In Situ Synthesis of Copper-Based Metal-Organic Frameworks with Ligand Defects for Electrochemical Reduction of CO2 into C2 Products.

Electrochemical reduction of CO2 into high-value-added products is a potential approach to solving environmental problems but is limited by poor product selectivity and low efficiency. Metal-organic framework (MOF) materials have been considered one of the most promising catalysts, but their application is limited by complicated preparation processes, especially during the synthesis of organic ligands. In this work, a new three-dimensional Cu-MOF (JXUST-301) with high porosity was constructed based on the naphthalene diimide (NDI) ligand. Furthermore, JXUST-301 with ligand defects (JXUST-301D) originating from the missing NDI unit was synthesized via an in situ reaction. The presence of ligand defects endows JXUST-301D with a better CO2RR performance with a FEC2 of 56.7% and a jC2 of -162.4 mA cm-2. Mechanistic studies revealed that the hierarchical pore structure and amino sites are created from the absence of the NDI unit, which promotes the exposure of catalytically active sites and CO2 enrichment. Furthermore, the electronic structure of the Cu sites is modulated to upshift the d-band center, facilitating chemical adsorption and activation of key reaction intermediates. This work provides new insight into the in situ preparation of efficient Cu-MOF catalysts by introducing defects for the CO2RR.

A Simple-Structured Perovskite Wavelength Sensor for Full-Color Imaging Application.

In this study, simple-structured wavelength sensors were developed by depositing two back-to-back Au/MAPbI3/Au photodetectors on an MAPbI3 single crystal. This sensor could quantitatively distinguish wavelengths. Further device analysis showed that both photodetectors possess entirely disparate optoelectronic properties. Consequently, the as-developed wavelength sensor could accurately distinguish incident-light wavelengths ranging from 265 to 860 nm with a resolution of less than 1.5 nm based on the relation between the photocurrent ratios of both photodetectors and the incident light wavelengths. Notably, a high resolution and wide detection range are among the optimum reported values for such sensors and enable full-color imaging. Furthermore, technology computer-aided design (TCAD) simulations showed that a mechanism involved in distinguishing wavelengths is attributed to the wavelength-dependent photon generation rate in MAPbI3 single crystals. The high-performance MAPbI3 wavelength sensor can potentially drive the research progress of perovskites in wavelength recognition and full-color imaging.

Origin of plasmonic Fano resonance in metal-hole/split-ring-resonator metamaterials disclosed by temporal coupled-mode theory.

In plasmonic Fano resonance, the interaction between a discrete plasmonic mode and a continuum of plasmonic mode gives rise to an asymmetric line shape in the scattering or absorption spectrum, enabling a wide range of applications such as sensing, switching, and slow light devices. Here, we establish a theoretical solution in the framework of temporal coupled-mode theory (TCMT) to study the three-dimensional (3D) and two-dimensional (2D) Fano resonances induced by strong coupling between metal hole (MH) and split ring resonator (SRR) array. We first separately analyze the transmission spectra of the MH array and SRR array under different polarized light excitation. We further investigate the electromagnetic field and charge density distribution corresponding to the resonant modes at the peak or valley wavelength of the transmission spectrum and figure out the electric/magnetic dipole feature of these resonance modes. We then establish a theoretical solution by TCMT for Fano resonances arising from the coupling of these modes. The calculated transmission spectrum is closely matching with the numerically simulated transmission spectrum for these Fano resonances in the MH-SRR array, which effectively elucidates that the asymmetry of the Fano resonances is caused by the coupling between bright and dark plasmonic modes involved in the two structures. Our results can help to understand the profound physics in such coupled plasmonic systems.

Tunable topological slow-light in gyromagnetic photonic crystal waveguides with unified magnetic field.

We have proposed a tunable topological slow-light in a photonic crystal (PC) waveguide with unified magnetic field. The waveguide is constructed by bringing close two gyromagnetic photonic crystals (GPCs) with different structural parameters and introducing a row of Al2O3 rods as the coupling layer. The two GPCs are applied with a unified external static magnetic field (ESMF) instead of two opposite ESMFs. Such waveguide supports a slow-light state originated from the coupling effect of two one-way edge states on both sides of the waveguide. By simply changing the strength of ESMF, one can achieve a tunable slow-light state with large normalized delay-bandwidth product (NDBP) (0.36< NDBP <0.84). Based on these excellent properties, we further design an optical delayer with a compact structure and expansibility simultaneously. This unique topological slow-light state with simple unified magnetic condition, high maneuverability and strong immunity to defects holds promise for many fields such as signal processing, optical modulation, and the design of various slow-light devices.

