Collision Induced Dissociation Products of Disulfide-Bonded Peptides: Ions Result from the Cleavage of More Than One Bond

Disulfide bonds are a post-translational modification (PTM) that can be scrambled or shuffled to non-native bonds during recombinant expression, sample handling, or sample purification. Currently, mapping of disulfide bonds is not easy because of various sample requirements and data analysis difficulties. One step towards facilitating this difficult work is developing a better understanding of how disulfide-bonded peptides fragment during collision induced dissociation (CID). Most automated analysis algorithms function based on the assumption that the preponderance of product ions observed during the dissociation of disulfide-bonded peptides result from the cleavage of just one peptide bond, and in this report we tested that assumption by extensively analyzing the product ions generated when several disulfide-bonded peptides are subjected to CID on a quadrupole time of flight (QTOF) instrument. We found that one of the most common types of product ions generated resulted from two peptide bond cleavages, or a double cleavage. We found that for several of the disulfide-bonded peptides analyzed, the number of double cleavage product ions outnumbered those of single cleavages. The influence of charge state and precursor ion size was investigated, to determine if those parameters dictated the amount of double cleavage product ions formed. It was found in this sample set that no strong correlation existed between the charge state or peptide size and the portion of product ions assigned as double cleavages. These data show that these ions could account for many of the product ions detected in CID data of disulfide bonded peptides. We also showed the utility of double cleavage product ions on a peptide with multiple cysteines present. Double cleavage products were able to fully characterize the bonding pattern of each cysteine where typical single b/y cleavage products could not.     

Bayesian decoding of neural spike trains

Perception, memory, learning, and decision making are processes carried out in the brain. The performance of such intelligent tasks is made possible by the communication of neurons through sequences of voltage pulses called spike trains. It is of great interest to have methods of extracting information from spike trains in order to learn about their relationship to behavior. In this article, we review a Bayesian approach to this problem based on state-space representations of point processes. We discuss some of the theory and we describe the way these methods are used in decoding motor cortical activity, in which the hand motion is reconstructed from neural spike trains.     

A relativistic meson-baryon description ofpp-Bremsstrahlung

We describe a relativistic approach to the calculation of nucleon-nucleon Bremsstrahlung, where all meson-baryon and meson-baryon-photon interactions can be calculated consistently and microscopically. In this first relativistic approach to the problem, we present numerical results including both single-scatter and rescatter contributions with a relativistic current density, within a model where the explicit photon coupling to meson-exchange currents are small. The need for high precision(p, pγ) measurements is stressed.     

Exponential attractors of optimal Lyapunov dimension for Navier-Stokes equations

In this paper we present a new construction of exponential attractors based on the control of Lyapunov exponents over a compact, invariant set. The fractal dimension estimate of the exponential attractor thus obtained is of the same order as the one for global attractors estimated through Lyapunov exponents. We discuss various applications to Navier-Stokes systems.     

Building addressable libraries: the use of electrochemistry for generating reactive Pd(II) reagents at preselected sites on a chip

A Pd(II) reagent has been generated at preselected sites on an electrochemically addressable chip. The reagent was used to effect the Wacker oxidation of an olefin substrate bound to the chip near the electrode. The use of ethyl vinyl ether in the solution above the chip effectively kept the Pd(II) reagent generated at the preselected electrode from migrating to neighboring electrodes and initiating Wacker oxidations at unwanted sites on the chip.