Graphite-like Charge Storage Mechanism in a 2D π-d Conjugated Metal-Organic Framework Revealed by Stepwise Magnetic Monitoring.

Quasi-two-dimensional (2D) fully π-d conjugated metal-organic frameworks (MOFs) have been widely employed as active materials of secondary batteries; however, the origin of their high charge storage capacity is still unknown. Some reports have proposed a mechanism by assuming the formation of multiple radicals on one organic ligand, although there is no firm evidence for such a mechanism, which would run counter to the resonance theory. In this work, we utilized various magnetometric techniques to monitor the formation and concentration of paramagnetic species during the electrochemical process of 2D π-d conjugated Cu-THQ MOF (THQ = tetrahydroxy-1,4-benzoquinone). The spin concentration of the fully reduced (discharged 1.5 V) electrode was estimated to be around only 0.1 spin-1/2 per CuO4 unit, which is much lower than that of the expected "diradical" form. More interestingly, a significant elevation of the temperature-independent paramagnetic term was simultaneously observed, which indicates the presence of delocalized π electrons in this discharged state. Such results were corroborated by first-principles density functional theory calculations and the electrochemically active density of states, which reveal the microscopic mechanism of the charge storage in the Cu-THQ MOF. Hence, a graphite-like charge storage mechanism, where the π-electron band accepts/donates electrons during the charge/discharge process, was suggested to explain the excessive charge storage of Cu-THQ. This graphite-like charge storage mechanism revealed by magnetic studies can be readily generalized to other π-d conjugated MOFs.

Direct photo-oxidation of methane to methanol over a mono-iron hydroxyl site.

Natural gas, consisting mainly of methane (CH4), has a relatively low energy density at ambient conditions (~36 kJ l-1). Partial oxidation of CH4 to methanol (CH3OH) lifts the energy density to ~17 MJ l-1 and drives the production of numerous chemicals. In nature, this is achieved by methane monooxygenase with di-iron sites, which is extremely challenging to mimic in artificial systems due to the high dissociation energy of the C-H bond in CH4 (439 kJ mol-1) and facile over-oxidation of CH3OH to CO and CO2. Here we report the direct photo-oxidation of CH4 over mono-iron hydroxyl sites immobilized within a metal-organic framework, PMOF-RuFe(OH). Under ambient and flow conditions in the presence of H2O and O2, CH4 is converted to CH3OH with 100% selectivity and a time yield of 8.81 ± 0.34 mmol gcat-1 h-1 (versus 5.05 mmol gcat-1 h-1 for methane monooxygenase). By using operando spectroscopic and modelling techniques, we find that confined mono-iron hydroxyl sites bind CH4 by forming an [Fe-OH···CH4] intermediate, thus lowering the barrier for C-H bond activation. The confinement of mono-iron hydroxyl sites in a porous matrix demonstrates a strategy for C-H bond activation in CH4 to drive the direct photosynthesis of CH3OH.

Magnetic field caused enhanced absorption and circular dichroism of an achiral plasmonic nanostructure.

In this paper, modulation of light-matter interactions by a magnetic field is used to generate circular dichroism (CD) from an achiral plasmonic nanostructure. Theoretical investigations show an increase in light absorption by the nanostructure in the presence of a magnetic field. The achiral nanostructure exhibits CD in external magnetic field parallel to circularly polarized light (CPL) incidence. The CD emergence is caused by modulation of electron motion to reduced/enhanced frequencies under CPL incidence. Compared to previous studies, in this paper the mechanism of CD emergence, and the physical reasoning behind the change in CD due to change in magnetic field direction and intensity, are explained. CD intensity increases with increasing magnetic field intensity, while CD sign changes on magnetic field direction reversal. Varying structural parameters significantly influences CD intensity. This study can be helpful in magneto-optics and in magneto-chiral applications.

Characterization of the Difference between Day and Night Temperatures on the Growth, Photosynthesis, and Metabolite Accumulation of Tea Seedlings.

