Photoredox Catalyzed Conia-Ene-Type Cyclization/Smiles Rearrangement Cascade Reactions to Access Substituted Methylenecarbocycles.

We report a novel visible-light-driven photoredox-catalyzed cascade reaction involving Conia-ene-type cyclization and Smiles rearrangement initiated from alkyne-tethered α-sulfonyl esters. This methodology not only facilitates the rapid synthesis of a broad spectrum of highly substituted methylenecarbocycles but also introduces a new mechanistic pathway with aryl group migration, surpassing the conventional 1,5-hydrogen shift typically observed in Conia-ene reactions.

Next-Generation Ultrathin Lightweight Electrode for pH-Universal Aqueous Flow Batteries.

Aqueous flow batteries (AFBs) are promising long-duration energy storage system owing to intrinsic safety, inherent scalability, and ultralong cycle life. However, due to the thicker (3-5 mm) and heavier (300-600 g m-2) nature, the current used graphite felt (GF) electrodes still limit the volume/weight power density of AFBs. Herein, a lightweight (≈50 g m-2) and ultrathin (≈0.3 mm) carbon microtube electrode (CME) is proposed derived from a scalable one-step carbonization of commercial cotton cloth. The unique loose woven structure composed of carbon microtube endows CME with excellent conductivity, abundant active sites, and enhanced electrolyte transport performance, thereby significantly reducing polarization in working AFBs. As a consequence, CME demonstrates excellent cycling performance in pH-universal AFBs, including acidic vanadium flow battery (maximum power density of 632.2 mW cm-2), neutral Zn-I2 flow battery (750 cycles with average Coulombic efficiency of 99.6%), and alkaline Zn-Fe flow battery (energy efficiency over 70% at 200 mA cm-2). More importantly, the estimated price of CME is only 5% of GF (≈3 vs ≈60 $ m-2). Therefore, it is reasonably anticipated that the lightweight and ultrathin CME may emerge as the next generation electrode for AFBs.

Hyphobacterium marinum sp. nov. and Hyphobacterium lacteum sp. nov., isolated from marine sediment.

Two bacterial strains, Y60-23T and HN-65T, were isolated from marine sediment samples collected from Xiaoshi Island, Weihai, and Dongzhai Harbour, Haikou, PR China, respectively. Based on the 16S rRNA gene sequences, strain Y60-23T exhibited 96.0% similarity to its most related type strain Hyphobacterium vulgare KCTC 52487T, while strain HN-65T exhibited 97.3% similarity to its most related type strain Hyphobacterium indicum 2ED5T. The 16S rRNA gene sequence similarity between the two strains was 95.8%. Phylogenetic analysis based on 16S rRNA gene sequences showed that strains Y60-23T and HN-65T belonged to the genus Hyphobacterium. Cells of strains Y60-23T and HN-65T were rod-shaped, Gram-stain-negative, aerobic, non-motile, prosthecate and multiplied by binary fission. The major cellular fatty acids (>10.0%) of strain Y60-23T were C18 : 1 ω7c and C17 : 0, while those of strain HN-65T were iso-C17 : 1 ω9c, iso-C17 : 0 and C18 : 1 ω7c. The major respiratory quinone in both strains was ubiquinone-10 (Q-10) and the major polar lipids were monoglycosyl diglyceride, sulfoquinovosyl diacylglycerol and glucuronopyranosyl diglyceride. The genomic DNA G+C contents of strains Y60-23T and HN-65T were 63.9 and 60.7 mol%, respectively. The average nucleotide identity value between the two strains was 72.1% and the DNA-DNA hybridization value was 18.4%, clearly distinguishing them from each other. According to the results of the phenotypic, chemotaxonomic, phylogenetic and genomic analyses, the two strains represented two novel species within the genus Hyphobacterium, for which the names Hyphobacterium marinum sp. nov. and Hyphobacterium lacteum sp. nov. were proposed with the type strains Y60-23T (=MCCC 1H01433T=KCTC 8172T) and HN-65T (=MCCC 1H01434T=KCTC 8169T), respectively.

