Total synthesis and antimalarial activity of symplostatin 4

The first total synthesis of symplostatin 4, a marine cyanobacterium-derived natural product, is described. Notable features of the route include the efficient preparation of three key fragments and final assembly to the natural product via sequential imide and amide couplings. Symplostatin 4 was also demonstrated to possess significant antimalarial activity (ED(50) of 74 nM against Plasmodium falciparum, strain 3D7).     

Comment on "Long time evolution of phase oscillator systems" [Chaos 19, 023117 (2009)

In a recent paper by Ott and Antonsen [Chaos 19, 023117 (2009)], it was shown for the case of Lorentzian distributions of oscillator frequencies that the dynamics of a very general class of large systems of coupled phase oscillators time-asymptotes to a particular simplified form given by Ott and Antonsen [Chaos 18, 037113 (2008)]. This comment extends this previous result to a broad class of oscillator distribution functions.     

Semi-Markov regime switching interest rate models and minimal entropy measure

In this paper, we present a discrete time regime switching binomial-like model of the term structure where the regime switches are governed by a discrete time semi-Markov process. We model the evolution of the prices of zero-coupon when given an initial term structure as in the model by Ho and Lee that we aim to extend. We discuss and derive conditions for the model to be arbitrage free and relate this to the notion of martingale measure. We explicitly show that due to the extra source of uncertainty coming from the underlying semi-Markov process, there are an infinite number of equivalent martingale measures. The notion of path independence is also studied in some detail, especially in the presence of regime switches. We deal with the market incompleteness by giving an explicit characterization of the minimal entropy martingale measure. We give an application to the pricing of a European bond option both in a Markov and semi-Markov framework. Finally, we draw some conclusions.     

An indirect probe of the possible half-metallic nature of LiFePO4 using resonant inelastic X-ray scattering

The Fe site in LiFePO₄ was probed resonantly and non-resonantly at the L_2,3 edge. A suspected half-metal, the experimental results were compared to band structure calculations to understand the electronic structure. We found that the probability of promoting an electron to the unoccupied band through simple photoexcitation or through scattering is highly influenced by magnon-exciton coupling. We have also found evidence that the correlation self-energy has a momentum-dependant component, causing spectral renormalization of the Fe 3d PDOS. Our experimental results are consistent with the predicted band, structure of LiFePO₄.     

Ultrafast dynamics of polybutadiene probed by optically heterodyne-detected optical-Kerr-effect spectroscopy

The ultrafast dynamics of polybutadiene have been studied using ultrafast optical-Kerr-effect spectroscopy. The data are compared with measurements on 1,3- and 1,4-pentadiene. The two diene derivatives have quite distinct subpicosecond dynamics, with an important contribution from an intramolecular torsional mode in the 1,4-derivative. The main part of the polymer spectral density can be assigned, by analogy with the data for 1,4-pentadiene, to intramolecular torsional motion about carbon–carbon single bonds. The picosecond diffusive orientational relaxation times of the dienes are not well described by simple hydrodynamics.     

Disappearing Wakes and Dispersion in Numerically Simulated Flows Through Tube Bundles

Flow through a staggered array or bundle of parallel rigid cylinders of diameter D is computed with the help of a three-dimensional direct numerical simulation (DNS) at various values of Reynolds number between 50 and 6000. Two different spacings L of the tubes, i.e. L/D= 2 and L/D= 3, have been considered. When Re 500 the flow is laminar. In that case the converging flow between a pair of adjacent cylinders brings the oppositely signed vorticity at the two edges of the wake closer together behind the upstream cylinder so that the vorticity decreases quickly due to cancellation by diffusion. At Re 6000, when the flow is highly turbulent, the wake vorticity disappears rather by turbulent diffusion. This disappearance of the wakes in the closely packed flows (i.e. L/D 2) causes the mean flow in a cell, which consists of the region around a single cylinder, to be effectively independent of that in other cells. Another consequence is that the mean velocity field can be very well approximated by potential flow except in a thin boundary layer along the cylinder and a short wake behind it. The results have been applied to the transport of scalars in closely packed arrays. As in other complex flows, the dispersion of the scalars is dominated by the divergence and convergence of the streamlines around the cylinder rather than by the wake turbulence. Approximate expressions are derived for this topologically influenced dispersion in terms of the geometry of the array. The fact when most of the flow in the array can be approximated by a potential flow, allows us to introduce a fast approximate calculation method to compute the dispersion.     

Front-End Electron Transfer Dissociation Coupled to a 21 Tesla FT-ICR Mass Spectrometer for Intact Protein Sequence Analysis

High resolution mass spectrometry is a key technology for in-depth protein characterization. High-field Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) enables high-level interrogation of intact proteins in the most detail to date. However, an appropriate complement of fragmentation technologies must be paired with FTMS to provide comprehensive sequence coverage, as well as characterization of sequence variants, and post-translational modifications. Here we describe the integration of front-end electron transfer dissociation (FETD) with a custom-built 21 tesla FT-ICR mass spectrometer, which yields unprecedented sequence coverage for proteins ranging from 2.8 to 29 kDa, without the need for extensive spectral averaging (e.g., ~60% sequence coverage for apo-myoglobin with four averaged acquisitions). The system is equipped with a multipole storage device separate from the ETD reaction device, which allows accumulation of multiple ETD fragment ion fills. Consequently, an optimally large product ion population is accumulated prior to transfer to the ICR cell for mass analysis, which improves mass spectral signal-to-noise ratio, dynamic range, and scan rate. We find a linear relationship between protein molecular weight and minimum number of ETD reaction fills to achieve optimum sequence coverage, thereby enabling more efficient use of instrument data acquisition time. Finally, real-time scaling of the number of ETD reactions fills during method-based acquisition is shown, and the implications for LC-MS/MS top-down analysis are discussed.

Open image in new window

Graphical Abstract ?