Microenvironment with NIR-Controlled ROS and Mechanical Tensions for Manipulating Cell Activities in Wound Healing.

The extracellular matrix (ECM) orchestrates cell behavior and tissue regeneration by modulating biochemical and mechanical signals. Manipulating cell-material interactions is crucial for leveraging biomaterials to regulate cell functions. Yet, integrating multiple cues in a single material remains a challenge. Here, near-infrared (NIR)-controlled multifunctional hydrogel platforms, named PIC/CM@NPs, are introduced to dictate fibroblast behavior during wound healing by tuning the matrix oxidative stress and mechanical tensions. PIC/CM@NPs are prepared through cell adhesion-medicated assembly of collagen-like polyisocyanide (PIC) polymers and cell-membrane-coated conjugated polymer nanoparticles (CM@NPs), which closely mimic the fibrous structure and nonlinear mechanics of ECM. Upon NIR stimulation, PIC/CM@NPs composites enhance fibroblast cell proliferation, migration, cytokine production, and myofibroblast activation, crucial for wound closure. Moreover, they exhibit effective and toxin removal antibacterial properties, reducing inflammation. This multifunctional approach accelerates healing by 95%, highlighting the importance of integrating biochemical and biophysical cues in the biomaterial design for advanced tissue regeneration.

Aligned Conjugated Polymer Nanofiber Networks in an Elastomer Matrix for High-Performance Printed Stretchable Electronics.

Conjugated polymer films are promising in wearable X-ray detection. However, achieving optimal film microstructure possessing good electrical and detection performance under large deformation via scalable printing remains challenging. Herein, we report bar-coated high-performance stretchable films based on a conjugated polymer P(TDPP-Se) and elastomer SEBS blend by optimizing the solution-processing conditions. The moderate preaggregation in solution and prolonged growth dynamics from a solvent mixture with limited dissolving capacity is critical to forming aligned P(TDPP-Se) chains/crystalline nanofibers in the SEBS phase with enhanced π-π stacking for charge transport and stress dissipation. The film shows a large elongation at break of >400% and high mobilities of 5.29 cm2 V-1 s-1 at 0% strain and 1.66 cm2 V-1 s-1 over 500 stretch-release cycles at 50% strain, enabling good X-ray imaging with a high sensitivity of 1501.52 µC Gyair-1 cm-2. Our work provides a morphology control strategy toward high-performance conjugated polymer film-based stretchable electronics.

Removing Conjugated Polymers from Aligned Carbon Nanotube Arrays.

Aligned carbon nanotube (A-CNT) with high semiconducting purity and high-density have been considered as one of the most promising active channels for field-effect transistors (FETs), but conjugated polymer dispersant residues on the surface of A-CNT have become the main obstacle for its further development in electronics applications. In this work, a series of removable conjugated polymers (CPs) are designed and synthesized to achieve favorable purification and alignment for CNT arrays with a high density of ≈360 CNTs/µm. Furthermore, a removal process of CPs on the CNT array film is developed. Raman spectra show that the CNTs in array film are almost not damaged after the removal process, and the G/D ratio is as high as 35. The field-effect transistors (FETs) are fabricated with a saturation current density up to 600 µA µm-1 and a current on-off ratio of ≈105, even with a relatively long channel length of ≈3 µm.

D-A Conjugated Polymer/CdS S-Scheme Heterojunction with Enhanced Interfacial Charge Transfer for Efficient Photocatalytic Hydrogen Generation.

Owing to the improved charge separation and maximized redox capability of the system, Step-scheme (S-scheme) heterojunctions have garnered significant research attention for efficient photocatalysis of H2 evolution. In this work, an innovative linear donor-acceptor (D-A) conjugated polymer fluorene-alt-(benzo-thiophene-dione) (PFBTD) is coupled with the CdS nanosheets, forming the organic-inorganic S-scheme heterojunction. The CdS/PFBTD (CP) composite exhibits an impressed hydrogen production rate of 7.62 mmol g-1 h-1 without any co-catalysts, which is ≈14 times higher than pristine CdS. It is revealed that the outstanding photocatalytic performance is attributed to the formation of rapid electron transfer channels through the interfacial Cd─O bonding as evidenced by the density functional theory (DFT) calculations and in situ X-ray photoelectron spectroscopy (XPS) analysis. The charge transfer mechanism involved in S-scheme heterojunctions is further investigated through the photo-irradiated Kelvin probe force microscopy (KPFM) analysis. This work provides a new point of view on the mechanism of interfacial charge transfer and points out the direction of designing superior organic-inorganic S-scheme heterojunction photocatalysts.