Suprathreshold Water Spray Stimulus Enhances Plant Defenses against Biotic Stresses in Tomato.

Mechanical stimuli can affect plant growth, development, and defenses. The role of water spray stimulation, as a prevalent mechanical stimulus in the environment, in crop growth and defense cannot be overlooked. In this study, the effects of water spray on tomato plant growth and defense against the chewing herbivore Helicoverpa armigera and necrotrophic fungus Botrytis cinerea were investigated. Suprathreshold water spray stimulus (LS) was found to enhance tomato plant defenses against pests and pathogens while concurrently modifying plant architecture. The results of the phytohormone and chemical metabolite analysis revealed that LS improved the plant defense response via jasmonic acid (JA) signaling. LS significantly elevated the level of a pivotal defensive metabolite, chlorogenic acid, and reduced the emissions of volatile organic compounds (VOCs) from tomato plants, thereby defending against pest and pathogen attacks. The most obvious finding to emerge from this study is that LS enhances tomato plant defenses against biotic stresses, which will pave the way for further work on the application of mechanical stimuli for pest management.

Enhancing Compatibility of Two-Step Tandem Catalytic Nitrate Reduction to Ammonia Over P-Cu/Co(OH)2.

Electrochemical nitrate reduction reaction (NO3RR) is a promising approach to realize ammonia generation and wastewater treatment. However, the transformation from NO3 - to NH3 involves multiple proton-coupled electron transfer processes and by-products (NO2 -, H2, etc.), making high ammonia selectivity a challenge. Herein, a two-phase nanoflower P-Cu/Co(OH)2 electrocatalyst consisting of P-Cu clusters and P-Co(OH)2 nanosheets is designed to match the two-step tandem process (NO3 - to NO2 - and NO2 - to NH3) more compatible, avoiding excessive NO2 - accumulation and optimizing the whole tandem reaction. Focusing on the initial 2e- process, the inhibited *NO2 desorption on Cu sites in P-Cu gives rise to the more appropriate NO2 - released in electrolyte. Subsequently, P-Co(OH)2 exhibits a superior capacity for trapping and transforming the desorbed NO2 - during the latter 6e- process due to the thermodynamic advantage and contributions of active hydrogen. In 1 m KOH + 0.1 m NO3 -, P-Cu/Co(OH)2 leads to superior NH3 yield rate of 42.63 mg h- 1 cm- 2 and NH3 Faradaic efficiency of 97.04% at -0.4 V versus the reversible hydrogen electrode. Such a well-matched two-step process achieves remarkable NH3 synthesis performance from the perspective of optimizing the tandem catalytic reaction, offering a novel guideline for the design of NO3RR electrocatalysts.

TLR2/NF-кB signaling may control expansion and function of regulatory T cells in patients with severe fever with thrombocytopenia syndrome (SFTS).

Severe fever with thrombocytopenia syndrome (SFTS) is a recently identified infectious ailment triggered by a new strain of bunyavirus. It is distinguished by elevated fatality rates, ranging from 12 % to 30 %. The mechanism underlying the development of severe illness caused by SFTS bunyavirus (SFTSV) is not yet fully understood. To evaluate the role of the TLR2 receptor pathway in regulating Treg function in the progression of SFTS disease and possible mechanisms, sequential serum samples from 29 patients with SFTS (15 mild, 14 severe cases) were examined. Flow cytometry was employed to scrutinize the phenotypic and functional characteristics of TLR2 expression on circulating CD4 T cells, CD8 T cells, and Tregs. In all admitted patients, the evaluation of correlations between the frequencies of the aforementioned cells and SFTS index (SFTSI) was conducted. For SFTS, the levels of TLR2 on CD4 T cells and Tregs were significantly heightened when compared to those in healthy subjects. Additionally, the expression of TLR2 on Tregs exhibited a positive correlation with Ki-67 expression in Tregs and the severity of disease. Additionally, compared with those in uninfected controls, the expression levels of NF-κB in Tregs were significantly increased. Collectively, Tregs may be activated and proliferate through the stimulation of the TLR2/NF-кB pathway in reaction to SFTSV infection.

