Diels-Alder chemistry at furan ring functionalized solid surfaces

A substrate-independent method for Diels-Alder chemistry at solid surfaces is described for the first time.     

Bis(fluoroalkyl)acrylic and methacrylic phosphate monomers, their polymers and some of their properties

Ten fluoromonomers of structure (R_FO)₂P(O)OCH₂CH₂OC(O)CRCH₂ were made in 30-64% yield by treating the chloridates (R_FO)₂P(O)Cl with HOCH₂CH₂OC(O)CRCH₂ in chloroform in the presence of triethylamine [R_F=CF₃CH₂, C₂F₅CH₂, C₃F₇CH₂, C₄F₉CH₂, C₄F₉CH₂CH₂ or C₆F₁₃CH₂CH₂; R  H or Me]. The chloromonomer (CCl₃CH₂O)₂P(O)OCH₂CH₂OC(O)CHCH₂ was obtained analogously in 29% yield. Polymerisation of the acrylate monomers, but not the methacrylate monomers, could be effected using α-azoisobutyronitrile as a radical initiator. Acrylic polymers having CF₃CH₂O, CCl₃CH₂O and C₆F₁₃CH₂CH₂O side-chains were obtained as translucent rubbers. Specimens of cotton fabric were treated with solutions of the polymers, and average water and oil repellency ratings measured. Fabric coated with the polymer with the C₆F₁₃CH₂CH₂O side-chain afforded protection from penetration of the test liquids. Treated fabrics were subjected to the limiting oxygen index (LOI) test according to BS EN ISO 4589-2 (1999): this test determines the point at which a material just burns in a volumetric flow of oxygen and nitrogen. The treated fabrics were more fire-resistant (LOI 22-29%) than the untreated fabric (LOI 18%). Fabric coated with the CCl₃CH₂O-based polymer can be considered fire-retardant (LOI 29%). The fluoromonomers were tested for anti-acetylcholinesterase activity and were found to be poor enzyme inhibitors; they are predicted to possess low acute toxicity.     

The BIOREMA project—part 3: International interlaboratory comparison for bio-ethanol test methods

The main objective of the reference materials for biofuel specifications (BIOREMA) project is the development of two test materials (one bio-ethanol material and one biodiesel material) with well-established reference values. Of a series of three papers, this part describes the material preparation, homogeneity study, stability study, and characterisation of the bio-ethanol material. The test material thus obtained was used in an interlaboratory comparison (ILC) to assess current practices and comparability amongst laboratories providing bio-ethanol testing services. Only 13 participants provided data, resulting in a small dataset for evaluation. Further, it appeared that for a number of laboratories, there was not sufficient material for the determination of all requested parameters. In most cases, as far as the data permit, it can be concluded that the consensus values (based on participant’s results) are in good agreement with the reference or the BIOREMA values (obtained by NMIs participating in the project). For three parameters, namely ethanol content, water content, and density, there is good agreement between the reference and consensus values. For these parameters, the reproducibility standard deviation is close to, or even smaller than, the expanded uncertainty associated with the reference value. A number of parameters show very poor reproducibility, for example, pH_e, electrolytic conductivity, and acidity. The same applies to sodium and copper content, which are very low and therefore challenging parameters to measure accurately. The results of the ILC underpin the need for certified reference materials and demonstrate the requirement for more robust quality control to improve the precision and trueness of the results from testing laboratories.     

Formal and total synthesis of (±)-cycloclavine

A ring fragmentation and intramolecular azomethine ylide 1,3-dipolar cycloaddition sequence of reactions was successfully used in the preparation of a known (±)-cycloclavine precursor in good overall yield. Results of efforts to incorporate the tetrasubstituted cyclopropane ring present in cycloclavine are also discussed.     

Hyperfine field and diffusion of μ+ in Fe single crystals

In recent positive-muon spin rotation experiment at TRIUMF on single crystal Fe, a clear temperature dependent change has been observed, for the first time, both in frequency and depolarization rates from 300 K down to 23 K. The μ⁺ depolarization was explained by the μ⁺ diffusion through inhomogeneous dipolar fields and the diffusion constant was found to obey an Arrhenius law (activation energy 17 meV) above 70 K but surprisingly deviated from this at lower temperatures, indicating quantum diffusion. We have also found that the μ⁺ hyperfine field has a temperature dependence slightly stronger than that of the magnetization.     

Formation of muonium and a muonic radical in fullerene

Three distinct electronic states were detected for positive muons (⁺) after implantation into a C₆₀ powder sample. About 40% of the ⁺ remained in the bare (diamagnetic) state, essentially an interstitial charged point particle. The rest of the muons were found to thermalize predominantly in two muonium (Mu=⁺ e^–) atomic species. A vacuum Mu state, with hyperfine coupling close to that of free Mu, most likely at the molecular center, and a muonic substituted radical, i.e. a hydrogen-like Mu addition to double bonds on the carbon rings. This opens up a rich subfield of fullerene spectroscopy using muons.     

The long term impact of a coherence based model for mathematics intervention

This article presents a large-scale longitudinal study of hundreds of students across the state of Kentucky that participated in a dual-focus mathematics intervention initiative when they were in the third grade. Rather than an exclusive focus on intervention, this initiative focused on both (i) high quality pull-out intervention and (ii) coherence between pull-out intervention and classroom instruction. The study found that over half of the third grade intervention students that participated in this initiative were classified as “novice” (the lowest possible performance category) on state standardized mathematics assessments at the end of the third grade. However, over the course of the following four years, the novice reduction rate of these students was significantly (p < .01) greater than other novices in Kentucky that did not participate in the initiative. These findings indicate that when implementing intervention initiatives to help students that are struggling with mathematics, it may be important to establish coherence between pull-out intervention and classroom instruction. The long term impact of this approach among traditionally underrepresented minorities suggest that this publication may provide insight into important equity issues where long-term analyses may sometimes be needed to capture the full impact of intervention initiatives.     

Influence of impurities on short range electron transport in GaAs

The influence of Cr impurities on muonium atom formation in GaAs has been studied using muon spin relaxation techniques with alternating electric fields. The results suggest that electron transport to and capture by the muon is suppressed by capture/scattering on intervening Cr centers. The length scale involved is estimated to be about 3x10(-6) cm. This offers an opportunity to study electron transport to positive centers in semiconductors on a microscopic scale.     

Evidence for static magnetism in the vortex cores of ortho-II YBa2Cu3O6.50

Evidence for static alternating magnetic fields in the vortex cores of underdoped YBa2Cu3O6+x is reported. Muon spin rotation measurements of the internal magnetic field distribution of the vortex state of YBa2Cu3O6.50 in applied fields of H = 1 T and H = 4 T reveal a feature in the high-field tail of the field distribution which is not present in optimally doped YBa2Cu3O6.95 and which fits well to a model with static magnetic fields in the vortex cores. The magnitude of the fields is estimated to be 18(2) G and decreases above T = 10 K. We discuss possible origins of the additional vortex core magnetism within the context of existing theories.