A Cross-linked n-Type Conjugated Polymer with Polar Side Chains Enables Ultrafast Pseudocapacitive Energy Storage.

Pseudocapacitors bridge the performance gap between batteries and electric double-layer capacitors by storing energy via a combination of fast surface/near-surface Faradaic redox processes and electrical double-layer capacitance. Organic semiconductors are an emerging class of pseudocapacitive materials that benefit from facile synthetic tunability and mixed ionic-electronic conduction. Reported examples are mostly limited to p-type (electron-donating) conjugated polymers, while n-type (electron-accepting) examples remain comparatively underexplored. This work introduces a new cross-linked n-type conjugated polymer, spiro-NDI-N, strategically designed with polar tertiary amine side chains. This molecular design aims to synergistically increase the electroactive surface area and boost ion transport for efficient ionic-electronic coupling. Spiro-NDI-N demonstrates excellent pseudocapacitive energy storage performance in pH-neutral aqueous electrolytes, with specific capacitance values of up to 532 F g-1 at 5 A g-1 and stable cycling over 5000 cycles. Moreover, it maintains a rate capability of 307 F g-1 at 350 A g-1 . The superior pseudocapacitive performance of spiro-NDI-N, compared to strategically designed structural analogues lacking either the cross-linked backbone or polar side chains, validates the essential role of its molecular design elements. More broadly, the design and performance of spiro-NDI-N provide a novel strategy for developing high-performance organic pseudocapacitors.

An anti-mycobacterial conjugated oligoelectrolyte effective against Mycobacterium abscessus.

Infections caused by nontuberculous mycobacteria have increased more than 50% in the past two decades and more than doubled in the elderly population. Mycobacterium abscessus (Mab), one of the most prevalent of these rapidly growing species, is intrinsically resistant to numerous antibiotics. Current standard-of-care treatments are not satisfactory, with high failure rate and notable adverse effects. We report here a potent anti-Mab compound from the flexible molecular framework afforded by conjugated oligoelectrolytes (COEs). A screen of structurally diverse, noncytotoxic COEs identified a lead compound, COE-PNH2, which was bactericidal against replicating, nonreplicating persisters and intracellular Mab.COE-PNH2 had low propensity for resistance development, with a frequency of resistance below 1.25 × 10-9 and showed no detectable resistance upon serial passaging. Mechanism of action studies were in line with COE-PNH2 affecting the physical and functional integrity of the bacterial envelope and disrupting the mycomembrane and associated essential bioenergetic pathways. Moreover, COE-PNH2 was well-tolerated and efficacious in a mouse model of Mab lung infection. This study highlights desirable in vitro and in vivo potency and safety index of this COE structure, which represents a promising anti-mycobacterial to tackle an unmet medical need.

Conjugated Polyelectrolyte Thin Films for Pseudocapacitive Applications.

A subclass of organic semiconductors known as conjugated polyelectrolytes (CPEs) is characterized by a conjugated backbone with ionic pendant groups. The water solubility of CPEs typically hinders applications of thin films in aqueous media. Herein, it is reported that films of an anionic CPE, namely CPE-K, drop cast from water produces single-component solid-state pseudocapacitive electrodes that are insoluble in aqueous electrolyte. That X-ray diffraction experiments reveal a more structurally ordered film, relative to the as-obtained powder from chemical synthesis, and dynamic light scattering measurements show an increase in aggregate particle size with increasing [KCl] indicate that CPE-K films are insoluble because of tight interchain contacts and electrostatic screening by the electrolyte. CPE-K film electrodes can maintain 85% of their original capacitance (84 F g-1 ) at 500 A g-1 and exhibit excellent cycling stability, where a capacitance retention of 93% after 100 000 cycles at a current density of 35 A g-1 . These findings demonstrate that it is possible to use initially water soluble ionic-organic materials in aqueous electrolytes, by increasing the electrolyte concentration. This strategy can be applied to the application of conjugated polyelectrolytes in batteries, organic electrochemical transistors, and electrochemical sensors, where fast electron and ion transport are required.

Real-Time Monitoring of Mitochondrial Damage Using Conjugated Oligoelectrolytes.

