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Due to the reduced absorption, light scattering, and tissue autofluorescence in the NIR-II (1000-1700 nm) region, significant efforts are underway to explore diverse material platforms for in vivo fluorescence imaging, particularly for cancer diagnostics and image-guided interventions. Of the reported imaging agents, nanoparticles derived from conjugated polymers (CPNs) offer unique advantages to alternative materials including biocompatibility, remarkable absorption cross-sections, exceptional photostability, and tunable emission behavior independent of cell labeling functionalities. Herein, the current state of NIR-II emitting CPNs are summarized and structure-function-property relationships are highlighted that can be used to elevate the performance of next-generation CPNs. Methods for particle processing and incorporating cancer targeting modalities are discussed, as well as detailed characterization methods to improve interlaboratory comparisons of novel materials. Contemporary methods to specifically apply CPNs for cancer diagnostics and therapies are then highlighted. This review not only summarizes the current state of the field, but offers future directions and provides clarity to the advantages of CPNs over other classes of imaging agents., (© 2024 Wiley‐VCH GmbH.)

Conjugated polymers are enabling the development of flexible bioelectronics, largely driven by their organic nature which facilitates modification and tuning to suit a variety of applications. As organic semiconductors, conjugated polymers require a dopant to exhibit electrical conductivity, which in physiological conditions can result in dopant loss and thereby deterioration in electronic properties. To overcome this challenge, "self-doped" and self-acid-doped conjugated polymers having ionized pendant groups covalently bound to their backbone are being developed. The ionized group in a "self-doped" polymer behaves as the counterion that maintains electroneutrality, while an external dopant is required to induce charge transfer. The ionized group in a self-acid-doped polymer induces charge transfer and behaves as the counterion balancing the charges. Despite their doping processes being different, the two terms, self-doped and self-acid-doped, are often used interchangeably in the literature. Here, the differences are highlighted in the doping mechanisms of self-doped and self-acid-doped polymers, and it is proposed that the term "self-doped" should be replaced by "self-compensated," while reserving the term self-acid-doped for polymers that are intrinsically doped without the need of an external dopant. This is followed by a summary of examples of self-acid-doping in bioelectronics, highlighting their stability in the conductive state under physiological conditions., (© 2023 The Authors. Advanced Healthcare Materials published by Wiley‐VCH GmbH.)

Conjugated polymers with integrating properties of delayed fluorescence and photovoltaic responses simultaneously are scarcely reported due to the generally contradictory requirements for molecular structures to achieve the two properties. Herein, an O-B(F)←N functionalized fused unit (M) with multiple resonance features, small energy gap between lowest singlet excited state (S 1 ) and triplet excited state (T 1 ) (ΔE ST = 0.23 eV), and delayed fluorescence (τ D = 0.75 µs), is designed. Selecting three benzodithiophene (BDT) derivatives as co-units to copolymerize with M, leading to a series of O-B(F)←N embedded polymers also maintaining delayed fluorescence (τ D = 0.4-0.5 µs). Moreover, p-type semiconductor characteristics are tested for these polymers with hole mobilities in the range of 10 -6 -10 -5 cm 2 /Vs. Devices with obviously photovoltaic responses are prepared using these polymers as donors and Y6 as the acceptor, affording a preliminary efficiency of 5.05%. This work successfully demonstrates an effective strategy to design conjugated polymers with integrating properties of delayed fluorescence and photovoltaic performance simultaneously by introducing O-B(F)←N functional groups to polymer backbones., (© 2024 Wiley‐VCH GmbH.)

Conjugated polymers (CPs) have been developed quickly as an emerging functional material with applications in optical and electronic devices, owing to their highly electron-delocalized backbones and versatile side groups for facile processibility, high mechanical strength, and environmental stability. CPs exhibit multistimuli responsive behavior and fluorescence quenching properties by incorporating azobenzene functionality into their molecular structures. Over the past few decades, significant progress has been made in developing functional azobenzene-based conjugated polymers (azo-CPs), utilizing diverse molecular design strategies and synthetic pathways. This article comprehensively reviews the rapidly evolving research field of azo-CPs, focusing on the structural characteristics and synthesis methods of general azo-CPs, as well as the applications of charged azo-CPs, specifically azobenzene-based conjugated polyelectrolytes (azo-CPEs). Based on their molecular structures, azo-CPs can be broadly categorized into three primary types: linear CPs with azobenzene incorporated into the side chain, linear CPs with azobenzene integrated into the main chain, and branched CPs containing azobenzene moieties. These systems are promising for biomedical applications in biosensing, bioimaging, targeted protein degradation, and cellular apoptosis., (© 2024 Wiley‐VCH GmbH.)

Biohybrid photocatalysts are composite materials that combine the efficient light-absorbing properties of synthetic materials with the highly evolved metabolic pathways and self-repair mechanisms of biological systems. Here, we show the potential of conjugated polymers as photosensitizers in biohybrid systems by combining a series of polymer nanoparticles with engineered Escherichia coli cells. Under simulated solar light irradiation, the biohybrid system consisting of fluorene/dibenzo [ b,d ]thiophene sulfone copolymer (LP41) and recombinant E. coli (i.e., a LP41/HydA BL21 biohybrid) shows a sacrificial hydrogen evolution rate of 3.442 mmol g -1 h -1 (normalized to polymer amount). It is over 30 times higher than the polymer photocatalyst alone (0.105 mmol g -1 h -1 ), while no detectable hydrogen was generated from the E. coli cells alone, demonstrating the strong synergy between the polymer nanoparticles and bacterial cells. The differences in the physical interactions between synthetic materials and microorganisms, as well as redox energy level alignment, elucidate the trends in photochemical activity. Our results suggest that organic semiconductors may offer advantages, such as solution processability, low toxicity, and more tunable surface interactions with the biological components over inorganic materials.

Conjugated polymers (CPs) have promising applications in biomedical fields, such as disease monitoring, real-time imaging diagnosis, and disease treatment. As a promising luminescent material with tunable emission, high brightness and excellent stability, CPs are widely used as fluorescent probes in biological detection and imaging. Rational molecular design and structural optimization have broadened absorption/emission range of CPs, which are more conductive for disease diagnosis and precision therapy. This review provides a comprehensive overview of recent advances in the application of CPs, aiming to elucidate their structural and functional relationships. The fluorescence properties of CPs and the mechanism of detection signal amplification are first discussed, followed by an elucidation of their emerging applications in biological detection. Subsequently, CPs-based imaging systems and therapeutic strategies are illustrated systematically. Finally, recent advancements in utilizing CPs as electroactive materials for bioelectronic devices are also investigated. Moreover, the challenges and outlooks of CPs for precision medicine are discussed. Through this systematic review, it is hoped to highlight the frontier progress of CPs and promote new breakthroughs in fundamental research and clinical transformation., (© 2024 Wiley‐VCH GmbH.)

