Growth of Size-Tunable Ag2O Polyhedra and Revelation of Their Bulk and Surface Lattices.

By primarily adjusting the reagent amounts, particularly the volume of AgNO3 solution introduced, Ag2O cubes with decreasing sizes from 440 to 79 nm, octahedra from 714 to 106 nm, and rhombic dodecahedra from 644 to 168 nm are synthesized. 733 nm cuboctahedra are also prepared for structural analysis. With in-house X-ray diffraction (XRD) peak calibration, shape-related peak shifts are recognizable. Synchrotron XRD measurements at 100 K reveal the presence of bulk and surface layer lattices. Bulk cell constants also deviate slightly. They show a negative thermal expansion behavior with shrinking cell constants at higher temperatures. The Ag2O crystals exhibit size- and facet-dependent optical properties. Bandgaps red-shift continuously with increasing particle sizes. Optical facet effect is also observable. Moreover, synchrotron XRD peaks of a mixture of Cu2O rhombicuboctahedra and edge- and corner-truncated cubes exposing all three crystal faces can be deconvoluted into three components with the bulk and the [111] microstrain phase as the major component. Interestingly, while the unheated Cu2O sample shows clear diffraction peak asymmetry, annealing the sample to 450 K yields nearly symmetric peaks even when returning the sample to room temperature, meaning even moderately high temperatures can permanently change the crystal lattice.

Dual-plasmonic Au@Cu7S4 yolk@shell nanocrystals for photocatalytic hydrogen production across visible to near infrared spectral region.

Near infrared energy remains untapped toward the maneuvering of entire solar spectrum harvesting for fulfilling the nuts and bolts of solar hydrogen production. We report the use of Au@Cu7S4 yolk@shell nanocrystals as dual-plasmonic photocatalysts to achieve remarkable hydrogen production under visible and near infrared illumination. Ultrafast spectroscopic data reveal the prevalence of long-lived charge separation states for Au@Cu7S4 under both visible and near infrared excitation. Combined with the advantageous features of yolk@shell nanostructures, Au@Cu7S4 achieves a peak quantum yield of 9.4% at 500 nm and a record-breaking quantum yield of 7.3% at 2200 nm for hydrogen production in the absence of additional co-catalysts. The design of a sustainable visible- and near infrared-responsive photocatalytic system is expected to inspire further widespread applications in solar fuel generation. In this work, the feasibility of exploiting the localized surface plasmon resonance property of self-doped, nonstoichiometric semiconductor nanocrystals for the realization of wide-spectrum-driven photocatalysis is highlighted.

Zhang-Rice singlets state formed by two-step oxidation for triggering water oxidation under operando conditions.

The production of ecologically compatible fuels by electrochemical water splitting is highly desirable for modern industry. The Zhang-Rice singlet is well known for the superconductivity of high-temperature superconductors cuprate, but is rarely known for an electrochemical catalyst. Herein, we observe two steps of surface reconstruction from initial catalytic inactive Cu1+ in hydrogen treated Cu2O to Cu2+ state and further to catalytic active Zhang-Rice singlet state during the oxygen evolution reaction for water splitting. The hydrogen treated Cu2O catalyst exhibits a superior catalytic activity and stability for water splitting and is an efficient rival of other 3d-transition-metal catalysts. Multiple operando spectroscopies indicate that Zhang-Rice singlet is real active species, since it appears only under oxygen evolution reaction condition. This work provides an insight in developing an electrochemical catalyst from catalytically inactive materials and improves understanding of the mechanism of a Cu-based catalyst for water oxidation.

Ligand-Promoted Cooperative Electrochemical Oxidation of Bio-Alcohol on Distorted Cobalt Hydroxides for Bio-Hydrogen Extraction.

