We report an ionic thermoelectric generator (iTEG) capable of delivering continuous power and large thermal voltages under a temperature gradient. Unlike conventional thermogalvanic cells, the current in our system arises from a reversible redox reaction driven by ionic thermodiffusion-induced thermal potentials. By systematically studying electrolytes with varying thermoelectric properties, we identified that self-assembled polyethylene glycol (PEG) clusters, stabilized by alkoxide end groups, are key to enable the output current. The iTEG achieved a maximum power density of 4.2 mW m-2 with an output voltage of 100 mV under a 20 K temperature difference. These findings establish a new design principle for ionic thermoelectric devices and provide insights into charge transfer process and redox reactions at electrode interfaces, with implications for energy technologies such as ion batteries and related electrochemical systems.

This study explores paired electrolysis, leveraging the oxygen reduction reaction (ORR) and industry-relevant lignosulfonate oxidation to enhance sustainable electrochemical processes. The anode reaction is driven by the direct oxidation of lignosulfonate, an abundant biopolymer derived from sulfite pulping, on bare graphite electrodes, eliminating the need for costly catalysts. This process occurs in a membrane electrolyzer, where the cathode catalyst dictates ORR selectivity: a carbon paper cathode modified by the conducting polymer poly(3,4-ethylenedioxythiophene) (PEDOT) favors hydrogen peroxide formation via a 2-electron pathway, while a platinum-modified carbon paper cathode facilitates full oxygen reduction to water via a 4-electron pathway. When applying a cell voltage of 0.7 V (a geometrical current density of 0.04 mA cm(-2)), the air-saturated catholyte had an 8-fold decrease in dissolved oxygen, which corresponded to 68% faradaic efficiency and an electrical energy consumption of 0.0233 W hour l(-1). Removing the low molecular weight lignosulfonate (<3.5 kDa) via dialysis minimizes membrane crossover but also reduces oxygen consumption rates. The oxidation process preserves the lignosulfonate backbone while enriching its quinone content, offering a novel, energy-efficient approach to biomass valorization. By integrating lignosulfonate oxidation with ORR, this work presents a cost-effective and sustainable alternative to conventional anodic processes, with potential applications in green hydrogen peroxide production and biobased electrochemical systems.

Hematopoietic stem cells (HSCs) are rare cells residing in the bone marrow and give rise to millions of new blood cells daily throughout life. Because of their multipotent, self-renewing nature, they have also been used for several decades to treat hematological disorders. However, HSCs are scarce and difficult to maintain ex vivo, demonstrating the need for developing novel in vitro methods to expand HSCs that mimic the complex in vivo microenvironment in suitable culture tissue plates, in extracellular matrix scaffolds, or on a biochip. One component to include in such an artificial microenvironment is HSC-related growth factors (GFs) immobilized on surfaces that mimic membrane-bound GFs in vivo. In this paper, we have initiated the development of an ex vivo system to study the immobilization of growth factors that sustain HSC maintenance and possibly expansion. However, since HSC-related GFs are expensive we have developed a proof-of-concept model using bovine serum albumin (BSA) as an alternative. Polypyrrole (PPy) was electrochemically synthesized in the presence of dicarboxylic acids with different hydrocarbon chain lengths and polycarboxylic acids with different molecular weights as dopants. BSA was immobilized on the PPy surface using 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide hydrochloride (EDC) and N-hydroxysuccinimide (NHS) to couple BSA to the carboxylic acid dopant of PPy. These PPy films with different dopants showed different abilities to immobilize BSA using EDC/NHS coupling and also different surface properties. In addition, owing to the interesting switchable properties of PPy upon alteration of the oxidation/reduction potential, the immobilized BSA could change its presentation on the PPy surface depending on the redox state. To characterize the PPy surfaces and to study the different immobilization results of BSA on these PPy variants with different dopants and different presentation behavior upon redox switching, the electrochemical properties, hydrophobicity, thickness, roughness, surface COOH density and fluorescence labeling were investigated. The results indicate that the polycarboxylic acid dopants could immobilize more BSA on the PPy surface. Moreover, the BSA in the as-fabricated state shows a "collapsed" presentation on the PPy surface, a "less collapsed" presentation in the oxidized state and an "erected" presentation in the reduced state. Cell viability studies using hematopoietic cells showed that the developed PPy-BSA surfaces did not negatively alter cell viability or cell proliferation compared to the control.

