Synthesis, Characterisation and Electrical Properties of Supramolecular DNA-Templated Polymer Nanowires of 2,5-(Bis-2-thienyl)-pyrrole

Supramolecular polymer nanowires have been prepared by using DNA-templating of 2,5-(bis-2-thienyl)-pyrrole (TPT) by oxidation with FeCl(3) in a mixed aqueous/organic solvent system. Despite the reduced capacity for strong hydrogen bonding in polyTPT compared to other systems, such as polypyrrole, the templating proceeds well. FTIR spectroscopic studies confirm that the resulting material is not a simple mixture and that the two types of polymer interact. This is indicated by shifts in bands associated with both the phosphodiester backbone and the nucleobases. XPS studies further confirm the presence of DNA and TPT, as well as dopant Cl(-) ions. Molecular dynamics simulations on a [{dA(24) :dT(24) }/{TPT}(4) ] model support these findings and indicate a non-coplanar conformation for oligoTPT over much of the trajectory. AFM studies show that the resulting nanowires typically lie in the 7-8?nm diameter range and exhibit a smooth, continuous, morphology. Studies on the electrical properties of the prepared nanowires by using a combination of scanned conductance microscopy, conductive AFM and variable temperature two-terminal I-V measurements show, that in contrast to similar DNA/polymer systems, the conductivity is markedly reduced compared to bulk material. The temperature dependence of the conductivity shows a simple Arrhenius behaviour consistent with the hopping models developed for redox polymers.     

Relativistic effects on the Fukui function

The extent of relativistic effects on the Fukui function, which describes local reactivity trends within conceptual density functional theory (DFT), and frontier orbital densities has been analysed on the basis of three benchmark molecules containing the heavy elements: Au, Pb, and Bi. Various approximate relativistic approaches have been tested and compared with the four-component fully relativistic reference. Scalar relativistic effects, as described by the scalar zeroth-order regular approximation methodology and effective core potential calculations, already provide a large part of the relativistic corrections. Inclusion of spin–orbit coupling effects improves the results, especially for the heavy p-block compounds. We thus expect that future conceptual DFT-based reactivity studies on heavy-element molecules can rely on one of the approximate relativistic methodologies.     

Preparation and investigation of vitamin B6-derived aminopyridinol antioxidants

3-Pyridinols bearing amine substitution para to the hydroxylic moiety have previously been shown to inhibit lipid peroxidation more effectively than typical phenolic antioxidants, for example, α-tocopherol. We report here high-yielding, large-scale syntheses of mono- and bicyclic aminopyridinols from pyridoxine hydrochloride (i.e., vitamin B(6)). This approach provides straightforward, scaleable access to novel, potent, molecular scaffolds whose antioxidant properties have been investigated in homogeneous solutions and in liposomal vesicles. These molecular aggregates mimic cell membranes that are the targets of oxidative damage in vivo.     

Communication: Direct observation of a hydrophobic bond in loop closure of a capped (-OCH2CH2-)n oligomer in water

The small r variation of the probability density P(r) for end-to-end separations of a -CH(2)CH(3) capped (-OCH(2)CH(2)-)(n) oligomer in water is computed to be closely similar to the CH(4)···CH(4) potential of mean force under the same circumstances. Since the aqueous solution CH(4)···CH(4) potential of mean force is the natural physical definition of a primitive hydrophobic bond, the present result identifies an experimentally accessible circumstance for direct observation of a hydrophobic bond which has not been observed previously because of the low solubility of CH(4) in water. The physical picture is that the soluble chain molecules carry the capping groups into aqueous solution, and permits them to find one another with reasonable frequency. Comparison with the corresponding results without the solvent shows that hydration of the solute oxygen atoms swells the chain molecule globule. This supports the view that the chain molecule globule might have a secondary effect on the hydrophobic interaction that is of first interest here. The volume of the chain molecule globule is important for comparing the probabilities with and without solvent because it characterizes the local concentration of capping groups. Study of other capping groups to enable x-ray and neutron diffraction measurements of P(r) is discussed.     