Conjugated oligoelectrolytes (COEs) comprise a class of fluorescent reporters with tunable optical properties and lipid bilayer affinity. These molecules have proven effective in a range of bioimaging applications; however, their use in characterizing specific subcellular structures remains restricted. Such capabilities would broaden COE applications to understand cellular dysfunction, cell communication, and the targets of different pharmaceutical agents. Here, we disclose a novel COE derivative, COE-CN, which enables the visualization of mitochondria, including morphological changes and lysosomal fusion upon treatment with depolarizing agents. COE-CN is characterized by the presence of imidazolium solubilizing groups and an optically active cyanovinyl-linked distyrylbenzene core with intramolecular charge-transfer characteristics. Our current understanding is that the relatively shorter molecular length of COE-CN leads to weaker binding within lipid bilayer membranes, which allows sampling of internal cellular structures and ultimately to different localization relative to elongated COEs. As a means of practical demonstration, COE-CN can be used to diagnose cells with damaged mitochondria via flow cytometry. Coupled with an elongated COE that does not translocate upon depolarization, changes in ratiometric fluorescence intensity can be used to monitor mitochondrial membrane potential disruption, demonstrating the potential for use in diagnostic assays.

Recyclable Conjugated Polyelectrolyte Hydrogels for Pseudocapacitor Fabrication.

In alignment with widespread interest in carbon neutralization and sustainable practices, we disclose that conjugated polyelectrolyte (CPE) hydrogels are a type of recyclable, electrochemically stable, and environmentally friendly pseudocapacitive material for energy storage applications. By leveraging ionic-electronic coupling in a relatively fluid medium, one finds that hydrogels prepared using a fresh batch of an anionic CPE, namely, Pris-CPE-K, exhibit a specific capacitance of 32.6 ± 6.6 F g-1 in 2 M NaCl and are capable of 80% (26.1 ± 6.5 F g-1) capacitance retention after 100,000 galvanostatic charge-discharge (GCD) cycles at a current density (J) of 10 A g-1. We note that equilibration under a constant potential prior to GCD analysis leads to the K+ counterions in the CPE exchanging with Na+ and, thus, the relevant active material Pris-CPE-Na. It is possible to remove the CPE material from the electrochemical cell via extraction with water and to carry out a simple purification through dialysis to produce a recycled material, namely Re-CPE-Na. The recycling workup has no significant detrimental impact on the electrochemical performance. Specifically, Re-CPE-Na hydrogels display an initial specific capacitance of 26.3 ± 1.2 F g-1 (at 10 A g-1) and retain 77% of the capacitance after a subsequent 100,000 GCD cycles. Characterization by NMR, FTIR, and Raman spectroscopies, together with XPS and GPC measurements, revealed no change in the structure of the backbone or side chains. However, rheological measurements gave evidence of a slight loss in G' and G''. Overall, that CPE hydrogels display recyclability argues in favor of considering them as a novel materials platform for energy storage applications within an economically viable circular recycling strategy.

Amidine-Based Cationic Conjugated Oligoelectrolytes with Antimicrobial Activity against Pseudomonas aeruginosa Biofilms.

Pseudomonas aeruginosa is an opportunistic Gram-negative bacterium that can cause high-morbidity infections. Due to its robust, flexible genome and ability to form biofilms, it can evade and rapidly develop resistance to antibiotics. Cationic conjugated oligoelectrolytes (COEs) have emerged as a promising class of antimicrobials. Herein, we report a series of amidine-containing COEs with high selectivity for bacteria. From this series, we identified 1b as the most active compound against P. aeruginosa (minimum inhibitory concentration (MIC) = 2 µg/mL) with low cytotoxicity (IC50 (HepG2) = 1024 µg/mL). The activity of 1b was not affected by known drug-resistant phenotypes of 100 diverse P. aeruginosa isolates. Moreover, 1b is bactericidal with a low propensity for P. aeruginosa to develop resistance. Furthermore, 1b is also able to inhibit biofilm formation at subinhibitory concentrations and kills P. aeruginosa in established biofilms. The in vivo efficacy of 1b was demonstrated in biofilm-associated murine wound infection models.

Interstellar photovoltaics.

The term 'Solar Cell' is commonly used for Photovoltaics that convert light into electrical energy. However, light can be harvested from various sources not limited to the Sun. This work considers the possibility of harvesting photons from different star types, including our closest neighbor star Proxima Centauri. The theoretical efficiency limits of single junction photovoltaic devices are calculated for different star types at a normalized light intensity corresponding to the AM0 spectrum intensity with AM0 = 1361 W/m2. An optimal bandgap of > 12 eV for the hottest O5V star type leads to 47% Shockley-Queisser photoconversion efficiency (SQ PCE), whereas a narrower optimal bandgap of 0.7 eV leads to 23% SQ PCE for the coldest red dwarf M0, M5.5Ve, and M8V type stars. Organic Photovoltaics (OPVs) are the most lightweight solar technology and have the potential to be employed in weight-restricted space applications, including foreseeable interstellar missions. With that in mind, the Sun's G2V spectrum and Proxima Centauri's M5.5Ve spectrum are considered in further detail in combination with two extreme bandgap OPV systems: one narrow bandgap system (PM2:COTIC-4F, Eg = 1.14 eV) and one wide bandgap system (PM6:o-IDTBR, Eg = 1.62 eV). Semi-empirically modeled JV-curves reveal that the absorption characteristics of the PM2:COTIC-4F blend match well with both the G2V and the M5.5Ve spectrum, yielding theoretical PCEs of 22.6% and 12.6%, respectively. In contrast, the PM6:o-IDTBR device shows a theoretical PCE of 18.2% under G2V illumination that drops sharply to 0.9% under M5.5Ve illumination.

