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Spatially confined photocatalysis has emerged as a viable strategy for the intensification of various redox reactions, but the influence of confined structure on reaction behavior is always overlooked in gas‐solid reactions. Herein, we report a nanomembrane with confining Cs3Bi2Br9 nanocrystals inside vertical channels of porous insulated silica thin sheets (CBB@SBA(⊥)) for photocatalytic nitric oxide (NO) abatement. The ordered one‐dimensional (1D) pore channels with mere 70 nm channel length provide a highly accessible confined space for catalytic reactions. A record‐breaking NO conversion efficiency of 98.2 % under a weight hourly space velocity (WHSV) of 3.0×106 mL g−1 h−1, as well as exceptionally high stability over 14 h and durability over a wide humidity range (RH=15–90 %) was realized over SBA(⊥) confined Cs3Bi2Br9, well beyond its nonconfined analogue and the Cs3Bi2Br9 confine in Santa Barbara Amorphous (SBA‐15). Mechanism studies suggested that the insulated pore channels of SBA(⊥) in CBB@SBA(⊥) endow concentrated electron field and enhanced mass transfer that render high exposure of reactive species and lower reaction barrier needs for ⋅O2− formation and NO oxidation, as well as prevents structural degradation of Cs3Bi2Br9. This work expands an innovative strategy for designing efficient photocatalysts for air pollution remediation. [ABSTRACT FROM AUTHOR]

Zinc homeostatic medicine is of great potential for cancer chemo‐immunotherapy; however, there are few reports on antitumor compounds that can trigger Zn2+‐mediated immune responses. In this work, we developed a novel cyclometalated PtIV‐terthiophene complex, Pt3, that not only induces DNA damage and cellular metabolism dysregulation, but also disrupts zinc homeostasis as indicated by the abnormal transcriptional level of zinc regulatory proteins, excess accumulation of Zn2+ in cytoplasm, and down‐regulation of metallothioneins (MTs), which further caused redox imbalance. The simultaneous disruption of zinc and redox homeostasis in response to Pt3 treatment activated gasdermin‐D mediated pyroptosis accompanied by cytoskeleton remodeling, thus releasing pro‐inflammatory cytokines to promote dendritic cell (DC) maturation and T cell tumor‐infiltration, eventually eliminating both primary and distant tumors in vivo. As far as we know, this is the first metal complex that can regulate zinc homeostasis to activate antitumor immunity. [ABSTRACT FROM AUTHOR]

The pseudopeptide backbone provided by N‐(2‐aminoethyl)‐glycine oligomers with attached nucleobases has been widely utilized in peptide nucleic acids (PNAs) as DNA mimics. Here we demonstrate the suitability of this backbone for the formation of structurally defined dye stacks. Toward this goal a series of peptide merocyanine (PMC) dye oligomers connected to a N‐(2‐aminoethyl)‐glycine backbone were prepared through peptide synthesis. Our concentration‐, temperature‐ and solvent‐dependent UV/Vis absorption studies show that under the control of dipole–dipole interactions, smaller‐sized oligomers consisting of one, two or three dyes self‐assemble into defined duplex structures containing two up to six chromophores. In contrast, upon further extension of the oligomer, the chosen peptide backbone cannot direct the formation of a defined duplex architecture anymore due to intramolecular aggregation between the dyes. For all aggregate species a moderate aggregation‐induced emission enhancement is observed. [ABSTRACT FROM AUTHOR]

Among the key characteristics of living systems are their ability to self‐replicate and the fact that they exist in an open system away from equilibrium. Herein, we show how the outcome of the competition between two self‐replicators, differing in size and building block composition, is different depending on whether the experiments are conducted in a closed vial or in an open and out‐of‐equilibrium replication–destruction regime. In the closed system, the slower replicator eventually prevails over the faster competitor. In a replication‐destruction regime, implemented through a flow system, the outcome of the competition is reversed and the faster replicator dominates. The interpretation of the experimental observations is supported by a mass‐action‐kinetics model. These results represent one of the few experimental manifestations of selection among competing self‐replicators based on dynamic kinetic stability and pave the way towards Darwinian evolution of abiotic systems. [ABSTRACT FROM AUTHOR]

In view of their excellent luminescence properties, nanocrystalline metal halide perovskites have diverse optoelectronic applications, including those related to anticounterfeiting. However, high‐quality optical anticounterfeiting typically requires multiple encryptions relying on several optical modes to ensure information security. Herein, an efficient anticounterfeiting strategy based on dual optical encryption is realized by combining up‐ and downconversion luminescence in a nanocomposite with NaYF4 : Er3+,Yb3+ as core and a CsMnCl3 as shell. The emission color of this nanocomposite depends on the penetration depth of incident radiation and can be changed by varying the excitation source (980 nm laser or UV light) to produce different luminescent patterns. This feature allows one to effectively improve the anticounterfeiting index and fabricate professional anticounterfeiting materials. [ABSTRACT FROM AUTHOR]

Nature segregates fundamental tasks such as information storage/transmission and catalysis between two different compound classes (e.g. polynucleotides for replication and folded polyamides for catalysis). This division of labor is likely a product of evolution, raising the question of how simpler systems in which replicators and folded macromolecules co‐exist may emerge in the transition from chemistry to biology. In synthetic systems, achieving co‐existence of replicators and foldamers in a single molecular network remains an unsolved problem. Previous work on dynamic molecular networks has given rise to either self‐replicating fibers or well‐defined foldamer structures (or completely un‐sorted complex systems). We report a system in which two cross‐reactive dithiol (nucleobase‐ and peptide‐based) building blocks self‐sort into a replicator fiber and foldamer that both emerge spontaneously and co‐exist. The self‐sorting behavior remains prevalent across different building block ratios as two phases of emergence occur: replicator growth followed by foldamer formation. This is attributed to the autocatalytic formation of the replicator fiber, followed by enrichment of the system in the remaining building block, which is subsequently incorporated into a foldamer. [ABSTRACT FROM AUTHOR]

