Toward Ultrahigh Rate and Cycling Performance of Cathode Materials of Sodium Ion Battery by Introducing a Bicontinuous Porous Structure.

The emerging sodium-ion batteries (SIBs) are one of the most promising candidates expected to complement lithium-ion batteries and diversify the battery market. However, the exploitation of cathode materials with high-rate performance and long-cycle stability for SIBs has remained one of the major challenges. To this end, an efficient approach to enhance rate and cycling performance by introducing an ordered bicontinuous porous structure into cathode materials of SIBs is demonstrated. Prussian blue analogues (PBAs) are selected because they are recognized as a type of most promising SIB cathode materials. Thanks to the presence of 3D continuous channels enabling fast Na+ ions diffusion as well as the intrinsic mechanical stability of bicontinuous architecture, the resultant PBAs exhibit excellent rate capability (80 mAh g-1 at 2.5 A g-1) and ultralong cycling life (>3000 circulations at 0.5 A g-1), reaching the top performance of the reported PBA-based cathode materials. This study opens a new avenue for boosting sluggish ion diffusion kinetics in electrodes of rechargeable batteries and also provides a new paradigm for solving the dilemma that electrodes' failure due to high-stress concentration upon ion storage.

pH-Modulated 1D Hierarchical Self-Assembly of a Brush-Like Poly-Para-Phenylene Homopolymer.

The controllable self-assembly of conjugated homopolymers, especially homopolymers without other segments (a prerequisite for phase separation), which can afford chances to achieve tunable optical/electronic properties, remains a great challenge due to their poor solubility and has remained rarely documented. Herein, a conjugated homopolymer (DPPP-COOH) is synthesized, which has a unique brush-like structure with a conjugated dendritic poly-para-phenylene (DPPP) backbone and alkyl-carboxyl side chains at both edges of the backbone. The introduction of carboxyl makes the brush-like homopolymer exhibit pH-modulated 1D hierarchical self-assembly behavior in dilute solution, and allows for flexible morphological regulation of the assemblies, forming some uncommon superstructures including ultralong nanowires (at pH 7), superhelices (at pH 10) and "single-wall" nanotubes (at pH 13), respectively. Furthermore, the good aqueous dispersibility and 1D feature endow the superstructures formed in a high-concentration neutral solution with high broad-spectrum antibacterial performance superior to that of many conventional 1D materials.

Electronic Structure of Isolated Graphene Nanoribbons in Solution Revealed by Two-Dimensional Electronic Spectroscopy.

Structurally well-defined graphene nanoribbons (GNRs) are nanostructures with unique optoelectronic properties. In the liquid phase, strong aggregation typically hampers the assessment of their intrinsic properties. Recently we reported a novel type of GNRs, decorated with aliphatic side chains, yielding dispersions consisting mostly of isolated GNRs. Here we employ two-dimensional electronic spectroscopy to unravel the optical properties of isolated GNRs and disentangle the transitions underlying their broad and rather featureless absorption band. We observe that vibronic coupling, typically neglected in modeling, plays a dominant role in the optical properties of GNRs. Moreover, a strong environmental effect is revealed by a large inhomogeneous broadening of the electronic transitions. Finally, we also show that the photoexcited bright state decays, on the 150 fs time scale, to a dark state which is in thermal equilibrium with the bright state, that remains responsible for the emission on nanosecond time scales.

Hyperbranched polyphthalocyanine micelles with dual PTT/PDT functions for bacteria eradication under an NIR window.

A Zinc phthalocyanine-based (ZnPc-PA) polymeric micelle around 70 nm and with dual-modal PTT/PDT functions for non-antibiotic bacteria eradication was developed. It showed an excellent bacterial killing efficiency of 95.2% and 96.7% in vitro against Methicillin-resistant Staphylococcus aureus (MRSA) and its biofilm, respectively. Furthermore, the in vivo experiments proved its great potential for implant-associated infection (IAI).

Plasma TNF-α and phosphorylated α-syn are associated with fatigue in patients with Parkinson's disease.

