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.

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.

Hierarchical Self-Assembly of Hyperbranched Polymer-Based Topological Supramolecular Amphiphiles.

Supramolecular polymers (SPs) are constructed through non-covalent interactions. The dynamic or reversible nature of SPs endows them unique physical and chemical properties, such as self-adaptive and stimuli-response abilities. The topological structures of SPs play an important role in determining the physicochemical properties and functionality. Hyperbranched polymers (HBPs) are highly branched 3D macromolecules with linear, dendritic, and terminal units, which makes them versatile candidates for the construction of SPs with fascinating architectures. The resultant HBP-based SPs perfectly integrated the dynamic/reversible nature of SPs and the 3D topological features and multifunctionality of HBP polymers. To date, various types of HBP-based SPs and their assemblies have been constructed, and their potential applications have been explored as well. This article overviews the current progress on self-assembly of HBP-based SPs. The strategies for construction of HBP-based SPs and their assemblies are discussed. Typical potential applications of the assemblies of HBP-based SPs are also introduced.

Association between neutrophil-to-lymphocyte ratio and motor subtypes in idiopathic Parkinson's disease: a prospective observational study.

BACKGROUND: Peripheral immunity and neuroinflammation interact with each other and they play important roles in the pathophysiology of idiopathic Parkinson's disease (IPD). There have been very few real-world reports on the relationship between peripheral immune inflammation and motor phenotypes of IPD. This study aimed to investigate the potential correlation between peripheral inflammatory indicators and motor subtypes in patients with IPD. METHODS: This observational, prospective case-control study examined patients with IPD and healthy controls (HC) matched for age and sex between September 2021 and July 2023 at the Affiliated Huaian No. 1 People's Hospital of Nanjing Medical University. The levels of peripheral inflammatory indicators were collected from each patient with IPD and HCs. Differences in the levels of peripheral inflammatory indicators among groups were compared. Binary logistic regression analysis was used to explore the inflammatory mechanism underlying the motor subtype of IPD. RESULTS: A total number of 94 patients with IPD were recruited at the Affiliated Huaian No. 1 People's Hospital of Nanjing Medical University between September 2021 and July 2023, including 49 males and 45 females, and 37 healthy volunteers matched for age and sex were also enrolled as the control group. Of the 94 patients with IPD, 42.6% performed as the TD motor subtype and 57.4% performed as the AR motor subtype. NLR and the plasma levels of IL-1ßand TNF-α in the IPD group were higher than those in the HC group (P < 0.05). The disease duration, Hoehn and Yahr (H-Y) stage, NLR, and the levels of IL-1ß in the AR group were higher than those in the TD group (P < 0.05). Additionally, IL-1ß plasma levels and NLR were positively correlated with disease duration, H-Y stage, movement disorder society-Unified Parkinson's Disease Rating Scale-III motor score, and AR subtype. The binary logistic regression model revealed that the plasma level of IL-1ß was mildly associated with the AR motor subtype and NLR was strongly associated with the AR motor subtype. The combination of NLR and IL-1ß showed better performance in identifying the AR motor subtype. CONCLUSION: NLR is strongly associated with the AR motor subtype in IPD, and peripheral immunity is probably involved in the pathogenesis of AR motor subtype in IPD.

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.

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.

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.

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.

A Supramolecular-Based Dual-Wavelength Phototherapeutic Agent with Broad-Spectrum Antimicrobial Activity Against Drug-Resistant Bacteria.

With the ever-increasing threat posed by the multi-drug resistance of bacteria, the development of non-antibiotic agents for the broad-spectrum eradication of clinically prevalent superbugs remains a global challenge. Here, we demonstrate the simple supramolecular self-assembly of structurally defined graphene nanoribbons (GNRs) with a cationic porphyrin (Pp4N) to afford unique one-dimensional wire-like GNR superstructures coated with Pp4N nanoparticles. This Pp4N/GNR nanocomposite displays excellent dual-modal properties with significant reactive-oxygen-species (ROS) production (in photodynamic therapy) and temperature elevation (in photothermal therapy) upon light irradiation at 660 and 808 nm, respectively. This combined approach proved synergistic, providing an impressive antimicrobial effect that led to the complete annihilation of a wide spectrum of Gram-positive, Gram-negative, and drug-resistant bacteria both in vitro and in vivo. The study also unveils the promise of GNRs as a new platform to develop dual-modal antimicrobial agents that are able to overcome antibiotic resistance.