We report here on protein–antibody conjugates (PACs) that are used for antibody‐directed delivery of protein therapeutics to specific cells. PACs have the potential to judiciously combine the merits of two prolific therapeutic approaches—biologics and antibody–drug conjugates. We utilize spherical polymer brushes to construct PACs using the combination of two simple and efficient functionally orthogonal click chemistries. In addition to the synthesis and characterization of these nanoparticles, we demonstrate that PACs are indeed capable of specifically targeting cells based on the presence of target antigen on the cell surface to deliver proteins. The potentially broad adaptability of PACs opens up new opportunities for targeted biologics in therapeutics and sensing. [ABSTRACT FROM AUTHOR]

With the increasing popularity and burgeoning progress of space technology, the development of ultralow‐temperature flexible functional materials is a great challenge. Herein, we report a highly emissive organic crystal combining ultralow‐temperature elasticity and self‐waveguide properties (when a crystal is excited, it emits light from itself, which travels through the crystal to the other end) based on a simple single‐benzene emitter. This crystal displayed excellent elastic bending ability in liquid nitrogen (LN). Preliminary experiments on optical waveguiding in the bent crystal demonstrated that the light generated by the crystal itself could be confined and propagated within the crystal body between 170 and −196 °C. These results not only suggest a guideline for designing functional organic crystals with ultralow‐temperature elasticity but also expand the application region of flexible materials to extreme environments, such as space technology. [ABSTRACT FROM AUTHOR]

Single‐atom nanozyme (SAzyme) has sparked increasing interest for catalytic antitumor treatment due to their more tunable and diverse active sites than natural metalloenzymes in complex physiological conditions. However, it is usually a hard task to precisely conduct catalysis at tumor sites after intravenous injection of those SAzyme with high reactivity. Moreover, the explorations of SAzymes in the anticancer application are still in its infancy and need to be developed. Herein, an in situ synthesis strategy for Cu SAzyme was constructed to convert adsorbed copper ions into isolated atoms anchored by oxygen atoms (Cu−O2/Cu−O4) via GSH‐responsive deformability of supports. Our results suggest that the in situ activation process could further facilitate the dissociation of copper ions and the consumption of glutathione, thereby leading to copper deposition in cytoplasm and triggering cuproptosis. Moreover, the in situ synthesis of Cu SAzyme with peroxidase‐like activity enabled the intracellular reactive oxygen species production, resulting in specifically disturbance of copper metabolism pathway. Meanwhile, the in situ exposed glucose transporter (GLUT) inhibitor phloretin (Ph) can block the glycose uptake to boost cuproptosis efficacy. Overall, this in situ activation strategy effectively diminished the off‐target effects of SACs‐induced catalytic therapies and introduced a promising treatment paradigm for advancing cuproptosis‐associated therapies. [ABSTRACT FROM AUTHOR]

We herein present an approach of photo‐induced disproportionation for preparation of Type‐I photodynamic agents. As a proof of concept, BODIPY‐based photosensitizers were rationally designed and prepared. The photo‐induced intermolecular electron transfer between homotypic chromophores leads to the disproportionation reaction, resulting in the formation of charged intermediates, cationic and anionic radicals. The cationic radicals efficiently oxidize the cellularimportant coenzyme, tetrahydrobiopterin (BH4), and the anionic radicals transfer electrons to oxygen to produce superoxide radicals (O2−⋅). One of our Type‐I photodynamic agents not only self‐assembles in water but also effectively targets the endoplasmic reticulum. It displayed excellent photocytotoxicity even in highly hypoxic environments (2 % O2), with a half‐maximal inhibitory concentration (IC50) of 0.96 μM, and demonstrated outstanding antitumor efficacy in murine models bearing HeLa tumors. [ABSTRACT FROM AUTHOR]

With the rapid development of external minimally invasive or noninvasive therapeutic modalities, ultrasound‐based sonodynamic therapy (SDT) is a new alternative for treating deep tumors. However, inadequate sonosensitizer efficiency and poor biosecurity limit clinical applications. In this study, we prepared an oxygen‐vacancy‐engineered W18O49−x nanobrush with a band gap of 2.79 eV for highly efficient SDT using a simple solvothermal method. The suitable band structures of the W18O49−x nanobrush endows it with the potential to simultaneously produce singlet oxygen (1O2), superoxide anions (⋅O2−), and hydroxyl radicals (⋅OH) under ultrasound irradiation. Additionally, abundant oxygen vacancies that serve as further charge traps that inhibit electron‐hole recombination are incidentally introduced through one‐step thermal reduction. Collectively, the in vitro and in vivo results demonstrate that the oxygen‐vacancy‐engineered W18O49−x nanobrush delivers highly efficient reactive oxygen species (ROS) for SDT in a very biosafe manner. Overall, this study provides a new avenue for discovering and designing inorganic nanosonosensitizers with enhanced therapeutic efficiencies for use in SDT. [ABSTRACT FROM AUTHOR]

Polymer–drug conjugates are promising as strategies for drug delivery, because of their high drug loading capacity and low premature release profile. However, the preparation of these conjugates is often tedious. In this paper, we report an efficient method for polymer–drug conjugates using an ultrafast and reversible click reaction in a post‐polymerization functionalization strategy. The reaction is based on the rapid condensation of boronic acid functionalities with salicylhydroxamates. The polymer, bearing the latter functionality, has been designed such that the reaction with boronic acid bearing drugs induces an in situ self‐assembly of the conjugates to form well‐defined nanostructures. We show that this method is not only applicable for molecules with an intrinsic boronic acid group, but also for the other molecules that can be linked to aryl boronic acids through a self‐immolative linker. The linker has been designed to cause traceless release of the attached drug molecules, the efficiency of which has been demonstrated through intracellular delivery. [ABSTRACT FROM AUTHOR]

