Controllable and Scale-Up Synthesis of Nickel-Cobalt Boride@Borate/RGO Nanoflakes via Reactive Impingement Mixing: A High-Performance Supercapacitor Electrode and Electrocatalyst.

Large-scale synthesis of graphene-based nanomaterials in stirred tank reactor (STR) often results in serious agglomeration because of the poor control during micromixing process. In this work, reactive impingement mixing is conducted in a two-stage impinging jet microreactor (TS-IJMR) for the controllable and scale-up synthesis of nickel-cobalt boride@borate core-shell nanostructures on RGO flakes (NCBO/RGO). Benefiting from the good process control and improved micromixing efficiency of TS-IJMR, NCBO/RGO nanosheet provides a large BET surface area, abundant of suitable mesopores (2-5 nm), fast ion diffusion, and facile electron transfer within the whole electrode. Therefore, NCBO/RGO electrode exhibits a high specific capacitance of 2383 F g-1 at 1 A g-1, and still retains 1650 F g-1 when the current density is increased to 20 A g-1, much higher than those of nickel boride@borate/RGO (NBO/RGO) and cobalt boride@borate/RGO (CBO/RGO) synthesized in TS-IJMR, as well as NCBO/RGO-S synthesized in STR. In addition, an asymmetric supercapacitor (NCBO/RGO//AC) is constructed with NCBO/RGO and activated carbon (AC), which displays a high energy density of 53.3 W h kg-1 and long cyclic lifespan with 91.8% capacitance retention after 5000 charge-discharge cycles. Finally, NCBO/RGO is used as OER electrocatalyst to possess a low overpotential of 309 mV at a current density of 10 mA cm-2 and delivers a good long-term durability for 10 h. This study opens up the potential of controllable and scale-up synthesis of NCBO/RGO nanosheets for high-performance supercapacitor electrode materials and OER catalysts.

FGFR1 and HER1 or HER2 co-amplification in breast cancer indicate poor prognosis.

Human epidermal growth factor receptor 1 or 2 (HER1/2), and fibroblast growth factor receptor 1 (FGFR1) signaling serve critical roles in the progression of breast cancer; however, cross-talk between HER1/2 and FGFR1 signaling has not been extensively studied. In the present study, the copy number variation status of FGFR1 and HER1/2, and the clinical implications and prognostic relevance of this, were evaluated in invasive ductal breast cancer (IDC) tissue samples. Quantitative polymerase chain reaction and fluorescence in situ hybridization were used to assess gene copy number variation in IDC samples, and the clinical characteristics and survival curves of patients with IDC were analyzed. The amplification of FGFR1 was identified in 16.0% of the samples (12 of 75), of HER1 in 26.7% (20 of 75), of HER2 in 37.3% (28 of 75), and of FGFR1 and HER1/2 simultaneously in 8.0% (6 of 75). FGFR1 and HER1/2 co-amplification were significantly correlated with distant metastasis (P=0.035), recurrence (P=0.026) and decreased disease-free survival time (P=0.042). This was the case for patients undergoing endocrine therapy (P=0.002) and chemotherapy (P=0.044). Taken together, the results indicate that patients with FGFR1 and HER1/2 co-amplification may exhibit a less favorable prognosis compared with patients with either FGFR1, HER1/2 amplification or without amplification.

Breast cancers with EGFR and HER2 co-amplification favor distant metastasis and poor clinical outcome.

ErbB signaling serves essential roles in invasive ductal carcinoma (IDC). The aim of the present study was to assess gene amplification in ErbB family members in IDC with clinical implications. Quantitative polymerase chain reaction and fluorescence in situ hybridization were performed on formalin-fixed paraffin-embedded tumor samples for gene amplification detection. The clinical and histopathological characteristics, as well as the prognostic significance, were analyzed. Among the 119 IDC patients evaluated, epidermal growth factor receptor [EGFR; also known as human epidermal growth factor receptor (HER)1], HER2, HER3 and HER4 gene amplification was observed in 30 (25.2%), 44 (36.9%), 0 (0.0%) and 1 (0.8%) patients, respectively. EGFR amplification was associated with estrogen receptor status (P=0.028) and higher possibilities of recurrence (P=0.015) and distant metastasis (following initial surgery) (P=0.011). In survival analysis, EGFR amplification was also associated with disease-free survival (DFS) (P=0.001) and overall survival (OS) (P=0.003). HER2 amplification was associated with larger tumor size (P=0.006), later clinical stage (P=0.003) and distant metastasis (following initial surgery) (P=0.006). In survival analysis, HER2 amplification was also associated with DFS (P=0.011). Notably, the present study identified a group of patients in whom EGFR and HER2 were co-amplified. This group of patients appeared to have a higher possibility of metastasis (when diagnosed) (P=0.014) and distant metastasis (following initial surgery) (P<0.001). In survival analysis, these patients were noticed to be associated with DFS (P<0.001) and OS (P=0.002). With respect to treatment regimen, this was also true for the DFS association with chemotherapy (P<0.001), radiotherapy (P<0.001) and hormonal therapy (P=0.001). The present results suggest that EGFR and HER2 amplification favor distant metastasis following initial surgery and are significantly associated with poor clinical outcome in breast cancer patients.