Fast and accurate detection of antimicrobial resistance in pathogens remains a challenge, and with the increase in antimicrobial resistance due to mis- and overuse of antibiotics, it has become an urgent public health problem. We demonstrate how infrared attenuated total reflection (IR-ATR) can be used as a simple method for assessment of bacterial susceptibility to antibiotics. This is achieved by monitoring the metabolic activities of bacterial cells via nutrient consumption and using this as an indicator of bacterial viability. Principal component analysis of the obtained spectra provides a tool for fast and simple discrimination of antimicrobial resistance in the acquired data. We demonstrate this concept using four bacterial strains and four different antibiotics, showing that the change in glucose concentration in the growth medium after 2 h, as monitored by IR-ATR, can be used as a spectroscopic diagnostic technique, to reduce detection time and to improve quality in the assessment of antimicrobial resistance in pathogens.

Aqueous organic redox flow battery (AORFB) is a technological route towards the large-scale sustainable energy storage. However, several factors need to be controlled to maintain the AORFB performance. Prevention of posolyte and negolyte cross-contamination in asymmetric AORFBs, one of the main causes of capacity decay, relies on their membranes' ability to prevent migration of the redox-active species between the two electrolytes. The barrier properties are often traded for a reduction in ionic conductivity which is crucial to enable the device operation. Another factor greatly affecting quinone-based AORFBs is the Michael addition reaction (MAR) on the charged posolyte, quinone, which has been identified as a major reason for all-quinone AORFBs performance deterioration. Herein, we investigate deterioration scenarios of an all-quinone AORFB using both experimental and computational methods. The study includes a series of membranes based on sulfonated cellulose nanofibrils and different membrane modifications. The layer-by-layer (LbL) surface modifications, i.e. the incorporation of inorganic materials and the reduction of the pore size of the sulfonated cellulose membranes, were all viable routes to reduce the passive diffusion permeability of membranes which correlated to an increased cycling stability of the battery. The kinetics of MAR on quinone was detected using NMR and its impact on the performance fading was modeled computationally. The localization of MAR close to the membrane, which can be assigned to the surface reactivity, affects the diffusion of MAR reagent and the deterioration dynamics of the present all-quinone AORFB.

In the domain of organic mixed ionic-electronic conductors (OMIECs), simultaneous transport and coupling of ionic and electronic charges are crucial for the function of electrochemical devices in organic electronics. Understanding conduction mechanisms and chemical reactions in operational devices is pivotal for performance enhancement and is necessary for the informed and systematic development of more promising materials. Surface-enhanced Raman spectroscopy (SERS) is a potent tool for monitoring electrochemical evolution and dynamic doping in operational devices, offering enhanced sensitivity to subtle spectral changes. We demonstrate the utility of SERS for in situ tracking of doping in OMIECs in an organic light-emitting electrochemical cell (LEC) containing a conjugated polymer (poly[2-methoxy-5-(2-ethylhexyloxy)-1,4-phenylenevinylene]; MEH-PPV), a molecular anion (lithium triflate), and an electrolyte network (poly(ethylene oxide); PEO). SERS enhancement is achieved via an interleaved layer of gold particles formed by spontaneous breakup of a deposited thin gold film. The results successfully highlight the ability of SERS to unveil time-resolved MEH-PPV doping and polaron formation, elucidating the effects of triflate ion transfer in the operating device and validating the electrochemical doping model in LECs.

The two-electron oxygen reduction reaction (ORR), powered by affordable renewable energy, presents a more promising and sustainable approach to hydrogen peroxide production than traditional methods. In this study, we introduce a membrane electrolyzer for ORR-to-H2O2 generation. The conducting polymer poly(3,4-ethylenedioxythiophene):poly(styrene sulfonate) (PEDOT:PSS) acts as the cathode that aids the oxygen reduction reaction through a two-electron pathway to produce H2O2. At the anode, we employed the oxidation of a model organic molecule, 4,5-dihydroxy-1,3-benzenedisulfonic acid disodium salt monohydrate (tiron). This catalyst-free anode process, as an alternative to the sluggish water oxidation reaction commonly used in classical electrolyzers, reduces voltage loss to release protons, cross the membrane, and feed the ORR at the cathode. Our study investigated the often-neglected issue of organic crossover during electrolyzer operation and its significant impact on transport behavior. This research paves the way for the development of crossover-free flow cells, extending the realm of electrochemical devices based on the electrolyte fed and the membrane. We introduce a membrane electrolyzer for the generation of hydrogen peroxide via oxygen reduction and catalyst-free oxidation of quinones. The study reports the effect of the applied coulombic forces on ions, which is the origin of crossover.