The concept of aggregation‐induced emission (AIE) has opened new opportunities in many research fields. Motivated by the unique feature of AIE fluorogens (AIEgens), during the past decade, many AIE molecular probes and AIE nanoparticle (NP) probes have been developed for sensing, imaging and theranostic applications with excellent performance outperforming conventional fluorescent probes. This Review summarizes the latest advancement of AIE molecular probes and AIE NP probes and their emerging biomedical applications. Special focus is to reveal how the AIE probes are evolved with the development of new multifunctional AIEgens, and how new strategies have been developed to overcome the limitations of traditional AIE probes for more translational applications via fluorescence imaging, photoacoustic imaging and image‐guided photodynamic/photothermal therapy. The outlook discusses the challenges and future opportunities for AIEgens to advance the biomedical field. [ABSTRACT FROM AUTHOR]

A large nonlinear optical (NLO) coefficient and a wide band gap are two crucial but contradictory parameters that are difficult to achieve simultaneously in a single infrared (IR) NLO compound. A salt‐inclusion chalcogenide (SIC), Li[LiCs2Cl][Ga3S6] (1), was prepared that presents a nanosized tunnel framework constructed from monotype chalcogenide tetrahedra. Highly oriented covalent GaS4 tetrahedra in the host lead to a moderate second harmonic generation response (0.7 AgGaS2), and ionic guests effectively broaden the band gap to the widest value (4.18 eV) among all IR NLO chalcogenides, thereby achieving a remarkable balance between NLO efficiency and band gap. [ABSTRACT FROM AUTHOR]

A new free carbon radical was obtained in a microwave‐assisted solvothermal reaction of the primary amine (1‐methyl‐1H‐benzo[d]imidazol‐2‐yl)methanamine with FeCl3⋅6 H2O in methanol at 140 °C. Through a combination of crystallography and electrospray ionization mass spectrometry, the reaction process was studied. The longest domino reaction includes 14 steps and forms up to 12 new covalent bonds (9 C−N and 3 C−C bonds) and 3 five‐membered heterocycles. For the first time, the homolytic cleavage of a C−O bond was used to synthesize a triarylmethyl radical. [ABSTRACT FROM AUTHOR]

Regulating autophagy to control the homeostatic recycling process of cancer cells is a promising anticancer strategy. Golgi apparatus is a substrate of autophagy but the Golgi‐autophagy (Golgiphagy) mediated antitumor pathway is rarely reported. Herein, we have developed a novel Golgi‐targeted platinum (II) complex Pt3, which is ca. 20 times more cytotoxic to lung carcinoma than cisplatin and can completely eliminate tumors after intratumoral administration in vivo. Its nano‐encapsulated system for tail vein administration also features a good anti‐tumor effect. Mechanism studies indicate that Pt3 induces substantial Golgi stress, indicated by the fragmentation of Golgi structure, down‐regulation of Golgi proteins (GM130, GRASP65/55), loss of Golgi‐dependent transport and glycosylation. This triggers Golgiphagy but blocks the subsequent fusion of autophagosomes with lysosomes, that is a dual role in autophagy regulation, resulting in loss of proteostasis and apoptotic cell death. As far as we know, Pt3 is the first Golgi‐targeted Pt complex that can trigger Golgi stress‐mediated dual‐regulation of autophagic flux and autophagy‐apoptosis crosstalk for highly efficient cancer therapy. [ABSTRACT FROM AUTHOR]

Reversible homolytic dissociation of the bis(pyrimidinenorcorrole) σ-dimer was elucidated by means of variable temperature ESR and 1H NMR spectroscopy, mass spectrometry, and optical spectrocopy. Dehydrogenation of the σ-dimer yielded another dimer displaying a singlet-triplet equilibrium in solution, strong NIR absorption (1570 nm), and a narrow electrochemical HOMO-LUMO gap (0.74 V). [ABSTRACT FROM AUTHOR]

An enantioselective β-carbon amination for enals is disclosed. The nitrogen atom from a protected hydrazine with suitable electronic properties readily behaves as a nucleophile. Addition of the nitrogen nucleophile to a catalytically generated N-heterocyclic-carbene-bound α,β-unsaturated acyl azolium intermediate constructs a new carbon-nitrogen bond asymmetrically. The pyrazolidinone products from our catalytic reactions are common scaffolds in bioactive molecules, and can be easily transformed into useful compounds such as β3-amino-acid derivatives. [ABSTRACT FROM AUTHOR]

The special structural morphology of hollow covalent organic frameworks (HCOFs) has an important influence on their applications. However, the rapid and precise control of morphology for HCOFs still remains largely challenging. Herein, we present a facile and universal two‐step strategy based on solvent evaporation and oxidation of imine bond for the controllable synthesis of HCOFs. The strategy enables to prepare HCOFs in a greatly shortened reaction time and seven kinds of HCOFs are fabricated by the oxidation of imine bond via hydroxyl radicals (⋅OH) generated from Fenton reaction. Importantly, a fascinating library of HCOFs with diverse nanostructures, including bowl‐like, yolk‐shell, capsule‐like and flower‐like morphologies, has been ingeniously constructed. Owing to the large cavities, the obtained HCOFs are ideal candidates for drug delivery, which are employed to load five small molecule drugs, achieving the enhanced sonodynamic cancer therapy in vivo. [ABSTRACT FROM AUTHOR]

Quantitation of lipid storage, unsaturation, and oxidation in live C. elegans has been a long-standing obstacle. The combination of hyperspectral stimulated Raman scattering imaging and multivariate analysis in the fingerprint vibration region represents a platform that allows the quantitative mapping of fat distribution, degree of fat unsaturation, lipid oxidation, and cholesterol storage in vivo in the whole worm. Our results reveal for the first time that lysosome-related organelles in intestinal cells are sites for storage of cholesterol in C. elegans. [ABSTRACT FROM AUTHOR]