Relation between the Co-O bond lengths and the spin state of Co in layered Cobaltates: a high-pressure study.

The pressure-response of the Co-O bond lengths and the spin state of Co ions in a hybrid 3d-5d solid-state oxide Sr2Co0.5Ir0.5O4 with a layered K2NiF4-type structure was studied by using hard X-ray absorption and emission spectroscopies. The Co-K and the Ir-L 3 X-ray absorption spectra demonstrate that the Ir5+ and the Co3+ valence states at ambient conditions are not affected by pressure. The Co Kß emission spectra, on the other hand, revealed a gradual spin state transition of Co3+ ions from a high-spin (S = 2) state at ambient pressure to a complete low-spin state (S = 0) at 40 GPa without crossing the intermediate spin state (S = 1). This can be well understood from our calculated phase diagram in which we consider the energies of the low spin, intermediate spin and high spin states of Co3+ ions as a function of the anisotropic distortion of the octahedral local coordination in the layered oxide. We infer that a short in-plane Co-O bond length (<1.90 Å) as well as a very large ratio of Co-Oapex/Co-Oin-plane is needed to stabilize the IS Co3+, a situation which is rarely met in reality.

Quantitative real-time polymerase chain reaction is an alternative method for the detection of HER-2 amplification in formalin-fixed paraffin-embedded breast cancer samples.

Fluorescent in situ hybridization (FISH) and immunohistochemistry (IHC) are the most common methods that are used to quantify HER-2 gene and protein levels, respectively, in human breast cancer. However, due to bad sample quality, some samples are unable to be subjected to a FISH assay. We evaluated 71 formalin-fixed paraffin-embedded (FFPE) breast carcinoma specimens by quantitative real-time polymerase chain reaction (qPCR), IHC, and FISH. We also performed qPCR and FISH assays on delayed formalin-fixed (DDF) samples. The qPCR results were in complete concordance with the results of IHC and FISH. In regards to the DDF samples, the HER-2 fluorescent signal seemed decayed compared with that of the DDF samples after 1 h. However, the qPCR method still works well up to 12 hours. Our results indicated that qPCR was obviously superior to FISH in cases that were not fixed in a reasonable amount of time. However, qPCR can be an alternative method by which to perform HER2 amplification assays in breast cancer.

Low temperature structural anomalies arising from competing exchange interactions in pyrochlore Nd2Ru2O7 probed by XRD and EXAFS.

Quantitative structural parameters of pyrochlore Nd2Ru2O7, with temperature dependence, have been derived upon fitting XRD and EXAFS data. An anomalous expansion of the lattice parameter and the Ru-O bond length indicates a structural instability at low temperatures; in particular, an increase in the non-thermal term of the mean square fluctuation in the bond length is the evidence for a static disorder of Ru atoms. This static disorder is closely correlated with a decrease in the average Ru-O-Ru bond angle with decreasing temperature, favoring the short-range ferromagnetic coupling in the material. This ferromagnetic coupling formed thus triggered the spin frustration at low temperature when the contradictory constraints of antiferromagnetic interaction act upon the same Ru site in the corner-sharing tetrahedrons of pyrochlore Nd2Ru2O7. This study demonstrates that the spin frustration arising from the competition of ferromagnetic/antiferromagnetic interactions in pyrochlore Nd2Ru2O7 will cause structural instability especially on the atomic scale, which provides a new point of view to help understand its particular magnetic state.

Atomic distribution and structural evolution of mesostructured PtRu nanoparticles electrodeposited on a microemulsion lyotropic liquid-crystalline template probed using EXAFS and XANES.

