Overcoming Electrostatic Interaction via Pulsed Electroreduction for Boosting the Electrocatalytic Urea Synthesis.

Electrocatalytic urea synthesis under ambient conditions offers a promising alternative strategy to the traditional energy-intensive urea industry protocol. Limited by the electrostatic interaction, the reduction reaction of anions at the cathode in the electrocatalytic system is not easily achievable. Here, we propose a novel strategy to overcome electrostatic interaction via pulsed electroreduction. We found that the reconstruction-resistant CuSiOx nanotube, with abundant atomic Cu-O-Si interfacial sites, exhibits ultrastability in the electrosynthesis of urea from nitrate and CO2. Under a pulsed potential approach with optimal operating conditions, the Cu-O-Si interfaces achieve a superior urea production rate (1606.1 µg h-1 mgcat. -1) with high selectivity (79.01 %) and stability (the Faradaic efficiency is retained at 80 % even after 80 h of testing), outperforming most reported electrocatalytic synthesis urea catalysts. We believe our strategy will incite further investigation into pulsed electroreduction increasing substrate transport, which may guide the design of ambient urea electrosynthesis and other energy conversion systems.

Constructing an ultrastable imidazole covalent organic framework for concurrent uranium detection and recovery.

Uranium is one of the most important strategic resources for the development of the nuclear industry, but its unintended release has created potential environmental and health risks. It is highly desired to explore new methods that enable concurrent uranium monitoring and recovery for environmental protection and sustainable development of the nuclear industry. Here, for the first time, an imidazole fluorescent covalent organic framework (named PyTT-Tp) with ultrastable skeleton and open nanopore channel is synthesized by condensing ammonium acetate, 1,3,5-triformylphloroglucinol and pyrene-4,5,9,10-tetrone. By precisely tailoring complexing ligands, PyTT-Tp shows an excellent uranium recovery capacity of 941.27 mg g-1 and reached equilibrium within 60 min, which can be attributed to dense selective uranium binding sites on the highly accessible open skeleton. In addition, due to the signal amplification of the pyrene-imidazole skeleton, it has an ultra-low detection limit of 4.92 nM UO22+ and an ultra-fast response time (2 s) suitable for on-site monitoring the uranium content of the extracted water. By modulating target complexing ligands, this approach can be extended to the monitoring and recovery of other strategic nuclides.

Chiral graphene plasmonic Archimedes' spiral nanostructure with tunable circular dichroism and enhanced sensing performance.

Circular dichroism spectroscopy is frequently used to characterize the chiral biomolecules by measuring the absorption spectra contrast between the left-handed circularly polarized light and the right-handed circularly polarized light. Compared with biomolecules, chiral metal plasmonic nanostructures also produce a strong circular dichroism response in the range of near-infrared. However, due to the large damping rate, the non-adjustable resonant frequency of the conventional metals, the applications of chiral metal plasmonic nanostructures in the fields of photoelectric detection and chemical and biochemical sensing are restricted. Here, we present a chiral graphene plasmonic Archimedes' spiral nanostructure that displays a significant circular dichroism response under the excitation of two polarizations of circularly polarized light. By manipulating the material and geometric parameters of the Archimedes' spiral, the stronger circular dichroism responses and modulation of the resonant wavelength are achieved. The optimized plasmonic nanostructure has outstanding refractive index sensing performance, where the sensitivity and figure of merit reach 7000nm/RIU and 68.75, respectively. Our proposed chiral graphene plasmonic Archimedes' spiral nanostructure might find potential applications in the fields of optical detection and high performance of index sensing.

Amorphous/Crystalline Hetero-Phase TiO2 -Coated α-Fe2 O3 Core-Shell Nanospindles: A High-Performance Artificial Nitrogen Fixation Electrocatalyst.

Electrochemical nitrogen fixation techniques have emerged as a promisingly sustainable approach to face the challenge associated with nitrogen activation of ammonia synthesis by the Haber-Bosch process under ambient conditions. Herein, the performance of electrocatalytic nitrogen reduction for the production of α-Fe2 O3 nanospindles coated with mesoporous TiO2 with different crystallinity [denoted as α-Fe2 O3 @mTiO2 -X (X=300, 400, and 500 °C)] were investigated. The as-prepared α-Fe2 O3 @mTiO2 -400 composite exhibits a large NH3 yield (27.2 µg h-1 mgcat. -1 ) at -0. 5 V vs. the reversible hydrogen electrode and a high Faradaic efficiency (13.3 %) in 0.1 m Na2 SO4 , with excellent electrochemical durability. This work presents a novel avenue for the rational design of efficient unique hetero-phase nanocatalysts toward sustainable electrocatalytic N2 fixation.

