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The growing awareness of the energy crisis and global warming has inspired researchers to pursue alternative cooling strategies. Radiative cooling is an environmentally friendly approach that dissipates excessive heat through the atmospheric long‐wave infrared transmission window (8–13 μm) to the cold universe. Metamaterials with unique photonic structures are applicable to radiative cooling and have been extensively studied. Incorporating meta‐elements to the fiber level of the fabric to construct metafibers is expected to achieve personal thermal management through radiative cooling. Compared with the conventional fiber manufacturing methods, the thermal drawing technique can mass‐produce multimaterial and multifunctional fibers with well‐defined structures. These in‐fiber micro‐ and nanostructures of light wavelength scale possess great potentials in radiative cooling applications, providing bright prospects for a new generation of metafiber‐based smart fabrics. Herein, the fundamental principles of radiative cooling and the metamaterials being used for radiative cooling are summarized. The textiles used for personal cooling and their preparation methods are also introduced. Finally, the article focuses on the preparation of micro‐ and nanostructures by the thermal drawing technique, which provides a potential solution for the large‐scale manufacture of metafibers for sustainable radiative cooling.

The prosperity in portable and wearable electronics has stimulated researchers to develop safe, environmentally friendly, and efficient energy‐storage technologies. Increased efforts have recently been made to fabricate high‐performance rechargeable aqueous alkaline batteries (RAABs) as the frontrunner to complement and even replace the dominant lithium‐ion batteries for large‐scale energy storage due to the limited lithium resources and the use of flammable and toxic organic electrolyte. Compared with the conventional planar RAABs, fiber‐shaped RAABs (FRAABs) manifest several intriguing features, such as miniaturization, adaptability, and weavability, making them an attractive candidate to power wearable and portable electronics. Herein, an overview of the recent progress in FRAABs by categories of fiber‐shaped aqueous rechargeable Zn‐based batteries, Fe−Ni batteries, and Bi−Ni batteries, with respect to the active electrode materials, device configurations, and battery properties, is comprehensively presented. Finally, the remaining challenges and possible solutions are emphasized as a useful guide for the further development of FRAABs.

Radiofrequency ablation (RFA), a critical therapy for hepatocellular carcinoma (HCC), carries a significant risk of recurrence and metastasis, particularly owing to mechanisms involving immune evasion and antigen downregulation via epigenetic modifications. This study introduces a "nano-epidrug" named MFMP. MFMP, which is composed of hollow mesoporous manganese dioxide (MnO 2 ) nanoparticles, FIDAS-5 as an MAT2A inhibitor, macrophage membrane, and anti-PD-L1 (aPD-L1), targets HCC cells. By selectively binding to these cells, MFMP initially reverses immune suppression via PD-L1 inhibition. After endocytosis, MFMP disassembles in the tumor microenvironment, releasing FIDAS-5 and Mn 2+ . FIDAS-5 prevents cGAS methylation, whereas Mn 2+ aids STING pathway restoration. In addition, FIDAS-5 reduces m 6 A RNA modification, suppressing EGFR expression. These changes enhance HCC antigenicity to promote cytotoxic T cell recognition and cytotoxic killing. Furthermore, MFMP mediates immunogenic cell death in HCC by synergizing with RFA through cGAS DNA demethylation, EGFR mRNA demethylation, and TBK1 protein phosphorylation, thereby inhibiting recurrence and metastasis and enhancing immune memory. Thus, MFMP is a potential adjunctive therapy requiring clinical validation., (© 2024 Wiley‐VCH GmbH.)

The exploration of nontoxic Sn-based perovskites as a viable alternative to their toxic Pb-based counterparts has garnered increased attention. However, the power conversion efficiency of Sn-based perovskite solar cells lags significantly behind their Pb-based counterparts. This study presents a ternary passivation strategy aimed at enhancing device performance, employing [6,6]-phenyl-C61-butyric-acid-methyl-ester (PCBM), poly(3-hexylthiophene) (P3HT), and indene C60 bisadduct (ICBA). These components play crucial roles in managing energy levels and enhancing carrier transportation, respectively. The results reveal that the introduction of the ternary system leads to improvements in carrier collection and transportation, accompanied by a suppression of the recombination process. Ultimately, the champion device achieves a remarkable performance with an efficiency of 14.64%. Notably, the device also exhibits robust operational and long-term stored stability., (© 2024 The Author(s). Small published by Wiley‐VCH GmbH.)

Sulfurized polyacrylonitrile (SPAN) recently emerges as a promising cathode for high-energy lithium (Li) metal batteries owing to its high capacity, extended cycle life, and liberty from costly transition metals. As the high capacities of both Li metal and SPAN lead to relatively small electrode weights, the weight and specific energy density of Li/SPAN batteries are particularly sensitive to electrolyte weight, highlighting the importance of minimizing electrolyte density. Besides, the large volume changes of Li metal anode and SPAN cathode require inorganic-rich interphases that can guarantee intactness and protectivity throughout long cycles. This work addresses these crucial aspects with an electrolyte design where lightweight dibutyl ether (DBE) is used as a diluent for concentrated lithium bis(fluorosulfonyl)imide (LiFSI)-triethyl phosphate (TEP) solution. The designed electrolyte (d = 1.04 g mL -1 ) is 40%-50% lighter than conventional localized high-concentration electrolytes (LHCEs), leading to 12%-20% extra energy density at the cell level. Besides, the use of DBE introduces substantial solvent-diluent affinity, resulting in a unique solvation structure with strengthened capability to form favorable anion-derived inorganic-rich interphases, minimize electrolyte consumption, and improve cell cyclability. The electrolyte also exhibits low volatility and offers good protection to both Li metal anode and SPAN cathode under thermal abuse., (© 2024 The Author(s). Advanced Materials published by Wiley‐VCH GmbH.)