Mesostructured PtRu nanoparticles were electrochemically reduced from their metallic salts directed by a hexagonally packed microemulsion lyotropic liquid-crystalline (MLLC) template. We investigated the structural evolution and atomic distribution of the MLLC-templated mesoporous PtRu nanoparticles (NPs) after electroreduction for varied duration using X-ray absorption near edge structure (XANES) and extended X-ray absorption fine structure (EXAFS) spectroscopy, complemented by energy-dispersive X-ray spectroscopy (EDS) and field-emission transmission electron microscopy (FE-TEM). The XANES data at the Ru L2,3 and Pt L3 edges show predominantly metallic states of Ru and Pt in the PtRu NPs upon electroreduction. The reduction of Ru(3+) ions in RuCl3 into Ru atoms involves intermediate RuCl-containing complexes. A more rapid reduction of Pt precursors and a release of Ru atoms from Ru precursors in two steps upon electroreduction resulted in aggregation into PtRu nanoparticles, featuring a Pt-rich core, a Ru-rich shell and a varied alloy extent of Ru, deduced from EXAFS data. The complementary results provide insight into the mechanism of growth and atomic distribution of mesostructured PtRu bimetallic nanoparticles from the use of the MLLC-type templates.

Synthesis and reactions of beta-diketiminato divanadium(I) inverted-sandwich complexes.

Reduction of VCl(2)(Nacnac) (Nacnac = HC(C(Me)NC(6)H(3)-iPr(2))(2)) with KC(8) in toluene leads to the formation of a toluene-bridged inverted-sandwich divanadium(I) complex, (mu-eta(6):eta(6)-C(7)H(8))[V(Nacnac)](2), which behaves as a source of V(Nacnac) and a multi-electron reductant in the two reactions studied in this report.

TiO2 nanotube-supported cu as the catalyst for selective NO reduction with NH3.

Catalyst supports composed of titanate nanotubes were prepared from hydrothermal treatment on TiO2 nanoparticles in NaOH followed by HCl washing. The nanotubes exhibited well-defined TiO2 anatase phase after calcination at 400 degrees C. The nanotube aggregates and other commercially available TiO2 nanoparticles, all with surface areas >300 m(2)/g, were impregnated with Cu and examined in selective catalytic reduction of NO with NH3. In catalyst preparation, the nanotubes were found to be more thermally stable than nanoparticles, withstanding agglomeration at elevated temperatures. The Cu species supported on the nanotubes showed a higher catalytic activity than those supported on the nanoparticles. Analysis with temperature programmed reduction, X-ray photoelectron spectroscopy, and NO adsorption reflected that the layered-titanate feature of the tube wall was advantageous for even distribution of the Cu species, thus leading to the high-catalytic activity of the tubular Cu/TiO2 catalyst.

Structural feature and catalytic performance of Cu species distributed over TiO2 nanotubes.

Copper oxide was deposited on tubular TiO2 via Cu2+ introduction into a titanate nanotube aggregate followed by calcination. The titanate has a layered structure allowing Cu intercalation and can readily transform into anatase TiO2 via calcination for condensation of the constituting layers. The activity of the tubular catalysts, with a Cu content of 2 wt %, in selective NO reduction with NH3 was compared with those of other 2 wt % Cu/TiO2 catalysts using TiO2 nanoparticles as the support. The Cu species supported on the nanotubes showed a higher activity than those supported on the nanoparticles. X-ray absorption near-edge structure (XANES) analysis showed that the Cu species on all the TiO2 supports are in the +2 state. Extended X-ray absorption fine structure (EXAFS) investigations of these catalysts reflected higher degrees of CuO dispersion and Cu2+ dissolution into the TiO2 lattice for the tubular Cu/TiO2 catalysts. Absence of CuO bulk detection by a temperature-programmed reduction analysis for the tubular catalysts confirmed the high CuO-dispersion feature of the tubular catalysts. The dissolution of Cu2+ to form a CuxTi1-xO2 type of solid solution was improved by using an in-situ ion-intercalation method for Cu deposition on the nanotubes. A fraction as high as 40% for Cu2+ dissolution was obtained for the tubular catalysts while only 20% was obtained for the particulate catalysts. The CuxTi1-xO2 species were considered one form of the active sites on the Cu/TiO2 catalysts.