A computational study of photoisomerization in Al3O3- ­clusters

Ab initio calculations are employed to understand the photoisomerization process in small Al3O3- clusters. This process is the first example of a photoinduced isomerization observed in an anion cluster gas-phase system. Potential energy surfaces for the ground state and the excited state (S1 and T1) are explored by means of B3LYP, MP2, CI-singles, and CASSCF methods. We demonstrate that the isomerization process occurs between the global minimum singlet state Book structure (C2v,1A1) and the triplet state Ring structure (C2v,3B2). The calculated vertical excitation energy is 3.62 eV at the CASSCF level of approximation, in good agreement with the experimental value (3.49 eV). A nonplanar conical intersection, which hosts the intersystem crossing between the S1 and T1 surfaces is identified at the region of around R(1,6)=2.4 Å. Beyond the experimental results, we predict, that this isomerization is reversible upon absorption of a phonon with energy of 1.92 eV. Our results describe a unique system, whose structure depends on its spin multiplicity; it exists as the Book structure on singlet states and as the Ring structure on triplet states

Structural and electronic properties of SrZrO3 and Sr(Ti,Zr) O3 alloys

Using hybrid density functional calculations, we study the electronic and structural properties of SrZrO3 and ordered Sr(Ti,Zr)O3 alloys. Calculations were performed for the ground-state orthorhombic (Pnma) and high-temperature cubic (Pm3m) phases of SrZrO3. The variation of the lattice parameters and band gaps with Ti addition was studied using ordered SrTixZr1-xO3 structures with x=0, 0.25, 0.5, 0.75, and 1. As Ti is added to SrZrO3, the lattice parameter is reduced and closely follows Vegard's law. On the other hand, the band gap shows a large bowing and is highly sensitive to the Ti distribution. For x=0.5, we find that arranging the Ti and Zr atoms into a 1×1SrZrO3/SrTiO3 superlattice along the [001] direction leads to interesting properties, including a highly dispersive single band at the conduction-band minimum (CBM), which is absent in both parent compounds, and a band gap close to that of pure SrTiO3. These features are explained by the splitting of the lowest three conduction-band states due to the reduced symmetry of the superlattice, lowering the band originating from the in-plane Ti 3dxy orbitals. The lifting of the t2g orbital degeneracy around the CBM suppresses scattering due to electron-phonon interactions. Our results demonstrate how short-period SrZrO3/SrTiO3 superlattices could be exploited to engineer the band structure and improve carrier mobility compared to bulk SrTiO3

Reaction pathways and mechanisms of the electrochemical degradation of phenol on different electrodes

Laboratory experiments were carried out on the kinetics and pathways of the electrochemical (EC) degradation of phenol at three different types of anodes, Ti/SnO2-Sb, Ti/RuO2, and Pt. Although phenol was oxidised by all of the anodes at a current density of 20 mA/cm2 or a cell voltage of 4.6 V, there was a considerable difference between the three anode types in the effectiveness and performance of EC organic degradation. Phenol was readily mineralized at the Ti/SnO2-Sb anode, but its degradation was much slower at the Ti/RuO2 and Pt anodes. The analytical results of high-performance liquid chromatography (HPLC) and gas chromatography coupled with mass spectrometry (GC/MS) indicated that the intermediate products of EC phenol degradation, including benzoquinone and organic acids, were subsequently oxidised rapidly by the Ti/SnO2-Sb anode, but accumulated in the cells of Ti/RuO2 and Pt. There was also a formation of dark-coloured polymeric compounds and precipitates in the solutions electrolyzed by the Ti/RuO2 and Pt anodes, which was not observed for the Ti/SnO 2-Sb cells. It is argued that anodic property not only affects the reaction kinetics of various steps of EC organic oxidation, but also alters the pathway of phenol electrolysis. Favourable surface treatment, such as the SnO2-Sb coating, provides the anode with an apparent catalytic function for rapid organic oxidation that is probably brought about by hydroxyl radicals generated from anodic water electrolysis. © 2005 Elsevier Ltd. All rights reserved.postprin

