Elevating the d-Band Center of Ni3S2 Nanosheets by Fe Incorporation to Boost the Oxygen Evolution Reaction.

Many attempts have been made to enhance the relatively poor electrochemical activity of Ni3S2 for the oxygen evolution reaction (OER) by elevating the d-band center. Unfortunately, only limited success has been encountered thus far. Owning to the lower electronegativity and one less 3d electron relative to Ni, Fe shows great potentials in upshifting the overall d-band center of Ni3S2 when incorporating into its crystal structures. Herein, to enhance the intrinsic activity by elevating the d-band center, Ni3S2 nanosheets incorporated with suitable Fe content have been fabricated by a facile one-step solvothermal method. The obtained Fe-incorporated Ni3S2 catalyst exhibits an outstanding OER performance in alkaline media, only requiring 244 mV overpotential (with a reduction of 210 mV compared to Ni3S2) at 50 mA cm-2 in 1 M KOH and without obvious degradation after sustaining for a 60 h test at a voltage above 1.5 V. Ultraviolet photoemission spectroscopy and density functional theory calculations consistently demonstrate that the superior performance of Fe-incorporated Ni3S2 is attributed to the upshift of the d-band center on neutralizing the electron densities of Ni, which optimize greatly the adsorption energy of the intermediate (OOH*) in the rate-determining Volmer step.

A RuCoBO Nanocomposite for Highly Efficient and Stable Electrocatalytic Seawater Splitting.

Efficient and stable electrocatalysts are critically needed for the development of practical overall seawater splitting. The nanocomposite of RuCoBO has been rationally engineered to be an electrocatalyst that fits these criteria. The study has shown that a calcinated RuCoBO-based nanocomposite (Ru2Co1BO-350) exhibits an extremely high catalytic activity for H2 and O2 production in alkaline seawater (overpotentials of 14 mV for H2 evolution and 219 mV for O2 evolution) as well as a record low cell voltage (1.466 V@10 mA cm-2) and long-term stability (230 h @50 mA cm-2 and @100 mA cm-2) for seawater splitting. The results show that surface reconstruction of Ru2Co1BO-350 occurs during hydrogen evolution reaction and oxygen evolution reaction, which leads to the high activity and stability of the catalyst. The reconstructed surface is highly resistant to Cl- corrosion. The investigation suggests that a new strategy exists for the design of high-performance Ru-based electrocatalysts that resist anodic corrosion during seawater splitting.

Interfacial Carbon Makes Nano-Particulate RuO2 an Efficient, Stable, pH-Universal Catalyst for Splitting of Seawater.

An electrocatalyst composed of RuO2 surrounded by interfacial carbon, is synthesized through controllable oxidization-calcination. This electrocatalyst provides efficient charge transfer, numerous active sites, and promising activity for pH-universal electrocatalytic overall seawater splitting. An electrolyzer with this catalyst gives current densities of 10 mA cm-2 at a record low cell voltage of 1.52 V, and shows excellent durability at current densities of 10 mA cm-2 for up to 100 h. Based on the results, a mechanism for the catalytic activity of the composite is proposed. Finally, a solar-driven system is assembled and used for overall seawater splitting, showing 95% Faraday efficiency.

A spatial homojunction of titanium vacancies decorated with oxygen vacancies in TiO2 and its directed charge transfer.

The n-p homojunction design in semiconductors could enable directed charge transfer, which is promising but rarely reported. Herein, TiO2 with a spatial n-p homojunction has been designed by decorating TiO2 nanosheets with Ti vacancies around nanostructured TiO2 with O vacancies. 2D 1H TQ-SQ MAS NMR, EPR and XPS show the junction of titanium vacancies and oxygen vacancies at the interface. This spatial homojunction contributes to a significant enhancement in photoelectrochemical and photocatalytic performance, especially photocatalytic seawater splitting. Density functional theory calculations of the charge density reveal the directional n-p charge transfer path at the interface, which is proposed at the atomic-/nanoscale to clarify the generation of rational junctions. The spatial n-p homojunction provides a facile strategy for the design of high-performance semiconductors.

Exploring Potential Mechanisms of Fludioxonil Resistance in Fusarium oxysporum f. sp. melonis.