Hydrogen is increasingly viewed as a game-changer in the clean energy sector. Renewable hydrogen production from water is industrialized by integrating water electrolysis and renewable electricity, but the current cost of water-born hydrogen remains high though. An ideal scenario would be to produce value-added chemicals along with hydrogen so the cost can be partially offset. Herein, facilitated bio-hydrogen extraction and biomass-derived chemical formation from sugar-derived 5-hydroxymethyfurfural (HMF) were achieved via the in-situ transformation of cobalt-bound electrocatalysts. The cyanide-bound cobalt hydroxide exhibited a low voltage at 1.55 V at 10 mA cm-2 for bio-hydrogen production, compared with an iridium catalyst (1.75 V). The interaction between the biomass intermediate and the cyanide ligand is suggested to be responsible for the improved activity.

4D spatiotemporal modulation of biomolecules distribution in anisotropic corrugated microwrinkles via electrically manipulated microcapsules within hierarchical hydrogel for spinal cord regeneration.

Although traditional 3D scaffolds or biomimetic hydrogels have been used for tissue engineering and regenerative medicine, soft tissue microenvironment usually has a highly anisotropic structure and a dynamically controllable deformation with various biomolecule distribution. In this study, we developed a hierarchical hybrid gelatin methacrylate-microcapsule hydrogel (HGMH) with Neurotrophin-3(NT-3)-loaded PLGA microcapsules to fabricate anisotropic structure with patterned NT-3 distribution (demonstrated as striped and triangular patterns) by dielectrophoresis (DEP). The HGMH provides a dynamic biomimetic sinuate-microwrinkles change with NT-3 spatial gradient and 2-stage time-dependent distribution, which was further simulated using a 3D finite element model. As demonstrated, in comparison with striped-patterned hydrogel, the triangular-patterned HGMH with highly anisotropic array of microcapsules exhibits remarkably spatial NT-3 gradient distributions that can not only guide neural stem cells (NSCs) migration but also facilitate spinal cord injury regeneration. This approach to construct hierarchical 4D hydrogel system via an electromicrofluidic platform demonstrates the potential for building various biomimetic soft scaffolds in vitro tailed to real soft tissues.

Silencing of PRDM5 increases cell proliferation and inhibits cell apoptosis in glioma.

AIM: PR-domain-containing 5 (PRDM5), a family member of PR-domain-containing zinc finger genes, has been reported to participate in modulate cellular processes, including cell growth, differentiation and apoptosis. It has also been found to function as a putative tumor suppressor in different types of cancer. The present study is the first, to the best of our knowledge, to report on the clinical significance of the expression of PRDM5 in glioma cell line. MATERIALS AND METHODS: Western blot analyse the expression of PRDM5 in glioma tissues and cells. 80 tissues microarray samples from patients with glioma were examined using immunohistochemical analysis. Glioblastoma U251 cells were transfected with PRDM5-siRNA and control-siRNA. U251cell proliferation was measured by flow cytometric analysis and plate colony formation assay. Cell apoptosis were detected using flow cytometric analysis. RESULTS: The results of western blot analysis and immunohistochemistry showed that the expression of PRDM5 was decreased in fresh glioma tissues, compared with that in normal brain tissues. Kaplan-Meier postoperative survival curves demonstrated that the low expression of PRDM5 was associated with poor prognosis in patients with glioma. In addition, suppression of PRDM5 promoted cell proliferation via regulating cell cycle progression. Finally, knocking down PRDM5 using small interfering RNA decreased the apoptosis of glioma cells. CONCLUSION: Taken together, these findings suggested that PRDM5 may be a novel therapeutic target of glioma.

Structural and Electronic Optimization of MoS2 Edges for Hydrogen Evolution.

The activity and accessibility of MoS2 edge sites are critical to deliver high hydrogen evolution reaction (HER) efficiency. Here, a porous carbon network confining ultrasmall N-doped MoS2 nanocrystals (N-MoS2/CN) is fabricated by a self-templating strategy, which realizes synergistically structural and electronic modulations of MoS2 edges. Experiments and density functional theory calculations demonstrate that the N dopants could activate MoS2 edges for HER, while the porous carbon network could deliver high accessibility of the active sites from N-MoS2 nanocrystals. Consequently, N-MoS2/CN possesses superior HER activity with an overpotential of 114 mV at 10 mA cm-2 and excellent stability over 10 h, delivering one of best MoS2-based HER electrocatalysts. Moreover, this study opens a new venue for optimizing materials with enhanced accessible catalytic sites for energy-related applications.

