Nanogrooved carbon microtubes for wet three‐dimensional printing of conductive composite structures

Recent advances in three‐dimensional (3D) printing have enabled the fabrication of interesting structures which are not achievable using traditional fabrication approaches. The 3D printing of carbon microtube composite inks allows fabrication of conductive structures for practical applications in soft robotics and tissue engineering. However, it is challenging to achieve 3D printed structures from solution‐based composite inks, which requires an additional process to solidify the ink. Here, we introduce a wet 3D printing technique which uses a coagulation bath to fabricate carbon microtube composite structures. We show that through a facile nanogrooving approach which introduces cavitation and channels on carbon microtubes, enhanced interfacial interactions with a chitosan polymer matrix are achieved. Consequently, the mechanical properties of the 3D printed composites improve when nanogrooved carbon microtubes are used, compared to untreated microtubes. We show that by carefully controlling the coagulation bath, extrusion pressure, printing distance and printed line distance, we can 3D print composite lattices which are composed of well‐defined and separated printed lines. The conductive composite 3D structures with highly customised design presented in this work provide a suitable platform for applications ranging from soft robotics to smart tissue engineering scaffolds. © 2019 Society of Chemical Industry     

Carbon corrosion mechanism on nitrogen-doped carbon support — A density functional theory study

In this work, density functional theory (DFT) calculations were used to investigate the mechanism of carbon corrosion on nitrogen-doped carbon support. Free energy diagrams were generated based on three proposed reaction pathways to evaluate corrosion mechanisms. The most energetically preferred mechanism on nitrogen-doped carbon was determined. The results show that the step of water dissociation to form ^#OH was the rate-determining step for gra-G-1N (graphene doped with graphitic N) and pyrr-G-1N (graphene doped with pyrrolic N). As for graphene doped with pyridinic N, the step of C^#OC^#O formation was critical. It was found that the control of nitrogen concentration was necessary for precisely designing optimized carbon materials. Abundance of nitrogen moieties aggravated the carbon corrosion. When the high potential was applied, specific types of graphitic N and pyridinic N were found to be favorable carbon modifications to improve carbon corrosion resistance. Moreover, the solvent effect was also investigated. The results provide theoretical insights and design guidelines to improve corrosion resistance in carbon support through material modification by inhibiting the adsorption of surface oxides (OH, O, and OOH).     

Large domain-wall currents in epitaxial Au/BiFeO3/SrRuO3 thin-film capacitors with modulated oxygen vacancy and wall densities

Large domain wall (DW) conductivity in an insulating ferroelectric plays an important role in the future nanosensors and nonvolatile memories. However, the wall current was usually too small to drive high-speed memory circuits and other agile nanodevices requiring high output-powers. Here, a large domain-wall current of 67.8 μA in a high on/off ratio of ~4460 was observed in an epitaxial Au/BiFeO₃/SrRuO₃ thin-film capacitor with the minimized oxygen vacancy concentration. The studies from read current-write voltage hysteresis loops and piezo-response force microscope images consistently showed remaining of partially unswitched domains after application of an opposite poling voltage that increased domain wall density and wall current greatly. A theoretical model was proposed to explain the large wall current. According to this model, the domain reversal occurs with the appearance of head-to-head and tail-to-tail 180° domain walls (DWs), resulting in the formation of highly conductive wall paths. As the applied voltage increased, the domain-wall number increased to enhance the on-state current, in agreement with the measurements of current-voltage curves. This work paves a way to modulate DW currents within epitaxial Au/BiFeO₃/SrRuO₃ thin-film capacitors through the optimization of both oxygen vacancy and domain wall densities to achieve large output powers of modern domain-wall nanodevices.     

