PubMed · 3521388
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D L Gerrard, H J Bowley. 1986. Raman spectroscopy.. https://doi.org/10.1021/ac00296a002
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Captive bubbles are commonly used to determine how interfacial films of pulmonary surfactant respond to changes in surface area, achieved by varying hydrostatic pressure. Although assumed to be isothermal, the gas phase temperature (Tg) would increase by >100 degrees C during compression from 1 to 3 atm if the process were adiabatic. To determine the actual change in temperature, we monitored pressure (P) and volume (V) during compressions lasting <1 s for bubbles with and without interfacial films and used P x V to evaluate Tg. P x V fell during and after the rapid compressions, consistent with reductions in n, the moles of gas phase molecules, because of increasing solubility in the subphase at higher P. As expected for a process with first-order kinetics, during 1 h after the rapid compression P x V decreased along a simple exponential curve. The temporal variation of n moles of gas was determined from P x V >10 min after the compression when the two phases should be isothermal. Back extrapolation of n then allowed calculation of Tg from P x V immediately after the compression. Our results indicate that for bubbles with or without interfacial films compressed to >3 atm within 1 s, the change in Tg is <2 degrees C.
Altogether eight keto and enol tautomers of guanine were studied theoretically in the gas phase, in a microhydrated environment (1 and 2 water molecules) and in bulk water. The structures of isolated, as well as mono- and dihydrated tautomers were determined by means of the RI-MP2 method using the extended TZVPP (5s3p2d1f/3s2p1d) basis set. The relative energies of isolated tautomers included the correction to higher correlation energy terms evaluated at the CCSD(T)/aug-cc-pVDZ level. The relative enthalpies at 0 K and relative free energies at 298 K were based on the above-mentioned relative energies and zero-point vibration energies, temperature-dependent enthalpy terms and entropies evaluated at the MP2/6-31G level. The keto form having hydrogen atom at N7 is the global minimum while the canonical form having hydrogen atom at N9 represents the first local minimum at all theoretical levels in vacuo and in the presence of 1 and 2 water molecules. All three unusual rare tautomers having hydrogens at N3 and N7, at N3 and N9, and also at N9 and N7 are systematically considerably less stable and can be hardly detected in the gas phase. The theoretical predictions fully agree with existing theoretical as well as experimental results. The effect of bulk solvent on the relative stability of guanine tautomers was studied by self-consistent reaction field and molecular dynamics free energy calculations using the thermodynamic integration method. Bulk solvent, surprisingly, strongly favored these three rare tautomers over all remaining low-energy tautomers and probably only these forms can exist in water phase. The global minimum (tautomer with hydrogens at N3 and N7) is by 13 kcal/mol more stable than the canonical form (3rd local minimum). Addition of one or two water molecules does not change the relative stability order of isolated guanine tautomers but the respective trend clearly supports the surprising stabilization of three rare forms.
Partitioning of eight targeted heavy metals (Cr, Mn, Cu, Pb, Sn, Co, Ni and Zn) was carried out during five trial burns in Izmit hazardous and clinical waste incinerator (IZAYDAS). Metal contents of the original wastes and their concentration in the bottom ash (BA), fly ash (FA), filter cake (FC) and flue gas were determined. Partitioning behavior of metals during the two-stage incineration was evaluated with respect to physico-chemical properties of feed waste and metals, and the operational conditions. Results suggest that combustion temperatures and retention times are the dominant parameters determining the volatility of metals in the first combustion chamber. Targeted metals were generally partitioned in the rank of bottom ash, filter cake, fly ash and flue gas. High filter cake/fly ash ratios showed that high temperatures in the second stage increase both the formation of gaseous metallic compounds and the enrichment of metals in fine particles. Since ESP could not be effective in removing fine particles and volatilized metallic compounds, the necessity of an additional system that would remove heavy metals efficiently was emphasized for the modern incinerators.