Bimetallic Porphyrin-Based Metal-Organic Framework as a Superior Photocatalyst for Enhanced Photocatalytic Hydrogen Production.

The meaningful and rational engineering of porphyrin-based catalysts with multimetallic active sites is very attractive toward photocatalytic hydrogen generation from water decomposition. Herein, three metal organic frameworks (MOFs) based on meso-tetrakis(4-carboxylphenyl)porphyrin (TCPP) were successfully constructed under solvothermal conditions. As a novel architectured photocatalyst (triclinic, C48H29N4O10PdYb), Pd/Yb-PMOF manifested diverse metal active sites, suitable bandgap positions, prominent visible light-collecting capacity, excellent carrier transfer efficiency, and obvious synergistic effect between ytterbium and palladium ions. Consequently, such a bimetallic MOF exhibited strengthened photocatalytic hydrogen evolution performance. Concretely, its hydrogen generation efficiency was up to 3196.42 µmol g-1 h-1 with 2 wt % Pt as a cocatalyst under visible light illumination. Our work demonstrates a promising strategy for highly efficient visible-light catalysts based on bimetallic-trimmed porphyrin MOFs.

Generalized binary spiral zone plates with a single focus obtained by feedforward neural network.

Traditional spiral zone plates (SZPs) have been widely used to generate optical vortices, but this structure suffers from multiple focuses. To eliminate high-order foci, the current method is to design a binary structure that has a sinusoidal transmittance function along the radial direction. With the rapid development of artificial neural networks, they can provide alternative methods to design novel SZPs with a single focus. In this paper, we first propose the concept of generalized binary spiral zone plates (GBSZPs), and train a feedforward neural network (FNN) to obtain the mapping relationship between the relative intensity of each focus and the structural parameters of GBSZPs. Then the structural parameters of GBSZPs with a single focus were predicted by the trained FNN. It is found by simulations and experiments that the intensities of high-order foci can be as low as 0.2% of the required first order. By analyzing the radial transmittance function, it is found that this structure has a different distribution function from the previous radial sinusoidal function, which reveals that the imperfect radial sinusoidal form also can guide the design of binary zone plates to eliminate high-order foci diffraction. These findings are expected to direct new avenue towards improving the performance of optical image processing and quantum computation.

A pan-cancer analysis revealing the role of LFNG, MFNG and RFNG in tumor prognosis and microenvironment.

BACKGROUND: Fringe is a glycosyltransferase involved in tumor occurrence and metastasis. However, a comprehensive analysis of the Fringe family members lunatic fringe (LFNG), manic fringe (MFNG), radical fringe (RFNG) in human cancers is lacking. METHODS: In this study, we performed a pan-cancer analysis of Fringe family members in 33 cancer types with transcriptomic, genomic, methylation data from The Cancer Genome Atlas (TCGA) project. The correlation between Fringe family member expression and patient overall survival, copy number variation, methylation, Gene Ontology enrichment, and tumor-infiltrating lymphocytes (TILs) was investigated by using multiple databases, such as cBioPortal, Human Protein Atlas, GeneCards, STRING, MSigDB, TISIDB, and TIMER2. In vitro experiments and immunohistochemical assays were performed to validate our findings. RESULTS: High expression levels of LFNG, MFNG, RFNG were closely associated with poor overall survival in multiple cancers, particularly in pancreatic adenocarcinoma (PAAD), uveal melanoma (UVM), and brain lower-grade glioma (LGG). Copy number variation analysis revealed that diploid and gain mutations of LFNG was significantly increased in PAAD and stomach adenocarcinoma (STAD), and significantly associated with the methylation levels in promoter regions. Significant differential genes between high and low expression groups of these Fringe family members were found to be consistently enriched in immune response and T cell activation pathway, extracellular matrix adhesion pathway, RNA splicing and ion transport pathways. Correlation between the abundance of tumor-infiltrating lymphocytes (TILs) and LFNG, MFNG, and RFNG expression showed that high LFNG expression was associated with lower TIL levels, particularly in PAAD. In vitro experiment by using pancreatic cancer PANC1 cells showed that LFNG overexpression promoted cell proliferation and invasion. Immunohistochemical assay in 90 PAAD patients verified the expression level of LFNG and its relationship with the prognosis. CONCLUSIONS: Our study provides a relatively comprehensive understanding of the expression, mutation, copy number, promoter methylation level changes along with prognosis values of LFNG, MFNG, and RFNG in different tumors. High LFNG expression may serve as a poor prognosis molecular marker for PAAD.