Sandwich-Nanostructured n-Cu2O/AuAg/p-Cu2O Photocathode with Highly Positive Onset Potential for Improved Water Reduction.

An n-Cu2O layer formed a high-quality buried junction with p-Cu2O to increase the photovoltage and thus to shift the turn-on voltage positively. Mott-Schottky measurements confirmed that the improvement benefited from a positive shift in flat-band potential. The obtained extremely positive onset potential, 0.8 VRHE in n-Cu2O/AuAg/p-Cu2O, is comparable with measurements from water reduction catalysts. The AuAg alloy sandwiched between the homojunction of n-Cu2O and p-Cu2O improved the photocatalytic performance. This alloy both served as an electron relay and promoted electron-hole pair generation in nearby semiconductors; the charge transfer between n-Cu2O and p-Cu2O in the sandwich structure was measured with X-ray absorption spectra. The proposed sandwich structure can be considered as a new direction for the design of efficient solar-related devices.

Two-Dimensional Cobalt Phosphate Hydroxide Nanosheets: A New Type of High-Performance Electrocatalysts with Intrinsic CoO6 Lattice Distortion for Water Oxidation.

Despite the recent advances in electrochemical water splitting, developing cost-effective and highly efficient electrocatalysts for oxygen evolution reaction (OER) still remains a substantial challenge. Herein, two-dimensional cobalt phosphate hydroxides (Co5(PO4)2(OH)4) nanosheets, a unique stacking-disordered phosphate-based inorganic material, are successfully prepared via a facile and scalable method for the first time to serve as a superior and robust electrocatalyst for water oxidation. On the basis of the detailed characterization (e.g., X-ray absorption near-edge structure and X-ray photoelectron spectroscopy), the obtained nanosheets consist of special zigzag CoO6 octahedral chains along with intrinsic lattice distortion and excellent hydrophilicity, in which these factors contribute to the highly efficient performance of prepared electrocatalysts for OER. Specifically, Co5(PO4)2(OH)4 deposited on glassy carbon electrode (loading amount ≈0.553 mg cm-2) can exhibit an unprecedented overpotential of 254 mV to drive a current density of 10 mA cm-2 with a small Tafel slope of 57 mV dec-1 in alkaline electrolytes, which outperforms the ones of CO3(PO4)2 (370 mV) and Co(OH)2 (360 mV) as well as other advanced catalysts. Evidently, this work has opened a new pathway to the rational design of promising metal phosphate hydroxides toward the efficient electrochemical energy conversion.

MEKK1, JNK, and SMAD3 mediate CXCL12-stimulated connective tissue growth factor expression in human lung fibroblasts.

BACKGROUND: In idiopathic pulmonary fibrosis, the interaction of CXCL12 and CXC receptor 4 (CXCR4) plays a critical role in lung fibrosis. Connective tissue growth factor (CTGF) overexpression underlies the development of pulmonary fibrosis. Our previous report showed that the Rac1-dependent extracellular signal-regulated kinase (ERK), c-Jun N-terminal kinase (JNK), and activator protein (AP)-1 pathways are involved in CXCL12-generated CTGF expression in human lung fibroblasts (WI-38). In present study, we additionally inspected the involvement of mitogen-activated protein kinase kinase kinase 1 (MEKK1)/JNK-dependent SMAD3 in CXCL12-triggered CTGF expression in WI-38 cells. METHODS: WI-38 cells were stimulated with CXCL12 in the absence or presence of specific inhibitors or small interfering RNAs (siRNAs). CTGF expression and signaling transduction molecules were assessed by Western blot, luciferase activity assay, or ChIP assay. RESULTS: CXCL-12-induced CTGF expression was attenuated by SIS3 (a SMAD3 inhibitor) and SMAD3 siRNA, but not by SB431542 (an activin receptor-like kinase 5, ALK5, inhibitor). CXCL12-stimulated CTGF expression was also attenuated by MEKK1 siRNA. Treatment of cells with CXCL12 caused an increase in SMAD3 phosphorylation at Ser208, translocation to nuclei, SMAD3-luciferase activity, and recruitment of SMAD3 to the CTGF promoter. Stimulation of cells with CXCL12 resulted in increase in JNK phosphorylation at Thr183/Tyr185 and MEKK1 phosphorylation at Thr261. Moreover, CXCL12-mediated SMAD3 phosphorylation or SMAD3-luciferase activity was inhibited by MEKK1 siRNA or SP600125. Finally, CXCL12-mediated JNK phosphorylation was attenuated by MEKK1 siRNA. CONCLUSION: In conclusion, results of this study suggest that CXCL12 activates the MEKK1/JNK signaling pathway, which in turn initiates SMAD3 phosphorylation, its translocation to nuclei, and recruitment of SMAD3 to the CTGF promoter, which ultimately induces CTGF expression in human lung fibroblasts.

