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.

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.

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.

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.

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.

MicroRNA-210 overexpression predicts poorer prognosis in glioma patients.

MicroRNA-210 (miR-210) levels are elevated in many tumor types, are frequently associated with hypoxia induction, and are correlated with poor prognosis in many solid tumors. miR-210 regulates cell growth, angiogenesis, invasion, and apoptosis of many human tumors. In this study, we investigated the clinical significance of miR-210 expression in common brain tumors, or human gliomas. Glioma samples and normal brain tissues were analyzed using real-time quantitative reverse transcriptase polymerase chain reaction to characterize the expression patterns of miR-210. The association of miR-210 expression with clinicopathological parameters and prognosis of glioma patients was statistically analyzed. Gliomas were further divided by grade: pilocytic astrocytoma (World Health Organization [WHO] grade I), diffuse astrocytomas (WHO grade II), anaplastic astrocytomas (WHO grade III), and glioblastoma (WHO grade IV). There was a significantly higher expression level of miR-210 amongst the glioma tissues as compared with normal brain tissues (p<0.001). Increased expression of miR-210 in glioma tissues was significantly associated with advanced pathological grade (p<0.001) and low Karnofsky Performance Score (p=0.014). In addition, increased miR-210 levels were also associated with poor progression-free survival (PFS) and overall survival (OS) rates when compared to the normal control (both p<0.001), as calculated by Kaplan-Meier survival and Cox regression analyses. Furthermore, subgroup analyses showed that miR-210 expression was significantly associated with poor PFS and OS of glioma patients with high pathological grades (III-IV: both p<0.001). miR-210 is highly expressed in human gliomas and confers a poor prognosis in glioma patients. These findings may bring the development of novel, tailored pharmacological therapies for glioma patients.

Neuroprotective effects of ischemic preconditioning and postconditioning on global brain ischemia in rats through the same effect on inhibition of apoptosis.

Transient forebrain or global ischemia induces neuronal death in vulnerable CA1 pyramidal cells with many features. A brief period of ischemia, i.e., ischemic preconditioning, or a modified reperfusion such as ischemic postconditioning, can afford robust protection of CA1 neurons against ischemic challenge. Therefore, we investigated the effect of ischemic preconditioning and postconditioning on neural cell apoptosis in rats. The result showed that both ischemic preconditioning and postconditioning may attenuate the neural cell death and DNA fragment in the hippocampal CA1 region. Further western blot study suggested that ischemic preconditioning and postconditioning down-regulates the protein of cleaved caspase-3, caspase-6, caspase-9 and Bax, but up-regulates the protein Bcl-2. These findings suggest that ischemic preconditioning and postconditioning have a neuroprotective role on global brain ischemia in rats through the same effect on inhibition of apoptosis.

The effect of shoe sole tread groove depth on the friction coefficient with different tread groove widths, floors and contaminants.

Slipping and falling are common phenomena in both workplaces and our daily activities. The risks associated with slipping and falling are related to the materials of footwear/floor, contamination condition, and geometric design of the sole. Shoe soles of various tread design are very common. Tread pattern of the shoe affects friction especially under liquid-contaminated conditions. Verification of the effects of tread groove depth is significant in assisting designers in designing proper footwear for workers exposed to slippery floor conditions. In this study, we measured the friction coefficients using the Neolite footwear pads on the terrazzo, steel, and vinyl floors under three liquid-contaminated conditions. A Brungraber Mark II slipmeter was used. The footwear pads had tread grooves with a width of either 3 or 9mm. The depth of the tread grooves ranged from 1 to 5mm. The results showed that tread groove depth affected the friction coefficients significantly. Higher friction values were recorded for footwear pads with deeper tread grooves on wet and water-detergent-contaminated floors. The averaged coefficient of friction (COF) gain per tread groove depth increase in millimeter under these two surface conditions ranged from 0.018 to 0.108, depending on the tread groove width, floor, and contaminant.

[Preliminary study of chromosome aberrations in pituitary adenoma].

BACKGROUND & OBJECTIVE: Pituitary adenoma is one of the most common intracranial benign tumor. This study was designed to seek the most suitable method for cytogenetic study of pituitary adenoma(PA), and then to analyze the genetic change of PA cell. METHODS: Twenty-five samples of primary PA were examined by R-banding through direct preparation(DP) and short-term culture(STC) to analyze genomic alterations. RESULTS: A karyotype of 17 samples was identified in 25 PAs by using the DP, whereas there was a karyotype of 21 samples by using the STC. An abnormal clonal karyotype was observed in 11 samples processed by the DP, however only 3 of 25 samples when processed by the STC. The common chromosomal alterations included gains of chromosomes X(6/25), 7(4/25), 8(2/25), 5(2/25) as well as losses of chromosomes 11(5/25), 9(4/25), 13(3/25), and the latter was observed predominantly in invasive PAs. CONCLUSIONS: DP is one of the most suitable methods for the cytogenetic study of PA. There were multiple regions of chromosomes with copy number changes in PA including gains of chromosomes X, 7, 8, and losses of chromosomes 11, 9, 13. However, structural chromosome aberrations are not common. The loss of chromosome and the abnormality of structure may have some correlation with the biologic behavior of PA.