3D Lanthanide Neodymium Porphyrin Metal-Organic Framework for Photocatalytic Oxidation of Styrene.

A novel three-dimensional lanthanide porphyrin-based MOF (Nd-PMOFs) was synthesized by using tetracarboxyphenyl porphyrin as the ligand and the lanthanide Nd as the coordination metal. Its specific crystal structure information was obtained by single-crystal diffraction with the space group C2/c and the empirical formula C72H45N6Nd2O15.25. This new Nd porphyrin-based MOF with an organic framework formed by a unique coordination method enables the effective separation of photogenerated electrons and holes under photoluminescence, giving it excellent photocatalytic property which could be verified by the characterization data. The photocatalytic performance was examined by taking tert-butyl hydroperoxide as the oxidant and Nd-PMOFs as the catalyst for photocatalytic oxidation of styrene to benzaldehyde with 91.4% conversion and 81.2% benzaldehyde selectivity under optimal reactions, which surpasses most of the results reported in the literature. Several styrenes with other substituents were screened to explore the general applicability of Nd-PMOF for photocatalysis of styrene, among which Nd-PMOFs also exhibited excellent photocatalytic performance. This work offers the possibility to apply lanthanide organometallic frameworks, which are widely used in fluorescent materials, to photocatalysis. In addition, it also provides a new method for the catalytic generation of benzaldehyde from styrene that is consistent with the needs of modern green development.

Dual-band giant spin-selective full-dimensional manipulation of graphene-based chiral meta-mirrors for terahertz waves.

The ability to simultaneous achieve circular dichroism (CD) and wavefront manipulation is extremely important for many practical applications, especially for detecting and imaging. However, many of the previously observed weakness chiral features are limited to nanostructures with complex three-dimensional building configurations, single narrow-band response, and no active tunability, which are getting farther and away from the goal of integration and miniaturization. Here, a platform of bi-layer all-graphene meta-mirrors with spin-selective full-dimensional manipulation is proposed to simultaneously achieve giant dual-band CD response and wavefront shaping, based on the principle of the hybridization coupling. By simply controlling the structural variables of the meta-mirror and the characteristic parameters of graphene, that is, the combination of passive and active regulation, the proposed design can selectively manipulate the polarization, amplitude, phase, and working frequency of the incident circularly polarized wave near-independently. As a proof of concept, we used the meta-mirror to design two metasurface arrays with spin-selective properties for dynamic terahertz (THz) wavefront shaping and near-field digital imaging, both of which show a high-performance dynamic tunability. This method could provide additional options for the next-generation intelligent THz communication systems.

Ultra-intense vortex laser generation from a seed laser illuminated axial line-focused spiral zone plate.

Relativistic vortex laser has drawn increasing attention in the laser-plasma community owing to its potential applications in various domains, e.g., generation of energetic charged particles with orbital angular momentum (OAM), high OAM X/γ-ray emission, high harmonics generation, and strong axial magnetic-field production. However, the generation of such relativistic vortex laser is still a challenge to the current laser technology. Using micro-structure targets named axial line-focused spiral zone plate (ALFSZP), we propose a novel scheme for ultra-intense vortex laser generation. In the scheme, a relativistic Gaussian laser pulse irradiates an ALFSZP, and diffracts as it passes through the ALFSZP. Due to the focusing and radial Hilbert transform capabilities of the ALFSZP, the seed laser is converted efficiently to a vortex one which is then well focused in a tunable focal volume. Three-dimensional particle-in-cell simulations indicate that using a seed laser pulse with intensity of 1.3 × 1020 W/cm2, the vortex laser intensity achieved is as high as 1.3 × 1021 W/cm2 with the averaged angular momentum per photon up to 0.73ℏ, promising diverse applications in various fields aforementioned.

All-dielectric metasurface for polarization-selective full-space complex amplitude modulations.

Metasurfaces have exhibited powerful capabilities in the modulation of electromagnetic waves. Here, we demonstrate the polarization-selective full-space complex amplitude modulations of incident electromagnetic waves using all-dielectric metasurfaces. This is done via ingeniously designed subwavelength-scale super-pixels. As a proof of concept, we design two metasurfaces working in transmission and reflection spaces: one generates two independent vortex beams and the other generates two pairs of foci of arbitrary intensity ratios. The proposed full-space complex amplitude modulation provides more choices for the manipulation of electromagnetic waves.

