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Monocomponent catalysts exhibit the limited catalytic conversion of polysulfides due to their intrinsic electronic structure, but their catalytic activity can be improved by introducing heteroatoms to regulate its electronic structure. However, the rational selection principles of doping elements remain unclear. Here, we are guided by theoretical calculations to select the suitable doping elements based on the balanced relationship between the adsorption strength of lithium polysulfides (LiPSs) and catalytic activity of lithium sulfide. We apply the screening method to develop a new catalyst of phosphorus doped RuSe 2 , manifesting the further enhanced conductivity compared with original RuSe 2 , facilitating charge transfer and further modulating the d-band center of RuSe 2 , thereby augmenting its effectiveness in interacting with LiPSs. Consequently, the assembled cell exhibits an areal capacity of 7.7 mAh cm -2 , even under high sulfur loading of 8.0 mg cm -2 and a lean electrolyte condition (5.0 μL mg -1 ). This rational screening strategy offers a robust solution for the design of advanced catalysts in the field of lithium-sulfur batteries and potentially other domains as well., (© 2024 Wiley-VCH GmbH.)

With the widespread application of highly integrated electronic devices, the urgent development of multifunctional polymer-based composite materials with high electromagnetic interference shielding effectiveness (EMI SE) and thermal conductivity capabilities is critically essential. Herein, a graphene/carbon felt/polyimide (GCF/PI) composite is prepared through constructing 3D van der Waals heterostructure by heating carbon felt and graphene at high temperature. The GCF-3/PI composite exhibits the highest through-plane thermal conductivity with 1.31 W·m -1 ·K -1 , when the content of carbon felt and graphene is 14.1 and 1.4 wt.%, respectively. The GCF-3/PI composite material achieves a thermal conductivity that surpasses pure PI by 4.9 times. Additionally, GCF-3/PI composite shows an outstanding EMI SE of 69.4 dB compared to 33.1 dB for CF/PI at 12 GHz. The 3D van der Waals heterostructure constructed by carbon felt and graphene sheets is conducive to the formation of continuous networks, providing fast channels for the transmission of phonons and carriers. This study provides a guidance on the impact of 3D van der Waals heterostructures on the thermal and EMI shielding properties of composites., (© 2024 Wiley‐VCH GmbH.)

Artificial enzymes, especially nanozymes, have attracted wide attention due to their controlled catalytic activity, selectivity, and stability. The rising Cerium-based nanozymes exhibit unique SOD-like activity, and Vanadium-based nanozymes always hold excellent GPx-like activity. However, most inflammatory diseases involve polymerase biocatalytic processes that require multi-enzyme activities. The nanocomposite can fulfill multi-enzymatic activity simultaneously, but large nanoparticles (>10 nm) cannot be excreted rapidly, leading to biosafety challenges. Herein, atomically precise Ce 12 V 6 clusters with a size of 2.19 nm are constructed. The Ce 12 V 6 clusters show excellent glutathione peroxidase (GPx) -like activity with a significantly lower Michaelis-Menten constant (K m , 0.0125 mM versus 0.03 mM of natural counterpart) and good activities mimic superoxide dismutase (SOD) and peroxidase (POD). The Ce 12 V 6 clusters exhibit the ability to scavenge the ROS including O 2 ·- and H 2 O 2 via the cascade reactions of multi-enzymatic activities. Further, the Ce 12 V 6 clusters modulate the proinflammatory cytokines including tumor necrosis factor-alpha (TNF-α), interleukin-6 (IL-6), and interleukin-1β (IL-1β) and consequently rescue the multi-organ failure in the lipopolysaccharide (LPS)-induced sepsis mouse model. With excellent biocompatibility, the Ce 12 V 6 clusters show promise in the treatment of sepsis., (© 2024 Wiley‐VCH GmbH.)

Optimizing the local electronic structure of electrocatalysts can effectively lower the energy barrier of electrochemical reactions, thus enhancing the electrocatalytic activity. However, the intrinsic contribution of the electronic effect is still experimentally unclear. In this work, the electron injection-incomplete discharge approach to achieve the electron accumulation (EA) degree on the nickel-iron layered double hydroxide (NiFe LDH) is proposed, to reveal the intrinsic contribution of EA toward oxygen evolution reaction (OER). Such NiFe LDH with EA effect results in only 262 mV overpotential to reach 50 mA cm -2 , which is 51 mV-lower compared with pristine NiFe LDH (313 mV), and reduced Tafel slope of 54.8 mV dec -1 than NiFe LDH (107.5 mV dec -1 ). Spectroscopy characterizations combined with theoretical calculations confirm that the EA near concomitant Vo can induce a narrower energy gap and lower thermodynamic barrier to enhance OER performance. This study clarifies the mechanism of the EA effect on OER activity, providing a direct electronic structure modulation guideline for effective electrocatalyst design., (© 2024 Wiley‐VCH GmbH.)

The rational design of heterogeneous catalysts is crucial for achieving optimal physicochemical properties and high electrochemical activity. However, the development of new amorphous-crystalline heterostructures is significantly more challenging than that of the existing crystalline-crystalline heterostructures. To overcome these issues, a coordination-assisted strategy that can help fabricate an amorphous NiO/crystalline NiCeO x (a-NiO/c-NiCeO x ) heterostructure is reported herein. The coordination geometry of the organic ligands plays a pivotal role in permitting the formation of coordination polymers with high Ni contents. This consequently provides an opportunity for enabling the supersaturation of Ni in the NiCeO x structure during annealing, leading to the endogenous spillover of Ni from the depths of NiCeO x to its surface. The resulting heterostructure, featuring strongly coupled amorphous NiO and crystalline NiCeO x , exhibits harmonious interactions in addition to low overpotentials and high catalytic stability in the oxygen evolution reaction (OER). Theoretical calculations prove that the amorphous-crystalline interfaces facilitate charge transfer, which plays a critical role in regulating the local electron density of the Ni sites, thereby promoting the adsorption of oxygen-based intermediates on the Ni sites and lowering the dissociation-related energy barriers. Overall, this study underscores the potential of coordinating different metal ions at the molecular level to advance amorphous-crystalline heterostructure design., (© 2024 Wiley‐VCH GmbH.)

Alkylamines form the backbone of countless nitrogen-containing small molecules possessing desirable biological properties. Despite advances in amine synthesis through transition metal catalysis and photoredox chemistry, multicomponent reactions that leverage inexpensive materials to transform abundant chemical feedstocks into three-dimensional α-substituted alkylamines bearing complex substitution patterns remain scarce. Here, we report the design of a catalyst-free electroreductive manifold that merges amines, carbonyl compounds and carbon-based radical acceptors under ambient conditions without rigorous exclusion of air and moisture. Key to this aminative carbofunctionalization process is the chemoselective generation of nucleophilic α-amino radical intermediates that readily couple with electrophilic partners, providing straightforward access to architecturally intricate alkylamines and drug-like scaffolds which are inaccessible by conventional means., (© 2024 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.)