Analytical solution to electromagnetic wave transport in planar magneto-optical waveguide: modal dispersion, coupling, and nonreciprocal flow.

The magneto-optical (MO) materials are essential for designing nonreciprocal devices, like isolators and circulators. Even though the study of MO effect has a long history, the recent works of fabricating nonreciprocal nanostructures, novel MO metamaterials, and topological photonics have garnered significant attention in both theoretical and experimental research of MO materials. In this work, we consider the planar MO waveguide mode. By setting the general form of the fields and utilizing the boundary conditions, the analytical solution of MO modes is obtained. We have shown the potential of such effective solution in analyzing the dispersions and transport behaviors of MO modes in the waveguide. Crossings and avoided crossings of modes will happen, which may due to the strong coupling of TE and TM modes in the waveguide. Faraday rotation can be observed during the propagation of MO modes and the energy flow will precess in the waveguide. These results can be applied in predicting the evolution of the modes in MO waveguides, which has potential in designing MO nonreciprocal devices.

Light transport through a magneto-optical medium: simple theory revealing fruitful phenomena.

Electromagnetic wave transmission in a magneto-optical (MO) medium is a basic and old topic but has raised new interest in recent years, because MO medium plays a vital role in optical isolator, topological optics, electromagnetic field regulation, microwave engineering, and many other technological applications. Here, we describe several fascinating physical images and classical physical variables in MO medium by using a simple and rigorous electromagnetic field solution approach. We can easily obtain explicit formulations for all relevant physical quantities, such as the electromagnetic field distribution, energy flux, reflection/transmission phase, reflection/transmission coefficients, and Goos-Hänchen (GH) shift in MO medium. This theory can help to deepen and broaden our physical understanding of basic electromagnetics, optics, and electrodynamics in application to gyromagnetic and MO homogeneous medium and microstructures, and might help to disclose and develop new ways and routes to high technologies in optics and microwave.

Mode conversion and separation in magneto-optical photonic crystal waveguide.

We present mode conversion in different magneto-optical photonic crystal (MOPC) waveguides. An odd-mode waveguide (OMW) and an even-mode waveguide (EMW) are designed by adjusting the geometric parameters of the waveguide. These waveguides are constructed by adding a layer of yttrium-iron-garnet (YIG) rods with opposing magnetic fields between an MOPC and an Al2O3 photonic crystal (PC). Due to the coupling effect caused by the middle layer of YIG rods, the OMW (or EMW) only supports an odd (or even) mode within a single-mode frequency range. Simulation results demonstrate that they can convert other modes into odd or even modes, and there is almost no power loss during the conversion. Most importantly, they are robust against backscattering from perfect electric conductors (PECs) and point defects. Based on these properties, we propose a device that can efficiently separate the odd and even modes into different ports. These results offer a novel approach to controlling the transmission modes of waveguides, which facilitates the interconnection of diverse topological magneto-optical waveguides.

Highly Stable Rare Earth Metal-Organic Frameworks for Fluorescence Recognition of Folic Acid, Proton Conduction, and Magnetic Refrigeration.

Four new isostructural rare earth metal-organic frameworks (RE-MOFs) were synthesized and full characterized, namely, {[(CH)2NH2]3[RE2(BTDBA)2(HCOO)]·5H2O·2DMF}n (H4BTDBA = (4',4'''-(benzo[c][1,2,5]thiadiazole-4,7-diyl)bis([1,1'-biphenyl]-3,5-dicarboxylic acid); RE = Eu (JXUST-34), Gd (JXUST-35), Tb (JXUST-36), and Dy (JXUST-37)). The single-crystal structures analysis shows that JXUST-34-37 are chain-based three-dimensional structures. Importantly, JXUST-34 exhibits excellent water, organic solvents, and acid-base stability, which can be used as a fluorescence sensor for folic acid and Al3+ with detection limits of 0.02 mM and 0.05 µM, respectively. The presence of free [(CH)2NH2]+ cations in the channels can engage the proton carrier during proton conduction. JXUST-34-37 display good proton conductivity, and the conductivities vary with relative humidity and temperatures, among which JXUST-37 has the highest conductivity of 9.66 × 10-3 S·cm-1 at 60 °C and 98% RH. The magnetic studies show that the -ΔSm of JXUST-35 reaches 16.13 J kg-1 K-1 at 2 K and ΔH = 7 T. JXUST-34-37 show multifunctional properties of fluorescence sensing, high proton conductivity, and magnetic refrigeration, which provides a new clue for the development of fluorescent-responsive, magnetic-refrigerant, and proton-conductive RE-MOF materials.

