(1)H nuclear magnetic resonance metabolomics analysis identifies novel urinary biomarkers for lung function.

Chronic obstructive pulmonary disease (COPD), characterized by chronic airflow limitation, is a serious public health concern. In this study, we used proton nuclear magnetic resonance ((1)H NMR) spectroscopy to identify and quantify metabolites associated with lung function in COPD. Plasma and urine were collected from 197 adults with COPD and from 195 without COPD.

Characterization of bright tobaccos by multivariate analysis of 13C CPMAS NMR spectra.

Univariate and multivariate statistics were applied to characterize cured bright tobacco samples on the basis of their 13C CPMAS NMR spectra and leaf constituent analysis. NMR spectra were obtained for 55 samples selected from a set of 134 samples of graded bright tobacco leaves from crop year 1999. Historical leaf constituent analyses were available for total alkaloids, reducing sugars, total nitrogen, and insoluble ash.

Carbon-centered radicals in cigarette smoke: acyl and alkylaminocarbonyl radicals.

The widely accepted mechanism of formation for carbon-centered radicals in the gas-phase cigarette smoke involves reactions of NO(2) and alkadienes. However, specific examples of such radicals have never been isolated from fresh cigarette smoke or their structure determined. We have identified two previously unrecognized classes of carbon-centered radicals, alkylaminocarbonyl and acyl radicals, that are unrelated to radicals that form by NO(x) chemistry.

Detection of tobacco smoke deposition by hyperpolarized krypton-83 MRI.

Despite the importance of the tobacco smoke particulate matter in the lungs to the etiology of pulmonary disease in cigarette smokers, little is currently known about the spatial distribution of particle deposition or the persistence of the resulting deposits in humans, and no satisfactory technique currently exists to directly observe tobacco smoke condensate in airways. In this proof-of-principle work, hyperpolarized (hp) 83Kr MRI and NMR spectroscopy are introduced as probes for tobacco smoke deposition in porous media. A reduction in the hp-83Kr longitudinal (T1) relaxation of up to 95% under near-ambient humidity, pressure and temperature conditions was observed when the krypton gas was brought into contact with surfaces that had been exposed to cigarette smoke.

A new look at radicals in cigarette smoke.

Radicals in cigarette smoke have been proposed to contribute to the harm caused by cigarette smoking. For the first time, using HPLC and high-resolution mass spectrometry analysis of stable radical adducts, we have identified specific radical species in cigarette smoke: 7 acyl and 11 alkylaminocarbonyl radicals. Their combined abundance measured in fresh whole smoke from a single 2R4F cigarette is approximately 225 nmol (1.

Formation of polycyclic aromatic hydrocarbons from tobacco: the link between low temperature residual solid (char) and PAH formation.

The formation of condensed ring polycyclic aromatic hydrocarbons (PAHs) from the pyrolysis of ground tobacco in helium over the temperature range of 350-600 degrees C was investigated. PAH yields in the ng/g range were detected and the maximum yields of all PAHs studied including benzo[a]pyrene (B[a]P) and benzo[a]anthracene (B[a]A) occurred between 500 and 550 degrees C. The pathway to PAH formation in the 350-600 degrees C temperature range is believed to proceed via a carbonization process where the residual solid (char) undergoes a chemical transformation and rearrangement to give a more condensed polycyclic aromatic structure that upon further heating evolves PAH moieties.

Hyperpolarized 83Kr and 129Xe NMR relaxation measurements of hydrated surfaces: implications for materials science and pulmonary diagnostics.

In this proof of principle work, a technique is introduced to study hydrated surfaces using hyperpolarized (hp) 83Kr NMR spectroscopy. The longitudinal (T1) relaxation of hp-83Kr is shown to be extremely sensitive to the presence of adsorbed water on hydrophilic borosilicate and hydrophobic siliconized glass surfaces. The krypton surface relaxation is found to be largely independent of the total gas pressure applied to the studied materials, and the presented technique is therefore fairly robust.

Involvement of semiquinone radicals in the in vitro cytotoxicity of cigarette mainstream smoke.

Free radicals in cigarette smoke have attracted a great deal of attention because they are hypothesized to be responsible in part for several of the pathologies related to smoking. Hydroquinone, catechol, and their methyl-substituted derivatives are abundant in the particulate phase of cigarette smoke, and they are known precursors of semiquinone radicals. In this study, the in vitro cytotoxicity of these dihydroxybenzenes was determined using the neutral red uptake (NRU) assay, and their radical-forming capacity was determined by electron paramagnetic resonance (EPR).

Characterization of char from the pyrolysis of tobacco.

Pyrolysis of tobacco was studied in oxidative and nonoxidative (inert) environments at atmospheric pressure and temperatures ranging from 150 to 750 degrees C. The objective was to study the effect of pyrolysis conditions on the characteristics of the solid residue, i.e.