Defect-engineered bimetallic oxides exhibit high potential for the electrolysis of small organic molecules. However, the ambiguity in the relationship between the defect density and electrocatalytic performance makes it challenging to control the final products of multi-step multi-electron reactions in such electrocatalytic systems. In this study, controllable kinetics reduction is used to maximize the oxygen vacancy density of a Cu─Co oxide nanosheet (CuCo 2 O 4 NS), which is used to catalyze the glycerol electrooxidation reaction (GOR). The CuCo 2 O 4-x NS with the highest oxygen-vacancy density (CuCo 2 O 4-x -2) oxidizes C3 molecules to C1 molecules with selectivity of almost 100% and a Faradaic efficiency of ≈99%, showing the best oxidation performance among all the modified catalysts. Systems with multiple oxygen vacancies in close proximity to each other synergistically facilitate the cleavage of C─C bonds. Density functional theory calculations confirm the ability of closely spaced oxygen vacancies to facilitate charge transfer between the catalyst and several key glycolic-acid (GCA) intermediates of the GOR process, thereby facilitating the decomposition of C2 intermediates to C1 molecules. This study reveals qualitatively in tuning the density of oxygen vacancies for altering the reaction pathway of GOR by the synergistic effects of spatial proximity of high-density oxygen vacancies., (© 2024 Wiley‐VCH GmbH.)

The cinnamoyl lipid compound youssoufene A1 (1), featuring a unique dearomatic carbon-bridged dimeric skeleton, exhibits increased inhibition against multidrug resistant Enterococcus faecalis as compared to monomeric youssoufenes. However, the formation process of this intriguing dearomatization/dimerization remains unknown. In this study, an unusual "gene-within-gene" thioesterase (TE) gene ysfF was functionally characterized. The gene was found to naturally encodes two proteins, an entire YsfF with α/β-hydrolase and 4-hydroxybenzoyl-CoA thioesterase (4-HBT)-like enzyme domains, and a nested YsfF HBT (4-HBT-like enzyme). Using an intracellular tagged carrier-protein tracking (ITCT) strategy, in vitro reconstitution and in vivo experiments, we found that: i) both domains of YsfF displayed thioesterase activities; ii) YsfF/YsfF HBT could accomplish the 6π-electrocyclic ring closure for benzene ring formation; and iii) YsfF and cyclase YsfX together were responsible for the ACP-tethered dearomatization/dimerization process, possibly through an unprecedented Michael-type addition reaction. Moreover, site-directed mutagenesis experiments demonstrated that N301, E483 and H566 of YsfF are critical residues for both the 6π-electrocyclization and dimerization processes. This study enhances our understanding of the multifunctionality of the TE protein family., (© 2024 Wiley‐VCH GmbH.)

Photodynamic therapy (PDT) depends on the light-irradiated exciting of photosensitizer (PS) to generate reactive oxygen species (ROS), which faces challenges and limitations in hypoxia and antioxidant response of cancer cells, and limited tissue-penetration of light. Herein, a multifunctional DNA/upconversion nanoparticles (UCNPs) complex is developed which enables controlled co-delivery of CRISPR-Cas9, hemin, and protoporphyrin (PP) for synergistic PDT. An ultralong single-stranded DNA (ssDNA) is prepared via rolling circle amplification (RCA), which contains recognition sequences of single guide RNA (sgRNA) for loading Cas9 ribonucleoprotein (RNP), G-quadruplex sequences for loading hemin and PP, and linker sequences for combining UCNP. Cas9 RNP cleaves the antioxidant regulator nuclear factor E2-related factor 2 (Nrf2), improving the sensitivity of cancer cells to ROS, and enhancing the synergistic PDT effect. The G-quadruplex/hemin DNAzyme mimicks horseradish peroxidase (HRP) to catalyze the endogenous H 2 O 2 to O 2 , overcoming hypoxia condition in tumors. The introduced UCNP converts NIR irradiation with deep tissue penetration to light with shorter wavelength, exciting PP to transform the abundant O 2 to 1 O 2 . The integration of gene editing and PDT allows substantial accumulation of 1 O 2 in cancer cells for enhanced cell apoptosis, and this synergistic PDT has shown remarkable therapeutic efficacy in a breast cancer mouse model., (© 2024 Wiley‐VCH GmbH.)

Giant heterometallic polyoxometalate (POM) clusters with precise atom structures, flexibly adjustable and abundant active sites are promising for constructing functional nanodrugs. However, current POM drugs are almost vacant in orthotopic brain tumor therapy due to the inability to effectively penetrate the blood-brain barrier (BBB) and low drug activity. Here, we designed the largest (3.0 nm × 6.0 nm) transition-metal-lanthanide co-encapsulated POM cluster {[Ce 10 Ag 6 (DMEA)(H 2 O) 27 W 22 O 70 ][B-α-TeW 9 O 33 ] 9 } 2 88- featuring 238 metal centers via synergistic coordination between two geometry-unrestricted Ce 3+ and Ag + linkers with tungsten-oxo cluster fragments. This POM was combined with brain-targeted peptide to prepare a brain-targeted nanodrug that could efficiently traverse BBB and target glioma cells. The Ag + active centers in the nanodrug specifically activate reactive oxygen species to regulate the apoptosis pathway of glioma cells with a low half-maximal inhibitory concentration (5.66 μM). As the first brain-targeted POM drug, it efficiently prolongs the survival of orthotopic glioma-bearing mice., (© 2024 Wiley-VCH GmbH.)

Along with the rapid development and ever-deepening understanding of nanoscience and nanotechnology, nanomaterials hold promise to mimic the highly evolved biological exquisite nanostructures and sophisticated functions. Here, inspired by the ubiquitous antibacterial nanostructures on the wing surfaces of some insects, a NiCo 2 O 4 nanozyme with self-adaptive hierarchical nanostructure is developed that can capture bacteria of various morphotypes via the physico-mechanical interaction between the nanostructure and bacteria. Moreover, the developed biomimetic nanostructure further exhibits superior peroxidase-like catalytic activity, which can catalytically generate highly toxic reactive oxygen species that disrupt bacterial membranes and induce bacterial apoptosis. Therefore, the mechano-catalytic coupling property of this NiCo 2 O 4 nanozyme allows for an extensive and efficient antibacterial application, with no concerns of antimicrobial resistance. This work suggests a promising strategy for the rational design of advanced antibacterial materials by mimicking biological antibiosis., (© 2023 Wiley-VCH GmbH.)

Slow electrochemistry kinetics and dendrite growth are major obstacles for lithium-sulfur (Li-S) batteries. The investigations over the polymorph effect require more endeavors to further access the related catalyst design principles. Herein, the systematic evaluation of CoTe 2 alloy with two polymorphs regarding sulfur reduction reaction (SRR) and lithium plating/stripping is reported. As disclosed by theoretical calculations and electrochemical measurements, the orthorhombic (o-) and hexagonal (h-) CoTe 2 make a substantial difference. The reactivity origin of the CoTe 2 polymorphs is explored. The higher position of d-band centers for the Co atoms on the o-CoTe 2 leads to a higher displacement of the antibonding state; the lower antibonding state occupancy, the more effective the interaction with the sulfide moieties and lithium. Hence, o-CoTe 2 annihilates h-CoTe 2 and exhibits better catalysis and more uniform lithium deposition, consolidated by excellent performance of full cell made of o-CoTe 2 . It keeps stable charging/discharging for 800 cycles at 0.5 C with only 0.055% capacity decay per cycle and even achieves an areal capacity of 6.5 mAh cm -2 at lean electrolyte and high sulfur loading of 6.4 mg cm -2 . This work establishes the mechanistic perspective about the catalysts in Li-S batteries and provides new insight into the unified solution., (© 2023 Wiley-VCH GmbH.)