Melon Fusarium wilt (MFW), which is caused by Fusarium oxysporum f. sp. melonis (FOM), is a soil-borne disease that commonly impacts melon cultivation worldwide. In the absence of any disease-resistant melon cultivars, the control of MFW relies heavily on the application of chemical fungicides. Fludioxonil, a phenylpyrrole fungicide, has been shown to have broad-spectrum activity against many crop pathogens. Sensitivity analysis experiments suggest that fludioxonil has a strong inhibitory effect on the mycelial growth of FOM isolates. Five fludioxonil-resistant FOM mutants were successfully generated by repeated exposure to fludioxonil under laboratory conditions. Although the mutants exhibited significantly reduced mycelial growth in the presence of the fungicide, there initially appeared to be little fitness cost, with no significant difference (p < 0.05) in the growth rates of the mutants and wild-type isolates. However, further investigation revealed that the sporulation of the fludioxonil-resistant mutants was affected, and mutants exhibited significantly (p < 0.05) reduced growth rates in response to KCl, NaCl, glucose, and mannitol. Meanwhile, molecular analysis of the mutants strongly suggested that the observed fludioxonil resistance was related to changes in the sequence and expression of the FoOs1 gene. In addition, the current study found no evidence of cross-resistance between fludioxonil and any of the other fungicides tested. These results indicate that fludioxonil has great potential as an alternative method of control for FOM in melon crops.

Design and synthesis of TiO2/C nanosheets with a directional cascade carrier transfer.

Directed transfer of carriers, akin to excited charges in photosynthesis, in semiconductors by structural design is challenging. Here, TiO2 nanosheets with interlayered sp2 carbon and titanium vacancies are obtained by low-temperature controlled oxidation calcination. The directed transfer of carriers from the excited position to Ti-vacancies to interlayered carbon is investigated and proven to greatly increase the charge transport efficiency. The TiO2/C obtained demonstrates excellent photocatalytic and photoelectrochemical activity and significant lithium/sodium ion storage performance. Further theoretical calculations reveal that the directional excited position/Ti-vacancies/interlayered carbon facilitate the spatial inside-out cascade electron transfer, resulting in high charge transfer kinetics.

Hierarchically Fractal PtPdCu Sponges and their Directed Mass- and Electron-Transfer Effects.

Fractal Pt-based materials with hierarchical structures and high self-similarity have attracted more and more attention due to their bioinspiring maximum optimization of energy utilization and mass transfer. However, their high-efficiency design of the mass- and electron-transfer still remains to be a great challenge. Herein, fractal PtPdCu hollow sponges (denoted as PtPdCu-HS) facilitating both directed mass- and electron-transfer are presented. Such directed transfer effects greatly promote electrocatalytic activity, regarded as 3.9 times the mass activity, 7.3 times the specific activity, higher poison tolerance, and higher stability than commercial Pt/C for the methanol oxidation reaction (MOR). A new "directed mass- and electron-transfer" concept, characteristics, and mechanism are proposed at the micro/nanoscale to clarify the structural design and functional enhancement of fractal electrocatalyst. This work displays new possibilities for designing novel nanomaterials with high activity and superior stability toward electrocatalysis or other practical applications.

Highly Dispersed Pt Nanoparticles Embedded in N-Doped Porous Carbon for Efficient Hydrogen Evolution.

A novel and facile strategy is presented to synthesize highly dispersed Pt nanoparticles embedded in N-doped porous carbon (Pt@NPC) via carbonization of Zn-containing metal-organic frameworks and chemical replacement of Zn with Pt. The as-prepared Pt@NPC exhibits superior activity and durability towards hydrogen evolution reaction (HER) in comparison with commercial Pt/C catalyst. The excellent HER performance of Pt@NPC can be ascribed to the combined features of catalyst and support material, including high dispersion and ultrathin particle size of Pt, high surface area and nitrogen doping of carbon support, and the strong interaction between metal and support.

[Expressions of Sry-related High Mobility Group Box 9 and Gastrokine-1 in Gastric Cancer and Their Relationships with Prognosis].

