The quest for single-enantiomer outcomes in free-radical chemistry

A significant challenge facing free-radical chemists is in the area of stereocontrol, specifically the ability to control the direction of reagent attack at a prochiral radical. While significant inroads have been made in the area of diastereoselective radical chemistry, less successful have been attempts to provide truly enantioselective processes. This article highlights recent efforts in the area of enantioselective free-radical reduction chemistry and describes how single-enantiomer outcomes are possible when simple enantiopure stannanes are used in conjunction with large, sterically-demanding Lewis acids. Selectivities in excess of 90% are now possible, with one example in excess of 99.5% ee provided.

Some unusual applications of the `Error-bar` feature in Excel spreadsheets

This paper demonstrates how the "error-bar" feature can be used to extend the utility of "worldware" spreadsheet packages in producing high-quality graphs for university teaching and learning, and for research. To further utilize the advantages of spreadsheets in university education, this paper seeks to overcome some of the earlier reservations about the lack of scientific plotting capabilities of spreadsheet applications. Specific examples of educational material in the areas of enzyme kinetics, vibrational spectroscopy, vibronic spectroscopy, and mass spectrometry are discussed. It is argued that, where practical, university educators should use "worldware" packages to prepare teaching aids, since these would better prepare their students for future employment. The use of software features for purposes that were not envisioned by the programmers has additional educational benefits in fostering flexibility and innovation. Other graphing packages can also use the "error-bar" feature in a manner similar to that described here for Excel.

Single enatiomer free-radical chemistry - Lewis acid-mediated reductions of racemic halides using chiral non-racemic stannanes

Additions of one to two equivalents of Lewis acids that include magnesium salts to free-radical reduction reactions involving ester functionalized radicals and (1R,2S,5R)-menthyldiphenyltin hydride 4, bis((1R,2S,5R)-menthyl)phenyltin hydride 5, tris((1R,2S,5R)-menthyl)tin hydride 6, bis((1R,2S,5R)-menthyl)-[8-(N,N-dimethylamino)naphthyl]tin hydride 12, bis((1R,2S,5R)-menthyl)-[1-((S)-N,N-dimethylaminoethyl)phenyl]tin hydride 13 or 3α-dimethylstannyl-5α-cholestane 14 result in remarkable enantioselectivities. Examples include (S)-naproxen ethyl ester 16, produced in 74% yield and greater than 99% ee at −78°C from the bromide and 5 in the presence of MgBr₂, and ethyl (R)-N-trifluoroacetyl-_D-phenylglycinate 18, obtained in 78% yield and 99% ee under identical conditions. Kinetic and computational studies provide insight into the origins of these observations.

The salt wedge position in a bar-blocked estuary subject to pulsed inflows

A series of laboratory experiments were carried out to investigate the response of a bar-blocked, saltwedge estuary to the imposition of both steady freshwater inflows and transient inflows that simulate storm events in the catchment area or the regular water releases from upstream reservoirs. The trapped salt water forms a wedge within the estuary, which migrates downstream under the influence of the freshwater inflow. The experiments show that the wedge migration occurs in two stages, namely (i) an initial phase characterized by intense shear-induced mixing at the nose of the wedge, followed by (ii) a relatively quiescent phase with significantly reduced mixing in which the wedge migrates more slowly downstream.

Provided that the transition time t_T between these two regimes satisfies t_T>g′h⁴L/q³α, as was the case for all our experiments and is likely to be the case for most estuaries, then the transition occurs at time t_T=1.2(gα³L⁶/g′³q²)^1/6, where g′=gΔρ/ρ0 is the reduced gravity, g the acceleration due to gravity, Δρ the density excess of the saline water over the density ρ₀ of the freshwater, q the river inflow rate per unit width, and L and α are the length and bottom slope of the estuary, respectively.