Currently, the effects of the differences between day and night temperatures (DIFs) on tea plant are poorly understood. In order to investigate the influence of DIFs on the growth, photosynthesis, and metabolite accumulation of tea plants, the plants were cultivated under 5 °C (25/20 °C, light/dark), 10 °C (25/15 °C, light/dark), and 15 °C (25/10 °C, light/dark). The results showed that the growth rate of the new shoots decreased with an increase in the DIFs. There was a downward trend in the photosynthesis among the treatments, as evidenced by the lowest net photosynthetic rate and total chlorophyll at a DIF of 15 °C. In addition, the DIFs significantly affected the primary and secondary metabolites. In particular, the 10 °C DIF treatment contained the lowest levels of soluble sugars, tea polyphenols, and catechins but was abundant in caffeine and amino acids, along with high expression levels of theanine synthetase (TS3) and glutamate synthase (GOGAT). Furthermore, the transcriptome data revealed that the differentially expressed genes were enriched in valine, leucine, and isoleucine degradation, flavone/flavonol biosyntheses, flavonoid biosynthesis, etc. Therefore, we concluded that a DIF of 10 °C was suitable for the protected cultivation of tea plants in terms of the growth and the quality of a favorable flavor of tea, which provided a scientific basis for the protected cultivation of tea seedlings.

Enhanced circular dichroism of cantilevered nanostructures by distorted plasmon.

Chiral structures have a wide range of applications, such as biometric identification, chemical analysis, and chiral sensing. The simple fabrication process of chiral nanostructures that can produce a significant circular dichroism (CD) effect remains a challenge. Here, a three-dimensional (3D) cantilever-shaped nanostructure, which inherits the chiral advantages of 3D nanostructures and simplicity of 2D nanostructures, is proposed. The nanostructure can be prepared by the combination of one-time electron beam lithography and oblique-angle deposition and consists of a thin metal film with periodic holes such that two hanging arms were attached to the edges of holes. The length of the cantilever and the height difference between the two arms can be adjusted by controlling the tilt angle of beam current during the deposition processes. Numerical calculations showed that the enhancement of CD signal was achieved by plasmon distortion on the metal film by the lower hanging part of the cantilever structure. Furthermore, signals can be actively adjusted using a temperature-sensitive polydimethylsiloxane (PDMS) material. The angle between the lower cantilever and the top metal film was regulated by the change in PDMS volume with temperature. The results provide a new way to fabricating 3D nanostructures and a new mechanism to enhance the CD signal. The proposed nanostructure may have potential applications, such as in ultra-sensitive detection and remote temperature readout, and is expected to be an ultra-compact detection tool for nanoscale structural and functional information.

In PICU acute kidney injury stage 3 or mortality is associated with early excretion of urinary renin.

BACKGROUND: Urinary renin is proposed to be a novel prognostic biomarker of acute kidney injury (AKI) in adults. The intention of our study was to evaluate the early predictive value of urinary renin for AKI and pediatric intensive care unit (PICU) mortality in critically ill children. METHODS: The first available urine sample during the first 24 h after admission was collected upon PICU admission for the measurement of renin using ELISA. Urinary renin concentrations were corrected for urinary creatinine (urinary renin-to-creatinine ratio, uRenCR). AKI was defined based on KDIGO criteria. RESULTS: Of the 207 children, 22 developed AKI, including 6 with stage 1, 6 with stage 2, and 10 with stage 3, and 14 died during PICU stay. There was a significant difference in uRenCR between non-AKI children and those with AKI stage 3 (P = 0.001), but not with AKI stage 1 or 2. The uRenCR remained associated with AKI stage 3 and PICU mortality after adjustment for potential confounders. The area under the receiver operating characteristic curve of uRenCR for discrimination of AKI stage 3 was 0.805, and PICU mortality was 0.801. CONCLUSIONS: Urinary renin was associated with the increased risk for AKI stage 3 and PICU mortality in critically ill children. IMPACT: Urinary renin is proposed to be a novel prognostic biomarker of AKI in adult patients. There are some differences between children and adults in physiological and pathophysiological characteristics. This study demonstrated that urinary renin was associated with the increased risk for AKI stage 3 and PICU mortality in critically ill children. Accurate identification of patients with severe renal injury or at high risk for mortality early in the disease course could augment the efficacy of available interventions and improve patient outcomes.

A Review of Vision-Laser-Based Civil Infrastructure Inspection and Monitoring.