The continuous reduction of clinically available antibiotics has made it imperative to exploit more effective antimicrobial therapies, especially for difficult-to-treat Gram-negative pathogens. Herein, it is shown that the combination of an antimicrobial nanozyme with the clinically compatible basic amino acid L-arginine affords a potent treatment for infections with Gram-negative pathogens. In particular, the antimicrobial activity of the antimicrobial nanozyme is dramatically increased by ≈1000-fold after L-arginine stimulation. Specifically, the combination therapy enhances bacterial outer and inner membrane permeability and promotes intracellular reactive oxygen species (ROS) generation. Moreover, the metabolomic and transcriptomic results reveal that combination treatment leads to the increased ROS-mediated damage by inhibiting the tricarboxylic acid cycle and oxidative phosphorylation, thereby inducing an imbalance of the antioxidant and oxidant systems. Importantly, L-arginine dramatically significantly accelerates the healing of infected wounds in mouse models of multidrug-resistant peritonitis-sepsis and skin wound infection. Overall, this work demonstrates a novel synergistic antibacterial strategy by combining the antimicrobial nanozymes with L-arginine, which substantively facilitates the nanozyme-mediated killing of pathogens by promoting ROS production., (© 2023 Wiley-VCH GmbH.)

The Cd-free Cu 2 ZnSnS 4 (CZTS) solar cell is an ideal candidate for producing low-cost clean energy through green materials owing to its inherent environmental friendliness and earth abundance. Nevertheless, sulfide CZTS has long suffered from severe open-circuit voltage (V OC ) deficits, limiting the full exploitation of performance potential and further progress. Here, an effective strategy is proposed to alleviate the nonradiative V OC loss by manipulating the phase evolution during the critical kesterite phase formation stage. With a Ge cap layer on the precursor, premature CZTS grain formation is suppressed at low temperatures, leading to fewer nucleation centers at the initial crystallization stage. Consequently, the CZTS grain formation and crystallization are deferred to high temperatures, resulting in enhanced grain interior quality and less unfavorable grain boundaries in the final film. As a result, a champion efficiency of 10.7% for Cd-free CZTS solar cells with remarkably high V OC beyond 800 mV (63.2% Schockley-Queisser limit) is realized, indicating that nonradiative recombination is effectively inhibited. This strategy may advance other compound semiconductors seeking high-quality crystallization., (© 2023 The Authors. Advanced Materials published by Wiley-VCH GmbH.)

Superlattices have considerable potential as sonosensitizers for cancer therapy because of their flexible and tunable band gaps, although they have not yet been reported. In this study, a Ti-based organic-inorganic superlattice with good electron-hole separation was synthesized, which consisted of orderly layered superlattices of 2,2'-bipyridine-5,5'-dicarboxylic acid (BPDC) and Ti-O layers. In addition, the superlattice was coordinated with Fe(III) and encapsulated doxorubicin (DOX) to prepare Ti-BPDC@Fe@DOX@PEG (TFDP) after biocompatibility modification. TFDP can realize the simultaneous generation of reactive oxygen species and release of DOX under ultrasound irradiation. Moreover, adjusting the Fe(III) content can effectively modulate the band gap of the superlattice and increase the efficiency of sonodynamic therapy (SDT). The mechanisms underlying this modulation were explored. TFDP with Fe(III) can also be used as a contrast agent for magnetic resonance imaging (MRI). Both in vitro and in vivo experiments demonstrated the ability of TFDP to precisely treat cancer using MRI-guided SDT/chemotherapy. This study expands the applications of superlattices as sonosensitizers with flexible and tailored modifications and indicates that superlattices are promising for precise and customized treatments., (© 2023 Wiley-VCH GmbH.)

After medicinal market research, it was found that the harvest time of Ligustri Lucidi Fructus (LLF) was chaotic in practice. In order to determine the optimal harvest period of LLF to ensure its pharmacological activity, metabolomics analysis of LLF at different harvest times based on ultra-high-performance liquid chromatography-triple quadrupole-(linear ion trap)-tandem mass spectrometry was established. In this study, 166 differential metabolites (DMs) in 448 metabolites at different harvest times were screened out based on variable importance in projection value, and among them, 94 DMs with regular trends of change in relative content (59 increased and 35 decreased with the growth period) were chosen to further research. The result of the multivariate statistical analysis showed that November was the optimal harvest period of LLF. Additionally, 10-hydroxyligustroside, oleoside 11-methyl ester, and salidroside were screened out to be used as the evaluation indicators of immature LLF, while specnuezhenide, nuezhenoside G13, and neonuezhenide were the evaluation indicators of mature LLF. This study provides fundamental insight for metabolite identification and proposes the best harvest period of LLF to avoid confusion in the medicinal market., (© 2023 Wiley-VCH GmbH.)

The "shuttle effect" and slow conversion kinetics of lithium polysulfides (LiPSs) are stumbling block for high-energy-density lithium-sulfur batteries (LSBs), which can be effectively evaded by advanced catalytic materials. Transition metal borides possess binary LiPSs interactions sites, aggrandizing the density of chemical anchoring sites. Herein, a novel core-shelled heterostructure consisting of nickel boride nanoparticles on boron-doped graphene (Ni 3 B/BG), is synthesized through a graphene spontaneously couple derived spatially confined strategy. The integration of Li 2 S precipitation/dissociation experiments and density functional theory computations demonstrate that the favorable interfacial charge state between Ni 3 B and BG provides smooth electron/charge transport channel, which promotes the charge transfer between Li 2 S 4 -Ni 3 B/BG and Li 2 S-Ni 3 B/BG systems. Benefitting from these, the facilitated solid-liquid conversion kinetics of LiPSs and reduced energy barrier of Li 2 S decomposition are achieved. Consequently, the LSBs employed the Ni 3 B/BG modified PP separator deliver conspicuously improved electrochemical performances with excellent cycling stability (decay of 0.07% per cycle for 600 cycles at 2 C) and remarkable rate capability of 650 mAh g -1 at 10 C. This study provides a facile strategy for transition metal borides and reveals the effect of heterostructure on catalytic and adsorption activity for LiPSs, offering a new viewpoint to apply boride in LSBs., (© 2023 Wiley-VCH GmbH.)

