Cluster-Cluster Co-Nucleation Induced Defective Polyoxometalate-Based Metal-Organic Frameworks for Efficient Tandem Catalysis.

The construction of defective sites is one of the effective strategies to create high-activity Metal-Organic frameworks (MOFs) catalysts. However, traditional synthesis methods usually suffer from cumbersome synthesis steps and disordered defect structures. Herein, a cluster-cluster co-nucleation (CCCN) strategy is presented that involves the in situ introduction of size-matched functional polyoxometalates (H6P2W18O62, {P2W18}) to intervene the nucleation process of cluster-based MOFs (UiO-66), achieving one-step inducement of exposed defective sites without redundant post-processing. POM-induced UiO-66 ({P2W18}-0.1@UiO-66) exhibits a classical reo topology for well-defined cluster defects. Moreover, the defective sites and the interaction between POM and skeletal cluster nodes are directly observed by Integrated Differential Phase Contrast in Scanning Transmission Electron Microscopy (iDPC-STEM). Owing to the molecular-level proximity between defective sites and POM in the same nano-reaction space, {P2W18}-0.1@UiO-66 exhibits efficient tandem catalysis in the preparation of γ-valerolactone (γ-GVL) from laevulinic acid (LA) by the combination of Lewis and Brønsted acids with 11 times higher performance than defective UiO-66 formed by conventional coordination modulation strategy. The CCCN strategy is applicable to different POM and has the potential to be extended to other cluster-based MOFs, which will pave a new way for the construction of functional MOFs with multi-centered synergistic catalysis.

Fabrication of a ZIF-on-lamella-zeolite architecture as a highly efficient catalyst for aldol condensation.

Designing composite catalysts that harness the strengths of individual components while mitigating their limitations is a fascinating yet challenging task in catalyst engineering. In this study, we aimed to enhance the catalytic performance by anchoring ZIF-67 nanoparticles of precise sizes onto lamella Si-MWW zeolite surfaces through a stepwise regrowth process. Co ions were initially grafted onto the zeolite surface using ultrasonication, followed by a seed-assisted secondary growth method. Si-MWW proved to be the ideal zeolite support due to its thin layered structure, large external surface area and substantial lateral dimensions. The abundant Si-OH groups on its surface played a crucial role in securely binding Co ions, limiting size growth and preventing undesirable ZIF-67 aggregation. The resulting ZIF-67/MWW composite with finely dispersed nano-scale ZIF-67 particles exhibited a remarkable catalytic performance and stability in the aldol condensation reactions involving acetone and various aldehydes. This approach holds promise for designing MOF/zeolite composite catalysts.

Protective effects and mechanisms of the Erzhi formula on glucocorticoid induced primary cortical neuron injury.

High concentrations of glucocorticoids (GC) can cross the blood-brain barrier into the brain parenchyma, triggering a stress state that can lead to a range of physiological changes. This study investigated whether Erzhi formula has neuroprotective effects against glucocorticoid damage by establishing a dexamethasone-induced primary cortical neuron injury model in vitro. The results showed that Erzhi formula could reduce dexamethasone-induced apoptosis in primary cultured cortical neurons and improve synaptic damage. Further, network pharmacological analysis revealed that Erzhi formula may exert antidepressant effects by multi-component, multi-target, and multi-pathway characteristics, in which Salidroside, Biochanin-A and other ingredients are key components, HSD11B1, NR3C1, and other proteins are key targets, and steroid metabolism may be a key process in its action. Moreover, our study found that the neuroprotective effect of Erzhi formula might be related to the 11ß-HSD1-GC/glucocorticoid receptor (GR) signaling pathway. The Erzhi formula could significantly inhibit the activity of 11ß-hydroxysteroid dehydrogenase 1 (11ß-HSD1) in vitro using homogeneous time-resolved fluorescence. In addition to providing evidence for the pharmacological effects of the Erzhi formula, the present study lays down the foundation for subsequent experiments.

Downregulation of RBM17 enhances cisplatin sensitivity and inhibits cell invasion in human hypopharyngeal cancer cells.