Suppression of the Smurf1 Expression Inhibits Tumor Progression in Gliomas.

Glioblastoma, one of the common malignant brain tumors, results in the highly death, but its underlying molecular mechanisms remain unclear. Smurf1, a member of Nedd4 family of HECT-type ligases, has been reported to contribute to tumorigenicity through several important biological pathways. Recently, it was also found to participate in modulate cellular processes, including morphogenesis, autophagy, growth, and cell migration. In this research, we reported the clinical guiding significance of the expression of Smurf1 in human glioma tissues and cell lines. Western blotting analysis discovered that the expression of Smurf1 was increased with WHO grade. Immunohistochemistry levels discovered that high expression of Smurf1 is closely consistent with poor prognosis of glioma. In addition, suppression of Smurf1 can reduce cell invasion and increase the E-cadherin expression, which is a marker of invasion. Our study firstly demonstrated that Smurf1 may promote glioma cell invasion and suppression of the Smurf1 may provide a novel treatment strategy for glioma.

Cutaneous Metastases of the Glioma.

Low grade glioma (LGG) is a very common primary brain neoplasm with a very good prognosis and the median survival of patients is approximately 8 years. With the development of current treatments such as surgery resection, radiotherapy, and chemotherapy, the recurrence rate and the distant metastasis rate of LGGs are largely decreased. Extracranial metastases are seldom happened. However, the authors present a pathologically proven patient with scalp metastasis, which was metastasized from LGG occurring site to the surgical scar 8 months following initial craniotomy and chemotherapy. The histopathologic examination of the primary site and the recurrent under the scalp are exactly similar. This grade of glioma was increased along with cutaneous metastases. A discussion of a series of the extracranial metastases of the glioma, especially for the surgical considerations, is also provided advice for the cutaneous metastases of the glioma.

Intracranial Enterogenous Cysts Close to the Brainstem Treated Through the Nerve Endoscope.

Enterogenous cysts (ECs) are rare, inborn lesions of central nervous system, which mostly occurred in the ventral side of the spinal cord as well as common in children; adult intracranial cysts are rare. Although the morbidity of intracranial ECs is quite low, we also can make a preliminary diagnosis of those patients with the help of imaging examination. In this article, we introduced 1 case of ECs ventral to the brainstem, which present images on magnetic resonance imaging as hypointense lesions on T1-weighted and high-intensity mass on T2-weighted image. In consideration of the difficulty of the surgical approach and the surgical visual field exposure, we use microscope and nerve endoscope to design personalized surgical approach to minimize the surgical injury. Pathologic examination showed that it was typical EC. Not only is the location extremely rare, but also the surgical method is uncommon in this disease. We not only study the intracranial ECs' manifestations, but also discuss the surgical approach and the application of nerve endoscope of our choice,which aims to provides a new surgical therapeutic approach for these lesions.

Identification of anti-HBV activities in Paeonia suffruticosa Andr. using GRP78 as a drug target on Herbochip®.