Structural health and construction security are important problems in civil engineering. Regular infrastructure inspection and monitoring methods are mostly performed manually. Early automatic structural health monitoring techniques were mostly based on contact sensors, which usually are difficult to maintain in complex infrastructure environments. Therefore, non-contact infrastructure inspection and monitoring techniques received increasing interest in recent years, and they are widely used in all aspects of infrastructure life, owing to their convenience and non-destructive properties. This paper provides an overview of vision-based inspection and vision-laser-based monitoring techniques and applications. The inspection part includes image-processing algorithms, object detection, and semantic segmentation. In particular, infrastructure monitoring involves not only visual technologies but also different fusion methods of vision and lasers. Furthermore, the most important challenges for future automatic non-contact inspections and monitoring are discussed and the paper correspondingly concludes with state-of-the-art algorithms and applications to resolve these challenges.

Dynamically adjustable-induced THz circular dichroism and biosensing application of symmetric silicon-graphene-metal composite nanostructures.

Induced circular dichroism (ICD) has been used to detect biomolecular conformations through the coupling between chiral molecules and achiral metal nanostructures with the localized surface plasmon (LSP). However, this ICD is always weak and cannot be dynamically adjusted. Here, we put dielectric and graphene nanostructures on a metal-substrate for restricting more light energies and obtaining dynamic adjustable performance. A composite nanostructure array composed of achiral silicon-nanorods on a metal-substrate and graphene-ribbons (ASMG) is theoretically investigated. Two strong ICD signals appear in the THz region. Near-field magnetic distributions of ASMG reveal that the two strong ICD signals are mainly due to the surface plasmon resonances (SPPs) on the metal-substrate and LSP in the graphene nanostructures, respectively. The ICD signals strongly depend on the geometric parameters of ASMG and are dynamically adjusted by just changing the Fermi levels of graphene-ribbons. In addition, left-handed ASMG and right-handed ASMG can be used to identify the chiral molecular solutions with different chiralities. The maximum enhancement factor of the chiral molecular solutions could reach up to 3500 times in the THz region. These results can help to design dynamically adjustable THz chiral sensors and promote their application in biological monitoring and asymmetric catalysis.

Enhanced circular dichroism of plasmonic chiral system due to indirect coupling of two unaligned nanorods with metal film.

Circular dichroism (CD) demonstrates broad application prospects in enantioselective catalysis, chiral separation, and ultrasensitive detection. Increasing the CD intensity of easily fabricated plasmonic nanostructures will promote the application of these artificial nanostructures. A chiral plasmonic system that consists of two unaligned nanorods and a metal film is proposed in this study to achieve a large CD effect. Indirect coupling of a nanorod-film-nanorod in the proposed chiral plasmonic system generates a larger CD intensity compared to the direct coupling of a nanorod-nanorod. In addition, the effects of structural parameters on the CD effect of the proposed system are numerically investigated. Results showed that the indirect coupling is strongly dependent on the separation between the nanorod and the metal film. The results of this study can provide an effective strategy to enhance the CD effect of plasmonic chiral systems.

Quantum Spin Liquid State in a Two-Dimensional Semiconductive Metal-Organic Framework.

Two-dimensional metal-organic frameworks (2D MOFs) have attracted much attention, as they are the crystalline materials that exhibit both conductivity and microporosity. Numerous efforts have been made to advance their application as chemiresistive sensors or electrochemical capacitors. However, the intrinsic physical properties and spin states of these materials remain poorly understood. Most of these 2D MOFs possess a honeycomb lattice, with a Kagomé lattice arrangement of metal cations. These structural characteristics suggest that these MOFs would be candidates for geometrically frustrated spin systems with unprecedented magnetic phenomena. Herein, by performing magnetic susceptibility and specific heat measurements at an ultralow temperature down to 38mK on a 2D semiconductive MOF, Cu3(HHTP)2, a quantum spin liquid state that arises from the geometrical frustration was suggested. This result illustrates the potential of strongly correlated MOFs as systems with emergent phenomena induced by unusual structural topologies.

Increasing the circular dichroism of the planar chiral nanostructure by inducing coupling between the coverage layer and the planar nanostructure.