Integrated nanodevices with the capability of storing energy are widely applicable and have thus been studied extensively. To meet the demand for flexible integrated devices, all-solid-state asymmetric supercapacitors that simultaneously realize energy storage and optoelectronic detection were fabricated by growing Co3O4 nanowires on nickel fibers, thus giving the positive electrode, and employing graphene as both the negative electrode and light-sensitive material. The as-assembled integrated systems were characterized by an improved energy storage, enhanced power density (at least by 1860 % enhanced) by improving the potential window from 0-0.6 V to 0-1.5 V, excellent photoresponse to white light, and superior flexibility of both the fiber-based asymmetric supercapacitor and the photodetector. Such flexible integrated devices might be used in smart and self-powered sensory, wearable, and portable electronics. [ABSTRACT FROM AUTHOR]

Owing to the high depth of tissue penetration, non‐invasiveness, and controllability, ultrasound (US)‐mediated sonodynamic therapy (SDT) has shown broad application prospects for tumor treatment. However, the electron‐hole separation inefficiency of sonosensitizers and the tumor hypoxia remain two major challenges limiting the effect of SDT. Here, ultrafine photoetched bismuth vanadate (BiVO4) nanorods modified with DSPE‐PEG2000 (PEBVO@PEG NRs) were fabricated to achieve in situ self‐supply of oxygen (O2) and reactive oxygen species (ROS) for hypoxic tumor therapy. The photoetching approach could enhance the charge separation by inducing enriched oxygen vacancies on the surface of BiVO4, thereby improving the generation efficiency of ROS and O2. The PEBVO@PEG overcome the main obstacles of traditional sonosensitizers in the SDT process and show promising sonodynamic therapeutic effects, thus providing new strategies for improving the performance of sonosensitizer and hypoxic tumor elimination. [ABSTRACT FROM AUTHOR]

Ihr gegenüber steht der Reduktionismus, in dessen Weltbild alle Objekte und Eigenschaften auf eine einzige Entität zurückzuführen sind, oder dass das Ganze nicht mehr als die Summe seiner Teile sei. Ein gutes Beispiel dafür, dass ein System deutlich mehr sein kann als die Summe seiner Teile, ist die aggregationsinduzierte Emission (AIE): Das Aggregat besitzt eine Eigenschaft (nämlich eine Lumineszenz), die seinen molekularen Bestandteilen komplett fehlt! Das AIE-Heft deckt eine Vielfalt an Themen ab, von bahnbrechenden Fortschritten bei den Strukturen und Mechanismen bis hin zu Anwendungsplattformen für Prozesstechnik, Informationsverschlüsselung, Bildschirme, Sensoren, Bildgebung und Theranostik. [Extracted from the article]

Sonodynamic therapy (SDT) has garnered growing interest owing to its high tissue penetration depth and minimal side effects. However, the lack of efficient sonosensitizers remains the primary limiting factor for the clinical application of this treatment method. Here, defect‐repaired graphene phase carbon nitride (g‐C3N4) nanosheets are prepared and utilized for enhanced SDT in anti‐tumor treatment. After defect engineering optimization, the bulk defects of g‐C3N4 are significantly reduced, resulting in higher crystallinity and exhibiting a polyheptazine imide (PHI) structure. Due to the more extended conjugated structure of PHI, facilitating faster charge transfer on the surface, it exhibits superior SDT performance for inducing apoptosis in tumor cells. This work focuses on introducing a novel carbon nitride nanomaterial as a sonosensitizer and a strategy for optimizing sonosensitizer performance by reducing bulk defects. [ABSTRACT FROM AUTHOR]

High‐performing n‐type polymers are crucial for the advance of organic electronics field, however strong electron‐deficient building blocks with optimized physicochemical properties for constructing them are still limited. The imide‐functionalized polycyclic aromatic hydrocarbons (PAHs) with extended π‐conjugated framework, high electron deficiency and good solubility serve as promising candidates for developing high‐performance n‐type polymers. Among the PAHs, phenanthrene (PhA) features a well‐delocalized aromatic π‐system with multiple modifiable active sites. However, the PhA‐based imides are seldom studied, mainly attributed to the synthetic challenge. Herein, we report two functionalized PhAs, CPOI and CPCNI, by simultaneously incorporating imide with carbonyl or dicyanomethylene onto PhA. Notably, the dicyanomethylene‐modified CPCNI exhibits a well stabilized LUMO energy level (−3.84 eV), attributed to the synergetic inductive effect from imide and cyano groups. Subsequently, based on CPOI and CPCNI, two polymers PCPOI‐Tz and PCPCNI‐Tz were developed. Applied to organic thin‐film transistors, owing to the strong electron‐deficiency of CPCNI, polymer PCPCNI‐Tz shows an improved electron mobility and largely decreased threshold voltage compared with PCPOI‐Tz. This work affords two structurally novel electron‐deficient building blocks and highlights the effectiveness of dual functionalization of PhAs with strong electron‐withdrawing groups for devising n‐type polymers. [ABSTRACT FROM AUTHOR]

Nanoconfined polymer molecules exhibit profound transformations in their properties and behaviors. Here, we present the synthesis of a polymer‐in‐MOF single ion conducting solid polymer electrolyte, where polymer segments are partially confined within nanopores ZIF‐8 particles through Lewis acid‐base interactions for solid‐state sodium‐metal batteries (SSMBs). The unique nanoconfinement effectively weakens Na ion coordination with the anions, facilitating the Na ion dissociation from salt. Simultaneously, the well‐defined nanopores within ZIF‐8 particles provide oriented and ordered migration channels for Na migration. As a result, this pioneering design allows the solid polymer electrolyte to achieve a Na ion transference number of 0.87, Na ion conductivity of 4.01×10−4 S cm−1, and an extended electrochemical voltage window up to 4.89 V vs. Na/Na+. The assembled SSMBs (with Na3V2(PO4)3 as the cathode) exhibit dendrite‐free Na‐metal deposition, promising rate capability, and stable cycling performance with 96 % capacity retention over 300 cycles. This innovative polymer‐in‐MOF design offers a compelling strategy for advancing high‐performance and safe solid‐state metal battery technologies. [ABSTRACT FROM AUTHOR]