Conjugated polymers exhibit excellent electrical and mechanical properties when their molecular weight (M w ) is above the critical molecular weight (M c ). The microstructural changes of polymers under strain are crucial to establish a structure-performance relationship. Herein, the tensile deformation of P(NDI2OD-T2) is visualized, and cracks are revealed either along the (100) crystal plane of side chain packing or along the main chain direction which depends on the M w is below or above the M c . When M w < M c , the film cracks along the (100) plane under small strains. When M w > M c , the polymer chains first undergo stretch-induced orientation and then fracture along the main chain direction at large strains. This is attributed to the fact that the low M w film exhibits large crystalline domains and the absence of interdomain connectivity, which are vulnerable to mechanical stress. In contrast, the high M w film displays a nearly amorphous morphology with adequate entanglements, the molecular chains can endure stresses in the stretching direction to release substantial strain energy under greater mechanical deformation. Therefore, the film with M w > M c exhibits the optimal electrical and mechanical performances simultaneously, i.e., the electron mobility is retained under 100% strain and after 100 stretching-releasing cycles., (© 2023 Wiley‐VCH GmbH.)

Nonstoichiometric direct arylation polycondensation of 2,2',3,3',5,5',6,6'-octafluorobiphenyl with excess of 2,7-diiodo-9,9-dioctyl-9H-fluorene is demonstrated. Pd/Ag dual-catalyst system under water/2-methyltetrahydrofuran biphasic conditions enables direct arylation under mild conditions and promotes the intramolecular transfer of a Pd catalyst walking through the fluorene moiety. The nonstoichiometric direct arylation polycondensation under the optimized reaction conditions produces the corresponding π-conjugated polymer with a high molecular weight and terminal octafluorobiphenyl units at both ends., (© 2023 Wiley-VCH GmbH.)

A series of thienoisoindigo (TIG)-based conjugated polymers (CPs) with high molecular weights are synthesized by direct arylation polycondensation (DArP) by using TIG derivatives as CBr monomer and multi-halogenated thiophene derivatives, i.e., (E)-1,2-bis(3,4-difluorothien-2-yl)ethene (4FTVT), (E)-1,2-bis(3,4-dichlorothien-2-yl)ethene (4ClTVT), 3,3',4,4'-tetrafluoro-2,2'-bithiophene (4FBT), and 3,3',4,4'-tetrachloro-2,2'-bithiophene (4ClBT), as CH monomers. Density functional theory (DFT) calculations reveal the high selectivity between α-CH bonds in 4FTVT, 4ClTVT, 4FBT, and 4ClBT and β-CH bonds in TIG CBr monomer. All four resulting CPs exhibit low optical bandgaps of ca. 1.20 eV and ambipolar transport characteristics with both electron and hole mobility above 0.1 cm 2  V -1  s -1 as elaborated with organic thin-film transistors (OTFTs). The polymer TIG-4FTVT delivers the best device performance. With this polymer, n-channel OTFTs with electron mobility up to 1.67 cm 2  V -1  s -1 and p-channel OTFTs with hole mobility up to 0.62 cm 2  V -1  s -1 are fabricated by modifying source/drain electrodes with polyethylenimine ethoxylated (PEIE) and MoO 3 , respectively, to selectively inject electrons and holes., (© 2023 Wiley-VCH GmbH.)

Conjugated polymers have received significant attention as potentially lightweight and highly tailorable alternatives to inorganic semiconductors, but their synthesis is often complex, produces toxic byproducts, and they are not typically designed to be degradable or recyclable. These drawbacks necessitate dedicated efforts to discover materials with design motifs that enable targeted and efficient degradation of conjugated polymers. In this vein, the synthetic simplicity of 1,4-dihydropyrrolo[3,2-b]pyrroles (DHPPs) is exploited to access azomethine-containing copolymers via a benign acid-catalyzed polycondensation protocol. Polymerizations involve reacting a dialdehyde-functionalized dihydropyrrolopyrrole with p-phenylenediamine as the comonomer using p-toluenesulfonic acid as a catalyst. The inherent dynamic equilibrium of the azomethine bonds subsequently enabled the degradation of the polymers in solution in the presence of acid. Degradation of the polymers is monitored via NMR, UV-vis absorbance, and fluorescence spectroscopies, and the polymers are shown to be fully degradable. Notably, while absorbance measurements reveal a continued shift to higher energies with extended exposure to acid, fluorescence measurements show a substantial increase in the fluorescence response upon degradation. Results from this study encourage the continued development of environmentally-conscious polymerizations to attain polymeric materials with useful properties while simultaneously creating polymers with structural handles for end-of-life management or/and recyclability., (© 2023 Wiley-VCH GmbH.)

3,4-Difluorothiophene-substituted aryls, i.e., 1,4-bis(3,4-difluorothiophen-2-yl)-benzene (Ph-2FTh), 1,4-bis(3,4-difluorothiophen-2-yl)-2,5-difluorobenzene (2FPh-2FTh), and 4,7-bis(3,4-difluorothiophen-2-yl)-2,1,3-benzothiadiazole (BTz-2FTh), are synthesized as C─H monomers for the synthesis of conjugated polymers (CPs) via direct arylation polycondensation (DArP) with diketopyrrolopyrrole (DPP) and isoindigo (IID) derivatives as C─Br monomers. The Gibbs free energies of activation for direct arylation (ΔG 298 K , kcal mol -1 ) for α─C─H bonds of thiophene moieties as calculated by density functional theory (DFT) are 14.3, 16.5, and 16.4 kcal mol -1 for Ph-2FTh, 2FPh-2FTh and BTz-2FTh, respectively, meaning that inserting an electron-deficient unit in 3,3',4,4'-tetrafluoro-2,2'-bithiophene (4FBT, ΔG 298K : 14.6 kcal mol -1 ) may cause a reactivity decrease of the C─H monomers. Photophysical and semiconducting properties of the resulting six CPs (i.e., DPP-Ph, DPP-2FPh, DPP-BTz, 2FIID-Ph, 2FIID-2FPh, and 2FIID-BTz) are characterized in detail. DPP-based CPs show ambipolar transport properties while IID-based ones exhibited n-type behavior owing to the deeper frontier molecular orbital energy levels of IID-based CPs. With source/drain electrodes modified with polyethylenimine ethoxylated, n-channel organic thin-film transistors with maximum electron mobility of 0.40, 0.54, 0.29, 0.05, 0.16, and 0.01 cm 2 V -1 s -1 for DPP-Ph, DPP-2FPh, DPP-BTz, 2FIID-Ph, 2FIID-2FPh, and 2FIID-BTz, respectively, are fabricated. DPP-2FPh exhibits the best device performance due to the good film morphology and the highest intermolecular packing order., (© 2023 Wiley-VCH GmbH.)