Most of advanced hypopharyngeal squamous cell carcinoma (HSCC) are resistant to chemotherapy, and there is still lack of effective treatment for HSCC now. The present study aimed to investigate whether downregulation of RNA-binding motif protein 17 (RBM17) could enhance cisplatin sensitivity and inhibit cell invasion in HSCC and the underlying mechanism. We observed that RBM17 was upregulated in tumor tissues and associated with poor progression. Treatment of FaDu cells with cisplatin increased RBM17 expression in mRNA levels. Downregulation of RBM17 enhanced cisplatin-mediated inhibition of FaDu cells. In addition, downregulation of RBM17 effectively suppressed tumor cell migration and invasion through the reversion of epithelial-mesenchymal transition. Moreover, downregulation of RBM17 could significantly slow tumor growth in FaDu xenograft tumor model. Liquid chromatography-mass spectrometry/mass spectrometry detection and independent PRM analysis showed that 21 differentially expressed proteins were associated with the downregulation of RBM17. Taken together, our study implied that downregulation of RBM17 could serve as a novel approach to enhance cisplatin sensitivity in HSCC.

Isolation and characterization of two new chroman-4-ones from the endophytic fungus Penicillium chrysogenum obtained from Eucommia ulmoides Oliver.

Two new chroman-4-ones penicichromanone A (1) and penicichromanone B (2), together with three known compounds conioxepinol C (3), emodin (4) and moniliphenone (5), were obtained from the endophytic fungus Penicillium chrysogenum, which was isolated from the bark of Eucommia ulmoides Oliver. The structures of 1 and 2 were elucidated by detailed analysis of HRESIMS, 1D/2D NMR and ECD spectra. All the compounds were evaluated for their anti-inflammatory activities using HEK293 cells, and compounds 1, 3, 4 and 5 exhibited significant inhibitory effects on TNF-α-stimulated NF-κB activation.

Photo- and Thermosensitive Polymer Membrane with a Tunable Microstructure Doped with Graphene Oxide Nanosheets and Poly(N-isopropylacrylamide) for the Application of Light-Cleaning.

Traditional polymer membranes exhibit a constant structure that makes adjustment of the filtration process difficult, such as flux changing and contaminant cleaning. Inspired by the automatically closing behavior of leaf stomata under strong light, we prepared a membrane with thermo- and photosensitivities, whose microstructure, as well as filtration properties, could be controlled by adjusting the light condition. The membrane was fabricated by the immersion phase inversion method with a casting solution of polyvinylidene fluoride-g-poly(N-isopropylacrylamide) (PVDF-g-PNIPAAm) and graphene oxide (GO) nanosheets. Additionally, the membrane could be heated to a high temperature in a short time under illumination, causing shrinkage of its PNIPAAm chains and expansion of its membrane pores. On the basis of the reversible photoinduced structural transformation, the membrane exhibited a high water gating ratio under the switching of light on/off. Moreover, we proposed a novel and simple method to clear the contaminant from the pores of the membrane via light, which we named "light-cleaning". Light-cleaning had a flux recovery rate of 99.2%, substantially higher than that of back-washing (62%). This work not only extends the controllability and functionality of the polymer membrane but also develops a new membrane cleaning system.

Preorganized helical chirality controlled homochiral self-assembly and circularly polarized luminescence of a quadruple-stranded Eu2L4 helicate.

ß-Diketones are one of the most widely used ligands for sensitizing the luminescence of lanthanide complexes due to their excellent sensitization abilities. However, the difficulties in introducing chiral groups to take part in the electronic transitions of conjugated systems limit their application in lanthanide circularly polarized luminescence (CPL) materials. In view of the inherent chirality of the helical structure, herein, a pair of homochiral quadruple-stranded helicates, Eu2L4, is assembled based on chiral bis-ß-diketonate ligands, wherein the two point chirality centers in the spacer preorganize the helical conformation of the ligand (3S,4S)/(3R,4R)-3,4-bis(4,4'-bis(4,4,4-trifluoro-1,3-dioxobutyl)phenoxyl)-1-benzylpyrrolidine, LSS/LRR. X-ray crystallographic analyses reveal that the R,R configurations of the chiral carbons in the spacer induce the M helical sense of the ligand, while the S,S configurations induce the P helical sense. Through the comprehensive spectral characterization in combination with semiempirical geometry optimization using the Sparkle/RM1 model, it is confirmed that the preorganized ligands successfully control the homochirality of the helicates. Moreover, the mirror-image CD and CPL spectra and NMR measurements confirm the formation of enantiomeric pairs and their diastereopurities in solution. Detailed photophysical and chiroptical characterization studies reveal that the helicates not only exhibit intense circularly polarized luminescence (CPL) with |glum| values reaching 0.10, but also show a high luminescence quantum yield of 34%. This study effectively combines the helical chirality of the helicates with the excellent sensitization ability of the ß-diketones, providing an effective strategy for the syntheses of chiral lanthanide CPL materials.