Enhancing bioremediation of petroleum-contaminated soil by sophorolipids-modified biochar: Combined metagenomic and metabolomic analyses.

In this study, sophorolipids (SLs)-modified biochar (BC-SLs) was used to enhance the bioremediation of petroleum hydrocarbons (PHs) contaminated soil. The biodegradation rate of petroleum hydrocarbons (PHs) by BC-SLs and BC treatments were 62.86 % and 52.64 % after 60 days of remediation experiments, respectively, higher than non-biochar treatment group (24.09 %). The metagenomic analysis showed that the abundance of petroleum-degrading bacteria Actinobacteria and Proteobacteria were increased by 3.8 % and 5.3 %, respectively in BC-SLs treatment, and the abundance of functional genes for PHs degradation, such as alkB, nidA and pcaG, were significantly increased by 12.85 %, 30.08 % and 21.01 %, respectively. The metabolomic analysis showed that BC-SLs facilitated the metabolic process of PHs, the microbial metabolism of petroleum hydrocarbons (PHs) became more active. Fatty acid degradation and polycyclic aromatic hydrocarbons (PAHs) degradation were up-regulated, indicating the promoting effect of the BC-SLs for PHs metabolism. The combined metagenomic and metabolomic analysis demonstrated the strong positive correlations between PHs metabolites and PHs-degrading bacteria, such as lauric acid vs. Actinobacteria, benzoic vs. Proteobacteria. The strong positive correlations between PHs metabolites and PHs-degrading genes were also observed, such as o-ehyltoluene vs. nahD, 4-isopropylbenzoic acid vs. etbAa. The modification of biochar with SLs increased the oxygen-containing functional groups on the surface of biochar. Meanwhile, the emulsification and solubilization of SLs promoted the bioavailability of PHs. The effects of BC-SLs on the nitrogen cycle during PHs remediation showed that it facilitated the accumulation of nitrogen-fixing genes, promoted nitrification but inhibited denitrification process. This study confirms that the application of BC-SLs is an effective remediation of PHs contamination and a sustainable method for controlling agricultural waste resources.

Small-size polyethylene and polylactic microplastic alterations on soil aggregate formation with soil sterilization.

Soil microplastic contamination is emerging as a significant environmental concern affecting soil properties and biota, including soil aggregation. This study aimed to determine the influence of soil microplastics on soil aggregation, their impact through effects on soil microorganisms, and their effects on water and mechanical stability of soil aggregates. Soil incubation experiments were conducted using sterilized and non-sterilized soils with 15-µm polyethylene and polylactic microplastics over one month. Sterilized soils showed more water-stable aggregates, particularly in the 0.25-0.5 mm fraction (+49%), with both polyethylene and polylactic MPs significantly increasing this fraction (+34% and +35%, respectively). However, no significant effects of soil sterilization and MP addition were found on mechanical stability. The addition of MPs tended to decrease aggregate surface roughness but not significantly (-17～21%). The study provides insights into the complex interactions between microplastics and soil aggregation, suggesting that MP effects may not necessarily be related to their toxicity on soil microbes but could involve various physical interactions.

Regulation of glycolysis-derived L-lactate production in astrocytes rescues the memory deficits and Aß burden in early Alzheimer's disease models.