Polarization-dependent and tunable absorption of terahertz waves based on anisotropic metasurfaces.

Metamaterial absorbers can achieve high-efficiency electromagnetic absorption in a specific band, which have been used in biochemical sensing, photoelectric detection, imaging and other fields. Tunable metamaterial absorbers provide more possibilities for the development of multifunctional electromagnetic absorption devices. Here we propose a tunable and polarization-dependent terahertz metamaterial absorber which can work for both linearly and circularly polarized waves. By introducing single layer graphene and vanadium dioxide (VO2), switching between the two working states and wide-range tuning of the absorption efficiency are realized. When VO2 is in insulating state, the absorber shows different tunable absorption performance for the x- or y-polarized terahertz waves, in which the maximum absorption rate is close to 100%. When VO2 is in metallic state, the metasurface behaves as a chiral absorber, and the maximum absorption difference between the two circular polarizations is about 0.45, while the tuning efficiency reaches 86.3%. Under the two working conditions, the absorber can maintain efficient absorption with a large incident angle. In addition, as an application exploration of the absorber, we demonstrated its application in tunable and polarization multiplexed near-field image display.

Lossless dielectric metasurface with giant intrinsic chirality for terahertz wave.

It is difficult for single-layer metal metasurfaces to excite in-plane component of magnetic dipole moment, so achieving giant intrinsic optical chirality remains challenging. Fortunately, displacement current in dielectric metasurfaces can form the in-plane magnetic moment which is not orthogonal to the electric dipole moment and forms intrinsic chirality. Here, we show a lossless all-silicon metasurface which achieves giant intrinsic chirality in terahertz band. The leaky waveguide mode in the chiral silicon pillars simultaneously excite the in-plane electric and magnetic dipole moments, which triggers the spin-selected backward electromagnetic radiation, and then realizes the chiral response. The theoretical value of circular dichroism in the transmission spectrum reaches 69.4%, and the measured one is 43%. Based on the photoconductivity effect of the silicon metasurface, we demonstrate optical modulation of the intrinsic chirality using near-infrared continuous wave. In addition, by arranging the two kinds of meta-atoms which are enantiomers, we show the spin-dependent and tunable near-field image display. This simple-prepared all-silicon metasurface provides a new idea for the design of terahertz chiral meta-devices, and it is expected to be applied in the fields of terahertz polarization imaging or spectral detection.

Dual-type fractal spiral zone plate for generating sequence of square optical vortices.

We propose a technique for generating a sequence of co-axial zero axial irradiance with a so-called dual-type fractal spiral zone plate (DTFSZP). Based on the Fresnel diffraction theory, we simulated the focusing performance of this optical device. The results reveal that DTFSZP has the remarkable ability of generating a sequence of optical vortices with larger depth of focus and high lateral resolution. The central diffracted image rotates in the vicinity of the focal plane. Moreover, the focusing performance follows a modulo-4 transmutation rule. Such optics promises a complementary and versatile high-resolution non-destructive tool for particle manipulation and provides potential application in three-dimensional optical alignment systems.

Fractal spiral zone plates.

We present diffractive optical elements with an extended depth of focus, namely, fractal spiral zone plates (FSZPs), which combine a fractal structure and spiral zone plates (SZPs) to generate a sequence of coaxial vortices in the focal volume along the propagation direction. The axial irradiance of the FSZPs is examined both experimentally and in a simulation and is compared with that of SZPs and that of fractal zone plates. The focusing properties of the FSZPs with different parameters are investigated, and a potential application to edge-enhancement images is also shown.

Characterization of the focusing performance of axial line-focused spiral zone plates.

Axial line-focused spiral zone plates were developed for operation at optical wavelengths. The design, fabrication, and diffraction properties of the proposed element are presented. Numerical results showed that hollow beams could be generated, and that the element can be employed for a multi-wavelength operation. The hollow beam within the focal depth was demonstrated experimentally, using a charge-coupled device camera and sliding guide. The results were consistent with those obtained by the simulations. The proposed optical device exhibits significant potential for various applications including optical manipulation and lithography.

INHIBITORY MECHANISM AGAINST OXIDATIVE STRESS AND BIOLOGICAL ACTIVITIES OF CANOLOL.