Dynamic tailoring of electromagnetic behaviors of graphene plasmonic oligomers by local chemical potential.

In the mid-infrared and terahertz (THz) regime, graphene supports tunable surface plasmon resonance (SPR) by controlling the chemical potential, which promotes light-matter interaction at the selected wavelength, showing exceptional promise for optoelectronic applications. In this article, we show that the electromagnetic (EM) response of graphene oligomers can be substantially modified by the modification of the local chemical potential, strengthening or reducing the intrinsic plasmonic modes. The effect mechanism is corroborated by a graphene nanocluster composed of 13 nanodisks with D6h symmetry; by transforming to D3h symmetry, the effect mechanism was retained and more available plasmonic resonance modes appeared. The intriguing properties open a new way to design nanodevices made of graphene oligomers with highly efficient photoresponse enhancement and tunable spectral selectivity for highly accurate photodetection.

Modeling the ponderomotive interaction of high-power laser beams with collisional plasma: the FDTD-based approach.

The ponderomotive interaction of high-power laser beams with collisional plasma is modeled in the nonrelativistic regime and is simulated using the powerful finite-difference time-domain (FDTD) method for the first time in literature. The nonlinear and dissipative dielectric constant function of the collisional plasma is deduced that takes the ponderomotive effect into account and is implemented in the discrete framework of FDTD algorithms. Maclaurin series expansion approach is applied for implementing the obtained physical model and the time average of the square of light field is extracted by numerically evaluating an integral identity based on the composite trapezoidal rule for numerical integration. Two numerical examples corresponding to two different types of laser beams, Gaussian beam and vortex Laguerre-Gaussian beam, propagating in collisional plasma, are presented for specified laser and plasma parameters to verify the validity of the proposed FDTD-based approach. Simulation results show the anticipated self-focusing and attenuation phenomena of laser beams and the deformation of the spatial density distributions of electron plasma along the beam propagation path. Due to the flexibility of FDTD method in light beam excitation and accurate complex material modeling, the proposed approach has a wide application prospect in the study of the complex laser-plasma interactions in a small scale.

Topologically protected edge states in graphene plasmonic crystals.

A two-dimensional graphene plasmonic crystal composed of periodically arranged graphene nanodisks is proposed. We show that the band topology effect due to inversion symmetry broken in the proposed plasmonic crystals is obtained by tuning the chemical potential of graphene nanodisks. Utilizing this kind of plasmonic crystal, we constructed N-shaped channels and realized topologically edged transmission within the band gap. Furthermore, topologically protected exterior boundary propagation, which is immune to backscattering, was also achieved by modifying the chemical potential of graphene nanodisks. The proposed graphene plasmonic crystals with ultracompact size are subject only to intrinsic material loss, which may find potential applications in the fields of topological plasmonics and high density nanophotonic integrated systems.

Electromagnetic field coupling characteristics in graphene plasmonic oligomers: from isolated to collective modes.

In this paper, we propose a plasmonic tetramer composed of coupled graphene nanodisks. The transformation from the isolated to the collective modes of the proposed structure is investigated by analysing the whispering-gallery modes and extinction spectra with various inter-nanodisk gap distances. In addition, the effect of introducing a central nanodisk into the tetramer on the extinction spectra is explored, which leads to Fano resonance. Furthermore, the refractive index sensing properties of the proposed graphene plasmonic oligomer have been demonstrated. The proposed nanostructures might pave the road toward the application of graphene plasmonic oligomers in fields such as nanophotonics, and chemical or biochemical sensing.

Lanthanide Coordination Polymer Nanoparticles as an Excellent Artificial Peroxidase for Hydrogen Peroxide Detection.

