Photoswitching Kinetics and Phase‐Sensitive Detection Add Discriminative Dimensions for Selective Fluorescence Imaging

Non‐invasive separation‐free protocols are attractive for analyzing complex mixtures. To increase selectivity, an analysis under kinetic control, through exploitation of the photochemical reactivity of labeling contrast agents, is described. The simple protocol is applied in optical fluorescence microscopy, where autofluorescence, light scattering, as well as spectral crowding presents limitations. Introduced herein is OPIOM (out‐of‐phase imaging after optical modulation), which exploits the rich kinetic signature of a photoswitching fluorescent probe to increase selectively and quantitatively its contrast. Filtering the specific contribution of the probe only requires phase‐sensitive detection upon matching the photoswitching dynamics of the probe and the intensity and frequency of a modulated monochromatic light excitation. After in vitro validation, we applied OPIOM for selective imaging in mammalian cells and zebrafish, thus opening attractive perspectives for multiplexed observations in biological samples.     

A comprehensive picture of the one-electron oxidation chemistry of enols, enolates and α-carbonyl radicals: oxidation potentials and characterization of radical intermediates

Oxidation potentials of 40 enols, enolates and some selected α-carbonyl radicals are presented along with their characterization by various techniques as applicable (X-ray, EPR, ENDOR, general TRIPLE, magnetic susceptibility measurements, UV-vis, fast scan cyclic voltammetry, isotope effects). The model compounds comprise representatives of stable simple enols linked to a multitude of substituents (alkyl, alkenyl, alkynyl, aryl, heteroaryl, propargyl alcohols) and of stable simple enols of amides. The results allow to clarify the primary reaction pathway of enol radical cations as a rapid deprotonation and—if warranted by the redox potential and the strength of the oxidant—a follow-up oxidation of the resultant α-carbonyl radical to the α-carbonyl cation. Moreover, the experimental oxidation potentials were linearly correlated with AM1 computed ionization potentials after correction for solvation. The correlation allows a reliable prediction of oxidation potentials of radicals including α-carbonyl radicals. After computing redox potentials of relevant radicals, the possibility of one-electron transfer between enolates and flavin and the involvement of various radicals of ascorbic acid in oxidation processes were assessed.     

Characterizations of self-combustion reactions (SCR) for the production of nanomaterials used as advanced cathodes in Li-ion batteries

In this work, self-combustion reactions (SCR) for the preparation of important cathode materials for rechargeable Li-ion batteries were investigated by thermal analytical tools (DSC, ARC, TGA), electron microscopy, XRD, various spectroscopies (MS, Raman, FTIR) and elemental analysis by ICP. The systems studied include solutions containing metal nitrates at the right stoichiometry and sucrose as a fuel, for the preparation of LiMn_0.5Ni_0.5O₂ (layered), LiMn_1.5Ni_0.5O₄ (spinel), LiMn_0.33Ni_0.33Co_0.33O₂ (layered), and LiMn_0.4Ni_0.4Co_0.2O₂ (layered). Similar products, which do not depend on the atmosphere of the processes (air or inert) were obtained by spontaneous SCR and the gradual heating of the same solutions by DSC, ARC, and TGA. The reactions involve the partial caramelization of sucrose, complicated by red-ox reactions with the nitrates that form solid products, whose organic part is finally decomposed around 400 °C. The presence of cobalt ions has a stabilizing effect, which is expressed by the low dissolution rates of Li ions from the solid products thus formed, into aqueous solutions. The reaction mechanisms are discussed herein.     

Measurement of Dihedral Angle Errors of a Large-Aperture Space Retroreflector: Separation of the Effect of Sag Due to Gravity

A 50-cm diameter hollow cube-corner retroreflector for a space application was tested with a 60-cm interferometer. To separate the effect of sag due to gravity, the interferograms were taken at six rotational positions, with the retroreflector mounted horizontally. The zero-gravity dihedral angles and the effect of sag were estimated from the interferograms.     

A Solution to the Weber Location Problem on the Sphere

In this paper we present an algorithm for the solution of the minisum location problem on the sphere. The algorithm is finite for the solution within a given accuracy of the optimal solution.     

Excitation and emission of metal electrons in atom-surface collisions

Electron-hole pair excitation and ionization probabilities are calculated for atomic collisions with metal surfaces at high incident energies. The method adopted is based on a Sudden Collision Approximation, and a realistic model is employed for the bound and continuum electronic states involved. The parameters used in the calculations are for Ar, He, H atoms impinging on a Li surface at 300 eV. The main results are: (1) Only single electron-hole pair excitations are important; multiple pair contributions are small. (2) The transitions are dominated by the behavior of the electronic wavefunctions in the tunneling region and may serve as a probe of this regime. (3) The excitation efficiency is in the order H ? Ar ? He, the effectiveness of hydrogen being due to its stronger, longer-range coupling. (4) The maximum excitation probabilities are for electrons ejected with relatively low excess energies. (5) Total transition probabilities are about 0.5 per collision for H, and about 0.1 for Ar, indicating that these are important, easily detectable processes. Experiments in this field should provide important information on electronic wavefunctions at the metal-gas interface, and on gas-metal interactions at high energies.     

A Finite Horizon Production Model with Variable Production Rates and Constant Demand Rate

In this paper we present a finite horizon single product single machine production problem. Demand rate and all the cost patterns do not change over time. However, end of horizon effects may require production rate adjustments at the beginning of each cycle. It is found that no such adjustments are required. The machine should be operated either at minimum speed (i.e. production rate = demand rate; shortage is not allowed), avoiding the buildup of any inventory, or at maximum speed, building up maximum inventories that are controlled by the optimal production lot size.