As a result of full-scale ongoing global efforts, the power conversion efficiency (PCE) of the organic-inorganic metal halide perovskite has skyrocketed. Unfortunately, the long-term operational stability for commercialization standards is still lagging owing to intrinsic defects such as ion migration-induced degradation, undercoordinated Pb 2+ , and shallow defects initiated by disordered crystal growth. Herein, we employed multifunctional, non-volatile tetra-methyl guanidine hydrochloride [TMGHCL] ionic liquid (IL) as an additive to elucidate defects' passivation effects on organic-inorganic metal halide perovskite. More specifically, the formation of hydrogen bonds between H + in GA + and I - and coordinate bonding between Cl - and undercoordinated Pb 2+ could significantly passivate these defects. The hypothesis was confirmed by both experimental and DFT simulations displaying that the optimized ratio of IL integration restrains ion migration, improving grains' size, and significantly elongating the carrier lifetime. Remarkably, the modified cell achieved a peak efficiency of 22.00 % with negligible hysteresis, compared to the control device's PCE of 20.12 %. In addition, the TMGHCL-based device retains its 93.29 % efficiency after 16 days of continuous exposure to air with a relative humidity of 35±5% and temperature of 25±5 °C. This efficient approach of adding IL to perovskites absorber can produce high PCE and has strong commercialization potential., (© 2024 Wiley-VCH GmbH.)

This article presents trioxa[9]circulene (3) as a novel member of hetero[n]circulenes. Its synthesis began with the synthesis of dimethoxydioxa[8]helicene (5) and used dimethoxydiepoxycyclononatrinaphthalene (4) as a key intermediate, despite the condensation reaction predominantly yielding a 1,4-addition byproduct. The structures and properties of 3-5 were extensively investigated using experimental and computational methods. Analysis of the crystal structures reveal elongation of the internal C-C bonds in the nine-membered ring of 3 compared to 4 and 5. Computational studies demonstrate the remarkable flexibility of trioxa[9]circulene's saddle-shaped polycyclic framework, while the other two compounds are rigid with large racemization barriers. Optically pure forms of 4 and 5 exhibit absorption and luminescence dissymmetry factors on the order of 10 -2 , with smaller values observed for compound 4. In the crystal structures, molecules of 3 stack to form columns with remarkable π-π overlap, and the π-π interactions of 4 exhibit short intermolecular C-to-C contacts. Consequently, the solution-processed film of 4 functioned as a p-type organic semiconductor in field effect transistors., (© 2024 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.)

Afterglow imaging holds great promise for ultrasensitive bioimaging due to its elimination of autofluorescence. Self-sustaining afterglow molecules (SAMs), which enable all-in-one photon sensitization, chemical defect formation and afterglow generation, possess a simplified, reproducible, and efficient superiority over commonly used multi-component systems. However, there is a lack of SAMs, particularly those with much brighter near-infrared (NIR) emission and structural flexibility for building high-contrast activatable imaging probes. To address these issues, this study for the first time reports a methylene blue derivative-based self-sustaining afterglow agent (SAN-M) with brighter NIR afterglow chemiluminescence peaking at 710 nm. By leveraging the structural flexibility and tunability, an activatable nanoprobe (SAN-MO) is customized for simultaneously activatable fluoro-photoacoustic and afterglow imaging of peroxynitrite (ONOO - ), notably with a superior activation ratio of 4523 in the afterglow mode, which is at least an order of magnitude higher than other reported activatable afterglow systems. By virtue of the elimination of autofluorescence and ultrahigh activation contrast, SAN-MO enables early monitoring of the LPS-induced acute inflammatory response within 30 min upon LPS stimulation and precise image-guided resection of tiny metastatic tumors, which is unattainable for fluorescence imaging., (© 2024 Wiley-VCH GmbH.)

The pursuit of highly efficient and stable wide-band gap (WBG) perovskite solar cells (PSCs), especially for monolithic perovskite/silicon tandem devices, is a key focus in achieving the commercialization of perovskite photovoltaics. In this study, we initially designed poly(ionic liquid)s (PILs) with varying alkyl chain lengths based on density functional theory calculations. Results pinpoint that PILs with longer alkyl chain lengths tend to exhibit more robust binding energy with the perovskite structure. Then we synthesized the PILs to craft a hydrophobic hydrogen-bonded polymer network (HHPN) that passivates the WBG perovskite/electron transport layer interface, inhibits ion migration and serves as a barrier layer against water and oxygen ingression. Accordingly, the HHPN effectively curbs nonradiative recombination losses while facilitating efficient carrier transport, resulting in substantially enhanced open-circuit voltage (V oc ) and fill factor. As a result, the optimized single-junction WBG PSC achieves an impressive efficiency of 23.18 %, with V oc as high as 1.25 V, which is the highest reported for WBG (over 1.67 eV) PSCs. These devices also demonstrate outstanding thermostability and humidity resistance. Notably, this versatile strategy can be extended to textured perovskite/silicon tandem cells, reaching a remarkable efficiency of 28.24 % while maintaining exceptional operational stability., (© 2023 Wiley-VCH GmbH.)

Afterglow luminescence imaging probes, with long-lived emission after cessation of light excitation, have drawn increasing attention in biomedical imaging field owing to their elimination of autofluorescence. However, current afterglow agents always suffer from an unsatisfactory signal intensity and complex systems consisting of multiple ingredients. To address these issues, this study reports a near-infrared (NIR) afterglow luminophore (TPP-DO) by chemical conjugation of an afterglow substrate and a photosensitizer acting as both an afterglow initiator and an energy relay unit into a single molecule, resulting in an intramolecular energy transfer process to improve the afterglow brightness. The constructed TPP-DO NPs emit a strong NIR afterglow luminescence with a signal intensity of up to 10 8  p/s/cm 2 /sr at a low concentration of 10 μM and a low irradiation power density of 0.05 W/cm 2 , which is almost two orders of magnitude higher than most existing organic afterglow probes. The highly bright NIR afterglow luminescence with minimized background from TPP-DO NPs allows a deep tissue penetration depth ability. Moreover, we develop a GSH-activatable afterglow probe (Q-TPP-DO NPs) for ultrasensitive detection of subcutaneous tumor with the smallest tumor volume of 0.048 mm 3 , demonstrating the high potential for early diagnosis and imaging-guided surgical resection of tumors., (© 2023 Wiley-VCH GmbH.)