Efficient Sorting of Semiconducting Single-Walled Carbon Nanotubes in Bio-Renewable Solvents Through Main-Chain Engineering of Conjugated Polymers.

Conjugated polymer sorting is recognized as an efficient and scalable method for the selective extraction of semiconducting single-walled carbon nanotubes (s-SWCNTs). However, this process typically requires the use of nonpolar and aromatic solvents as the dispersion medium, which are petroleum-based and carry significant production hazards. Moreover, there is still potential for improving the efficiency of batch purification. Here, this study presents fluorene-based conjugated polymer that integrates diamines containing ethylene glycol chains (ODA) as linkers within the main chain, to effectively extract s-SWCNTs in bio-renewable solvents. The introduction of ODA segments enhances the solubility in bio-renewable solvents, facilitating effective wrapping of s-SWCNTs in polar environments. Additionally, the ODA within the main chain enhances affinity to s-SWCNTs, thereby contributing to increased yields and purity. The polymer achieves a high sorting yield of 55% and a purity of 99.6% in dispersion of s-SWCNTs in 2-Methyltetrahydrofuran. Thin-film transistor arrays fabricated with sorted s-SWCNTs solution through slot-die coating exhibit average charge carrier mobilities of 20-23 cm2 V⁻¹ s⁻¹ and high on/off current ratios exceeding 105 together with high spatial uniformity. This study highlights the viability of bio-renewable solvents in the sorting process, paving the way for the eco-friendly approach to the purification of SWCNTs.

Nanoconfined Supercooled Water in Hydrated Two-Dimensional Polyaniline for Sub-Zero Solid-State Zinc-Ion Hybrid Capacitor.

Solid-state electrochemical energy systems have attracted numerous attentions for their excellent performance, high safety, and low cost. Recently, ice of aqueous electrolytes is reported as a new kind solid-state electrolyte for low-temperature solid-state devices. However, the lack of kinetically favorable electrodes hampers the performance of this new class of icy electrolyte-based solid-state devices at sub-zero temperatures. In this work, a hydrated layered polyaniline cathode active material (h-LPANi) with nanoconfined supercooled water by metatungstate clusters is utilized to improve the performance of sub-zero solid-state zinc ion hybrid capacitors (ZIHCs). The interlayer confined hydrated network of h-LPANi improves kinetics, surpassing pristine polyaniline and conventional porous carbon-based active materials. At -15 °C, the solid-state iced ZIHCs with h-LPANi cathode demonstrate an areal energy density of 580.0 µWh cm-2 at 1.1 mW cm-2 and 155.7 µWh cm-2 at 43.3 mW cm-2, surpassing other low-temperature solid-state ZIHCs with conventional cathodes.

Single Atom Ag Bonding Between PF3T Nanocluster and TiO2 Leads the Ultra-Stable Visible-Light-Driven Photocatalytic H2 Production.

Atomic Ag cluster bonding is employed to reinforce the interface between PF3T nano-cluster and TiO2 nanoparticle. With an optimized Ag loading (Ag/TiO2 = 0.5 wt%), the Ag atoms will uniformly disperse on TiO2 thus generating a high density of intermediate states in the band gap to form the electron channel between the terthiophene group of PF3T and the TiO2 in the hybrid composite (denoted as T@Ag05-P). The former expands the photon absorption band width and the latter facilitates the core-hole splitting by injecting the photon excited electron (from the excitons in PF3T) into the conduction band (CB) of TiO2. These characteristics enable the high efficiency of H2 production to 16 580 µmol h-1 g-1 and photocatalysis stability without degradation under visible light exposure for 96 h. Compared to that of hybrid material without Ag bonding (TiO2@PF3T), the H2 production yield and stability are improved by 4.1 and 18.2-fold which shows the best performance among existing materials in similar component combination and interfacial reinforcement. The unique bonding method offers a new prospect to accelerate the development of photocatalytic hydrogen production technologies.

