天然有机质对纳米碳管环境行为的影响研究进展

随着纳米技术的快速发展,大量的纳米碳管(CNTs)不可避免地释放到环境中。由于其较大的憎水性表面,CNTs与有机污染物和天然有机质(NOM)强烈地相互作用。综述了NOM存在下CNTs的环境行为,包括NOM对CNTs分散特性和吸附有机污染物特性的影响。着重论述了NOM的理化性质对CNTs分散的影响,"拉拉链"或"胶束包裹"是主要的分散机制。强调应该对不同分散机制下分散的CNTs与有机污染物的相互作用给予更多的关注,提出了目前在液相环境中直接测定CNTs表面积的新思路,并对今后的研究方向进行了展望。     

Ultrathin two-dimensional materials for photo- and electrocatalytic hydrogen evolution

Sustainable hydrogen production via photocatalytic, electrocatalytic, and synergetic photoelectrocatalytic processes has been regarded as an effective strategy to address both energy and environmental crises. Due to their unique structures and properties, emerging ultrathin two-dimensional (2D) materials can bring about promising opportunities to realize high-efficiency hydrogen evolution. This review presents a critical appraisal of advantages and advancements for ultrathin 2D materials in catalytic hydrogen evolution, with an emphasis on structure–activity relationship. Furthermore, strategies for tailoring the microstructure, electronic structure, and local atomic arrangement, so as to further boost the hydrogen evolution activity, are discussed. Finally, we also present the existing challenges and future research directions regarding this promising field.     

Nonlinearity of bituminous mixtures

This paper presents an experimental characterization of the strain dependency of the complex modulus of bituminous mixtures for strain amplitude levels lower than about \(110~\upmu\mbox{m}/\mbox{m}\). A series of strain amplitude sweep tests are performed at different temperatures (8, 10, 12 and 14°C) and frequencies (0.3, 1, 3 and 10 Hz), during which complex modulus is monitored. For each combination of temperature and frequency, four maximum strain amplitudes are targeted (50, 75, 100 and \(110~\upmu\mbox{m}/\mbox{m}\)). For each of them, two series of 50 loading cycles are applied, respectively at decreasing and increasing strain amplitudes. Before each decreasing strain sweep and after each increasing strain sweep, 5 cycles are performed at constant maximum targeted strain amplitude.Experimental results show that the behavior of the studied material is strain dependent. The norm of the complex modulus decreases and phase angle increases with strain amplitude. Results are presented in Black and Cole–Cole plots, where characteristic directions of nonlinearity can be identified. Both the effects of nonlinearity in terms of the complex modulus variation and of the direction of nonlinearity in Black space seem to validate the time–temperature superposition principle with the same shift factors as for linear viscoelasticity.The comparison between results obtained during increasing and decreasing strain sweeps suggests the existence of another phenomenon occurring during cyclic loading, which appears to systematically induce a decrease of the norm of the complex modulus and an increase of the phase angle, regardless of the type of the strain sweep (increasing or decreasing).     

Distinguishable Detection of Ultraviolet,Visible, and Infrared Spectrum with High‐Responsivity Perovskite‐Based Flexible Photosensors

Distinguishable detection of the ultraviolet, visible, and infrared spectrum is promising and significant for the super visual system of artificial intelligences. However, it is challenging to provide a photosensor with such broad spectral response ability. In this work, the ultraviolet, visible, and infrared spectrum is distinguished by developing serial photosensors based on perovskite/carbon nanotube hybrids. Oraganolead halide perovskites (CH₃NH₃PbX₃) possess remarkable optoelectronic properties and tunable optical band gaps by changing the halogens, and integration with single‐walled carbon nanotubes can further improve their photoresponsivities. The CH₃NH₃PbCl₃‐based photosensor shows a responsivity up to 10⁵ A W^?1 to ultraviolet and no obvious response to visible light, which is superior to that of most ultraviolet sensors. The CH₃NH₃PbBr₃‐based photosensor exhibits a high responsivity to visible light. Serial devices of the two hybrid photosensors with comparable electric and sensory performances can distinguish the spectrum of ultraviolet, visible, and infrared even with varying light intensities. The photosensors also demonstrate excellent mechanical flexibility and bending stability. By taking full advantages of the oraganolead halide perovskites, this work provides flexible high‐responsivity photosensors specialized for ultraviolet, and gives a simple strategy for distinguishable detection of ultraviolet, visible, and infrared spectrum based on the serial flexible photosensors.     