Structural modulation of membrane-intercalating conjugated oligoelectrolytes decouples outer membrane permeabilizing and antimicrobial activities.

We report a series of membrane-intercalating conjugated oligoelectrolytes (MICOEs) to probe how structural features impact bacterial membrane integrity and antibiotic activity. Minimum inhibitory concentrations (MICs) and outer membrane (OM) permeability correlated to different structural parameters suggesting that the antimicrobial mechanism is not related to OM permeabilization. However, lipid order parameters and MICs correlated to the same structural feature suggesting a possible link.

A Broad Light-Harvesting Conjugated Oligoelectrolyte Enables Photocatalytic Nitrogen Fixation in a Bacterial Biohybrid.

We report a rationally designed membrane-intercalating conjugated oligoelectrolyte (COE), namely COE-IC, which endows aerobic N2 -fixing bacteria Azotobacter vinelandii with a light-harvesting ability that enables photosynthetic ammonia production. COE-IC possesses an acceptor-donor-acceptor (A-D-A) type conjugated core, which promotes visible light absorption with a high molar extinction coefficient. Furthermore, COE-IC spontaneously associates with A. vinelandii to form a biohybrid in which the COE is intercalated within the lipid bilayer membrane. In the presence of L-ascorbate as a sacrificial electron donor, the resulting COE-IC/A. vinelandii biohybrid showed a 2.4-fold increase in light-driven ammonia production, as compared to the control. Photoinduced enhancement of bacterial biomass and production of L-amino acids is also observed. Introduction of isotopically enriched 15 N2 atmosphere led to the enrichment of 15 N-containing intracellular metabolites, consistent with the products being generated from atmospheric N2 .

Increased Nitrogenase Activity in Solar-Driven Biohybrids Containing Non-photosynthetic Bacteria and Conducting Polymers.

A conductive polymer-based photosynthetic biohybrid is constructed to enhance biological nitrogen fixation by increasing nitrogenase activity in the non-photosynthetic bacterium Azotobacter Chroococcum (A. Chroococcum). The light-harvesting cationic poly(fluorene-alt-phenylene) (PFP) electrostatically binds to the surface of the bacteria and possesses satisfactory conductivity to facilitate electron transfer to the bacterium, promoting the nitrogen fixation pathway through redox proteins on the surface of the bacteria when under illumination. Therefore, the nitrogenase activity, hydrogen, NH4 + -N and L-amino acids production are increased by 260 %, 37 %, 44 %, and 47 %, respectively. The expression levels of nifD and nifK encoding molybdenum-iron (MoFe) protein and relevant nitrogen-fixing proteins are up-regulated. These photoactive conductive polymer-bacteria biohybrids provide a new method for improving the biological nitrogen fixation capability of non-photosynthetic nitrogen-fixing bacteria.

An n-Type Conjugated Oligoelectrolyte Mimics Transmembrane Electron Transport Proteins for Enhanced Microbial Electrosynthesis.

Interfacing bacteria as biocatalysts with an electrode provides the basis for emerging bioelectrochemical systems that enable sustainable energy interconversion between electrical and chemical energy. Electron transfer rates at the abiotic-biotic interface are, however, often limited by poor electrical contacts and the intrinsically insulating cell membranes. Herein, we report the first example of an n-type redox-active conjugated oligoelectrolyte, namely COE-NDI, which spontaneously intercalates into cell membranes and mimics the function of endogenous transmembrane electron transport proteins. The incorporation of COE-NDI into Shewanella oneidensis MR-1 cells amplifies current uptake from the electrode by 4-fold, resulting in the enhanced bio-electroreduction of fumarate to succinate. Moreover, COE-NDI can serve as a "protein prosthetic" to rescue current uptake in non-electrogenic knockout mutants.

Antimicrobial Conjugated Oligoelectrolytes Containing Triphenylphosphonium Solubilizing Groups.