Aberrant energy metabolism in the brain is a common pathological feature in the preclinical Alzheimer's Disease (AD). Recent studies have reported the early elevations of glycolysis-involved enzymes in AD brain and cerebrospinal fluid according to a large-scale proteomic analysis. It's well-known that astrocytes exhibit strong glycolytic metabolic ability and play a key role in the regulation of brain homeostasis. However, its relationship with glycolytic changes and cognitive deficits in early AD patients is unclear. Here, we investigated the mechanisms by which astrocyte glycolysis is involved in early AD and its potential as a therapeutic target. Our results suggest that Aß-activated microglia can induce glycolytic-enhanced astrocytes in vitro, and that these processes are dependent on the activation of the AKT-mTOR-HIF-1α pathway. In early AD models, the increase in L-lactate produced by enhanced glycolysis of astrocytes leads to spatial cognitive impairment by disrupting synaptic plasticity and accelerating Aß aggregation. Furthermore, we find rapamycin, the mTOR inhibitor, can rescue the impaired spatial memory and Aß burden by inhibiting the glycolysis-derived L-lactate in the early AD models. In conclusion, we highlight that astrocytic glycolysis plays a critical role in the early onset of AD and that the modulation of glycolysis-derived L-lactate by rapamycin provides a new strategy for the treatment of AD.

Visible Light-Promoted Aromatization-Driven Deconstructive Fluorination of Spiro Carbocycles.

A visible light-promoted aromatization-driven deconstructive fluorination of spiro carbocycles is presented. A series of spiro dihydroquinazolinones reacted efficiently with NFSI under visible light irradiation to afford the 2-(4-fluoroalkyl)quinazolin-4(3H)-ones in good yields with excellent functional group tolerance. A radical pathway involving C-C bond cleavage and F atom transfer is proposed for the reaction. In addition, the ring-opening chlorination of spiro dihydroquinazolinones with NCS was also applicable.

GhEXL3 participates in brassinosteroids regulation of fiber elongation in Gossypium hirsutum.

Cotton fiber (Gossypium hirsutum) serves as an ideal model for investigating the molecular mechanisms of plant cell elongation at the single-cell level. Brassinosteroids (BRs) play a crucial role in regulating plant growth and development. However, the mechanism by which BR influences cotton fiber elongation remains incompletely understood. In this study, we identified EXORDIUM-like (GhEXL3) through transcriptome analysis of fibers from BR-deficient cotton mutant pagoda 1 (pag1) and BRI1-EMS-SUPPRESSOR 1 (GhBES1.4, encoding a central transcription factor of BR signaling) overexpression cotton lines. Knockout of GhEXL3 using CRISPR/Cas9 was found to impede cotton fiber elongation, while its overexpression promoted fiber elongation, suggesting a positive regulatory function for GhEXL3 in fiber elongation. Furthermore, in vitro ovule culture experiments revealed that the overexpression of GhEXL3 partially counteracted the inhibitory effects of brassinazole (BRZ) on cotton fiber elongation, providing additional evidence of GhEXL3 involvement in BR signaling pathways. Moreover, our findings demonstrate that GhBES1.4 directly binds to the E-box (CACGTG) motif in the GhEXL3 promoter region and enhances its transcription. RNA-seq analysis revealed that overexpression of GhEXL3 upregulated the expression of EXPs, XTHs, and other genes associated with fiber cell elongation. Overall, our study contributes to understanding the mechanism by which BR regulates the elongation of cotton fibers through the direct modulation of GhEXL3 expression by GhBES1.4.

Multiple pulp stones emerge across all teeth during mixed dentition: A case report.

BACKGROUND: This paper reports a rare presentation of multiple pulp stones (PSs) emerging in all teeth during mixed dentition. It offers valuable insights into the clinical diagnosis, treatment, and prognosis of multiple PSs, shedding light on their occurrence during the mixed dentition period. CASE SUMMARY: A 10-year-old girl presented with repeated pain in the mandibular right posterior teeth. Intraoral examination revealed carious lesions, abnormal tooth shapes, and anomalies in tooth number. Radiographic examinations showed multiple PSs with diverse shapes, sizes, and quantities in all teeth, alongside anomalies in tooth shape and number. Root canal therapy was initiated, but the patient initially lacked timely follow-up. Upon return for treatment completion, an extracted tooth revealed irregular calculus within the pulp cavity. CONCLUSION: This case underscores the importance of considering multiple PSs in mixed dentition, necessitating comprehensive evaluation and management strategies.

