Relative edge energy in the stability of transition metal nanoclusters of different motifs

When a structure is reduced to a nanometer scale, the proportion of the lowly-coordinated edge atoms increases significantly, which can play a crucial role in determining both their geometric and electronic properties, as demonstrated by the recently established generalized Wulff construction principle [S. F. Li, et al., Phys. Rev. Lett., 2013, 111, 115501]. Consequently, it is of great interest to clarify quantitatively the role of the edge atoms that dominate the motifs of these nanostructures. In principle, establishing an effective method valid for determining the absolute value of the surface energy and particularly the edge energy for a given nanostructure is expected to resolve such a problem. However, hitherto, it is difficult to obtain the absolute edge energy of transition metal clusters, particularly when their sizes approach the nanometer regime. In this paper, taking Ru nanoclusters as a prototypical example, our first-principles calculations introduce the concept of relative edge energy (REE), reflecting the net edge atom effect over the surface (facet) atom effect, which is fairly powerful to quasi-quantitatively estimate the critical size at which the crossover occurs between different configurations of a given motif, such as from an icosahedron to an fcc nanocrystal. By contrast, the bulk effect should be re-considered to rationalize the power of the REE in predicting the relative stability of larger nanostructures between different motifs, such as fcc-like and hcp-like nanocrystals

Template-free synthesis of Nd0.1Bi0.9FeO3 nanotubes with large inner diameter and wasp-waisted hysteresis loop

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Substrate co-doping modulates electronic metal-support interactions and significantly enhances single-atom catalysis

Transitional metal nanoparticles or atoms deposited on appropriate substrates can lead to highly economical, efficient, and selective catalysis. One of the greatest challenges is to control the electronic metal–support interactions (EMSI) between the supported metal atoms and the substrate so as to optimize their catalytic performance. Here, from first-principles calculations, we show that an otherwise inactive Pd single adatom on TiO2(110) can be tuned into a highly effective catalyst, e.g. for O2 adsorption and CO oxidation, by purposefully selected metal–nonmetal co-dopant pairs in the substrate. Such an effect is proved here to result unambiguously from a significantly enhanced EMSI. A nearly linear correlation is noted between the strength of the EMSI and the activation of the adsorbed O2 molecule, as well as the energy barrier for CO oxidation. Particularly, the enhanced EMSI shifts the frontier orbital of the deposited Pd atom upward and largely enhances the hybridization and charge transfer between the O2 molecule and the Pd atom. Upon co-doping, the activation barrier for CO oxidation on the Pd monomer is also reduced to a level comparable to that on the Pd dimer which was experimentally reported to be highly efficient for CO oxidation. The present findings provide new insights into the understanding of the EMSI in heterogeneous catalysis and can open new avenues to design and fabricate cost-effective single-atom-sized and/or nanometer-sized catalysts

The abnormal electrical and optical properties in Na and Ni codoped BiFeO3 nanoparticles

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Fluid flow induced calcium response in bone cell network

In our previous work, bone cell networks with controlled spacing and functional intercellular gap junctions had been successfully established by using microcontact printing and self assembled monolayers technologies [Guo, X. E., E. Takai, X. Jiang, Q. Xu, G. M. Whitesides, J. T. Yardley, C. T. Hung, E. M. Chow, T. Hantschel, and K. D. Costa. Mol. Cell. Biomech. 3:95-107, 2006]. The present study investigated the calcium response and the underlying signaling pathways in patterned bone cell networks exposed to a steady fluid flow. The glass slides with cell networks were separated into eight groups for treatment with specific pharmacological agents that inhibit pathways significant in bone cell calcium signaling. The calcium transients of the network were recorded and quantitatively evaluated with a set of network parameters. The results showed that 18 alpha-GA (gap junction blocker), suramin (ATP inhibitor), and thapsigargin (depleting intracellular calcium stores) significantly reduced the occurrence of multiple calcium peaks, which were visually obvious in the untreated group. The number of responsive peaks also decreased slightly yet significantly when either the COX-2/PGE(2) or the NOS/nitric oxide pathway was disrupted. Different from all other groups, cells treated with 18 alpha-GA maintained a high concentration of intracellular calcium following the first peak. In the absence of calcium in the culture medium, the intracellular calcium concentration decreased slowly with fluid flow without any calcium transients observed. These findings have identified important factors in the flow mediated calcium signaling of bone cells within a patterned network.</p

