Polycyclic aromatic hydrocarbons (PAHs) were measured in mainstream and sidestream tobacco smoke from 14 commercial brands of cigarettes purchased in Italy during 2001-2002. The PAHs detected in smoke and analysed with HPLC and a fluorimetric detector were: fluoranthene, pyrene, benzo[a]anthracene, chrysene, benzo[a]pyrene, benzo[b] fluoranthene, benzo[k] fluoranthene, benzo[g,h,i]perylene and dibenzo[a,h]anthracene. The PAH levels in mainstream smoke from different cigarette brands obtained using an official smoking machine varied by about threefold (from 118 to 374 ng per cigarette for total PAHs and from 23.5 to 100 ng per cigarette for carcinogenic PAHs). Total PAH levels in mainstream smoke were correlated with tar content (r = 0.615, P < 0.05, n = 14). Total PAH content in sidestream smoke, measured by collection of all the smoke produced by a lit cigarette in a glass chamber, was about tenfold higher compared with mainstream smoke. The PAH content in sidestream smoke was relatively uniform (2.3-3.9 and 0.49-1.21 micro g per cigarette for total and carcinogenic PAHs, respectively) and was not correlated with tar content. These results indicate that cigarette manufacturing and filter characteristics influence the PAH composition of mainstream smoke, but have no effect on the PAH content in sidestream smoke, which is the main determinant of smokers' and non-smokers' exposure to PAHs in environmental tobacco smoke.

A series of analogous nitratomethyl compounds of carbon and silicon of the formula types Me(3)ElCH(2)ONO(2) (1a/1b), Me(2)El(CH(2)ONO(2))(2) (2a/2b), MeEl(CH(2)ONO(2))(3) (3a/3b), (CH(2))(4)El(CH(2)ONO(2))(2) (4a/4b), and (CH(2))(5)El(CH(2)ONO(2))(2) (5a/5b) were synthesized [El = C (a), Si (b); (CH(2))(4)El = (sila)cyclopentane-1,1-diyl; (CH(2))(5)El = (sila)cyclohexane-1,1-diyl]. All compounds were characterized by using NMR, IR, and Raman spectroscopy and mass spectrometry. In addition, the crystal structures of Me(2)C(CH(2)ONO(2))(2) (2a), (CH(2))(4)C(CH(2)ONO(2))(2) (4a), Me(2)Si(CH(2)ONO(2))(2) (2b), and (CH(2))(5)Si(CH(2)ONO(2))(2) (5b) were determined by single-crystal X-ray diffraction. The gas-phase structures of the C/Si analogues 1a and 1b were determined by electron diffraction and compared with the results of quantum chemical calculations at different levels of theory. The thermal stabilities of the C/Si pairs 1a/1b-5a/5b were investigated by using DSC. In addition, their friction and impact sensitivities were measured with standard BAM methods. The extreme sensitivities of the silicon compounds 1b-5b compared to those of the corresponding carbon analogues 1a-5a were discussed in terms of the structures of the C/Si analogues and possible geminal Si...O interactions.

Various energetic polynitro esters, carbamates, and nitrocarbamates that were derived from the amino acid glycine were fully characterized by single-crystal X-ray diffraction, vibrational spectroscopy (IR and Raman), multinuclear NMR spectroscopy, elemental analysis, and differential scanning calorimetry (DSC). Owing to their positive oxygen balance, the suitability of these compounds as potential oxidizers in energetic formulations was investigated and discussed. In addition, the heats of formation of the products were calculated by using the Gaussian 09 program package at the CBS-4M level of theory. From these values and the calculated densities (from the X-ray data), several detonation parameters, such as detonation pressure, velocity, energy, and temperature, were computed by using the EXPLO5 code. Furthermore, their sensitivities towards impact, friction, and electrostatic discharge were tested by using a drop hammer, a friction tester (both BAM certified), and a small-scale electrical-discharge device, respectively.

A great number of binary neutral phosphorus sulfides was discovered and investigated. However all stable representatives of this family of compounds adopt a polycyclic structure in contrast to their lighter homologues, the nitrogen oxides. Acyclic representatives can be stabilized by adduct formation with a nitrogen base. The bis(pyridine) adduct py2P2S5 of the unstable acyclic phosphorus sulfide P2S5 is readily obtained stirring P4S10 in pyridine at ambient temperature. X‐ray diffraction studies on single crystals of py2P2S5·0.5 py (1b) show a N2O5 like structure for the P2S5 framework. The long P–N distances of 1.86 Å indicate only weak coordination of the pyridine molecules to phosphorus. Single crystal X‐ray diffraction studies on py2P2S4.34O0.66 (2) reveal the presence of py2P2S4O (3) together with py2P2S5 in the crystal. Compound 3 contains the mixed phosphorus oxide sulfide molecule P2S4O stabilized as bis(pyridine) adduct. It is readily obtained from pyP2S5 by oxidation with KMnO4 in pyridine. The oxygen atom occupies the bridging position between the two phosphorus atoms. Quantum chemical calculations at the MPW1PW91 level of theory as well as DTA/TG thermal analyses confirm the weak coordination of the pyridine molecules in py2P2S5, py2P2S4O, and py2P2S7 to phosphorus.

The new phosphorus sulfide P(2)S(7), stabilized as the bis(pyridinium) adduct, was obtained from the reaction of P(4)S(10) and sulfur in pyridine, and could be isolated in the form of colourless block-shaped crystals which were characterized using single crystal X-ray diffraction. Coordination of pyridine is weak (d(P-N) = 187 pm) which is supported also by quantum chemical calculations.