Decoupling Conductivity, Heterogeneous Electron Transfer Rate, and Diffusion in Organic Molecular Electrocatalysis: Oxygen Reduction Reaction on Poly(3,4-ethylenedioxythiophene).

The electrified production of hydrogen peroxide (HO) by oxygen reduction reaction (ORR) is attractive to increase the sustainability of chemical industry. Here the same chains of intrinsically conductive polymer, poly(3,4-ethylenedioxythiophene) (PEDOT) are utilized, as ORR electrocatalyst, while varying polymeric primary dopants (PSS and Nafion) and the level of secondary doping with DMSO. These changes modulate various properties of the film, such as its microscale organization and electronic conductivity.

Elucidating the Supramolecular Interaction of Positively Supercharged Fluorescent Protein with Anionic Phthalocyanines.

Developing bioinspired materials to convert sunlight into electricity efficiently is paramount for sustainable energy production. Fluorescent proteins are promising candidates as photoactive materials due to their high fluorescence quantum yield and absorption extinction coefficients in aqueous media. However, developing artificial bioinspired photosynthetic systems requires a detailed understanding of molecular interactions and energy transfer mechanisms in the required operating conditions.

Halide Engineering in Mixed Halide Perovskite-Inspired CuAgBiI for Solar Cells with Enhanced Performance.

CuAgBiI (CABI) is a promising perovskite-inspired absorber for solar cells due to its direct band gap and high absorption coefficient. However, the nonradiative recombination caused by the high extrinsic trap density limits the performance of CABI-based solar cells. In this work, we employ halide engineering by doping bromide anions (Br) in CABI thin films, in turn significantly improving the power conversion efficiency (PCE).

Visualizing Noncovalent Interactions and Property Prediction of Submicron-Sized Charge-Transfer Crystals from ab-initio Determined Structures.

The charge-transfer (CT) interactions between organic compounds are reflected in the (opto)electronic properties. Determining and visualizing crystal structures of CT complexes are essential for the design of functional materials with desirable properties. Complexes of pyranine (PYR), methyl viologen (MV), and their derivatives are the most studied water-based CT complexes.

Organic Electrochemical Transistor Aptasensor for Interleukin-6 Detection.

We demonstrate an organic electrochemical transistor (OECT) biosensor for the detection of interleukin 6 (IL6), an important biomarker associated with various pathological processes, including chronic inflammation, inflammaging, cancer, and severe COVID-19 infection. The biosensor is functionalized with oligonucleotide aptamers engineered to bind specifically IL6. We developed an easy functionalization strategy based on gold nanoparticles deposited onto a poly(3,4-ethylenedioxythiophene) doped with polystyrenesulfonate (PEDOT:PSS) gate electrode for the subsequent electrodeposition of thiolated aptamers.

Disequilibrating azobenzenes by visible-light sensitization under confinement.

Photoisomerization of azobenzenes from their stable isomer to the metastable state is the basis of numerous applications of these molecules. However, this reaction typically requires ultraviolet light, which limits applicability. In this study, we introduce disequilibration by sensitization under confinement (DESC), a supramolecular approach to induce the -to- isomerization by using light of a desired color, including red.

Programmable and Self-Healable Liquid Crystal Elastomer Actuators Based on Halogen Bonding.

Shape-changing polymeric materials have gained significant attention in the field of bioinspired soft robotics. However, challenges remain in versatilizing the shape-morphing process to suit different tasks and environments, and in designing systems that combine reversible actuation and self-healing ability. Here, we report halogen-bonded liquid crystal elastomers (LCEs) that can be arbitrarily shape-programmed and that self-heal under mild thermal or photothermal stimulation.

Antimony-Bismuth Alloying: The Key to a Major Boost in the Efficiency of Lead-Free Perovskite-Inspired Photovoltaics.

The perovskite-inspired Cu AgBiI (CABI) material has been gaining increasing momentum as photovoltaic (PV) absorber due to its low toxicity, intrinsic air stability, direct bandgap, and a high absorption coefficient in the range of 10  cm . However, the power conversion efficiency (PCE) of existing CABI-based PVs is still seriously constrained by the presence of both intrinsic and surface defects. Herein, antimony (III) (Sb ) is introduced into the octahedral lattice sites of the CABI structure, leading to CABI-Sb with larger crystalline domains than CABI.

New tricks and emerging applications from contemporary azobenzene research.