BACKGROUD: Fatigue is one of the most common non-motor symptoms among patients with Parkinson's disease (PD).However, the pathogenesis keeps largely unknown. Moreover, it is lack of objective biomarker. OBJECTIVE: To investigate the relationship between plasma inflammatory cytokines and α-syn levels and fatigue in patients with PD. METHODS: A total of 63 PD patients were enrolled, including 35 patients with fatigue and 28 patients without fatigue. We compared the difference between plasma cytokines and alpha-synuclein (α-syn) in the two groups. Meanwhile, we analyzed the relationship between plasma cytokines and p-α-syn levels and fatigue. RESULTS: PD patients with fatigue had older age, longer disease duration, more severe motor scores. There were significant differences in the plasma levels of IL-1ß, IL-18, TNF-α, and phosphorylated α-syn (p-α-syn) between the two groups. The plasm inflammatory cytokine levels (IL-1ß, IL-18 and TNF-α) were positively associated with FSS scores. Moreover, the plasma p-α-syn level was significantly positively correlated with FSS scores. Furthermore, the higher PDQ-39 scores and higher plasma levels of TNF-α and p-α-syn were strongly associated with fatigue in PD. The ROC curve analysis showed the AUC of TNF-α for fatigue in PD was 0.663 with a sensitivity of 65.71% and specificity of 67.86%, while the AUC of p-α-syn was 0.786 with a sensitivity of 74.29% and specificity of 64.29%. The combination of TNF-α and p-α-syn improves the AUC to 0.803 with a sensitivity of 88.57% and specificity of 64.29%. CONCLUSION: The high plasma levels of TNF-α and p-α-syn were strongly associated with fatigue in PD.

Nitrogen-Doped Carbon Cubosomes as an Efficient Electrocatalyst with High Accessibility of Internal Active Sites.

Porous carbon particles (PCPs) present considerable potential for applications across a wide range of fields, particularly within the realms of energy and catalysis. The control of their overall morphologies and pore structures has remained a big challenge. Here, using metal-organic frameworks (MOFs) as the precursor and polymer cubosomes (PCs) as the template, nitrogen-doped carbon cubosomes (SP-NCs) with a single primitive bicontinuous architecture are prepared. SP-NCs inherit the high porosity of MOFs, generating a high specific surface area of 825 m2 g-1 and uniformly distributed active sites with a 5.9 at % nitrogen content. Thanks to the presence of three-dimensional continuous mesochannels that enable much higher accessibility of internal active sites over those of their porous counterparts' lack of continuous channels, SP-NCs exhibit superior electrocatalytic performance for oxygen reduction reaction with a half-wave potential of 0.87 V, situating them in the leading level of the reported carbon electrocatalysts. Serving as an air cathode catalyst of the Zn-air battery, SP-NCs exhibit excellent performance, outperforming the commercial Pt/C catalysts.

Soil bacterium manipulates antifungal weapons by sensing intracellular type IVA secretion system effectors of a competitor.

Soil beneficial bacteria can effectively inhibit bacterial pathogens by assembling contact-dependent killing weapons, such as the type IVA secretion system (T4ASS). It's not clear whether these antibacterial weapons are involved in biotrophic microbial interactions in soil. Here we showed that an antifungal antibiotic 2,4-DAPG production of the soil bacterium, Pseudomonas protegens can be triggered by another soil bacterium, Lysobacter enzymogenes, via T4ASS by co-culturing on agar plates to mimic cell-to-cell contact. We demonstrated that the induced 2,4-DAPG production of P. protegens is achieved by intracellular detection of the T4ASS effector protein Le1519 translocated from L. enzymogenes. We defined Le1519 as LtaE (Lysobacter T4E triggering antifungal effects), which specifically stimulates the expression of 2,4-DAPG biosynthesis genes in P. protegens, thereby protecting soybean seedlings from infection by the fungus Rhizoctonia solani. We further found that LtaE directly bound to PhlF, a pathway-specific transcriptional repressor of the 2,4-DAPG biosynthesis, then activated the 2,4-DAPG production. Our results highlight a novel pattern of microbial interspecies and interkingdom interactions, providing a unique case for expanding the diversity of soil microbial interactions.

Hybrid Polymer Vesicles: Controllable Preparation and Potential Applications.

Hybrid polymer vesicles contain functional nanoparticles (NPs) in their walls, interfaces, coronae, or cavities. NPs render the hybrid vesicles with specific physical properties, while polymers endow them with structural stability and may significantly reduce the high toxicity of NPs. Therefore, hybrid vesicles integrate fascinating multifunctions from both NPs and polymeric vesicles, which have gained tremendous attention because of their diverse promising applications. Various types of delicate hybrid polymeric vesicles with size control and tunable localization of NPs in different parts of vesicles have been constructed via in situ and ex situ strategies, respectively. Their potential applications have been widely explored, as well. This review presents the progress of block copolymer (BCP) vesicle systems containing different types of NPs including metal NPs, magnetic NPs, and semiconducting quantum dots (QDs), etc. The strategies for controlling the location of NPs within hybrid vesicles are discussed. Typical potential applications of the elegant hybrid vesicles are also highlighted.