Polydiacetylenes, as a class of conjugated polymers with alternating conjugated C═C and C≡C bonds, have emerged as a promising probe material for biomedical Raman imaging, given their ultrastrong Raman scattering intensity. However, the relationship between the structure, especially the molecular length of polydiacetylenes, and their Raman scattering intensity remains unclear. In this work, a series of water-soluble polydiacetylenes, namely poly(deca-4,6-diynedioic acid) (PDDA) with different molecular weights (MWs), is prepared through controlled polymerization and degradation. The ultraviolet-visible (UV-vis) absorption spectroscopic and Raman spectroscopic studies on these polymers reveal that the Raman scattering intensity of PDDA increases nonlinearly with the MW. The MW-Raman scattering intensity relationship in the polymerization process is completely different from that in the degradation process. In contrast, the Raman scattering intensity increases more linearly with the maximal absorbance of the polymer, and the relationship between the Raman scattering intensity and the maximal absorbance of PDDA in the polymerization process is consistent with that in the degradation process. The Raman scattering intensity of PDDA hence exhibits a better dependence on the effective conjugation length of the polymer, which should guide the future design of conjugated polymers for Raman imaging applications., (© 2023 Wiley-VCH GmbH.)

An unprecedented poly(thiophene iminoborane)-a boron-nitrogen analogue of the well-established conjugated organic polymer poly(thiophene vinylene)-is presented. The polymer synthesis is achieved by selective Si/B exchange polycondensation of a 2,5-diborylthiophene with a 2,5-diaminothiophene derivative. For the latter, a facile synthetic strategy is devised, which makes this versatile, strongly electron-releasing building block easily accessible. The novel polymer and a series of monodisperse thiophene iminoborane oligomers reveal systematic bathochromic shifts in their absorption with increasing chain length, and thus extended π-conjugation over the BN units along the backbone, which is further supported by TD-DFT calculations., (© 2023 The Authors. Macromolecular Rapid Communications published by Wiley-VCH GmbH.)

Multi-scale organization of molecular and living components is one of the most critical parameters that regulate charge transport in electroactive systems-whether abiotic, biotic, or hybrid interfaces. In this article, an overview of the current state-of-the-art for controlling molecular order, nanoscale assembly, microstructure domains, and macroscale architectures of electroactive organic interfaces used for biomedical applications is provided. Discussed herein are the leading strategies and challenges to date for engineering the multi-scale organization of electroactive organic materials, including biomolecule-based materials, synthetic conjugated molecules, polymers, and their biohybrid analogs. Importantly, this review provides a unique discussion on how the dependence of conduction phenomena on structural organization is observed for electroactive organic materials, as well as for their living counterparts in electrogenic tissues and biotic-abiotic interfaces. Expansion of fabrication capabilities that enable higher resolution and throughput for the engineering of ordered, patterned, and architecture electroactive systems will significantly impact the future of bioelectronic technologies for medical devices, bioinspired harvesting platforms, and in vitro models of electroactive tissues. In summary, this article presents how ordering at multiple scales is important for modulating transport in both the electroactive organic, abiotic, and living components of bioelectronic systems., (© 2023 The Authors. Advanced Science published by Wiley-VCH GmbH.)

The charge carrier mobility of organic field-effect transistors (OFETs) has been remarkably improved through several engineering approaches and techniques by targeting pivotal parts. Herein, an ultrathin perovskite channel layer that boosts the field-effect mobility of conjugated polymer OFETs by forming perovskite-conjugated polymer hybrid semiconducting channel is introduced. The optimized lead-iodide-based perovskite-conjugated polymer hybrid channel transistors show enhanced hole mobility of over 4 cm 2  V -1  s -1 (average = 2.10 cm 2  V -1  s -1 ) with high reproducibility using a benchmark poly(3-hexylthiophene) (P3HT) polymer and employing high-k fluorinated polymer dielectrics. A significant hole carrier mobility enhancement of ≈200-400% in benzo[1,2-b:4,5:b']dithiophene (BDT)-based conjugated polymers is also demonstrated by exploring certain interactive groups with perovskite. This significant enhancement in the transistor performance is attributed to the increased charge carrier density in the hybrid semiconducting channel and the perovskite-polymer interactions. The findings of this paper demonstrate an exceptional engineering approach for carrier mobility enhancement in hybrid perovskite-conjugated-polymer-based electronic devices., (© 2023 Wiley-VCH GmbH.)

Hypothesis: Mixed polymer brushes (MPBs) could be synthesized by surface dilution of homopolymer brushes and subsequent grafting of other type of chains in the formed voids. Nanophase separation and dynamics of surface-grafted chains could be tailored by modification of their molecular architecture. Mixed polyelectrolyte and conjugated chains contribute synergistically to tailor properties of the coating., Experiments: A new synthetic strategy that allowed spatially controlled grafting of poly(sodium 4-styrenesulfonate) chains (PSSNa) in close neighborhood of poly(3-methylthienyl methacrylate) (PMTM) brushes (precursors of the conjugated chains) using surface-initiated polymerizations was developed. The final mixed conjugated/polyelectrolyte brushes were prepared by template polymerization of pendant thiophene groups in PMTM chains. Surface dynamics and nanophase separation of MPBs were studied by nanoscale resolution IR imaging, SIMS profiling and AFM mapping in selective solvents., Findings: Unconjugated MPBs were shown to undergo vertical, and horizontal nanophase separation, while the size and shape of the nanodomains were dependent on molar ratio of the mixed chains and their relative lengths. Generation of the conjugated chains led to diminishing of nanophase separation thanks to stronger mutual interactions of conjugated PMTM and PSSNa (macromolecular mixing). The obtained systems demonstrated tunable interfacial structure and resistance switching phenomenon desired in construction of smart surfaces or memristive devices., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2022 Elsevier Inc. All rights reserved.)

To improve the performance of organic field-effect transistors (OFETs) employing π-conjugated polymers, a basic understanding of the relationships between the material properties and device characteristics is crucial. Although the density of states (DOS) distribution is one of the essential material properties of semiconducting polymers, insights into how the DOS shape affects the mobility (µ), subthreshold swing (S), and contact resistance (R C ) in OFETs remain lacking. In this study, by combining sensitive DOS measurements and multilayered OFET structures, it is experimentally demonstrated that narrower DOS widths in the polymer channels lead to higher µ, smaller S, and lower R C . By contrast, variation of the DOS in the bulk layer does not affect the performance. These results demonstrate a direct relationship between the polymer properties and OFET performance and highlight the importance of controlling the DOS width in π-conjugated polymers., (© 2022 Wiley-VCH GmbH.)