BACKGROUND: Herbochip® technology is a high throughput drug screening platform in a reverse screening manner, in which potential chemical leads in herbal extracts are immobilized and drug target proteins can be used as probes for screening process [BMC Complementary and Alternative Medicine (2015) 15:146]. While herbal medicines represent an ideal reservoir for drug screenings, here a molecular chaperone GRP78 is demonstrated to serve as a potential target for antiviral drug discovery. METHODS: We cloned and expressed a truncated but fully functional form of human GRP78 (hGRP781-508) and used it as a probe for anti-HBV drug screening on herbochips. In vitro cytotoxicity and in vitro anti-HBV activity of the herbal extracts were evaluated by MTT and ELISA assays, respectively. Finally, anti-HBV activity was confirmed by in vivo assay using DHBV DNA levels in DHBV-infected ducklings as a model. RESULTS: Primary screenings using GRP78 on 40 herbochips revealed 11 positives. Four of the positives, namely Dioscorea bulbifera, Lasiosphaera fenzlii, Paeonia suffruticosa and Polygonum cuspidatum were subjected to subsequent assays. None of the above extracts was cytotoxic to AML12 cells, but P. cuspidatum extract (PCE) was found to be cytotoxic to HepG2 2.2.15 cells. Both PCE and P. suffruticosa extract (PSE) suppressed secretion of HBsAg and HBeAg in HepG2 2.2.15 cells. The anti-HBV activity of PSE was further confirmed in vivo. CONCLUSION: We have demonstrated that GRP78 is a valid probe for anti-HBV drug screening on herbochips. We have also shown that PSE, while being non-cytotoxic, possesses in vitro and in vivo anti-HBV activities. Taken together, our data suggest that PSE may be a potential anti-HBV agent for therapeutic use.

Synthesis of Cu2O nanoparticle films at room temperature for solar water splitting.

A Cu2O nanoparticle film using ZnO nanorods as a sacrificial scaffold was fabricated near 23°C, for applications in photoelectrochemical (PEC) water splitting. Three chemical solutions were utilized to convert ZnO nanorods to a Cu2O nanoparticle film - solutions of CuCl2 and NaOH, NaBH4 and NaOH, respectively. The structural evolution from ZnO through Cu(OH)2 and metallic Cu to Cu2O phase was analyzed at each stage with X-ray diffraction and X-ray absorption spectra. The energy bandgap was deduced from IPCE; the concentration of carriers and flat-band of a Cu2O nanoparticle film were obtained from a Mott-Schottky plot. Significantly, the Cu2O nanoparticle film exhibited a useful PEC response to water oxidation. This nanostructure synthesized with no energy requirement can not only illustrate a great prospect for solar generation of hydrogen but also offer a blueprint for the future design of photocatalysts.

Thermally activated Cu/Cu2S/ZnO nanoarchitectures with surface-plasmon-enhanced Raman scattering.

Hierarchical Cu/Cu2S/ZnO nanoarchitectures were fabricated via an electroplated ZnO nanorod array in the first step, followed by the growth of Cu2S nanostructures for the application of surface-enhanced Raman scattering (SERS) detection. The Cu/Cu2S nanostructures as grown were thermally treated at 150-300°C under a nitrogen atmosphere to improve the crystalline quality, and, unexpectedly, to induce plasmonic Cu nanoshells on the surface of Cu2S. With 4-aminothiophenol (4-ATP) as probing molecules, SERS experiments showed that the thermally treated Cu/Cu2S/ZnO nanostructures exhibit excellent detection performance, so that they can serve as active and cost-effective SERS substrates for ultrasensitive detection. The enhancement is attributed to the coupling between Cu2S and plasmonic Cu, as confirmed by electromagnetic field simulations. This novel hierarchical substrate shows satisfactory reproducibility and a linear dependence of intensity on analyte concentration, revealing an advantage of this method for easily scaled production.

Upregulation of Interferon Regulatory Factor 6 Promotes Neuronal Apoptosis After Traumatic Brain Injury in Adult Rats.