Azobenzenes have many faces. They are well-known as dyes, but most of all, azobenzenes are versatile photoswitchable molecules with powerful photochemical properties. Azobenzene photochemistry has been extensively studied for decades, but only relatively recently research has taken a steer towards applications, ranging from photonics and robotics to photobiology.

A high-conductivity n-type polymeric ink for printed electronics.

Conducting polymers, such as the p-doped poly(3,4-ethylenedioxythiophene):poly(styrene sulfonate) (PEDOT:PSS), have enabled the development of an array of opto- and bio-electronics devices. However, to make these technologies truly pervasive, stable and easily processable, n-doped conducting polymers are also needed. Despite major efforts, no n-type equivalents to the benchmark PEDOT:PSS exist to date.

Sequential Doping of Ladder-Type Conjugated Polymers for Thermally Stable n-Type Organic Conductors.

Doping of organic semiconductors is a powerful tool to optimize the performance of various organic (opto)electronic and bioelectronic devices. Despite recent advances, the low thermal stability of the electronic properties of doped polymers still represents a significant obstacle to implementing these materials into practical applications. Hence, the development of conducting doped polymers with excellent long-term stability at elevated temperatures is highly desirable.

Ground-state electron transfer in all-polymer donor-acceptor heterojunctions.

Doping of organic semiconductors is crucial for the operation of organic (opto)electronic and electrochemical devices. Typically, this is achieved by adding heterogeneous dopant molecules to the polymer bulk, often resulting in poor stability and performance due to dopant sublimation or aggregation. In small-molecule donor-acceptor systems, charge transfer can yield high and stable electrical conductivities, an approach not yet explored in all-conjugated polymer systems.

Impact of Singly Occupied Molecular Orbital Energy on the n-Doping Efficiency of Benzimidazole Derivatives.

We investigated the impact of singly occupied molecular orbital (SOMO) energy on the n-doping efficiency of benzimidazole derivatives. By designing and synthesizing a series of new air-stable benzimidazole-based dopants with different SOMO energy levels, we demonstrated that an increase of the dopant SOMO energy by only ∼0.3 eV enhances the electrical conductivity of a benchmark electron-transporting naphthalenediimide-bithiophene polymer by more than 1 order of magnitude.

Halogen-Bond-Assisted Photoluminescence Modulation in Carbazole-Based Emitter.

Halogen bonding between a carbazole-based, pyridine-substituted organic semiconductor and a common halogen-bond donor (pentafluoroiodobenzene) yields efficient halogen-bond-driven fluorescence modulation in solution. Steady-state, time-resolved emission and absorption spectroscopy as well as density functional theory studies demonstrate that the fluorescence modulation arises from halogen-bond-induced intramolecular charge transfer. Fluorescence modulation offers a range of possibilities both in solution and in the solid state, for instance providing a potential pathway for the design of tunable luminescent materials for light-emitting devices.

Subpicosecond to Second Time-Scale Charge Carrier Kinetics in Hematite-Titania Nanocomposite Photoanodes.

Water splitting with hematite is negatively affected by poor intrinsic charge transport properties. However, they can be modified by forming heterojunctions to improve charge separation. For this purpose, charge dynamics of TiO2:α-Fe2O3 nanocomposite photoanodes are studied using transient absorption spectroscopy to monitor the evolution of photogenerated charge carriers as a function of applied bias voltage.

Vapor Phase Processing of α-Fe₂O₃ Photoelectrodes for Water Splitting: An Insight into the Structure/Property Interplay.

Harvesting radiant energy to trigger water photoelectrolysis and produce clean hydrogen is receiving increasing attention in the search of alternative energy resources. In this regard, hematite (α-Fe2O3) nanostructures with controlled nano-organization have been fabricated and investigated for use as anodes in photoelectrochemical (PEC) cells. The target systems have been grown on conductive substrates by plasma enhanced-chemical vapor deposition (PE-CVD) and subjected to eventual ex situ annealing in air to further tailor their structure and properties.

Photophysical study of a self-assembled donor-acceptor two-layer film on TiO2.

The self-assembled monolayer (SAM) technique was employed to fabricate a two-layer donor-acceptor film on the surface of TiO2. The approach is based on using donor and acceptor compounds with anchoring groups of different lengths. The acceptor, a fullerene derivative, has a carboxyl anchor attached to the fullerene moiety via a short linker that places the fullerene close to the surface.