Silk fibers have unique mechanical properties, and many studies of silk aim at understanding how these properties are related to secondary structure content, which often is determined by infrared spectroscopy. We report significant method-induced irreversible structural changes to both natural and synthetic spider silk fibers, derived from the widely used attenuated total reflection Fourier-transform infrared (ATR-FTIR) technique. By varying the force used to bring fibers into contact with the internal reflection elements of ATR-FTIR accessories, we observed correlated and largely irreversible changes in the secondary structure, with shape relaxation under pressure occurring within minutes. Fitting of spectral components shows that these changes agree with transformations from the alpha-helix to the beta-sheet secondary structure with possible contributions from other secondary structure elements. We further confirm the findings with IR microspectroscopy, where similar differences were seen between the pressed and unaffected regions of spider silk fibers. Our findings show that ATR-FTIR spectroscopy requires care in its use and in the interpretation of the results.

Abstract Green and scalable materials are essential to fulfill the need of electrification for transitioning into a fossil‐fuels free society, and sustainability is a requirement for all new technologies. Rechargeable batteries are one of the most important elements for electrification, enabling the transition to mobile electronics, electrical vehicles and grid storage. We here report synthesis and characterization of polyelectrolyte complexes of alginate and chitosan, both biopolymers deriving from the sea, for transport of zinc ions in hydrogel electrolytes. We have used vibrational spectroscopy, thermal measurements and microscopy, as well as transport measurements with ohmic or blocking contacts. The transference number for zinc ions is close to 1, the conductivity is ≈10 mS/cm, with stability at Zn interfaces seen through 7000 cycles in symmetric zinc//zinc cell.

We have prepared a series of ampholytic polymer films, using a self-initiated photografting and photopolymerization (SI-PGP) method to sequentially polymerize first anionic (deuterated methacrylic acid (dMAA)) and thereafter cationic (2-aminoethyl methacrylate (AEMA)) monomers to investigate the SI-PGP grafting process. Dry films were investigated by ellipsometry, X-ray, and neutron reflectometry, and their swelling was followed over a pH range from 4.5 to 10.5 with spectroscopic ellipsometry. The deuterated monomer allows us to separate the distributions of the two components by neutron reflectometry. Growth of both polymers proceeds via grafting of solution-polymerized fragments to the surface, and also the second layer is primarily grafted to the substrate and not as a continuation of the existing chains. The polymer films are stratified, with one layer of near 1:1 composition and the other layer enriched in one component and located either above or below the former layer. The ellipsometry results show swelling transitions at low and high pH but with no systematic variation in the pH values where these transitions occur. The results suggest that grafting density in SI-PGP-prepared homopolymers could be increased via repeated polymerization steps, but that this process does not necessarily increase the average chain length.

Green hydrogen is identified as one of the prime clean energy carriers due to its high energy density and a zero emission of CO2. A possible solution for the transport of H2 in a safe and low-cost way is in the form of liquid organic hydrogen carriers (LOHCs). As an alternative to loading LOHC with H2 via a two-step procedure involving preliminary electrolytic production of H2 and subsequent chemical hydrogenation of the LOHC, we explore here the possibility of electrochemical hydrogen storage (EHS) via conversion of proton of a proton donor into a hydrogen atom involved in covalent bonds with the LOHC (R) via a protoncoupled electron transfer (PCET) reaction: 2nH++2ne-+Rox $nH02Rred. We chose 9-fluorenone/ fluorenol (Fnone/Fnol) conversion as such a model PCET reaction. The electrochemical activation of Fnone via two sequential electron transfers was monitored with in-situ and operando spectroscopies in absence and in presence of different alcohols as proton donors of different reactivity, which enabled us to both quantify and get the mechanistic insight on PCET. The possibility of hydrogen extraction from the loaded carrier molecule was illustrated by chemical activation.(c) 2022 Science Press and Dalian Institute of Chemical Physics, Chinese Academy of Sciences. Published by ELSEVIER B.V. and Science Press.