Photodynamic therapy (PDT), which utilizes type I photoreactions, has great potential as an effective cancer treatment because of its hypoxia-tolerant superiority over the commonly used type II pathway. A few type I photosensitizers are exploited; however, they majorly induce cytotoxicity and possess poor tumor specificity and low-efficient theranostics. To resolve this issue, herein an aminopeptidase N (APN)-activated type I phototheranostic probe (CyA) is reported for anti-hypoxic PDT in conjunction with immunotherapy for effective cancer treatment. CyA can specifically activate near-infrared fluorescence, photoacoustic signals, and phototoxicity following APN-induced substrate cleavage and the subsequent generation of active phototheranostic molecules (such as CyBr). CyA endows specific imaging capabilities and effective phototoxicity toward tumor cells overexpressing APN under both normoxia and hypoxia. In addition, the locally activatable PDT induces systemic antitumor immune responses. More importantly, the integration of localized activated PDT and systemic immunotherapy evokes enhanced therapeutic effects with improved tumor inhibition efficiency in live mice compared with individual treatments. This study aims to present an activatable phototheranostic probe for effective hypoxia-tolerant PDT and combination therapy., (© 2023 Wiley-VCH GmbH.)

This article presents two groups of V-shaped π-scaffolds that consist of two N-heteroacene units fused with either a rigid or flexible eight-membered ring. These rigid and flexible N-heteroacene dimers were synthesized through the condensation of tetraphenylenetetraone with the corresponding diamine and the Pd-catalyzed cross-coupling of tetrabromodibenzo[a,e]cyclooctatetraene with the corresponding diamine, respectively. A comparison of electronic structures and properties of the two groups of V-shaped N-heteroacene dimers shows subtle difference between the rigid and flexible eight-membered ring linkers in forming extended π-systems. X-ray crystallography of these V-shaped molecules has revealed interesting π-π interaction modes, which are dependent on the central connecting units and substituting groups. These π-π interactions between the V-shaped π-scaffolds have enabled the molecules to function as organic semiconductors in solution-processed field effect transistors., (© 2023 Wiley-VCH GmbH.)

Hematogenous metastasis is the main approach for colorectal cancer liver metastasis (CRCLM). However, as the gatekeepers in the tumor vessels, the role of TPCs in hematogenous metastasis remains largely unknown, which may be attributed to the lack of specific biomarkers for TPC isolation. Here, microdissection combined with a pericyte medium-based approach is developed to obtain TPCs from CRC patients. Proteomic analysis reveals that TRP channel-associated factor 2 (TCAF2), a partner protein of the transient receptor potential cation channel subfamily M member 8 (TRPM8), is overexpressed in TPCs from patients with CRCLM. TCAF2 in TPCs is correlated with liver metastasis, short overall survival, and disease-free survival in CRC patients. Gain- and loss-of-function experiments validate that TCAF2 in TPCs promotes tumor cell motility, epithelial-mesenchymal transition (EMT), and CRCLM, which is attenuated in pericyte-conditional Tcaf2-knockout mice. Mechanistically, TCAF2 inhibits the expression and activity of TRPM8, leading to Wnt5a secretion in TPCs, which facilitates EMT via the activation of the STAT3 signaling pathway in tumor cells. Menthol, a TRPM8 agonist, significantly suppresses Wnt5a secretion in TPCs and CRCLM. This study reveals the previously unidentified pro-metastatic effects of TPCs from the perspective of cold-sensory receptors, providing a promising diagnostic biomarker and therapeutic target for CRCLM., (© 2023 The Authors. Advanced Science published by Wiley-VCH GmbH.)

The photoelectric properties of nontoxic Sn-based perovskite make it a promising alternative to toxic Pb-based perovskite. It has superior photovoltaic performance in comparison to other Pb-free counterparts. The facile oxidation of Sn 2+ to Sn 4+ presents a notable obstacle in the advancement of perovskite solar cells that utilize Sn, as it adversely affects their stability and performance. The study revealed the presence of a Sn 4+ concentration on both the upper and lower surfaces of the perovskite layer. This discovery led to the adoption of a bi-interface optimization approach. A thin layer of Sn metal was inserted at the two surfaces of the perovskite layer. The implementation of this intervention yielded a significant decrease in the levels of Sn 4+ and trap densities. The power conversion efficiency of the device was achieved at 14.31 % through the optimization of carrier transportation. The device exhibited operational and long-term stability., (© 2023 Wiley-VCH GmbH.)

Precise detection of early osteolytic metastases is crucial for their treatment but remains challenging in the clinic because of the limited sensitivity and specificity of traditional imaging techniques. Although fluorescence imaging offers attractive features for the diagnosis of osteolytic metastases, it is hampered by limited penetration depth. To address this issue, a fluoro-photoacoustic dual-modality imaging probe comprising a near-infrared dye caged by a cathepsin K (CTSK)-cleavable peptide sequence on one side and functionalized with osteophilic alendronate through a polyethylene glycol linker on the other side is reported. Through systematic in vitro and in vivo experiments, it is demonstrated that in response to CTSK, the probe generated both near-infrared fluorescent and photoacoustic signals from bone metastatic regions, thus offering a potential strategy for detecting deep-seated early osteolytic metastases., (© 2023 The Authors. Advanced Science published by Wiley-VCH GmbH.)

Cancer-associated fibroblasts (CAFs) are the major components of the tumor-associated matrix and play an important role in tumor progression and immunosuppression. Therefore, precise theranostics of CAFs are beneficial for CAFs-targeted therapies. However, imaging agents enabling precise theranostics of CAFs have been rarely exploited. To tackle this issue, a molecular pro-theranostic probe (FMP) with activatable fluorescence, photoacoustic (PA) imaging, and photodynamic therapy (PDT) is developed in response to fibroblast activation protein α (FAPα) overexpressed in >90% types of CAFs and some tumor cells. Attributed to efficient activatable phototoxicity toward CAFs and tumor cells, together with activated immunogenic cell death (ICD), complete tumor regression of primary tumors and abscopal effect of distant tumors are observed in a 4T1-tumor-bearing mice model. By integration with PD-L1 checkpoint blockade immunotherapy, enhanced systemic immune responses are evoked to obtain long-lasting tumor suppression of both primary and distant tumors as well as arrest systemic cancer metastasis in living mice., (© 2023 Wiley-VCH GmbH.)