Glycerol is a byproduct of biodiesel production. Selective photoelectrochemical oxidation of glycerol to high value‐added chemicals offers an economical and sustainable approach to transform renewable feedstock as well as store green energy at the same time. In this work, we synthesized monoclinic WO3 nanosheets with exposed (002) facets, which could selectively oxidize glycerol to glyceric acid (GLYA) with a photocurrent density of 1.7 mA cm−2, a 73 % GLYA selectivity and a 39 % GLYA Faradaic efficiency at 0.9 V vs. reversible hydrogen electrode (RHE) under AM 1.5G illumination (100 mW cm−2). Compared to (200) facets exposed WO3, a combination of experiments and theoretical calculations indicates that the superior performance of selective glycerol oxidation mainly originates from the better charge separation and prolonged carrier lifetime resulted from the plenty of surface trapping states, lower energy barrier of the glycerol‐to‐GLYA reaction pathway, more abundant active sites and stronger oxidative ability of photogenerated holes on the (002) facets exposed WO3. Our findings show great potential to significantly contribute to the sustainable and environmentally friendly chemical processes via designing high performance photoelectrochemical cell via facet engineering for renewable feedstock transformation. [ABSTRACT FROM AUTHOR]

Developing low‐cost and high‐performance n‐type polymer semiconductors is essential to accelerate the application of organic thermoelectrics (OTEs). To achieve this objective, it is critical to design strong electron‐deficient building blocks with simple structure and easy synthesis, which are essential for the development of n‐type polymer semiconductors. Herein, we synthesized two cyano‐functionalized highly electron‐deficient building blocks, namely 3,6‐dibromopyrazine‐2‐carbonitrile (CNPz) and 3,6‐Dibromopyrazine‐2,5‐dicarbonitrile (DCNPz), which feature simple structures and facile synthesis. CNPz and DCNPz can be obtained via only one‐step reaction and three‐step reactions from cheap raw materials, respectively. Based on CNPz and DCNPz, two acceptor–acceptor (A–A) polymers, P(DPP‐CNPz) and P(DPP‐DCNPz) are successfully developed, featuring deep‐positioned lowest unoccupied molecular orbital (LUMO) energy levels, which are beneficial to n‐type organic thin‐film transistors (OTFTs) and OTEs performance. An optimal unipolar electron mobility of 0.85 and 1.85 cm2 V−1 s−1 is obtained for P(DPP‐CNPz) and P(DPP‐DCNPz), respectively. When doped with N‐DMBI, P(DPP‐CNPz) and P(DPP‐DCNPz) show high n‐type electrical conductivities/power factors of 25.3 S cm−1/41.4 μW m−1 K−2, and 33.9 S cm−1/30.4 μW m−1 K−2, respectively. Hence, the cyano‐functionalized pyrazine CNPz and DCNPz represent a new class of structurally simple, low‐cost and readily accessible electron‐deficient building block for constructing n‐type polymer semiconductors. [ABSTRACT FROM AUTHOR]

Titelbild: Li[LiCs2Cl][Ga3S6]: A Nanoporous Framework of GaS4 Tetrahedra with Excellent Nonlinear Optical Performance (Angew. In ihrem Forschungsartikel auf S. 4700 beschreiben S. Zhu et al. die De-novo-Synthese von hydroxyliertem Benzofuran und die Realisierung einer kollektiven Totalsynthese von hydroxylierten benzofuranhaltigen Naturstoffen. In der Zuschrift auf S. 4860 beschreiben J. H. van Esch et al. die Herstellung biomimetischer, unter Spannung erstarrender Hydrogele durch die Selbstassemblierung molekularer Gelbildner. [Extracted from the article]

The phototoxicity of photosensitizers (PSs) pre and post photodynamic therapy (PDT), and the hypoxic tumor microenvironment are two major problems limiting the application of PDT. While activatable PSs can successfully address the PS phototoxicity pre PDT, and type I PS can generate reactive oxygen species (ROS) effectively in hypoxic environment, very limited approaches are available for addressing the phototoxicity post PDT. There is virtually no solution available to address all these issues using a single design. Herein, we propose a proof‐of‐concept on‐demand switchable photosensitizer with quenched photosensitization pre and post PDT, which could be activated only in tumor hypoxic environment. Particularly, a hypoxia‐normoxia cycling responsive type I PS TPFN‐AzoCF3 was designed to demonstrate the concept, which was further formulated into TPFN‐AzoCF3 nanoparticles (NPs) using DSPE‐PEG‐2000 as the encapsulation matrix. The NPs could be activated only in hypoxic tumors to generate type I ROS during PDT treatment, but remain non‐toxic in normal tissues, pre or after PDT, thus minimizing side effects and improving the therapeutic effect. With promising results in in vitro and in vivo tumor treatment, this presented strategy will pave the way for the design of more on‐demand switchable photosensitizers with minimized side effects in the future. [ABSTRACT FROM AUTHOR]

Dual‐mode emission materials, combining phosphorescence and delayed fluorescence, offer promising opportunities for white‐light afterglow. However, the delayed fluorescence lifetime is usually significantly shorter than that of phosphorescence, limiting the duration of white‐light emission. In this study, a carbazole‐based host–guest system that can be activated by both ultraviolet (UV) and visible light is reported to achieve balanced phosphorescence and delayed fluorescence, resulting in a long‐lived white‐light afterglow. Our study demonstrated the critical role of a charge transfer state in the afterglow mechanism, where the charge separation and recombination process directly determined the lifetime of afterglow. Simultaneously, an efficient reversed intersystem crossing process was obtained between the singlet and triplet charge transfer states, which facilitating the delayed fluorescence properties of host–guest system. As a result, delayed fluorescence lifetime was successfully prolonged to approach that of phosphorescence. This work presents a delayed fluorescence lifetime improvement strategy via doping method to realize durable white‐light afterglow. [ABSTRACT FROM AUTHOR]