Centimeter-scale low-damage micromachining on single-crystal 4H–SiC substrates using a femtosecond laser with square-shaped Flat-Top focus spots

Femtosecond (fs) lasers have been proved to be reliable tools for high-precision and high-quality micromachining of ceramic materials. Nevertheless, fs laser processing using a single-mode beam with a Gaussian intensity distribution is difficult to obtain large-area flat and uniform processed surfaces. In this study, we utilize a customized diffractive optical element (DOE) to redistribute the laser pulse energy from Gaussian to square-shaped Flat-Top profile to realize centimeter-scale low-damage micromachining on single-crystal 4H–SiC substrates. We systematically investigated the effects of processing parameters on the changes in surface morphology and composition, and an optimal processing strategy was provided. Mechanisms of the formation of surface nanoparticles and the removal of surface micro-burrs were discussed. We also examined the distribution of subsurface defects caused by fs laser processing by removing a thin surface layer with a certain depth through chemical mechanical polishing (CMP). Our results show that laser-induced periodic surface structures (LIPSSs) covered by fine SiO₂ nanoparticles form on the fs laser-processed areas. Under optimal parameters, the redeposition of SiO₂ nanoparticles can be minimized, and the surface roughness Sa of processed areas reaches 120 ± 8 nm after the removal of a 10 μm thick surface layer. After the laser processing, micro-burrs on original surfaces are effectively removed, and thus the average profile roughness Rz of 2 mm long surface profiles decreases from 920 ± 120 nm to 286 ± 90 nm. No visible micro-pits can be found after removing ~1 μm thick surface layer from the laser-processed substrates.     

Targeting S1PRs as a Therapeutic Strategy for Inflammatory Bone Loss Diseases—Beyond Regulating S1P Signaling

As G protein coupled receptors, sphingosine-1-phosphate receptors (S1PRs) have recently gained attention for their role in modulating inflammatory bone loss diseases. Notably, in murine studies inhibiting S1PR2 by its specific inhibitor, JTE013, alleviated osteoporosis induced by RANKL and attenuated periodontal alveolar bone loss induced by oral bacterial inflammation. Treatment with a multiple S1PRs modulator, FTY720, also suppressed ovariectomy-induced osteoporosis, collagen or adjuvant-induced arthritis, and apical periodontitis in mice. However, most previous studies and reviews have focused mainly on how S1PRs manipulate S1P signaling pathways, subsequently affecting various diseases. In this review, we summarize the underlying mechanisms associated with JTE013 and FTY720 in modulating inflammatory cytokine release, cell chemotaxis, and osteoclastogenesis, subsequently influencing inflammatory bone loss diseases. Studies from our group and from other labs indicate that S1PRs not only control S1P signaling, they also regulate signaling pathways induced by other stimuli, including bacteria, lipopolysaccharide (LPS), bile acid, receptor activator of nuclear factor κB ligand (RANKL), IL-6, and vitamin D. JTE013 and FTY720 alleviate inflammatory bone loss by decreasing the production of inflammatory cytokines and chemokines, reducing chemotaxis of inflammatory cells from blood circulation to bone and soft tissues, and suppressing RANKL-induced osteoclast formation.     

锁紧机构防脱落保持架设计与分析

针对锁紧机构保持架在恶略环境下,反复振动过程中保持架上钢球脱落问题,提出了一种新型防脱落保持架设计方案,重点介绍了锁紧机构中保持架的工作形式,通过ANSYS进行有限元仿真分析,得出新型保持架结构满足刚强度要求以及热变形要求,且在随机振动6.06 g条件位移小,能有效免锁紧机构直线运动时钢球从外部脱落的可能,提高了锁紧机构工作过程中的可靠性与安全性.     

Ablative Radiotherapy Reprograms the Tumor Microenvironment of a Pancreatic Tumor in Favoring the Immune Checkpoint Blockade Therapy

The low overall survival rate of patients with pancreatic cancer has driven research to seek a new therapeutic protocol. Radiotherapy (RT) is frequently an option in the neoadjuvant or palliative settings for pancreatic cancer treatment. This study explored the effect of RT protocols on the tumor microenvironment (TME) and their consequent impact on anti-programmed cell death ligand-1 (PD-L1) therapy. Using a murine orthotopic pancreatic tumor model, UN-KC-6141, RT-disturbed TME was examined by immunohistochemical staining. The results showed that ablative RT is more effective than fractionated RT at recruiting T cells. On the other hand, fractionated RT induces more myeloid-derived suppressor cell infiltration than ablative RT. The RT-disturbed TME presents a higher perfusion rate per vessel. The increase in vessel perfusion is associated with a higher amount of anti-PD-L1 antibody being delivered to the tumor. Animal survival is increased by anti-PD-L1 therapy after ablative RT, with 67% of treated animals surviving more than 30 days after tumor inoculation compared to a median survival time of 16.5 days for the control group. Splenocytes isolated from surviving animals were specifically cytotoxic for UN-KC-6141 cells. We conclude that the ablative RT-induced TME is more suited than conventional RT-induced TME to combination therapy with immune checkpoint blockade.     

