The first total synthesis of (+)-mucosin

The first total synthesis of (+)-mucosin has been completed allowing assignment of the absolute stereochemistry of the natural product. A zirconium induced co-cyclisation was utilised to install the correct stereochemistry of the four contiguous stereocentres around the unusual bicyclo[4.3.0]nonene core

Analytic Examples, Measurement Models and Classical Limit of Quantum Backflow

We investigate the backflow effect in elementary quantum mechanics - the phenomenon in which a state consisting entirely of positive momenta may have negative current and the probability flows in the opposite direction to the momentum. We compute the current and flux for states consisting of superpositions of gaussian wave packets. These are experimentally realizable but the amount of backflow is small. Inspired by the numerical results of Penz et al (M.Penz, G.Gr\"ubl, S.Kreidl and P.Wagner, J.Phys. A39, 423 (2006)), we find two non-trivial wave functions whose current at any time may be computed analytically and which have periods of significant backflow, in one case with a backwards flux equal to about 70 percent of the maximum possible backflow, a dimensionless number $c_{bm} \approx 0.04$, discovered by Bracken and Melloy (A.J.Bracken and G.F.Melloy, J.Phys. A27, 2197 (1994)). This number has the unusual property of being independent of $\hbar$ (and also of all other parameters of the model), despite corresponding to an obviously quantum-mechanical effect, and we shed some light on this surprising property by considering the classical limit of backflow. We discuss some specific measurement models in which backflow may be identified in certain measurable probabilities.Comment: 33 pages, 14 figures. Minor revisions. Published versio

Progression and assessment in foreign languages at Key Stage 2

The teaching of primary languages has been increasing steadily, in response to the future entitlement for all Key Stage 2 (KS2) pupils aged 7-11 to learn a foreign language by 2010. However, there remain concerns about progression both within KS2 and through to secondary school and about how learners' progress is assessed. This paper presents findings on the issues of progression and assessment taken from case studies which formed part of a project funded by the then Department for Education and Skills (DfES), now the Department for Children, Schools and Families (DCSF). This project set out to evaluate 19 local authority (LA) Pathfinders in England that were piloting the introduction of foreign language learning at KS2 between 2003 and 2005. Findings revealed that there was inconsistency between schools, even within each LA Pathfinder, in the use of schemes of work and that assessment was generally underdeveloped in the majority of the Pathfinders. In order to set these findings in context, this paper examines the issues of progression and assessment in foreign language learning in England. Finally, it investigates the challenges English primary schools face in terms of progression and assessment in the light of the new entitlement and discusses implications for the future. Managing progression, both within KS2 and through to secondary school at KS3 (ages 11-14), is one of the key factors in determining the overall success of starting languages in primary school

Electronic Spectroscopy of He@C60+ for Astrochemical Consideration

The electronic spectrum of the endohedral fullerene He@C+60 observed by messenger spectroscopy in a cryogenic ion trap is presented. The role played by the messanger tag in the adopted experimental method is evaluated by recording spectra of He@C+60 − Hen with n = 1−4. The results indicate a linear shift of ∼ 0.7 Å in the wavelengths allowing accurate gas phase values to be reported. The presence of the helium inside the cage shifts the absorption bands by 2−3 Å toward shorter wavelengths compared to C+60. The magnitude of this displacement will enable searches for the spectral signatures of this fullerene analogue in interstellar environments by absorption spectroscopy. The implications for potential astronomical detection are discussed

Human Herpesvirus 8 Seroprevalence among Prostate Cancer Case Patients and Control Subjects

n/

Microbial Contamination of Allende and Murchison Carbonaceous Chondrites; Developing a Protocol for Life Detection in Extraterrestrial Materials Using Biotechnology

The arguments used to refute the McKay et al., (1996) hypothesis of possible Martian life in ALH84001 failed to use contamination of the meteorite as a source. This has worrying implications for our ability to detect terrestrial microbiota in meteorites and therefore any potential extraterrestrial biosignatures in both meteorites and possible returned samples. We report on imaging and microbial culturing of both Allende and Murchison carbonaceous chondrites and on the use of molecular biology techniques on a sample of Allende. Contaminating fungi and bacteria were observed (in the case of Murchison) and cultured from both meteorites. DNA was successfully extracted and subsequent PCR showed the presence of both bacterial and fungal DNA although no Archaea were detected. These results show that it is possible to use molecular biological techniques on very small quantities (300 mg) of extraterrestrial material

Solid-state 3He^3\mathrm{He} NMR of the superconducting rubidium endofulleride Rb3(3He@C60)\mathrm{Rb_3(^3He@C_{60})}

A new variant of the superconducting fulleride $\mathrm{Rb_{3}C_{60}}$ is presented, with $\mathrm{^{3}He}$ atoms encapsulated in the $\mathrm{C_{60}}$ cages. The $\mathrm{^{3}He}$ nuclei act as sensitive NMR probes embedded in the material. The superconducting and normal states are characterised by $\mathrm{^{3}He}$ NMR. Evidence is found for co-existing vortex liquid and vortex solid phases below the superconducting transition temperature. A strong dependence of the spin-lattice relaxation time constant on spectral frequency is observed in the superconducting state, as revealed by two-dimensional NMR utilising an inverse Laplace transform. Surprisingly, this phenomenon persists, in attenuated form, at temperatures well above the superconducting transition.Comment: 20 pages, 15 figure

Cytochrome c Can Form a Well-Defined Binding Pocket for Hydrocarbons

Cytochrome c can acquire peroxidase activity when it binds to cardiolipin in mitochondrial membranes. The resulting oxygenation of cardiolipin by cytochrome c provides an early signal for the onset of apoptosis. The structure of this enzyme-substrate complex is a matter of considerable debate. We present three structures at 1.7-2.0 Å resolution of a domain-swapped dimer of yeast iso-1-cytochrome c with the detergents, CYMAL-5, CYMAL-6, and ω-undecylenyl-β-d-maltopyranoside, bound in a channel that places the hydrocarbon moieties of these detergents next to the heme. The heme is poised for peroxidase activity with water bound in place of Met80, which serves as the axial heme ligand when cytochrome c functions as an electron carrier. The hydroxyl group of Tyr67 sits 3.6-4.0 Å from the nearest carbon of the detergents, positioned to act as a relay in radical abstraction during peroxidase activity. Docking studies with linoleic acid, the most common fatty acid component of cardiolipin, show that C11 of linoleic acid can sit adjacent to Tyr67 and the heme, consistent with the oxygenation pattern observed in lipidomics studies. The well-defined hydrocarbon binding pocket provides atomic resolution evidence for the extended lipid anchorage model for cytochrome c/cardiolipin binding. Dimer dissociation/association kinetics for yeast versus equine cytochrome c indicate that formation of mammalian cytochrome c dimers in vivo would require catalysis. However, the dimer structure shows that only a modest deformation of monomeric cytochrome c would suffice to form the hydrocarbon binding site occupied by these detergents