Current status and new experimental diagnostic methods of invasive fungal infections after hematopoietic stem cell transplantation.

Invasive fungal infections (IFIs) are common and life-threatening complications in post-hematopoietic stem cell transplantation (post-HSCT) recipients, Severe IFIs can lead to systemic infection and organ damage, which results in high mortality in HSCT recipients. With the development of the field of fungal infection diagnosis, more and more advanced non-culture diagnostic tools have been developed, such as glip biosensors, metagenomic next-generation sequencing, Magnetic Nanoparticles and Identified Using SERS via AgNPs+ , and artificial intelligence-assisted diagnosis. The advanced diagnostic approaches contribute to the success of HSCT and improve the overall survival of post-HSCT leukemia patients by supporting therapeutical decisions. This review provides an overview of the characteristics of two high-incidence IFIs in post-HSCT recipients and discusses some of the recently developed IFI detection technologies. Additionally, it explores the potential application of cationic conjugated polymer fluorescence resonance energy transfer (CCP-FRET) technology for IFI detection. The aim is to offer insights into selecting appropriate IFI detection methods and gaining an understanding of novel fungal diagnostic approaches in laboratory settings.

Polyarene Oxides with Tunable Quinone Units for Photocatalytic CO2 Reduction: A Simple Strategy toward Effective and Selective Catalysts.

The photocatalytic transformation of carbon dioxide (CO2) into valuable chemicals is a challenging process that requires effective and selective catalysts. However, most polymer-based photocatalysts with electron donor-acceptor (D-A) structures are synthesized with a fixed D-A ratio by using expensive monomers. Herein, we report a simple strategy to prepare polyarene oxides (PAOs) with quinone structural units via oxidation treatment of polyarene (PA). The resultant PAOs show tunable D-A structures and electronic band positions depending on the degree of oxidation, which can catalyze the photoreduction of CO2 with water under visible light irradiation, generating CO as the sole carbonaceous product without H2 generation. Especially, the PAO with an oxygen content of 17.6% afforded the highest CO production rate of 161.9 µmol g-1 h-1. It is verified that the redox transformation between quinone and phenolic hydroxyl in PAOs achieves CO2 photoreduction coupled with water oxidation. This study provides a facile way to access conjugated polymers with a tunable D-A structure and demonstrates that the resultant PAOs are promising photocatalysts for CO2 reduction.

Artificial neural networks in the modeling of the catalytic activity of a biosensor composed of conjugated polymers and urease.

Thin films of conjugated polymer and enzyme can be used to unravel the interaction between components in a biosensor. Using artificial neural networks (ANNs) improves data interpretability and helps construct models with great capacity for classifying and processing information. The present work used kinetic data from the catalytic activity of urease immobilized in different conjugated polymers to create ANN models using time, substrate concentration, and absorbance as input variables since the models had absorbance in a posterior instant as output value to explore the predictivity of the ANNs. The performance of the models was evaluated by Pearson's correlation coefficient (ρ) and mean squared error (MSE) values. After the learning process, a series of new experiments were performed to verify the generality of the models. As the main results, the best ANN model presented 0.9980 and 3.0736 × 10-5 for ρ and MSE, respectively. For the simulation step, intermediary values of substrate concentration were used. The mean absolute percentage error (MAPE) values were 3.34, 3.07, and 3.78 for 12 mM, 22 mM, and 32 mM concentrations, respectively. Overall, with the simulations, it was possible to ascertain the interpolatory capacity of the model, which has a learning mechanism based on absorbance and time as variables. Thus, the potential of ANNs would be in their use in pre-evaluations, helping to determine the substrate concentration at which there is higher catalytic activity or in determining the linear range of the sensor.

Regioselective Synthesis of Pyrrole-Based Poly(arylenevinylene)s via Mn-Catalyzed Hydroarylation Polyaddition.

