Measurement of DNA adducts using surface-enhanced Raman spectroscopy

Hazardous pollutants emitted from energy-related technologies, chemical industries, or waste materials are of increasing public concern because of their potential adverse health effects. Many pollutants have chemical groups of toxicological importance that can be characterized and detected by Raman spectroscopy. Raman spectroscopy, however, has not been widely used in trace organic detection, even though the information contained in a Raman spectrum is valuable for chemical identification. One limitation of conventional Raman spectroscopy is its low sensitivity, which often necessitates the use of powerful and costly laser sources for sample excitation. Raman spectroscopists have recently been able to analyze dilute biological samples as a result of enhancements in the Raman scattering cross section by factors up to 10(10) when a compound is adsorbed on or near a special electron-conducting surface. These spectacular enhancement factors of the normally weak Raman scattering process help overcome the low sensitivity of Raman spectroscopy through a combination of electromagnetic and chemical interactions between the analyte molecule and the surface. The technique associated with this phenomenon is known as surface-enhanced Raman scattering spectroscopy (SERS). The special conductive surface responsible for the scattering enhancement is referred to as a SERS substrate. For the past few years we have developed the SERS technique, using practical SERS-active substrate materials based on silver-coated microspheres deposited on glass. A wide variety of biomarkers have been investigated, including benzo[a]pyrene, dibenz[a,h]anthracene epoxides, 1,N9-ethenoadenine, 3,N4-ethenocytosine, and other substances. These biomarkers were measured at nanogram and subnanogram levels. The experimental results are of great analytical interest, since these chemicals are difficult to detect by other techniques, such as luminescence spectroscopy, because of the weak luminescence quantum yields of these DNA adducts. In this paper the potential usefulness of the SERS technique for assessing environmental and health effects from human exposure to toxic pollutants is demonstrated.