A simple model, based on conversion of the kinetic energy of the freshwater inflow into potential energy to mix the salt layer, was developed to predict the displacement xw over time t of the saltwedge nose from its initial position. For continuous inflows subject to t<t_T, the model predicts the saltwedge displacement as x_w/h=1.1 (t/τ)^1/3, where the normalizing length and time scales are h=(q²/g)^1/3 and τ=g′α²h4L/q³, respectively. For continuous inflows subject to t>tT, the model predicts the displacement as xw/h=0.45N1/6(t/τ)1/6/α, where N=q²/g′h²L is a non-dimensional number for the problem. This model shows very good agreement with the experiments. For repeated, pulsed discharges subject to t<t_T, the saltwedge displacement is given by (xw/h)3−(x0/h)(xw/h)2=1.3t/τ, where x₀ is the initial displacement following one discharge event but prior to the next event. For pulsed discharges subject to t>t_T, the displacement is given by (xw/h)⁶−(x0/h)(xw/h)⁵=0.008N(t/τ)/α⁶. This model shows very good agreement with the experiments for the initial discharge event but does systematically underestimate the wedge position for the subsequent pulses. However, the positional error is less than 15%.

Media/ting change: the print media's role in mediating education policy in a period of radical reform in Victoria, Australia

This paper draws upon critical discourse analysis, cultural studies and communication theory, studies on media and educational reform, and the work of Bernstein, Bourdieu and Luhmann in particular, to explore how the print and media 'mediated' a period of educational change marked by moves to self-management in schools in Victoria, Australia. It considers how the media was mobilized by various education stakeholders, and in turn informed relations between schools and government, through policy discourses and texts. It considers why and how particular themes became media 'issues', how schools and teachers responded to these issues, and how the media was used by various stakeholders in education to shape policy debates. It is based on a year-long qualitative study that explored critical incidents and representations about education in the print media over a year in the daily press. It illustrates the ways in which a neo-liberal Victorian government mobilized the media to gain strategic advantage to promote radical education reform policies, considers the media effects of this media/tion process on schools and teachers, and conceptualizes how school and system performance is fed from and into media representations, public perceptions and community understandings of schools and teachers' work.

Numerical investigation of austenite grain size distribution in square-diamond pass hot bar rolling

In this study, the austenite grain size (AGS) for hot bar rolling of AISI4135 steel was predicted based on two different AGS evolution models available in the literature. In order to predict the AGS more accurately, both models were integrated with a three-dimensional non-isothermal finite element program by implementing a modified additivity rule. The predicted results based on two models for the square-diamond (S-D) and round-oval (R-O) pass bar rolling processes were compared with the experimental data available in the literature. Then, numerical predictions depending on various process parameters such as interpass time, temperature, and roll speed were made to compare both models and investigate the effect of these parameters on the AGS distributions. Such numerical results were found to be beneficial to understand the effect of the microstructure evolution model on the rolling processes better and control the processes more accurately.

Analytical model of pass-by-pass strain in rod (or bar) rolling and its applications to prediction of austenite grain size

Rod rolling is a process where the deformation state of the workpiece between the work rolls is quite different from the strip rolling process. However, in most microstructure evolution models, the simple area strains (natural logarithm of the area reduction ratio) multiplied by a constant have been used to compute pass-by-pass evolution of austenite grain size (AGS) in rod (or bar) rolling, without any verification. The strains at a given pass play a crucial role in determining the recrystallization behavior (static or dynamic). In this study, an analytical model that calculates the pass-by-pass strain and strain rate in rod rolling has been developed and verified by conducting four-pass (oval–round) bar and plate rolling experiments. Numerical simulations have then been carried out for the four-pass rolling sequence using the area strain model and the new analytical model, focusing on the effect of the method for calculating the strain on the recrystallization behavior and evolution of AGS. The AGS predicted was compared with those obtained from hot torsion tests. It is shown that the analytical model developed in this study is more appropriate in the analysis of bar (or rod) rolling. It was found that the recrystallization behavior and evolution of AGS during this process were influenced significantly by the calculation method for the deformation parameters (strain and strain rate). The pass-by-pass strain obtained from the simple area strain model is inadequate to be used as an input to the equations for recrystallization and AGS evolution under these rolling conditions.