New molecular scaffolds of C-, Z- and box-shaped configurations are constructed by fusing phenazine and pyrene units with oxanorbornene. As revealed by X-ray crystallography, the C-shaped molecules exhibit two interesting π-π stacking modes of phenazine depending on the substituting groups, and the box-shaped molecule accommodates two chloroform molecules in the cavity and forms H-bonds with another four molecules of chloroform. The C- and Z-shaped molecules as a pair of diastereomers exhibit almost the same charge transfer absorption and emission including positive solvatochromism, indicating that the intramolecular charge transfer between pyrene (π-donor) and phenazine (π-acceptor) is not dependent on the overall molecular geometry., (© 2023 Wiley-VCH GmbH.)

Fluorescence imaging in the second near-infrared (NIR-II) window holds great promise for in vivo visualization of amyloid-β (Aβ) pathology, which can facilitate characterization and deep understanding of Alzheimer's disease (AD); however, it has been rarely exploited. Herein, we report the development of NIR-II fluorescent reporters with a donor-π-acceptor (D-π-A) architecture for specific detection of Aβ plaques in AD-model mice. Among all the designed probes, DMP2 exhibits the highest affinity to Aβ fibrils and can specifically activate its NIR-II fluorescence after binding to Aβ fibrils via suppressed twisted intramolecular charge transfer (TICT) effect. With suitable lipophilicity for ideal blood-brain barrier (BBB) penetrability and deep-tissue penetration of NIR-II fluorescence, DMP2 possesses specific detection of Aβ plaques in in vivo AD-model mice. Thus, this study presents a potential agent for non-invasive imaging of Aβ plaques and deep deciphering of AD progression., (© 2022 Wiley-VCH GmbH.)

Construction of catalytic covalent organic frameworks (COFs) for oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) is significant but rarely demonstrated. In this work, we have first constructed bifunctional COFs towards ORR and OER by integrating diarylamine derivatives into the Co-porphyrin based frameworks. Both of the new COFs (CoTAPP-PATA-COF and CoTAPP-BDTA-COF) have good ordered structures, high surface areas, and robust chemical stability. The diarylamine units, as a typical electron donor and redox-active cores, promote intramolecular electron transport along the frameworks and improve the electrochemically active surface areas. Thus, the COFs showed higher catalytic activities than that of the COF without redox-active units. CoTAPP-PATA-COF had a halfwave potential of 0.80 V towards ORR, and delieved an overpotential of 420 mV for OER in 0.1 M KOH. The theoretical calculation revealed introducing diarylamine unites improved the oxygen electrocatalysis., (© 2022 Wiley-VCH GmbH.)

Electrosynthesis of H 2 O 2 is a promising alternative to the anthraquinone oxidation process because of its low energy utilization and cost-effectiveness. Heteroatom-doped carbons-based catalysts have been widely developed for H 2 O 2 synthesis. However, their doping degree, defective degree, and location of active sites are difficult to be preciously controlled at molecular level. Herein, a dioxin-linked covalent organic framework (COF) is used as the template to preciously construct different metal-N 2 sites along the porous walls for H 2 O 2 synthesis. By tuning the metal centers, the catalyst with Ca-N 2 sites enables to catalyze H 2 O 2 production with selectivity over 95% from 0.2 to 0.6 V versus RHE, while the H 2 O 2 yields for Co sites or Ni sites are 20% and 60% in the same potential range. In addition, the turnover frequency (TOF) values for Ca-N 2 sites are 11.63 e -1 site -1 s -1 , which are 58 and 20 times higher than those of Co and Ni sites (0.20 and 0.57 e -1 site -1 s -1 ). The theoretical calculations further reveal that the OOH* desorption on Ca sites is easier than those on Co or Ni sites, and thus catalyzes the oxygen reduction reaction in the 2e - pathway with high efficiency., (© 2022 Wiley-VCH GmbH.)

Imaging to evaluate tumor-associated neutrophils (TANs) is imperative for cancer immunotherapy but remains challenging. We herein report an activatable semiconducting polymer nanoprobe (SPCy) for near-infrared fluorescence (NIRF) and photoacoustic (PA) imaging of neutrophil elastase (NE), a biomarker of TANs. SPCy comprises a semiconducting polymer conjugated with a hemicyanine (hemi-Cy) dye caged by a NE-cleavable peptide as the side chain. After systemic administration, SPCy passively targets the tumor and reacts with NE to "uncage" the hemi-Cy, leading to enhanced NIRF and PA signals of the hemi-Cy but unchanged signals of the SP. Such NE-activated ratiometric NIRF and enhanced PA signals of SPCy correlate with the intratumoral population of TANs. Thus, this study not only presents the first TAN-specific PA probe, but also provides a general molecular design strategy for PA imaging of other immune-related biomarkers to facilitate screening of cancer immunotherapeutics., (© 2022 Wiley-VCH GmbH.)

In vivo simultaneous visualization of multiple biomarkers is critical to accurately diagnose disease and decipher fundamental processes at a certain pathological evolution, which however is rarely exploited. Herein, a multimodal activatable imaging probe (P- 125 I) is reported with activatable fluoro-photoacoustic and radioactive signal for in vivo imaging of biomarkers (i.e., hepsin and prostate-specific membrane antigen (PSMA)) associated with prostate cancer diagnosis and prognosis. P- 125 I contains a near-infrared (NIR) dye that is caged with a hepsin-cleavable peptide sequence and linked with a radiolabeled PSMA-targeted ligand (PSMAL). After systemic administration, P- 125 I actively targets the tumor site via specific recognition between PSMA and PSMAL moiety and in-situ generates of activated fluoro-photoacoustic signal after reacting with hepsin to release the free dye (uncaged state). P- 125 I achieves precisely early detection of prostate cancer and renal clearance to alleviate toxicity issues. In addition, the accumulated radioactive and activated photoacoustic signal of probe correlates well with the respective expression level of PSMA and hepsin, which provides valuable foreseeability for cancer progression and prognosis. Thus, this study presents a multimodal activatable probe for early detection and in-depth deciphering of prostate cancer., (© 2022 Wiley-VCH GmbH.)