Tunable Superstructures of Dendronized Graphene Nanoribbons in Liquid Phase.

In this Communication, we report the first synthesis of structurally well-defined graphene nanoribbons (GNRs) functionalized with dendritic polymers. The resultant GNRs possess grafting ratios of 0.59-0.68 for the dendrons of different generations. Remarkably, the precise 3D branched conformation of the grafted dendrons affords the GNRs unprecedented 1D supramolecular self-assembly behavior in tetrahydrofuran (THF), yielding nanowires, helices and nanofibers depending on the dimension of the dendrons. The GNR superstructures in THF exhibit near-infrared absorption with maxima between 650 and 700 nm, yielding an optical bandgap of 1.2-1.3 eV. Ultrafast photoconductivity analyses unveil that the helical structures exhibit the longest free carrier (3.5 ps) and exciton lifetime (several hundred ps) among the three superstructure systems. This study opens pathways for tunable construction of ordered GNR superstructures with promising optoelectronic applications.

Overexpression of OsPIN2 Regulates Root Growth and Formation in Response to Phosphate Deficiency in Rice.

The response of root architecture to phosphate (P) deficiency is critical in plant growth and development. Auxin is a key regulator of plant root growth in response to P deficiency, but the underlying mechanisms are unclear. In this study, phenotypic and genetic analyses were undertaken to explore the role of OsPIN2, an auxin efflux transporter, in regulating the growth and development of rice roots under normal nutrition condition (control) and low-phosphate condition (LP). Higher expression of OsPIN2 was observed in rice plants under LP compared to the control. Meanwhile, the auxin levels of roots were increased under LP relative to control condition in wild-type (WT) plants. Compared to WT plants, two overexpression (OE) lines had higher auxin levels in the roots under control and LP. LP led to increased seminal roots (SRs) length and the root hairs (RHs) density, but decreased lateral roots (LRs) density in WT plants. However, overexpression of OsPIN2 caused a loss of sensitivity in the root response to P deficiency. The OE lines had a shorter SR length, lower LR density, and greater RH density than WT plants under control. However, the LR and RH densities in the OE lines were similar to those in WT plants under LP. Compared to WT plants, overexpression of OsPIN2 had a shorter root length through decreased root cell elongation under control and LP. Surprisingly, overexpression of OsPIN2 might increase auxin distribution in epidermis of root, resulting in greater RH formation but less LR development in OE plants than in WT plants in the control condition but levels similar of these under LP. These results suggest that higher OsPIN2 expression regulates rice root growth and development maybe by changing auxin distribution in roots under LP condition.

Intrinsic Properties of Single Graphene Nanoribbons in Solution: Synthetic and Spectroscopic Studies.

We report a novel type of structurally defined graphene nanoribbons (GNRs) with uniform width of 1.7 nm and average length up to 58 nm. These GNRs are decorated with pending Diels-Alder cycloadducts of anthracenyl units and N- n-hexadecyl maleimide. The resultant bulky side groups on GNRs afford excellent dispersibility with concentrations of up to 5 mg mL-1 in many organic solvents such as tetrahydrofuran (THF), two orders of magnitude higher than the previously reported GNRs. Multiple spectroscopic studies confirm that dilute dispersions in THF (<0.1 mg mL-1) consist mainly of nonaggregated ribbons, exhibiting near-infrared emission with high quantum yield (9.1%) and long lifetime (8.7 ns). This unprecedented dispersibility allows resolving in real-time ultrafast excited-state dynamics of the GNRs, which displays features of small isolated molecules in solution. This study achieves a breakthrough in the dispersion of GNRs, which opens the door for unveiling obstructed GNR-based physical properties and potential applications.

Supramolecular Nanostructures of Structurally Defined Graphene Nanoribbons in the Aqueous Phase.