Circular dichroism (CD) has been widely studied in recent decades because of its wide application in biomedical detection. Nanostructures with different heights (NDH) usually increase the transmission CD effect. To achieve such nanostructures, one needs to repeatedly perform the electron-beam lithography (EBL) method twice or more, layer-by-layer, which is a very complicated process. Here, we propose a method to prepare NDH by combining the EBL and oblique angle deposition (OAD) techniques. L-shaped planar silver nanostructures are prepared using EBL and normal electron beam deposition, and the OAD method is then used to partially cover one arm of the L-shaped nanostructure. Numerical simulations reveal that the height difference in the two arms of the L-shaped NDH (LSNDH) causes a difference in the polarization directions of the left- (LCP) and right-circularly polarized (RCP) incident light, thereby, generating CD effects. A 2D material is used to cover the LSNDH to further increase the charge polarization direction differences, which considerably increases the CD effect. These results are useful in simplifying and increasing the convenience of the preparation method of 3D chiral nanostructures. Furthermore, the proposed nanostructure may have potential application in biosensor, such as chiral enantiomer sensors.

Predicting Retrosynthetic Reactions Using Self-Corrected Transformer Neural Networks.

Synthesis planning is the process of recursively decomposing target molecules into available precursors. Computer-aided retrosynthesis can potentially assist chemists in designing synthetic routes; however, at present, it is cumbersome and cannot provide satisfactory results. In this study, we have developed a template-free self-corrected retrosynthesis predictor (SCROP) to predict retrosynthesis using transformer neural networks. In the method, the retrosynthesis planning was converted to a machine translation problem from the products to molecular linear notations of the reactants. By coupling with a neural network-based syntax corrector, our method achieved an accuracy of 59.0% on a standard benchmark data set, which outperformed other deep learning methods by >21% and template-based methods by >6%. More importantly, our method was 1.7 times more accurate than other state-of-the-art methods for compounds not appearing in the training set.

Circular dichroism of spatially complementary chiral nanostructures.

Circular dichroism (CD) is widely used in biology, medicine, and physics. Three-dimensional (3D) chiral structures have been extensively studied because of their ability to produce significant CD effects. Previously reported 3D chiral structures are limited due to the complexity of fabrication processes and CD mechanisms. Here, spatially complementary chiral nanostructure (SCCN) arrays, which comprise bottom silver films with zigzag-shaped nanoslit and top complementary silver zigzag-shaped nanowires, are theoretically and experimentally shown to provide the CD effect. SCCN arrays are prepared experimentally by combining electron beam lithography (EBL) with normal electron beam deposition (NEBD) method and by utilizing EBL and NEBD only once. Numerical results demonstrate that localized surface plasmon excited on top complementary silver zigzag-shaped nanowires and surface plasmon polariton excited on bottom silver films with zigzag-shaped nanoslit result in the CD effect of SCCN arrays. In addition, the CD effect can be tuned by changing the width of the top complementary silver zigzag-shaped nanowires. Such type of chiral nanostructures has easy tunability, simple fabrication, and a better understanding of chiral optical response, which provides a new design for spatially chiral optoelectronic devices.

Giant circular dichroism of chiral L-shaped nanostructure coupled with achiral nanorod: anomalous behavior of multipolar and dipolar resonant modes.

Chirality, which has long been known as an intrinsic property of living organisms, has caught the interest of researchers due to the rapid emergence of chiral metamaterials. The chiroptical response of noble metal nanostructures in visible and near-infrared regions has been widely investigated. Herein, we propose a bilayer Ag metastructure, in which a chiral L-shaped nanostructure at the bottom is coupled with an achiral nanorod acquiring different positions in the top layer with respect to the long and/or short arm of the chiral L-shaped nanostructure at the bottom layer. The metastructure generates a giant circular dichroism (CD) signal resulting from the strong coupling of the multipolar and dipolar resonant modes on the two layers, in the visible and near-infrared regions. With changing the position of the achiral nanorod, an unusual reversal of the CD spectra is observed, along with a fourfold increase in CD intensity in the short wavelength range due to the multipolar resonant modes. The position of the achiral nanorod is tailored by the azimuthal angle of the substrate during the fabrication of the metastructure using the oblique angle deposition method. This study provides insights into the variation of the coupling strength between a chiral L-shaped nanostructure and an achiral nanorod. The results can be useful in designing chiral-achiral composite nanoantennas for sensing devices.

