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Artificial light harvesting, a process that involves converting sunlight into chemical potential energy, is considered to be a promising part of the overall solution to address urgent global energy challenges. Conjugated polyelectrolyte complexes (CPECs) are particularly attractive for this purpose due to their extended electronic states, tunable assembly thermodynamics, and sensitivity to their local environment. Importantly, ionically assembled complexes of conjugated polyelectrolytes can act as efficient donor-acceptor pairs for electronic energy transfer (EET). However, to be of use in material applications, we must understand how modifying the chemical structure of the CPE backbone alters the EET rate beyond spectral overlap considerations. In this report we investigate the dependence of the EET efficiency and rate on the electronic structure and excitonic wave function of the CPE backbone. To do so, we synthesized a series of alternating copolymers where the electronic states are systematically altered by introducing comonomers with electron withdrawing and electron-rich character while keeping the linear ionic charge density nearly fixed. We find evidence that the excitonic coupling may be significantly affected by the exciton delocalization radius, in accordance with analytical models based on the line-dipole approximation and quantum chemistry calculations. Our results imply that care should be taken when selecting CPE components for optimal CPEC EET. These results have implications for using CPECs as key components in water-based light-harvesting materials, either as standalone assemblies or as adsorbates on nanoparticles and thin films.

Conjugated polymers are promising photoactive materials for heterogeneous photocatalysis, but their limited solubility hinders the scalability in practical use. Herein, we develop polymer composites using processable conjugated polyelectrolytes and ionomers to fabricate photocatalytic thin films with visible light activity. The composite of conjugated polyelectrolytes and ionomers with identical counter anions in their side chains enables compatibility in solvents and stabilized charged states within the composite. This facilitates the development of stable coatings on diverse substrates and enhances charge separation and transport. The resulting photocatalytic thin films exhibited a 1.5‐fold increase in photocurrent response and a 7.0‐fold increase in mechanical strength compared to the pristine conjugated polymer. Photoactive coatings with polymer composites showcase the potential for synergistic photocatalytic oxidation of NADH, organic dye, and sulfide under visible light irradiation. The photocatalytic thin films are stable, versatile, and scalable for various photocatalytic reactions, showing promise for developing upscaled photoreactors. [ABSTRACT FROM AUTHOR]

Multidrug resistance to clinical chemotherapeutic drugs severely limits antitumor efficacy and patient survival. The integration of chemotherapy with photothermal therapy (PTT) and reactive nitrogen species has become a major strategy to enhance cancer treatment efficacy. Herein, a multifunctional peroxynitrite (ONOO−) nanogenerator (PBT/NO/Pt) for NIR‐II fluorescence (NIR‐II FL)/NIR‐II photoacoustic (NIR‐II PA) imaging‐guided chemo/NIR‐II PTT/ONOO− combination therapy is reported. The multifunction nanogenerator is developed by co‐loading a pH‐sensitive nitric oxide donor (DETA NONOate) and nicotinamide adenine dinucleotide phosphate oxidases trigger superoxide (O2•−) generator chemotherapy drug (CDDP) to an NIR‐II excitation‐conjugated polyelectrolyte (PNC11BA). PNC11BA has non‐conjugated alkyl chain segments in the polymer backbone and abundant positively charged phenylboronic acid in its side chains, which support the anti‐quenching of NIR‐II FL and the integration of DETA NONOate and CDDP into PBT/NO/Pt. In the acidic tumor microenvironment, the coordination bonds between CDDP and PNC11BA are cleaved, releasing CDDP for chemotherapeutic activity. The simultaneous release of nitric oxide (NO) and O2•− rapidly leads to the in situ generation of the more cytotoxic reactive physiological nitrogen species ONOO−. In vitro and in vivo results prove that PBT/NO/Pt exhibited a markedly ONOO− enhanced chemo–photothermal synergistic therapy for SKOV3/DDP tumor by downregulating the intracellular glutathione and increasing CDDP–DNA adducts. [ABSTRACT FROM AUTHOR]

Abstract Multidrug resistance to clinical chemotherapeutic drugs severely limits antitumor efficacy and patient survival. The integration of chemotherapy with photothermal therapy (PTT) and reactive nitrogen species has become a major strategy to enhance cancer treatment efficacy. Herein, a multifunctional peroxynitrite (ONOO−) nanogenerator (PBT/NO/Pt) for NIR‐II fluorescence (NIR‐II FL)/NIR‐II photoacoustic (NIR‐II PA) imaging‐guided chemo/NIR‐II PTT/ONOO− combination therapy is reported. The multifunction nanogenerator is developed by co‐loading a pH‐sensitive nitric oxide donor (DETA NONOate) and nicotinamide adenine dinucleotide phosphate oxidases trigger superoxide (O2•−) generator chemotherapy drug (CDDP) to an NIR‐II excitation‐conjugated polyelectrolyte (PNC11BA). PNC11BA has non‐conjugated alkyl chain segments in the polymer backbone and abundant positively charged phenylboronic acid in its side chains, which support the anti‐quenching of NIR‐II FL and the integration of DETA NONOate and CDDP into PBT/NO/Pt. In the acidic tumor microenvironment, the coordination bonds between CDDP and PNC11BA are cleaved, releasing CDDP for chemotherapeutic activity. The simultaneous release of nitric oxide (NO) and O2•− rapidly leads to the in situ generation of the more cytotoxic reactive physiological nitrogen species ONOO−. In vitro and in vivo results prove that PBT/NO/Pt exhibited a markedly ONOO− enhanced chemo–photothermal synergistic therapy for SKOV3/DDP tumor by downregulating the intracellular glutathione and increasing CDDP–DNA adducts.

