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Hydroxyl radical-induced oxidation of proteins and peptides can lead to the cleavage of the peptide, leading to a release of fragments. Here, we used high-performance liquid chromatography tandem mass spectrometry (HPLC-MS/MS) and pre-column online ortho-phthalaldehyde (OPA) derivatization-based amino acid analysis by HPLC with diode array detection and fluorescence detection to identify and quantify free amino acids released upon oxidation of proteins and peptides by hydroxyl radicals. Bovine serum albumin (BSA), ovalbumin (OVA) as model proteins, and synthetic tripeptides (comprised of varying compositions of the amino acids Gly, Ala, Ser, and Met) were used for reactions with hydroxyl radicals, which were generated by the Fenton reaction of iron ions and hydrogen peroxide. The molar yields of free glycine, aspartic acid, asparagine, and alanine per peptide or protein varied between 4 and 55%. For protein oxidation reactions, the molar yields of Gly (∼32-55% for BSA, ∼10-21% for OVA) were substantially higher than those for the other identified amino acids (∼5-12% for BSA, ∼4-6% for OVA). Upon oxidation of tripeptides with Gly in C-terminal, mid-chain, or N-terminal positions, Gly was preferentially released when it was located at the C-terminal site. Overall, we observe evidence for a site-selective formation of free amino acids in the OH radical-induced oxidation of peptides and proteins, which may be due to a reaction pathway involving nitrogen-centered radicals.
Small, mobile propane gas vessels are widely spread and comprise additional hazards in case of a surrounding, intensive fire. The aim of the presented work is to holistically investigate the potential consequences of failure of these off-the-shelf propane gas vessels in case of an absence or malfunction of safety devices. In order to generate a statistically valid dataset, a total of 15 identical propane gas bottles without pressure relief device, each containing m = 11 kg of liquid propane, were underfired in horizontal position. For each selected fire type (wood fire, petrol pool fire, propane gas fire), five vessels were tested under identical conditions. Next to extensive camera equipment including a high-speed camera, systems to record the internal pressure of the gas cylinder, the resulting shock wave overpressure (three positions) and the flame and vessel temperature (three + three positions) during the underfiring were used. Also the unsteady, highly dynamical thermal radiation caused by the explosion of the expanding gas cloud was logged. The fragments were georeferenced and weighed after each test. The experiments prove the failure of all the gas cylinders at a burst pressure of pb = [71 … 98 bar] with a fragmentation into up to seven parts (average: four objects) and a subsequent explosion of the expanding vapour after mixing with the surrounding air. The overpressure measured in the close-up range (distance to the cylinder d = 5 m) resulting from the shockwave caused by the cylinder burst was up to pmax = 0.27 bar, which can potentially lead to significant injuries to humans and damage to building structures and infrastructure, especially in connection with the explosion and the resultant thermal radiation. The distance covered by the fragments after the failure was up to r = 260 m; 47% of the fragments hit the ground more than r = 50 m away from the position of failure.
Small, mobile propane gas vessels are widely spread and comprise additional hazards in case of a surrounding, intensive fire. The aim of the presented work is to holistically investigate the potential consequences of failure of these off-the-shelf propane gas vessels in case of an absence or malfunction of safety devices. In order to generate a statistically valid dataset, a total of 15 identical propane gas bottles without pressure relief device, each containing m = 11 kg of liquid propane, were underfired in horizontal position. For each selected fire type (wood fire, petrol pool fire, propane gas fire), five vessels were tested under identical conditions. Next to extensive camera equipment including a high-speed camera, systems to record the internal pressure of the gas cylinder, the resulting shock wave overpressure (three positions) and the flame and vessel temperature (three + three positions) during the underfiring were used. Also the unsteady, highly dynamical thermal radiation caused by the explosion of the expanding gas cloud was logged. The fragments were georeferenced and weighed after each test. The experiments prove the failure of all the gas cylinders at a burst pressure of pb = [71 … 98 bar] with a fragmentation into up to seven parts (average: four objects) and a subsequent explosion of the expanding vapour after mixing with the surrounding air. The overpressure measured in the close-up range (distance to the cylinder d = 5 m) resulting from the shockwave caused by the cylinder burst was up to pmax = 0.27 bar, which can potentially lead to significant injuries to humans and damage to building structures and infrastructure, especially in connection with the explosion and the resultant thermal radiation. The distance covered by the fragments after the failure was up to r = 260 m; 47% of the fragments hit the ground more than r = 50 m away from the position of failure.