A Bioinspired, Highly Transparent Surface with Dry-Style Antifogging, Antifrosting, Antifouling, and Moisture Self-Cleaning Properties.

Transparent coatings with antireflection, antifogging, antifrosting, antifouling, and moisture self-cleaning properties can dramatically improve the efficiency and convenience of optical elements and thus are highly desirable for practical applications. Here, it is demonstrated that a bionic nanocone surface (BNS) fabricated by a facile, low-cost process consisting of template-assisted prepolymer curing followed by surface modification can possess the multiple functions listed above. The polymer coating firmly adheres to a glass substrate due to bonding agents. After SiO2 nanoparticle deposition and low-surface-energy fluorosilane modification, the coating shows low microdroplet adhesion. As a result, the as-prepared BNS exhibits a high transmittance when exposed to fog and good clarity even when the temperature decreases to -20 °C in a humid environment. Dipping the BNS into exemplified graphite powder has almost no influence on the transparency, and the BNS can realize self-cleaning of moisture when the surface is covered with a thick layer of man-made contaminants.

Chiral response of a metasurface composed of nanoholes and tilted nanorods.

Circular dichroism (CD) of metasurfaces has been used in biological monitoring, analytical chemistry, and perfect polarization converters. In this work, a metasurface consisting of nanoholes and tilted nanorods is proposed to achieve the CD effect. Numerical calculations show that electrical current forms between the film and the tilted nanorods under circularly polarized light illumination, and CD effects originate from the coupling between the current oscillations at the film and those on the tilted nanorods. This electrical oscillation mode provides unique coupling mechanisms for the CD effect. In addition, CD is strongly dependent on the structural parameters, and the resonant modes can be tuned by modulating the currents on the film. These results are helpful for designing novel chiral optical structures and provide unique methods for circular polarizers.

Enhanced circular dichroism of tilted zigzag-shaped nanohole arrays.

Circular dichroism (CD) of nanostructures is in great demand for applications in biological molecules, photocurrent devices, and photocatalysis. Planar nanostructures can be prepared in a concise manner, and their CD effects have gained much research interest. In this study, tilted zigzag-shaped nanohole (TZSN) arrays are proposed, and the CD effect is studied by the finite element method. A strong resonance occurs in the gap by tuning the charge distributions between adjacent nanoholes. Meanwhile, the CD effect of TZSN arrays is strongly dependent on the structural parameters of TZSN. Results provide a novel method for tuning the CD effects of nanohole arrays on a film.

Exploration of Li-Organic Batteries Using Hexaphyrin as an Active Cathode Material.

Lithium-collaborating organic batteries (Li-[28]hexs) were investigated with [28]hexaphyrin(1.1.1.1.1.1) as an active electrode material. Each hexaphyrin of [28]Hex cathode ideally involved four electrons per unit cycle and performed a typical charge/discharge processes of Li-organic battery. Li-[28]Hex batteries set with fast charging rates showed reasonably stable charge and discharge performances over 200 cycles even though it caused incomplete (2~3 electrons) charge/discharge cycles due to failing the complete charging process. UV absorption changes of [28]hexaphyrin in CH2Cl2 were supplementary for the electrochemical oxidation, which performed a conversion from [28]hexaphyrin to [26]hexaphyrin.

Tunable asymmetric transmission through tilted rectangular nanohole arrays in a square lattice.

Asymmetric transmission (AT) holds significant applications in controlling polarization and propagation directions of electromagnetic waves. In this paper, tilted rectangular nanohole (TRNH) arrays in a square lattice are proposed to realize an AT effect. Numerical results show two AT modes in the transmission spectrum, and they are ascribed to the localized surface plasmon resonances around the two ends of TRNH and surface plasmon polaritons on the golden film. AT properties of the TRNH strongly depend on structural parameters, such as width, length, thickness, and tilted angle of TRNH. Results provide a novel mechanism for generating AT effect and offer potential plasmonic device applications, such as asymmetric wave splitters and optical isolators.