NMR spectral analysis of strongly second-order 6-, 8-, 9- and 10- spin-systems (1H─19F, 19F─19F,and 13C─19F) in perfluorotoluyl- and tetrafluoro-pyridyl-aromatics using the lineshape method ANATOLIA

A simple to use nuclear magnetic resonance analysis method has been tested on complex ¹H, ¹⁹F, and ¹³C multiplets. This open-source line-shape analysis method analysis of total lineshape (ANATOLIA)¹ provides some significant advantages over traditional assign-iterate methods of NMR spectral analysis by avoiding false minima and progressing optimisation to the global minimum. The target molecules are 1-perfluorotol-4-yl-2-perfluorotol-4-yl-oxymethyl-1H-benzimidazole (molecule-I) and 1-tetrafluoropyrid-4-yl-2-tetrafluoropyrid-4-yl-thio-1H-benzimidazole (molecule-II) which were produced as part of a family of fluorinated drug scaffolds prepared for anticancer and antiparasitic screening. Spectra display significant second-order effects with ¹H Δδ = 3.68 and 4.67 Hz for the aromatic hydrogen “triplets”, with ¹⁹F ⁴J_AA', ⁴J_BB', ⁴J_XX', and ⁴J_YY' coupling constants range from +4.8 to −14.0 Hz and for ¹³C-isotopomers ¹⁹F Δδ of up to 111.56 Hz. A spin-system of six coupling nuclei (H_aH_bH_cH_d F_YF_Y') was analysed in 12 s, a spin-system of nine coupling fluorine nuclei (AA'BB'CCC-YY') was analysed within 2 min, and 10 coupling nuclei (XX'YY'ZZZ-BB'-H_d) was optimised in 6 min using a laptop computer. ANATOLIA was also robust enough to be able to yield accurate spectral values from inaccurate input values. In both compounds, a fluorine–fluorine coupling constant was identified between the two fluoro-aromatic rings (F_BB' and F_YY') of +4.05 and +4.67 Hz and attributed to a through-space interaction. Ab initio structure optimisations and coupling constant calculations provided useful input data for spectral analysis. A modern ¹⁹F nuclear magnetic resonance spectrum of perfluorotoluene (octafluorotoluene) and analysis from 1975 was used as a test data set to assess ANATOLIA.     

The effect of olefinic terminal chains on the mesomorphic properties of 4,4'-disubstituted diphenyldiacetylenes

New diphenyldiacetylenes of the type with A, B = H and/or F; m = 0, 1; n = 1-4; and X = C n H 2n + 1 , F, CF 3 or CN were synthesized and their mesomorphic properties determined by hot stage polarizing microscopy and DSC. When m = 0, all of these compounds showed only a nematic phase except when X = CF 3 when both nematic and smectic A phases were seen. Both clearing and melting temperatures were higher than those reported for substitution with the corresponding alkyl chains but the much larger increase in clearing temperatures produced considerably wider nematic phases. Eutectic mixtures of a few of these olefins yielded nematic materials also having much wider temperature ranges and higher clearing temperatures than the eutectic mixtures of the alkyl compounds, while retaining their high birefringence and low viscosities. Such materials are of interest for beam-steering devices.

Four of the diacetylenes with m = 1 ( A, B = H) were also prepared ( X = C 6 H 13 , F, n = 2, 3). When X was C 6 H 13 ( n = 2), the nematic range was smaller in the 2- than in the 1-olefin but wider than in the alkyl series. When X = F, either no nematic phase or a monotropic one was observed, whereas the 1-olefins gave a much wider nematic phase. Both transition temperatures were lower than those for the corresponding 1-olefin and alkyl analogues. The compound with X = C 6 H 13 and n = 2 had a melting temperature below room temperature.     

