Continuous sample deposition from reversed-phase liquid chromatography to tracks on a matrix-assisted laser desorption/ionization precoated target for the analysis of protein digests

Peptide mass fingerprinting by matrix-assisted laser desorption/ionization (MALDI)-mass spectrometry (MS) is one of the standard high-throughput methods for protein identification today. Traditionally this method has been based on spotting peptide mixtures onto MALDI targets. While this method works well for more abundant proteins, low-abundance proteins mixed with high-abundance proteins tend to go undetected due to ion suppression effects, instrumental dynamic range limitations and chemical noise interference. We present an alternative approach where liquid chromatography (LC) effluent is continuously collected as linear tracks on a MALDI target. In this manner the chromatographic separation is spatially preserved on the target, which enables generation of off-line LC-MS and LC-MS/MS data by MALDI. LC-MALDI sample collection provides improved sensitivity and dynamic range, spatial resolution of peptides along the sample track, and permits peptide mass mapping of low-abundance proteins in mixtures containing high-abundance proteins. In this work, standard and ribosomal protein digests are resolved and captured using LC-MALDI sample collection and analyzed by MALDI-TOF-MS.     

Facility location in the presence of forbidden regions,I: Formulation and the case of Euclidean distance with one forbidden circle

A constrained form of the Weber problem is formulated in which no path is permitted to enter a prespecified forbidden region $\text{R}$ of the plane. Using the calculus of variations the shortest path between two points $\text{x}\text{,}\text{y}\text{?}\text{R}$ which does not intersect $\text{R}$ is determined. If $\text{d(}\text{x}\text{,}\text{y}\text{)}$ is unconstrained distance, we denote the shortes distance along a feasible path by $\text{d}\text{(}\text{x}\text{y}\text{)}$. The constrained Weber problem is, then: given points $\text{x}{}_{\mathrm{j}}\text{?}\text{R}$ and positive weights w_j, j = 1,2,…,n, find a point $\text{x}\text{?}\text{R}$ such that

$\text{f(}\text{x}\text{)=}\text{Σ}\text{n}\text{j=1}\text{d(}\text{x}\text{,}\text{x}{}_{\mathrm{j}}\text{)}$

is a minimum.An algorithm is formulated for the solution of this problem when $\text{d(}\text{x}\text{,}\text{y}\text{)}$ is Euclidean distance and $\text{R}$ is a single circular region. Numerical results are presented.     

Electric field buildup and relaxation for chemical diffusion

By applying Maxwell's equation (Poisson's law) to the flux equations for ionic diffusion it is shown that analytical solutions for the flux of charge and the compensating electrical field can be derived for the limits t→0 and t→∞. (Actually the long time limit becomes appropriate after a time equivalent to a small multiple of the mean time between successive jumps of all ions.) These expressions permit derivation of the Nernst-Planck equations and their generalization to multi-component systems without any self-contradictory assumptions. They also allow an approximate interpolation between the two limiting time periods so that a close approximation of the field and flux is obtained for the entire time interval. It should be noted that the flux of charge changes sign during the process and tends to zero much more quickly than the electric field. The scaling constants for time, energy and electrical flux are evaluated in general and for conditions relevant to alkali ion exchange in a silicate glass near the glass transition temperature. Values for the time constant, the maximum field, and the maximum flux are of the order of fractional micro-seconds, one megavolt/cm, and one ampere/cm², respectively.     

European Synchrotron Users Unified

The landscape of synchrotron radiation facilities in Europe is diverse. In addition to the flagship ESRF, several national facilities exist or came into operation recently. In contrast to ESRF, which is financed for use by member countries, access of foreign users to national facilities is not easy. Even if their proposals pass the review process, they can only perform the experiments if funding is allocated to cover not only travel expenses, board and lodging of the experimenters, but also some compensation for the facility's operational costs; this is because national facilities are primarily funded for the home-country's users at that nation's costs.     

Lagrangian Point State Estimation with Optimized, Redundant Induction Coil Gauges

This research effort studies the use of redundant induction coil gauges to reduce state estimation uncertainties for moving Lagrangian points (LPs); e.g. discrete points, moving interfaces, projectiles, etc. The technique embeds a small, high-strength magnet at the LP and simultaneously tracks the magnet continuously with five (5) or more induction coils along a single axis of motion. A calibrated coil gauge model is presented as a function of LP position and velocity. The optimized LP state (position and velocity) estimate based upon redundant LP observations allows direct solution for LP velocity; requiring only one differentiation step to obtain acceleration. A specific experimental implementation (Particulate Materials Meso-scale Diagnostics system) is simulated to evaluate and minimize the expected state estimation errors. Induction coil signals with various levels of noise are simulated based upon a prescribed LP state variation with time. The state optimization algorithm attempts to recover the truth state values. Worst-case position estimation errors of ±0.3 mm and velocity estimation errors of ±0.46 m/s are determined for LPs travelling 0–1,000 m/s at realistic in-lab data noise levels.     

Influence of Gold Nanoparticle Film Porosity on the Chemiresistive Sensing Performance

The porosity of 1‐hexanethiol‐functionalised gold nanoparticle films was assessed and utilised as chemiresistor sensors. Electrochemical capacitance measurements showed that the accessibility of electrolytes of different ionic strengths into the pores depended on the thickness of the electric double layer formed. A large variation in capacitance was measured in 0.01–1000 mM NaClO₄, implying a wide pore size distribution. The change in morphology of the nanoparticle films upon storage in air, water and ethanol for two weeks was investigated. There was a significant decrease in the electrochemical capacitance at high electrolyte concentrations for the ethanol‐stored films compared to the freshly‐prepared films suggesting a decrease in the number of small pores of radii in the range of 0.3–3 nm. This was further supported by optical topographical measurements where a decrease in the thickness of ethanol‐stored films was observed relative to the freshly‐prepared films. The porous nature of the nanoparticle films was found to have an effect on the chemical sensing behaviour. When used as chemiresistor sensors, for the detection of heptane in water, the ethanol‐stored films provided larger resistance changes and longer response times. This suggests that the more densely packed ethanol‐stored films provided more sites that enabled film swelling, and that diffusion of the analyte occurred through the narrower water‐filled pores. This demonstrates the effect of different storage conditions on film morphology and subsequently sensor response.     

Conversion of Penicillin G Into Cephalexin Employing a Second-Order Asymmetric Transformation

2′5- and 2′R- and S- cephalexin, (5b) and (5c) respectively, both available in six stages from penicillin G, have each been converted to the more useful 2′R-isomer (5a) by a base catalysed epimerization and selective crystallization process involving the N-nitrosoimidazolidinyl derivatives (7).     

Esrf 10th users meeting

We explored diffraction enhanced imaging (DEI) in both planar and computed tomography (CT) modes for early detection of beta amyloid deposition, a hallmark feature in Alzheimer's disease (AD). Since amyloid plaques precede clinical symptoms by years, their early detection is of great interest. These findings were correlated with results from synchrotron infrared microspectroscopic imaging and X-ray fluorescence microscopy, to determine the secondary structure of the amyloid beta protein and metal concentration in the amyloid plaques, respectively.