The morphological stability of an organic photovoltaic (OPV) device is greatly affected by the dynamics of donors and acceptors occurring near the device's operational temperature. These dynamics can be quantified by the glass transition temperature (T g ) of conjugated polymers (CPs). Because flexible side chains possess much faster dynamics, the cleavage of the alkyl side chains will reduce chain dynamics, leading to a higher T g . In this work, the T g s for CPs are systematically studied with controlled side chain cleavage. Isothermal annealing of polythiophenes featuring thermally cleavable side chains at 140 °C, is found to remove more than 95% of alkyl side chains in 24 h, and raise the backbone T g from 23 to 75 °C. Coarse grain molecular dynamics simulations are used to understand the T g dependence on side chain cleavage. X-ray scattering indicates that the relative degree of crystallization remains constantduring isothermal annealing process. The effective conjugation length is not influenced by thermal cleavage; however, the density of chromophore is doubled after the complete removal of alkyl side chains. The combined effect of enhancing T g and conserving crystalline structures during the thermal cleavage process can provide a pathway to improving the stability of optoelectronic properties in future OPV devices., (© 2022 Wiley-VCH GmbH.)

Donor-acceptor conjugated polymers are considered advanced semiconductor materials for the development of thin-film electronics. One of the most attractive families of polymeric semiconductors in terms of photovoltaic applications are benzodithiophene-based polymers owing to their highly tunable electronic and physicochemical properties, and readily scalable production. In this work, we report the synthesis of three novel push-pull benzodithiophene-based polymers with different side chains and their investigation as hole transport materials (HTM) in perovskite solar cells (PSCs). It is shown that polymer P3 that contains triisopropylsilyl side groups exhibits better film-forming ability that, along with high hole mobilities, results in increased characteristics of PSCs. Encouraging a power conversion efficiency (PCE) of 17.4% was achieved for P3 -based PSCs that outperformed the efficiency of devices based on P1 , P2 , and benchmark PTAA polymer. These findings feature the great potential of benzodithiophene-based conjugated polymers as dopant-free HTMs for the fabrication of efficient perovskite solar cells.

Three-terminal synaptic transistor has drawn significant research interests for neuromorphic computation due to its advantage of facile device integrability. Lately, bulk-heterojunction-based synaptic transistors with bipolar modulation are proposed to exempt the use of an additional floating gate. However, the actual correlation between the channel's ambipolarity, memory characteristic, and synaptic behavior for a floating-gate free transistor has not been investigated yet. Herein, by studying five diketopyrrolopyrrole-benzotriazole dual-acceptor random conjugated polymers, a clear correlation among the hole/electron ratio, the memory retention characteristic, and the synaptic behavior for the polymer channel layer in a floating-gate free transistor is described. It reveals that the polymers with balanced ambipolarity possess better charge trapping capabilities and larger memory windows; however, the high ambipolarity results in higher volatility of the memory characteristics, namely poor memory retention capability. In contrast, the polymer with a reduced ambipolarity possesses an enhanced memory retention capability despite showing a reduced memory window. It is further manifested that this enhanced charge retention capability enables the device to present artificial synaptic characteristics. The results highlight the importance of the channel's ambipolarity of floating-gate free transistors on the resultant volatile memory characteristics and synaptic behaviors., (© 2022 The Authors. Advanced Science published by Wiley-VCH GmbH.)

The molecular weight is a key factor affecting the properties of conjugated polymers. To determine the critical molecular weights of conjugated polymers modified with siloxane side chains, poly-diketo-pyrrolopyrrole-selenophene (PTDPPSe-5Si) samples with molecular weights ranging from 20 to 350 kDa are synthesized. The critical molecular weight of the polymer is determined in the range of 60-100 kDa by testing the viscosity of the solution. When the molecular weight of the 27-60 kDa polymers is below the critical molecular weight, they exhibit a high crystallinity and low ductility. When the molecular weight of the 100 kDa polymer reaches the critical molecular weight, the crystallinity decreases, and the ductility increases. As the molecular weight increases, the polymer film also gradually changes from brittle to ductile. Furthermore, when the molecular weight of the 315 kDa polymer is much higher than the critical molecular weight, the film exhibits a significant ductility, which results in the polymer films showing no pronounced cracks after high-percentage stretching. Additionally, due to the oriented alignment of the molecular chains caused by stretching, the carrier mobility in the parallel direction becomes 2.14-fold of the initial film., (© 2022 Wiley-VCH GmbH.)

Each year a rising number of infections can not be successfully treated owing to the increasing pandemic of antibiotic resistant pathogens. The global shortage of innovative antibiotics fuels the emergence and spread of drug resistant microbes. Basic research, development, and applications of alternative therapies are urgently needed. Since the 90´s, light-mediated therapies have promised to be the next frontier combating multidrug-resistance microbes. These platforms have demonstrated to be a reliable, rapid, and efficient alternative to eliminate tenacious pathogens while avoiding the emergence of resistance mechanisms. Among the materials showing antimicrobial activity triggered by light, conjugated polymers (CPs) have risen as the most promising option to tackle this complex situation. These materials present outstanding characteristics such as high absorption coefficients, great photostability, easy processability, low cytotoxicity, among others, turning them into a powerful class of photosensitizer (PS)/photothermal agent (PTA) materials. Herein, we summarize and discuss the advances in the field of CPs with applications in photodynamic inactivation and photothermal therapy towards bacteria elimination. Additionally, a section of current challenges and needs in terms of well-defined benchmark experiments and conditions to evaluate the efficiency of phototherapies is presented., Competing Interests: Declaration of Competing Interest The authors declare no competing financial interest., (Copyright © 2022 Elsevier B.V. All rights reserved.)

Molecular ordering of conjugated polymers both in solution-state aggregates and in solid-state microstructures is a determining factor of the charge transport properties in optoelectronic devices. However, the effect of backbone conformation in conjugated polymers on assembly structures is still unclear. Herein, to understand such backbone conformation effect, three novel chlorinated benzodifurandionge-based oligo(p-phenylene vinylene) (BDOPV) polymers are systematically developed. These BDOPV-based polymers exhibit significantly twisted backbone conformation (near 90° interunit torsion angle) between conjugated units, which can prevent polymer chains from forming ordered assembly structures by increasing conformational energy penalty in closely packed chains. A higher rotational barrier of the torsion angle would further prevent polymer chains from assembling, finally resulting in nonaggregated chains in solution and highly disordered solid-state packing structures. This work will deepen the understanding of the relationship between polymer backbone conformation and assembly structures, contributing to the exploration of the structure-property relationship of polymers., (© 2022 Wiley-VCH GmbH.)

