018YFB0703600]; National Natural Science Foundation of China [51872133]; Guangdong Innovative and Entrepreneurial Research Team Program [2016ZT06G587]; Guangdong Provincial Key Laboratory Program from the Department of Science and Technology of Guangdong Province [2021B1212040001]; Tencent Foundation through the XPLORER PRIZE; Swedish Government Strategic Research Area in Materials Science on Functional Materials at Linkoping University (Faculty Grant SFO-Mat-LiU) [2009 00971]; Knut and Alice Wallenberg foundation through the Wallenberg Academy Fellows program [KAW-2020.0196]; Swedish Foundation for Strategic Research (SSF) [RIF 14-0074]; German Science Foundation (DFG) [SFB 917]