Bevel-edge epitaxy of ferroelectric rhombohedral boron nitride single crystal.

Within the family of two-dimensional dielectrics, rhombohedral boron nitride (rBN) is considerably promising owing to having not only the superior properties of hexagonal boron nitride1-4-including low permittivity and dissipation, strong electrical insulation, good chemical stability, high thermal conductivity and atomic flatness without dangling bonds-but also useful optical nonlinearity and interfacial ferroelectricity originating from the broken in-plane and out-of-plane centrosymmetry5-23. However, the preparation of large-sized single-crystal rBN layers remains a challenge24-26, owing to the requisite unprecedented growth controls to coordinate the lattice orientation of each layer and the sliding vector of every interface. Here we report a facile methodology using bevel-edge epitaxy to prepare centimetre-sized single-crystal rBN layers with exact interlayer ABC stacking on a vicinal nickel surface. We realized successful accurate fabrication over a single-crystal nickel substrate with bunched step edges of the terrace facet (100) at the bevel facet (110), which simultaneously guided the consistent boron-nitrogen bond orientation in each BN layer and the rhombohedral stacking of BN layers via nucleation near each bevel facet. The pure rhombohedral phase of the as-grown BN layers was verified, and consequently showed robust, homogeneous and switchable ferroelectricity with a high Curie temperature. Our work provides an effective route for accurate stacking-controlled growth of single-crystal two-dimensional layers and presents a foundation for applicable multifunctional devices based on stacked two-dimensional materials.

Lithium Ion Intercalation-Induced Metal-Insulator Transition in Inclined-Standing Grown 2D Non-Layered Cr2S3 Nanosheets.

Gate-controlled ionic intercalation in the van der Waals gap of 2D layered materials can induce novel phases and unlock new properties. However, this strategy is often unsuitable for densely packed 2D non-layered materials. The non-layered rhombohedral Cr2S3 is an intrinsic heterodimensional superlattice with alternating layers of 2D CrS2 and 0D Cr1/3. Here an innovative chemical vapor deposition method is reported, utilizing strategically modified metal precursors to initiate entirely new seed layers, yields ultrathin inclined-standing grown 2D Cr2S3 nanosheets with edge instead of face contact with substrate surfaces, enabling rapid all-dry transfer to other substrates while ensuring high crystal quality. The unconventional ordered vacancy channels within the 0D Cr1/3 layers, as revealed by cross-sectional scanning transmission electron microscope, permitting the insertion of Li+ ions. An unprecedented metal-insulator transition, with a resistance modulation of up to six orders of magnitude at 300 K, is observed in Cr2S3-based ionic field-effect transistors. Theoretical calculations corroborate the metallization induced by Li-ion intercalation. This work sheds light on the understanding of growth mechanism, structure-property correlation and highlights the diverse potential applications of 2D non-layered Cr2S3 superlattice.

Neutrophil extracellular traps in central nervous system (CNS) diseases.

Excessive induction of inflammatory and immune responses is widely considered as one of vital factors contributing to the pathogenesis and progression of central nervous system (CNS) diseases. Neutrophils are well-studied members of inflammatory and immune cell family, contributing to the innate and adaptive immunity. Neutrophil-released neutrophil extracellular traps (NETs) play an important role in the regulation of various kinds of diseases, including CNS diseases. In this review, current knowledge on the biological features of NETs will be introduced. In addition, the role of NETs in several popular and well-studied CNS diseases including cerebral stroke, Alzheimer's disease, multiple sclerosis, amyotrophic lateral sclerosis (ALS), and neurological cancers will be described and discussed through the reviewing of previous related studies.

Achieving Reliable and Ultrafast Memristors via Artificial Filaments in Silk Fibroin.