[Analysis of the therapeutic effect of trochanteric flip osteotomy combined with Kocher-Langenbeck approach for high acetabular posterior wall fracture].

OBJECTIVE: Evaluation of the clinical efficacy of f trochanteric flip osteotomy combined with Kocher-Langenbeck approach for high acetabular posterior wall fracture. METHODS: Between January 2020 and December 2022, 20 patients with high acetabular posterior wall fractures were retrospectively analyzed, including 12 males and 8 females, aged 18 to 75 years old. They were divided into two groups according to the different surgical methods. Ten patients were treated with greater trochanteric osteotomy combined with Kocher-Langenbeck approach as the observation group, including 5 males and 5 females, aged from 18 to 75 years old. Ten patients were treated with Kocher-Langenbeck approach alone as the control group, including 7 males and 3 females, aged from 18 to 71 years old. Matta reduction criteria were used to evaluate the reduction quality of the two groups, and Harris score was used to compare the hip function of the two groups at the latest follow-up. The operation time, blood loss and postoperative complications of the two groups were analyzed. RESULTS: All patients were followed up for 10 to 24 months. According to the Matta fracture reduction quality evaluation criteria, the observation group achieved anatomical reduction in 6 cases, satisfactory reduction in 3 cases, and unsatisfactory reduction in 1 case, while the control group only achieved anatomical reduction in 3 cases, satisfactory reduction in 3 cases, and unsatisfactory reduction in 4 cases. At the final follow-up, the Harris hip score ranged from 71.4 to 96.6 in the observation group and 65.3 to 94.5 in the control group. According to the results of Harris score. The hip joint function of the observation group was excellent in 6 cases, good in 3 cases, and fair in 1 case. The hip joint function of the control group was excellent in 2 cases, good in 3 cases, fair in 3 cases, and poor in 2 cases. In the observation group, the intraoperative blood loss ranged from 300 to 700 ml, and the operation duration ranged from 120 to 180 min;in the control group, the intraoperative blood loss ranged from 300 to 650 ml, and the operation duration ranged from 100 to 180 min. Complications in the observation group included 1 case of traumatic arthritis and 1 case of heterotopic ossification, while complications in the control group included 3 cases of traumatic arthritis, 3 cases of heterotopic ossification and 1 case of hip abduction weakness. CONCLUSION: Trochanteric flip osteotomy combined with the Kocher-Langenbeck approach significantly improved anatomical fracture reduction rates, enhanced excellent and good hip joint function outcomes, and reduced surgical complication incidence compared to the Kocher-Langenbeck approach alone. Clinical application of this combined approach is promising, although larger studies are needed for further validation.

Application of an Auditory-Based Feedback Distortion to Modify Gait Symmetry in Healthy Individuals.

BACKGROUND: Augmenting auditory feedback through an error-augmentation paradigm could facilitate the perception and correction of gait asymmetry in stroke survivors, but how such a paradigm should be tailored to individual asymmetry profiles remains unclear. Before implementing the paradigm in rehabilitation, we need to investigate the instantaneous effects of distorted footstep sound feedback on gait symmetry in healthy young adults. METHODS: Participants (n = 12) walked on a self-paced treadmill while listening to their footstep sounds, which were distorted unilaterally according to five conditions presented randomly: small delay; small advance; large delay; large advance; or unmodified (control). The primary outcomes were swing time ratio (SWR) and step length ratio (SLR). Secondary outcomes included walking speed, bilateral swing time, step length, and maximum toe height, as well as hip, knee, and ankle angle excursions. RESULTS: SWR (p < 0.001) but not SLR (p ≥ 0.05) was increased in all distorted feedback conditions compared to the control condition. Increased swing time on the perturbed side ipsilateral to feedback distortion was observed in the advanced conditions (p < 0.001), while swing time increased bilaterally in the delayed conditions (p < 0.001) but to a larger extent on the unperturbed side contralateral to feedback distortion. Increases in swing time were accompanied by larger maximum toe height as well as larger hip and knee joint excursions (p < 0.05 to p < 0.001). No differences in any outcomes were observed between small and large feedback distortion magnitudes. CONCLUSIONS: Distorted footstep sound feedback successfully elicits adaptation in temporal gait symmetry (SWR), with distinct modulation patterns for advanced vs. delayed footstep sounds. Spatial symmetry (SLR) remains unaltered, likely because auditory feedback primarily conveys temporal information. This research lays the groundwork to implement personalized augmented auditory feedback in neurorehabilitation.

