New York City Firefighters (FDNY-FFs) were exposed to particulate matter and combustion/pyrolysis products during and after the World Trade Center (WTC) collapse. Ten months after the collapse, induced sputum (IS) samples were obtained from 39 highly exposed FDNY-FFs (caught in the dust cloud during the collapse on 11 September 2001) and compared to controls to determine whether a unique pattern of inflammation and particulate matter deposition, compatible with WTC dust, was present. Control subjects were 12 Tel-Aviv, Israel, firefighters (TA-FFs) and 8 Israeli healthcare workers who were not exposed to WTC dust. All controls volunteered for this study, had never smoked, and did not have respiratory illness. IS was processed by conventional methods. Retrieved cells were differentially counted, and metalloproteinase-9 (MMP-9), particle size distribution (PSD), and mineral composition were measured. Differential cell counts of FDNY-FF IS differed from those of health care worker controls (p < 0.05) but not from those of TA-FFs. Percentages of neutrophils and eosinophils increased with greater intensity of WTC exposure (< 10 workdays or ≥ 10 workdays; neutrophils p = 0.046; eosinophils p = 0.038). MMP-9 levels positively correlated to neutrophil counts (p = 0.002; r = 0.449). Particles were larger and more irregularly shaped in FDNY-FFs (1–50 μm; zinc, mercury, gold, tin, silver) than in TA-FFs (1–10 μm; silica, clays). PSD was similar to that of WTC dust samples. In conclusion, IS from highly exposed FDNY-FFs demonstrated inflammation, PSD, and particle composition that was different from nonexposed controls and consistent with WTC dust exposure.

Enantioselective surfactant-templated thin films were fabricated through the sol-gel (SG) process. The enantioselectivity is general in the sense that it discriminates between pairs of enantiomers not used for the imprinting process. The chiral cationic surfactant (-)-N-dodecyl-N-methylephedrinium bromide (1) was used as the surfactant template, and after its extraction chiral domains were created. The chiral discriminative feature of these films was examined by challenging with pure enantiomer solutions for rebinding. Selective adsorption was shown using (R)- and (S)-propranolol, (R)-2 and (S)-2, respectively, and (R)- and (S)-2,2,2-trifluoro-1-(9-anthryl)ethanol, (R)-3 and (S)-3, respectively, as the chiral probes. The selective adsorption was measured by fluorescence analysis, and the chiral selectivity factors were found to be 1.6 for 2 and 2.25 for 3. In both cases, (R)-enantiomer was adsorbed preferably. The resulting material was characterized by transmission electron microscopy, by diffraction, and by surface area measurements, and was found to be semicrystalline with short-range ordered domains (50 A) of hexagonal symmetry.

Thin films with enantioselective properties for electrochemically active chiral probes were developed. Enantioselectivity was accomplished via molecular imprinting. The films were fabricated through the sol-gel technique and were spin-coated on ITO electrodes. The chiral selectivity recognition was detected using two enantiomer pairs: D- and L-3,4-dihydroxyphenylalanine (D- and L-dopa) and (R)- and (S)-N,N'-dimethylferrocenylethylamine [(R)-Fc and (S)-Fc]. A defined chiral cavity was obtained by selection of functional monomers that interact with the template molecule, followed by its removal. Chiral selection properties were measured by cyclic voltammetry and square wave voltammetry. For both template molecules, very good chiral recognition was revealed by electrochemical measurement. The nonspecific adsorption measured for reference nonimprinted films was negligible (less than 5%). Dopa imprinted films revealed both high sensitivity, by the detection of 1 nM (0.2 ppb) concentration, and excellent selectivity, when challenged with a series of catechol derivatives. Fc-imprinted films were able to detect ca. 2 ppm of the target molecule, with very good enantioselectivity and low nonspecific adsorption. To our knowledge, this is the first report of successful molecular imprinting of a ferrocene derivative.

Chirally imprinted sol-gel thin films were fabricated through the molecular imprinting technique. The films were spin coated on glass plate substrates. Enantioselective discrimination of these films was observed toward three different templates. In each case a different enantiomer pair was selected as a template and a sol mixture was tailored accordingly. By extracting the template molecule a defined chiral cavity was created. The enantiomer pairs were (R)-and (S)-propranolol, (R)-and (S)-2,2,2-trifluoro-1-(9-anthryl) ethanol, and D-and L-3,4-dihydroxyphenylalanine (D-and L-dopa). Selective adsorption properties of the resulted films toward the imprinted molecules were measured by radioactive and fluorescence analysis. In all cases, preferred adsorption of one enantiomer was revealed. This preference was due to configuration match between the cavity and the adsorbed molecule. Nonspecific adsorption was remarkably low and was measured for reference nonimprinted films.