Herein, we report the synthesis, structural analysis, optical and chiroptical properties of a novel quadruple helicene, which has two [6] and two [7]helicene moieties fused in a contorted framework of 92 sp 2 carbon atoms. It was synthesized by the Scholl reaction of a perylene-containing substrate with the formation of eight carbon-carbon bonds on the perylene unit in a single synthetic operation. Chemical oxidation of the quadruple helicene with tris(4-bromophenyl)ammoniumyl hexachloroantimonate resulted in an air-stable dication, which exhibits the same helicity in its four helicene moieties as unambiguously identified by single-crystal X-ray crystallography. The quadruple helicene exhibits unusual near-infrared absorption and emission with absorption and emission maxima at 848 nm and 977 nm, respectively, and its isolated enantiomers exhibit electronic circular dichroism in the near-infrared and visible-light regions., (© 2021 Wiley-VCH GmbH.)

Atomically thin bismuth oxyselenide (Bi 2 O 2 Se) exhibits attractive properties for electronic and optoelectronic applications, such as high charge-carrier mobility and good air stability. Recently, the development of Bi 2 O 2 Se-based heterostructures have attracted enormous interests with promising prospects for diverse device applications. Although the electrical properties of Bi 2 O 2 Se-based heterostructures have been widely studied, the interlayer charge transfer in these heterostructures remains elusive, despite its importance in harnessing their emergent functionalities. Here, a comprehensive experimental investigation on the interlayer charge transfer properties of two heterostructures formed by Bi 2 O 2 Se and representative transition metal dichalcogenides (namely, WS 2 /Bi 2 O 2 Se and MoS 2 /Bi 2 O 2 Se) is reported. Kelvin probe force microscopy is used to measure the work functions of the samples, which are further employed to establish type-II band alignment of both heterostructures. Photoluminescence quenching is observed in each heterostructure, suggesting high charge transfer efficiency. Time-resolved and layer-selective pump-probe measurements further prove the ultrafast interlayer charge transfer processes and formation of long-lived interlayer excitons. These results establish the feasibility of integrating 2D Bi 2 O 2 Se with other 2D semiconductors to fabricate heterostructures with novel charge transfer properties and provide insight for understanding the performance of optoelectronic devices based on such 2D heterostructures., (© 2021 Wiley-VCH GmbH.)

The synthesis of new carbazole-fused polycyclic aromatics with interesting geometry and useful properties was explored using Scholl reactions. As found from the Scholl reactions of substrates having two carbazole units linked at different positions through o-phenylene, oxidative coupling of carbazole units occurred in a regioselective manner with new carbon-carbon bonds preferably formed at C3 and C4 in N-alkyl carbazoles. A new N-containing aromatic bowl was characterized by single-crystal X-ray crystallography, and new p-type organic semiconductors exhibited field effect mobility of up to 0.070 cm 2  V -1  s -1 in solution-processed thin-film transistors., (© 2021 Wiley-VCH GmbH.)

Replacement of the allylic C=C-C unit with a N-B-N unit at each of the three zigzag edges of [4]triangulene gives rise to B 3 N 6 -[4]triangulene, which is envisioned to represent a key structural unit of a new hypothetical boron carbon nitride (BC 4 N). A tert-butylated B 3 N 6 -[4]triangulene has been successfully synthesized by three-fold nitrogen-directed borylation, and the X-ray crystallographic analysis indicates that its slightly bent triangular polycyclic framework can be viewed as a 1,3,5-triphenylbenzene connected by three 4π-electron N-B-N units. The HN-B-NH moiety provides a dual hydrogen-bond donor, which forms H-bonds with halide or carboxylate anions in solution, and form DD-AA hydrogen-bond arrays with 2,7-di(tert-butyl)-pyrene-4,5,9,10-tetraone in the co-crystal. Moreover, the blue fluorescence of B 3 N 6 -[4]triangulene in solution is responsive to binding p-nitrobenzoate anion through hydrogen bonds., (© 2021 Wiley-VCH GmbH.)

Zigzag carbon nanobelts are a long-sought-after target for organic synthesis. Herein we report new strategies for designing and synthesizing unprecedented zigzag carbon nanobelts, which present a wave-like arrangement of hexagons in the unrolled lattice of (n,0) single wall carbon nanotubes (n=16 or 24). The precursors of these zigzag carbon nanobelts are hybrid cyclic arylene oligomers consisting of meta-phenylene and 2,6-naphthalenylene as well as para-phenylene units. The Scholl reactions of these cyclic arylene oligomers form multiple carbon-carbon bonds selectively at the α-positions of naphthalene units resulting in the corresponding zigzag carbon nanobelts. As monitored with fluorescence spectroscopy, one of these nanobelts binds C 60 with an association constant as high as (6.6±1.1)×10 6  M -1 in the solution in toluene. Computational studies combining linear regression analysis and hypothetical homodesmotic reactions reveal that these zigzag nanobelts have strain in the range of 67.5 to 69.6 kcal mol -1 , and the ladderization step through Scholl reactions is accompanied by increase of strain as large as 69.6 kcal mol -1 . The successful synthesis of these nanobelts demonstrates the powerfulness and efficiency of Scholl reactions in synthesizing strained polycyclic aromatics., (© 2021 Wiley-VCH GmbH.)

