Graphene nanoribbons grown in hBN stacks for high-performance electronics.

Van der Waals encapsulation of two-dimensional materials in hexagonal boron nitride (hBN) stacks is a promising way to create ultrahigh-performance electronic devices1-4. However, contemporary approaches for achieving van der Waals encapsulation, which involve artificial layer stacking using mechanical transfer techniques, are difficult to control, prone to contamination and unscalable. Here we report the transfer-free direct growth of high-quality graphene nanoribbons (GNRs) in hBN stacks. The as-grown embedded GNRs exhibit highly desirable features being ultralong (up to 0.25 mm), ultranarrow (<5 nm) and homochiral with zigzag edges. Our atomistic simulations show that the mechanism underlying the embedded growth involves ultralow GNR friction when sliding between AA'-stacked hBN layers. Using the grown structures, we demonstrate the transfer-free fabrication of embedded GNR field-effect devices that exhibit excellent performance at room temperature with mobilities of up to 4,600 cm2 V-1 s-1 and on-off ratios of up to 106. This paves the way for the bottom-up fabrication of high-performance electronic devices based on embedded layered materials.

Tip Growth of Quasi-Metallic Bilayer Graphene Nanoribbons with Armchair Chirality.

Graphene nanoribbons (GNRs), quasi one-dimensional (1D) narrow strips of graphene, have shown promise for high-performance nanoelectronics due to their exceptionally high carrier mobility and structurally tunable bandgaps. However, producing chirality-uniform GNRs on insulating substrates remains a big challenge. Here, we report the successful growth of bilayer GNRs with predominantly armchair chirality and ultranarrow widths (<5 nm) on insulating hexagonal boron nitride (h-BN) substrates using chemical vapor deposition (CVD). The growth of GNRs is catalyzed by transition metal nanoparticles, including Fe, Co, and Ni, through a unique tip-growth mechanism. Notably, GNRs catalyzed by Ni exhibit a high purity (97.3%) of armchair chirality. Electron transport measurements indicate that the ultrathin bilayer armchair GNRs exhibit quasi-metallic behavior. This quasi-metallicity is further supported by density functional theory (DFT) calculations, which reveal a significantly reduced bandgap in bilayer armchair GNRs. The chirality-specific GNRs reported here offer promising advancements for the application of graphene in nanoelectronics.

Block Copolymer as a Surface Modifier to Monodisperse Patchy Silica Nanoparticles for Superhydrophobic Surfaces.

Monodisperse patchy silica nanoparticles (PSNPs) less than 100 nm are prepared based on the seed-regrowth method using a poly(ethylene oxide) (PEO)-poly(propylene oxide) (PPO)-PEO-type block copolymer as a surface modifier. Well-defined patches are controllably synthesized through area-selective deposition of silica onto the surface of seeds. After colloidal PSNPs are further modified with trimethylchlorosilane, the advancing and receding contact angles of water for PSNPs are 168 ± 2° and 167 ± 2°, respectively. The superhydrophobic and transparent coatings on the various types of substrates are obtained by a simple drop-casting procedure. Additionally, almost the same superhydrophobicity can be achieved by using colloidal PSNPs via redispersing the powder of superhydrophobic PSNPs in ethanol.

Iron accumulation in ovarian microenvironment damages the local redox balance and oocyte quality in aging mice.

Accumulating oxidative damage is a primary driver of ovarian reserve decline along with aging. However, the mechanism behind the imbalance in reactive oxygen species (ROS) is not yet fully understood. Here we investigated changes in iron metabolism and its relationship with ROS disorder in aging ovaries of mice. We found increased iron content in aging ovaries and oocytes, along with abnormal expression of iron metabolic proteins, including heme oxygenase 1 (HO-1), ferritin heavy chain (FTH), ferritin light chain (FTL), mitochondrial ferritin (FTMT), divalent metal transporter 1 (DMT1), ferroportin1(FPN1), iron regulatory proteins (IRP1 and IRP2) and transferrin receptor 1 (TFR1). Notably, aging oocytes exhibited enhanced ferritinophagy and mitophagy, and consistently, there was an increase in cytosolic Fe2+, elevated lipid peroxidation, mitochondrial dysfunction, and augmented lysosome activity. Additionally, the ovarian expression of p53, p21, p16 and microtubule-associated protein tau (Tau) were also found to be upregulated. These alterations could be phenocopied with in vitro Fe2+ administration in oocytes from 2-month-old mice but were alleviated by deferoxamine (DFO). In vivo application of DFO improved ovarian iron metabolism and redox status in 12-month-old mice, and corrected the alterations in cytosolic Fe2+, ferritinophagy and mitophagy, as well as related degenerative changes in oocytes. Thereby in the whole, DFO delayed the decline in ovarian reserve and significantly increased the number of superovulated oocytes with reduced fragmentation and aneuploidy. Together, our findings suggest that aging-related disturbance in ovarian iron homeostasis contributes to excessive ROS production and that iron chelation may improve ovarian redox status, and efficiently delay the decline in ovarian reserve and oocyte quality in aging mice. These data propose a novel intervention strategy for preserving the ovarian reserve function in elderly women.