Canolol is a decarboxylated derivative of sinapic acid. Due to lipophilic nature, canolol is an excellent orally bioavailable phenol. It mainly occurs in roasted rapeseeds. It is documented in the literature as a potent antioxidant and safe for human health. The mode of antioxidant activity of canolol involves the suppression of various free radicals such as 02, ONOO and 'OOH. As evident from the literature, few studies have been carried out to explore the free radical scavenging activity of canolol. Thus, the objective of this review article is to summarize the available literature about free radical scavenging potential of this promising phenol to pave the path for further investigations about biological activities of canolol.

1-Deoxynojirimycin: Occurrence, Extraction, Chemistry, Oral Pharmacokinetics, Biological Activities and In Silico Target Fishing.

1-Deoxynojirimycin (DNJ, C6H13NO4, 163.17 g/mol), an alkaloid azasugar or iminosugar, is a biologically active natural compound that exists in mulberry leaves and Commelina communis (dayflower) as well as from several bacterial strains such as Bacillus and Streptomyces species. Deoxynojirimycin possesses antihyperglycemic, anti-obesity, and antiviral features. Therefore, the aim of this detailed review article is to summarize the existing knowledge on occurrence, extraction, purification, determination, chemistry, and bioactivities of DNJ, so that researchers may use it to explore future perspectives of research on DNJ. Moreover, possible molecular targets of DNJ will also be investigated using suitable in silico approach.

POTENTIAL APPROACHES FOR REDUCING AMYLOID ß PRODUCTION.

Alzheimer's disease (AD), a neurodegenerative disorder, is associated with the mitochondrial dysfunction, defective synapses, and impaired cognition in elderly patients. The accumulation of amyloid ß (Aß) in synapses and synaptic mitochondria is thought one of the critical pathological events of synaptic defect and impaired mitochondrial dynamics in AD neurons. In order to understand disease progression and designing therapeutic agents using available molecular targets, extensive research is in progress throughout the world. However, no drug has been reported, up to now, as effectively preventing and treating moiety for AD, due to hidden knowledge about exact mode of AD pathogenesis. However, some hypotheses based-drugs, possessing capability of regulating amyloid ß precursor protein, have been indicated for alleviation of psychological and behavioral symptoms of AD patients. This review article briefly describes the recent developments made for exploring the Aß induced-mitochondrial defects in AD and some treatment possibilities through Aß-targeting approaches for AD therapy.

Ultrasonography of lower limb vascular angiopathy and plaque formation in type 2 diabetes patients and finding its relevance to the carotid atherosclerotic formation.

OBJECTIVE: One of the major complications of diabetes is blood vessel disease, termed angiopathy, which is characterized by abnormal angiogenesis. The objective of this study was to discuss the characteristics of lower limb vascular angiopathy and plaque formation in type 2 diabetes patients and finding its relevance to the carotid atherosclerotic plaque formation, thus directing the clinical diagnosis and treatment. METHODS: The ultrasonography was used to monitor the patients with carotid artery and lower limb artery. RESULTS: Compared with the control group, decreased blood flow to lower limb and lower limb angiopathy occurred more obviously in dorsal artery of foot than in popliteal artery. The study revealed that the detection rate of the prevalence of carotid atherosclerosis plaque and lower limb arterial plaque and the combination of plaque both carotid and lower limb arteries in diabetic patients was 369:342:296 (about 1.25:1.15:1) and that the prevalence of carotid plaque and lower limb arterial plaque in all subjects with plaque was 71.3%. The risk of plaque formation also had positive correlation with patient's age. Color Doppler ultrasound had a clinical significance in the early diagnosis and curative effect observation in type 2 diabetes with lower limb angiopathy. The risk of simultaneous plaque formation in both carotid artery and lower extremity artery was greater in type 2 diabetes than that of control subjects, but they were not necessarily to occur simultaneously. The symptoms were inconspicuous in the early course of diabetes. CONCLUSION: The application of ultrasound monitoring in patients with carotid artery and lower limb artery might play a role in early warning, delaying the occurrence of macrovascular diseases, and slowing down the development of macroangiopathy such as cerebral infarction and diabetic foot and so on, thus providing a significant basis for clinical diagnosis and treatment.

Ketone Synthesis via Irradiation-Induced Generation of a Persistent Ketyl Radical from Acyl Azolium Salts.

A novel three-component α-acylated difunctionalization of alkenes strategy has been developed on the basis of a direct hydrogen atom transfer (HAT) process of photoinduced acyl azolium salts. With simple irradiation without the catalyst, a variety of olefins can be directly converted into ketone derivatives, including 1,4-dione, ß-silyl ketone, 1,5-dione, etc. Mechanistic investigations indicated that the unique reactivity of the acyl azonium triplet excited state is crucial to the strategy's success.