Invited for the cover of this issue is the group of Guillermo C. Bazan, Kaixi Zhang and co-workers at the National University of Singapore The image depicts the activity of lead compound DM6P acting on a model bacteria membrane. Read the full text of the article at 10.1002/chem.202203803.

A broad-spectrum synthetic antibiotic that does not evoke bacterial resistance.

BACKGROUND: Antimicrobial resistance (AMR) poses a critical threat to public health and disproportionately affects the health and well-being of persons in low-income and middle-income countries. Our aim was to identify synthetic antimicrobials termed conjugated oligoelectrolytes (COEs) that effectively treated AMR infections and whose structures could be readily modified to address current and anticipated patient needs. METHODS: Fifteen chemical variants were synthesized that contain specific alterations to the COE modular structure, and each variant was evaluated for broad-spectrum antibacterial activity and for in vitro cytotoxicity in cultured mammalian cells. Antibiotic efficacy was analyzed in murine models of sepsis; in vivo toxicity was evaluated via a blinded study of mouse clinical signs as an outcome of drug treatment. FINDINGS: We identified a compound, COE2-2hexyl, that displayed broad-spectrum antibacterial activity. This compound cured mice infected with clinical bacterial isolates derived from patients with refractory bacteremia and did not evoke bacterial resistance. COE2-2hexyl has specific effects on multiple membrane-associated functions (e.g., septation, motility, ATP synthesis, respiration, membrane permeability to small molecules) that may act together to negate bacterial cell viability and the evolution of drug-resistance. Disruption of these bacterial properties may occur through alteration of critical protein-protein or protein-lipid membrane interfaces-a mechanism of action distinct from many membrane disrupting antimicrobials or detergents that destabilize membranes to induce bacterial cell lysis. INTERPRETATION: The ease of molecular design, synthesis and modular nature of COEs offer many advantages over conventional antimicrobials, making synthesis simple, scalable and affordable. These COE features enable the construction of a spectrum of compounds with the potential for development as a new versatile therapy for an imminent global health crisis. FUNDING: U.S. Army Research Office, National Institute of Allergy and Infectious Diseases, and National Heart, Lung, and Blood Institute.

Antimicrobial Conjugated Oligoelectrolytes Containing Triphenylphosphonium Solubilizing Groups.

Conjugated oligoelectrolytes (COEs) are an emerging class of amphiphilic antimicrobial compounds with a modular molecular framework suitable for simple chemical derivatization. Here, a series of COE derivatives with a stilbene-conjugated segment and triphenylphosphonium (TPP) pendant groups was designed and synthesized to understand how lipophilic cationic groups impact antimicrobial activity. In vitro evaluations against ESKAPE pathogens showed broad-spectrum activity towards multi-drug resistant (MDR) bacteria and mycobacteria, with TPP groups enhancing antimicrobial activity towards clinically relevant Gram-negative strains compared to their ammonium analogues. We studied the interactions of DM6P, the most active TPP-COE compound, with various membrane assays. Treatment of bacterial cells with DM6P showed enhanced permeability of cell membranes without inducing the development of significant bacterial resistance. Moreover, DM6P eliminated 99.99 % of methicillin-resistant Staphyloccocus aureus (MRSA) in an in vivo wound model. These results represent a promising chemical strategy for increasing the activity spectrum of membrane-active COE antibiotics to tackle challenging drug-resistant targets.

Water-soluble extracellular vesicle probes based on conjugated oligoelectrolytes.

We developed a series of transmembrane conjugated oligoelectrolytes (COEs) with tunable optical emissions from the UV to the near IR to address the false-positive problem when detecting nanometer-sized extracellular vesicles (EVs) by flow cytometry. The amphiphilic molecular framework of COEs is defined by a linear conjugated structure and cationic charged groups at each terminal site. Consequently, COEs have excellent water solubility and the absence of nanoaggregates at concentrations up to 50 µM, and unbound COE dyes can be readily removed through ultrafiltration. These properties enable unambiguous and simple detection of COE-labeled small EVs using flow cytometry with negligible background signals. We also demonstrated the time-lapsed tracking of small EV uptake into mammalian cells and the endogenous small EV labeling using COEs. Briefly, COEs provide a class of membrane-targeting dyes that behave as biomimetics of the lipid bilayer and a general and practical labeling strategy for nanosized EVs.

Designer co-beta-peptide copolymer selectively targets resistant and biofilm Gram-negative bacteria.