PAK4 is Required for Meiotic Resumption, Spindle Assembly, and Cortical Migration in Mouse Oocytes During Meiotic Maturation.

Oocyte meiotic errors can cause infertility, miscarriage, and birth defects. Here the role and the underlying mechanism of p21 activated kinase 4 (PAK4) in mouse oocyte meiosis is evaluated. It is found that PAK4 expression and its phosphorylation are detected in high level at germinal vesicle (GV) stage, and gradually decreased after meiotic resumption in oocytes. PAK4 has direct physical interaction with both mitogen-activated protein kinases 1/2 (MEK1/2) and Paxillin, they are colocalized on the spindle structure during metaphases I and II. Phospho-PAK4 is distributed beneath the cytoplasmic membrane and on the chromosomes, and colocalized with the microtubule organizing center (MTOC) proteins, Pericentrin and γ-tubulin, as well as phosphor-MEK1/2 and phosphor-Paxillin on spindle poles. PAK4 inhibition by chemical inhibitor LCH-7749944, specific Pak4 morpholino oligo or the dominant negative mutant Pak4K350, 351 M influence the meiotic resumption, spindle assembly and its cortical migration, and associated with the downregulation in the dephosphorylation of cyclin dependent kinase 1 (CDK1) and the levels of Cyclin B1, MEK1/2, Paxillin, g-tubulin, acetylated a-tubulin, Arp3, and Cofilin phosphorylation in oocytes. In sum, PAK4 functions to sustain the rational levels of Cyclin B1, MEK1/2, Paxillin, y-tubulin, acetylated a-tubulin, Arp3, and phosphor-Cofilin in mouse oocytes, thereby promotes the meiotic resumption, spindle assembly, and migration during meiotic maturation.

PLD1 promotes spindle assembly and migration through regulating autophagy in mouse oocyte meiosis.

PLD1 has been implicated in cytoskeletal reorganization and vesicle trafficking in somatic cells; however, its function remains unclear in oocyte meiosis. Herein, we found PLD1 stably expresses in mouse oocytes meiosis, with direct interaction with spindle, RAB11A+ vesicles and macroautophagic/autophagic vacuoles. The genetic or chemical inhibition of PLD1 disturbed MTOC clustering, spindle assembly and its cortical migration, also decreased PtdIns(4,5)P2, phosphorylated CFL1 (p-CFL1 [Ser3]) and ACTR2, and their local distribution on MTOC, spindle and vesicles. Furthermore in PLD1-suppressed oocytes, vesicle size was significantly reduced while F-actin density was dramatically increased in the cytoplasm, the asymmetric distribution of autophagic vacuoles was broken and the whole autophagic process was substantially enhanced, as illustrated with characteristic changes in autophagosomes, autolysosome formation and levels of ATG5, BECN1, LC3-II, SQSTM1 and UB. Exogenous administration of PtdIns(4,5)P2 or overexpression of CFL1 hyperphosphorylation mutant (CFL1S3E) could significantly improve polar MTOC focusing and spindle structure in PLD1-depleted oocytes, whereas overexpression of ACTR2 could rescue not only MTOC clustering, and spindle assembly but also its asymmetric positioning. Interestingly, autophagy activation induced similar defects in spindle structure and positioning; instead, its inhibition alleviated the alterations in PLD1-depleted oocytes, and this was highly attributed to the restored levels of PtdIns(4,5)P2, ACTR2 and p-CFL1 (Ser3). Together, PLD1 promotes spindle assembly and migration in oocyte meiosis, by maintaining rational levels of ACTR2, PtdIns(4,5)P2 and p-CFL1 (Ser3) in a manner of modulating autophagy flux. This study for the first time introduces a unique perspective on autophagic activity and function in oocyte meiotic development.Abbreviations: ACTR2/ARP2: actin related protein 2; ACTR3/ARP3: actin related protein 3; ATG5: autophagy related 5; Baf-A1: bafilomycin A1; BFA: brefeldin A; GAPDH: glyceraldehyde-3-phosphate dehydrogenase; GOLGA2/GM130: golgin A2; GV: germinal vesicle; GVBD: germinal vesicle breakdown; IVM: in vitro maturation; MAP1LC3/LC3: microtubule-associated protein 1 light chain 3; MI: metaphase of meiosis I; MII: metaphase of meiosis II; MO: morpholino; MTOC: microtubule-organizing center; MTOR: mechanistic target of rapamycin kinase; PB1: first polar body; PLA: proximity ligation assay; PLD1: phospholipase D1; PtdIns(4,5)P2/PIP2: phosphatidylinositol 4,5-bisphosphate; RAB11A: RAB11A, member RAS oncogene family; RPS6KB1/S6K1: ribosomal protein S6 kinase B1; SQSTM1/p62: sequestosome 1; TEM: transmission electron microscopy; TUBA/α-tubulin: tubulin alpha; TUBG/γ-tubulin: tubulin gamma; UB: ubiquitin; WASL/N-WASP: WASP like actin nucleation promoting factor.