Teachers in transition: Moving towards CAS-supported classrooms

In the near future many teachers may be required to incorporate CAS into their teaching practices. Based on classroom observations and interviews over two years, this paper reports how two teachers made the transition from using graphics calculators to CAS calculators while teaching differential calculus to upper secondary school students. Both teachers taught with CAS in ways that were consistent with their beliefs about learning and teaching. Over two years, the teachers' teaching approaches and purpose for use of technology were stable and seemed to be underpinned by their beliefs about learning. In contrast, both teachers made changes to the content they taught (and thus what they used technology for) in response to new institutional knowledge. Content choice seemed to be underpinned by the teachers' purpose for teaching. Other influences impacted on what the teachers taught and how they taught it: the teachers' content knowledge, their pedagogical content knowledge, and the lack of legitimacy of CAS as a tool for learning and during examinations in the trial school and wider educational community. The extent of differences noted between the responses of just two teachers indicates that there will be many responses to using CAS in classrooms, as teachers aim to achieve different learning goals and interpret their responsibilities to students in different ways.     

Analysis of thermally induced multistable composites

This paper models the non-linear flexural response of laminates that have piecewise variation of lay-up in the planform, using finite element analysis. Attention is focused on the effects that thermal stresses have on the potential multiple shapes of a composite structure. Unsymmetric laminates may possess more than a single equilibrium configuration, and during the cool-down the solution thus bifurcates at a critical temperature. In static analyses, numerical solutions are often coaxed to converge into one or the other branch of the solution. A methodology to overcome this problem is presented. Such modelling is necessary to allow application of multistable composite within morphing aircraft structures as multistable composites could provide a viable solution for the realisation of shape-adaptable structures.     

An improved algorithm for solving biobjective integer programs

A parametric algorithm for identifying the Pareto set of a biobjective integer program is proposed. The algorithm is based on the weighted Chebyshev (Tchebycheff) scalarization, and its running time is asymptotically optimal. A number of extensions are described, including: a technique for handling weakly dominated outcomes, a Pareto set approximation scheme, and an interactive version that provides access to all Pareto outcomes. Extensive computational tests on instances of the biobjective knapsack problem and a capacitated network routing problem are presented.     

A Note on Groups Associated with 4-Arc-Transitive Cubic Graphs

A cubic (trivalent) graph is said to be 4-arc-transitive ifits automorphism group acts transitively on the 4-arcs of (wherea 4-arc is a sequence v₀, v₁, ... v₄ of vertices of such thatv_i–1 is adjacent to v_i for 1 i 4, and v_i–1 v_i+1for 1 i < 4). In his investigations into graphs of thissort, Biggs defined a family of groups 4⁺(a^m), for m = 3,4,5...,each presented in terms of generators and relations under theadditional assumption that the vertices of a circuit of lengthm are cyclically permuted by some automorphism. In this paperit is shown that whenever m is a proper multiple of 6, the group4⁺(a^m) is infinite. The proof is obtained by constructing transitivepermutation representations of arbitrarily large degree.     

Intra- versus intermolecular hydrogen bonds in salicylamide derivatives

The crystal structures, solid-state infrared patterns, and thermal properties of two polymorphs of 4-nitrosalicylanilide are presented. In both polymorphs, intramolecular hydrogen bonds are found between the phenol oxygen and the amide proton, and intermolecular hydrogen bonds are found between the amide carbonyl oxygen and the phenol proton. These hydrogen bond patterns are compared to those found in other known salicylamide derivatives and an analysis is given of the factors contributing to preferences for intra- or intermolecular hydrogen bonds in these structures. Crystal data: polymorph, orthorhombic,Pbca,a=11.003(4),b=27.959(7),c=7.622(5) Å,Z=4,V=2345(3) ų, andR=0.038 (1351 reflections); polymorph, monoclinic,P2₁/a,a=28.36(1),b=11.64(1),c=7.293(8) Å,=90.68(6)°,Z=8,V=2408 ų, andR=0.043 (2425 reflections).     