The practical implementation of memristors in neuromorphic computing and biomimetic sensing suffers from unexpected temporal and spatial variations due to the stochastic formation and rupture of conductive filaments (CFs). Here, the biocompatible silk fibroin (SF) is patterned with an on-demand nanocone array by using thermal scanning probe lithography (t-SPL) to guide and confine the growth of CFs in the silver/SF/gold (Ag/SF/Au) memristor. Benefiting from the high fabrication controllability, cycle-to-cycle (temporal) standard deviation of the set voltage for the structured memristor is significantly reduced by ≈95.5% (from 1.535 to 0.0686 V) and the device-to-device (spatial) standard deviation is also reduced to 0.0648 V. Besides, the statistical relationship between the structural nanocone design and the resultant performance is confirmed, optimizing at the small operation voltage (≈0.5 V) and current (100 nA), ultrafast switching speed (sub-100 ns), large on/off ratio (104 ), and the smallest switching slope (SS < 0.01 mV dec-1 ). Finally, the short-term plasticity and leaky integrated-and-fire behavior are emulated, and a reliable thermal nociceptor system is demonstrated for practical neuromorphic applications.

Infinite Twisted Polycatenanes.

Poly[n]catenanes have exceptional mechanical bonding properties that give them tremendous potential for use in the development of molecular machines and soft materials. Synthesizing these compounds has, however, proven to be a formidable challenge. Herein, we describe a concise method for the construction of twisted polycatenanes. Our approach involves using preorganized double helicates as templates, linked crosswise in a linear fashion by either silver ions or triple bonds. By using this approach, we successfully synthesized twisted polycatenanes with both coordination and covalent bonding employing Ag(I) ions and ethynylene units, respectively, as the linkages and leveraging the same Ag(I)-templated double helicate in both cases. Synthesis with Ag(I) ions formed a single-crystalline one-dimensional (1D) coordination poly[n]catenane, and synthesis using ethynylene units generated 1D fibers which self-assembled with solvents to form a gel. Our results confirm the potential of multi-stranded metallohelicates for creating sophisticated mechanically interlocked molecules and polymers, which could pave the way for exploration in the realms of molecular nanotopology and materials design.

Achieving Ferroelectricity in a Centrosymmetric High-Performance Semiconductor by Strain Engineering.

Phase engineering by strain in 2D semiconductors is of great importance for a variety of applications. Here, a study of the strain-induced ferroelectric (FE) transition in bismuth oxyselenide (Bi2 O2 Se) films, a high-performance (HP) semiconductor for next-generation electronics, is presented. Bi2 O2 Se is not FE at ambient pressure. At a loading force of ≳400 nN, the piezoelectric force responses exhibit butterfly loops in magnitude and 180° phase switching. By carefully ruling out extrinsic factors, these features are attributed to a transition to the FE phase. The transition is further supported by the appearance of a sharp peak in optical second-harmonic generation under uniaxial strain. In general, solids with paraelectrics at ambient pressure and FE under strain are rare. The FE transition is discussed using first-principles calculations and theoretical simulations. The switching of FE polarization acts as a knob for Schottky barrier engineering at contacts and serves as the basis for a memristor with a huge on/off current ratio of 106 . This work adds a new degree of freedom to HP electronic/optoelectronic semiconductors, and the integration of FE and HP semiconductivity paves the way for many exciting functionalities, including HP neuromorphic computing and bulk piezophotovoltaics.

Post-Processing Trimming of Silicon Photonic Devices Using Femtosecond Laser.

Fabrication errors inevitably occur in device manufacturing owing to the limited processing accuracy of commercial silicon photonic processes. For silicon photonic devices, which are mostly processing-sensitive, their performances usually deteriorate significantly. This remains an unsolved issue for mass production, particularly for passive devices, because they cannot be adjusted once fixed in processes. This study presents a post-processing trimming method to compensate for fabrication errors by changing the cladding equivalent refractive indices of devices with femtosecond lasers. The experimental results show that the resonant wavelengths of micro-ring resonators can be regularly shifted within their free spectral range via tuning the illuminating area, focusing position, emitting power, and scanning speed of the trimming femtosecond laser with an acceptable loss increase. These experiments, as well as the trimming experiments in improving the phase balance of Mach-Zehnder interferometer switches, indicate that the femtosecond laser trimming method is an effective and fast method for silicon photonic devices.

Customizing 2.5D Out-of-Plane Architectures for Robust Plasmonic Bound-States-in-the-Continuum Metasurfaces.