Hydrogen adsorption capacity of adatoms on double carbon vacancies of graphene: A trend study from first principles

Structural stability and hydrogen adsorption capacity are two key quantities in evaluating the potential of metal-adatom decorated graphene for hydrogen storage and related devices. We have carried out extensive density functional theory calculations for the adsorption of hydrogen molecules on 12 different adatom (Ag, Au, Ca, Li, Mg, Pd, Pt, Sc, Sr, Ti, Y, and Zr) decorated graphene surfaces where the adatoms are found to be stabilized on double carbon vacancies, thus overcoming the "clustering problem" that occurs for adatoms on pristine graphene. Ca and Sr are predicted to bind the greatest number, namely six, of H2 molecules. We find an interesting correlation between the hydrogen capacity and the change of charge distribution with increasing H2 adsorption, where Ca, Li, Mg, Sc, Ti, Y, Sr, and Zr adatoms are partial electron donors and Ag, Au, Pd, and Pt are partial electron acceptors. The "18-electron rule" for predicting maximum hydrogen capacity is found not to be a reliable indicator for these systems. © 2013 American Physical Society

Lower bounds on the dilation of plane spanners

(I) We exhibit a set of 23 points in the plane that has dilation at least $1.4308$, improving the previously best lower bound of $1.4161$ for the worst-case dilation of plane spanners. (II) For every integer $n\geq13$, there exists an $n$-element point set $S$ such that the degree 3 dilation of $S$ denoted by $\delta_0(S,3) \text{ equals } 1+\sqrt{3}=2.7321\ldots$ in the domain of plane geometric spanners. In the same domain, we show that for every integer $n\geq6$, there exists a an $n$-element point set $S$ such that the degree 4 dilation of $S$ denoted by $\delta_0(S,4) \text{ equals } 1 + \sqrt{(5-\sqrt{5})/2}=2.1755\ldots$ The previous best lower bound of $1.4161$ holds for any degree. (III) For every integer $n\geq6$, there exists an $n$-element point set $S$ such that the stretch factor of the greedy triangulation of $S$ is at least $2.0268$.Comment: Revised definitions in the introduction; 23 pages, 15 figures; 2 table

Corticosterone Potentiation of Cocaine-Induced Reinstatement of Conditioned Place Preference in Mice is Mediated by Blockade of the Organic Cation Transporter 3

The mechanisms by which stressful life events increase the risk of relapse in recovering cocaine addicts are not well understood. We previously reported that stress, via elevated corticosterone, potentiates cocaine-primed reinstatement of cocaine seeking following self-administration in rats and that this potentiation appears to involve corticosterone-induced blockade of dopamine clearance via the organic cation transporter 3 (OCT3). In the present study, we use a conditioned place preference/reinstatement paradigm in mice to directly test the hypothesis that corticosterone potentiates cocaine-primed reinstatement by blockade of OCT3. Consistent with our findings following self-administration in rats, pretreatment of male C57/BL6 mice with corticosterone (using a dose that reproduced stress-level plasma concentrations) potentiated cocaine-primed reinstatement of extinguished cocaine-induced conditioned place preference. Corticosterone failed to re-establish extinguished preference alone but produced a leftward shift in the dose–response curve for cocaine-primed reinstatement. A similar potentiating effect was observed upon pretreatment of mice with the non-glucocorticoid OCT3 blocker, normetanephrine. To determine the role of OCT3 blockade in these effects, we examined the abilities of corticosterone and normetanephrine to potentiate cocaine-primed reinstatement in OCT3-deficient and wild-type mice. Conditioned place preference, extinction and reinstatement of extinguished preference in response to low-dose cocaine administration did not differ between genotypes. However, corticosterone and normetanephrine failed to potentiate cocaine-primed reinstatement in OCT3-deficient mice. Together, these data provide the first direct evidence that the interaction of corticosterone with OCT3 mediates corticosterone effects on drug-seeking behavior and establish OCT3 function as an important determinant of susceptibility to cocaine use

