Determination of post-translational modifications of proteins by high-sensitivity, high-resolution Fourier transform ion cyclotron resonance mass spectrometry

The response of a cell to its extracellular environment is a multi-step process beginning with signal transduction that is governed by "subtle changes" often resulting in protein expression. Proteomics is the tracking of this protein expression. Post-translational modification (PTM) is a "subtle change" that has a major influence on signal transduction. Phosphorylation and glycosylation propagate signals by sequential, reversible modifications. High-sensitivity, high-resolution and multiple MS capabilities of Fourier transform ion cyclotron resonance mass spectrometry permit localization of the PTM(s) with electron-capture dissociation, and then structural determination of the PTM with infrared multiphoton dissociation.     

Palladium‐Catalyzed Synthesis of Ammonium Sulfinates from Aryl Halides and a Sulfur Dioxide Surrogate: A Gas‐ and Reductant‐Free Process

Sulfonyl‐derived functional groups populate a broad range of useful molecules and materials, and despite a variety of preparative methods being available, processes which introduce the most basic sulfonyl building block, sulfur dioxide, using catalytic methods, are rare. Described herein is a simple reaction system consisting of the sulfur dioxide surrogate DABSO, triethylamine, and a palladium(0) catalyst for effective convertion of a broad range of aryl and heteroaryl halides into the corresponding ammonium sulfinates. Key features of this gas‐ and reductant‐free reaction include the low loadings of palladium (1 mol %) and ligand (1.5 mol %) which can be employed, and the use of isopropyl alcohol as both a solvent and formal reductant. The ammonium sulfinate products are converted in situ into a variety of sulfonyl‐containing functional groups, including sulfones, sulfonyl chlorides, and sulfonamides.     

On Regular Orbits of Elements of Classical Groups in Their Permutation Representations

Let H be a simple finite classical group not isomorphic to PSL(n, q) for any n, q. We prove that every cyclic subgroup of H has a regular orbit on every nontrivial permutation H-set.     

Automated data reduction for hydrogen/deuterium exchange experiments,enabled by high-resolution fourier transform ion cyclotron resonance mass spectrometry

Mass analysis of proteolytic fragment peptides following hydrogen/deuterium exchange offers a general measure of solvent accessibility/hydrogen bonding (and thus conformation) of solution-phase proteins and their complexes. The primary problem in such mass analyses is reliable and rapid assignment of mass spectral peaks to the correct charge state and degree of deuteration of each fragment peptide, in the presence of substantial overlap between isotopic distributions of target peptides, autolysis products, and other interferant species. Here, we show that at sufficiently high mass resolving power (m/Δm_50% ≥ 100,000), it becomes possible to resolve enough of those overlaps so that automated data reduction becomes possible, based on the actual elemental composition of each peptide without the need to deconvolve isotopic distributions. We demonstrate automated, rapid, reliable assignment of peptide masses from H/D exchange experiments, based on electrospray ionization FT-ICR mass spectra from H/D exchange of solution-phase myoglobin. Combined with previously demonstrated automated data acquisition for such experiments, the present data reduction algorithm enhances automation (and thus expands generality and applicability) for high-resolution mass spectrometry-based analysis of H/D exchange of solution-phase proteins.     

Simultaneous Controllability of PSD and MWD in Emulsion Polymerisation

A sensitivity study of particle size distribution (PSD) and molecular weight distribution (MWD) responses to perturbations in initiator, surfactant, monomer and chain transfer agent in a semi‐batch emulsion polymerisation is presented. The objective is to provide a systematic study on the ability to simultaneously control both PSD and MWD, towards inferential control of end‐use product properties. This would lead towards identification of the practical feasible regions of operability. All inputs appeared to have an intrinsic and simultaneous influence on end‐time PSD and MWD. Trends shown in experimental results have been explained in a mechanistic sense and also compared to simulation results from a combined PSD/MWD population balance model. The preliminary comparison between experiment and simulation highlights areas to be focussed on with respect to model improvement.

     

Advanced supply chain planning with mixtures of backorders,lost sales,and lost contract

This paper investigates a supply chain system in which a supplier prepares for the selling season by building stock levels prior to the beginning of the season and shortages realized at the beginning of the season are represented as mixtures of backorders and lost sales. Backlogged items are replenished as soon as possible through an emergency procurement as opposed to waiting until the next scheduled delivery as in many continuous review scenarios, and the backorder rate is modeled as a piecewise linear function of the magnitude of the shortage. The often intangible cost associated with lost sales and customer goodwill is also quantified. In particular, the buyer and supplier are engaged in a contractual agreement and the loss of customer goodwill from the supplier’s perspective is represented as the expected cost associated with violating the conditions of the contract. The likelihood of contract cancellation is also represented as a function of the magnitude of shortage. The optimal solution is derived in closed form for the case of exponential demand distribution, and an example problem is illustrated with numerical data in order to demonstrate calculation of the optimal solution and corresponding sensitivity analysis for demand distributions in which the solution cannot be expressed in closed form.