Three sulfonate‐containing polyelectrolytes are elaborately designed and used to passivate perovskite film with the anti‐solvent method. Under the influence of the secondary monomer, three copolymers present various chemical configurations and deliver different modification effects. Fluorene‐thiophene copolymer STF has linear and highly‐conjugated chain. STF‐perovskite film presents large crystal grains. Fluorene‐carbazole copolymer SCF has flexible chain and easily enters into grain boundary areas. SCF‐perovskite film is homogenous and continuous. Fluorene‐fluorene copolymer SPF agglomerates on the surface and is not applicable to the anti‐solvent method. The full investigation demonstrates that STF and SCF not only conduct surface defect passivation, but also improve the film quality by being involved in the perovskite's crystallization process. Compared with the control device, the devices with STF and SCF deliver high efficiency and excellent stability. The unencapsulated devices with STF and SCT maintain ≈80% of the initial power conversion efficiency (PCE) after 40 days of storage under 30–40% relative humidity. SCF performs better and the device maintains 60% of the initial PCE after 20 days of storage under 60–80% relative humidity. [ABSTRACT FROM AUTHOR]

Environmentally-benign materials play a pivotal role in advancing the scalability of energy storage devices. In particular, conjugated polymers constitute a potentially greener alternative to inorganic- and carbon-based materials. One challenge to wider implementation is the scarcity of n-doped conducting polymers to achieve full cells with high-rate performance. Herein, this work demonstrates the use of a self-doped n-doped conjugated polymer, namely poly(benzodifurandione) (PBDF), for fabricating aqueous supercapacitors. PBDF demonstrates a specific capacitance of 202 ± 3 F g -1 , retaining 81% of the initial performance over 5000 cycles at 10 A g -1 in 2 m NaCl ( aq ) . PBDF demonstrates rate performances of up to 100 and 50 A g -1 at 1 and 2 mg cm -2 , respectively. Electrochemical impedance analysis reveals a surface-mediated charge storage mechanism. Improvements can be achieved by adding reduced graphene oxide (rGO), thereby obtaining a specific capacitance of 288 ± 8 F g -1 and high-rate operation (270 A g -1 ). The performance of PBDF is examined in symmetric and asymmetric membrane-less cells, demonstrating high-rate performance, while retaining 83% of the initial capacitance after 100 000 cycles at 10 A g -1 . PBDF thus offers new prospects for energy storage applications, showcasing both desirable performance and stability without the need for additives or binders and relying on environmentally friendly solutions., (© 2024 Wiley‐VCH GmbH.)

[Display omitted] • A conjugated polyelectrolyte, PhH-1T, was adopted as a chemical dopant. • PhH-1T provided efficient chemical doping and blend in conjugated polymers. • PhH-1T-doped P3HT organic field-effect transistors improved charge mobility. • Importance of backbone within polymeric dopant for doping was demonstrated. The introduction of extrinsic materials into host materials has been extensively considered for resolving the challenge of intrinsically low charge movement within semiconducting polymers. One of the difficult issues is developing a dopant that can provide a sufficient interfacial area between host and dopant as well as maintain an efficient charge transport pathway without significantly altering the morphological and crystalline properties of semiconducting polymers. Herein, we propose the use of conjugated polyelectrolyte (CPE), a new highly mixable and mutual dopant for achieving enhanced charge mobility in host conjugated polymers. We found that CPE has more homogeneous dispersion in host polymers than non-conjugated polymeric dopants. This results in enhanced charge mobility in the organic field-effect transistor (OFET) based on a novel p-type semiconducting polymer, poly(3-hexylthiophene) (P3HT) (from 0.076 to 0.135 cm2 V−1 s−1). Atomic force microscopy and grazing incident X-ray diffraction measurements were used to confirm the non-destructive behavior of CPE within P3HT. Therefore, it is believed that CPE is promising for use as a homogeneous chemical dopant for polymer semiconductors. [ABSTRACT FROM AUTHOR]

Biological photoresponsive ion transport systems consistently attract researchers' attention owing to their remarkable functions of harvesting energy from nature and participating in visual perception systems. Designing and constructing artificial light-driven ion transport devices to mimic biological counterparts remains a challenge owing to fabrication limitations in nanoconfined spaces. Herein, a typical conjugated polyelectrolyte (PFN-Br) was assembled onto a laminated MoS 2 M using simple solution-processing vacuum filtration, resulting in a heterogeneous three- and two-dimensional nanoporous membrane. The designed band alignment between PFN-Br and MoS 2 enables effective directional ion transport under irradiation in an equilibrium solution, even against a 30-fold concentration gradient. The staggered energy structure of PFN-Br and MoS 2 enhances charge separation and establishes a photogenerated potential as the driving force for ion transport. Additionally, the activation energy barrier for ion transport across the heterogeneous membrane decreased by 60% after light irradiation, considerably improving ion transport flux. The easy fabrication and high performance of the membrane in light-powered ion transport provide promising approaches for designing nanofluidic devices with possible applications in energy conversion, light-enhanced biosensing, and photoresponsive ionic devices.