Mn-catalyzed hydroarylation polyaddition of 1-(2-pyrimidinyl)pyrrole (1a) with aromatic diynes is investigated. The use of commercially available MnBr(CO)5 as a precatalyst under the optimized reaction conditions resulted in a site- and regioselective hydroarylation polyaddition, affording the corresponding poly(arylenevinylene)s (PAVs) with excellent vinylene selectivity. The reaction protocol eliminates the production of stoichiometric amounts of byproducts from the monomers. The nonstoichiometric polyaddition of an excess amount of 1a with aromatic diynes is also demonstrated. The 2-pyrimidinyl substituent promoted the intramolecular transfer of the Mn catalyst walking through the 1a moiety.

Highly Stretchable Conjugated Polymer/Elastomer Blend Films with Sandwich Structure.

The physical blending of high-mobility conjugated polymers with ductile elastomers provides a simple way to realize high-performance stretchable films. However, how to control the morphology of the conjugated polymer and elastomer blend film and its response to mechanical fracture processes during stretching are not well understood. Herein, a sandwich structure is constructed in the blend film based on a conjugated polymer poly[(5-fluoro-2,1,3-benzothiadiazole-4,7-diyl)(4,4-dihexadecyl-4H-cyclopenta[2,1-b:3,4-b″]dithiophene-2,6-diyl)(6-fluoro-2,1,3-benzothiadiazole-4,7-diyl)(4,4-dihexadecyl-4H-cyclopenta[2,1-b:3,4-b″]dithiophene-2,6-diyl)] (PCDTFBT) and an elastomer polystyrene-block-poly(ethylene-ran-butylene)-block-polystyrene (SEBS). The sandwich structure is composed of a PCDTFBT:SEBS mixed layer laminated with a PCDTFBT-rich layer at both the top and bottom surfaces. During stretching, the external strain energy can be effectively dissipated by the deformation of the crystalline PCDTFBT domains and amorphous SEBS phases and the recrystallization of the PCDTFBT chains. This endows the blend film with excellent ductility, with a large crack onset strain exceeding 1100%, and minimized the electrical degradation of the blend film at a large strain. This study indicates that the electrical and mechanical performance of conjugated polymer/elastomer blend films can be improved by manipulating their microstructure.

Molecular Design of Naphthalene- and Carbazole-Based Monomers for Regiospecific Synthesis of Poly(arylenevinylene)s via Co-Catalyzed Hydroarylation Polyaddition.

This study focuses on the development of regiospecific hydroarylation polyaddition of naphthalene- and carbazole-based monomers with diynes under mild reaction conditions at room temperature. A 1-pyrazole substituent serves as an appropriate directing group for a Co-catalyst to efficiently activate the C-H bonds of generally inactive six-membered aromatic hydrocarbons. The 1-pyrazole groups in 2,6-di(1-pyrazolyl)naphthalene adopt planar conformations and act as directing groups, resulting in a smooth hydroarylation reaction. In contrast, the reaction with 1,5-di(1-pyrazolyl)naphthalene do not proceed. The polyaddition reaction of 2,6-di(1-pyrazolyl)naphthalene selectively proceeds at 3,7-positions under mild reaction conditions at 30 °C, and yields corresponding poly(arylenevinylene) (PAV) with high molecular weight. This molecular design is also applicable to the hydroarylation polyaddition of carbazole; the polyaddition reaction of 9-(2-ethylhexyl)-3,6-di(1-pyrazolyl)carbazole selectively occurred at 2,7-positions. The optical and electronic properties of the synthesized compounds are evaluated. The obtained PAVs serve as an emitting material in organic light-emitting diode (OLED). This study aims to develop a Co-catalyzed hydroarylation polyaddition via C-H activation of generally inactive polyaromatic hydrocarbons (PAHs) under mild conditions.

Building Uniformly Structured Polymer Memristors via a 2D Conjugation Strategy for Neuromorphic Computing.

