We have studied the UV-vis and vibrational spectra of the brevetoxins PbTx-2, PbTx-3, PbTx-9, and 2, 3, 27, 28, 41, 43-hexahydro(reduced) PbTx-3. The absorption at 194 nm ( epsilon 18 000 L mol-1 cm-1) of PbTx-2 and PbTx-3 is assigned to the pi - pi * transition of the lactone conjugated double bonds. The n - pi * transition of the lactone is seen at 239 nm ( epsilon 2 800 L mol-1 cm-1). The absorption band at 208 nm for PbTx-2 is assigned to the conjugated double bonds of the aldehyde function located on the K-ring side chain. The inelastic electron tunneling spectra of PbTx-2, PbTx-3, PbTx9, and fully reduced PbTx-3 are presented and the vibrational bands are assigned. We show that inelastic electron tunneling spectroscopy can be used to monitor and measure the vibrational fingerprint of the brevetoxins at a level as low as 1 ng.
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