Short total syntheses of the avenaciolide family of natural products

The avenaciolide family of natural products are small α-methylene bis-γ-lactones that exhibit a wide variety of biological activities. Herein we report concise syntheses of five members of this family of natural products along with the synthesis of one non-natural analogue. The syntheses proceed in five or six steps from simple, commercially available compounds and feature a key oxidative cyclization/lactonization reaction that likely occurs via a radical mechanism.     

Oxodealkenylative Cleavage of Alkene C(sp3)−C(sp2) Bonds: A Practical Method for Introducing Carbonyls into Chiral Pool Materials

Reported herein is a one-pot protocol for the oxodealkenylative introduction of carbonyl functionalities into terpenes and terpene-derived compounds. This transformation proceeds by Criegee ozonolysis of an alkene, reductive cleavage of the resulting α-alkoxy hydroperoxide, trapping of the generated alkyl radical with 2,2,6,6-tetramethylpiperidin-1-yl (TEMPO), and subsequent oxidative fragmentation with MMPP. Using readily available starting materials from chiral pool, a variety of carbonyl-containing products have been accessed rapidly in good yields.     

Residue-specific 13C' CSA tensor principal components for ubiquitin: correlation between tensor components and hydrogen bonding

The residue-specific 13C' CSA tensor principal components, sigma(11), sigma(22), sigma(33), and the tensor orientation defined by the rotation angles beta and gamma have been determined by solution NMR for uniformly labeled ubiquitin partially aligned in four different media. Spurious chemical shift deviations due to solvent effects were corrected with an offset calculated by linear regression of the residual dipolar couplings and chemical shifts at increasing alignment strengths. Analysis of this effect revealed no obvious correlation to solvent exposure. Data obtained in solution from a protein offer a better sampling of 13C' CSA for different amino acid types in a complex heterogeneous environment, thereby allowing for the evaluation of structural variables that would be challenging to achieve by other methods. The 13C' CSA principal components cluster about the average values previously determined, and experimental correlations observed between sigma(11), sigma(22) tensorial components and C'O...H(N) hydrogen bonding are discussed. The inverse association of sigma(11) and sigma(22) exemplify the calculated and solid-state NMR observed effect on the tensor components by hydrogen bonding. We also show that 13C' CSA tensors are sensitive to hydrogen-bond length but not hydrogen-bond angle. This differentiation was previously unavailable. Similarly, hydrogen bonding to the conjugated NH of the same peptide plane has no detectable effect. Importantly, the observed weak correlations signify the presence of confounding influences such as nearest-neighbor effects, side-chain conformation, electrostatics, and other long-range factors to the 13C' CSA tensor. These analyses hold future potential for exploration provided that more accurate data from a larger number of proteins and alignments become available.     

A New Approach to Crushing 3-Manifold Triangulations

The crushing operation of Jaco and Rubinstein is a powerful technique in algorithmic 3-manifold topology: it enabled the first practical implementations of 3-sphere recognition and prime decomposition of orientable manifolds, and it plays a prominent role in state-of-the-art algorithms for unknot recognition and testing for essential surfaces. Although the crushing operation will always reduce the size of a triangulation, it might alter its topology, and so it requires a careful theoretical analysis for the settings in which it is used. The aim of this short paper is to make the crushing operation more accessible to practitioners and easier to generalise to new settings. When the crushing operation was first introduced, the analysis was powerful but extremely complex. Here we give a new treatment that reduces the crushing process to a sequential combination of three “atomic” operations on a cell decomposition, all of which are simple to analyse. As an application, we generalise the crushing operation to the setting of non-orientable 3-manifolds, where we obtain a new practical and robust algorithm for non-orientable prime decomposition. We also apply our crushing techniques to the study of non-orientable minimal triangulations.     

Giant tunneling electroresistance effect driven by an electrically controlled spin valve at a complex oxide interface

A giant tunneling electroresistance effect may be achieved in a ferroelectric tunnel junction by exploiting the magnetoelectric effect at the interface between the ferroelectric barrier and a magnetic La(1-x)Sr(x)MnO3 electrode. Using first-principles density-functional theory we demonstrate that a few magnetic monolayers of La(1-x)Sr(x)MnO3 near the interface act, in response to ferroelectric polarization reversal, as an atomic-scale spin valve by filtering spin-dependent current. This produces more than an order of magnitude change in conductance, and thus constitutes a giant resistive switching effect.     

Demonstration of a high-field short-period superconducting helical undulator suitable for future TeV-scale linear collider positron sources

The first demonstration of a full-scale working undulator module suitable for future TeV-scale positron-electron linear collider positron sources is presented. Generating sufficient positrons is an important challenge for these colliders, and using polarized e(+) would enhance the machine's capabilities. In an undulator-based source polarized positrons are generated in a metallic target via pair production initiated by circularly polarized photons produced in a helical undulator. We show how the undulator design is developed by considering impedance effects on the electron beam, modeling and constructing short prototypes before the successful fabrication, and testing of a final module.     

Fractional differential equations and Lyapunov functionals

We consider a scalar fractional differential equation, write it as an integral equation, and construct several Lyapunov functionals yielding qualitative results about the solution. It turns out that the kernel is convex with a singularity and it is also completely monotone, as is the resolvent kernel. While the kernel is not integrable, the resolvent kernel is positive and integrable with an integral value of one. These kernels give rise to essentially different types of Lyapunov functionals. It is to be stressed that the Lyapunov functionals are explicitly given in terms of known functions and they are differentiated using Leibniz’s rule. The results are readily accessible to anyone with a background of elementary calculus.     

Investigation of ligand exchange reactions in aqueous uranyl carbonate complexes using computational approaches

Carbonate anion exchange reactions with water in the uranyl-carbonate and calcium-uranyl-carbonate aqueous systems have been investigated using computational methods. Classical molecular dynamics (MD) simulations with the umbrella sampling technique were employed to determine potentials of mean force for the exchange reactions of water and carbonate. The presence of calcium counter-ions is predicted to increase the stability of the uranyl-carbonate species in accordance with previous experimental observations. However, the free energy barrier to carbonate exchange with water is found to be comparable both in the presence and absence of calcium cations. Possible implications of these results for uranyl adsorption on mineral surfaces are discussed. Density functional theory (DFT) calculations were also used to confirm the trends observed in classical molecular dynamics simulations and to corroborate the validity of the potential parameters employed in the MD scheme.