Structurally well-defined graphene nanoribbons (GNRs) have attracted great interest because of their unique optical, electronic, and magnetic properties. However, strong π-π interactions within GNRs result in poor liquid-phase dispersibility, which impedes further investigation of these materials in numerous research areas, including supramolecular self-assembly. Structurally defined GNRs were synthesized by a bottom-up strategy, involving grafting of hydrophilic poly(ethylene oxide) (PEO) chains of different lengths (GNR-PEO). PEO grafting of 42-51 % percent produces GNR-PEO materials with excellent dispersibility in water with high GNR concentrations of up to 0.5 mg mL-1 . The "rod-coil" brush-like architecture of GNR-PEO resulted in 1D hierarchical self-assembly behavior in the aqueous phase, leading to the formation of ultralong nanobelts, or spring-like helices, with tunable mean diameters and pitches. In aqueous dispersions the superstructures absorbed in the near-infrared range, which enabled highly efficient conversion of photon energy into thermal energy.

Quantitative Control of Pore Size of Mesoporous Carbon Nanospheres through the Self-Assembly of Diblock Copolymer Micelles in Solution.

This paper reports facile synthesis of nitrogen-doped mesoporous carbon nanospheres (MCNSs) with average diameters of around 300 nm and well-controlled pore sizes ranging from 8 to 38 nm, by employing polystyrene-b-poly(ethylene oxide) (PS-b-PEO) diblocks with different PS block lengths as the soft templates and dopamine as the carbon-rich precursor. For the first time, a linear equation is achieved for the quantitative control of the average pore size of MCNSs by simply adjusting a block length of diblock copolymer. The resultant MCNSs possess high surface areas of up to 450 m(2) g(-1) and nitrogen doping contents of up to ≈3 wt%. As electrode materials of supercapacitors, the MCNSs exhibit excellent electrochemical performance with high specific capacitances of up to 350 F g(-1) at 0.1 A g(-1) , superior rate capability, and cycling stability. Interestingly, the specific capacitance of the MCNSs reduces linearly with increasing pore size, whereas the normalized capacitance by specific surface area remains invariable. This represents a new spectrum of the relationship between electrochemical capacitance and pore size (>5 nm) for porous carbons, which makes a complement to the existing spectra focusing on pore diameters of <5 nm.

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.

Fe3O4-doped mesoporous carbon cathode with a plumber's nightmare structure for high-performance Li-S batteries.

Shuttling of lithium polysulfides and slow redox kinetics seriously limit the rate and cycling performance of lithium-sulfur batteries. In this study, Fe3O4-dopped carbon cubosomes with a plumber's nightmare structure (SP-Fe3O4-C) are prepared as sulfur hosts to construct cathodes with high rate capability and long cycling life for Li-S batteries. Their three-dimensional continuous mesochannels and carbon frameworks, along with the uniformly distributed Fe3O4 particles, enable smooth mass/electron transport, strong polysulfides capture capability, and fast catalytic conversion of the sulfur species. Impressively, the SP-Fe3O4-C cathode exhibits top-level comprehensive performance, with high specific capacity (1303.4 mAh g-1 at 0.2 C), high rate capability (691.8 mAh gFe3O41 at 5 C), and long cycling life (over 1200 cycles). This study demonstrates a unique structure for high-performance Li-S batteries and opens a distinctive avenue for developing multifunctional electrode materials for next-generation energy storage devices.

Type IV secretion system effector sabotages multiple defense systems in a competing bacterium.

Effector proteins secreted by bacteria that infect mammalian and plant cells often subdue eukaryotic host cell defenses by simultaneously affecting multiple targets. However, instances when a bacterial effector injected in the competing bacteria sabotage more than a single target have not been reported. Here, we demonstrate that the effector protein, LtaE, translocated by the type IV secretion system from the soil bacterium Lysobacter enzymogenes into the competing bacterium, Pseudomonas protegens, affects several targets, thus disabling the antibacterial defenses of the competitor. One LtaE target is the transcription factor, LuxR1, that regulates biosynthesis of the antimicrobial compound, orfamide A. Another target is the sigma factor, PvdS, required for biosynthesis of another antimicrobial compound, pyoverdine. Deletion of the genes involved in orfamide A and pyoverdine biosynthesis disabled the antibacterial activity of P. protegens, whereas expression of LtaE in P. protegens resulted in the near-complete loss of the antibacterial activity against L. enzymogenes. Mechanistically, LtaE inhibits the assembly of the RNA polymerase complexes with each of these proteins. The ability of LtaE to bind to LuxR1 and PvdS homologs from several Pseudomonas species suggests that it can sabotage defenses of various competitors present in the soil or on plant matter. Our study thus reveals that the multi-target effectors have evolved to subdue cell defenses not only in eukaryotic hosts but also in bacterial competitors.

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.