Optimal Siting of Electric Vehicle Charging Stations Using Pythagorean Fuzzy VIKOR Approach

Site selection for electric vehicle charging stations (EVCSs) is the process of determining the most suitable location among alternatives for the construction of charging facilities for electric vehicles. It can be regarded as a complex multicriteria decision-making (MCDM) problem requiring consideration of multiple conflicting criteria. In the real world, it is often hard or impossible for decision makers to estimate their preferences with exact numerical values. Therefore, Pythagorean fuzzy set theory has been frequently used to handle imprecise data and vague expressions in practical decision-making problems. In this paper, a Pythagorean fuzzy VIKOR (PF-VIKOR) approach is developed for solving the EVCS site selection problems, in which the evaluations of alternatives are given as linguistic terms characterized by Pythagorean fuzzy values (PFVs). Particularly, the generalized Pythagorean fuzzy ordered weighted standardized distance (GPFOWSD) operator is proposed to calculate the utility and regret measures for ranking alternative sites. Finally, a practical example in Shanghai, China, is included to demonstrate the proposed EVCS sitting model, and the advantages are highlighted by comparing the results with other relevant methods.Peer Reviewe

Genome wide association mapping of grain arsenic, copper, molybdenum and zinc in rice (Oryza sativa L.) grown at four international field sites

Peer reviewedPublisher PD

The generalized Hamiltonian model for the shafting transient analysis of the hydro turbine generating sets.

yesTraditional rotor dynamics mainly focuses on the steady- state behavior of the rotor and shafting. However, for systems such as hydro turbine generating sets (HTGS) where the control and regulation is frequently applied, the shafting safety and stabilization in transient state is then a key factor. The shafting transient state inevitably involves multiparameter domain, multifield coupling, and coupling dynamics. In this paper, the relative value form of the Lagrange function and its equations have been established by defining the base value system of the shafting. Takingthe rotation angle and the angular speed of the shafting as a link, the shafting lateral vibration and generator equations are integrated into the framework of generalized Hamiltonian system. The generalized Hamiltonian control model is thus established. To make the model more general, additional forces of the shafting are taken as the input excitation in proposed model. The control system of the HTGS can be easily connected with the shafting model to form the whole simulation system of the HTGS. It is expected that this study will build a foundation for the coupling dynamics theory using the generalized Hamiltonian theory to investigate coupling dynamic mechanism among the shafting vibration, transient of hydro turbine generating sets, and additional forces of the shafting.National Natural Science Foundation of China under Grant Nos. 51179079 and 5083900

Genome-wide copy number variation study in anorectal malformations

Anorectal malformations (ARMs, congenital obstruction of the anal opening) are among the most common birth defects requiring surgical treatment (2-5/10 000 live-births) and carry significant chronic morbidity. ARMs present either as isolated or as part of the phenotypic spectrum of some chromosomal abnormalities or monogenic syndromes. The etiology is unknown. To assess the genetic contribution to ARMs, we investigated single-nucleotide polymorphisms and copy number variations (CNVs) at genome-wide scale. A total of 363 Han Chinese sporadic ARM patients and 4006 Han Chinese controls were included. Overall, we detected a 1.3-fold significant excess of rare CNVs in patients. Stratification of patients by presence/absence of other congenital anomalies showed that while syndromic ARM patients carried significantly longer rare duplications than controls (P = 0.049), non-syndromic patients were enriched with both rare deletions and duplications when compared with controls (P = 0.00031). Twelve chromosomal aberrations and 114 rare CNVs were observed in patients but not in 868 controls nor 11 943 healthy individuals from the Database of Genomic Variants. Importantly, these aberrations were observed in isolated ARM patients. Gene-based analysis revealed 79 genes interfered by CNVs in patients only. In particular, we identified a de novo DKK4 duplication. DKK4 is a member of the WNT signaling pathway which is involved in the development of the anorectal region. In mice, Wnt disruption results in ARMs. Our data suggest a role for rare CNVs not only in syndromic but also in isolated ARM patients and provide a list of plausible candidate genes for the disorder.postprin