Achievements in polymer chemistry enables to design artificial phase boundaries modified by imprints of selected molecules and some larger structures. These structures seem very useful for the design of new materials suitable for affinity chromatography and sensors. In this review, we are overviewing the synthesis of molecularly imprinted polymers (MIPs) and the applicability of these MIPs in the design of affinity sensors. Such MIP-based layers or particles can be used as analyte-recognizing parts for sensors and in some cases they can replace very expensive compounds (e.g.: antibodies, receptors etc.), which are recognizing analyte. Many different polymers can be used for the formation of MIPs, but conducing polymers shows the most attractive capabilities for molecular-imprinting by various chemical compounds. Therefore, the application of conducting polymers (e.g.: polypyrrole, polyaniline, polythiophene, poly(3,4-ethylenedioxythiophene), and ortho-phenylenediamine) seems very promising. Polypyrrole is one of the most suitable for the development of MIP-based structures with molecular imprints by analytes of various molecular weights. Overoxiation of polypyrrole enables to increase the selectivity of polypyrrole-based MIPs. Methods used for the synthesis of conducting polymer based MIPs are overviewed. Some methods, which are applied for the transduction of analytical signal, are discussed, and challenges and new trends in MIP-technology are foreseen., (Copyright © 2022 Elsevier B.V. All rights reserved.)

The high stability and conductivity of 3,4-disubstituted polythiophenes such as poly(3,4-ethylenedioxythiophene) (PEDOT) make them attractive candidates for commercial applications. However, next-generation nanoelectronic devices require novel macromolecular strategies for the precise synthesis of advanced polymer structures as well as their arrangement. In this report, we present a synthetic route to make ladder-like polymer brushes with poly(3,4-propylenedioxythiophene) (PProDOT)-conjugated chains. The brushes were prepared via a self-templating surface-initiated technique (ST-SIP) that combines the surface-initiated atom transfer radical polymerization (SI-ATRP) of bifunctional ProDOT-based monomers and subsequent oxidative polymerization of the pendant ProDOT groups in the parent brushes. The brushes prepared in this way were characterized by grazing-angle FTIR, XPS spectroscopy, and AFM. Steady-state and time-resolved photoluminescence measurements were used to extract the information about the structure and effective conjugation length of PProDOT-based chains. Stability tests performed in ambient conditions and under exposure to standardized solar light revealed the remarkable stability of the obtained materials.

Gene therapy has attracted great attention due to its applications in disease treatment. The key point for gene therapy is how to improve the efficiency of gene delivery and precisely control gene expression. Conjugated polymers (CPs) have hydrophobic π-conjugated backbones and modifiable side chains, which provide desired photophysical properties and have been applied in the field of bio-sensing, biomedical and gene-based therapies. Herein, we summarize the strategies of DNA delivery and small interfering RNA (siRNA) delivery based on cationic conjugated polymers, in addition, the strategies for precisely control the expression of target gene by photothermal-responsive conjugated polymers for cancer therapy and gene editing are described. Finally, future challenges of efficient and safe gene delivery strategies are presented, and perspectives in the precise control of gene expression are also discussed., (© 2022 Wiley-VCH GmbH.)

This review is dedicated to the development of molecularly imprinted polymers (MIPs) and the application of MIPs in sensor design. MIP-based biological recognition parts can replace receptors or antibodies, which are rather expensive. Conducting polymers show unique properties that are applicable in sensor design. Therefore, MIP-based conducting polymers, including polypyrrole, polythiophene, poly(3,4-ethylenedioxythiophene), polyaniline and ortho-phenylenediamine are frequently applied in sensor design. Some other materials that can be molecularly imprinted are also overviewed in this review. Among many imprintable materials conducting polymer, polypyrrole is one of the most suitable for molecular imprinting of various targets ranging from small organics up to rather large proteins. Some attention in this review is dedicated to overview methods applied to design MIP-based sensing structures. Some attention is dedicated to the physicochemical methods applied for the transduction of analytical signals. Expected new trends and horizons in the application of MIP-based structures are also discussed.

High performance organic field effect transistor devices based on intrinsically scalable materials are of great significance in wearable electronics. In this work, an exclusive approach is reported to rationale the carrier mobility and stretchability of the conjugate polymers (CPs) by modifying the symmetry of the side chains species. Semiconductor CPs with symmetrical alkyl side chains (P(C-C)), symmetrical siloxane side chains (P(Si-Si)), and asymmetrical silicon-carbon side chains (P(C-Si)) are synthesized to investigate the influence of these side chains on the carrier mobility and mechanical behavior. The result shows that silicon-carbon asymmetric side chains can modulate the aggregation degree of polymer chains with a coherence length of 134 Å and maintain the mobility at 0.90 cm 2 V -1 s -1 . P(C-Si) exhibits superior tensile properties that even elongation up to 100% the value of mobility retains a majority properties. The main reason is that the lowest coherence length of P(C-Si) polymer leads to an increased proportion of amorphous zones in its polymer film, which efficiently dissipates mechanical stresses. This study provides an efficient strategy for the design and synthesis of the CPs with high carrier transport properties-mechanical stability., (© 2021 Wiley-VCH GmbH.)

As a noninvasive therapeutic technique, photodynamic therapy (PDT) has attracted numerous research interests for cancer therapy. Nevertheless, the residual photosensitizers (PSs) still produce reactive oxygen species (ROS) and damage normal cells under sunlight after PDT, which limits their practical application in clinic. Herein, the authors propose a self-degradable type-I PS based on conjugated polymer, which is composed of aggregation-induced emission (AIE) and imidazole units. Due to the effective conjugated skeleton and unique AIE properties, thus-obtained polymers can effectively generate superoxide radical (O 2 -• produced by the conjugated polymers can further lead to the self-degradation of the polymer to form nontoxic micro-molecules. It not only helps to resolve the potential phototoxicity problems of residual PSs, but also can accelerate the metabolism of the conjugated polymers to avoid the potential biotoxicity of drug accumulation. This work develops a self-degradable type-I PS, which can turn off the generation of ROS in time after PDT, providing a novel strategy to balance the PDT effect and postoperative safety.2 -• produced by the conjugated polymers can further lead to the self-degradation of the polymer to form nontoxic micro-molecules. It not only helps to resolve the potential phototoxicity problems of residual PSs, but also can accelerate the metabolism of the conjugated polymers to avoid the potential biotoxicity of drug accumulation. This work develops a self-degradable type-I PS, which can turn off the generation of ROS in time after PDT, providing a novel strategy to balance the PDT effect and postoperative safety., (© 2021 The Authors. Advanced Science published by Wiley-VCH GmbH.)

Conventional conjugated polymer (CP) films based on organic field-effect transistors (OFETs) tend to limit the performance of gas sensors owing to restricted analyte diffusion and limited interactions with the charge carriers that accumulate in the first few monolayers of the CP film in contact with the dielectric layer. Herein, a facile strategy is presented for modulating the morphology and charge-transport properties of nanoporous CP films using shearing-assisted phase separation of polymer blends for fabricating OFET-based chemical sensors. This approach enables the formation of nanoporous films with pore size and thickness in the ranges of 90-550 and 7-27 nm, respectively, which can be controlled simply by varying the shear rate. The resulting OFET sensors exhibit excellent sensing performance when exposed to NH 3 gas, demonstrating a high responsivity (≈70.7%) at 10 ppm and good selectivity toward NH 3 over various organic solvent vapors. After a comprehensive analysis of the morphology and electrical properties of the CP films, it is concluded that morphological features, such as film thickness and surface area, affect the sensing performance of nanoporous-film-based OFET sensors more significantly compared to the charge-transport characteristics of the films.