Development of real-time non-invasive imaging probes to assess infiltration and activation of cytotoxic T cells (CTLs) is critical to predict the efficacy of cancer immunotherapy, which however remains challenging. Reported here is an activatable semiconducting polymer nanoprobe (SPNP) for near-infrared fluorescence (NIRF) and photoacoustic (PA) imaging of a biomarker (granzyme B) associated with activation of CTLs. SPNP comprises a semiconducting polymer (SP) conjugated with a granzyme B cleavable and dye-labeled peptide as the side chain, both of which emit NIRF and PA signals. After systemic administration, SPNP passively targets the tumor and in situ reacts with granzyme B to release the dye-labeled peptide, leading to decreased NIRF and PA signals from the dye but unchanged signals from the polymer. Such ratiometric NIRF and PA signals of SPNP correlate well with the expression level of granzyme B and intratumoral population of CTLs. Thus, this study not only presents the first PA probes for in vivo imaging of immune activation but also provides a molecular design strategy that can be generalized for molecular imaging of other immune-related biomarkers., (© 2020 Wiley-VCH GmbH.)

The application of double electron-electron resonance (DEER) with site-directed spin labeling (SDSL) to measure distances in proteins and protein complexes in living cells puts rigorous restraints on the spin-label. The linkage and paramagnetic centers need to resist the reducing conditions of the cell. Rigid attachment of the probe to the protein improves precision of the measured distances. Here, three two-armed Gd III complexes, Gd III -CLaNP13a/b/c were synthesized. Rather than the disulfide linkage of most other CLaNP molecules, a thioether linkage was used to avoid reductive dissociation of the linker. The doubly Gd III labeled N55C/V57C/K147C/T151C variants of T4Lysozyme were measured by 95 GHz DEER. The constructs were measured in vitro, in cell lysate and in Dictyostelium discoideum cells. Measured distances were 4.5 nm, consistent with results from paramagnetic NMR. A narrow distance distribution and typical modulation depth, also in cell, indicate complete and durable labeling and probe rigidity due to the dual attachment sites., (© 2020 The Authors. Published by Wiley-VCH GmbH.)

As redox-active based supercapacitors are known as highly desirable next-generation supercapacitor electrodes, the targeted design of two ferrocene-functionalized (Fc(COOH) 2 ) clusters based on coinage metals, [(PPh 3 ) 2 AgO 2 CFcCO 2 Ag(PPh 3 ) 2 ] 2 ⋅7 CH 3 OH (SC 1 : super capacitor) and [(PPh 3 ) 3 CuO 2 CFcCO 2 Cu(PPh 3 ) 3 ]⋅3 CH 3 OH (SC 2 ), is reported. Both structures are fully characterized by various techniques. The structures are utilized as energy storage electrode materials, giving 130 F g -1 and 210 F g -1 specific capacitance at 1.5 A g -1 in Na 2 SO 4 electrolyte, respectively. The obtained results show that the presence of Cu I instead of Ag I improves the supercapacitive performance of the cluster. Further, to improve the conductivity, the PSC 2 ([(PPh 3 ) 2 CuO 2 CFcCO 2 ] ∞ ), a polymeric structure of SC 2 , was synthesized and used as an energy storage electrode. PSC 2 displays high conductivity and gives 455 F g -1 capacitance at 3 A g -1 . The PSC 2 as a supercapacitor electrode presents a high power density (2416 W kg -1 ), high energy density (161 Wh kg -1 ), and long cycle life over 4000 cycles (93 %). These results could lead to the amplification of high-performance supercapacitors in new areas to develop real applications and stimulate the use of the targeted design of coordination polymers without hybridization or compositions with additive materials., (© 2020 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Indolo[3,2-b]carbazole presents a π-skeleton with a remarkable electronic structure and interesting potential applications. It is, however, also associated with ambiguity and controversy. Herein, new derivatives of indolo[3,2-b]carbazole are reported and they have enabled a comprehensive study on the electronic structure of indolo[3,2-b]carbazole and the development of a new n-type organic semiconductor. Experimental and computational studies show that indolo[3,2-b]carbazole has a largely localized p-benzoquinonediimine moiety and significant antiaromaticity. When substituted with (4-silylethynyl)phenyl groups, the indolo[3,2-b]carbazole exhibits one-dimensional π-π stacking and functions as an n-type organic semiconductor in solution-processed field effect transistors., (© 2020 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Discriminative detection of invasive and noninvasive breast cancers is crucial for their effective treatment and prognosis. However, activatable probes able to do so in vivo are rare. Herein, we report an activatable polymeric reporter (P-Dex) that specifically turns on near-infrared (NIR) fluorescent and photoacoustic (PA) signals in response to the urokinase-type plasminogen activator (uPA) overexpressed in invasive breast cancer. P-Dex has a renal-clearable dextran backbone that is linked with a NIR dye caged with an uPA-cleavable peptide substrate. Such a molecular design allows P-Dex to passively target tumors, activate NIR fluorescence and PA signals to effectively distinguish invasive MDA-MB-231 breast cancer from noninvasive MCF-7 breast cancer, and ultimately undergo renal clearance to minimize the toxicity potential. Thus, this polymeric reporter holds great promise for the early detection of malignant breast cancer., (© 2020 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Photoacoustic (PA) imaging agents detect disease tissues and biomarkers with increased penetration depth and enhanced spatial resolution relative to traditional optical imaging, and thus hold great promise for clinical applications. However, existing PA imaging agents often encounter the issues of slow body excretion and low-signal specificity, which compromise their capability for in vivo detection. Herein, a fluoro-photoacoustic polymeric renal reporter (FPRR) is synthesized for real-time imaging of drug-induced acute kidney injury (AKI). FPRR simultaneously turns on both near-infrared fluorescence (NIRF) and PA signals in response to an AKI biomarker (γ-glutamyl transferase) with high sensitivity and specificity. In association with its high renal clearance efficiency (78% at 24 h post-injection), FPRR can detect cisplatin-induced AKI at 24 h post-drug treatment through both real-time imaging and optical urinalysis, which is 48 h earlier than serum biomarker elevation and histological changes. More importantly, the deep-tissue penetration capability of PA imaging results in a signal-to-background ratio that is 2.3-fold higher than NIRF imaging. Thus, the study not only demonstrates the first activatable PA probe for real-time sensitive imaging of kidney function at molecular level, but also highlights the polymeric probe structure with high renal clearance., (© 2020 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Synthetic metal complexes can be used as paramagnetic probes for the study of proteins and protein complexes. Herein, two transition metal NMR probes (TraNPs) are reported. TraNPs are attached through two arms to a protein to generate a pseudocontact shift (PCS) using cobalt(II), or paramagnetic relaxation enhancement (PRE) with manganese(II). The PCS analysis of TraNPs attached to three different proteins shows that the size of the anisotropic component of the magnetic susceptibility depends on the probe surroundings at the surface of the protein, contrary to what is observed for lanthanoid-based probes. The observed PCS are relatively small, making cobalt-based probes suitable for localized studies, such as of an active site. The obtained PREs are stronger than those obtained with nitroxide spin labels and the possibility to generate both PCS and PRE offers advantages. The properties of TraNPs in comparison with other cobalt-based probes are discussed., (© 2019 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.)