Stereoselective C-glycosylation reactions are increasingly gaining attention in carbohydrate chemistry because they enable glycosyl precursors, readily accessible as anomeric mixtures, to converge to a single diastereomeric product. However, controlling the stereochemical outcome through transition-metal catalysis remains challenging, and methods that leverage bench-stable heteroaryl glycosyl sulfone donors to facilitate glycosylation are rare. Herein, we show two complementary nonprecious metal catalytic systems, based on iron or nickel, which are capable of promoting efficient C-C coupling between heteroaryl glycosyl sulfones and aromatic nucleophiles or electrophiles through distinct mechanisms and modes of activation. Diverse C-aryl glycosides were secured with excellent selectivity, scope, and functional-group compatibility, and reliable access to both α and β isomers was possible for key sugar residues., (© 2023 Wiley-VCH GmbH.)

The syntheses and magnetic properties of organometallic heterometallic compounds [K(THF) 6 ]{Co I [(μ 3 -HAN)RE 2 Cp* 4 ] 2 } (1-RE) and [K(Crypt)] 2 {Co I [(μ 3 -HAN)RE 2 Cp* 4 ] 2 } (2-RE) containing hexaazatrinaphthylene radicals (HAN⋅ 3- ) and four rare earth (RE) ions are reported. 1-RE shows isolable species with ligand-based mixed valency as revealed by cyclic voltammetry (CV) thus leading to the isolation of 2-RE via one-electron chemical reduction. Strong electronic communication in mixed-valency supports stronger overall ferromagnetic behaviors in 2-RE than 1-RE containing Gd and Dy ions. Ac magnetic susceptibility data reveal 1-Dy and 2-Dy both exhibit slow magnetic relaxation. Importantly, larger coercive field was observed in the hysteresis of 2-Dy at 2.0 K, indicating the enhanced SMM behavior compared with 1-Dy. Ligand-based mixed-valency strategy has been used for the first time to improve the magnetic coupling in lanthanide (Ln) SMMs, thus opening up new ways to construct strongly coupled Ln-SMMs., (© 2023 Wiley-VCH GmbH.)

Phosphorylation is one of the most common post-translational modifications (PTMs) and is closely related to protein activity and function, playing a critical role during cancer development. Quantitative phosphoproteomic strategies have been widely used to study the underlying mechanisms of cancer progression or drug resistance. In this report, we analyzed the association of phosphosite levels originated from our previously reported proteogenomic study in hepatocellular carcinoma (HCC) with clinical parameters, including prognosis, recurrence, and Tumor-Node-Metastasis (TNM) stages. By using both the log-rank test and univariate Cox proportional hazards regression analysis, we found that the abundance levels of 1712 phosphosites were associated with prognosis and those of 393 phosphosites associated with recurrence. Besides, 692 phosphosites had different abundance levels among TNM stages (I, II, III+IV) by Analysis of Variance (ANOVA) test. Gene ontology (GO) biological process and Kyoto Encyclopedia of Genes and Genomes (KEGG) pathway enrichment analyses were performed using proteins with these statistically significant phosphosites. In conclusion, we provided a dataset resource for clinically associated phosphosites in HCC, which may be beneficial to liver cancer related basic research., (© 2022 Wiley-VCH GmbH.)

Pharmacological targeting of endoplasmic reticulum (ER) stress represents one of important methods for disease therapy, which, however, is significantly suppressed by the ER homeostatic processe. Herein, a proof-of-concept strategy is reported for persistent stimulation of ER stress via preventing ER stress adaptation by utilizing multifunctional peptide assemblies. The strategy is established via creation of peptide assemblies with ER-targeting and chaperone glucose-regulated protein 78 (GRP78)-inhibiting functions. The peptides assemblies form well-defined nanofibers that are retrieved by ER organelles in human cervical cancer cell. The underlying mechanism studies unravel that the ER-accumulated peptide assemblies simultaneously stimulate ER stress and inhibit GRP78 refolding activity and thereby promoting endogenous protein aggregation. Combining the internalized peptide assemblies with the induced protein aggregates leads to the persistent stimulation of ER stress. The persistent ER stress induced by the peptide assemblies bestows their application in sensitizing cancer chemotherapy. Both in vitro and in vivo results confirm the enhanced cytotoxicity of drug toyocamycin against HeLa cells by peptide assemblies, thus efficiently inhibiting in vivo tumor growth. The strategy reported here discloses the fundamental keys for efficient promotion of ER stress, thus providing the guidance for development of ER-targeting-assisted cancer chemotherapy in the future., (© 2022 Wiley-VCH GmbH.)

Copper-based materials are known for converting CO 2 into deep reduction products via electrochemical reduction reaction (CO 2 RR). As the major multicarbon products (C 2+ ), ethanol (C 2 H 5 OH) and ethylene (C 2 H 4 ) are believed to share a common oxygenic intermediate according to theoretical studies, while the key factors that bifurcate C 2 H 5 OH and C 2 H 4 pathways on Cu-based catalysts are not fully understood. Here, a surface oxophilicity regulation strategy to enhance C 2 H 5 OH production in CO 2 RR is proposed, demonstrated by a Cu-Sn bimetallic system. Compared with bare Cu catalyst, the Cu-Sn bimetallic catalysts show improved C 2 H 5 OH but suppressed C 2 H 4 selectivity. The experimental results and theoretical calculations demonstrate that the surface oxophilicity of Cu-Sn catalysts plays an important role in steering the protonation of the key oxygenic intermediate and guides the reaction pathways to C 2 H 5 OH. This study provides new insights into the electrocatalyst design for enhanced production of oxygenic products from CO 2 RR by engineering the surface oxophilicity of copper-based catalysts., (© 2022 The Authors. Advanced Science published by Wiley-VCH GmbH.)

Toward the well-explored lithium-sulfur (Li-S) catalytic chemistry, the slow adsorption-migration-conversion kinetics of lithium polysulfides on catalytic materials and Li 2 S deposition-induced passivation of active sites limit the rapid and complete conversion of sulfur. Conceptively, molecular architectures can provide atom-precise models to understand the underlying active sites responsible for selective adsorption and conversion of LiPSs and Li 2 S 2 /Li 2 S species. Here, an octanuclear Zn(II) (Zn 8 ) cluster is presented, which features a metallacalix[8]arene with double cavities up and down the Zn 8 ring. The central Zn 8 ring and the specific double cavities with organic ligands of different electronegativity and bonding environments render active sites with variable steric hindrance and interaction toward the sulfur-borne species. An intramolecular tandem transformation mechanism is realized exclusively by Zn 8 cluster, which promotes the self-cleaning of active sites and continuous electrochemical reaction. Notably, the external azo groups and internal Zn/O sites of Zn 8 cluster in sequence stimulate the adsorption and conversion of long chain Li 2 S x (x ≥ 4) and short chain Li 2 S/Li 2 S 2 , contributing to remarkable rate performance and cycling stability. This work pioneers the application of metallacalix[n]arene clusters with atom-precise structure in Li-S batteries, and the proposed mechanism advances the molecule-level understanding of Li-S catalytic chemistry., (© 2022 Wiley-VCH GmbH.)

