Comparison of electrospray ionization, atmospheric pressure chemical ionization, and atmospheric pressure photoionization for the analysis of dinitropyrene and aminonitropyrene LC-MS/MS

The only relevant source for human exposure to dinitropyrenes is diesel engine emissions. Due to this specificity, dinitropyrenes may be used as biomarkers for monitoring human exposure to diesel engine emissions. Only few analytical methods have been described for the quantitation of dinitropyrenes and their metabolites, aminonitropyrenes, and diaminopyrenes. Therefore, for dinitropyrenes, aminonitropyrenes, and diaminopyrenes were selected as model compounds for the development of a sensitive HPLC-MS/MS method (high performance liquid chromatography coupled to triple quadrupole mass spectrometry) was to quantify polyaromatic amines and nitroarenes in biological matrices was developed optimal methods by comparing electrospray ionization (ESI), atmospheric pressure chemical ionization (APCI), and atmospheric pressure photoionization (APPI) sources. Dinitropyrene was not effectively ionized and diaminopyrene yielded mainly [M·]+ ions by electrospray ionization. With APCI and APPI, precursor ions of diaminopyrene and aminonitropyrene were [M + H]+ and [M·]− for dinitropyrene. Precursor ions with [M − 30·]− for dinitropyrene and [M − 30 + H]+ for aminonitropyrene were observed. Reversed and normal phase HPLC-MS/MS with ESI, APCI and APPI were optimized separately with respect to unequivocal analyte identification and sensitivity. Normal phase HPLC coupled to APPI-MS/MS gave the highest precision and sensitivity for aminonitropyrene (6%/0.2 pg on column) and dinitropyrene (9%/0.5 pg on column). The limit of detection in spiked rat plasma was 5 pg/100 μL for aminonitropyrene (accuracy 82%) and 10 pg/100 μL for dinitropyrene (accuracy 105%). In plasma of rats treated with dinitropyrene by oral administration, no detectable levels of dinitropyrene but higher aminonitropyrene levels compared with intratracheal instillation were observed. These findings clearly demonstrate that dinitropyrene was absorbed after oral and intratracheal application and that a reduction of nitro groups occurs to a high extent in the reductive environment of the intestine. To our knowledge, this is the first time that aminonitropyrene was observed in plasma after intratracheal or oral administration directly demonstrating the reductive metabolism of dinitropyrene in vivo

The Potential of Restarts for ProbSAT

This work analyses the potential of restarts for probSAT, a quite successful algorithm for k-SAT, by estimating its runtime distributions on random 3-SAT instances that are close to the phase transition. We estimate an optimal restart time from empirical data, reaching a potential speedup factor of 1.39. Calculating restart times from fitted probability distributions reduces this factor to a maximum of 1.30. A spin-off result is that the Weibull distribution approximates the runtime distribution for over 93% of the used instances well. A machine learning pipeline is presented to compute a restart time for a fixed-cutoff strategy to exploit this potential. The main components of the pipeline are a random forest for determining the distribution type and a neural network for the distribution's parameters. ProbSAT performs statistically significantly better than Luby's restart strategy and the policy without restarts when using the presented approach. The structure is particularly advantageous on hard problems.Comment: Eurocast 201

Noise-induced switching between vortex states with different polarization in classical two-dimensional easy-plane magnets

In the 2-dimensional anisotropic Heisenberg model with XY-symmetry there are non-planar vortices which exhibit a localized structure of the z-components of the spins around the vortex center. We study how thermal noise induces a transition of this structure from one polarization to the opposite one. We describe the vortex core by a discrete Hamiltonian and consider a stationary solution of the Fokker-Planck equation. We find a bimodal distribution function and calculate the transition rate using Langer's instanton theory (1969). The result is compared with Langevin dynamics simulations for the full many-spin model.Comment: 15 pages, 4 figures, Phys. Rev. B., in pres

Intrinsic hole mobility and trapping in a regio-regular poly(thiophene)

The transport properties of high-performance thin-film transistors (TFT) made with a regio-regular poly(thiophene) semiconductor (PQT-12) are reported. The room-temperature field-effect mobility of the devices varied between 0.004 cm2/V s and 0.1 cm2/V s and was controlled through thermal processing of the material, which modified the structural order. The transport properties of TFTs were studied as a function of temperature. The field-effect mobility is thermally activated in all films at T<200 K and the activation energy depends on the charge density in the channel. The experimental data is compared to theoretical models for transport, and we argue that a model based on the existence of a mobility edge and an exponential distribution of traps provides the best interpretation of the data. The differences in room-temperature mobility are attributed to different widths of the shallow localized state distribution at the edge of the valence band due to structural disorder in the film. The free carrier mobility of the mobile states in the ordered regions of the film is the same in all structural modifications and is estimated to be between 1 and 4 cm2/V s.Comment: 20 pages, 8 figure

Aqueous Self-Assembly of a Protein-Mimetic Ampholytic Block Copolypeptide

This report describes the aggregation behavior of an ABC-type ampholytic block copolypeptide, poly(ethylene oxide)-block-poly(l-lysine)-block-poly(l-glutamate), in aqueous media in dependence of pH. Polypeptide secondary structures and self-assemblies are investigated by circular dichroism (CD), Fourier transform infrared (FT-IR) and NMR spectroscopy, zeta potential measurements, analytical ultracentrifugation (AUC), dynamic/static light scattering (DLS/SLS), and cryogenic transmission electron microscopy (cryo-TEM). The polymer chains tend to form vesicles when the hydrophobic polypeptide helix is located at the chain end (acidic pH) and are existing as single chains when it is located in the center and flanked by the two hydrophilic segments (basic pH). Precipitation occurs in the intermediate pH range due to polyion complexation of the charged polypeptide segments

Electron spin relaxation of the PO3 2- radical in ferroelectric betaine phosphite and in the proton glass betaine phosphate/betaine phosphite

Measurements of the electron spin-lattice relaxation time T1 and the phase memory time TM of the PO3 2- radical in γ-irradiated betaine phosphite and betaine phosphate/betaine phosphite are presented. The temperature dependence of T1 indicates the interaction of the electron spin with two groups of optical branches via Raman processes in both crystals. An additional relaxation path due to the interaction with two-level local tunneling states has been observed in the mixed crystal confirming glassy behaviour. The TM temperature dependence reflects thermally activated local motional effects of the PO3 group in both crystals. © 1994

Evidence for Different Freeze-Out Radii of High- and Low-Energy Pions Emitted in Au+Au Collisions at 1 GeV/nucleon

Double differential production cross sections of negative and positive pions and the number of participating protons have been measured in central Au+Au collisions at 1 GeV per nucleon incident energy. At low pion energies the pi^- yield is strongly enhanced over the pi^+ yield. The energy dependence of the pi^-/pi^+ ratio is assigned to the Coulomb interaction of the charged pions with the protons in the reaction zone. The deduced Coulomb potential increases with increasing pion c.m. energy. This behavior indicates different freeze-out radii for different pion energies in the c.m.~frame.Comment: IKDA is the Institute for Nuclear Physics in Darmstadt/German