Hydrogen bonding in macrocyclic receptor systems

Abstract

The interactions of macrocyclic polyethers with alkali and alkaline earth cations have been well studied and much about their chemistry is now well understood. Less well examined or comprehended are hydrogen bond interactions. A combination of ion selective electrode binding constant determination techniques and fast atom bombardment mass spectrometry are brought to bear on this problem. It is found that all-oxygen crown ethers and their derivatives exhibit quite different complexation behaviour with ammonium salts than do their various azacrown counterparts.     

Biaxial bulge testing of polymeric sheets

The through thickness total strains of hydrostatically bulged domes of materials are usually determined indirectly. The in-plane circumferential strains are readily measured, and then constancy of volume is invoked to determine the “missing” or unknown strain. Some of our recent work with polymers has shown that volume constancy in large-scale deformation does not hold so that the usual computations of stress and strain during bulging of sheet may be in error. We describe an electrical device that reduces such errors by directly measuring the through thickness (and, thus, the thickness “strain”) for nonmetallic materials.     

Solvent Effect and Reactivity Trend in the Aerobic Oxidation of 1,3‐Propanediols over Gold Supported on Titania: NMR Diffusion and Relaxation Studies

In recent work, it was reported that changes in solvent composition, precisely the addition of water, significantly inhibits the catalytic activity of Au/TiO₂ catalyst in the aerobic oxidation of 1,4‐butanediol in methanol due to changes in diffusion and adsorption properties of the reactant. In order to understand whether the inhibition mechanism of water on diol oxidation in methanol is generally valid, the solvent effect on the aerobic catalytic oxidation of 1,3‐propanediol and its two methyl‐substituted homologues, 2‐methyl‐1,3‐propanediol and 2,2‐dimethyl‐1,3‐propanediol, over a Au/TiO₂ catalyst has been studied here using conventional catalytic reaction monitoring in combination with pulsed‐field gradient nuclear magnetic resonance (PFG‐NMR) diffusion and NMR relaxation time measurements. Diol conversion is significantly lower when water is present in the initial diol/methanol mixture. A reactivity trend within the group of diols was also observed. Combined NMR diffusion and relaxation time measurements suggest that molecular diffusion and, in particular, the relative strength of diol adsorption, are important factors in determining the conversion. These results highlight NMR diffusion and relaxation techniques as novel, non‐invasive characterisation tools for catalytic materials, which complement conventional reaction data.     

An investigation of preservice teachers’ use of guess and check in solving a semi open-ended mathematics problem

Open-ended problems have been regarded as powerful tools for teaching mathematics. This study examined the problem solving of eight mathematics/science middle-school teachers. A semi-structured interview was conducted with (PTs) after completing an open-ended triangle task with four unique solutions. Of particular emphasis was how the PTs used a specific heuristic strategy. The results showed that the primary strategy PTs employed in attempting to solve the triangle problem task was guess and check; however, from the PTs’ reflections, we found there existed misapplications of guess and check as a systematic problem-solving strategy. In order to prepare prospective teachers to effectively teach, teacher educators should pay more attention to the mathematical proficiency of PTs, particularly their abilities to systematically and efficiently use guess and check while solving problems and explain their solutions and reasoning to middle-school students.     

Multiple cation binding by bola-amphiphilic crown ethers: Assessment by fast atom bombardment mass spectrometry

Abstract

Bola-amphiphiles having two aza-18-crown-6 ether rings attached by a covalent spacer (O—O) and an analogous tris (macrocycle) (O—O—O) have been prepared and their cation complexation behavior has been assessed by fast atom bombardment and collisionally activated dissociation tandem mass spectrometry; the key finding is that two cations may simultaneously be complexed by a two- or three-crown system and that this complexation may also involve an anion.