Tetraphenylethylene@Graphene Oxide with Switchable Fluorescence Triggered by Mixed Solvents for the Application of Repeated Information Encryption and Decryption.

Aggregation-induced emission (AIE) materials present unique solid-state fluorescence. However, there remains a challenge in the switching of fluorescence quenching/emitting of AIE materials, limiting the application in information encryption. Herein, we report a composite of tetraphenylethylene@graphene oxide (TPE@GO) with switchable microstructure and fluorescence. We choose GO as a fluorescence quencher to control the fluorescence of TPE by controlling the aggregation structure. First, TPE coating with an average thickness of about 31 nm was deposited at the GO layer surface, which is the critical thickness at which the fluorescence can be largely quenched because of the fluorescence resonance energy transfer. After spraying a mixed solvent (good and poor solvents of TPE) on TPE@GO, a blue fluorescence of TPE was emitted during the drying process. During the treatment of mixed solvents, the planar TPE coating was dissolved in THF first and then the TPE molecules aggregated into nanoparticles (an average diameter of 65 nm) in H2O during the volatilization of THF. We found that the fluorescence switching of the composite is closely related to the microstructural change of TPE between planar and granular structures, which can make the upper TPE molecules in and out of the effective quenching region of GO. This composite, along with the treatment method, was used as an invisible ink in repeated information encryption and decryption. Our work not only provides a simple strategy to switch the fluorescence of solid-state fluorescent materials but also demonstrates the potential for obtaining diverse material structures through compound solvent treatment.

Clinical significance of USP7 and EZH2 in predicting prognosis of laryngeal squamous cell carcinoma and their possible functional mechanism.

BACKGROUND: Laryngeal squamous cell carcinoma (LSCC) is one of the most prevalent cancer types in the world. The ubiquitin specific protease 7 (USP7), a kind of deubiquitylating enzyme, has been reported to play multifaceted roles in different tumor types. EZH2 has been found to be highly expressed in various malignantcells and high expression of EZH2 is closely related to tumor growth infiltration, lymph node involvement, clinical stage, and poor prognosis. The aim of this study was to investigate the expression and function of USP7 and EZH2 in LSCC. CASE PRESENTATION: Immunohistochemical staining and histochemical staining were performed to explore the expression of USP7 and EZH2 in both LSCC tissues and adjacent normal laryngeal tissues. Chi-square test, univariate analysis, and multivariate analysis were conducted to statistically evaluate the clinical significance of USP7 and EZH2. CONCLUSIONS: USP7and EZH2 affects LSCC evolution; USP7 and EZH2 were upregulated in LSCC tissues, which can serve as independent prognostic predictors, and potential therapeutic targets for LSCC.

Cloning and Tissue-Specific Expression of a Chitin Deacetylase Gene from Helicoverpa armigera (Lepidoptera: Noctuidae) and Its Response to Bacillus thuringiensis.