The interferon regulatory factor (IRF) family was first discovered as a set of transcriptional regulators of the type I interferon system in 1988. In mammals, the IRF family includes nine members that play important roles in the immune system, oncogenesis, and apoptosis. However, the distribution and the function of IRF6 in the central nervous system are limited. In this study, we established an adult rat traumatic brain injury (TBI) model. Compared to the sham brain cortex, Western blot and immunohistochemistry showed significant upregulation of IRF6 in the ipsilateral brain cortex after TBI. Immunofluorescence double-labeling showed that IRF6 completely co-localized with neurons, not astrocytes or oligodendrocytes. Furthermore, we detected that the neuronal apoptosis marker active caspase-3 co-localized with IRF6 in neurons. Additionally, IRF6 knockdown in PC12 cells in vitro resulted in a decrease in active caspase-3 expression and an increase in Bcl-2 and p-Akt expression. We conclude that IRF6 might promote neuronal apoptosis by inhibiting Akt phosphorylation after TBI.

MicroRNA-210 regulates cell proliferation and apoptosis by targeting regulator of differentiation 1 in glioblastoma cells.

MicroRNAs (miRNAs) are small noncoding RNAs that negatively regulate protein biosynthesis and participate in the pathogenesis of various tumours. Previous studies have shown that miR-210 is highly expressed in different types of human cancers, including glioblastoma multiforme (GBM). However, the role that miR-210 plays in GBM remains unclear. Here, we detected the expression and examined the function of miRNA-210 in GBM cells. Furthermore, we investigated the possible molecular mechanisms by which miRNA-210 mediates cell proliferation and apoptosis. Fifteen GBM and five normal brain tissues, in addition to the U87MG and U251 GBM cell lines, were analysed in this study. We found that miR-210 was upregulated in GBM tissues and cell lines when compared to normal brain tissue. Cell counting and flow cytometric assay results demonstrated that upregulation of miR-210 induced cell proliferation and decreased cell apoptosis, respectively. In addition, downregulation of miR-210 inhibited cell proliferation and induced apoptosis. We also detected a miR-210 target, regulator of differentiation 1 (ROD1), which is involved in GBM progression. Knockdown of ROD1 reversed the growth arrest and apoptosis that were originally induced by miR-210 inhibition. We propose that miR-210 regulates cell proliferation and apoptosis in GBM cells by targeting ROD1. Our findings may provide a new potential therapeutic target for the treatment of GBM.

MicroRNA-320 inhibits cell proliferation in glioma by targeting E2F1.

MicroRNAs (miRs) are a class of small non-coding RNAs that are involved in the regulation of gene expression, and in cancer development and progression. In the present study, miR-320 expression was found to be significantly reduced in glioma tissue in comparison with that in adjacent healthy tissues. In the present study, in vitro analyses demonstrated that overexpression of miR-320 inhibited cell proliferation and metastasis, while antisense miR-320 oligonucleotides enhanced cell proliferation and migration in U251 and SHG-44 glioma cell lines, compared with that in negative control cells. Protein expression of E2F1, a cell-cycle regulator, was negatively regulated by miR-320. Therefore, the present study provides novel insights into the association between miR-320 and glioma development.

Nrdp1 is Associated with Neuronal Apoptosis in Lipopolysaccharide-Induced Neuroinflammation.

Neuregulin receptor degradation protein-1 (Nrdp1), a kind of ring finger E3 ubiquitin ligase, is expressed in several adult tissues, including the heart, testis, prostate and brain. Studies of this molecule have demonstrated its great importance in regulating cell growth, apoptosis and oxidative stress in various cell types. However, information regarding its expression and possible function in the central nervous system is still limited. In this study, we performed a neuroinflammation model by lipopolysaccharide (LPS) lateral ventral injection in adult rats. It was found that the expression of Nrdp1 was significantly increased in cerebral cortex after LPS injection. Immunofluorescence indicated that Nrdp1 was located in the neurons, but not astrocytes or microglia. Furthermore, there was a concomitant up-regulation of active caspase-3 and decreased expression of BRUCE (an inhibitor of apoptosis protein). In addition, decreasing Nrdp1 levels by RNA interference in cortical primary neurons reduced active caspase-3 expression but induced up-regulation of BRUCE. Collectively, all these results suggested that Nrdp1 might play a role in neuronal apoptosis by reducing the expression of BRUCE in neuroinflammation after LPS injection.