Bound states in the continuum (BICs) have a superior ability to confine electromagnetic waves and enhance light-matter interactions. However, the quality-factor of quasi-BIC is extremely sensitive to structural perturbations, thus the BIC metasurfaces usually require a very-high precision nanofabrication technique that greatly restricts their practical applications. Here, distinctive 2.5D out-of-plane architectures based plasmonic symmetry protected (SP)-BIC metasurfaces are proposed, which could deliver robust quality factors even with large structural perturbations. The high-throughput fabrication of such SP-BIC metasurfaces is realized by using the binary-pore anodic aluminum oxide template technique. Moreover, the deep neural network (DNN) is adapted to conduct multiparameter fittings, where the 2.5D hetero-out-of-plane architectures with robust high quality-factors and figures of merit are rapidly predicted and fabricated. Finally, owning to its large second-order surface sensitivity, the desired 2.5D hetero-out-of-plane architecture demonstrates a detection limit of endotoxin as low as 0.01 EU mL-1 , showing a good perspective of biosensors and others.

Graphene Metamaterial 3D Conformal Coating for Enhanced Light Harvesting.

Silicon (Si) photovoltaic devices present possible avenues for overcoming global energy and environmental challenges. The high reflection and surface recombination losses caused by the Si interface and its nanofabrication process are the main hurdles for pursuing a high energy conversion efficiency. However, recent advances have demonstrated great success in improving device performance via proper Si interface modification with the optical and electrical features of two-dimensional (2D) materials. Firmly integrating large-area 2D materials with 3D Si nanostructures with no gap in between, which is essential for optimizing device performance, has rarely been achieved by any technique due to the complex 3D morphology of the nanostructures. Here we propose the concept of a 3D conformal coating of graphene metamaterials, in which the 2D graphene layers perfectly adapt to the 3D Si curvatures, leading to a universal 20% optical reflection decrease and a 60% surface passivation improvement. In a further application of this metamaterial 3D conformal coating methodology to standard Si solar cells, an overall 23% enhancement of the solar energy conversion efficiency is achieved. The 3D conformal coating strategy could be readily extended to various optoelectronic and semiconductor device systems with peculiar performance, offering a pathway for highly efficient energy-harvesting and storage solutions.

NLRP3 Inflammasome in Atherosclerosis: Putting Out the Fire of Inflammation.

Atherosclerosis (AS) is a chronic inflammatory disease with thickening or hardening of the arteries, which led to the built-up of plaques in the inner lining of an artery. Among all the clarified pathogenesis, the over-activation of inflammatory reaction is one of the most acknowledged one. The nucleotide-binding domain leucine-rich repeat (NLR) and pyrin domain containing receptor 3 (NLRP3) inflammasome, as a vital and special form of inflammation and innate immunity, has been widely revealed to participate in the onset and development of AS. This review will introduce the process of the pathogenesis and progression of AS, and will describe the biological features of the NLRP3 inflammasome. Furthermore, the role of the NLRP3 inflammasome in AS and the possible mechanisms will be discussed. In addition, several kinds of agents with the effect of anti-atherosclerotic taking advantage of the NLRP3 inflammasome intervention will be described and discussed in detail, including natural compounds (baicalin, dihydromyricetin, luteolin, 5-deoxy-rutaecarpine (R3) and Salvianolic acid A, etc.), microRNAs (microRNA-30c-5p, microRNA-9, microRNA-146a-5p, microRNA-16-5p and microRNA-181a, etc.), and autophagy regulators (melatonin, dietary PUFA and arglabin, etc.). We aim to provide novel insights in the exploration of the specific mechanisms of AS and the development of new treatments of AS.

Spatial defects nanoengineering for bipolar conductivity in MoS2.