PD‐1 Blockade for Improving the Antitumor Efficiency of Polymer–Doxorubicin Nanoprodrug

Chemotherapy is well recognized to induce immune responses during some chemotherapeutic drugs‐mediated tumor eradication. Here, a strategy involving blocking programmed cell death protein 1 (PD‐1) to enhance the chemotherapeutic effect of a doxorubicin nanoprodrug HA‐Psi‐DOX is proposed and the synergetic mechanism between them is further studied. The nanoprodrugs are fabricated by conjugating doxorubicin (DOX) to an anionic polymer hyaluronic acid (HA) via a tumor overexpressed matrix metalloproteinase sensitive peptide (CPLGLAGG) for tumor targeting and enzyme‐activated drug release. Once accumulated at the tumor site, the nanoprodrug can be activated to release antitumor drug by tumor overexpressed MMP‐2. It is found that HA‐Psi‐DOX nanoparticles can kill tumor cells effectively and initiate an antitumor immune response, leading to the upregulation of interferon‐γ. This cytokine promotes the expression of programmed cell death protein‐ligand 1 (PD‐L1) on tumor cells, which will cause immunosuppression after interacting with PD‐1 on the surface of lymphocytes. The results suggest that the therapeutic efficiency of HA‐Psi‐DOX nanoparticles is significantly improved when combined with checkpoint inhibitors anti‐PD‐1 antibody (α‐PD1) due to the neutralization of immunosuppression by blocking the interaction between PD‐L1 and PD‐1. This therapeutic system by combining chemotherapy and immunotherapy further increases the link between conventional tumor therapies and immunotherapy.     

Large‐Stroke Electrochemical Carbon Nanotube/Graphene Hybrid Yarn Muscles

Artificial muscles are reported in which reduced graphene oxide (rGO) is trapped in the helical corridors of a carbon nanotube (CNT) yarn. When electrochemically driven in aqueous electrolytes, these coiled CNT/rGO yarn muscles can contract by 8.1%, which is over six times that of the previous results for CNT yarn muscles driven in an inorganic electrolyte (1.3%). They can contract to provide a final stress of over 14 MPa, which is about 40 times that of natural muscles. The hybrid yarn muscle shows a unique catch state, in which 95% of the contraction is retained for 1000 s following charging and subsequent disconnection from the power supply. Hence, they are unlike thermal muscles and natural muscles, which need to consume energy to maintain contraction. Additionally, these muscles can be reversibly cycled while lifting heavy loads.     

In Situ Chelating Synthesis of Hierarchical LiNi1/3Co1/3Mn1/3O2 Polyhedron Assemblies with Ultralong Cycle Life for Li‐Ion Batteries

Layered lithium transition‐metal oxides, with large capacity and high discharge platform, are promising cathode materials for Li‐ion batteries. However, their high‐rate cycling stability still remains a large challenge. Herein, hierarchical LiNi_1/3Co_1/3Mn_1/3O₂ polyhedron assemblies are obtained through in situ chelation of transition metal ions (Ni²⁺, Co²⁺, and Mn²⁺) with amide groups uniformly distributed along the backbone of modified polyacrylonitrile chains to achieve intimate mixing at the atomic level. The assemblies exhibit outstanding electrochemical performances: superior rate capability, high volumetric energy density, and especially ultralong high‐rate cyclability, due to the superiority of unique hierarchical structures. The polyhedrons with exposed active crystal facets provide more channels for Li⁺ diffusion, and meso/macropores serve as access shortcuts for fast migration of electrolytes, Li⁺ and electrons. The strategy proposed in this work can be extended to fabricate other mixed transition metal‐based materials for advanced batteries.     