Objective To explore the expressions of Sry-related high mobility group box 9(SOX9)and gastrokine-1(GKN1) in gastric cancer tissues and their relationships with clinicopathologic features and prognosis of patients.Methods Immunohistochemistry was used to detect the expressions of SOX9 and GKN1 in 70 cases of gastric cancer tissues and corresponding paracancerous tissues including 27 cases of intestinal metaplasia and 43 cases of normal gastric mucosa. The relationships of SOX9 and GKN1 expressions with clinicopathological features and prognosis were analyzed in gastric cancer tissues.Results The high expression rates of SOX9 in gastric cancer tissues,intestinal metaplasia,and normal gastric mucosa were 92.9%(65/70),77.8%(21/27),and 55.8%(24/43),respectively(χ 2=21.722,P<0.001). Positive nuclear and cytoplasmic staining was observed. The high nuclear expression rate of SOX9 in gastric cancer tissues was 67.1%,which was significantly higher than those of intestinal metaplasia(37.0%,P=0.007)and normal gastric mucosa(23.3%,P<0.001). The high cytoplasmic expression rate of GKN1 in normal gastric mucosa was 76.7%,which was significantly higher than those of intestinal metaplasia(44.4%,P=0.006)and gastric cancer tissues(37.1%,P<0.001). Univariate analysis demonstrated that the nuclear expression of SOX9 in gastric cancer was associated with the degree of tissue differentiation(P=0.007),while the cytoplasmic expression of GKN1 was associated with both the degree of tissue differentiation(P=0.002)and whether the pathological type was a signet-ring cell carcinoma(P=0.009). Furthermore,the nuclear expression of SOX9 was negatively correlated with the expression of GKN1 in gastric cancer(χ 2=15.424,P<0.001). The 5-year survival rates of patients with high or low nuclear expression of SOX9 were 33.8% and 67.5%,respectively(P=0.016).The 5-year survival rates of patients with high or low expression of GKN1 were 60.0% and 35.6%,respectively(P=0.044). Further research indicated that 5-year survival rate of patients with high nuclear expression of SOX9 and low expression of GKN1 was 28.8%. Cox multivariate regression analysis showed that TNM stage(stage Ⅱ:HR=7.435,95%CI:1.313-42.096,P=0.023;stage Ⅲ:HR=12.214,95%CI:2.677-55.721,P=0.001)and nuclear expression level of SOX9(HR=3.297,95%CI:1.199-9.065,P=0.021)were independent risk factors for the prognosis of gastric cancer patients.Conclusions Changes in the expressions of SOX9 and GKN1 may be associated with the malignant biological behavior of gastric cancer. SOX9 may be a potential prognostic factor. The combined detection of SOX9 and GKN1 expression and the further study of their molecular mechanism may provide new clues for early diagnosis,targeted therapy,and prognostic prediction of gastric cancer.

[Therapeutic effect of vadian neurectomy under the nasal endoscope on the vasomotor rhinitis].

OBJECTIVE: To explore the therapeutic effect of vadian neurectomy under the nasal endoscope on the vasomotor rhinitis. METHODS: Anatomic measurements of vadian canal in 14 cadavers were carried out, and vadian neurectomy under the nasal endoscope was performed on 51 patients with vasomotor rhinitis. RESULTS: Anatomic measurements showed vadian canal was located behind the sphenoid-palatine hole, and its external orifice was shaped as infundibular. The vertical diameter was (3.5+/-0.9) mm and the horizontal diameter was (2.9+/-0.5) mm. The distance to the rotundum foramen and nasal septum was (6.1+/-1.2) mm and (10.5+/-5.9) mm. Longitudinal axes of the vadian canal was (27.0+/-9.6) degrees with the horizontal plane, and (7.8+/-2.5) degree with the sagittal plane. Among the 51 patients, 41(80.4%) patients showed complete response and 3(5.9%) partial response at the 5-year follow-up. CONCLUSION: Vadian neurectomy under nasal endoscope is an effective technique for vasomotor rhinitis.

[Genomic instability in nasopharyngeal carcinoma].

OBJECTIVE: To evaluate the effect of genomic instability on prognostics in nasopharyngeal carcinoma. METHODS: Genomic instability was assessed by inter-simple sequence repeats polymerase chain reaction (inter-SSR PCR) in 38 patients with nasopharyngeal carcinoma. Characterization and verification of band alterations shared in different tumors were carried out by sequencing and nest PCR. RESULTS: Thirty-one (81.6%) of the 38 patients showed genomic altercations, and genomic instability index ranged 0 to 16.2 percent. A gain-based genomic damage shared in 6 tumors was identified on chromosome 6q27. Genomic alteration was significantly more in patients less than 5-year survival than those with more than 5-year survival (P<0.05). CONCLUSION: Genomic instability can be an early event marker in carcinogenesis of nasopharyngeal carcinoma. Aggravation of genomic alterations is a poor prognosis for cancer recovery.