Lanthanide coordination polymer nanoparticles (Ln-CPNs) have been recently demonstrated as excellent platforms for biomolecule detection. In this work, we synthesized novel cerium coordination polymer nanoparticles ATP-Ce-Tris CPNs in a simple and quick way using ATP molecules as the biocompatible ligands to Ce(3+) ions in tris(hydroxymethyl)aminomethane hydrochloric (Tris-HCl) solution. In view of the excellent free radical scavenging property of cerium compounds, which is ascribed to the mixed valence state (Ce(3+), Ce(4+)) and the reversible switch from Ce(3+) to Ce(4+), the synthesized ATP-Ce-Tris CPNs was used as artificial peroxidase to selectively and sensitively detect H2O2. The sensing mechanism depends on the oxidation of the fluorescent ATP-Ce(III)-Tris CPNs to nonfluorescent ATP-Ce(IV)-Tris CPNs by H2O2. Compared with those inorganic cerium oxide sensors, this kind of fluoresence ATP-Ce-Tris CPNs sensor needs no additional organic redox dye, such as ABTS (2,20-azino-bis(3-ethylbenzthiazoline-6-sulfonic acid), TMB (3,3,5,5-tetramethylbenzidine), or fluorescein as signal molecules. Moreover, such ATP-Ce-Tris CPNs sensor exhibited a more sensitive response to H2O2 with a detection limit down to 0.6 nM, which is 2 orders of magnitude lower than those of cerium oxide sensors. This sensing platform was further extended to the detection of glucose in combination with the specific catalytic effect of glucose oxidase (GOx) for the oxidation of glucose and formation of H2O2.

Surface-plasmon-polariton whispering-gallery mode analysis of the graphene monolayer coated InGaAs nanowire cavity.

In this article, we proposed and numerically studied the surface plasmon polariton whispering gallery mode properties of the graphene coated InGaAs nanowire cavity. The quality factor and the mode area were investigated as a function of the chemical potential, the cavity radius and the wavelength. A high cavity quality factor of 235 is predicted for a 5 nm radius cavity, accompanied by a mode area as small as3.75×10(-5)(λ(0))(2), when the chemical potential is 1.2 eV. The proposed structure offers a potential solution to high density integration of the nanophotonic devices with an ultra-compact footprint.

Investigation of plasmonic whispering-gallery mode characteristics for graphene monolayer coated dielectric nanodisks.

In this Letter, we theoretically studied high-quality (Q) factor plasmonic whispering-gallery modes (WGMs) with ultrasmall mode volumes in graphene monolayer coated semiconductor nanodisks in the mid-infrared range. The influence of the chemical potential, the relaxation time of graphene, and the radius of the nanodisk on the cavity Q factor and the mode volume was numerically investigated. The numerical simulations showed that the plasmonic WGMs excited in this cavity had a deep subwavelength mode volume of 1.4×10(-5)(λ(0)/2n)(3), a cavity Q factor as high as 266 at a temperature lower than 250 K, and, consequently, a large Purcell factor of ∼1.2×10(7) when the chemical potential and relaxation time were assumed to be 0.9 eV and 1.4 ps, respectively. The results provide a possible application of plasmonic WGMs in the integration of nano-optoelectronic devices based on graphene.

The long non-coding RNA BDNF-AS induces neuronal cell apoptosis by targeting miR-125b-5p in Alzheimer's disease models.

BACKGROUND: At least 55 million individuals suffer from dementia globally, of which Alzheimer's disease (AD) accounts for 60-70% of cases. Alzheimer's disease is the only major cause of death that is still growing. However, the molecular mechanisms are largely unknown in the progress of AD. OBJECTIVES: The goal of the study was to assess whether lncRNA brain-derived neurotrophic factor antisense (BDNF-AS) could affect processes underlying the regulation of neuronal cell apoptosis in rat and cellular models of AD by directing the expression of miR-125b-5p. MATERIAL AND METHODS: The amyloid-ß (Aß)1-42-induced rat and cellular models of AD were established. Changes in learning and memory in rats were detected with the use of the Morris water maze. Cell viability and apoptosis were determined using the 3-(4,5-dimethylthiazol-2-yl)-2,5 diphenyl tetrazolium bromide (MTT) test and flow cytometry. Reverse transcription-quantitative polymerase chain reaction (RT-qPCR) was applied to detect the expression of lncRNA BDNF-AS and miR-125b-5p, and western blotting was utilized to examine proteins. The correlations between lncRNA BDNF-AS and miR-125b-5p were demonstrated using dual-luciferase reporter gene assays. RESULTS: Our results showed that BDNF-AS was upregulated and miR-125b-5p was downregulated in the rat and cellular AD models. The addition of si-BDNF-AS and miR-125b-5p mimics shortened the escape latency and swimming distance in the rat model. Furthermore, the knockdown of BDNF-AS or the administration of miR-125b-5p mimic significantly suppressed cell apoptosis, cell inflammatory, and inflammatory pathway-related proteins, while these cellular activities were promoted in rat and cellular models of AD. Additionally, miR-125b-5p was found to be a BDNF-AS target gene that was linked negatively with BDNF-AS in AD. CONCLUSIONS: Through regulation of miR-125b-5p, lncRNA BDNF-AS suppressed cell death, inflammation and inflammatory pathway-related proteins in AD models, which provides a potential biomarker and therapeutic target in the clinical treatment of AD.