Dominoreaktionen. In der Zuschrift auf S. 3788 ff. präsentieren M.‐H. Zeng et al. die Synthese eines freien Kohlenstoffradikals durch die Dominoreaktion eines primären Amins mit FeCl3⋅6 H2O in Methanol unter Solvothermalbedingungen. [ABSTRACT FROM AUTHOR]

Electrochemical CO2 reduction to value‐added chemicals or fuels offers a promising approach to reduce carbon emissions and alleviate energy shortage. Cu‐based electrocatalysts have been widely reported as capable of reducing CO2 to produce a variety of multicarbon products (e.g. ethylene and ethanol). In this work, we develop sulfur‐doped Cu2O electrocatalysts, which instead can electrochemically reduce CO2 to almost exclusively formate. We show that a dynamic equilibrium of S exists at the Cu2O‐electrolyte interface, and S‐doped Cu2O undergoes in situ surface reconstruction to generate active S‐adsorbed metallic Cu sites during the CO2 reduction reaction (CO2RR). Density functional theory (DFT) calculations together with in situ infrared absorption spectroscopy measurements show that the S‐adsorbed metallic Cu surface can not only promote the formation of the *OCHO intermediate but also greatly suppress *H and *COOH adsorption, thus facilitating CO2‐to‐formate conversion during the electrochemical CO2RR. [ABSTRACT FROM AUTHOR]

The shortage of narrow band gap polymer acceptors with high electron mobility is the major bottleneck for developing efficient all‐polymer solar cells (all‐PSCs). Herein, we synthesize a distannylated electron‐deficient biselenophene imide monomer (BSeI‐Tin) with high purity/reactivity, affording an excellent chance to access acceptor–acceptor (A–A) type polymer acceptors. Copolymerizing BSeI‐Tin with dibrominated monomer Y5‐Br, the resulting A–A polymer PY5‐BSeI shows a higher molecular weight, narrower band gap, deeper‐lying frontier molecular orbital levels and larger electron mobility than the donor–acceptor type counterpart PY5‐BSe. Consequently, the PY5‐BSeI‐based all‐PSCs deliver a remarkable efficiency of 17.77 % with a high short‐circuit current of 24.93 mA cm−2 and fill factor of 75.83 %. This efficiency is much higher than that (10.70 %) of the PY5‐BSe‐based devices. Our study demonstrates that BSeI is a promising building block for constructing high‐performance polymer acceptors and stannylation of electron‐deficient building blocks offers an excellent approach to developing A–A type polymers for all‐PSCs and even beyond. [ABSTRACT FROM AUTHOR]

Developing high‐performance but low‐cost n‐type polymers remains a significant challenge in the commercialization of organic field‐effect transistors (OFETs). To achieve this objective, it is essential to design the key electron‐deficient units with simple structures and facile preparation processes, which can facilitate the production of low‐cost n‐type polymers. Herein, by sequentially introducing fluorine and cyano functionalities onto trans‐1,3‐butadiene, we developed a series of structurally simple but highly electron‐deficient building blocks, namely 1,4‐dicyano‐butadiene (CNDE), 3‐fluoro‐1,4‐dicyano‐butadiene (CNFDE), and 2,3‐difluoro‐1,4‐dicyano‐butadiene (CNDFDE), featuring a highly coplanar backbone and deep‐positioned lowest unoccupied molecular orbital (LUMO) energy levels (−3.03–4.33 eV), which render them highly attractive for developing n‐type semiconducting polymers. Notably, all these electron‐deficient units can be easily accessed by a two‐step high‐yield synthetic procedure from low‐cost raw materials, thus rendering them highly promising candidates for commercial applications. Upon polymerization with diketopyrrolopyrrole (DPP), three copolymers were developed that demonstrated unipolar n‐type transport characteristics in OFETs with the highest electron mobility of >1 cm2 V−1 s−1. Hence, CNDE, CNFDE, and CNDFDE represent a class of novel, simple, and efficient electron‐deficient units for constructing low‐cost n‐type polymers, thereby providing valuable insight for OFET applications. [ABSTRACT FROM AUTHOR]

A facile photoetching approach is described that alleviates the negative effects from bulk defects by confining the oxygen vacancy (Ovac) at the surface of BiVO4 photoanode, by 10‐minute photoetching. This strategy could induce enriched Ovac at the surface of BiVO4, which avoids the formation of excessive bulk defects. A mechanism is proposed to explain the enhanced charge separation at the BiVO4 /electrolyte interface, which is supported by density functional theory (DFT) calculations. The optimized BiVO4 with enriched surface Ovac presents the highest photocurrent among undoped BiVO4 photoanodes. Upon loading FeOOH/NiOOH cocatalysts, photoetched BiVO4 photoanode reaches a considerable water oxidation photocurrent of 3.0 mA cm−2 at 0.6 V vs. reversible hydrogen electrode. An unbiased solar‐to‐hydrogen conversion efficiency of 3.5 % is realized by this BiVO4 photoanode and a Si photocathode under 1 sun illumination. [ABSTRACT FROM AUTHOR]