Endothelial colony forming cells (ECFCs) represent the most suitable cellular substrate to induce revascularization of ischemic tissues. Recently, optical excitation of the light-sensitive conjugated polymer, regioregular Poly (3-hexyl-thiophene), rr-P3HT, was found to stimulate ECFC proliferation and tube formation by activating the non-selective cation channel, Transient Receptor Potential Vanilloid 1 (TRPV1). Herein, we adopted a multidisciplinary approach, ranging from intracellular Ca 2+ imaging to pharmacological manipulation and genetic suppression of TRPV1 expression, to investigate the effects of photoexcitation on intracellular Ca 2+ concentration ([Ca 2+ ] i ) in circulating ECFCs plated on rr-P3HT thin films. Polymer-mediated optical excitation induced a long-lasting increase in [Ca 2+ ] i that could display an oscillatory pattern at shorter light stimuli. Pharmacological and genetic manipulation revealed that the Ca 2+ response to light was triggered by extracellular Ca 2+ entry through TRPV1, whose activation required the production of reactive oxygen species at the interface between rr-P3HT and the cell membrane. Light-induced TRPV1-mediated Ca 2+ entry was able to evoke intracellular Ca 2+ release from the endoplasmic reticulum through inositol-1,4,5-trisphosphate receptors, followed by store-operated Ca 2+ entry on the plasma membrane. These data show that TRPV1 may serve as a decoder at the interface between rr-P3HT thin films and ECFCs to translate optical excitation in pro-angiogenic Ca 2+ signals., (Copyright © 2021. Published by Elsevier Ltd.)

The electrochemical deposition of poly(3,4-ethylenedioxythiophene) (PEDOT) has been carried out previously in the presence of a variety of counterions. Previous studies have shown that elongated nanofibrillar structures of PEDOT would form reproducibly when certain counterions such as poly(acrylic acid) (PAA) were added to the reaction mixture. However, details of the nanofibril nucleation and growth stages were not yet clear. Here, we describe the structural evolution of PEDOT nanofibrils using liquid-phase transmission electron microscopy (LPTEM). We measured the growth velocities of nanofibrils in different directions at various stages of the process and their intensity profiles, and we have estimated the number of EDOT monomers involved. We observed that fibrils initially grew anisotropically in a direction nominally perpendicular to the local edge of the electrodes, with rates that were faster along their lengths as compared those along to their widths and thicknesses. These real-time observations have helped us elucidate the nucleation and growth of PEDOT nanofibrils during electrochemical deposition.

Owing to their excellent mechanical flexibility, mixed-conducting electrical property, and extraordinary chemical turnability, conjugated polymers have been demonstrated to be an ideal bioelectronic interface to deliver therapeutic effect in many different chronic diseases. This review article summarizes the latest advances in implantable electronics using conjugated polymers as electroactive materials and identifies remaining challenges and opportunities for developing electronic medicine. Examples of conjugated polymer-based bioelectronic devices are selectively reviewed in human clinical studies or animal studies with the potential for clinical adoption. The unique properties of conjugated polymers are highlighted and exemplified as potential solutions to address the specific challenges in electronic medicine., (© 2021 Wiley-VCH GmbH.)

Conjugated polymers have immense potential for their use as semiconducting materials in organic optoelectronic devices. The improvement of synthetic methods for conjugated polymers is important for the practical application of conjugated polymers. For mass production, synthetic methods must be developed by considering the concerns regarding cost and environment. Reduction in the number of synthetic steps is an efficient approach to address these concerns. The utilization of direct CH functionalization is a reasonable strategy in monomer and polymer syntheses, because the prefunctionalization steps for CC bond formation can be eliminated. This review summarizes the recent developments in the efficient syntheses of conjugated polymers as well as their monomers via direct arylation (CH/CX coupling) and cross-dehydrogenative coupling (CH/CH coupling) reactions., (© 2020 Wiley-VCH GmbH.)

Most organic luminescent dyes usually show poor emission in solid due to aggregation-caused quenching due to nonspecific intermolecular interaction, such as π-π stacking. Furthermore, since commodity molecules having near-infrared (NIR) emission properties tend to have extended π-conjugated systems, development of luminescent organic materials with solid-state NIR emission has been still challenging. Herein, the series of the azobenzene complexes with the perpendicularly-protruded aryl derivative at the boron atom toward π-conjugated system is synthesized. From the optical measurements, it is shown that these complexes can show crystallization-induced emission enhancement behaviors. The donor-acceptor type π-conjugated polymers composed of the azobenzene complexes are also synthesized. Highly-efficient NIR emission from the phenyl-substituted polymers both in solution (λ PL  = 742 nm, Φ PL  = 15%) and film states (λ PL  = 793 nm, Φ PL  = 9%) is obtained. Furthermore, emission wavelengths can be tuned by changing the substituent at the boron atom to the modified aryl groups. From mechanistic studies including theoretical calculations, it is shown that electronic interaction is allowable between the aryl substituent to the π-conjugated system through the tetradentate boron., (© 2020 Wiley-VCH GmbH.)

The growth of bacteria and the formation of complex bacterial structures on biomedical devices is a major challenge in modern medicine. The aim of this study was to develop a biocompatible, conducting and antibacterial polymer coating applicable in biomedical engineering. Since conjugated polymers have recently aroused strong interest as controlled delivery systems for biologically active compounds, we decided to employ a poly(3,4-ethylenedioxythiophene) (PEDOT) matrix to immobilize a powerful, first-line antibiotic: tetracycline (Tc). Drug immobilization was carried out simultaneously with the electrochemical polymerization process, allowing to obtain a polymer coating with good electrochemical behaviour (charge storage capacity of 19.15 ± 6.09 mC/cm 2 ) and high drug loading capacity (194.7 ± 56.2 μg/cm 2 ). Biological activity of PEDOT/Tc matrix was compared with PEDOT matrix and a bare Pt surface against a model Gram-negative bacteria strain of Escherichia coli with the use of LIVE/DEAD assay and SEM microscopy. Finally, PEDOT/Tc was shown to serve as a robust electroactive coating exhibiting antibacterial activity., (Copyright © 2021 Elsevier B.V. All rights reserved.)