Polymer memristors represent a highly promising avenue for the advancement of next-generation computing systems. However, the intrinsic structural heterogeneity characteristic of most polymers often results in organic polymer memristors displaying erratic resistive switching phenomena, which in turn lead to diminished production yields and compromised reliability. In this study, a 2D conjugated polymer, named PBDTT-BPQTPA, is synthesized by integrating the coplanar bis(thiophene)-4,8-dihydrobenzo[1,2-b:4,5-b]dithiophene (BDTT) as an electron-donating unit with a quinoxaline derivative serving as an electron-accepting unit. The incorporation of triphenylamine groups at the quinoxaline termini significantly enhances the polymer's conjugation and planarity, thereby facilitating more efficient charge transport. The fabricated polymer memristor with the structure of Al/PBDTT-BPQTPA/ITO exhibits typical non-volatile resistive switching behavior under high voltage conditions, along with history-dependent memristive properties at lower voltages. The unique memristive behavior of the device enables the simulation of synaptic enhancement/inhibition, learning algorithms, and memory operations. Additionally, the memristor demonstrates its capability for executing logical operations and handling decimal calculations. This study offers a promising and innovative approach for the development of artificial neuromorphic computing systems.

Hole Mobility Enhancement in Benzo[1,2-b:4,5-b']Dithiophene-Based Conjugated Polymer Transistors through Directional Alignment, Perovskite Functionalization and Solid-State Electrolyte Gating.

Tunability in electronic and optical properties has been intensively explored for developing conjugated polymers and their applications in organic and perovskite-based electronics. Particularly, the charge carrier mobility of conjugated polymer semiconductors has been deemed to be a vital figure-of-merit for achieving high-performance organic field-effect transistors (OFETs). In this study, the systematic hole carrier mobility improvement of benzo[1,2-b:4,5-b']dithiophene-based conjugated polymer in perovskite-functionalized organic transistors is demonstrated. In conventional OFETs with a poly(methyl methacrylate) (PMMA) gate dielectric, improvements in hole mobility of 0.019 cm2 V-1 s-1 are measured using an off-center spin-coating technique, which exceeds those of on-center counterparts (0.22 ± 0.07 × 10-2 cm2 V-1 s-1). Furthermore, the mobility drastically increases by adopting solid-state electrolyte gating, corresponding to 2.99 ± 1.03 cm2 V-1 s-1 for the control, and the best hole mobility is 8.03 cm2 V-1 s-1 (average ≈ 6.94 ± 0.59 cm2 V-1 s-1) for perovskite-functionalized OFETs with a high current on/off ratio of >106. The achieved device performance would be attributed to the enhanced film crystallinity and charge carrier density in the hybrid perovskite-functionalized organic transistor channel, resulting from the high-capacitance electrolyte dielectric.

Cationic conjugated polymer coupled non-conjugated segments for dually enhanced NIR-II fluorescence and lower-temperature photothermal-gas therapy.

The lack of a simple design strategy to obtain ideal conjugated polymers (CPs) with high absorbance and fluorescence (FL) in the near-infrared-II (NIR-II; 1000-1700 nm) region still hampers the success of NIR-II light-triggered phototheranostics. Herein, novel phototheranostic nanoparticles (PPN-NO NPs) were successfully prepared by coloading a cationic NIR-II CPs (PBC-co-PBF-NMe3) and a NO donor (S-nitroso-N-acetylpenicillamine, SNAP) onto a 1:1 mixture of DSPE-PEG5000 and dimyristoylphosphatidylcholine (DMPC) for NIR-II FL and NIR-II photoacoustic (PA) imaging-guided low-temperature NIR-II photothermal therapy (PTT) and gas combination therapy for cancer treatment. A precise NIR-II FL dually enhanced design tactic was proposed herein by integrating flexible nonconjugated segments (C6) into the CPs backbone and incorporating quaternary ammonium salt cationic units into the CPs side chain, which considerably increased the radiative decay pathway, resulting in desirable NIR-II FL intensity and balanced NIR-II absorption and NIR PTT properties. The phototheranostic PPN-NO NPs exhibited distinguished NIR-II FL and PA imaging performance in tumor-bearing mice models. Furthermore, the low-temperature photothermal effect of PPN-NO NPs could initiate NO release upon 980 nm laser irradiation, efficiently suppressing tumor growth owing to the combination of low-temperature NIR-II PTT and NO gas therapy in vitro and in vivo.

A solar-to-chemical conversion efficiency up to 0.26% achieved in ambient conditions.