Metal‐organic framework catalysts bring new opportunities for CO2 electrocatalysis. Herein, we first conduct density‐functional theory calculations and predict that Co‐based porphyrin porous organic layers (Co‐PPOLs) exhibit good activity for CO2 conversion because of the low *CO adsorption energy at Co‐N4 sites, which facilitates *CO desorption and CO formation. Then, we prepare two‐dimensional Co‐PPOLs with exclusive Co‐N4 sites through a facile surfactant‐assisted bottom‐up method. The ultrathin feature ensures the exposure of catalytic centers. Together with large specific area, high electrical conductivity and CO2 adsorption capability, Co‐PPOLs achieve a peak faradaic efficiency for CO production (FECO=94.2 %) at a moderate potential in CO2 electroreduction, accompanied with good stability. Moreover, Co‐PPOLs reach an industrial‐level current above 200 mA in a membrane electrode assembly reactor, and maintain near‐unity CO selectivity (FECO>90 %) over 20 h in CO2 electrolysis. [ABSTRACT FROM AUTHOR]

Polymer electrolyte membrane water electrolysis (PEMWE) has been regarded as a promising technology for renewable hydrogen production. However, acidic oxygen evolution reaction (OER) catalysts with long‐term stability impose a grand challenge in its large‐scale industrialization. In this review, critical factors that may lead to catalyst's instability in couple with potential solutions are comprehensively discussed, including mechanical peeling, substrate corrosion, active‐site over‐oxidation/dissolution, reconstruction, oxide crystal structure collapse through the lattice oxygen‐participated reaction pathway, etc. Last but not least, personal prospects are provided in terms of rigorous stability evaluation criteria, in situ/operando characterizations, economic feasibility and practical electrolyzer consideration, highlighting the ternary relationship of structure evolution, industrial‐relevant activity and stability to serve as a roadmap towards the ultimate application of PEMWE. [ABSTRACT FROM AUTHOR]

Electrochemically reducing CO2 to valuable fuels or feedstocks is recognized as a promising strategy to simultaneously tackle the crises of fossil fuel shortage and carbon emission. Sn‐based catalysts have been widely studied for electrochemical CO2 reduction reaction (CO2RR) to make formic acid/formate, which unfortunately still suffer from low activity, selectivity and stability. In this work, halogen (F, Cl, Br or I) was introduced into the Sn catalyst by a facile hydrolysis method. The presence of halogen was confirmed by a collection of ex situ and in situ characterizations, which rendered a more positive valence state of Sn in halogen‐incorporated Sn catalyst as compared to unmodified Sn under cathodic potentials in CO2RR and therefore tuned the adsorption strength of the key intermediate (*OCHO) toward formate formation. As a result, the halogen‐incorporated Sn catalyst exhibited greatly enhanced catalytic performance in electrochemical CO2RR to produce formate. [ABSTRACT FROM AUTHOR]

We report an oxygen vacancy (Vo)‐rich metallic MoO2−x nano‐sea‐urchin with partially occupied band, which exhibits super CO2 (even directly from the air) photoreduction performance under UV, visible and near‐infrared (NIR) light illumination. The Vo‐rich MoO2−x nano‐sea‐urchin displays a CH4 evolution rate of 12.2 and 5.8 μmol gcatalyst−1 h−1 under full spectrum and NIR light illumination in concentrated CO2, which is ca. 7‐ and 10‐fold higher than the Vo‐poor MoO2−x, respectively. More interestingly, the as‐developed Vo‐rich MoO2−x nano‐sea‐urchin can even reduce CO2 directly from the air with a CO evolution rate of 6.5 μmol gcatalyst−1 h−1 under NIR light illumination. Experiments together with theoretical calculations demonstrate that the oxygen vacancy in MoO2−x can facilitate CO2 adsorption/activation to generate *COOH as well as the subsequent protonation of *CO towards the formation of CH4 because of the formation of a highly stable Mo−C−O−Mo intermediate. [ABSTRACT FROM AUTHOR]

Crystalline nanotube array would create great opportunity for novel electrical application. Herein we report the first example of a metal halide based crystalline nanotube array which is constructed from an unprecedented giant [PbII18I54(I2)9] wheel cluster, as determined by synchrotron Xray diffraction. The electrical properties of the single crystal were studied and the present compound shows typical semiconductivity and highly anisotropic conductivity. [ABSTRACT FROM AUTHOR]

Endo/lysosomal escape of gene vectors and the subsequent unpacking of nucleic acids in cytosol are two major challenges for efficient gene delivery. Herein, we report a polymeric gene delivery vector, which consists of a photosensitizer (PS) with aggregation-induced emission (AIE) characteristics and oligoethylenimine (OEI) conjugated via an aminoacrylate (AA) linker that can be cleaved by reactive oxygen species (ROS). In aqueous media, the polymer could self-assemble into bright red fluorescent nanoparticles (NPs), which can efficiently bind to DNA through electrostatic interaction for gene delivery. Upon visible light irradiation, the generated ROS can break the endo/lysosomal membrane and the polymer, resulting in light-controlled endo/lysosomal escape and unpacking of DNA for efficient gene delivery. The smart polymer represents the first successful gene vector to simultaneously address both challenges with a single light excitation process. [ABSTRACT FROM AUTHOR]

The traditional method to achieve ultralong organic phosphorescence (UOP) is to hybrid nπ* and ππ* configurations in appropriate proportion, which are contradictory to each other for improving efficiency and lifetime of phosphorescence. In this work, through replacing the electron‐donating aromatic group with a methoxy group and combining intramolecular halogen bond to promote intersystem crossing and suppress non‐radiative transition, an efficient UOP molecule (2Br‐OSPh) has been synthesized with the longest lifetime and brightest UOP among its isomers. As compared to CzS2Br, which has a similar substituted position of bromine atom and a larger kisc (the rate of intersystem crossing), the smaller ΔETT* (the energy gap between monomeric phosphorescence and aggregated state phosphorescence) in 2Br‐OSPh could accelerate the transition from T1 to T1*. This research indicates that both generation and accumulation of triplet excitons play an important role in realizing efficient UOP materials. [ABSTRACT FROM AUTHOR]

