Organic–inorganic hybrid two-dimensional (2D) perovskites have recently attracted great attention in optical and optoelectronic applications due to their inherent natural quantum-well structure. We ...report the growth of high-quality millimeter-sized single crystals belonging to homologous two-dimensional (2D) hybrid organic–inorganic Ruddelsden–Popper perovskites (RPPs) of (BA)2(MA) n −1Pb n I3 n +1 (n = 1, 2, and 3) by a slow evaporation at a constant-temperature (SECT) solution-growth strategy. The as-grown 2D hybrid perovskite single crystals exhibit excellent crystallinity, phase purity, and spectral uniformity. Low-threshold lasing behaviors with different emission wavelengths at room temperature have been observed from the homologous 2D hybrid RPP single crystals. Our result demonstrates that solution-growth homologous organic–inorganic hybrid 2D perovskite single crystals open up a new window as a promising candidate for optical gain media.
Coupling urea oxidation reaction (UOR) with hydrogen evolution reaction (HER) is an effective energy‐saving technique for hydrogen generation. However, exploring efficient bifunctional ...electrocatalysts under high current density is still challenging. Herein, hierarchical Fe doped cobalt selenide coupled with FeCo layered double hydroxide (Fe‐Co0.85Se/FeCo LDH) array as a self‐supported superior bifunctional heterojunction electrode is rationally designed for both UOR and HER. The unique heterostructure facilitates electron transfer and interface interactions through local interfacial Co‐Se/O‐Fe bonding environment modulation, improving reaction kinetics and intrinsic activity. As a result, the heterostructured electrocatalyst exhibits ultralow potentials of −0.274 and 1.48 V to reach 500 mA cm−2 for catalyzing the HER and UOR, respectively. Particularly, the full urea electrolysis system driven by Fe‐Co0.85Se/FeCo LDH delivers 300 mA cm−2 at a relatively low potential of 1.57 V, which is 150 mV lower than the conventional water electrolysis. The combination of in situ characterization and theoretical analysis reveal that the active sites with the adjustable electronic environment are induced by the interfacial bonding of the heterojunction, facilitating the water decomposition of HER and the stabilization of intermediates in UOR. This work inspires the interfacial environment modulation to optimize advanced electrocatalysts for energy‐saving H2 production.
The heterostructure constructed by Fe doped Co0.85Se and FeCo LDH can induce the modulation of local interfacial bonding environment and optimize the d‐band center to benefit the intermediates adsorption/desorption during urea oxidation reaction. As a result, a low cell voltage of 1.57 V at 300 mA cm−2 for urea water splitting is achieved based on the heterostructure.
Designing well‐defined interfacial chemical bond bridges is an effective strategy to optimize the catalytic activity of metal–organic frameworks (MOFs), but it remains challenging. Herein, a facile ...in situ growth strategy is reported for the synthesis of tightly connected 2D/2D heterostructures by coupling MXene with CoBDC nanosheets. The multifunctional MXene nanosheets with high conductivity and ideal hydrophilicity as bridging carriers can ensure structural stability and sufficient exposure to active sites. Moreover, the Co–O–Ti bond bridging formed at the interface effectively triggers the charge transfer and modulates the electronic structure of the Co‐active site, which enhances the reaction kinetics. As a result, the optimized CoBDC/MXene exhibits superior hydrogen evolution reaction (HER) activity with low overpotentials of 29, 41, and 76 mV at 10 mA cm−2 in alkaline, acidic, and neutral electrolytes, respectively, which is comparable to commercial Pt/C. Theoretical calculation demonstrates that the interfacial bridging‐induced electron redistribution optimizes the free energy of water dissociation and hydrogen adsorption, resulting in improved hydrogen evolution. This study not only provides a novel electrocatalyst for efficient HER at all pH conditions but also opens up a new avenue for designing highly active catalytic systems.
A novel CoBDC/MXene electrocatalyst with 2D/2D heterostructure is prepared by a facile in situ growth strategy, in which the formation of interfacial Co–O–Ti bridges effectively tunes the electron distribution and catalytic reaction energy barrier, leading to ultralow hydrogen evolution reaction overpotentials at all pH conditions.
Photocatalytic epoxide alcoholysis through C−O bond cleavage and formation has emerged as an alternative to synthesizing anti‐tumoral pharmaceuticals and fine chemicals. However, the lack of crucial ...evidence to interpret the interaction between reactants and photocatalyst surface makes it challenging for photocatalytic epoxide alcoholysis with both high activity and regioselectivity. In this work, we report the hierarchical ZnIn2S4@CdS photocatalyst for epoxide alcoholysis with high regioselectivity nearly 100 %. Mechanistic studies unveil that the precise activation switch on exposed Zn acid sites for C−O bond polarization and cleavage has a critical significance for achieving efficient photocatalytic performance. Furthermore, the establishment of Z‐scheme heterojunction facilitates the interface charge separation and transfer. Remarkably, the underlying regioselective photocatalytic reaction pathway has been distinctly revealed.