Regulation of hydrogen bonding network between cellulose nanofibers by rare earth ion Y3.

Cellulose is regarded as the most abundant biomass, and nanocellulose derived from it has numerous applications in environmentally friendly materials. However, owing to the abundant hydroxyl groups on surface, nanocellulose is prone to agglomeration when transported, stored, or made into materials, which destroys material performance and limits its use. In this study, a feasible method was presented for regulating the hydrogen bonding strength between cellulose nanofibers (CNFs) by adding a minute quantity of rare earth ions Y3+ during cellulose nanofibrillation. It was found that the strength of hydrogen bonding between CNFs can be regulated by controlling the quantity of Y3+ in the system. The dispersibility and stability of CNFs, as well as the mechanical properties of CNFs films and CNFs-reinforced papers can be improved by 43.07 % and by 64.05 % after adding only 0.05 or 0.075 wt% Y3+. The possible mechanism of CNFs hydrogen bonding network reconstruction was proposed.

Tunable growth of one-dimensional graphitic materials: graphene nanoribbons, carbon nanotubes, and nanoribbon/nanotube junctions.

Graphene nanoribbons (GNRs) and carbon nanotubes (CNTs), two representative one-dimensional (1D) graphitic materials, have attracted tremendous research interests due to their promising applications for future high-performance nanoelectronics. Although various methods have been developed for fabrication of GNRs or CNTs, a unified method allowing controllable synthesis of both of them, as well as their heterojunctions, which could largely benefit their nano-electronic applications, is still lacking. Here, we report on a generic growth of 1D carbon using nanoparticles catalyzed chemical vapor deposition (CVD) on atomically flat hexagonal boron nitride (h-BN) substrates. Relative ratio of the yielded GNRs and CNTs is able to be arbitrarily tuned by varying the growth temperature or feeding gas pressures. The tunability of the generic growth is quantitatively explained by a competing nucleation theory: nucleation into either GNRs or CNTs by the catalysts is determined by the free energy of their formation, which is controlled by the growth conditions. Under the guidance of the theory, we further realized growth of GNR/CNT intramolecular junctions through changing H2 partial pressure during a single growth process. Our study provides not only a universal and controllable method for growing 1D carbon nanostructures, but also a deep understanding of their growth mechanism, which would largely benefit future carbon-based electronics and optoelectronics.

Catalytic Growth of Ultralong Graphene Nanoribbons on Insulating Substrates.