In recent years, asymmetric catalysis of ynamides has attracted much attention, but these reactions mostly constructed central chirality, except for a few examples on the synthesis of axially chiral compounds which exclusively relied on noble‐metal catalysis. Herein, a facile access to axially chiral N‐heterocycles enabled by chiral Brønsted acid‐catalyzed 5‐endo‐dig cyclization of ynamides is disclosed, which represents the first metal‐free protocol for the construction of axially chiral compounds from ynamides. This method allows the practical and atom‐economical synthesis of valuable N‐arylindoles in excellent yields with generally excellent enantioselectivities. Moreover, organocatalysts and ligands based on such axially chiral N‐arylindole skeletons are demonstrated to be applicable to asymmetric catalysis. [ABSTRACT FROM AUTHOR]

The nucleus is considered the ideal target for anti‐tumor therapy because DNA and some enzymes in the nucleus are the main causes of cell canceration and malignant proliferation. However, nuclear target drugs with good biosafety and high efficiency in cancer treatment are rare. Herein, a nuclear‐targeted material MeTPAE with aggregation‐induced emission (AIE) characteristics was developed based on a triphenylamine structure skeleton. MeTPAE can not only interact with histone deacetylases (HDACs) to inhibit cell proliferation but also damage telomere and nucleic acids precisely through photodynamic treatment (PDT). The cocktail strategy of MeTPAE caused obvious cell cycle arrest and showed excellent PDT anti‐tumor activity, which offered new opportunities for the effective treatment of malignant tumors. [ABSTRACT FROM AUTHOR]

Degradable bioplastics have attracted growing interest worldwide. However, it is challenging to develop bioplastics with a simple processing procedure, strong mechanical performance, good biocompatibility, and adjustable physicochemical properties. Herein, we introduced structural proteins as building blocks and developed a simple environmentally friendly approach to fabricate diverse protein‐based plastics. A cost‐effective and high‐level production approach was developed through batch fermentation of Escherichia coli to produce the biomaterials. These bioplastics possess super plasticity, biocompatibility, biodegradability, and high resistance to organic solvents. Their structural and mechanical properties can be precisely controlled. Besides, high density information storage and hemostatic applications were realized in the bioplastic system. The customizable bioplastics have great potential for applications in numerous fields and are capable to scale up to the industrial level. [ABSTRACT FROM AUTHOR]

An ideal cancer treatment should not only destroy primary tumors but also improve the immunogenicity of the tumor microenvironment to achieve a satisfactory anti‐tumor immune effect. We designed a carbonic anhydrase IX (CAIX)‐anchored rhenium(I) photosensitizer, named CA‐Re, that not only performs type‐I and type‐II photodynamic therapy (PDT) with high efficiency under hypoxia (nanomolar‐level phototoxicity), but also evokes gasdermin D (GSDMD) mediated pyroptotic cell death to effectively stimulate tumor immunogenicity. CA‐Re could disrupt and self‐report the loss of membrane integrity simultaneously. This promoted the maturation and antigen‐presenting ability of dendritic cells (DCs), and fully activated T cells dependent adaptive immune response in vivo, eventually eliminating distant tumors at the same time as destroying primary tumors. To the best of our knowledge, CA‐Re is the first metal complex‐based pyroptosis inducer. [ABSTRACT FROM AUTHOR]

Preparation of non‐conjugated polymers with long‐wavelength emission and high quantum yield (QY) is still a huge challenge. Herein, we report the first example of linear non‐conjugated polyester exhibiting yellow–green clusteroluminescence (CL) and a high QY of 38 %. We discovered that the polyester P3 with balanced flexibility and rigidity showed the longest CL wavelength and highest QY. Systematically photophysical characterization unravel the key role of ester cluster in the CL and the cluster formation via the aggregate of ester units was visualized. Moreover, P3 was demonstrated to be a highly selective, quick‐responsive (ca. 1.2 min) and sensitive detector (detection limit is 0.78 μM) for irons owing to the fast disassociation of clusters by irons. This work not only gains further mechanistic insight into CL but also provides a new strategy to design high‐efficiency and long‐wavelength CL, meanwhile, enlightens the glorious application prospect of luminescent polyester. [ABSTRACT FROM AUTHOR]

Nanomaterials that combine diagnostic and therapeutic functions within a single nanoplatform are highly desirable for molecular medicine. Herein we report a novel theranostic platform based on a conjugated-polyelectrolyte (CPE) polyprodrug that contains functionality for image, chemo- and photodynamic therapy (PDT), and on-demand drug release upon irradiation with a single light source. Specifically, the PEGylated CPE serves as a photosensitizer and a carrier, and is covalently conjugated to doxorubicin through a linker that can be cleaved by reactive oxygen species (ROS). Under appropriate light irradiation, the CPE can generate ROS, not only for PDT, but also for on-demand drug release and chemotherapy. This nanoplatform will offer on-demand PDT and chemotherapy with drug release triggered by one light switch, which has great potential in cancer treatment. [ABSTRACT FROM AUTHOR]

Surface plasmon resonances (SPRs) have been found to promote chemical reactions. In most oxidative chemical reactions oxygen molecules participate and understanding of the activation mechanism of oxygen molecules is highly important. For this purpose, we applied surface-enhanced Raman spectroscopy (SERS) to find out the mechanism of SPR-assisted activation of oxygen, by using p-aminothiophenol (PATP), which undergoes a SPR-assisted selective oxidation, as a probe molecule. In this way, SPR has the dual function of activating the chemical reaction and enhancing the Raman signal of surface species. Both experiments and DFT calculations reveal that oxygen molecules were activated by accepting an electron from a metal nanoparticle under the excitation of SPR to form a strongly adsorbed oxygen molecule anion. The anion was then transformed to Au or Ag oxides or hydroxides on the surface to oxidize the surface species, which was also supported by the heating effect of the SPR. This work points to a promising new era of SPR-assisted catalytic reactions. [ABSTRACT FROM AUTHOR]