New antimicrobials are urgently needed to combat Gram-negative bacteria, particularly multi-drug resistant (MDR) and phenotypically resistant biofilm species. At present, only sequence-defined alpha-peptides (e.g. polymyxin B) can selectively target Gram-negative bacterial lipopolysaccharides. We show that a copolymer, without a defined sequence, shows good potency against MDR Gram-negative bacteria including its biofilm form. The tapered blocky co-beta-peptide with controlled N-terminal hydrophobicity (#4) has strong interaction with the Gram-negative bacterial lipopolysaccharides via its backbone through electrostatic and hydrogen bonding interactions but not the Gram-positive bacterial and mammalian cell membranes so that this copolymer is non-toxic to these two latter cell types. The new #4 co-beta-peptide selectively kills Gram-negative bacteria with low cytotoxicity both in vitro and in a mouse biofilm wound infection model. This strategy provides a new concept for the design of Gram-negative selective antimicrobial peptidomimetics against MDR and biofilm species.

Non-photosynthetic bacteria produce photocurrent mediated by NADH.

In recent years, the concern from the global climate change has driven an urgent need to develop clean energy technologies that do not involve combustion process that emit carbon into the atmosphere. A promising concept is microbial fuel cells that utilize bacteria as electron donors in a bio-electrochemical cell performing a direct electron transfer via conductive protein complexes or by secretion of redox active metabolites such as quinone or phenazine derivatives. In the case of photosynthetic bacteria (cyanobacteria) electrons can also be extracted from the photosynthetic pathway mediated mostly by NADH and NADPH. In this work, we show for the first time that the intact non-photosynthetic bacteria Escherichia coli can produce photocurrent that is enhanced upon addition of an exogenous electron mediator. Furthermore, we apply 2D-fluorescence measurement to show that NADH is released from the bacterial cells, which may apply as a native electron mediator in microbial fuel cells.

Enabling Electron Injection for Microbial Electrosynthesis with n-Type Conjugated Polyelectrolytes.

Microbial electrosynthesis-using renewable electricity to stimulate microbial metabolism-holds the promise of sustainable chemical production. A key limitation hindering performance is slow electron-transfer rates at biotic-abiotic interfaces. Here a new n-type conjugated polyelectrolyte is rationally designed and synthesized and its use is demonstrated as a soft conductive material to encapsulate electroactive bacteria Shewanella oneidensis MR-1. The self-assembled 3D living biocomposite amplifies current uptake from the electrode ≈674-fold over controls with the same initial number of cells, thereby enabling continuous synthesis of succinate from fumarate. Such functionality is a result of the increased number of bacterial cells having intimate electronic communication with the electrode and a higher current uptake per cell. This is underpinned by the molecular design of the polymer to have an n-dopable conjugated backbone for facile reduction by the electrode and zwitterionic side chains for compatibility with aqueous media. Moreover, direct arylation polycondensation is employed instead of the traditional Stille polymerization to avoid non-biocompatible tin by-products. By demonstrating synergy between living cells with n-type organic semiconductor materials, these results provide new strategies for improving the performance of bioelectrosynthesis technologies.

Structurally Resemblant Dopants Enhance Organic Room-Temperature Phosphorescence.

Doping has shown very promising potential in endowing room-temperature phosphorescence (RTP) properties of organic phosphors with minimal effort. Here, a new isomer design and doping strategy is reported that is applicable to dibenzothiophene (DBT) and its derivatives. Three isomers are synthesized to study the dopant effect on enhancing RTP of DBT derivatives. It is found that isomer dopants bearing close resemblance to the host with matched highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) energy levels and small energy difference between singlet- and triplet-excited states can yield efficient RTP for the doped system. Meanwhile, phosphorescence color from yellow to red is achieved by varying isomer dopants used for doping the DBT derivatives. This work represents an RTP enhancement strategy based on isomer design and doping to construct luminescent organic phosphors.

Conjugated Oligoelectrolytes for Long-Term Tumor Tracking with Incremental NIR-II Emission.

The design and synthesis of the near-infrared (NIR)-II emissive conjugated oligoelectrolyte COE-BBT are reported. COE-BBT has a solubility in aqueous media greater than 50 mg mL-1 , low toxicity, and a propensity to intercalate lipid bilayers, wherein it exhibits a higher emission quantum yield relative to aqueous media. Addition of COE-BBT to cells provides two emission channels, at ≈500 and ≈1020 nm, depending on the excitation wavelength, which facilitates in vitro confocal microscopy and in vivo animal imaging. The NIR-II emission of COE-BBT is used to track intracranial and subcutaneous tumor progression in mice. Of relevance is that the total NIR-II intensity increases over time. This phenomenon is attributed to a progressive attenuation of a COE-BBT self-quenching effect within the cells due to the expected dye dilution per cell as the tumor proliferates.