Hollow CdS nanocages wrapped in ultrathin ZnIn2S4 nanosheets were synthesized to form the hierarchical photocatalyst ZnIn2S4@CdS. Surface‐exposed Zn acid centers and the Z‐Scheme pathway between ZnIn2S4 and CdS promote the polarization of epoxide molecules and interfacial charge transfer, leading to photoredox‐catalyzed regioselective alcoholysis of epoxides.
N6‐methyladenosine (m6A) is a well‐known modification of RNA. However, as a key m6A methyltransferase, METTL16 has not been thoroughly studied in gastric cancer (GC). Here, the biological role of ...METTL16 in GC and its underlying mechanism was studied. Immunohistochemistry was used to detect the expression of METTL16 and relationship between METTL16 level and prognosis of GC was analysed. CCK8, colony formation assay, EdU assay and xenograft mouse model were used to study the effect of METTL16. Regulatory mechanism of METTL16 in the progression of GC was studied through flow cytometry analysis, RNA degradation assay, methyltransferase inhibition assay, RT‐qPCR and Western blotting. METTL16 was highly expressed in GC cells and tissues and was associated with prognosis. In vitro and in vivo experiments confirmed that METTL16 promoted proliferation of GC cells and tumour growth. Furthermore, down‐regulation of METTL16 inhibited proliferation by G1/S blocking. Significantly, we identified cyclin D1 as a downstream effector of METTL16. Knock‐down METTL16 decreased the overall level of m6A and the stability of cyclin D1 mRNA in GC cells. Meanwhile, inhibition of methyltransferase activity reduced the level of cyclin D1. METTL16‐mediated m6A methylation promotes proliferation of GC cells through enhancing cyclin D1 expression.
Rational heterointerface engineering is crucial for superior and robust hydrogen evolution reaction (HER). Herein, a delicate organic‐inorganic hybrid heterojunction based on the assembly of oxalate ...with polyaniline (PANI) for HER at high‐current‐densities is envisioned. Strong π–d electron coupling is achieved between the delocalized π electrons of PANI and the localized d electrons of oxalate metal sites. The CoC2O4 nanosheets are grown on nickel foam (NF) with Ni2+ ions substitution by the precursor etching. By virtue of the synergy of hetero ions and π–d electron coupling, metal sites obtain sufficient exposure and electronic structure optimization. Surprisingly, the phase transition of oxalate during HER in the alkaline environment does not weaken the π–d electronic coupling of the organic‐inorganic hybrid interfaces. Inheritable interfacial electron interaction provides a reliable guarantee for robust stability at high‐current‐densities while endowing the hybrid materials with extremely low overpotentials. As expected, post‐phase reconstructed Co0.59Ni0.41(OH)2@PANI/NF displays impressive HER activity, with a low overpotential of 43 mV@−10 mA cm−2 and robust stability at −1000 mA cm−2 for 30 h in the alkaline environment. This study sheds light on the rational heterostructure interface design and promotes the architecture of an impressive electrocatalysts system.
This study constructs robust organic‐inorganic hybrid interfaces between bimetallic oxalate and polyaniline with strong π–d electronic coupling. The oxalate undergoes phase reconstruction to form hydroxide during hydrogen evolution reaction (HER) in the alkaline environment. Benefiting from the strong electronic coupling, the hybrid interfaces after the reconstruction remain structurally stable to achieve superior HER activity at high‐current‐densities.
A typical feature of marine foods is that they are rich in docosahexaenoic acid (DHA) and eicosapentaenoic acid (EPA), which have formed a large-scale global industry. DHA/EPA phospholipids (PLs) are ...ubiquitous in marine foods and are the main DHA/EPA molecular forms in fish roe, shrimp and shellfish. Much attention has been focused on the bioavailability and health benefits that are influenced by the type and esterified form of dietary fatty acids. Recently, numerous findings have suggested that dietary DHA/EPA-PLs are superior to the triacylglycerol (TAG) or ethyl ester forms in exerting their functional properties through specific mechanisms of action. However, there is no comprehensive review covering the health benefits of dietary marine DHA/EPA-enriched PLs. In this paper, we review publications on the nutritional functions of DHA/EPA-enriched glycerophospholipids, including the effects on brain function, antitumor activity, lipid metabolism, and glucose metabolism. The current research status regarding the active ingredients, sources, models, treatment, duration, and mechanisms are presented. In addition, the way in which the structure-activity relationship of DHA/EPA-PLs is affected by ester-bond structure at the sn-1 position, fatty acid at the sn-2 position and polar head group at the sn-3 position is also reviewed. DHA/EPA-PLs are one of the major n-3 long-chain polyunsaturated fatty acid dietary forms in our diet, and we should maximize the ability to fully exploit the nutritional properties of DHA/EPA.
