Photochemistry and Photobiology of lmidazole‐4(5)‐Methylidene Malonic Acid: An Analog of Both E‐ and Z‐Urocanic Acid*

Imidazole-4(5)-methylidene malonic acid (IMMA) may be thought of as having its imidazole and carboxyl functionalities permanently fixed in a configuration that is simultaneously analogous to both E- (trans) and Z- (cis) urocanic acid (UA). Because the UA isomers affect the photoinactivation of bacteriophage single-stranded DNA differently (E-UA increases and Z-UA decreases viral DNA inactivation), IMMA was similarly tested and was found to change the inactivation rate by a factor of 0.43, which is intermediate between the values for E- and Z-UA (1.6 and 0.014, respectively). The IMMA likewise sensitizes double-stranded DNA by a factor of 10.3 compared to a value of 13 for UA. In several ways the effects of IMMA parallel the distinctive effects of UA on the UV inactivation of single- and double-stranded DNA, including the ability to prevent the formation of cyclobutane pyrimidine dimers in irradiated single-stranded DNA and to sensitize a large increase in the formation of those dimers in irradiated double-stranded DNA. The IMMA photodecarboxylates to UA with a low quantum efficiency (ca 1 × 10−3) and photochemically binds to calf-thymus DNA.