Liquid chromatographic determination of 4,4'-dinitrocarbanilide, the active component of the infertility agent nicarbazin, in chicken, duck, goose, and snake eggs

4,4'-Dinitrocarbanilide (DNC) was extracted from chicken, duck, goose, and snake eggs and isolated by reversed-phase liquid chromatography. DNC was detected by ultraviolet absorbance at 347 nm and quantitated by comparison with a calibration standard. Recoveries of DNC from fortified control chicken, duck, goose, and snake egg samples were determined for DNC levels of 0.16, 10, and 16 microg/g. The mean recoveries from chicken, duck, goose, and snake eggs were 92 +/- 4, 88 +/- 9, 87 +/- 7, and 95 +/- 6%, respectively. The method limits of detection for DNC in chicken, duck, goose, and snake eggs ranged from 0.015 to 0.035 microg/g. The reported method is much simpler than and equally efficient as previous methods developed for the determination of DNC residues in egg contents.     

Oxidation of nitrided si(100) by gaseous atomic and molecular oxygen

The nitridation of Si(100) by ammonia and the subsequent oxidation of the nitrided surface by both gaseous atomic and molecular oxygen was investigated under ultrahigh vacuum (UHV) conditions using X-ray photoelectron spectroscopy (XPS). Nitridation of Si(100) by the thermal decomposition of NH3 results in the formation of a subsurface nitride and a decrease in the concentration of surface dangling bond sites. On the basis of changes in the N1s spectra obtained after NH3 adsorption and decomposition, we estimate that the nitride resides about four to five layers below the vacuum-solid interface and that the concentration of surface dangling bonds after nitridation is only 59% of its value on Si(100)-(2 x 1). Oxidation of the nitrided surface is found to produce an oxide phase that remains in the outer layers of the solid and interacts only weakly with the underlying nitride for oxygen coverages up to 2.5 ML. Slight changes in the N1s spectra observed after oxidizing at 300 K are suggested to arise primarily from the introduction of strain within the nitride, and by the formation of a small amount of Si2=N-O species near the nitride-oxide interface. The nitrogen bonding environment changes negligibly after oxidizing at 800 K, which is indicative of greater phase separation at elevated surface temperature. Nitridation is also found to significantly reduce the reactivity of the Si(100) surface toward both atomic and molecular oxygen. A comparison of the oxygen uptake on the clean and nitrided surfaces shows quantitatively that the decrease in dangling bond concentration is responsible for the reduced activity of the nitrided surface toward oxidation, and therefore that dangling bonds are the initial adsorption site for both gaseous oxygen atoms and molecules. Increasing the surface temperature is found to promote the uptake of oxygen when O2 is used as the oxidant, but brings about only a small enhancement in the uptake of gaseous O-atoms. The different effects of surface temperature on the uptake of O versus O2 are interpreted in terms of the efficiency at which dangling bond pairs are regenerated on the surface at elevated temperature and the different site requirements for the adsorption of O and O2.     

‘Sacrificial’ supramolecular assembly and pressure-induced polymerization: toward sequence-defined functionalized nanothreads

Limited supramolecular strategies have been utilized to synthesize sequence-defined polymers, despite the prominence of noncovalent interactions in materials design. Herein, we illustrate the utility of ‘sacrificial’ aryl-perfluoroaryl supramolecular synthons to synthesize sp³-hybridized nanothreads from sp²-enriched reactants. Our strategy features A–B reactant pairs in the form of a phenol:pentafluorophenol co-crystal that is preorganized for an electronically-biased and sequence-defined polymerization. The polymerization, initiated at 12 GPa, affords an alternating copolymer featuring exogenous –OH functionalities. The external substitution is confirmed through IR spectroscopy. Importantly, the inclusion of the functional unit provides the first experimental glimpse at reaction mechanism: keto–enol tautomerization that can only occur during cycloaddition is observed through IR spectroscopy. Our approach realizes the first example of a functionalized nanothread and attains sequence definition through sacrificial supramolecular preorganization and presents a further approach for de novo design of complex nanothreads.

Supramolecular synthons are exploited to synthesize –OH functionalized sp³-rich sequence-defined nanothreads using pressure-induced polymerization of a phenol:pentafluorophenol co-crystal.