Imparting Designer Biorecognition Functionality to Metal–Organic Frameworks by a DNA‐Mediated Surface Engineering Strategy

Surface functionality is an essential component for processing and application of metal–organic frameworks (MOFs). A simple and cost‐effective strategy for DNA‐mediated surface engineering of zirconium‐based nanoscale MOFs (NMOFs) is presented, capable of endowing them with specific molecular recognition properties and thus expanding their potential for applications in nanotechnology and biotechnology. It is shown that efficient immobilization of functional DNA on NMOFs can be achieved via surface coordination chemistry. With this strategy, it is demonstrated that such porphyrin‐based NMOFs can be modified with a DNA aptamer for targeting specific cancer cells. Furthermore, the DNA–NMOFs can facilitate the delivery of therapeutic DNA (e.g., CpG) into cells for efficient recognition of endosomal Toll‐like receptor 9 and subsequent enhanced immunostimulatory activity in vitro and in vivo. No apparent toxicity is observed with systemic delivery of the DNA–NMOFs in vivo. Overall, these results suggest that the strategy allows for surface functionalization of MOFs with different functional DNAs, extending the use of these materials to diverse applications in biosensor, bioimaging, and nanomedicine.     

Modulating the Surface State of SiC to Control Carrier Transport in Graphene/SiC

Silicon carbide (SiC) with epitaxial graphene (EG/SiC) shows a great potential in the applications of electronic and photoelectric devices. The performance of devices is primarily dependent on the interfacial heterojunction between graphene and SiC. Here, the band structure of the EG/SiC heterojunction is experimentally investigated by Kelvin probe force microscopy. The dependence of the barrier height at the EG/SiC heterojunction to the initial surface state of SiC is revealed. Both the barrier height and band bending tendency of the heterojunction can be modulated by controlling the surface state of SiC, leading to the tuned carrier transport behavior at the EG/SiC interface. The barrier height at the EG/SiC(000‐1) interface is almost ten times that of the EG/SiC(0001) interface. As a result, the amount of carrier transport at the EG/SiC(000‐1) interface is about ten times that of the EG/SiC(0001) interface. These results offer insights into the carrier transport behavior at the EG/SiC heterojunction by controlling the initial surface state of SiC, and this strategy can be extended in all devices with graphene as the top layer.     

Highly sensitive and rapidly responding room-temperature NO<Subscript>2</Subscript> gas sensors based on WO<Subscript>3</Subscript> nanorods/sulfonated graphene nanocomposites

Metal oxide/graphene nanocomposites are emerging as promising materials for developing room-temperature gas sensors. However, the unsatisfactory performances owing to the relatively low sensitivity, slow response, and recovery kinetics limit their applications. Herein, a highly sensitive and rapidly responding room-temperature NO₂ gas sensor based on WO₃ nanorods/sulfonated reduced graphene oxide (S-rGO) was prepared via a simple and cost-effective hydrothermal method. The optimal sensor response of the WO₃/S-rGO sensor toward 20 ppm NO₂ is 149% in 6 s, which is 4.7 times higher and 100 times faster than that of the corresponding WO₃/rGO sensors. In addition, the sensor exhibits excellent reproducibility, selectivity, and extremely fast recovery kinetics. The mechanism of the WO₃/S-rGO nanocomposite gas sensor is investigated in detail. In addition to the high transport capability of S-rGO as well as its excellent NO₂ adsorption ability, the superior sensing performance of the S-rGO/WO₃ sensor can be attributed to the favorable charge transfer occurring at the S-rGO/WO₃ interfaces. We believe that the strategy of compositing a metal oxide with functionalized graphene provides a new insight for the future development of room-temperature gas sensors.

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