Pre- and in-service teachers’ perceived value of an experimental real analysis course for teachers

Prospective secondary mathematics teachers are usually required to complete several university advanced mathematics courses before being certified to teach secondary mathematics. However, teachers usually do not find these courses to be valuable for their teaching. We designed an experimental real analysis course with the goal of making real analysis content useful and relevant to teaching. Our approach was to ground the real analysis content in pedagogical situations that problematized a secondary mathematics topic, where the nuances of teaching secondary mathematics could be informed by the real analysis that was covered. The experimental course was implemented in a graduate teacher education programme with 32 pre- and in-service teachers (PISTs). After the course, we conducted focus group interviews with 20 of these PISTs to get feedback on how the course was valuable to their teaching practice. Many PISTs found the course to be valuable for teaching secondary mathematics, as well as for their understanding of secondary mathematics and real analysis.     

Role of Context in Risk-Based Reasoning

In this article we report the influence of contextual factors on mathematics and science teachers' reasoning in risk-based decision-making. We examine previous research that presents judgments of risk as being subjectively influenced by contextual factors and other research that explores the role of context in mathematical problem-solving. Our own approach has been to develop carefully designed software tools that support the user to empathize with a hypothetical person, Deborah, who suffers from a medical condition. The tools were used by a group of teachers who were asked to help Deborah decide whether to have an operation that could cure the condition but which carries particular risks. In order to make this decision, the teachers were required to model the risks of the operation and also the lifestyle decisions that Deborah might make. We trace the teachers' efforts to coordinate judgments of likelihood and impact. The data emphasize the sensitivity of reasoning to matters of context; we set out in detail the various ways in which the process was affected by context.     

Visualization technique for uncertainty budgets: Onion charts

A concise graphical depiction, the “onion” chart, is described for presenting uncertainty budgets for any measurand, y, having a set of component variances, . The onion chart consists of a concentric series of rings. Each ring is constructed from the set of fractional contributions, . The outer ring includes all and depicts the combined standard uncertainty, u _c (y), where u _c ²(y) ≡ ∑u _i ²(y). Moving inward, each successive ring deletes the largest remaining . A “reduced” is calculated for that ring from the remaining set of , with the fractional contributions calculated using the “reduced” . This format facilitates rapid visual comparison of the importance of each component, with minor components becoming visible as the larger components are successively deleted. An example is presented using data from pH metrology, including the physical interpretation of the resulting diagram.     

Magnetization-dependent shift in ferromagnet/superconductor/ferromagnet trilayers with a strong ferromagnet

We have measured the superconducting transition temperature Tc of Ni/Nb/Ni trilayers when the magnetizations of the two outer Ni layers are parallel (P) and antiparallel (AP). The largest difference in occurs when the Nb thickness is just above the critical thickness at which superconductivity disappears completely. We have observed a difference in Tc between the P and AP states as large as 41 mK--a significant increase over earlier results in samples with higher Tc and with a CuNi alloy in place of the Ni. Our result also demonstrates that strong elemental ferromagnets are promising candidates for future investigations of ferromagnet/superconductor heterostructures.     

Novel diborane-analogue transition structures for borane reactions with alkyl halides

Ab initio and DFT calculations were performed to examine the mechanisms of reduction of alkyl halides and formaldehyde by borane. With alkyl halides, the optimized transition structure geometry resembled diborane, with a pair of hydrogen atoms bridging the boron and carbon atoms by three-center-two-electron bonds. A similar transition structure was found for the reduction of formaldehyde, although it was not the lowest-energy transition structure. Solvation by dimethyl ether or dimethyl sulfide disrupted this bridging with chloromethane, while both ligands dissociated from borane during the reduction of formaldehyde. The high calculated activation free energies of alkyl halide reduction are consistent with their observed lack of reactivity with borane.     

Cu(HF2)(pyz)2]BF4 (pyz = pyrazine): long-range magnetic ordering in a pseudo-cubic coordination polymer comprised of bridging HF2- and pyrazine ligands

[Cu(HF2)(pyz)2]BF4 consists of rare mu(1,3) bridging HF2- anions and micro-pyrazine ligands leading to a 3D pseudo-cubic framework that antiferromagnetically orders below 1.54(1) K.