Dual-omics reveals temporal differences in acute sympathetic stress-induced cardiac inflammation following α1 and ß-adrenergic receptors activation.

Sympathetic stress is prevalent in cardiovascular diseases. Sympathetic overactivation under strong acute stresses triggers acute cardiovascular events including myocardial infarction (MI), sudden cardiac death, and stress cardiomyopathy. α1-ARs and ß-ARs, two dominant subtypes of adrenergic receptors in the heart, play a significant role in the physiological and pathologic regulation of these processes. However, little is known about the functional similarities and differences between α1- and ß-ARs activated temporal responses in stress-induced cardiac pathology. In this work, we systematically compared the cardiac temporal genome-wide profiles of acute α1-AR and ß-AR activation in the mice model by integrating transcriptome and proteome. We found that α1- and ß-AR activations induced sustained and transient inflammatory gene expression, respectively. Particularly, the overactivation of α1-AR but not ß-AR led to neutrophil infiltration at one day, which was closely associated with the up-regulation of chemokines, activation of NF-κB pathway, and sustained inflammatory response. Furthermore, there are more metabolic disorders under α1-AR overactivation compared with ß-AR overactivation. These findings provide a new therapeutic strategy that, besides using ß-blocker as soon as possible, blocking α1-AR within one day should also be considered in the treatment of acute stress-associated cardiovascular diseases.

Immunosuppressive Bibenzyl-phenylpropane Hybrids from Dendrobium devonianum.

Two new bibenzyl-phenylpropane hybrids, dendrophenols A and B (1 and 2), along with nine known bibenzyls, were isolated from the aerial part of Dendrobium devonianum Paxt. Their structures were determined by extensive spectroscopic methods and methylation. Bioassays revealed that compounds 1-9 were specifically immunosuppressive to T lymphocytes with IC50 values ranging from 0.41 to 9.4 µM, of which compounds 1 (IC50 =1.62 µM) and 2 (IC50 =0.41 µM) were promising immunosuppressive agents for T lymphocytes with the selectivity indices of 19.9 and 79.5, respectively.

Horsfielenigans A and B, Two Rearranged Lignans with Anti-Inflammatory Effects from Horsfieldia kingii.

Seven lignans were isolated from 70 % aqueous acetone extracts of the twigs and leaves of Horsfieldia kingii. Among these, new compounds 1-3 were identified by spectroscopic techniques, with horsfielenigans A and B (1 and 2) being particularly noteworthy for their rare ß-benzylnaphthalene skeleton, where compound 1 contains an oxabicyclo[3,2,1]octane moiety. In vitro evaluation of bioactivity against nitric oxide (NO) production in LPS-activated RAW264.7 macrophages revealed inhibitory effects by 1 (IC50 =7.3 µM) and 2 (IC50 =9.7 µM).

Robust topological one-way edge states in radius-fluctuated photonic Chern topological insulators.

Recent developments in topological photonics have shown that the introduction of disorders can yield the innovative and striking transport phenomena. Here, we theoretically investigate topological one-way edge states in radius-fluctuated photonic Chern topological insulators (PCTIs), which are composed of two-dimensional gyromagnetic photonic crystals with cylinder site fixed but with cylinder radius fluctuated. We use a fluctuation index to characterize the degree of radius fluctuation, employ two empirical parameters to inspect the evolution of topological one-way edge states, and verify the stability of topological one-way edge states by calculating massive samples with various random numbers. We find that as the radius-fluctuation strength increases, there arises a competition between topological one-way edge state, Anderson localization state and trivial bulk state. We reveal that the Anderson localization state appears far more easily in the radius-fluctuation PCTI with even a weak strength compared with the position-perturbed PCTI with a strong randomness. We also demonstrate that the topological one-way edge states are protected against a strong fluctuation much larger than the fabrication errors in practical experiments. Our results show that the PCTIs consisting of gyromagnetic photonic crystals have a high-tolerance for the material and sample fabrication errors, and this would provide a deeper understanding of fundamental topology physics.

Adjustable enhanced Goos-Hänchen shift in a magneto-optic photonic crystal waveguide.