Biodegradable shape memory polymers are promising biomaterials for stents used in minimally invasive surgical procedures such as intestinal stents. Herein, a series of biodegradable shape memory polyurethanes (SMPUs) containing a novel phenylalanine-derived chain extender (PHP) are synthesized. Inspired by the fact that the function of biomacromolecules such as proteins is rich and varied because of the multiple combinations of the amino acid in highly evolved biosystems, this study finds that the sequence distribution of PHP in SMPU will also have a great influence on the phase structure and degradation behavior, especially the difference of surface morphology caused by degradation. Considering that the transition temperature (T trans ) of SMPU obtained is higher than physiological temperature, oxidized carbon black (OCB) with the ability of photothermal conversion is introduced into SMPU, which can not only endow SMPU with near-infrared response shape recovery characteristics, but also enhance phase separation degree and mechanical properties of them. SMPU/OCB composites show excellent shape memory effect and rapid photothermal response, and they can be degraded by chymotrypsin with an adjustable degradation rate. These SMPU/OCB composites show broad potential for application as intestinal stents., (© 2022 Wiley-VCH GmbH.)

Being one important class in dendrimer chemistry, internally functionalized dendrimers (IFDs) are still exiguous. Here, the first construction of IFDs involving fully substituted 1,2,3-triazole rings as interior functionality carriers is demonstrated. Through divergent or convergent synthetic protocols established on the efficient iridium-catalyzed annulation of internal 1-thioalkynes with organic azides, sequence-controlled heterolayered dendrimers with different branched structures are achieved in a convenient manner. 1 H NMR, mass spectrometry, and size exclusion chromatography characterizations well identify their architecture and high purity., (© 2022 Wiley-VCH GmbH.)

Silicon (Si) is regarded as the most promising anode material for high-energy lithium-ion batteries (LIBs) due to its high theoretical capacity, and low working potential. However, the large volume variation during the continuous lithiation/delithiation processes easily leads to structural damage and serious side reactions. To overcome the resultant rapid specific capacity decay, the nanocrystallization and compound strategies are proposed to construct hierarchically assembled structures with different morphologies and functions, which develop novel energy storage devices at nano/micro scale. The introduction of assembly strategies in the preparation process of silicon-based materials can integrate the advantages of both nanoscale and microstructures, which significantly enhance the comprehensive performance of the prepared silicon-based assemblies. Unfortunately, the summary and understanding of assembly are still lacking. In this review, the understanding of assembly is deepened in terms of driving forces, methods, influencing factors and advantages. The recent research progress of silicon-based assembled anodes and the mechanism of the functional advantages for assembled structures are reviewed from the aspects of spatial confinement, layered construction, fasciculate structure assembly, superparticles, and interconnected assembly strategies. Various feasible strategies for structural assembly and performance improvement are pointed out. Finally, the challenges and integrated improvement strategies for assembled silicon-based anodes are summarized., (© 2022 The Authors. Advanced Science published by Wiley-VCH GmbH.)

Ghrelin contributes to the communication between the brain and gastrointestinal (GI) tract. Both decreased ghrelin levels and functional GI disorders are early events in Parkinson's disease (PD) patients and animal models. However, the reason is not clear. Here it is found that choline acetyltransferase (ChAT)-positive neurons in the dorsal motor nucleus of the vagus nerve (DMV), are lost in PD transgenic mice. In response to the selective damaging of DMV neurons with mu p75-SAP, a rapid reduction both in plasma total and active ghrelin levels is observed. While by contrast, chemogenetic activation of DMV cholinergic neurons can increase the plasma ghrelin levels. Impairment of cholinergic neurons is accompanied by GI disorders, including decreased stool wet weight, stool dry weight, small intestine advancing rate, and gastric emptying rate, while exogenous ghrelin treatment can partially ameliorate GI dysfunction of A53T α-synuclein transgenic mice. Using pseudorabies virus retrograde trace method, the existence of a direct pathway from the stomach fundus to the DMV is shown. Taken together, the findings suggest that the reduction in plasma ghrelin levels in the early stages of PD may be the result of the lesion of cholinergic neurons in the DMV, thus linking neurodegeneration and GI dysfunction in PD., (© 2022 The Authors. Advanced Science published by Wiley-VCH GmbH.)

Coupling materials chemistry systems to biological processes is a promising way to rationally modulate lysosomal functions. A proton-driven dynamic assembly of a DNA nanoframework inside cells coupled with the lysosome-mediated endocytosis pathways/lysosomal maturation, gives the rational modulation of lysosomal functions, which we term "lysosome interference". Through lysosome-mediated endocytosis, the DNA nanoframework with acid-responsive semi-i-motif enters the lysosome and assembles into an aggregate in a process triggered by lysosomal acidity. The aggregate is suitable for long-term retention. The consumption of protons resulted in lysosomal acidity reduction and hydrolase activity attenuation, thus hindering the degradation of nucleic acid drugs in the lysosome and improving gene silencing effects. This study shows a new way to achieve lysosome interference by coupling the subcellular microenvironment with a precisely programmable assembly system., (© 2022 Wiley-VCH GmbH.)

The improvement of lithium-sulfur batteries is still impeded by notorious shuttling effect and sluggish kinetics on the S cathode, and rampant Li dendrite formation on the Li anode makes it worse. Herein, a type of single-atom dispersed Mo on nitrogen-doped graphene (Mo/NG) with a distinctive Mo-N 2 O 2 -C coordination structure first serving as a multifunctional material is designed by a structure-oriented strategy to solve Li and S electrochemistry. Mo/NG with superior intrinsic properties endowed by the unique coordination configuration adsorbs soluble polysulfides and promotes bidirectional conversion of LiPSs at the cathode side. Meanwhile, the suitable binding strength of Mo/NG with lithium ions endows it with an attractive lithiophilic feature. Specifically, Mo/NG is able to work as the adaptor to redistribute lithium ions on the interface of separator and homogenize the lithium ion flux. Due to the suitable binding ability with Li + , it does not interfere with the diffusion of lithium ions across and provides tunnels exclusive to lithium ions to generate fast and homogeneous flux. Ascribed to such unique multifunctionality, Li-S batteries assembled with Mo/NG exhibit excellent electrochemical performance including long cycling stability over 1000 cycles and high areal capacities under high sulfur mass loading., (© 2022 Wiley-VCH GmbH.)

The tumor suppressor p53 is the most frequently mutated gene in human cancer and more than half of cancers contain p53 mutations. The development of novel and effective therapeutic strategies for p53 mutant cancer therapy is a big challenge and highly desirable. Ubiquitin-specific protease 7 (USP7), also known as HAUSP, is a deubiquitinating enzyme and proposed to stabilize the oncogenic E3 ubiquitin ligase MDM2 that promotes the proteosomal degradation of p53. Herein, we report the design and characterization of U7D-1 as the first selective USP7-degrading Proteolysis Targeting Chimera (PROTAC). U7D-1 showed selective and effective USP7 degradation, and maintained potent cell growth inhibition in p53 mutant cancer cells, with USP7 inhibitor showing no activity. These data clearly demonstrated the practicality and importance of PROTAC as a preliminary chemical tool for investigating USP7 protein functions and a promising method for potential p53 mutant cancer therapy., (© 2022 Wiley-VCH GmbH.)