Bottom-up Solution Synthesis of Graphene Nanoribbons with Precisely Engineered Nanopores.

The incorporation of nanopores into graphene nanostructures has been demonstrated as an efficient tool in tuning their band gaps and electronic structures. However, precisely embedding the uniform nanopores into graphene nanoribbons (GNRs) at the atomic level remains underdeveloped especially for in-solution synthesis due to the lack of efficient synthetic strategies. Herein we report the first case of solution-synthesized porous GNR (pGNR) with a fully conjugated backbone via the efficient Scholl reaction of tailor-made polyphenylene precursor (P1) bearing pre-installed hexagonal nanopores. The resultant pGNR features periodic subnanometer pores with a uniform diameter of 0.6 nm and an adjacent-pores-distance of 1.7 nm. To solidify our design strategy, two porous model compounds (1 a, 1 b) containing the same pore size as the shortcuts of pGNR, are successfully synthesized. The chemical structure and photophysical properties of pGNR are investigated by various spectroscopic analyses. Notably, the embedded periodic nanopores largely reduce the π-conjugation degree and alleviate the inter-ribbon π-π interactions, compared to the nonporous GNRs with similar widths, affording pGNR with a notably enlarged band gap and enhanced liquid-phase processability.

A general synthetic method towards conjugated microporous polymers with ordered bicontinuous mesostructures.

This work demonstrates a universal approach, based on the self-assembly of block copolymers, for the synthesis of novel conjugated microporous polymers (CMPs) with bicontinuous mesostructures. Three hexaazatriphenylene (Aza)-fused CMPs (Aza-CMPs) with double diamond structures were synthesized. The study broadens the spectrum of bicontinuous porous materials and opens a new route for synthesizing CMPs with new topologies.

Targeted photothermal release of antibiotics by a graphene nanoribbon-based supramolecular glycomaterial.

Here, we report the simple construction of a supramolecular glycomaterial for the targeted delivery of antibiotics to P. aeruginosa in a photothermally-controlled manner. A galactose-pyrene conjugate (Gal-pyr) was developed to self-assemble with graphene nanoribbon-based nanowires via π-π stacking to produce a supramolecular glycomaterial, which exhibits a 1250-fold enhanced binding avidity toward a galactose-selective lectin when compared to Gal-pyr. The as-prepared glycomaterial when loaded with an antibiotic that acts as an inhibitor of the bacterial folic acid biosynthetic pathway eradicated P. aeruginosa-derived biofilms under near-infrared light irradiation due to the strong photothermal effect of the nanowires accelerating antibiotic release.

Block Copolymer Self-Assembly Directed Synthesis of Porous Materials with Ordered Bicontinuous Structures and Their Potential Applications.

Porous materials with their ordered bicontinuous structures have attracted great interest owing to ordered periodic structures as well as 3D interconnected network and pore channels. Bicontinuous structures may favor efficient mass diffusion to the interior of materials, thus increasing the utilization ratio of active sites. In addition, ordered bicontinuous structures confer materials with exceptional optical and magnetic properties, including tunable photonic bandgap, negative refraction, and multiple equivalent magnetization configurations. The attractive structural advantages and physical properties have inspired people to develop strategies for preparing bicontinuous-structured porous materials. Among a few synthetic approaches, the self-assembly of block copolymers represents a versatile strategy to prepare various bicontinuous-structured functional materials with pore sizes and lattice parameters ranging from 1 to 500 nm. This article overviews progress in this appealing area, with an emphasis on the synthetic strategies, the structural control (including topologies, pore sizes, and unit cell parameters), and their potential applications in energy storage and conversion, metamaterials, photonic crystals, cargo delivery and release, nanoreactors, and biomolecule selection.

Self-Assembly of Peapod-like Micrometer Tubes from a Planet-Satellite-type Supramolecular Megamer.