Tribenzo[a,c,e]cyclooctene oligomers, which are potential precursors for synthesis of negatively curved nanographenes and nanobelts, have been designed and synthesized. The key to this synthesis is connecting 1,3-di(4-t-butylphenyl)-dibenzo[e,i]-2H-cyclopentacycloocten-2-one, dibenzo[3,4 : 7,8]cycloocta[1,2-c : 5,6-c']difuran and the Sondheimer-Wong diyne through Diels-Alder reactions. As revealed by X-ray crystallography, the trimer with a C 8 -C 6 -C 8 -C 6 -C 8 backbone is shaped like a letter C in the crystalline state., (© 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Herein, we report two novel derivatives of hexabenzoperylene (HBP) that are functionalized with ester groups. Methyl acetate functionalized HBP (1) in single crystals self-assembles into a supramolecular nanosheet, which has a two-dimensional π-stack of HBP sandwiched between two layers of ester groups. With the same self-assembly motif, active ester-functionalized HBP (2) in field effect transistors has enabled differentiation of tertiary amines from primary and secondary amines, in agreement with the fact that active ester reacts with primary and secondary amines but not with tertiary amines to form amides., (© 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Optical imaging has played a pivotal role in biology and medicine, but it faces challenges of relatively low tissue penetration and poor signal-to-background ratio due to light scattering and tissue autofluorescence. To overcome these issues, second near-infrared fluorescence, self-luminescence, and photoacoustic imaging have recently emerged, which utilize an optical region with reduced light-tissue interactions, eliminate real-time light excitation, and detect acoustic signals with negligible attenuation, respectively. Because there are only a few endogenous molecules absorbing or emitting above the visible region, development of contrast agents is essential for those deep-tissue optical imaging modalities. Organic semiconducting agents with π-conjugated frameworks can be synthesized to meet different optical imaging requirements due to their easy chemical modification and legible structure-property relation. Herein, the deep-tissue optical imaging applications of organic semiconducting agents including small-molecule agents and nanoparticle derivatives are summarized. In particular, the molecular engineering and nanoformulation approaches to further improve the tissue penetration and detection sensitivity of these optical imaging modalities are highlighted. Finally, current challenges and potential opportunities in this emerging subfield of biomedical imaging are discussed., (© 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Molecular engineering of tetraazapentacene with different numbers of fluorine and chlorine substituents fine-tunes the frontier molecular orbitals, molecular vibrations, and π-π stacking for n-type organic semiconductors. Among the six halogenated tetraazapentacenes studied herein, the tetrachloro derivative (4Cl-TAP) in solution-processed thin-film transistors exhibits electron mobility of 14.9 ± 4.9 cm 2 V -1 s -1 with a maximum value of 27.8 cm 2 V -1 s -1 , which sets a new record for n-channel organic field-effect transistors. Computational studies on the basis of crystal structures shed light on the structure-property relationships for organic semiconductors. First, chlorine substituents slightly decrease the reorganization energy of the tetraazapentacene whereas fluorine substituents increase the reorganization energy as a result of fine-tuning molecular vibrations. Second, the electron transfer integral is very sensitive to subtle changes in the 2D π-stacking with brickwork arrangement. The unprecedentedly high electron mobility of 4Cl-TAP is attributed to the reduced reorganization energy and enhanced electron transfer integral as a result of modification of tetraazapentacene with four chlorine substituents., (© 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Theranostics provides opportunities for precision cancer therapy. However, theranostic probes that simultaneously turn on their diagnostic signal and pharmacological action only in respond to a targeted biomarker have been less exploited. We herein report the synthesis of a macrotheranostic probe that specifically activates its near-infrared fluorescence (NIRF), photoacoustic (PA), and photothermal signals in the presence of a cancer-overexpressed enzyme for imaging-guided cancer therapy. Superior to the small-molecule counterpart probe, the macrotheranostic probe has ideal biodistribution and renal clearance, permitting passive targeting of tumors, in situ activation of multimodal signals, and effective photothermal ablation. Our study thus provides a macromolecular approach towards activatable multimodal phototheranostics., (© 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Detection of metastatic tumor tissues is crucial for cancer therapy; however, fluorescence agents that allow to do share the disadvantage of low signal-to-background ratio due to tissue autofluorescence. The development of amphiphilic poly(p-phenylenevinylene) derivatives that can self-assemble into the nanoagent (SPPVN) in biological solutions and emit near-infrared afterglow luminescence after cessation of light irradiation for ultrasensitive imaging of metastatic tumors in living mice is herein reported. As compared with the counterpart nanoparticle (PPVP) prepared from the hydrophobic PPV derivate, SPPVN has smaller size, higher energy transfer efficiency, and brighter afterglow luminescence. Moreover, due to the higher PEG density of SPPVN relative to PPVP poly(ethylene glycol), SPPVN has a better accumulation in tumor. Such a high sensitivity and ideal biodistribution allow SPPVN to rapidly detect xenograft tumors with the size as small as 1 mm 3 and tiny peritoneal metastatic tumors that are almost invisible to naked eye, which is not possible for PPVP. Moreover, the oxygen-sensitive afterglow makes SPPVN potentially useful for in vivo imaging of oxygen levels. By virtue of enzymatic biodegradability and ideal in vivo clearance, these organic agents can serve as a platform for the construction of advanced afterglow imaging tools., (© 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

