Kinetics and mechanisms for the adsorption, dissociation, and diffusion of hydrogen in Ni and Ni/YSZ slabs: a DFT study

The adsorption, dissociation, and diffusion of hydrogen in Ni(100) and Ni(100)/YSZ(100) slabs with two different interfaces (Ni/cation and Ni/O interface) have been studied by the density functional theory (DFT) with the Perdew-Wang functional. The H(2) molecule is found to preferentially absorb on a Top (T) site with side-on configuration on the Ni(100) surface, while the H-atom is strongly bound at a fcc Hollow (H) site. The barrier for the H(2) dissociation on both surfaces is calculated to be only ~0.1 eV. The potential energy pathways of H diffusion on pure Ni and Ni/YSZ with the two different interfaces are studied. Our calculated results show that the H-atom diffusion occurs via surface path rather than the bulk path. For the bulk path in Ni/YSZ, H-atom migration can occur more readily at the Ni/cation interface compared to the Ni/O interface. The existence of vacancy in the interface region is found to improve the mobility of H-atoms at the interface of Ni/YSZ slab. The rate constants for hydrogen dissociation and diffusion in pure Ni and Ni/YSZ are predicted.     

Discovery of antagonist peptides against bacterial helicase-primase interaction in B. stearothermophilus by reverse yeast three-hybrid

Developing small-molecule antagonists against protein-protein interactions will provide powerful tools for mechanistic/functional studies and the discovery of new antibacterials. We have developed a reverse yeast three-hybrid approach that allows high-throughput screening for antagonist peptides against essential protein-protein interactions. We have applied our methodology to the essential bacterial helicase-primase interaction in Bacillus stearothermophilus and isolated a unique antagonist peptide. This peptide binds to the primase, thus excluding the helicase and inhibiting an essential interaction in bacterial DNA replication. We provide proof of principle that our reverse yeast three-hybrid method is a powerful "one-step" screen tool for direct high-throughput antagonist peptide selection against any protein-protein interaction detectable by traditional yeast two-hybrid systems. Such peptides will provide useful "leads" for the development of new antibacterials.     

Refining estimates of invariant and deflating subspaces for large and sparse matrices and pencils

We consider the refinement of estimates of invariant (or deflating) subspaces for a large and sparse real matrix (or pencil) in $\mathbb {R}^{n \times n}$ , through some (generalized) nonsymmetric algebraic Riccati equations or their associated (generalized) Sylvester equations via Newton’s method. The crux of the method is the inversion of some well-conditioned unstructured matrices via the efficient and stable inversion of the associated structured but near-singular matrices. All computations have complexity proportional to $n$ , under appropriate assumptions, as illustrated by several numerical examples.     

Acceleration of two-grid stabilized mixed finite element method for the Stokes eigenvalue problem

This paper provides an accelerated two-grid stabilized mixed finite element scheme for the Stokes eigenvalue problem based on the pressure projection. With the scheme, the solution of the Stokes eigenvalue problem on a fine grid is reduced to the solution of the Stokes eigenvalue problem on a much coarser grid and the solution of a linear algebraic system on the fine grid. By solving a slightly different linear problem on the fine grid, the new algorithm significantly improves the theoretical error estimate which allows a much coarser mesh to achieve the same asymptotic convergence rate. Finally, numerical experiments are shown to verify the high efficiency and the theoretical results of the new method.     

Subsonic irrotational flows in a two-dimensional finitely long curved nozzle

This is a continuation of our previous paper Du et al. (http://www.ims.cuhk.edu.hk/publications/reports/2012-06.pdf), where we have characterized a set of physical boundary conditions that ensures the existence and uniqueness of subsonic irrotational flow in a flat nozzle. In this paper, we will investigate the influence of the incoming flow angle and the geometry structure of the nozzle walls on subsonic flows in a finitely long curved nozzle. It turns out to be interesting that the incoming flow angle and the angle of inclination of nozzle walls play the same role as the end pressure for the stabilization of subsonic flows. In other words, the L ² and L ^∞ bounds of the derivative of these two quantities cannot be too large, similar as we have indicated in Du et al. (http://www.ims.cuhk.edu.hk/publications/reports/2012-06.pdf) for the end pressure. The curvatures of the nozzle walls will also play an important role in the stability of the subsonic flow.     