Olefin-linked cationic covalent organic frameworks for efficient extraction of ReO4-/99TcO4.

Efficient extraction of radioactive 99TcO4- from strong acid/base solutions by porous adsorbents is extremely desirable but remains a great challenge. To overcome the challenge, here we report the first example of an olefin-linked cationic covalent organic framework (COF) named BDBI-TMT with excellent acid, base and radiation stability is synthesized by integrating robust imidazolium salt-based linkers with triazine building blocks. BDBI-TMT shows an ultra-fast adsorption kinetics (equilibrium is reached within 1 min) and an excellent ReO4- (a non-radioactive surrogate of 99TcO4-) capture capacity of 726 mg g-1, which can be attributed to the abundance of precisely tailored imidazolium salt-based units on the highly accessible pore walls of the ordered pore channels. Furthermore, the formation of the highly conjugated bulky alkyl skeleton enhances the hydrophobicity of BDBI-TMT, which significantly improves not only the affinity toward ReO4-/99TcO4- but also the chemical stability, allowing selective and reversible extraction of ReO4-/99TcO4- even under extreme conditions. This work demonstrates the great potential of olefin-linked cationic COFs for ReO4-/99TcO4- extraction, providing a new avenue to construct high-performance porous adsorbents for radionuclide remediation.

Nano-crumples induced Sn-Bi bimetallic interface pattern with moderate electron bank for highly efficient CO2 electroreduction.

CO2 electroreduction reaction offers an attractive approach to global carbon neutrality. Industrial CO2 electrolysis towards formate requires stepped-up current densities, which is limited by the difficulty of precisely reconciling the competing intermediates (COOH* and HCOO*). Herein, nano-crumples induced Sn-Bi bimetallic interface-rich materials are in situ designed by tailored electrodeposition under CO2 electrolysis conditions, significantly expediting formate production. Compared with Sn-Bi bulk alloy and pure Sn, this Sn-Bi interface pattern delivers optimum upshift of Sn p-band center, accordingly the moderate valence electron depletion, which leads to weakened Sn-C hybridization of competing COOH* and suitable Sn-O hybridization of HCOO*. Superior partial current density up to 140 mA/cm2 for formate is achieved. High Faradaic efficiency (>90%) is maintained at a wide potential window with a durability of 160 h. In this work, we elevate the interface design of highly active and stable materials for efficient CO2 electroreduction.

Group Velocity Modulation and Light Field Focusing of the Edge States in Chirped Valley Graphene Plasmonic Metamaterials.

The valley degree of freedom, like the spin degree of freedom in spintronics, is regarded as a new information carrier, promoting the emerging valley photonics. Although there exist topologically protected valley edge states which are immune to optical backscattering caused by defects and sharp edges at the inverse valley Hall phase interfaces composed of ordinary optical dielectric materials, the dispersion and the frequency range of the edge states cannot be tuned once the geometrical parameters of the materials are determined. In this paper, we propose a chirped valley graphene plasmonic metamaterial waveguide composed of the valley graphene plasmonic metamaterials (VGPMs) with regularly varying chemical potentials while keeping the geometrical parameters constant. Due to the excellent tunability of graphene, the proposed waveguide supports group velocity modulation and zero group velocity of the edge states, where the light field of different frequencies focuses at different specific locations. The proposed structures may find significant applications in the fields of slow light, micro-nano-optics, topological plasmonics, and on-chip light manipulation.

"Fast" Plasmons Propagating in Graphene Plasmonic Waveguides with Negative Index Metamaterial Claddings.

We propose the monolayer graphene plasmonic waveguide (MGPW), which is composed of graphene core sandwiched by two graphene metamaterial (GMM) claddings and investigate the properties of plasmonic modes propagating in the waveguide. The effective refraction index of the GMMs claddings takes negative (or positive) at the vicinity of the Dirac-like point in the band structure. We show that when the effective refraction index of the GMMs is positive, the plasmons travel forward in the MGPW with a positive group velocity (vg > 0, vp > 0). In contrast-for the negative refraction index GMM claddings-a negative group velocity of the fundamental mode (vg < 0, vp > 0) appears in the proposed waveguide structure when the core is sufficiently narrow. A forbidden band appears between the negative and positive group velocity regions, which is enhanced gradually as the width of the core increases. On the other hand, one can overcome this limitation and even make the forbidden band disappear by increasing the chemical potential difference between the nanodisks and the ambient graphene of the GMM claddings. The proposed structure offers a novel scheme of on-chip electromagnetic field and may find significant applications in the future high density plasmonic integrated circuit technique.