The last decade has witnessed multiple helicenes arising as an interesting class of nonplanar polycyclic aromatics of inherent multihelicity. These molecules present esthetic structures and interesting properties not available to helicenes of single helicity. Herein an overview of multiple helicenes with respect to structures, stereochemical dynamics, synthesis, and applications is provided. Recently reported multiple helicenes are surveyed with an emphasis on molecular structures and stereochemistry of multiple carbohelicenes. After this survey, the synthesis of multiple helicenes through the Scholl reaction is discussed and recent applications of multiple helicenes in organic electronics are summarized. On the basis of these discussions, conclusions are reached on the current status of multiple helicenes and an outlook for this field is provided., (© 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Regulation of enzyme activity is fundamentally challenging but practically meaningful for biology and medicine. However, noninvasive remote control of enzyme activity in living systems has been rarely demonstrated and exploited for therapy. Herein, we synthesize a semiconducting polymer nanoenzyme with photothermic activity for enhanced cancer therapy. Upon near-infrared (NIR) light irradiation, the activity of the nanoenzyme can be enhanced by 3.5-fold to efficiently digest collagen in the tumor extracellular matrix (ECM), leading to enhanced nanoparticle accumulation in tumors and consequently improved photothermal therapy (PTT). This study thus provides a promising strategy to remotely regulate enzyme activity for cancer therapy., (© 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

This study presents a new type of negatively curved nanographene (C 86 H 32 ) that contains an unprecedented pattern of heptagons. A tert-butylated derivative of C 86 H 32 was successfully synthesized using tetrabenzodipleiadiene as a key building block. This synthesis involved a ring expansion reaction as a key step to form the seven-membered rings in the framework of tetrabenzodipleiadiene. The single-crystal structure reveals a saddle-shaped molecule with a highly bent naphthalene moiety at the center of the polycyclic backbone. As found from the DFT calculations, this aromatic saddle is flexible at room temperature and has a saddle-shaped geometry as the dominant conformation. The DFT calculations along with experimental results show that the attachment of t-butyl groups to the central tetrabenzodipleiadiene moiety of nanographene C 86 H 32 can stabilize the saddle conformation and make this nanographene less flexible., (© 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Early detection of skin diseases is imperative for their effective treatment. However, fluorescence molecular probes that allow this are rare. The first activatable near-infrared (NIR) fluorescent molecular probe is reported for sensitive imaging of keloid cells, skin cells from abnormal scar fibrous lesions. As keloid cells have high expression levels of fibroblast activation protein-alpha (FAPα), the probe (FNP1) is designed to have a caged NIR dye and a FAPα-cleavable peptide substrate linked by a self-immolative segment. FNP1 can quickly and specifically turn on its fluorescence at 710 nm by 45-fold in the presence of FAPα, allowing it to effectively recognize keloid cells from normal skin cells. Integration of FNP1 with a simple microneedle-assisted topical application enables sensitive detection of keloid cells in metabolically-active human skin tissue with a theoretical limit of detection down to 20 000 cells., (© 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Herein we report synthesis, structure and properties of a new type of twisted nanographene, which contains an [8]circulene moiety in a polycyclic framework of 96 sp 2 carbon atoms. The key steps in this synthesis are the Diels-Alder reaction of a macrocyclic diyne and the subsequent Scholl reaction forming the [8]circulene moiety. Two incompletely cyclized products were isolated from the Scholl reaction, providing insight into the cyclization of the strained octagon. This nanographene is twisted along two directions with end-to-end twists of 142.4° and 140.2° as revealed by X-ray crystallography, and is flexible at room temperature as found from the computational and experimental studies., (© 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Herein, two novel N-phenylated N-heteroacenes (1 and 2) are reported, along with details of their synthesis, structures, and properties. Compound 1 is a N-hetero analogue of rubrene, but differs from rubrene by having a bent backbone and behaving as an insulator in the solid state owing to the lack of π-π interactions. Compound 2 is a N-hetero analogue of 6,13-diphenylpentacene (DPP) with essentially the same molecular geometry and crystal packing as DPP, but exhibiting a field effect mobility higher than that of DPP by two orders of magnitude., (© 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Herein, we report two new types of twisted polycyclic arenes (2 a, b and 3 a, b) with constitutionally isomeric π-backbones, which are synthesized by controlling the Scholl reaction of 1,2,4,5-tetra(naphth-2-yl)-3,6-diphenylbenzene (1) with properly positioned electron-donating substituents. With a polycyclic backbone containing two [5]helicene and four [4]helicene moieties, 2 a and b are new members of multiple helicenes with interesting stereochemistries. The as-synthesized 2 a and b are the twisted isomers, and thermal isomerization of twisted-2 b results in anti-2 b, a more stable stereoisomer. Both twisted- and anti-2 b have been fully characterized, and the thermal isomerization of twisted-2 b has been studied with 1 H NMR spectroscopy and DFT calculations. Compounds 3 a and b are new members of twistacenes, the benzannulated pentacene backbone of which exhibits an end-to-end twist as found from the crystal structure. Twisted- and anti-2 b are also found to function as p-type semiconductors in solution-processed thin film transistors, whereas the thin films of 3 b appear insulating presumably due to the lack of π-π interactions., (© 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

An original gadolinium-hybridized plasmonic gold nanocomposite is fabricated to provide an insightful and attractive strategy to overcome both the physiological and pathological barriers of tumor, and increase the transportation and permeability of imaging agents and drugs in tumor interior for achieving high-sensitive multimodal imaging and simultaneously improving the therapeutic efficacy of cancer., (© 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Solution-processed n-channel organic thin-film transistors (OTFTs) that exhibit a field-effect mobility as high as 11 cm(2) V(-1) s(-1) at room temperature and a band-like temperature dependence of electron mobility are reported. By comparison of solution-processed OTFTs with vacuum-deposited OTFTs of the same organic semiconductor, it is found that grain boundaries are a key factor inhibiting band-like charge transport., (© 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)