Structure of nanofibrillated cellulose layers at the o/w interface

The nature of layers formed by cellulose nanofibrils that had been surface modified (hydrophobized) at the oil/water (o/w) interface was investigated. The aim of the study was to clarify the mechanism underlying the excellent ability of these nanoparticles to stabilize emulsions. Layers of hydrophobized nanofibrillated cellulose spread at the o/w interface were deposited on glass slides by the Langmuir-Blodgett deposition technique. Overall evaluation of layer structures was performed by image analysis based on a Quadtree decomposition of images obtained from a flatbed scanner. A more detailed characterization of the layer structures was performed by Atomic Force Microscopy (AFM), and Field-Emission Scanning Electron Microscopy (FE-SEM). The results show that nanofibrils that were able to stabilize emulsions occur as single, dispersed fibrils or form large, network-like aggregates at the o/w interface. Fibrils that were insufficiently hydrophobized and therefore did not stabilize emulsions were only partially deposited and formed small, compact aggregates. We conclude that it is likely that the network formation is the main mechanism by which the fibrils prevent coalescence of emulsion droplets.     

A Water Molecule Triggers Guest Exchange at a Mono-Zinc Centre Confined in a Biomimetic Calixarene Pocket: a Model for Understanding Ligand Stability in Zn Proteins

In this study, the ligand exchange mechanism at a biomimetic Zn^II centre, embedded in a pocket mimicking the possible constrains induced by a proteic structure, is explored. The residence time of different guest ligands (dimethylformamide, acetonitrile and ethanol) inside the cavity of a calix[6]arene-based tris(imidazole) tetrahedral zinc complex was probed using 1D EXchange SpectroscopY NMR experiments. A strong dependence of residence time on water content was observed with no exchange occurring under anhydrous conditions, even in the presence of a large excess of guest ligand. These results advocate for an associative exchange mechanism involving the transient exo-coordination of a water molecule, giving rise to 5-coordinate Zn^II intermediates, and inversion of the pyramid at the Zn^II centre. Theoretical modelling by DFT confirmed that the associative mechanism is at stake. These results are particularly relevant in the context of the understanding of kinetic stability/lability in Zn proteins and highlight the key role that a single water molecule can play in catalysing ligand exchange and controlling the lability of Zn^II in proteins.     

A Connection between Singular Stochastic Control and Optimal Stopping

We show that the value function of a singular stochastic control problem is equal to the integral of the value function of an associated optimal stopping problem. The connection is proved for a general class of diffusions using the method of viscosity solutions.     

Complexation by N-(3,6,9-trioxadecyl)monoaza-12-crown-4 lariat ether: a “calabash” complex of a potassium cation by a synthetic macrocycle containing a total of only seven donor atoms

Structural and cation binding data for the title compound demonstrate that the large value of K_s results from complete K⁺ cation encapsulation by one nitrogen and six oxygen atoms despite the presence of a twelve-membered macroring.     

Limits on the high-energy gamma and neutrino fluxes from the SGR 1806-20 giant flare of 27 December 2004 with the AMANDA-II detector

On 27 December 2004, a giant gamma flare from the Soft Gamma-Ray Repeater 1806-20 saturated many satellite gamma-ray detectors, being the brightest transient event ever observed in the Galaxy. AMANDA-II was used to search for down-going muons indicative of high-energy gammas and/or neutrinos from this object. The data revealed no significant signal, so upper limits (at 90% C.L.) on the normalization constant were set: 0.05(0.5) TeV-1 m;{-2} s;{-1} for gamma=-1.47 (-2) in the gamma flux and 0.4(6.1) TeV-1 m;{-2} s;{-1} for gamma=-1.47 (-2) in the high-energy neutrino flux.     

A new 2-carboxylate-substituted 4,4'-bipyridine ligand: coordination chemistry of 4,4'-bipyridine-2-carboxylic acid and its synthetic intermediate 2-methyl-4,4'-bipyridine

The first monocarboxylate-substituted 4,4'-bipyridine ligand, 4,4'-bipyridine-2-carboxylic acid (4-(pyridin-4-yl)pyridine-2-carboxylic acid (PPCAH)), has been successfully synthesized from 4,4'-bipyridine. Reactions with transition metals zinc and manganese were used to establish the coordination characteristics of the product, 4,4'-bipyridine-2-carboxylic acid, and of the synthetic intermediate, 2-methyl-4,4'-bipyridine, by single-crystal X-ray diffraction. The ligand PPCAH is useful for the formation of metal-containing building blocks that can be used in the assembly of mixed-metal framework materials. The synthesis and structure of one such mixed-metal coordination polymer, Cu(PPCA)(2)HgI(2), is also presented.     

A forest building process on simple graphs

Consider the following process on a simple graph without isolated vertices: order the edges randomly and keep an edge if and only if it contains a vertex which is not contained in some preceding edge. The resulting set of edges forms a spanning forest of the graph.The probability of obtaining $k$ components in this process for complete bipartite graphs is determined as well as a formula for the expected number of components in any graph. A generic recurrence and some additional basic properties are discussed.     

Weak convergence of Galerkin approximations for fractional elliptic stochastic PDEs with spatial white noise

The numerical approximation of the solution to a stochastic partial differential equation with additive spatial white noise on a bounded domain is considered. The differential operator is assumed to be a fractional power of an integer order elliptic differential operator. The solution is approximated by means of a finite element discretization in space and a quadrature approximation of an integral representation of the fractional inverse from the Dunford–Taylor calculus. For the resulting approximation, a concise analysis of the weak error is performed. Specifically, for the class of twice continuously Fréchet differentiable functionals with second derivatives of polynomial growth, an explicit rate of weak convergence is derived, and it is shown that the component of the convergence rate stemming from the stochasticity is doubled compared to the corresponding strong rate. Numerical experiments for different functionals validate the theoretical results.     

Modification and validation of the mixed-format Engineering Concept Assessment for middle school students using many-facet Rasch measurement

Integrating engineering into the K-12 science curriculum continues to be a focus in national reform efforts in science education. Although there is an increasing interest in research in and practice of integrating engineering in K-12 science education, to date only a few studies have focused on the development of an assessment tool to measure students’ understanding of engineering design. Most of the existing measures focus only on knowledge and understanding of engineering design concepts using multiple-choice items with the exception of the mixed-format Engineering Concept Assessment (ECA). Also, advanced measurement models are lacking application in the testing of such mixed-format assessments in science education. This study applied many-faceted Rasch measurement to the modified ECA for eighth-grade (ECA/M8) and a newly constructed rubric applied by five judges across 497 eighth-grade students’ responses after experiencing an integrated learning unit on the engineering design process. The results supported the fit of the items and rubric rating scales to the Rasch specifications. Recommendations are made for item wording, and further reliability and validity testing of the ECA/M8, and use of the ECA/M8 in science education and research.