Sodium-ion batteries (SIBs) have emerged as an alternative technology because of their merits in abundance and cost. Realizing their real applications, however, remains a formidable challenge. One is that among the limitations of anode materials, the alloy-type candidates tolerate fast capacity fading during cycling. Here, a 3D framework superstructure assembled with carbon nanobelt arrays decorated with a metallic bismuth (Bi) nanospheres coated carbon layer by thermolysis of Bi-based metal-organic framework nanorods is synthesized as an anode material for SIBs. Due to the unique structural superiority, the anode design promotes excellent sodium-storage performance in terms of high capacity, excellent cycling stability, and ultrahigh rate capability up to 80 A g -1 with a capacity of 308.8 mAh g -1 . The unprecedented sodium-storage ability is not only attributed to the unique hybrid architecture, but also to the production of a homogeneous and thin solid electrolyte interface layer and the formation of uniform porous nanostructures during cycling in the ether-based electrolyte. Importantly, deeper understanding of the underlying cause of the performance improvement is illuminated, which is vital to provide the theoretical basis for application of SIBs., (© 2022 Wiley-VCH GmbH.)

Bone marrow stem cells (BMSCs) engineered cartilage (BEC) is prone to endochondral ossification in a submuscular environment due to the process of vascular infiltration, which limits its application in repairing tracheal cartilage defects. Bevacizumab, an antitumor drug with pronounced antiangiogenic activity, is successfully laden into a poly(L-lactide-co-caprolactone) system to prepare bevacizumab-laden nanofiber (BevNF) characterized by 5% and 10% bevacizumab concentrations. The in vitro results reveal that a sustained release of bevacizumab can be realized from BevNF, exhibiting inhibitive cytotoxicity toward human umbilical vein endothelial cells whereas non-cytotoxicity toward BMSCs-induced chondrocytes. A model is also established by encapsulating BEC within BevNF, aiming to realize an antiangiogenic niche under conditions of sustained and localized release of bevacizumab to inhibit the process of vascular invasion, resulting in the eventual stabilization of the cartilaginous phenotype and promotion of the process of cartilage maturation in the submuscular environment. These results also confirm that the chondrogenesis stability of BEC increases with an increase in the bevacizumab concentration, and 10% BevNF is sufficient to protect BEC from vascularization. This demonstrates that the use of BevNF can potentially help develop an effective strategy for regulating the submuscular stability of BEC to repair the defects formed in tracheal cartilage., (© 2022 Wiley-VCH GmbH.)

Exploring appropriate precursors has been proposed to be a promising strategy for the creation of artificial enzymes that are emerging as alternatives of natural enzymes. Herein, inspired by the catalytic activities of ribose nucleic acid, using ribonucleosides as precursors including adenosine, guanosine, cytidine, and uridine, respectively, four carbonic aggregates, namely, carbon dots (A-CDs, G-CDs, C-CDs, and U-CDs) to mimic artificial enzymes are synthesized. All the CDs show a planar graphene-like structure and thus can intercalatively bind with DNA double helix. Different from the other three CDs, the uridine-derived U-CDs exhibit unique catalytic property, which can mediate the topological transformation of DNA from supercoiled to nicked open-circular conformation. U-CDs can catalyze oxidation of O 2 to generate singlet oxygen 1 O 2 via a Haber-Weiss reaction, and consequently mediate oxidative cleavage of phosphate backbone in DNA and release the torsional energy stored in supercoiled DNA. Explorations reveal that the unique highly active oxygenated species, namely, quinone groups that are on the edge of U-CDs, play a key role in the catalytic production of 1 O 2 . This work represents a new insight that using natural biomolecules in living systems as precursors can create new species beyond life., (© 2022 Wiley-VCH GmbH.)

CRISPR/Cas9 is emerging as a platform for gene therapeutics, and the treatment efficiency is expected to be enhanced by combination with other therapeutic agents. Herein, we report a proton-activatable DNA-based nanosystem that enables co-delivery of Cas9/sgRNA and DNAzyme for the combined gene therapy of cancer. Ultra-long ssDNA chains, which contained the recognition sequences of sgRNA in Cas9/sgRNA, DNAzyme sequence and HhaI enzyme cleavage site, were synthesized as the scaffold of the nanosystem. The DNAzyme cofactor Mn 2+ was used to compress DNA chains to form nanoparticles and acid-degradable polymer-coated HhaI enzymes were assembled on the surface of nanoparticles. In response to protons in lysosome, the polymer coating was decomposed and HhaI enzyme was consequently exposed to recognize and cut off the cleavage sites, thus triggering the release of Cas9/sgRNA and DNAzyme to regulate gene expressions to achieve a high therapeutic efficacy of breast cancer., (© 2022 Wiley-VCH GmbH.)

The fabrication of biomimetic tracheas with a architecture of cartilaginous rings alternately interspersed between vascularized fibrous tissue (CRVFT) has the potential to perfectly recapitulate the normal tracheal structure and function. Herein, the development of a customized chondroitin-sulfate-incorporating type-II atelocollagen (COL II/CS) scaffold with excellent chondrogenic capacity and a type-I atelocollagen (COL I) scaffold to facilitate the formation of vascularized fibrous tissue is described. An efficient modular ring strategy is then adopted to develop a CRVFT-based biomimetic trachea. The in vitro engineering of cartilaginous rings is achieved via the recellularization of ring-shaped COL II/CS scaffolds using bone marrow stem cells as a mimetic for native cartilaginous ring tissue. A CRVFT-based trachea with biomimetic mechanical properties, composed of bionic biochemical components, is additionally successfully generated in vivo via the alternating stacking of cartilaginous rings and ring-shaped COL I scaffolds on a silicone pipe. The resultant biomimetic trachea with pedicled muscular flaps is used for extensive tracheal reconstruction and exhibits satisfactory therapeutic outcomes with structural and functional properties similar to those of native trachea. This is the first study to utilize stem cells for long-segmental tracheal cartilaginous regeneration and this represents a promising method for extensive tracheal reconstruction., (© 2021 Wiley-VCH GmbH.)

Cyclic organic amines are emerging as excellent building blocks to assemble organic-inorganic hybrid phase transition materials due to their flexible cyclic structure. Here, we have assembled a 1D organic-inorganic hybrid dielectric material C 5 H 6 NOPbBr 3 (1) by alloying the cyclic organic amine 3-hydroxypyridine. 1 displays a remarkable switchable dielectric response induced by an order-disorder transformation of the organic moiety, this transformation behaviour is confirmed by DSC and Hirshfeld surface measurements. More interestingly, 1 has a narrowband emission (FWHM=4.64 nm) at 590 nm; FWHM is a major quality figure for narrowband photodetectors. In addition, 1 exhibits semiconducting properties with an indirect bandgap of 2.78 eV by the analysis of the UV-Vis absorption results., (© 2021 Wiley-VCH GmbH.)