SLC25A12 inhibits Japanese encephalitis virus replication by interacting with the NS1 and enhancing the type I interferon response.

Japanese encephalitis virus (JEV) is a mosquito-borne, zoonotic orthoflavivirus causing human encephalitis and reproductive disorders in pigs. Cell-intrinsic antiviral restriction factors are the first line of defense that prevent a virus from establishing a productive infection, while the molecular mechanism of the virus-host interaction is still not fully understood. Our in vitro experiments demonstrated that the Solute Carrier Family 25 Member 12 (SLC25A12) interacted with the JEV nonstructural protein 1 (NS1) and inhibited JEV replication. Furthermore, we showed that knockdown or knockout of SLC25A12 promoted JEV replication, while overexpression of SLC25A12 repressed viral replication. Finally, we demonstrated that SLC25A12 increased IRF7 mRNA levels, which promoted IFN-ß expression and subsequently induced antiviral effects. Collectively, our study revealed that SLC25A12 interacted with NS1, inhibiting viral RNA synthesis and transcription and enhancing type I interferon induction for antiviral effects.

Enhancing homology-directed repair efficiency with HDR-boosting modular ssDNA donor.

Despite the potential of small molecules and recombinant proteins to enhance the efficiency of homology-directed repair (HDR), single-stranded DNA (ssDNA) donors, as currently designed and chemically modified, remain suboptimal for precise gene editing. Here, we screen the biased ssDNA binding sequences of DNA repair-related proteins and engineer RAD51-preferred sequences into HDR-boosting modules for ssDNA donors. Donors with these modules exhibit an augmented affinity for RAD51, thereby enhancing HDR efficiency across various genomic loci and cell types when cooperated with Cas9, nCas9, and Cas12a. By combining with an inhibitor of non-homologous end joining (NHEJ) or the HDRobust strategy, these modular ssDNA donors achieve up to 90.03% (median 74.81%) HDR efficiency. The HDR-boosting modules targeting an endogenous protein enable a chemical modification-free strategy to improve the efficacy of ssDNA donors for precise gene editing.

Ultrastructure and distribution of antennal sensilla of parasitic wasp, Cotesia gregalis (Hymenoptera: Braconidae).

Cotesia gregalis Yang et Wei (Hymenoptera: Braconidae) is a gregarious koinobiont endoparasitic wasp attacking the larvae of fall webworm, Hyphantria cunea, an important invasive insect pest in China. To better understand the parasitic wasps' mating and parasitic behaviors, we examined the morphology of the antennae of adult C. gregalis, as well as the type, number, and distribution of antennal sensilla, via scanning electron microscopy. The antennae of female and male C. gregalis are filiform and comprise a scape, pedicel, and 16 flagellomeres. The female antennae are significantly shorter than those of male. A total of nine morphological types of antennal sensilla (mechanoreceptor and chemoreceptor) are presented in both sexes, including four mechanoreceptors (sensilla chaetica [two subtypes], sensilla trichodea and Böhm bristles); five chemoreceptors (sensilla basiconica [two subtypes], sensilla placodea, sensilla styloconica, and sensilla coelocapitula). There is no difference in the type and distribution of antennal sensilla between males and females, but the number and length of some antennal sensilla show sexual dimorphism. The functional morphology of the sensilla of C. gregalis is discussed by comparison with other parasitic wasps. These findings provide foundation for further research on the chemical communication and host localization mechanisms of C. gregalis. RESEARCH HIGHLIGHTS: The first report of morphology and distribution pattern of the antennal sensilla in C. gregalis is discussed. A total of seven main types and nine antennal sensilla subtypes are observed in male and female C. gregalis. The type and distribution of antennal sensilla in males and females are identical; however, the number and length of certain antennal sensilla show sexual dimorphism.

