A combined isotropic-kinematic hardening model for the simulation of warm forming and subsequent loading at room temperature

A coupled isotropic-kinematic hardening material model was developed based on phenomenological observations of performed two stage experiments on a medium carbon steel – SAE 1144, where the first deformation is performed at elevated temperatures and the second deformation at room temperature. Above all, deformations with orthogonal loading at various temperatures were investigated in order to determine the influence of the loading direction as well as of the temperature. Bergström’s theory of work hardening as well as the nonlinear kinematic hardening of an Armstrong–Frederick type were used as a basis for the model development. In the proposed model a relationship between material coefficients of the classical Bergström model and temperature was investigated. The aim of the new material model was to introduce the least possible amount of new parameters as well as to facilitate the mathematical determination of parameters during the fitting of the model with experimental data. The developed model was implemented in an in-house FE-Code in order to simulate the material behavior due to the dynamic strain aging and the hardening behavior after the dynamic strain aging process. Representative simulation results were compared with the experimental data in order to validate the efficiency and the application range of the model.     

Genotoxicity screening for N-nitroso compounds. Electrochemical and electrochemiluminescent detection of human enzyme-generated DNA damage from N-nitrosopyrrolidine

We report for the first time voltammetric/electrochemiluminescent sensors applied to predict genotoxicity of N-nitroso compounds bioactivated by human cytochrome P450 enzymes.     

Shifting unoccupied spectral space in mass spectrum of peptide fragment ions

Ions near the high-end border of a mass defect distribution plot for native peptide fragment ions have potential as signature markers that are based on mass-to-charge ratio determination. The specificity of these marker ions, including phosphoryl ions, can be improved by removing interfering isobaric ions from the border region on the distribution plot. These interfering ions are rich in Asp and Glu content. The masses of amino acid residues and peptides are rescaled from the IUPAC scale (¹²C=12 u as the mass reference) to the averagine scale (averagine mass=111 u* as the mass reference with zero mass defect; u*: the mass unit on the averagine scale), using a scaling factor of 0.999493894. It is theoretically predicted that esterification of Asp and Glu side-chain carboxylates with n-butanol can achieve a sufficient retreat of the high-end border on a mass defect distribution plot based on the use of mass spectrometers with better-than-medium resolution. Theoretical calculations and laboratory experiments are performed to examine effects of various esterifications on the averagine-scale mass defect distribution of peptide fragment ions and on the specificity of two positive phosphoryl ions: the phosphotyrosine immonium ion and a cyclophosphoramidate ion.     

Comparison of DNA‐Reactive Metabolites from Nitrosamine and Styrene Using Voltammetric DNA/Microsomes Sensors

Voltammetric sensors made with films of polyions, double‐stranded DNA and liver microsomes adsorbed layer‐by‐layer onto pyrolytic graphite electrodes were evaluated for reactive metabolite screening. This approach features simple, inexpensive screening without enzyme purification for applications in drug or environmental chemical development. Cytochrome P450 enzymes (CYPs) in the liver microsomes were activated by an NADPH regenerating system or by electrolysis to metabolize model carcinogenic compounds nitrosamine and styrene. Reactive metabolites formed in the films were trapped as adducts with nucleobases on DNA. The DNA damage was detected by square‐wave voltammetry (SWV) using Ru(bpy) as a DNA‐oxidation catalyst. These sensors showed a larger rate of increase in signal vs. reaction time for a highly toxic nitrosamine than for the moderately toxic styrene due to more rapid reactive metabolite‐DNA adduct formation. Results were consistent with reported in vivo TD₅₀ data for the formation of liver tumors in rats. Analogous polyion/ liver microsome films prepared on 500 nm silica nanoparticles (nanoreactors) and reacted with nitrosamine or styrene, provided LC‐MS or GC analyses of metabolite formation rates that correlated well with sensor response.