We have presented adjustable enhanced Goos-Hänchen (GH) shift in a magneto-optical photonic crystal (MOPC) waveguide. The waveguide consists of a top layer of ferrite rods and a lower MOPC with opposite biased dc external magnetic fields (EMFs), and it supports both odd-like and even-like modes simultaneously. The simulation results show the odd-like mode can cause an enhanced negative GH shift, while the even-like mode can result in an enhanced positive GH shift. The physical reason for such negative and positive GH shifts is attributed to the efficient mode coupling and propagation behaviors of the electromagnetic (EM) wave in the waveguide. Furthermore, we have realized the switchable negative/positive GH shift by altering the direction combination of the EMFs. In addition, the magnitudes of both GH shifts can be adjusted by changing the strength of EMF or the width of the waveguide. These results provide new ways to control the transmission behaviors of EM wave and hold promise in applications such as detections, optical switches, and sensors.

Controllable one-way add-drop filter based on magneto-optical photonic crystal with ring resonator and microcavities.

We have proposed a controllable topological add-drop filter (ADF) by utilizing the one-way transmission property and resonant coupling effect of topological photonic states in magneto-optical photonic crystal (MOPC) system. The ADF is symmetrically constructed by a central ring resonator (RR) with each side a MO microcavity and a topological waveguide formed by MOPC/Al2O3 PCs. The topological waveguide supports one-way transmission and the microcavity is used to adjust resonant frequency and improve filtering performance. Based on the symmetry of structure and the adjustability of magnetic field, the input and output ports can be reconfigured conveniently to realize the dropping and adding functions of the ADF. Such an ADF possesses merits of nearly perfect filtering performance, convenient adjustability of resonance mode, and strong robustness against various defects. Moreover, we further design an optical demultiplexer consisting of two PCRRs which is able to separate two different resonant modes independently and efficiently. These results hold promise in many fields such as optical communications and wavelength-division multiplexing.

Prediction and Observation of Robust One-Way Bulk States in a Gyromagnetic Photonic Crystal.

We report a two-dimensional heterogeneous Haldane model composed of alternately stacking modified Haldane lattices with opposite next-nearest-neighbor hoppings, and predict the emergence of robust one-way bulk states by an ab initio theoretical calculation. These unique bulk states transport unidirectionally and are robust against backscattering from impurities in the strip bulk. By analogy with the heterogeneous Haldane model, we further confirm by numerical simulations and experimental measurements the existence of robust one-way bulk states in a two-dimensional microwave gyromagnetic photonic crystal, and demonstrate their robust one-way property over a long-distance even in the presence of metallic obstacles. Our study provides the strong support for the generalization and application of band theories to fermionic and bosonic systems, and paves a way for the implementation of high-throughput robust energy transmission materials and devices.

Insight into Isolation and Characterization of Phenolic Compounds from Hawthorn (Crataegus pinnatifida Bge.) with Antioxidant, Anti-Acetylcholinesterase, and Neuroprotective Activities.

Recent epidemiologic studies have demonstrated a link between the consumption of daily functional fruits rich in phenols and the prevention of disease for neurodegenerative disorders. Hawthorn products are derived from the functional fruit hawthorn, which is rich in phenols and has been used around the world for centuries. In order to explore the phenolic components in hawthorn, the investigation of the ethanol extract led to the separation of five new phenol compounds (1a/1b, 2-4), including one pair of enantiomers (1a/1b), along with seven disclosed analogs (5-11). Their structures were elucidated based on extensive spectroscopic analyses and electronic circular dichroism (ECD). The compounds (1-11) were tested for antioxidant activities by 2,2-diphenyl-1-picrylhydrazyl (DPPH), 2,2'-azino-bis (3-ethylbenzothiazoline-6-sulphonicacid) (ABTS), and ferric reducing antioxidant power (FRAP) methods. Apart from that, monomeric compounds 2, 4, and 6 exhibited more potent protective capabilities against H2O2 (hydrogen peroxide)-induced SH-SY5Y cells. Meanwhile, electronic analyses were performed using the highest occupied molecular orbital (HOMO), and the lowest unoccupied molecular orbital (LUMO) to analyze compounds 2, 4, and 6. Furthermore, compounds (1-11) measured acetylcholinesterase (AChE) inhibitory activities, and 2, 4, and 6 possessed greater AChE inhibitory activity than donepezil. At the same time, molecular docking was used to investigate the possible mechanism of the interaction between active compounds (2, 4, and 6) and AChE.

Ferroptosis-Enhanced Cancer Immunity by a Ferrocene-Appended Iridium(III) Diphosphine Complex.

