Some photophysical studies of cis- and trans-urocanic acid

Abstract

Urocanic acid, an important human skin chromophore, undergoes a variety of photochemical transformations when exposed to the near-UV portion of sunlight and natural daylight, the principal reaction being the transformation from the stable trans- or (E)-form of the chromophore (trans-UA) to the biologically active cis- or (Z)-form (cis-UA), which is claimed to induce immunosuppression linked to the onset of skin cancer. This study is concerned with the comparative photophysical behaviour of the two urocanic acid isomers in aqueous solution using both continuous irradiation and pulsed irradiation techniques. The UV absorption maximum for both isomers occurs in the region of 270 nm with the absorption shape varying characteristically with pH, the cis-isomer showing a lower overall molar absorptivity. Both isomers exhibit weak fluorescence (quantum yields estimated to be less than 10⁻⁴) with each isomer showing small differences in the way in which pH and excitation wavelength influence the fluorescence emission characteristics. Pulsed nanosecond laser irradiation at 266 nm of aqueous solutions at pH 7 shows that both isomers undergo photo-ionisation with a quantum yield of 0.02 for the hydrated electron production, a quantum yield value comparable with that for photoisomerisation at this wavelength. Laser flash studies also show that the photo-ionised species reacts efficiently with oxygen (quenching rate k_Q = 1.3 × 10⁹ M⁻¹ s⁻¹), while some preliminary experiments indicate that both cis- and trans-urocanic acids react with the semiquinone radical of L-3,4-dihydroxyphenylalanine (L-DOPA) with a fast reaction rate constant of approximately 5 × 10⁷ M⁻¹ s⁻¹. The photophysical characteristics of trans-UA and cis-UA reported here are discussed in the context of other recent pulsed irradiation studies on urocanic acid over nanosecond and picosecond time scales, in an attempt to clarify the complex photo-behaviour of this interesting biomolecule.