For polymer semiconductors, the backbone structure plays an essential role in determining their physicochemical properties and charge transport behaviors. In this work, two donor-acceptor-type polymers (P-BDF and P-NDF) based on benzodifuranone (BDF) and naphthodifunarone (NDF) as electron-deficient moieties and indaceno-dithiophene as electron-rich groups are designed, synthesized and, for the first time, applied in organic field-effect transistor. P-BDF and P-NDF differ from their backbone structures while P-BDF has a more planar backbone conformation due to its smaller conjugated core size and P-NDF features a perpendicular-extended main chain structure. As a result, P-BDF polymer exhibits bathochromic optical absorption, deeper molecular orbital energy levels, and more importantly, closer π-stacking and stronger aggregation in the solid state and thus affords a more promising hole mobility of up to 0.85 cm 2 V -1 s -1 in OFET devices, while that of the P-NDF-based devices is only 0.55 cm 2 V -1 s -1 . The results suggest the great potential of BDF/NDF-type chromophores in constructing novel organic semiconductors and also indicate that the main chain coplanarity of polymer semiconductors is more essential than the sole extension of π-conjugations (especially at the perpendicular direction of polymer main chains) for the design of high-performance OFET materials., (© 2021 Wiley-VCH GmbH.)

Structurally complex π-conjugated polymers hold great promise as key components in sensor and electronic devices; however, their syntheses have not been a trivial task. From a synthetic efficiency perspective, it would be more attractive to access these materials using convenient and efficient methods from simple building blocks. One such synthetic tool, multicomponent polymerization, can accommodate modularity and provide highly efficient syntheses. This feature article outlines several multicomponent polymerization strategies for the synthesis of various π-conjugated polymers, which are classified based upon how the monomers are aligned during polymerization. Additionally, the challenges and outlooks of this field are highlighted and discussed., (© 2020 Wiley-VCH GmbH.)

The presence of excited-states and charge-separated species was identified through UV and visible laser pump and visible/near-infrared probe femtosecond transient absorption spectroscopy in spin coated films of poly[ N -9″-heptadecanyl-2,7-carbazole- alt -5,5-(4,7-di-2-thienyl-2',1',3'-benzothiadiazole)] (PCDTBT) nanoparticles and mesoparticles. Optical gain in the mesoparticle films is observed after excitation at both 400 and 610 nm. In the mesoparticle film, charge generation after UV excitation appears after around 50 ps, but little is observed after visible pump excitation. In the nanoparticle film, as for a uniform film of the pure polymer, charge formation was efficiently induced by UV excitation pump, while excitation of the low energetic absorption states (at 610 nm) induces in the nanoparticle film a large optical gain region reducing the charge formation efficiency. It is proposed that the different intermolecular interactions and molecular order within the nanoparticles and mesoparticles are responsible for their markedly different photophysical behavior. These results therefore demonstrate the possibility of a hitherto unexplored route to stimulated emission in a conjugated polymer that has relatively undemanding film preparation requirements.

Fluorescent conjugated polymers (CPs) have attracted considerable interest in biosensing owing to their high fluorescence, tunable bandgap, and good biocompatibility. Aiming at acquiring the desired optical responses of CPs for bioapplications, it is essential that the CPs bind to biological targets with high efficacy and affinity. However, the efficient binding of CPs is largely driven by their effective interaction with target surfaces. In this Review, we will focus on the different surface interactions that pervade between CPs and biological targets. The multiple surface interactions can lead to changes in spatial conformation and distribution of CPs, which manifest alterable optical properties of CPs based on accumulation of target-directed CPs, Förster resonance energy transfer mechanism, and metal-enhanced fluorescence mechanism. Then, we display diverse bioapplications applying CPs-based surface interactions, such as cell imaging, imaging-guided detection, and photodynamic therapy. Finally, the challenges and future developments to control the efficient attachment of CPs to biological targets are discussed. We expect that the understanding of surface interactions between CPs and biological targets benefits the CPs-based system design and expands their applications in biological detections and therapies.

A p-type thermoelectric conjugated polymer based on indacenodithiophene and benzothiadiazole is designed and synthesized by replacing normal aliphatic side chains ( P1 ) with conjugated aromatic benzene substituents ( P2 ). The introduced bulky substituent on P2 is detrimental to form the intensified packing of polymers, therefore, it hinders the efficient transporting of the charge carriers, eventually resulting in a lower conductivity compared to that of the polymers bearing aliphatic side chains ( P1 ). These results reveal that the modification of side chains on conjugated polymers is crucial to rationally designed thermoelectric polymers with high performance.

Bioelectrochemical systems (BESs) provide favorable opportunities for the sustainable conversion of energy from biological metabolism. Biological photovoltaics (BPVs) and microbial fuel cells (MFCs) respectively realize the conversion of renewable solar energy and bioenergy into electrical energy by utilizing electroactive biological extracellular electron transfer, however, along with this energy conversion progress, relatively poor durability and low output performance are challenges as well as opportunities. Advances in improving bio-electrode interface compatibility will help to solve the problem of insufficient performance and further have a far-reaching impact on the development of bioelectronics. Conjugated polymers (CPs) with specific optical and electrical properties (absorption and emission spectra, energy band structure and electrical conductivity) afforded by π-conjugated backbones are conducive to enhancing the electron generation and output capacity of electroactive organisms. Furthermore, the water solubility, functionality, biocompatibility and mechanical properties optimized through appropriate modification of side chain provide a more adaptive contact interface between biomaterials and electrodes. In this minireview, we summarize the prominent contributions of CPs in the aspect of augmenting the photovoltaic response of BPVs and power supply of MFCs, and specifically discussed the role of CPs with expectation to provide inspirations for the design of bioelectronic devices in the future., (© 2020 Wiley-VCH GmbH.)

A facile method to prepare hydrophilic polymers by a postpolymerization nucleophillic aromatic substitution reaction of fluoride on an emissive conjugated polymer (CP) backbone is reported. Quantitative functionalization by a series of monofunctionalized ethylene glycol oligomers, from dimer to hexamer, as well as with high molecular weight polyethylene glycol is demonstrated. The length of the ethylene glycol sidechains is shown to have a direct impact on the surface wettability of the polymer, as well as its solubility in polar solvents. However, the energetics and band gap of the CPs remain essentially constant. This method therefore allows an easy way to modulate the wettability and solubility of CP materials for a diverse series of applications., (© 2020 The Authors. Published by WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Chronic wounds are characterized by a localized pH change from acidic (healthy) to alkaline (unhealthy), which can be harnessed to act as a switch for drug release from a polymer medium covering the wound for improved healing. To realize this, a new polymer dressing material is needed to help heal chronic wounds. Polypyrrole (PPy) is a biocompatible electroactive polymer that has been proven as a successful drug delivery mechanism, but currently lacks the capacity for scalable clinical applications due to its poor processability. In this study, PPy films with and without microstructures were produced using electrochemical oxidation and subsequently doped with fluorescein, a model drug molecule. To increase the drug loading capacity, microstructures were created through soft template polymerization of pyrrole around hydrogen gas bubbles. Fluorescein release was measured using UV spectroscopy over a pH range of 2 to 11, showing increased release at higher pH values. Microstructured films showed an increased doping capacity compared to flat PPy films, attributed to the increase in drug incorporation sites. The pH-activated release mechanism was shown to be successful and can be applied as a pH-sensitive biosensor and drug delivery system in vitro.