Ferroptosis is a programmed cell death pathway discovered in recent years, and ferroptosis-inducing agents have great potential as new antitumor candidates. Here, we report a IrIII complex (Ir1) containing a ferrocene-modified diphosphine ligand that localizes in lysosomes. Under the acidic environments of lysosomes, Ir1 can effectively catalyze Fenton-like reaction, produce hydroxyl radicals, induce lipid peroxidation, down-regulate glutathione peroxidase 4, and result in ferroptosis. RNA sequencing analysis shows that Ir1 can significantly affect pathways related to ferroptosis and cancer immunity. Accordingly, Ir1 can induce immunogenic cells death and suppress tumor growth in vitro, regulate T cell activity and immune microenvironments in vivo. In conclusion, we show the potential of small molecules with ferroptosis-inducing capabilities for effective cancer immunotherapy.

Simultaneous Photoactivation of cGAS-STING Pathway and Pyroptosis by Platinum(II) Triphenylamine Complexes for Cancer Immunotherapy.

Activation of the cyclic GMP-AMP synthase-stimulator of the interferon gene (cGAS-STING) pathway is a potent anticancer immunotherapeutic strategy, and the induction of pyroptosis is a feasible way to stimulate the anticancer immune responses. Herein, two PtII complexes (Pt1 and Pt2) were designed as photoactivators of the cGAS-STING pathway. In response to light irradiation, Pt1 and Pt2 could damage mitochondrial/nuclear DNA and the nuclear envelope to activate the cGAS-STING pathway, and concurrently induce pyroptosis in cancer cells, which evoked an intense anticancer immune response in vitro and in vivo. Overall, we present the first photoactivator of the cGAS-STING pathway, which may provide an innovative design strategy for anticancer immunotherapy.

Phase 2 study using oral thalidomide-cyclophosphamide-prednisone for idiopathic multicentric Castleman disease.

Idiopathic multicentric Castleman disease (iMCD) is a rare lymphoproliferative disorder. The anti-interleukin 6 (IL-6) therapy siltuximab is not available everywhere, and is not effective for over one-half of patients. Alternative treatment approaches are urgently needed. In the first iMCD clinical trial directed against a target other than IL-6 signaling, we investigated a thalidomide-cyclophosphamide-prednisone (TCP) regimen in newly diagnosed iMCD patients. This single-center, single-arm, phase 2 study enrolled 25 newly diagnosed iMCD patients between June 2015 and June 2018. The TCP regimen (thalidomide 100 mg daily for 2 years; oral cyclophosphamide 300 mg/m2 weekly for 1 year; prednisone 1 mg/kg twice a week for 1 year) was administered for 2 years or until treatment failure. The primary end point was durable tumor and symptomatic response for at least 24 weeks. Twelve patients (48%) achieved the primary end point with no relapse, 3 patients (12%) demonstrated stable disease, and 10 patients (40%) were evaluated as treatment failure. Even when considering all patients, there were significant (P < .05) improvements in median symptom score, IL-6 level, hemoglobin, erythrocyte sedimentation rate, albumin, and immunoglobulin G. Among responders, the median levels of all evaluated parameters significantly improved, to the normal range, after treatment. The regimen was well tolerated. One patient died of pulmonary infection and 1 patient had a grade 3 adverse event (rash); 2 patients died following disease progression. Estimated 1-year progression-free survival and overall survival were 60% and 88%, respectively. The TCP regimen is an effective and safe treatment of newly diagnosed iMCD patients, particularly when siltuximab is unavailable. This trial was registered at www.clinicaltrials.gov as #NCT03043105.

Zero GVD slow-light originating from a strong coupling of one-way modes in double-channel magneto-optical photonic crystal waveguides.

We have studied the coupling effect of topological photonic states in a double-channel magneto-optical photonic crystal waveguide by introducing a two-stranded ordinary Al2O3 photonic crystal as the coupling layer. There exist both M1 (odd) and M2 (even) one-way modes simultaneously in the bandgap. Interestingly, M1 mode is always a fast-light mode with large group velocity (vg) and large group velocity dispersion (GVD) regardless what the radius (RA) of Al2O3 rods is. However, when RA is appropriate, M2 mode becomes a very slow-light mode exhibiting near-zero vg and zero GVD simultaneously. The physical reason of such slow-light is attributed to the strong coupling effect between the one-way edge modes in both sub-waveguides. Furthermore, the simulation results show that the robustness of both the fast- and slow-light modes are extremely strong against perfect electric conductor defect and the one-way transmittance is close to 100%. Besides, the PEC defect can cause significant phase delay. These results hold promise for many fields such as signal processing, optical modulation, and the design of various topological devices.