Multiple Fano Resonances with Tunable Electromagnetic Properties in Graphene Plasmonic Metamolecules.

Multiple Fano resonances (FRs) can be produced by destroying the symmetry of structure or adding additional nanoparticles without changing the spatial symmetry, which has been proved in noble metal structures. However, due to the disadvantages of low modulation depth, large damping rate, and broadband spectral responses, many resonance applications are limited. In this research paper, we propose a graphene plasmonic metamolecule (PMM) by adding an additional 12 nanodiscs around a graphene heptamer, where two Fano resonance modes with different wavelengths are observed in the extinction spectrum. The competition between the two FRs as well as the modulation depth of each FR is investigated by varying the materials and the geometrical parameters of the nanostructure. A simple trimer model, which emulates the radical distribution of the PMM, is employed to understand the electromagnetic field behaviors during the variation of the parameters. Our proposed graphene nanostructures might find significant applications in the fields of single molecule detection, chemical or biochemical sensing, and nanoantenna.

Mo-Doped FeP Nanospheres for Artificial Nitrogen Fixation.

Electrochemical conversion of N2 to NH3 under ambient conditions is a promising and environmentally friendly route compared with the CO2-emitting and energy-intensive Haber-Bosch process. Nevertheless, due to ultrahigh stability of N2, it is urgent to explore efficient catalysts to weaken and activate the N≡N bond. Here, we report the Mo-doped iron phosphide (Mo-FeP) nanosphere as a valid transition-metal-based catalyst for electrochemical N2-to-NH3 fixation under ambient conditions. This catalyst exhibits excellent catalytic performance with a NH4+ yield rate (13.1 µg h-1 mg-1) and Faradaic efficiency (7.49%) at -0.3 and -0.2 V vs reversible hydrogen electrode (RHE), respectively. However, the FeP catalyst without doped Mo species displays weak catalytic performance. We found that the better catalytic performance of Mo-FeP might be due to the doping of Mo species, which is favorable for the polarization of adsorbed N2 molecules, making the N≡N bond more viable to dissociate.

WITHDRAWN: MicroRNA-125b can Target p38MAPK to Resolve Intermittent Hypoxia- Induced Dementia in Murine Models

The article entitled, "MicroRNA-125b can Target p38MAPK to Resolve Intermittent Hypoxia-Induced Dementia in Murine Models" submitted in Current Neurovascular Research (CNR) by Dr. Xu Chen has been withdrawn from the journal in accordance with BSP Editorial Policies.

Potential contribution of microRNA-125b targeting p38MAPK to relieving intermittent hypoxia-induced dementia of rat models.

Allowing for the correlation between intermittent hypoxia and impaired cognition, we intended to figure out whether and how dementia-relevant biomolecules (e.g. miR-125b and p38MAPK) might participate in weakening of intelligence in the context of intermittent hypoxia. Within this investigation, four groups of rat models were established, including rats treated with none, 10% continuous hypoxic (CH), 10% chronic intermittent hypoxia (CIH) and 5% chronic intermittent hypoxia (CIH). Moreover, the learning, memorizing and cognitive abilities of rats were evaluated through performing morris water maze, spatial navigation test and spatial probe test, respectively. Furthermore, expressions of miR-125b and p38MAPK were determined based on reverse transcription-polymerase chain reaction (RT-PCR) or western blotting. And the luciferase reporter gene assay was prepared to validate the targeted relationship between miR-125b and p38MAPK. Consequently, our study results showed that intermittent hypoxia generated more serious cognitive impairment to rats than persistent hypoxia (P < 0.05), and the rats treated with intermittent hypoxia were observed with down-regulated miR-125b expression and up-regulated phospho-p38MAPK expression (P < 0.05). Furthermore, the in-vitro tests exhibited that down-regulated expression of miR-125b and phosphorylation of p38MAPK could promote apoptosis of SH-SY5Y cells, and also depress their viability and proliferation (P < 0.05). The luciferase reporter gene assay also validated a targeted relationship between miR-125b and p38MAPK in SH-SY5Y cells. In conclusion, miR-125b targeting p38MAPK might be involved with modifying learning, memorizing and cognitive abilities of rats that were managed with intermittent hypoxia, which might provide theoretical basis for treating intermittent hypoxia-related dementia.