Integrated model for thermo-mechanical controlled process in rod (or bar) rolling

This study presents an integrated model for computing the thermo-mechanical parameters (cross-sectional shape of workpiece, the pass-by-pass strain and strain rate and the temperature variation during rolling and cooling between inter-stands) and metallurgical parameters (recrystallisation behaviour and austenite grain size—AGS), to assess the potential for developing “Thermo-Mechanical Controlled Process” technology in rod (or bar) rolling, which has been a well-known technical terminology in strip (or plate) rolling since 1970s.

The advantage of this model is that metallurgical and mechanical parameters are obtained simultaneously in a short computation time compared with other models. The model has been applied to a rod mill to predict the exit cross-sectional shape, area and AGS per pass by incorporating the equations for AGS evolution being used in strip rolling. At the finishing train of rod mills, the strain rates reach as high as 1000–3000 s−1 and the inter-pass times are around 10–60 ms.

The results show that the proposed model is an efficient tool for evaluating the effects of process-related parameters on product quality and dimensional tolerance of the products in rod (or bar) rolling. The results of the simulation demonstrated that the equation for AGS evolution being used in strip rolling might have limitations when applied directly to rod rolling at a high strain rate.

A comparative study of microstructures and mechanical properties obtained by bar and plate rolling

Microstructures and mechanical properties of a low carbon steel were studied after plate rolling and bar rolling. Plate rolling is characterized as a monotonic compressive loading, while bar rolling is characterized as a cross-compressive loading. A four-pass plate rolling and bar rolling experiment was designed so that the material experiences the same amount of strain at each pass during rolling. The rolling experiment was performed at moderately high temperatures (450, 550 and 650 °C). The microstructures and mechanical properties of the low carbon steel acquired from the two types of rolling experiments were compared. The results revealed that differences of loading path attributed by monotonic loading (plate rolling) and cross loading (bar rolling) significantly influenced the microstructures and mechanical properties such as yield stress, ultimate tensile stress, strain hardening exponent and elongation of the low carbon steel.

Synthesis, characterization and enantioselective free radical reductions of (1R,2S,5R)-menthyldiphenylgermane and its enantiomer

(1R,2S,5R)-Menthyldiphenylgermane and its enantiomer have been prepared in a few steps from germanium tetrachloride. The initial step in this sequence, namely the reaction between germanium tetrachloride and menthylmagnesium chloride, produces menthylgermanium trichloride, which is the exclusive product of this Grignard reaction, presumably due to the bulk of the menthyl group. When used at a low temperature (−78 °C) and in conjunction with Lewis acids, such as magnesium salts, these chiral germanes are capable of reducing ester functionalized radicals in high enantioselectivity, but in low-moderate yield. For example, (R)-naproxen ethyl ester was obtained in 15% yield and 99% ee by reaction in toluene of 2-bromonaproxen ethyl ester with (1R,2S,5R)-menthyldiphenylgermane in toluene at −78 °C in the presence of magnesium bromide. At 80 °C, (1R,2S,5R)-menthyldiphenylgermane reacted with primary alkyl radicals with a rate constant of 1.02 × 10⁶ M⁻¹ s⁻¹. Kinetic studies reveal the Arrhenius expression for this reaction to be: log(k/M⁻¹ s⁻¹) = (11.1 ± 0.4) − (34.6 ± 3.1)/θ where θ=2.3RT kJ mol⁻¹.

Local Austenite grain size distribution in hot bar rolling of AISI 4135 Steel

In this paper, the local distribution of austenite grain size (AGS) was experimentally determined by conducting single round-oval and square-diamond pass hot bar rolling experiments of AISI4135 steel. The rolling experiments were carried out using the laboratory mill. The local distribution of AGS was also determined numerically. In order to predict AGS distribution, the AGS evolution model was combined with three dimensional non-isothermal finite element analyses by adopting a modified additivity rule. AGS evolution model was experimentally determined from hot torsion test according to Hodgson's model. The predicted results were in a reasonably good agreement with experimental results.