Artificial photosynthesis in ambient conditions is much less efficient than the solar-to-biomass conversion (SBC) processes in nature. Here, we successfully mimic the NADP-mediated photosynthetic processes in green plants by introducing redox moieties as the electron acceptors in the present conjugated polymeric photocatalyst. The current artificial process substantially promotes the charge carrier separation efficiency and the oxygen reduction efficiency, achieving a photosynthesis rate for converting Earth-abundant water and oxygen in air into hydrogen peroxide as high as 909 µmol⋅g-1⋅h-1 and a solar-to-chemical conversion (SCC) efficiency up to 0.26%. The SCC efficiency is more than two times higher than the average SBC efficiency in nature (0.1%) and the highest value under ambient conditions. This study presents a strategy for efficient SCC in the future.

A Strategy of On-Demand Immune Activation for Antifungal Treatment Using Near-Infrared Responsive Conjugated Polymer Nanoparticles.

Pathogenic fungal infection is a major clinical threat because pathogenic fungi have developed resistant mechanisms to evade the innate immune response, especially interactions with macrophages. Herein, a strategy to activate immune responses of macrophages to fungi based on near-infrared (NIR) responsive conjugated polymer nanoparticles (CPNs-M) is reported for antifungal immunotherapy. Under NIR light irradiation, CPNs-M exposes ß-glucan on the surface of fungal conidia by photothermal damage and drug released from CPNs-M. The exposed ß-glucan elicits macrophage recognition and subsequently activates calcium-calmodulin (Ca2+-CaM) signaling followed by the LC3-associated phagocytosis (LAP) pathway to kill fungal conidia. Consequently, a remarkable elimination of intracellular fugal conidia and successful treatment of fungal pneumonia are achieved. This remote regulation strategy to restore pathogen-immune cell interaction on demand provides a new insight into combatting intractable intracellular infections.

Impact of Plasmonic and Dielectric Substrates on the Whispering-Gallery Modes in Self-Assembled Fluorescent Semiconductor Polymer Microspheres.

In this work, the impact of metallic and dielectric conducting substrates, gold and indium tin oxide (ITO)-coated glass, on the whispering gallery modes (WGMs) of semiconductor π-conjugated polymer microspheres is investigated. Hyperspectral mapping was performed to obtain the excitation-position-dependent emission spectra of the microspheres. Substrate-dependent quenching of WGMs sensitive to mode polarization was observed and explained. On a glass substrate, both transverse-electric (TE) and transverse-magnetic (TM) WGMs are quenched due to frustrated total internal reflection. On a gold substrate, however, only the TM WGMs are allowed in symmetry to leak into surface plasmons. An atomically flat gold substrate with subwavelength slits was used to experimentally verify the leakage of WGMs into the surface plasmon polaritons (SPPs). This work provides insight into the damping mechanisms of WGMs in microspheres on metallic and dielectric substrates.

Organic Transistors Based on Highly Crystalline Donor-Acceptor π-Conjugated Polymer of Pentathiophene and Diketopyrrolopyrrole.

Oligomers and polymers consisting of multiple thiophenes are widely used in organic electronics such as organic transistors and sensors because of their strong electron-donating ability. In this study, a solution to the problem of the poor solubility of polythiophene systems was developed. A novel π-conjugated polymer material, PDPP-5Th, was synthesized by adding the electron acceptor unit, DPP, to the polythiophene system with a long alkyl side chain, which facilitated the solution processing of the material for the preparation of devices. Meanwhile, the presence of the multicarbonyl groups within the DPP molecule facilitated donor-acceptor interactions in the internal chain, which further improved the hole-transport properties of the polythiophene-based material. The weak forces present within the molecules that promoted structural coplanarity were analyzed using theoretical simulations. Furthermore, the grazing incidence wide-angle X-ray scanning (GIWAXS) results indicated that PDPP-5Th features high crystallinity, which is favorable for efficient carrier migration within and between polymer chains. The material showed hole transport properties as high as 0.44 cm2 V-1 s-1 in conductivity testing. Our investigations demonstrate the great potential of this polymer material in the field of optoelectronics.