Abnormal variation of band gap in Zn doped Bi0.9La0.1FeO3 nanoparticles: Role of Fe-O-Fe bond angle and Fe-O bond anisotropy

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Calcium response in osteocytic networks under steady and oscillatory fluid flow

The fluid flow in the lacunar-canalicular system of bone is an essential mechanical stimulation on the osteocyte networks. Due to the complexity of human physical activities, the fluid shear stress on osteocyte bodies and processes consists of both steady and oscillatory components. In this study, we investigated and compared the intracellular calcium ([Ca2+](i)) responses of osteocytic networks under steady and oscillatory fluid flows. An in vitro osteocytic network was built with MLO-Y4 osteocyte-like cells using micro-patterning techniques to simulate the in vivo orderly organization of osteocyte networks. Sinusoidal oscillating fluid flow or unidirectional steady flow was applied on the cell surface with 2 Pa peak shear stress. It was found that the osteocytic networks were significantly more responsive to steady flow than to oscillatory flow. The osteocytes can release more calcium peaks with higher magnitudes at a faster speed under steady flow stimulation. The [Ca2+](i) signaling transients under the steady and oscillatory flows have significantly different spatiotemporal characters, but a similar responsive percentage of cells. Further signaling pathway studies using inhibitors showed that endoplasmic reticulum (ER) calcium store, extracellular calcium source, ATP, PGE(2) and NO related pathways play similar roles in the [Ca2+](i) signaling of osteocytes under either steady or oscillating flow. The spatiotemporal characteristics of [Ca2+](i) transients under oscillating fluid flow are affected more profoundly by pharmacological treatments than under the steady flow. Our findings support the hypothesis that the [Ca2+](i) responses of osteocytic networks are significantly dependent on the profiles of fluid flow

Assessing impacts of climate change and human activities on streamflow and sediment discharge in the Ganjiang River basin (1964-2013)

© 2019 by the authors. National large-scale soil and water conservation controls on the Gangjiang River basin have been documented, but the effect of governance on regional watershed hydrology and how the main driving factors act have not been systematically studied yet. To do this, this study evaluated changing trends and detected transition years for both streamflow and sediment discharge using long-term historical records at seven hydrological stations in the Ganjiang River basin over the past 50 years. The double mass curve (DMC) method was used to quantify the effects of both climate change and human activities on hydrological regime shifts. The results showed that the distributions of precipitation, streamflow, and sediment discharge within a year are extremely uneven and mainly concentrated in the flood season of Jiangxi Province. None of the stations showed significant trends over time for either annual precipitation or streamflow, while the annual sediment discharge at most stations decreased significantly over time. The estimation of sediment discharge via DMC indicated that after the transition years, there were rapid reductions in sediment discharge at all hydrological stations, and the average decline degree of midstream and downstream were much larger than that of upstream. Human activities, especially the increase of vegetation cover and construction of large and medium-sized reservoirs, provided a significantly greater contribution to the reduction of sediment discharge than did precipitation changes. As a case study of river evolution under global change environment, this study could provide scientific basis for the control of soil erosion and the management of water resources in Ganjiang River, as well as for the related research of Poyang Lake and the Yangtze River basin of China

Broadband gradient impedance matching using an acoustic metamaterial for ultrasonic transducers

2016-2017 > Academic research: refereed > Publication in refereed journal201804_a bcmaVersion of RecordPublishe