Nitrone [2]rotaxanes: Simultaneous chemical protection and electrochemical activation of a functional group

We report on the use of the hydrogen bond accepting properties of neutral nitrone moieties to prepare benzylic-amide-macrocycle-containing [2]rotaxanes in yields as high as 70 %. X-Ray crystallography shows the presence of up to four intercomponent hydrogen bonds between the amide groups of the macrocycle and the two nitrone groups of the thread. Dynamic 1H NMR studies of the rates of macrocycle pirouetting in nonpolar solutions indicate that amide-nitrone hydrogen bonds are particularly strong, ~1.3 and ~0.2 kcal mol-1 stronger than similar amide-ester and amide-amide interactions, respectively. In addition to polarizing the N-O bond through hydrogen bonding, the rotaxane structure affects the chemistry of the nitrone groups in two significant ways: The intercomponent hydrogen bonding activates the nitrone groups to electrochemical reduction, a one electron reduction of the rotaxane being stablized by a remarkable 400 mV (8.1 kcal mol-1) with respect to the same process in the thread; encapsulation, however, protects the same functional groups from chemical reduction with an external reagent (and slows down electron transfer to and from the electroactive groups in cyclicvoltammetry experiments). Mechanical interlocking with a hydrogen bonding molecular sheath thus provides a route to an encapsulated polarized functional group and radical anions of significant kinetic and thermodynamic stability.

Experimental and finite element analysis of a double strap joint between steel plates and normal modulus CFRP

Strengthening of steel structures using externally-bonded carbon fibre reinforced polymers ‘CFRP’ is a rapidly developing technique. This paper describes the behaviour of axially loaded flat steel plates strengthened using carbon fibre reinforced polymer sheets. Two steel plates were joined together with adhesive and followed by the application of carbon fibre sheet double strap joint with different bond lengths. The behaviour of the specimens was further investigated by using nonlinear finite element analysis to predict the failure modes and load capacity. In this study, bond failure is the dominant failure mode for normal modulus (240 GPa) CFRP bonding which closely matched the results of finite elements. The predicted ultimate loads from the FE analysis are found to be in good agreement with experimental values.

Evaluating parent-child group music therapy programmes: challenges and successes for Sing & Grow

Sing & Grow is an early intervention music therapy programme for families with children from birth to 3 years of age, who are socially, economically, or physically disadvantaged. It aims to improve parenting skills and confidence, promote positive parent–child interactions, stimulate child development, and provide social networking opportunities. Music and song activities are used in a therapeutic context to enhance parenting skills, improve parent–child interactions, provide essential developmental stimulation for children, promote social support for parenting, and strengthen links between parents and community services.

A Krylov-based finite state projection algorithm for solving the chemical master equation arising in the discrete modelling of biological systems

Biochemical reactions underlying genetic regulation are often modelled as a continuous-time, discrete-state, Markov process, and the evolution of the associated probability density is described by the so-called chemical master equation (CME). However the CME is typically difficult to solve, since the state-space involved can be very large or even countably infinite. Recently a finite state projection method (FSP) that truncates the state-space was suggested and shown to be effective in an example of a model of the Pap-pili epigenetic switch. However in this example, both the model and the final time at which the solution was computed, were relatively small. Presented here is a Krylov FSP algorithm based on a combination of state-space truncation and inexact matrix-vector product routines. This allows larger-scale models to be studied and solutions for larger final times to be computed in a realistic execution time. Additionally the new method computes the solution at intermediate times at virtually no extra cost, since it is derived from Krylov-type methods for computing matrix exponentials. For the purpose of comparison the new algorithm is applied to the model of the Pap-pili epigenetic switch, where the original FSP was first demonstrated. Also the method is applied to a more sophisticated model of regulated transcription. Numerical results indicate that the new approach is significantly faster and extendable to larger biological models.

The influence of conformity and group identity on drink walking intentions : comparing intentions to drink walk across risky pedestrian crossing scenarios

Despite the dangers associated with drink walking, limited research is currently available regarding the factors which influence individuals to engage in this risky behaviour. This study examined the influence of psychosocial factors upon individuals’ intentions to drink walk across four experimental scenarios (and a control condition). Specifically, a 2 × 2 repeated measures design was utilised in which all of the scenarios incorporated a risky pedestrian crossing situation (i.e., a pedestrian crossing against a red man signal) but differed according to the level of group identity (i.e., low/strangers and high/friends) and conformity (low and high). Individuals were assessed for their intentions to drink walk within each of these different scenarios. Undergraduate students (N = 151), aged 17–30 years, completed a questionnaire. Overall, most of the study's hypotheses were supported with individuals reporting the highest intentions to drink walk when in the presence of friends (i.e., high group identity) and their friends were said to be also crossing against the red man signal (i.e., high conformity). The findings may have significant implications for the design of countermeasures to reduce drink walking. For instance, the current findings would suggest that potentially effective strategies may be to promote resilience to peer influence as well as highlight the negative consequences associated with following the behaviour of other intoxicated pedestrians who are crossing against a red signal.