An original approach for Raman spectroscopy analysis of radioactive materials and its application to americium‐containing samples

An approach for Raman measurements of highly radioactive samples is presented here. The innovative part of this approach lies in the fact that no single part of the Raman equipment is in direct contact with the radioactive sample, as the sample is sealed in an alpha‐tight capsule. Raman analysis is effectively performed through the optical‐grade quartz window closing the capsule. This allows performing micro‐Raman measurements on radioactive samples with no limitations on the laser source wavelength, polarisation mode, spectrometer mode and microscope mode (provided the focal length of the microscope objective is greater than the thickness of the quartz window and with sub mg samples). Some example results are shown and discussed. In particular, some spectral features of americium‐containing oxide nuclear fuel specimens are presented. Raman spectra clearly reveal in these specimens the presence of abundant oxygen defects induced in the fcc fluorite lattice by trivalent americium. In order to complete the analysis the Raman spectrum of pure americium dioxide was also measured with a lower energy excitation source compared with previous research. The current results seem to be consistent with the possible occurrence of a photolysis process induced by the Raman laser, resulting in the formation of hyperstoichiometric americium sesquioxide Am₂O_{3 + z}. Such a photolytic process is deemed to be unavoidable when visible lasers are used as excitation sources for the Raman analysis of americium dioxide. © 2015 The Authors Journal of Raman Spectroscopy Published by John Wiley & Sons, Ltd.     

Traceless solid-phase synthesis of 2,4,6-chlorodiamino and triaminopyrimidines

An effective traceless solid-phase synthesis of chloro-diaminopyrimidines via an amino-de-chlorination reaction of polymer-bound 4-alkoxycarbonylamino-2,6-dichloropyrimidines has been developed. After release from the polymer the target molecules were obtained in good to excellent purity, although with modest regiocontrol. Further reaction of solid-supported N-alkoxycarbonyl-chloro-diaminopyrimidines with secondary amines afforded triaminopyrimidines in good purity under mild conditions, whereas less nucleophilic primary amines did not perform well under the conditions explored so far.     

Algorithms for flows over time with scheduling costs

Mathematical Programming - Flows over time have received substantial attention from both an optimization and (more recently) a game-theoretic perspective. In this model, each arc has an associated...     

Single cell manipulation, analytics, and label-free protein detection in microfluidic devices for systems nanobiology

Single cell analytics for proteomic analysis is considered a key method in the framework of systems nanobiology which allows a novel proteomics without being subjected to ensemble-averaging, cell-cycle, or cell-population effects. We are currently developing a single cell analytical method for protein fingerprinting combining a structured microfluidic device with latest optical laser technology for single cell manipulation (trapping and steering), free-solution electrophoretical protein separation, and (label-free) protein detection. In this paper we report on first results of this novel analytical device focusing on three main issues. First, single biological cells were trapped, injected, steered, and deposited by means of optical tweezers in a poly(dimethylsiloxane) microfluidic device and consecutively lysed with SDS at a predefined position. Second, separation and detection of fluorescent dyes, amino acids, and proteins were achieved with LIF detection in the visible (VIS) (488 nm) as well as in the deep UV (266 nm) spectral range for label-free, native protein detection. Minute concentrations of 100 fM injected fluorescein could be detected in the VIS and a first protein separation and label-free detection could be achieved in the UV spectral range. Third, first analytical experiments with single Sf9 insect cells (Spodoptera frugiperda) in a tailored microfluidic device exhibiting distinct electropherograms of a green fluorescent protein-construct proved the validity of the concept. Thus, the presented microfluidic concept allows novel and fascinating single cell experiments for systems nanobiology in the future.     

On classical electrodynamics of point particles and mass renormalization: Some preliminary results

Apparently, no rigorous results exist for the dynamics of a classical point particle interacting with the electromagnetic field, as described by the standard Maxwell-Lorentz equations. Some results are given here for the corresponding linearized system (dipole approximation) in the presence of a mechanical linear restoring force. We consider a regularization of the system (Pauli-Fierz model), and explicitly solve the Cauchy problem in terms of normal modes. Then we study the limit of the particle's motion as the regularization is removed. We prove that the particle's motion corresponding to smooth initial data for the field has a well-defined limit if mass is renormalized, while the motion is trivial (i.e. the particle does not move at all) if mass is not renormalized. Moreover, the limit particle's motion corresponding to an interesting class of initial data satifies exactly the Abraham-Lorentz-Dirac equation. Finally, for generic initial data the limit motion is runaway.     

A branch and bound algorithm for scheduling trains in a railway network

The paper studies a train scheduling problem faced by railway infrastructure managers during real-time traffic control. When train operations are perturbed, a new conflict-free timetable of feasible arrival and departure times needs to be re-computed, such that the deviation from the original one is minimized. The problem can be viewed as a huge job shop scheduling problem with no-store constraints. We make use of a careful estimation of time separation among trains, and model the scheduling problem with an alternative graph formulation. We develop a branch and bound algorithm which includes implication rules enabling to speed up the computation. An experimental study, based on a bottleneck area of the Dutch rail network, shows that a truncated version of the algorithm provides proven optimal or near optimal solutions within short time limits.     

Stretching of polymers in isotropic turbulence: a statistical closure

We present a new closure for the mean rate of stretching of a dissolved polymer by homogeneous isotropic turbulence. The polymer is modeled by a bead-spring-type model (e.g., Oldroyd B, FENE-P, Giesekus) and the analytical closure is obtained assuming the Lagrangian velocity gradient can be modeled as a Gaussian, white-noise stochastic process. The resulting closure for the mean stretching depends upon the ratio of the correlation time for strain and rotation. Additionally, we derived a second-order expression for circumstances when strain and rotation have a finite correlation time. Finally, the base level closure is shown to reproduce results from direct numerical simulations by simply modifying the coefficients.     

Cocrystal Formation through Mechanochemistry: from Neat and Liquid‐Assisted Grinding to Polymer‐Assisted Grinding

Mechanochemistry is an effective method for the preparation of multicomponent crystal systems. In the present work, we propose an alternative to the established liquid‐assisted grinding (LAG) approach. Polymer‐assisted grinding (POLAG) is demonstrated to provide a new class of catalysts for improving reaction rate and increasing product diversity during mechanochemical cocrystallization reactions. We demonstrate that POLAG provides advantages comparable to the conventional liquid‐assisted process, whilst eliminating the risk of unwanted solvate formation as well as enabling control of resulting particle size. It represents a new approach for the development of functional materials through mechanochemistry, and possibly opens new routes toward the understanding of the mechanisms and pathways of mechanochemical cocrystal formation.