Producing thick films of conducting polymers by a low‐cost manufacturing technique would enable new applications. However, removing huge solvent volume from diluted suspension or dispersion (1–3 wt%) in which conducting polymers are typically obtained is a true manufacturing challenge. In this work, a procedure is proposed to quickly remove water from the conducting polymer poly(3,4‐ethylenedioxythiophene:poly(4‐styrene sulfonate) (PEDOT:PSS) suspension. The PEDOT:PSS suspension is first flocculated with 1 m H2SO4 transforming PEDOT nanoparticles (≈50–500 nm) into soft microparticles. A filtration process inspired by pulp dewatering in a paper machine on a wire mesh with apertures dimension between 60 µm and 0.5 mm leads to thick free‐standing films (≈0.5 mm). Wire mesh clogging that hinders dewatering (known as dead‐end filtration) is overcome by adding to the flocculated PEDOT:PSS dispersion carbon fibers that aggregate and form efficient water channels. Moreover, this enables fast formation of thick layers under simple atmospheric pressure filtration, thus making the process truly scalable. Thick freestanding PEDOT films thus obtained are used as electrocatalysts for efficient reduction of oxygen to hydrogen peroxide, a promising green chemical and fuel. The inhomogeneity of the films does not affect their electrochemical function.

A common way of determining the majority charge carriers of pristine and doped semiconducting polymers is to measure the sign of the Seebeck coefficient. However, a polarity change of the Seebeck coefficient has recently been observed to occur in highly doped polymers. Here, it is shown that the Seebeck coefficient inversion is the result of the density of states filling and opening of a hard Coulomb gap around the Fermi energy at high doping levels. Electrochemical n‐doping is used to induce high carrier density (>1 charge/monomer) in the model system poly(benzimidazobenzophenanthroline) (BBL). By combining conductivity and Seebeck coefficient measurements with in situ electron paramagnetic resonance, UV–vis–NIR, Raman spectroelectrochemistry, density functional theory calculations, and kinetic Monte Carlo simulations, the formation of multiply charged species and the opening of a hard Coulomb gap in the density of states, which is responsible for the Seebeck coefficient inversion and drop in electrical conductivity, are uncovered. The findings provide a simple picture that clarifies the roles of energetic disorder and Coulomb interactions in highly doped polymers and have implications for the molecular design of next‐generation conjugated polymers.

Self-initiated photografting and photopolymerization (SI-PGP) uses UV illumination to graft polymers to surfaces without additional photoinitiators using the monomers as initiators, "inimers". A wider use of this method is obstructed by a lack of understanding of the resulting, presumably heterogeneous, polymer structure and of the parallel degradation under continuous UV illumination. We have used neutron reflectometry to investigate the structure of hydrated SI-PGP-prepared poly(HEMA-co-PEG10MA) (poly(2-hydroxyethyl methacrylate-co-(ethyl-ene glycol)10 methacrylate)) films and compared parabolic, sigmoidal, and Gaussian models for the polymer volume fraction distributions. Results from fitting these models to the data suggest that either model can be used to approximate the volume fraction profile to similar accuracy. In addition, a second layer of deuterated poly(methacrylic acid) (poly(dMAA)) was grafted over the existing poly(HEMA-co-PEG10MA) layer, and the resulting double-grafted films were also studied by neutron reflectometry to shed light on the UV-polymerization process and the inevitable UV-induced degradation which competes with the grafting.

Neutron reflectivity at the solid/liquid interface offers unique opportunities for resolving the structure-function relationships of interfacial layers in soft matter science. It is a non-destructive technique for detailed analysis of layered structures on molecular length scales, providing thickness, density, roughness, and composition of individual layers or components of adsorbed films. However, there are also some well-known limitations of this method, such as the lack of chemical information, the difficulties in determining large layer thicknesses, and the limited time resolution. We have addressed these shortcomings by designing and implementing a portable sample environment for in situ characterization at neutron reflectometry beamlines, integrating infrared spectroscopy under attenuated total reflection for determination of molecular entities and their conformation, and spectroscopic ellipsometry for rapid and independent measurement of layer thicknesses and refractive indices. The utility of this combined setup is demonstrated by two projects investigating (a) pH-dependent swelling of polyelectrolyte layers and (b) the impact of nanoparticles on lipid membranes to identify potential mechanisms of nanotoxicity.