In situ forest with lycopsid trees bearing lobed rhizomorphs from the Upper Devonian of Lincheng, China.

The earliest forests in the Devonian were reported from only four localities worldwide. The tree lycopsids, sometimes as the primary elements of Devonian forests, had evolved several types of rooting systems. In recent years, we found and excavated a Late Devonian (Famennian, 374-359 Ma) lycopsid forest from Zhejiang Province, China. The fossil forest occurs at seven locations of Lincheng Town of Changxing County and mainly consists of in situ small tree lycopsid (Heliodendron longshanense gen. et sp. nov.) stems usually connected to lobed cormose rhizomorphs. The four short lobes of each rhizomorph often branch once and bear roots arranged radially. Allometry is observed between the trunk diameter of Heliodendron and the length of its rhizomorphic lobes, indicating that the trunk develops later than the rhizomorph in tree lycopsid plants. The Devonian witnessed the transformation from clastic nonlycopsid dominated forests to Carboniferous swampy forests dominated by giant lycopsid trees. These trees form a multigenerational community, as shown by the in situ preserved stems at various levels within the same area due to frequent sedimentation events.

Synthesis of NiII porphyrin-NiII 5,15-diazaporphyrin hybrid tapes.

NiII porphyrin (P) and NiII 5,15-diazaporphyrin (DAP) hybrid tapes were synthesized by Suzuki-Miyaura cross-coupling reactions of meso- or ß-borylated P with ß-brominated DAP followed by intramolecular oxidative fusion reactions. Meso-ß doubly linked hybrid tapes were synthesized by oxidation of singly linked precursors with DDQ-FeCl3. Synthesis of triply linked hybrid tapes was achieved by oxidation with DDQ-FeCl3-AgOTf with suppression of peripheral ß-chlorination. In these tapes, DAP segments were present as a 20π-electronic unit, but their local antiaromatic contribution was trivial. Remarkably, these hybrid tapes were stable and exhibited extremely enhanced absorption bands in the NIR region and multiple reversible redox waves. A pentameric hybrid tape showed a remarkably sharp and red-shifted band at 1168 nm with ε = 5.75 × 105 M-1 cm-1. Singly linked P-DAP dyads were oxidized with DDQ-FeCl3 to give stable radicals, which were oxidized further to afford dimeric hybrid tapes possessing a nitrogen atom at the peripheral-side meso-position.

Correlated Charge Density Wave Insulators in Chirally Twisted Triple Bilayer Graphene.

Electrons residing in a flat-band system can play a vital role in triggering spectacular phenomenology due to relatively large interactions and spontaneous breaking of different degeneracies. In this work, we demonstrate chirally twisted triple bilayer graphene, a new moiré structure formed by three pieces of helically stacked Bernal bilayer graphene, as a highly tunable flat-band system. In addition to the correlated insulators showing at integer moiré fillings, commonly attributed to interaction induced symmetry broken isospin flavors in graphene, we observe abundant insulating states at half-integer moiré fillings, suggesting a longer-range interaction and the formation of charge density wave insulators which spontaneously break the moiré translation symmetry. With weak out-of-plane magnetic field applied, as observed half-integer filling states are enhanced and more quarter-integer filling states appear, pointing toward further quadrupling moiré unit cells. The insulating states at fractional fillings combined with Hartree-Fock calculations demonstrate the observation of a new type of correlated charge density wave insulators in graphene and points to a new accessible twist manner engineering correlated moiré electronics.