A new photo-crosslinkable donor polymer, PM6-Br50 facilitates the fabrication of p- PHJ OPDs through LbL deposition of D and A materials overcoming solvent-imposed constraints. The integration of a p- PHJ architecture with a conjugated polyelectrolyte as a hole-transport layer resulted in a significantly reduced dark current, leading to a remarkably high specific detectivity. [Display omitted] • A new polymer donor is synthesized by introduction of photo-crosslinkable side chains. • Layer-by-layer OPDs are fabricated utilizing a photo-crosslinkable polymer donor. • A conjugated polyelectrolyte-based HTL is employed to inhibit electron injection. • A significantly high detectivity is achieved with a suppressed dark current. The effective reduction of dark (or noise) current presents a significant hurdle in enhancing the detectivity of organic photodetectors (OPDs). To address this challenge, a photo-crosslinkable donor polymer, PM6-Br50, is synthesized by introducing bromoalkyl side-chains onto the PM6 structure. This modification enables the formation of a pseudo planar heterojunction (p- PHJ) structure of crosslinked donor/acceptor through a layer-by-layer (LbL) sequential process without the necessity for an semi-orthogonal solvent. This innovation effectively overcomes solvent-related limitations in the LbL process. Additionally, we replace the semi-metallic hole-transport layer (HTL), PEDOT:PSS, with a semiconducting conjugated polyelectrolyte (TPAFS-TMA) with a high conduction band. The p- PHJ configuration, featuring pure donor/anode and pure acceptor/cathode contacts, enhances the charge injection barrier for electrons (holes) from the anode (cathode) in the dark under reverse bias, effectively minimizing dark current. Furthermore, the TPAFS-TMA HTL serves to impede electron injection from the anode. Through the synergistic combination of these two strategies, a significantly reduced dark current density (4.03 × 10−10 A cm−2) is measured by four orders of magnitude, compared to the bulk heterojunction OPDs with PEDOT:PSS. Furthermore, we measure remarkably high shot noise-based and total noise current-based specific detectivities of 4.27 × 1013 and 6.97 × 1012 cm Hz1/2 W−1 (with linear dynamic range of 73.7 dB), respectively. [ABSTRACT FROM AUTHOR]

Organic photovoltaic (OPV) cells have experienced significant development in the last decades after the introduction of nonfullerene acceptor molecules with top power conversion efficiencies reported over 19% and considerable versatility, for example, with application in transparent/semitransparent and flexible photovoltaics. Yet, the optimization of the operational stability continues to be a challenge. This study presents a comprehensive investigation of the use of a conjugated polyelectrolyte polymer (CPE-Na) as a hole layer (HTL) to improve the performance and longevity of OPV cells. Two different fabrication approaches were adopted: integrating CPE-Na with PEDOT:PSS to create a composite HTL and using CPE-Na as a stand-alone bilayer deposited beneath PEDOT:PSS on the ITO substrate. These configurations were compared against a reference device employing PEDOT:PSS alone, as the HTL increased efficiency and fill factor. The instruments with CPE-Na also demonstrated increased stability in the dark and under simulated operational conditions. Device-based PEDOT:PSS as an HTL reached T80 after 2500 h while involving CPE-Na in the device kept at T90 in the same period, evidenced by a reduced degradation rate. Furthermore, the impedance spectroscopy and photoinduced transient methods suggest optimized charge transfer and reduced charge carrier recombination. These findings collectively highlight the potential of CPE-Na as a HTL optimizer material for nonfluorine OPV cells.

This study describes the formation, size control, and penetration behavior of polymer nanodots (Pdots) consisting of single or few chain polythiophene-based conjugated polyelectrolytes (CPEs) via nanophase separation between good solvent and poor solvent of CPE. Though the chain singularity may be associated with dilution nanophase separation suggests that molecules of a good solvent create a thermodynamically driven solvation layer surrounding the CPEs and thereby separating the single chains even in their poor solvents. This statement is therefore corroborated with emission intensity/lifetime, particle size, and scattering intensity of polyelectrolyte in good and poor solvents. Regarding the augmented features, Pdots are implemented into cell imaging studies to understand the nuclear penetration and to differentiate the invasive characteristics of breast cancer cells. The python based red, green, blue (RGB) color analysis   depicts that Pdots have more nuclear penetration ability in triple negative breast cancer cells due to the different nuclear morphology in shape and composition and Pdots have penetrated cell membrane as well as extracellular matrix in spheroid models. The current Pdot protocol and its utilization in cancer cell imaging are holding great promise for gene/drug delivery to target cancer cells by explicitly achieving the very first priority of nuclear intake., (© 2024 Wiley‐VCH GmbH.)