Graphene nanoribbons (GNRs) with widths of a few nanometers are promising candidates for future nanoelectronic applications due to their structurally tunable bandgaps, ultrahigh carrier mobilities, and exceptional stability. However, the direct growth of micrometer-long GNRs on insulating substrates, which is essential for the fabrication of nanoelectronic devices, remains an immense challenge. Here, the epitaxial growth of GNRs on an insulating hexagonal boron nitride (h-BN) substrate through nanoparticle-catalyzed chemical vapor deposition is reported. Ultranarrow GNRs with lengths of up to 10 µm are synthesized. Remarkably, the as-grown GNRs are crystallographically aligned with the h-BN substrate, forming 1D moiré superlattices. Scanning tunneling microscopy reveals an average width of 2 nm and a typical bandgap of ≈1 eV for similar GNRs grown on conducting graphite substrates. Fully atomistic computational simulations support the experimental results and reveal a competition between the formation of GNRs and carbon nanotubes during the nucleation stage, and van der Waals sliding of the GNRs on the h-BN substrate throughout the growth stage. This study provides a scalable, single-step method for growing micrometer-long narrow GNRs on insulating substrates, thus opening a route to explore the performance of high-quality GNR devices and the fundamental physics of 1D moiré superlattices.

Block copolymer-assisted synthesis of monodisperse colloidal patchy nanoparticles.

Amphiphilic block copolymers are able to assemble into spherical micelles in an aqueous solution. Spherical micelles are expected to adsorb on the surface of colloidal nanoparticles (NPs) through hydrogen-bonding interaction. Hence, it should be possible to guide the area-selective deposition of precursors onto the exposed surface of colloidal seeds, where no micelles are adsorbed. Using colloidal silica and polydopamine nanospheres as seeds, block copolymer F127 and P123 are used as surface modifiers to guide the controlled solution-phase deposition of precursors on a selectively exposed surface of seed NPs, leading to the formation of patchy NPs. Effects of the addition amount of tetraethoxysilane (TEOS), types of block copolymers, and the volume fraction of miscible organic solvents on the size and morphology of patchy silica NPs are investigated systematically through electron microscopic imaging. Block copolymer micelles adsorption model for the formation of colloidal patchy NPs is first proposed. Our study suggests that the shape and size of patchy silica NPs are determined by the amount of TEOS and dielectric constant of solution.

Uniform cobalt nanoparticles embedded in hexagonal mesoporous nanoplates as a magnetically separable, recyclable adsorbent.

Novel hexagonal nanoplates (NPLs) comprised of mesoporous carbon containing imbedded magnetic Co nanoparticles (CoAl2O4 phase) are prepared through direct carbonization of polydopamine (PDA)-coated CoAl layered double hydroxide (LDH). A uniform PDA coating initially covers the surface of LDH by dopamine self-polymerization under mild conditions. Well-dispersed Co nanoparticles are formed in the NPLs by the partial reduction of cobalt from Co2+ to Co0 with surface carbon during the heat treatment process. The surface morphology and specific surface area of the as-prepared NPLs can be tailored by adjusting the initial dopamine concentration and carbonization temperature. The mesoporous NPLs exhibit excellent sorption of rhodamine B (RhB) dye and fast magnetic separation in aqueous solution. Over 95% of RhB can be adsorbed within 2 min and the adsorption reaches equilibrium after about 30 min. The maximum adsorption capacity approaches 172.41 mg/g. After regeneration, this adsorbent can be recycled easily by magnetic separation and still possess good adsorption capacity for RhB removal, even after five cycles.

Fabrication of nano copper oxide evenly patched on cubic sodium tantalate for oriented photocatalytic reduction of carbon dioxide.

A synthetic process was exploited to fabricate patchy CuO evenly planted on cubic NaTaO3 for photocatalytically reducing CO2 in isopropanol. The nano patches of CuO with about 15 nm in size were uniformly distributed on the surface of NaTaO3 via a phase-transfer protocol and solvothermal synthesis. The crystal phase, morphology, composition, optical absorption and charge separation of as-prepared CuO-NaTaO3 were characterized by XRD, SEM, TEM, EDX, XPS, UV-Vis and PL. The results of photocatalytic reduction of CO2 confirmed that the CuO patched NaTaO3 possessed better ability to separate charge carriers and selectively reduce CO2 to methanol than CuO directly loaded NaTaO3 using the traditional liquid phase reduction procedure after comparing the methanol yields. Furthermore, 5 wt% CuO patched NaTaO3 led to the highest methanol yield of 1302.22 µmol g-1 h-1. A redox mechanism was proposed and illustrated in a schematic diagram.