An N-path user equilibrium for transportation networks

The traditional trip-based approach to transportation modeling has been employed for the past decade. The last step of the trip-based modeling approach is traffic assignment, which has been typically formulated as a user equilibrium (UE) problem. In the conventional perspective, the definition of UE traffic assignment is the condition that no road user can unilaterally change routes to reduce their travel time. An equivalent definition is that the travel times of all the used paths between any given origin–destination pair are equal and less than those of the unused paths. The underlying assumption of the UE definition is that road users have full information on the available transportation paths and can potentially use any path if the currently used path is overly congested. However, a more practical scenario is that each road user has a limited path set within which she/he can choose routes from. In this new scenario, we call the resulting user equilibrium an N-path user equilibrium (NPUE), in which each road user has only N paths to select from when making route choices in the network. We introduce a new formulation of the NPUE and derive optimality conditions based on this formulation. Different from traditional modeling framework, the constraints of the proposed model are of linear form, which makes it possible to solve the problem with conventional convex programming techniques. We also show that the traditional UE is a special case of an NPUE and prove the uniqueness of the resulting flow pattern of the NPUE. To efficiently solve this problem, we devise path-based and link-based solution algorithms. The proposed solution algorithms are empirically applied to networks of various sizes to examine the impact of constrained user path sets. Numerical results demonstrate that NPUE results can differ significantly from UE results depending on the number of paths available to road users. In addition, we observed an interesting phenomenon, where increasing the number of paths available to road users can sometimes decrease the overall system performance due to their selfish routing behaviors. This paradox demonstrates that network information should be provided with caution, as such information can do more harm than good in certain transportation systems.     

Coordination polymers based on building blocks of dimethyltin(IV) Chloride iso‐thiocyanate and dimethyltin(IV) di‐iso‐thiocyanate with pyrazine‐2‐carboxylate and 4, 4′‐bipyridine

The reaction of 4,4′‐bipy with dimethyltin(IV) chloride iso‐thiocyanate affords the one‐dimensional (1D) coordination polymer, [Me₂Sn(NCS)Cl·(4,4′‐bipy)]_n ( 1 ), whereas reaction of dimethyltin(IV) dichloride with sodium pyrazine‐2‐carboxylate in the presence of potassium iso‐thiocyanate affords the two‐dimensional (2D) coordination polymer, {[Me₂Sn(C₄H₃N₂COO)₂]₂ [Me₂Sn(NCS)₂]}_n ( 2 ). Both coordination polymers were characterized by elemental analysis and infrared spectroscopy in addition to ¹H and ¹³C NMR spectroscopy of the soluble coordination polymer ( 1 ). A single‐crystal structure determination showed that the asymmetric unit in 1 contains Me₂Sn(NCS)Cl and 4,4′‐bipy moieties and a 1D infinite rigid chain structure forms through bridging of the 4,4′‐bipy ligand between tin atoms and the geometry around the tin atom is a distorted octahedral. Coordination polymer 2 contains two distinct tin atom geometrics in which one tin atom is seven coordinate, and the other is six coordinate. The two tin atom environments are best described as a pentagonal bipyramidal in the former and distorted octahedral in the latter where the carboxylate groups bridge the two tin atoms and construct a 2D‐coordination polymer. The ¹¹⁹Sn NMR spectroscopy indicates the octahedral geometry of 1 retains in solution. © 2011 Wiley Periodicals, Inc. Heteroatom Chem 22:699–706, 2011; View this article online at wileyonlinelibrary.com . DOI 10.1002/.20736     

New Dihydroagarofuranoid Sesquiterpenes from Celastrus paniculatus

The six new dihydro‐β‐agarofuranoid sesquiterpenes 1 – 6 and three known compounds were isolated from the whole plant of Celastrus paniculatus. The structures including relative configurations were elucidated by means of spectroscopic analyses. Compounds 1 – 6 were evaluated for cytotoxicity against a panel of three human‐tumor cell lines.     

Solvent effect in the chromatographic enantioseparation of 1,1′-bi-2-naphthol on a polysaccharide-based chiral stationary phase

Enantioseparation of 1,1′-bi-2-naphthol (BINOL) was performed on a polysaccharide-based chiral stationary phase, Chiralcel OD-H, under normal-phase mode. The effects of polar modifier in the mobile phase on the retention, enantioseparation and elution order were investigated in detail. Solvent-induced reversal of elution order for BINOL was observed. When linear alcohols were adopted, R-BINOL was always eluted first. S-BINOL was eluted first when 2-propanol was used as a polar modifier. Enantioseparation could not be obtained when sec-butyl alcohol or tert-butyl alcohol was used as a polar modifier. When isoamyl alcohol or cyclohexanol was used as a polar modifier, favorable enantioseparation was obtained as with 1-pentanol or 1-hexanol; also, R-BINOL was the first-eluted enantiomer. It is worth emphasizing that significantly better enantioseparation was obtained when higher alcohols were used as polar modifier of the mobile phase. A nonlinear characteristic for the ln α against 1/T plots was universally observed in this study though the ln k against 1/T plots exhibited a linear feature. Associated with the obtained thermodynamic parameters, some interesting inferences about chiral recognition mechanism were proposed.     

关于丢番图方程(12n)~x+(35n)~y=(37n)~z

运用同余及元素阶的性质,证明对任意正整数n,丢番图方程(12n)x+(35n)y=(37n)z仅有正整数解(x,y,z)=(2,2,2).