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Palladium diselenide (PdSe2), a peculiar noble metal dichalcogenide, has emerged as a new two-dimensional material with high predicted carrier mobility and a widely tunable band gap for device ...applications. The inherent in-plane anisotropy endowed by the pentagonal structure further renders PdSe2 promising for novel electronic, photonic, and thermoelectric applications. However, the direct synthesis of few-layer PdSe2 is still challenging and rarely reported. Here, we demonstrate that few-layer, single-crystal PdSe2 flakes can be synthesized at a relatively low growth temperature (300 °C) on sapphire substrates using low-pressure chemical vapor deposition (CVD). The well-defined rectangular domain shape and precisely determined layer number of the CVD-grown PdSe2 enable us to investigate their layer-dependent and in-plane anisotropic properties. The experimentally determined layer-dependent band gap shrinkage combined with first-principle calculations suggest that the interlayer interaction is weaker in few-layer PdSe2 in comparison with that in bulk crystals. Field-effect transistors based on the CVD-grown PdSe2 also show performances comparable to those based on exfoliated samples. The low-temperature synthesis method reported here provides a feasible approach to fabricate high-quality few-layer PdSe2 for device applications.
Cranio‐spinal volume and pressure changes associated with the cardiac‐cycle and respiration are altered in Chiari I malformation (CMI) due to obstruction of cerebrospinal fluid (CSF) flow at the ...foramen magnum. With the introduction of motion‐sensitive MRI sequences, it was envisioned that these could provide noninvasive information about volume–pressure dynamics at the cranio‐cervical junction in CMI hitherto available only through invasive pressure measurements. Since the early 1990s, multiple studies have assessed CSF flow and brain motion in CMI. However, differences in design and varied approaches in the presentation of results and conclusions makes it difficult to fully comprehend the role of MR imaging of CSF flow and brain motion in CMI. In this review, a cohesive summary of the current status of MRI assessment of CSF flow and brain motion in CMI is presented. Simplified versions of the results and conclusions of previous studies are presented by dividing the studies in distinct topics: 1) comparing CSF flow and brain motion between healthy subjects (HS) and CMI patients (before and after surgery), 2) comparing CSF flow and brain motion to CMI severity and symptoms, and 3) comparing CSF flow and brain motion in CMI with and without syringomyelia. Finally, we will discuss our vision of the future directions of MR imaging in CMI patients.
Evidence Level
2.
Technical Efficacy
5.
To report long‐term results of a randomized controlled trial that compared cisplatin/fluorouracil/docetaxel (TPF) induction chemotherapy (IC) plus concurrent chemoradiotherapy (CCRT) with CCRT alone ...in locoregionally advanced nasopharyngeal carcinoma (NPC). Patients with stage III–IVB (except T3–4 N0) NPC were randomly assigned to receive IC plus CCRT (n = 241) or CCRT alone (n = 239). IC included three cycles of docetaxel (60 mg/m2 d1), cisplatin (60 mg/m2 d1), and fluorouracil (600 mg/m2/d civ d1–5) every 3 weeks. Patients from both groups received intensity‐modulated radiotherapy concurrently with three cycles of 100 mg/m2 cisplatin every 3 weeks. After a median follow‐up of 71.5 months, the IC plus CCRT group showed significantly better 5‐year failure‐free survival (FFS, 77.4% vs. 66.4%, p = 0.019), overall survival (OS, 85.6% vs. 77.7%, p = 0.042), distant failure‐free survival (88% vs. 79.8%, p = 0.030), and locoregional failure‐free survival (90.7% vs. 83.8%, p = 0.044) compared to the CCRT alone group. Post hoc subgroup analyses revealed that beneficial effects on FFS were primarily observed in patients with N1, stage IVA, pretreatment lactate dehydrogenase ≥170 U/l, or pretreatment plasma Epstein–Barr virus DNA ≥6000 copies/mL. Two nomograms were further developed to predict the potential FFS and OS benefit of TPF IC. The incidence of grade 3 or 4 late toxicities was 8.8% (21/239) in the IC plus CCRT group and 9.2% (22/238) in the CCRT alone group. Long‐term follow‐up confirmed that TPF IC plus CCRT significantly improved survival in locoregionally advanced NPC with no marked increase in late toxicities and could be an option of treatment for these patients.
What's new?
Despite advances in the treatment of nasopharyngeal carcinoma, approximately 30% of high‐risk patients experience recurrence after treatment. Here the authors find that combining the conventional chemoradiotherapy with a triple induction chemotherapy (cisplatin/fluorouracil/docetaxel) prolonged survival of patients with locoregionally advanced cancer, even after more than 70 months of follow‐up. The combination treatment increased acute, but not late, toxicities, and the authors propose that it could present a new treatment option for this patient group.
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