FOXQ1 promotes pancreatic cancer cell proliferation, tumor stemness, invasion and metastasis through regulation of LDHA-mediated aerobic glycolysis.

Pancreatic cancer (PC), a gastrointestinal tract malignant tumor, has a poor prognosis due to early metastasis and limited response to chemotherapy. Therefore, identifying novel therapeutic approaches for PC is critical. Epithelial-mesenchymal transition (EMT) is known as the vital progress in PC development, we constructed the EMT-related prognosis model to screen out that FOXQ1 probably involving in the EMT regulation. FOXQ1 has been linked to the malignant process in a number of cancers. However, its function in PC is unknown. In our work, the expression of FOXQ1 was elevated in PC tissues, and a high level of FOXQ1 in PC was linked to patients' poor prognosis. FOXQ1 overexpression promoted aerobic glycolysis and enhanced PC cell proliferation, tumor stemness, invasion, and metastasis. Whereas, FOXQ1 silencing showed the reverse effect. Furthermore, mechanistic studies indicated that FOXQ1 promotes LDHA transcription, and thus modulates aerobic glycolysis to enhance PC cell proliferation, tumor stemness, invasion, and metastasis by increasing LDHA expression. Therefore, these novel data suggest that FOXQ1 may be a possible therapeutic target in PC.

Loss of function of GATA3 regulates FRA1 and c-FOS to activate EMT and promote mammary tumorigenesis and metastasis.

Basal-like breast cancers (BLBCs) are among the most aggressive cancers, partly due to their enrichment of cancer stem cells (CSCs). Breast CSCs can be generated from luminal-type cancer cells via epithelial-mesenchymal transition (EMT). GATA3 maintains luminal cell fate, and its expression is lost or reduced in BLBCs. However, deletion of Gata3 in mice or cells results in early lethality or proliferative defects. It is unknown how loss-of-function of GATA3 regulates EMT and CSCs in breast cancer. We report here that haploid loss of Gata3 in mice lacking p18Ink4c, a cell cycle inhibitor, up-regulates Fra1, an AP-1 family protein that promotes mesenchymal traits, and downregulates c-Fos, another AP-1 family protein that maintains epithelial fate, leading to activation of EMT and promotion of mammary tumor initiation and metastasis. Depletion of Gata3 in luminal tumor cells similarly regulates Fra1 and c-Fos in activation of EMT. GATA3 binds to FOSL1 (encoding FRA1) and FOS (encoding c-FOS) loci to repress FOSL1 and activate FOS transcription. Deletion of Fra1 or reconstitution of Gata3, but not reconstitution of c-Fos, in Gata3 deficient tumor cells inhibits EMT, preventing tumorigenesis and/or metastasis. In human breast cancers, GATA3 expression is negatively correlated with FRA1 and positively correlated with c-FOS. Low GATA3 and FOS, but high FOSL1, are characteristics of BLBCs. Together, these data provide the first genetic evidence indicating that loss of function of GATA3 in mammary tumor cells activates FOSL1 to promote mesenchymal traits and CSC function, while concurrently repressing FOS to lose epithelial features. We demonstrate that FRA1 is required for the activation of EMT in GATA3 deficient tumorigenesis and metastasis.

On-demand multiplexed vortex beams for terahertz polarization detection based on metasurfaces.

The manipulation of polarization states is crucial for tailoring light-matter interactions and has great applications in fundamental science. Nevertheless, conventional polarization measurement approaches are extremely challenging to determine the polarization state of incident terahertz (THz) beams. The combination of metasurfaces and inhomogeneous vector vortex beams (VVBs) provides a new solution for integrated polarization-related functional devices. Herein, a general design strategy for spin-multiplexing all-silicon metasurfaces is presented and demonstrated in THz polarization detection. The employment of basic building blocks with a high aspect ratio (AR) imparts a greater degree of freedom for generating vector beams, and those basic blocks are subsequently utilized to explore the visualized polarization state. With the assistance of a THz near-field scanning system, we evaluate the capability of reconstructing the incident polarization state from the longitudinal polarization component multiplexed by vortex beams with tight focusing characteristics. Not only that, we also utilize the polarization with dynamically varying behavior as the illumination method to elucidate the evolution trend of the polarization state under a single snapshot and establish a visualized parametric model. This work paves the way to realize ultra-compact THz polarization detection-related devices for future applications in remote sensing, high-resolution imaging, and communications.