Bistable switches (electrical switching between "ON" and "OFF" bistable states) have gradually developed into an ideal category of highly intelligent materials, due to their significant applications in optical technology, signal processors, data storage and other switchable media applications in the field of electrical devices. Here, we successfully designed and synthesized [(FC 6 H 4 C 2 H 4 NH 3 ) 2 MCl 4 ] n (FC 6 H 4 C 2 H 4 NH 3 + )=deprotonated 4-fluoro- phenethylamine; M=Cd (1), Mn (2)), which realized the coupling of thermo-dielectric switching characteristics, semi-conductor characteristics and photo-luminescent properties. DSC (differential scanning calorimetry) and dielectric measurements show that 1 is a sensitive dielectric bistable switch between the high dielectric (ON) and low dielectric (OFF) states. The temperature-variable single crystal structure shows that the both 1 and 2 undergo a high-temperature reversible phase transition around 383 K/380 K, which is caused by the order-disordered transformation of organic cations and the slight distortion of the inorganic framework. In particular, 1 shows outstanding switchable dielectric behavior and semiconducting properties. Further, 1 and 2 emit strong green and yellow luminescence at 527 and 595 nm, respectively., (© 2021 Wiley-VCH GmbH.)

The multifunctional two-dimensional (2D) organic-inorganic hybrid perovskites have potential applications in many fields, such as, semiconductor, energy storage and fluorescent device etc. Here, a 2D Ruddlesden-Popper (RP) perovskite (IPA) 2 (FA)Pb 2 I 7 (1, IPA + =C 3 H 9 NI + , FA + =CN 2 H 5 + ) is determined for its photophysical properties. Strikingly, 1 reveals a solid reversible phase transition with T c of 382 K accompanied by giant entropy change of 40 J mol -1  K -1 . Further optical investigations indicate that 1 reveals a narrow direct bandgap (2.024 eV) attributed to the slight bending of I-Pb-I edge and inorganic [Pb 2 I 7 ] n layer and a superior photoluminescence (PL) emission with super long lifetime of 0.1607 ms. It is believed that this work will pave an avenue to further design multifunctional semiconductors that combines energy storage and photoelectric materials., (© 2021 Wiley-VCH GmbH.)

Lithium-sulfur battery (LSB) is regarded as a preferential option for next-generation energy-storage system, but the lithium polysulfides (LiPSs) shuttling effect and the uncontrollable growth of dendritic Li in the anode impede its commercial viability. To address both of the issues simultaneously, a well-designed hybrid of MgO ultrafine nanocrystals dispersed on graphene-supported carbon nanosheets (MCG) is developed via a facile self-template strategy as dual-functional host for both sulfur and lithium. Relying on the coordination of strong LiPS-capturing capability, the shuttling effect is inhibited. Furthermore, the lithiophilic configuration with high specific surface area induce homogenous Li deposition, thus preventing the formation of disordered lithium dendrite. Integrating all these advantages, a full cell based on S@MCG cathode and Li@MCG@Cu anode exhibits a stable capacity at 0.5 C for 150 cycles with a low capacity fading rate. Furthermore, the full cell achieves a high capacity retention of 85.5% at a high S areal loading of 3.82 mg cm -2 under the condition of a low electrolyte/sulfur ratio (E/S) of 6.5 µL mg -1 and negative/positive capacity ratio (N/P) of 3. This strategy satisfying both cathode and anode host provides a viable approach to realize high-energy-density and dendrite-free LSBs., (© 2021 Wiley-VCH GmbH.)

Herein, we report the crucial importance of C-defective sites on the CO adsorption over ϵ-Fe 2 C and η-Fe 2 C Fischer-Tropsch catalysts via systematic DFT calculations. The simulated XRD and Wulff construction show the significant differences in their equilibrium shapes and most exposed surfaces. It is observed that the ϵ-Fe 2 C exposes a high proportion (89 %) of facets (1 2 ‾ 1) with similar structure to that of η-Fe 2 C (011) which has been proved to be the active surface of CO activation., (© 2020 Wiley-VCH GmbH.)

One of the major pursuits of biomedical science is to develop advanced strategies for theranostics, which is expected to be an effective approach for achieving the transition from conventional medicine to precision medicine. Supramolecular assembly can serve as a powerful tool in the development of nanotheranostics with accurate imaging of tumors and real-time monitoring of the therapeutic process upon the incorporation of aggregation-induced emission (AIE) ability. AIE luminogens (AIEgens) will not only enable fluorescence imaging but will also aid in improving the efficacy of therapies. Furthermore, the fluorescent signals and therapeutic performance of these nanomaterials can be manipulated precisely owing to the reversible and stimuli-responsive characteristics of the supramolecular systems. Inspired by rapid advances in this field, recent research conducted on nanotheranostics with the AIE effect based on supramolecular assembly is summarized. Here, three representative strategies for supramolecular nanomaterials are presented as follows: a) supramolecular self-assembly of AIEgens, b) the loading of AIEgens within nanocarriers with supramolecular assembly, and c) supramolecular macrocycle-guided assembly via host-guest interactions. Meanwhile, the diverse applications of such nanomaterials in diagnostics and therapeutics have also been discussed in detail. Finally, the challenges of this field are listed in this review., (© 2020 Wiley-VCH GmbH.)

Using reverse thinking of the aggregation-induced emission (AIE) principle, we demonstrate an ingenious and universal protocol for amplifying molecular motions to boost photothermal efficiency of fibers. Core-shell nanofibers having the olive oil solution of AIE-active molecules as the core surrounded by PVDF-HFP shell were constructed by coaxial electrospinning. The molecularly dissolved state of AIE-active molecules allows them to freely rotate and/or vibrate in nanofibers upon photoexcitation and thus significantly elevates the proportion of non-radiative energy dissipation, affording impressive heat-generating efficiency. Photothermal evaluation shows that the core-shell nanofibers with excellent durability can reach up to 22.36 % of photothermal conversion efficiency, which is 26-fold as the non-core-shell counterpart. Such a core-shell fiber can be used for photothermal textiles and solar steam generation induced by natural sunlight with green and carbon-zero emission., (© 2020 Wiley-VCH GmbH.)