This study presents interesting self-assembly of peapod-like micrometer tubes from a planet-satellite-type supramolecular megamer, which was constructed through the specific host-guest molecular recognition between azobenzene (AZO)-functionalized hyperbranched poly(ethyl-3-oxetanemethanol)-star-poly(ethylene oxide) (HSP-AZO) and ß-cyclodextrin(CD)-based hydrophilic hyperbranched polyglycerol (CD-g-HPG). A peapod-like structure with micrometer-sized tube as the pod and vesicles encapsulated inside as the peas was formed through sequential vesicle entosis, linear association, and fusion processes. Dissipative particle dynamics (DPD) simulations support the structural possibility of the supramolecular peapod formation and its mechanism. UV light irradiation could lead to the disassembly of the peapod-like structure. This study expands the family of supramolecular polymers and opens a new avenue to develop bioinspired complex hierarchical nanoarchitectures at the microscopic level.

One-Dimensional Helical Nanostructures from the Hierarchical Self-Assembly of an Achiral "Rod-Coil" Alternating Copolymer.

The self-assembly of alternating copolymers (ACPs) has attracted considerable interest due to their unique alternating nature. However, compared with block copolymers, their self-assembly behavior remains much less explored and their reported self-assembled structures are limited. Here, the formation of supramolecular helical structures by the self-assembly of an achiral rod-coil alternating copolymer named as poly(quarter(3-hexylthiophene)-alt-poly(ethylene glycol)) (P(Q3HT-alt-PEG)), is reported. The copolymer exhibits an interesting hierarchical self-assembly process, driven by the π-π stacking of the Q3HT segments and the solvophobic interaction of the alkyl chains in tetrahydrofuran (THF)-isopropanol mixed solvents. The copolymer first self-assembled into thin nanobelts with a uniform size, then grows to helical nanoribbons and eventually twisted into helical nanowires with an average diameter of 25 ± 9 nm and a mean pitch of 80 ± 10 nm. Dissipative particle dynamics (DPD) simulation supports the formation course of the helical nanowires. Furthermore, the addition of (S)-ethyl lactate and (R)-ethyl lactate in the self-assembly of P(Q3HT-alt-PEG) results in the formation of left-handed and right-handed chiral nanowires, respectively, demonstrating the tunability of the chirality of the helical wires. This study expands the library of ordered self-assembled structures of ACPs, and also brings a new strategy and mechanism to construct helical supramolecular structures.

Block Copolymer Self-Assembly Guided Synthesis of Mesoporous Carbons with In-Plane Holey Pores for Efficient Oxygen Reduction Reaction.

In this paper, a simple approach, using interfacial self-assembly of block copolymers (BCPs) on self-sacrificial templates, for preparing mesoporous carbons with in-plane holey pores, including nitrogen atom-doped carbon nanosheets and nanoflowers (denoted as NHCSs and NHCFs), is reported. The approach employs sheet- or flower-like layered double hydroxide as the templates, P123 copolymer as the pore-directing agent, and m-phenylenediamine as the carbon source. The holey mesopores may shorten the mass transfer distance in the internal active sites of stacked nanosheets, while the 3D packing mode of nanosheets can reduce pore blockage caused by their tight stacking. Profiting from these structural advantages, acting as electrocatalysts for oxygen reduction reaction (ORR), both NHCSs and NHCFs show excellent catalytic performance better than that of carbon nanosheets without holey pores. Particularly, NHCFs exhibit a high half-wave-potential (0.82 V) and a limiting current density (5.4 mA cm-2 ), close to those of commercial Pt-C catalysts. This study provides valuable clues on building mesoporous materials with in-plane holey pores as well as on the effect of pore structure and stacking mode of 2D materials on their electrocatalytic ORR performance.

Near-Infrared Light-Triggered Bacterial Eradication Using a Nanowire Nanocomposite of Graphene Nanoribbons and Chitosan-Coated Silver Nanoparticles.

Bacterial infection is a major threat to human health. However, many antibacterial agents currently used are severely limited due to drug-resistance, and the development of side effects. Herein, we have developed a non-antibiotic nanocomposite consisting of chitosan (ChS) coated silver nanoparticles (AgNPs) and graphene nanoribbon (GNR)-based nanowires for light-triggered eradication of bacteria. The presence of AgNP/ChS significantly enhanced the interactions of the GNR nanowires with Pseudomonas aeruginosa, a clinically common Gram-negative bacterium. Which enables the highly effective photothermal eradication of bacteria by GNR upon near-infrared light irradiation. The nanocomposite was shown to be applicable for the light-triggered eradication of bacterial biofilms and the inhibition of bacterial growth on medical patches used for abdominal-wall hernia surgery.