Understanding the atomistic origin of defects in two-dimensional transition metal dichalcogenides, their impact on the electronic properties, and how to control them is critical for future electronics and optoelectronics. Here, we demonstrate the integration of thermochemical scanning probe lithography (tc-SPL) with a flow-through reactive gas cell to achieve nanoscale control of defects in monolayer MoS2. The tc-SPL produced defects can present either p- or n-type doping on demand, depending on the used gasses, allowing the realization of field effect transistors, and p-n junctions with precise sub-µm spatial control, and a rectification ratio of over 104. Doping and defects formation are elucidated by means of X-Ray photoelectron spectroscopy, scanning transmission electron microscopy, and density functional theory. We find that p-type doping in HCl/H2O atmosphere is related to the rearrangement of sulfur atoms, and the formation of protruding covalent S-S bonds on the surface. Alternatively, local heating MoS2 in N2 produces n-character.

Free-standing graphene oxide mid-infrared polarizers.

Mid-infrared (MIR) represents a crucial spectral region for applications in spectroscopy, sensing, imaging, security and industry screening, owing to the strong characteristic vibrational transitions of many important molecules. However, the current MIR compatible materials are fragile, hazardous, and costly, which hampers the performance of MIR devices. Here, we developed a versatile transmittance-based Kramers-Kronig method and obtained the optical properties of graphene oxide in the MIR region, unveiling its application potentials as a novel MIR compatible material. As an example, we demonstrated free-standing graphene oxide MIR polarizers with large extinction ratio (∼20 dB) and controllable working wavelength up to 25 µm, by using the low-cost and flexible direct laser writing technique. Our transmittance-based KK method offers a versatile approach to obtain the optical properties of novel atomic-scale low-dimensional materials in the less developed MIR region and opens up opportunities in high performing functional MIR devices.

Sub-10 nm Resolution Patterning of Pockets for Enzyme Immobilization with Independent Density and Quasi-3D Topography Control.

The ability to precisely control the localization of enzymes on a surface is critical for several applications including biosensing, bionanoreactors, and single molecule studies. Despite recent advances, fabrication of enzyme patterns with resolution at the single enzyme level is limited by the lack of lithography methods that combine high resolution, compatibility with soft, polymeric structures, ease of fabrication, and high throughput. Here, a method to generate enzyme nanopatterns (using thermolysin as a model system) on a polymer surface is demonstrated using thermochemical scanning probe lithography (tc-SPL). Electrostatic immobilization of negatively charged sulfonated enzymes occurs selectively at positively charged amine nanopatterns produced by thermal deprotection of amines along the side-chain of a methacrylate-based copolymer film via tc-SPL. This process occurs simultaneously with local thermal quasi-3D topographical patterning of the same polymer, offering lateral sub-10 nm resolution, and vertical 1 nm resolution, as well as high throughput (5.2 × 104 µm2/h). The obtained single-enzyme resolution patterns are characterized by atomic force microscopy (AFM) and fluorescence microscopy. The enzyme density, the surface passivation, and the quasi-3D arbitrary geometry of these patterned pockets are directly controlled during the tc-SPL process in a single step without the need of markers or masks. Other unique features of this patterning approach include the combined single-enzyme resolution over mm2 areas and the possibility of fabricating enzymes nanogradients.

Resilient Graphene Ultrathin Flat Lens in Aerospace, Chemical, and Biological Harsh Environments.

The development of ultrathin flat lenses has revolutionized the lens technologies and holds great promise for miniaturizing the conventional lens system in integrated photonic applications. In certain applications, the lenses are required to operate in harsh and/or extreme environments, for example aerospace, chemical, and biological environments. Under such circumstances, it is critical that the ultrathin flat lenses can be resilient and preserve their outstanding performance. However, the majority of the demonstrated ultrathin flat lenses are based on metal or semiconductor materials that have poor chemical, thermal, and UV stability, which limit their applications. Herein, we experimentally demonstrate a graphene ultrathin flat lens that can be applied in harsh environments for different applications, including a low Earth orbit space environment, strong corrosive chemical environments (pH = 0 and pH = 14), and biochemical environment. The graphene lenses have extraordinary environmental stability and can maintain a high level of structural integrity and outstanding focusing performance under different test conditions. Thus, it opens tremendous practical application opportunities for ultrathin flat lenses.

Supramolecular platinum(ii) complexes with highly efficient monomer luminescence.

