Spectroscopic detection of chiral compounds is often hampered by a low sensitivity. For Raman optical activity (ROA), the signal can be dramatically increased in surface-enhanced experiments. So far, however, reproducible surface-enhanced ROA (SEROA) spectra were obtained for a reporter molecule only via induced chirality, and the intensities were just proportional to the Raman scattering. In the present study, we show that the signal can be substantially increased if colloidal silver nanoparticles are prepared already in the presence of a chiral analyte. In this case, both the analyte's and reporter's bands are visible. In addition, some experiments provided bisignate SEROA patterns, thus significantly enhancing information about the molecular structure provided by this spectroscopic method. Increased electronic circular dichroism (ECD) of the capped aggregated colloids suggests that ECD and polarized Raman scattering (ECD-Raman) contribute to the monosignate SEROA intensities, while well-dispersed nonaggregating colloids are important for observation of true (bisignate) molecular vibrational SEROA.

Department of Analytical Chemistry University of Chemistry and Technology Technická 5 Prague 16628 Czech Republic

Department of Optics Palacký University Olomouc 17 listopadu 12 Olomouc 77146 Czech Republic

Institute of Organic Chemistry and Biochemistry Academy of Sciences Flemingovo náměstí 2 Prague 16610 Czech Republic

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