Cells adhering onto surfaces sense and respond to chemical and physical surface features. The control over cell adhesion behavior influences cell migration, proliferation, and differentiation, which are important considerations in biomaterial design for cell culture, tissue engineering, and regenerative medicine. Here, we report on a supramolecular-based approach to prepare reversible self-assembled monolayers (rSAMs) with tunable lateral mobility and dynamic control over surface composition to regulate cell adhesion behavior. These layers were prepared by incubating oxoacid-terminated thiol SAMs on gold in a pH 8 HEPES buffer solution containing different mole fractions of ω-(ethylene glycol)2-4- and ω-(GRGDS)-, α-benzamidino bolaamphiphiles. Cell shape and morphology were influenced by the strength of the interactions between the amidine-functionalized amphiphiles and the oxoacid of the underlying SAMs. Dynamic control over surface composition, achieved by the addition of inert filler amphiphiles to the RGD-functionalized rSAMs, reversed the cell adhesion process. In summary, rSAMs featuring mobile bioactive ligands offer unique capabilities to influence and control cell adhesion behavior, suggesting a broad use in biomaterial design, tissue engineering, and regenerative medicine.

Sea stars can adhere to various underwater substrata using an adhesive secretion of which Sfp1 is a major component. Sfp1 is a multimodular protein composed of four subunits (Sfp1 Alpha, Beta, Delta, and Gamma) displaying different functional domains. We recombinantly produced two fragments of Sfp1 comprising most of its functional domains: the C-terminal part of the Beta subunit (rSfp1 Beta C-term) and the Delta subunit (rSfp1 Delta). Surface plasmon resonance analyses of protein adsorption onto different model surfaces showed that rSfp1 Beta C-term exhibits a significantly higher adsorption than the fibrinogen control on hydrophobic, hydrophilic protein-resistant, and charged self-assembled monolayers, while rSfp1 Delta adsorbed more on negatively charged and on protein-resistant surfaces compared to fibrinogen. Truncated recombinant rSfp1 Beta C-term proteins were produced in order to investigate the role of the different functional domains in the adsorption of this protein. The analysis of their adsorption capacities on glass showed that two mechanisms are involved in rSfp1 Beta C-term adsorption: (1) one mediated by the EGF-like domain and involving Ca2+ and Mg2+ ions, and (2) one mediated by the sequence of Sfp1 Beta with no homology with known functional domain in databases, in the presence of Na+, Ca2+ and Mg2+ ions.

Polyampholytic poly(2-aminoethyl methacrylate-co-sulfopropyl methacrylate) (p(AEMA-co-SPMA)) thin films were prepared by self-initiated photopolymerization and photografting (SIPGP) and are demonstrated to be a potential alternative to films prepared from zwitterionic poly(sulfobetaine methacrylate) (pSBMA) for antifouling applications. SIPGP allows polymerization from aqueous solutions containing only monomers, implying that p(AEMA-co-SPMA) thin films can be prepared simply and inexpensively without the risk of introducing potentially toxic substances necessary in many controlled polymerization reactions. For the polymers, wettabilities were studied by contact angle goniometry, the compositions of the films were determined by infrared and X-ray photoelectron spectroscopies, and streaming current measurements were used to assess their net charge. The antibiofouling properties were compared via adsorption of fibrinogen and bovine serum albumin, settlement of algal zoospores, and the growth of sporelings of the marine alga Ulva lactuca. The fouling of the p(AEMA-co-SPMA) copolymer was in several respects similar to that of the zwitterionic pSBMA and suggests that it is potentially suitable for applications under high-salinity conditions, such as marine or physiological environments.

We embedded IR-resonant microparticles as visible scatterers and thermal emitters in a transparent nanocellulose composite, to form a metamaterial that provides radiative cooling while simultaneously functioning as an optical diffuser.