Chronic HCV infection can lead to cirrhosis and is associated with increased mortality. Interleukin (IL)-10-producing B cells (B10 cells) are regulatory cells that suppress cellular immune responses. Here, we aimed to determine whether HCV induces B10 cells and assess the roles of the B10 cells during HCV infection. HCV-induced B10 cells were enriched in CD19 hi and CD1d hi CD5 + cell populations. HCV predominantly triggered the TLR2-MyD88-NF-κB and AP-1 signaling pathways to drive IL-10 production by B cells. In a humanized murine model of persistent HCV infection, to neutralize IL-10 produced by B10 cells, mice were treated with pcCD19scFv-IL-10R, which contains the genes coding the anti-CD19 single-chain variable fragment (CD19scFv) and the extracellular domain of IL-10 receptor alpha chain (sIL-10Ra). This treatment resulted in significant reduction of B10 cells in spleen and liver, increase of cytotoxic CD8 + T-cell responses against HCV, and low viral loads in infected humanized mice. Our results indicate that targeting B10 cells via neutralization of IL-10 may offer a novel strategy to enhance anti-HCV immunotherapy., (© 2020 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Organic luminescent materials with high quantum yields and/or white-light-emitting properties in particular play a crucial role in labeling and optoelectronic devices. In this work we have synthesized a new 2,3,6,7-tetramethoxy-9,10-di-p-tolylanthracene-bridged pillar[5]arene dimer with persistent mazarine blue fluorescent emission and much higher quantum yields in both solution and the solid state in comparison with its corresponding emissive linker without pillarene units, which exhibits typical aggregation-caused quenching. According to the fluorescence data and single-crystal analyses, their contrasting fluorescent performances can be rationally ascribed to their different stacking structures and intermolecular interactions. Three fluorescent guests containing different chromophores and/or terminal binding sites have also been synthesized to interact with the pillar[5]arene dimer to construct supramolecular ensembles with highly controllable luminescence, taking advantage of the stimuli-responsive properties of the supramolecular host-guest interactions. Intriguingly, multicolor fluorescence, including white-light emission (0.31, 0.35), which is in high demand, has been achieved by tuning the molar ratio of the host and guest and/or by changing the solvent system. This strategy holds great potential for the design and development of fluorescent materials with high quantum yields, controllable emission wavelength, and good stimuli-responsiveness., (© 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Linear copolymer hosts bearing a number of pillar[5]arene dangling side chains are synthesized for the facile construction of highly emissive supramolecular polymer networks (SPNs) upon noncovalently cross-linking with a series of tetraphenyethylene (TPE)-based tetratopic guests terminated with different functional groups through supramolecular host-guest interactions. An extremely high fluorescence quantum yield (98.22%) of the SPNs materials is obtained in tetrahydrofuran (THF) by fine-tuning the parameters, and meanwhile supramolecular light-harvesting systems based on spherical supramolecular nanoparticles are constructed by interweaving 9,10-distyrylanthracene (DSA) and TPE-based guest molecules of aggregation-induced emission (AIE) with the copolymer hosts in the mixed solvent of THF/H 2 O. The present study not only illustrates the restriction of the intramolecular rotations (RIR)-ruled emission enhancement mechanism regulated particularly by macrocyclic arene-containing copolymer hosts, but also suggests a new self-assembly approach to construct high-performance light-harvesting materials., (© 2019 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

The increasing occurrence of bacterial infection at the wound sites is a serious global problem, demanding the rapid development of new antibacterial materials for wound dressing to avoid the abuse of antibiotics and thereby antibiotic resistance. In this work, the authors first report on antibacterial N-halamine polymer nanomaterials based on a strategic copolymerization of 3-allyl-5,5-dimethylhydantoin (ADMH) and methyl methacrylate (MMA), which exhibits in vitro and in vivo antimicrobial efficacy against pathogenic bacteria including Staphylococcus aureus and Escherichia coli. Particularly, when a biological evaluation is run for wound therapy, the N-halamine polymer nanomaterials exhibit a powerful antibacterial efficiency and wound healing ability after a series of histological examination of mouse wound. After the evaluation of biological and chemical surroundings, the proposed four-stage mechanism suggests that, with unique antibacterial NCl bonds, the N-halamine polymer nanomaterials can disrupt the bacterial membrane, as a result causing intracellular content leaked out and thereby cell death. Based on the synergistic action of antibacterial and wound therapy, the N-halamine polymer nanomaterials are expected to be promising as wound dressing materials in medical healing and biomaterials., (© 2019 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

A novel mechanistic strategy for probing the energy migration through constructing the interfacial energy transfer (IET) in a core-shell-shell nanostructure is reported. In this design, the trilayer nanostructure is composed of a sensitizing core, a migratory interlayer, and a detective shell layer that interact with each other only by IET and the latter two shell layers are nonresponsive to the incident irradiation. This model is well applied in investigating the energy migration over the Tb, Gd, and Yb sublattices, and the results show that the Gd sublattice holds the best energy migratory performance. Moreover, the finding of energy migration over the Yb sublattice enables the 808 nm excited long-lived upconversion of Tb 3+ and Eu 3+ , which exhibits unique time-gating performance for information security. The results provide a facile and powerful nanosized model for an in-depth understanding of the fundamentals involving lanthanide interactions, which will further help excite new chances for the frontier applications of lanthanide-based luminescent materials., (© 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

The singlet oxygen ( 1 O 2 ) generation ability of a photosensitizer (PS) is pivotal for photodynamic therapy (PDT). Transition metal complexes are effective PSs, owing to their high 1 O 2 generation ability. However, non-negligible cellular toxicity, poor biocompatibility, and easy aggregation in water limit their biomedical applications. In this work, a series of red-emitting aggregation-induced emission (AIE) Ir(III) complexes containing different numbers of Ir centers (mono-, di-, and trinuclear) and the corresponding nanoparticles (NPs) AIE-NPs, are designed and synthesized. The increase of 1 O 2 generation ability is in line with the increasing number of Ir centers. Compared with the pure Ir(III) complexes, the corresponding NPs offer multiple advantages: (i) brighter emission; (ii) higher phosphorescence quantum yields; (iii) longer excited lifetime; (iv) higher 1 O 2 generation ability; (v) better biocompatibility; and (vi) superior cellular uptake. Both in vitro and in vivo experiments corroborate that AIE-NPs with three iridium centers possess potent cytotoxicity toward cancer cells and effective inhibition of tumor growth. To the best of knowledge, this work is the first example of NPs of multinuclear AIE Ir(III) complexes as PSs for enhanced PDT. This study offers a new method to improve the efficiency of PSs for clinical cancer treatments., Competing Interests: The authors declare no conflict of interest.

Four supramolecular assemblies are fabricated from two pillararene tetramers with aggregation-induced emission properties (SH and LH) and two different lengths of neutral guests with three binding sites (arms) for pillararene cavities (SG and LG) through host-guest interactions, and their fluorescent behaviors in organic solvent are investigated. SG⊂SH exhibits the largest fluorescent enhancement in chloroform due to supramolecular assembly-induced emission enhancement, while only LG⊂LH turns into supramolecular gel with stimuli responsiveness owing to their most flexible arms., (© 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

In this study, poly(glycidyl methacrylate-ethyleneglycol dimethacrylate) monolith functionalized with cobalt phthalocyanine tetracarboxylic acid is prepared. The polymer monolithic material is used for glycopeptides enrichment coupled with MALDI-TOF MS. By taking advantage of cobalt phthalocyanine including hydrogen bonds between isoindole subunits of phthalocyanine and glycans, coordination interaction between cobalt and glycopeptides, the monolithic material is successfully applied to the enrichment of glycopeptides efficiently and selectively. With IgG and horse radish peroxidase as the model glycoproteins, 28 and 17 glycopeptides could be identified respectively after enrichment with the monolith, only four and three glycopeptides could be obtained for direct analysis. The monolith is also employed to the digests mixture of BSA and IgG (50:1, m/m), indicating the high enrichment selectivity of glycopeptides even in the presence of a large interference ratio. The detection limit is determined to be 6.7 fmol, implying that the present method had great potential for trace sample analysis. In addition, the monolith was successfully applied to the enrichment of N-linked glycans in human serum samples, demonstrating its great potential for the analysis of glycoproteins., (© 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)