Synthesis of Highly Fluorinated Arene Complexes of [Rh(Chelating Phosphine)]+ Cations,and their use in Synthesis and Catalysis

The synthesis of rhodium complexes with weakly binding highly fluorinated benzene ligands is described: 1,2,3-F₃C₆H₃, 1,2,3,4-F₄C₆H₂ and 1,2,3,4,5-F₅C₆H are shown to bind with cationic [Rh(Cy₂P(CH₂)_xPCy₂)]⁺ fragments (x=1, 2). Their structures and reactivity with alkenes, and use in catalysis for promoting the Tishchenko reaction of a simple aldehyde, are demonstrated. Key to the synthesis of these complexes is the highly concentrated reaction conditions and use of the [Al{OC(CF₃)₃}₄]⁻ anion.     

The Order of Automorphisms of Quasigroups

We prove quadratic upper bounds on the order of any autotopism of a quasigroup or Latin square, and hence also on the order of any automorphism of a Steiner triple system or 1‐factorization of a complete graph. A corollary is that a permutation σ chosen uniformly at random from the symmetric group will almost surely not be an automorphism of a Steiner triple system of order n, a quasigroup of order n or a 1‐factorization of the complete graph . Nor will σ be one component of an autotopism for any Latin square of order n. For groups of order n it is known that automorphisms must have order less than n, but we show that quasigroups of order n can have automorphisms of order greater than n. The smallest such quasigroup has order 7034. We also show that quasigroups of prime order can possess autotopisms that consist of three permutations with different cycle structures. Our results answer three questions originally posed by D.  Stones.     

Patterned ground formation and convection in porous media with a phase change

The influence of a water-ice phase change on the onset of natural convection is examined for a saturated porous layer overlying a frozen region. Darcy's law is used and a parabolic equation of state is assumed for water. From a linear instability analysis we obtain predictions for the onset of convection in the melted region and the corresponding criticial wavenumber. The critical numbers are calculated by employing finite differences and solving the associated generalized eigenvalue problem. We study the effect varying thermal conductivities and boundary conditions have on these predictions. The analysis is applied to the formation of patterned ground, a geophysical phenomenon of stone borders forming regular hexagonal patterns. The theoretical model for patterned ground is based on natural convection in saturated soil below which is a cold permafrost layer.     

Studies of multicomponent Kinugasa reactions in aqueous media

Micelle-promoted, copper-catalyzed multicomponent Kinugasa reactions were studied in aqueous media. Reactions were performed in a ‘single pot’ for a series of in situ generated C,N-diphenylnitrones with Cu(I) phenylacetylide providing β-lactams in yields of 45-85%. Substituents affect the reaction by either accelerating cycloaddition or minimizing side reactions.     

Sulfur fixation on bagasse activated carbon by chemical treatment and its effect on acid dye adsorption

Heteroatoms are known to introduce specific surface functionalities that can enhance the adsorption properties of carbons. Sulfur fixation on bagasse-activated carbon was conducted by a low temperature chemical treatment with sulfuric acid followed by physical activation with CO₂ at 900?°C. The effect of sulfur fixation on the surface chemical properties of bagasse-activated carbons were investigated and on their subsequent acid dye removal (CIBA AB80) behavior. Surface chemical development were examined and followed using Fourier transform infrared spectroscopy (FTIR), heteroatom analysis and carbon surface acidity. Functional group stability with thermal treatment was also investigated. The textural properties of the activated carbons were characterized by nitrogen adsorption. Chemical pre-treatment and gasification was able to fix up to 0.2 wt% of sulfur on the activated carbon. Although the sulfur fixed by chemical treatment is low, this method introduced several advantages in comparison to fixation by thermal methods. The chemical method did not interfere with the textural development of the carbon, as found in thermal methods. In addition, the surface chemistry generated by these levels of sulfur groups was sufficient to increase the uptake of acid blue dyes by more than 700% based on adsorption capacities normalized by the surface area of the carbon.     

Super‐fast oil uptake using porous ultra‐high molecular weight polyethylene sheets

This paper presents the oil uptake of porous sorbent polymer sheets consisting of ultra‐high molecular weight polyethylene. A comprehensive set of experiments are performed showing the saturation contact time, retention value, mechanical properties, oil pick‐up ratio, pick‐up density, and dynamic dripping profile. Kinetic modeling of the oil sorption is also provided. The experimental results show a good correlation with the pseudo‐second order model. The sheets exhibit high oil uptake speeds, requiring less than 2 min in contact with the oil to reach saturation. The sheets fulfill the criteria of high uptake kinetics, high sorption capacity, and high mechanical strength simultaneously. Those characteristics enable their use in practical spill response. Copyright © 2014 John Wiley & Sons, Ltd.     

Comparison of Three Plasma Sources for Ambient Desorption/Ionization Mass Spectrometry

Plasma-based desorption/ionization sources are an important ionization technique for ambient surface analysis mass spectrometry. In this paper, we compare and contrast three competing plasma based desorption/ionization sources: a radio-frequency (rf) plasma needle, a dielectric barrier plasma jet, and a low-temperature plasma probe. The ambient composition of the three sources and their effectiveness at analyzing a range of pharmaceuticals and polymers were assessed. Results show that the background mass spectrum of each source was dominated by air species, with the rf needle producing a richer ion spectrum consisting mainly of ionized water clusters. It was also seen that each source produced different ion fragments of the analytes under investigation: this is thought to be due to different substrate heating, different ion transport mechanisms, and different electric field orientations. The rf needle was found to fragment the analytes least and as a result it was able to detect larger polymer ions than the other sources. Figure

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