Graphene nanoribbon-based supramolecular ensembles with dual-receptor targeting function for targeted photothermal tumor therapy.

Triple negative breast cancer (TNBC) is one of the most malignant subtypes of breast cancer. Here, we report the construction of graphene nanoribbon (GNR)-based supramolecular ensembles with dual-receptor (mannose and αvß3 integrin receptors) targeting function, denoted as GNR-Man/PRGD, for targeted photothermal treatment (PTT) of TNBC. The GNR-Man/PRGD ensembles were constructed through the solution-based self-assembly of mannose-grafted GNRs (GNR-Man) with a pyrene-tagged αvß3 integrin ligand (PRGD). Enhanced PTT efficacies were achieved both in vitro and in vivo compared to that of the non-targeting equivalents. Tumor-bearing live mice were administered (tail vein) with GNR-Man/PRGD and then each mice group was subjected to PTT. Remarkably, GNR-Man/PRGD induced complete ablation of the solid tumors, and no tumor regrowth was observed over a period of 15 days. This study demonstrates a new and promising platform for the development of photothermal nanomaterials for targeted tumor therapy.

Asymmetric Vesicles Self-Assembled by Amphiphilic Sequence-Controlled Polymers.

The asymmetric distribution of lipids on the inner and outer membranes of a cell plays a pivotal role in the physiological and immunological activities of life. It has inspired the elaboration of synthetic asymmetric vesicles for the discovery of advanced materials and functions. The asymmetric vesicles were generally prepared by amphiphilic block copolymers. We herein report on the formation of asymmetric vesicles self-assembled by amphiphilic sequence-controlled polymers with two hydrophilic segments SU and TEO. We also developed an efficient fluorescence titration method with europium(III) ions (Eu3+) to determine the uneven distribution of SU and TEO. SU units are preferentially located on the outer membrane and TEO on the inner membrane of the resulting vesicles, which is facilitated by the electrostatic repulsion of SU and the U-shaped folding of the hydrophobic backbone of the resulting polymers. This work shows that sequence-controlled polymers with alternating monomer sequence provide a powerful toolbox for the elaboration of important yet challenging self-assembled structures for emerging functions and properties.

Experimental Observation of Strong Exciton Effects in Graphene Nanoribbons.

Graphene nanoribbons (GNRs) with atomically precise width and edge structures are a promising class of nanomaterials for optoelectronics, thanks to their semiconducting nature and high mobility of charge carriers. Understanding the fundamental static optical properties and ultrafast dynamics of charge carrier generation in GNRs is essential for optoelectronic applications. Combining THz spectroscopy and theoretical calculations, we report a strong exciton effect with binding energy up to ∼700 meV in liquid-phase-dispersed GNRs with a width of 1.7 nm and an optical band gap of ∼1.6 eV, illustrating the intrinsically strong Coulomb interactions between photogenerated electrons and holes. By tracking the exciton dynamics, we reveal an ultrafast formation of excitons in GNRs with a long lifetime over 100 ps. Our results not only reveal fundamental aspects of excitons in GNRs (strong binding energy and ultrafast exciton formation etc.) but also highlight promising properties of GNRs for optoelectronic devices.

Tunable low-dimensional self-assembly of H-shaped bichromophoric perylenediimide Gemini in solution.

A material with diverse self-assembled morphologies is extremely important and highly desirable because such samples can provide tunable optical and electronic properties, which are critical in applications such as organic photovoltaics, microelectronics and bio-imaging. Moreover, the synthesis and controllable self-assembly of H-shaped bichromophoric perylenediimides (PDIs) are needed to advance these materials in organic photovoltaics, microelectronics and bio-imaging; however, this has remained a great challenge thus far. Here, we successfully synthesize a novel H-shaped bichromophoric PDI Gemini through the palladium-catalyzed coupling reaction. The as-prepared PDI Gemini exhibited unprecedented tunable self-assembly behavior in solution, yielding diverse low-dimensional superstructures, such as one-dimensional (1D) helices, two-dimensional (2D) rectangular nanocrystals, pyramid-shaped parallelograms, ultralarge micro-sheets, and uniform nanospheres, under different self-assembly conditions. Of particular interest, the 2D hierarchical superstructures along with their formation mechanisms represent the first finding in the self-assembly of PDI-based molecules. This study opens a new avenue for tunable self-assembly of conjugated molecules and affords opportunities for the fabrication of novel self-assembled optical and electronic materials based on PDI molecules.