A new platinum(ii) complex containing a quaternary ammonium group was synthesized. The monomer and excimer emission of the complex could be tuned via the solvophobic effect, which was accompanied by transformation from a fiber to ribbon-like morphology.

Dynamic Photochemical and Optoelectronic Control of Photonic Fano Resonances via Monolayer MoS2 Trions.

Active tunability of photonic resonances is of great interest for various applications such as optical switching and modulation based on optoelectronic materials. Manipulation of charged excitons in atomically thin transition metal dichalcogenides (TMDCs) like monolayer MoS2 offers an unexplored route for diverse functionalities in optoelectronic nanodevices. Here, we experimentally demonstrate the dynamic photochemical and optoelectronic control of the photonic crystal Fano resonances by optical and electrical tuning of monolayer MoS2 refractive index via trions without any chemical treatment. The strong spatial and spectral overlap between the photonic Fano mode and the active MoS2 monolayer enables efficient modulation of the Fano resonance. Our approach offers new directions for potential applications in the development of optical modulators based on emerging 2D direct band gap semiconductors.

Observation of Third-order Nonlinearities in Graphene Oxide Film at Telecommunication Wavelengths.

All-optical switches have been considered as a promising solution to overcome the fundamental speed limit of the current electronic switches. However, the lack of a suitable third-order nonlinear material greatly hinders the development of this technology. Here we report the observation of ultrahigh third-order nonlinearity about 0.45 cm2/GW in graphene oxide thin films at the telecommunication wavelength region, which is four orders of magnitude higher than that of single crystalline silicon. Besides, graphene oxide is water soluble and thus easy to process due to the existence of oxygen containing groups. These unique properties can potentially significantly advance the performance of all-optical switches.

Highly efficient and ultra-broadband graphene oxide ultrathin lenses with three-dimensional subwavelength focusing.

Nanometric flat lenses with three-dimensional subwavelength focusing are indispensable in miniaturized optical systems. However, they are fundamentally challenging to achieve because of the difficulties in accurately controlling the optical wavefront by a film with nanometric thickness. Based on the unique and giant refractive index and absorption modulations of the sprayable graphene oxide thin film during its laser reduction process, we demonstrate a graphene oxide ultrathin (∼200 nm) flat lens that shows far-field three-dimensional subwavelength focusing (λ(3)/5) with an absolute focusing efficiency of >32% for a broad wavelength range from 400 to 1,500 nm. Our flexible graphene oxide lenses are mechanically robust and maintain excellent focusing properties under high stress. The simple and scalable fabrication approach enables wide potential applications in on-chip nanophotonics. The wavefront shaping concept opens up new avenues for easily accessible, highly precise and efficient optical beam manipulations with a flexible and integratable planar graphene oxide ultrathin film.

A frozen matrix hybrid optical nonlinear system enhanced by a particle lens.

In this work, a Graphene Oxide (GO) nano-sheet and SiO2 micro-bead hybrid system based on a frozen matrix was investigated for its enhanced optical nonlinear performance. A frozen matrix is a novel approach that hosts the optical nonlinear nano-particles, which combines the strengths from both liquid and solid phase systems for high performance photonic applications. SiO2 micro-beads were used to induce a local field enhancement effect that improved the optical nonlinearity of GO nano-sheets. The nonlinear performance of the hybrid system is several orders higher than the existing GO nano-sheet liquid dispersion. In addition, this frozen matrix and the local field enhancement effect are two facile and versatile methods that can be applied to many types of nano-particle dispersions.

Remarkable luminescence enhancement of chloroplatinum(II) complexes of hexaethylene glycol methyl ether substituted 2,6-bis(benzimidazol-2'-yl)pyridine in water triggered by PF6⁻.

Three chloroplatinum(II) complexes of 2,6-bis(benzimidazol-2'-yl)pyridine bearing hexaethylene glycol methyl ether are almost nonemissive in dilute aqueous solutions. Upon addition of excessive hexafluorophosphate salts to their dilute aqueous solutions, one of them was found to show a remarkable luminescence enhancement.