A thermo-responsive conjugated polymer, PFBT-gPA is synthesized by grafting the poly(N-isopropylacrylamide) (PNIPAAm) to the side chains of a conjugated polyfluorene derivative through atom transfer radical polymerization (ATRP). PFBT-gPA undergoes a reversible phase transition in water below and above the lower critical solution temperature (LCST) and the process is studied by differential scanning calorimetry (DSC) analysis and UV/vis absorption spectra. PFBT-gPA shows a good photostability under UV light irradiation especially above the LCST. Moreover, the photosensitizing performance of PFBT-gPA could be tuned simply by changing temperature. The unique properties of PFBT-gPA promise its potential applications in sensing and photodynamic therapy., (© 2020 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Brain-inspired synaptic transistors have been considered as a promising device for next-generation electronics. To mimic the behavior of a biological synapse, both data processing and nonvolatile memory capability are simultaneously required for a single electronic device. In this work, a simple approach to realize a synaptic transistor with improved memory characteristics is demonstrated by doping an ionic additive, tetrabutylammonium perchlorate (TBAP), into an active polymer semiconductor without using any extra charge storage layer. TBAP doping is first revealed to improve the memory window of a derived transistor memory device from 19 to 32 V (∼68% enhancement) with an on/off current ratio over 10 3 at V = -10 V. Through morphological analysis and theoretical calculations, it is revealed that the association of anion with polymers enhances the charge retention capability of the polymer and facilitates the interchain interactions to result in improved memory characteristics. More critically, the doped device is shown to successfully mimic the synaptic behaviors, such as paired-pulse facilitation (PPF), excitatory and inhibitory postsynaptic currents, and spike-rate dependent plasticity. Notably, the TBAP-doped device is shown to deliver a PPF index of up to 204% in contrast to the negligible value of an undoped device. This study describes a novel approach to prepare a synaptic transistor by doping conjugated polymers, which can promote the future development of artificial neuromorphic systems.G = -10 V. Through morphological analysis and theoretical calculations, it is revealed that the association of anion with polymers enhances the charge retention capability of the polymer and facilitates the interchain interactions to result in improved memory characteristics. More critically, the doped device is shown to successfully mimic the synaptic behaviors, such as paired-pulse facilitation (PPF), excitatory and inhibitory postsynaptic currents, and spike-rate dependent plasticity. Notably, the TBAP-doped device is shown to deliver a PPF index of up to 204% in contrast to the negligible value of an undoped device. This study describes a novel approach to prepare a synaptic transistor by doping conjugated polymers, which can promote the future development of artificial neuromorphic systems.

Enzyme-based assays have been extensively used for the early diagnosis of disease-related biomarkers. However, these assays are time-consuming, resource-intensive, and infrastructure-dependent, which renders them unsuitable and impractical for use in resource-constrained areas. Thus, there is a strong demand for a biocompatible and potentially generalizable sensor that can rapidly detect cancer biomarkers at ultralow concentration. Herein, an enzyme-free, cost-efficient, and easy-to-use assay based on a novel approach that entails fluorescent molecularly imprinting conjugated polythiophenes (FMICPs) for cancer biomarkers detection is developed. The promising conjugated polythiophenes structure, with a PLQY as high as 55%, provides a straightforward, and affordable method for free-enzyme signal generation. More importantly, the feasibility of integrating printed-paper technology with a sensitive and cost-effective smartphone and portable prototype testing device that could be utilized for rapid point-of-care (POC) cancer diagnostics is successfully introduced. Significantly, the unique structure of FMICP nanofibers (FMICP NFs) displays superior performance with enhanced sensitivity that is 80 times higher than that of pristine FMICP. This assay could lower the limits of detection to 15 fg mL -1 and 3.5 fg mL -1 for α-fetoprotein (AFP) and carcinoembryonic antigen (CEA), respectively, which are three orders of magnitude exceeding that of the standard enzyme-based assay. Moreover, the developed sensors are successfully applied to the fast diagnosis of AFP in liver cancer patients and the FMICP and FMICP NFs results are in excellent agreement with those of clinical ELISA., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020 Elsevier B.V. All rights reserved.)

Amplified Spontaneous Emission (ASE) threshold represents a crucial parameter often used to establish if a material is a good candidate for applications to lasers. Even if the ASE properties of conjugated polymers have been widely investigated, the specific literature is characterized by several methods to determine the ASE threshold, making comparison among the obtained values impossible. We quantitatively compare 9 different methods employed in literature to determine the ASE threshold, in order to find out the best candidate to determine the most accurate estimate of it. The experiment has been performed on thin films of an homopolymer, a copolymer and a host:guest polymer blend, namely poly(9,9-dioctylfluorene) (PFO), poly(9,9-dioctylfluorene-cobenzothiadiazole) (F8BT) and F8BT:poly(3- hexylthiophene) (F8BT:rrP3HT), applying the Variable Pump Intensity (VPI) and the Variable Stripe Length (VSL) methods. We demonstrate that, among all the spectral features affected by the presence of ASE, the most sensitive is the spectral linewidth and that the best way to estimate the ASE threshold is to determine the excitation density at the beginning of the line narrowing. We also show that the methods most frequently used in literature always overestimate the threshold up to more than one order of magnitude.

In this article, the detailed photoexcitation dynamics which combines nonadiabatic molecular dynamics with electronic transitions shows the occurrence of amplified spontaneous emission (ASE) in conjugated polymers, accompanied by spontaneous electric polarization. The elaborate molecular dynamic process of ultrafast photoexcitation can be described as follows: Continuous external optical pumping (laser of 70 µJ/cm 2 ) not only triggers the appearance of an instantaneous four-level electronic structure but causes population inversion for ASE as well. At the same time, the phonon spectrum of the conjugated polymer changes, and five local infrared lattice vibrational modes form at the two ends, which break the original symmetry in the system and leads to charge accumulation at the ends of the polymer chain without an external electric field. This novel phenomenon gives a brand-new avenue to explain how the lattice vibrations play a role in the evolution of the stimulated emission, which leads to an ultrafast effect in solid conjugated polymers.

New, biocompatible materials with favorable antibacterial activity are highly desirable. In this work, we develop a unique conjugated polymer featuring aggregation-induced emission (AIE) for reliable bacterial eradication. Thanks to the AIE and donor-π-acceptor structure, this polymer shows a high reactive oxygen species (ROS)-generation ability compared to a low-mass model compound and the common photosensitizer Chlorin E6. Moreover, the selective binding of pathogenic microorganisms over mammalian cells was found, demonstrating its biocompatibility. The effective growth inhibition of bacteria upon polymer treatment under light irradiation was validated in vitro and in vivo. Notably, the recovery from infection after treatment with our polymer is faster than that with cefalotin. Thus, this polymer holds great promise in fighting against bacteria-related infections in practical applications., (© 2020 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)