Reusable Polyacrylonitrile-Sulfur Extractor of Heavy Metal Ions from Wastewater

Mercury, lead, and cadmium are among the most toxic and carcinogenic heavy metal ions (HMIs), posing serious threats to the sustainability of aquatic ecosystems and public health. There is an urgent need to remove these ions from water by a cheap but green process. Traditional methods have insufficient removal efficiency and reusability. Structurally robust, large surface-area adsorbents functionalized with high-selectivity affinity to HMIs are attractive filter materials. Here, an adsorbent prepared by vulcanization of polyacrylonitrile (PAN), a nitrogen-rich polymer, is reported, giving rise to PAN-S nanoparticles with cyclic π-conjugated backbone and electronic conductivity. PAN-S can be coated on ultra-robust melamine (ML) foam by simple dipping and drying. In agreement with hard/soft acid/base theory, N- and S-containing soft Lewis bases have strong binding to Hg²⁺, Pb²⁺, Cu²⁺, and Cd²⁺, with extraordinary capture efficiency and performance stability. Furthermore, the used filters, when collected and electrochemically biased in a recycling bath, can release the HMIs into the bath and electrodeposit on the counter-electrode as metallic Hg⁰, Pb⁰, Cu⁰, and Cd⁰, and the PAN-S@ML filter can then be reused at least 6 times as new. The electronically conductive PAN-S@ML filter can be fabricated cheaply and holds promise for scale-up applications.     

Lithiation MXene Derivative Skeletons for Wide-Temperature Lithium Metal Anodes

Lithium (Li) metal, as an appealing candidate for the next-generation of high-energy-density batteries, is plagued by its safety issue mainly caused by uncontrolled dendrite growth and infinite volume expansion. Developing new materials that can improve the performance of Li-metal anode is one of the urgent tasks. Herein, a new MXene derivative containing pure rutile TiO₂ and N-doped carbon prepared by heat-treating MXene under a mixing gas, exhibiting high chemical activity in molten Li, is reported. The lithiation MXene derivative with a hybrid of LiTiO₂-Li₃N-C and Li offers outstanding electrochemical properties. The symmetrical cell assembling lithiation MXene derivative hybrid anode exhibits an ultra-long cycle lifespan of 2000 h with an overpotential of ≈30 mV at 1 mA cm⁻², which overwhelms Li-based anodes reported so far. Additionally, long-term operations of 34, 350, and 500 h at 10 mA cm⁻² can be achieved in symmetrical cells at temperatures of −10, 25, and 50 °C, respectively. Both experimental tests and density functional theory calculations confirm that the LiTiO₂-Li₃N-C skeleton serves as a promising host for Li infusion by alleviating volume variation. Simultaneously, the superlithiophilic interphase of Li₃N guides Li deposition along the LiTiO₂-Li₃N-C skeleton to avoid dendrite growth.     

Epitaxial Growth of 2D Materials on High-Index Substrate Surfaces

Recently, the successful synthesis of wafer-scale single-crystal graphene, hexagonal boron nitride (hBN), and MoS₂ on transition metal surfaces with step edges boosted the research interests in synthesizing wafer-scale 2D single crystals on high-index substrate surfaces. Here, using hBN growth on high-index Cu surfaces as an example, a systematic theoretical study to understand the epitaxial growth of 2D materials on various high-index surfaces is performed. It is revealed that hBN orientation on a high-index surface is highly dependent on the alignment of the step edges of the surface as well as the surface roughness. On an ideal high-index surface, well-aligned hBN islands can be easily achieved, whereas curved step edges on a rough surface can lead to the alignment of hBN along with different directions. This study shows that high-index surfaces with a large step density are robust for templating the epitaxial growth of 2D single crystals due to their large tolerance for surface roughness and provides a general guideline for the epitaxial growth of various 2D single crystals.