Asymmetric synthesis of the erythrinan alkaloid system using a chiral lithium amide base desymmetrisation as the key step

A new asymmetric approach to the erythrinan alkaloid system is described, which involves chiral base desymmetrisation of a ring fused imide and a 6-exo-trig radical cyclisation as the key steps.     

Reinforcing effect of bi- and tri-cyclopolyprenols on ‘primitive’ membranes made of polyprenyl phosphates

Cholesterol plays the role of membrane reinforcer in eukaryotes, whereas hopanoids play the same role in bacteria. Which components could have reinforced ‘primitive’ membranes? We describe here an efficient biomimetic synthesis of bi- and tri-cyclopolyprenols and demonstrate that these compounds reinforce the membranes of polyprenyl phosphate, which we speculated as ‘primitive’ membranes.     

Synthetic studies towards ptilomycalin A: total synthesis of crambescidin 359

A potentially biomimetic synthesis of the guanidine-containing marine natural product crambescidin 359 via a double Michael addition of guanidine to a suitably functionalised bis-enone is reported.     

Interactive Statistical Mechanics and Nonlinear Filtering

This paper connects non-equilibrium statistical mechanics and optimal nonlinear filtering. The latter concerns the observation-conditional behaviour of Markov signal processes, and thus provides a tool for investigating statistical mechanics with partial observations. These allow entropy reduction, illustrating Landauer’s Principle in a quantitative way. The joint process comprising a signal and its nonlinear filter is irreversible in its invariant distribution, which therefore corresponds to a non-equilibrium stationary state of the associated joint system. Macroscopic entropy and energy flows are identified for this state. Since these are driven by observations internal to the system, they do not cause entropy increase, and so the joint system makes statistical mechanical sense in reverse time. Time reversal yields a dual system in which the signal and filter exchange roles. Despite the structural similarity of the original and dual systems, there is a substantial asymmetry in their complexities. This reveals the direction of time, despite the systems being in stationary states that do not produce entropy. This work was partially supported by Leverhulme Trust Research Fellowship 2003/0426, by MURI Grant F49620-02-1-0325 (Complex Adaptive Networks for Co-operative Control), by ARO-MURI Grant DAAD19-00-1-0466 (Data Fusion in Large Arrays of Microsensors (sensor web)) and by NSF-ITR Grant CCR-0325774 Collaborative Research: New Approaches to Experimental Design and Statistical Analysis of Genomic and Structural Biological Data from Multiple Sources.     

The Role of Emotions in Multi-Organizational Decision-Making

This paper addresses two questions. (i) What is the role of emotions in decision-making? (ii) Can emotions be attributed to organizations, and is their role in decisions made between organizations the same as in decisions made between individual people? The answers given to question (ii) are yes and yes. The proposed answer to question (i) is based upon a game-theoretic approach, which considers how emotions may be of strategic benefit to game players.     

General method of preparation of mesoporous M/Si3N4 nano-composites via a non-aqueous sol-gel route

We report a general method for the preparation of transition-metal silicon nitride nanocomposites; for example, mesoporous Pd-Si3N4 nanocomposite materials with high surface area were prepared by pyrolysis of a silicon palladium imide-chloride complex which was synthesized by reaction of silicon diimide gel with palladium chloride. These porous nanocomposites catalyse organic reactions.     

Aristotelinone and serratoline: New indole alkaloids from Aristotelia serrata W.R.B. Oliver

Aristotelinone and serratoline, two new Aristotelia alkaloids, are shown to have indole and indolenine structures respectively from their spectra and reduction products.     

Probing active site geometry using high pressure and secondary isotope effects in an enzyme-catalysed 'deep' H-tunnelling reaction

We report the first study of the effects of hydrostatic pressure on α-2° KIEs for an enzyme-catalysed H-transfer reaction that occurs by 'deep' tunnelling. High pressure causes a significant decrease in the observed α-2° KIE on the pre-steady-state hydride transfer from NADH to FMN in the flavoprotein morphinone reductase. We have recently shown that high pressure causes a reduction in macroscopic reaction barrier width for this reaction. Using DFT vibrational analysis of a simple active site model, we posit that the decrease in α-2° KIE with pressure may arise due to a decrease in the vibrational coupling between the NADH primary (transferred) and secondary hydrogens in the 'tunnelling ready configuration', which more closely resembles the reactant state than the transition state.