Chitin deacetylases (CDAs) convert chitin into chitosan, the N-deacetylated form of chitin, which influences the mechanical and permeability properties of structures such as the cuticle and peritrophic matrices. In this article, a new CDA encoding gene, Hacda2, was cloned by reverse transcription-polymerase chain reaction method in Helicoverpa armigera (Hübner) (Lepidoptera: Noctuidae), with an open reading frame of 1,611 bp. The deduced protein composed of 536 amino acid residues with a signal peptide, a chitin-binding domain, a low-density lipoprotein receptor class A domain, and a polysaccharide deacetylase-like catalytic domain. The highest expression level of Hacda2 was detected in fat body among tissues tested in the fifth-instar larvae using real-time quantitative polymerase chain reaction method. Feeding of Bacillus thuringiensis (Bt) (Bacillales: Bacillaceae) diet changed the expression level of Hacda1, Hacda2, Hacda5a, and Hacda5b significantly and differentially in the third-instar larvae. Hacda5a and Hacda5b expression were initially down-regulated and then up-regulated, whereas, the expression level of Hacda1 and Hacda2 was suppressed constantly postfeeding on Bt diet. These results suggested that HaCDAs may be involved in the response of H. armigera larvae to Bt and may be helpful to elucidate the roles of HaCDAs in the action of Bt cry toxin. The potential of HaCDAs to be used as synergists of Bt insecticidal protein needs to be further tested.

Riluzole is a promising pharmacological inhibitor of bilirubin-induced excitotoxicity in the ventral cochlear nucleus.

BACKGROUND AND PURPOSE: Bilirubin encephalopathy as a result of hyperbilirubinemia is a devastating neurological disorder that occurs mostly in the neonatal period. To date, no effective drug treatment is available. Glutamate-mediated excitotoxicity is likely an important factor causing bilirubin encephalopathy. Thus, drugs suppressing the overrelease of glutamate may protect the brain against bilirubin excitotoxicity. Riluzole is a prescription drug known for its antiglutamatergic function. This study was conducted in the rat's ventral cochlear nucleus, a structure highly sensitive to bilirubin toxicity, to find whether riluzole can be used to inhibit bilirubin toxicity. EXPERIMENTAL APPROACH: Electrophysiology changes were detected by perforated patch clamp technique. Calcium imaging using Rhod-2-AM as an indicator was used to study the intracellular calcium. Cell apoptosis and necrosis were measured by PI/Hoechst staining. KEY RESULTS: In the absence of bilirubin, riluzole effectively decreased the frequency of spontaneous excitatory postsynaptic currents (sEPSCs) and suppressed neuronal firing but did not change the amplitude of sEPSC and glutamate-activated currents (I(Glu)). Moreover, riluzole inhibited bilirubin-induced increases in the frequency of sEPSC and neuronal firing. Riluzole could prevent the bilirubin-induced increase in intracellular calcium, mediated by AMPA and NMDA receptors. Furthermore, riluzole significantly reduced bilirubin-induced cell death. CONCLUSIONS AND IMPLICATIONS: These data suggest that riluzole can protect neurons in the ventral cochlear nucleus from bilirubin-induced hyperexcitation and excitotoxicity through reducing presynaptic glutamate release.

Taurine protects against bilirubin-induced hyperexcitation in rat anteroventral cochlear nucleus neurons.

No effective medication for hyperbilirubinemia yet exists. Taurine is believed to exert a neuroprotective action. The aim of the present study was to determine whether taurine protected neurons of the rat anteroventral cochlear nucleus (AVCN) against bilirubin-induced neuronal hyperexcitation. AVCN neurons were isolated from 13 to 15-day-old Sprague-Dawley rats. The effects of bilirubin on the spontaneous excitatory postsynaptic currents (sEPSCs) and action potential currents were compared with those exerted by bilirubin and taurine together. Bilirubin dramatically increased the frequencies of sEPSCs and action potential currents, but not sEPSC amplitude. Taurine suppressed the enhanced frequency of action potentials induced by bilirubin, in a dose-dependent manner. In addition, taurine decreased the amplitude of voltage-dependent calcium channel currents that were enhanced upon addition of bilirubin. We explored the mechanism of the protective effects exerted by taurine using GABAA and glycine receptor antagonists, bicuculline and strychnine, respectively. Addition of bicuculline and strychnine eliminated the protective effects of taurine. Neither bilirubin nor taurine affected the sensitivity of the glutamate receptor. Our findings thus indicate that taurine protected AVCN neurons against bilirubin-induced neuronal hyperexcitation by activating the GABAA and glycine receptors and inhibiting calcium flow through voltage-gated channels. Thus, taurine may be effective in treatment of neonatal hyperbilirubinemia.