New phototriggers: extending the p-hydroxyphenacyl pi-pi absorption range.
[equation--see text] Introducing 3-methoxy or 3,5-dimethoxy substituents on the 4-hydroxyphenacyl (pHP) photoremovable protecting group has been explored with two excitatory gamma-amino acids, L-glutamic acid and gamma-amino butyric acid (GABA). These substituents significantly extend the absorption range of the pHP chromophore, e.g., the tail of absorption bands of 2a,b extend above 400 nm, well beyond the absorptions of aromatic amino acids and nucleotides. Irradiation releases the amino acids with rate constants of approximately 10(7) s(-)(1) and appearance efficiencies (Phi(app)) of 0.03-0.04. The photoproducts are formed through the pHP excited triplet and are primarily products of photoreduction and photohydrolysis. 1a,b also rearranged to the phenylacetic acid 3.
Conrad
P G
PG
Department of Chemistry, University of Kansas, Lawrence 66045, USA.
Givens
R S
RS
Weber
J F
JF
Kandler
K
K
D000098:Acetophenones / Q000737:chemistry / Q000528:radiation effects; D000818:Animals; D001640:Bicuculline / Q000494:pharmacology; D004553:Electric Conductivity; D004583:Electrons; D018698:Glutamic Acid / Q000737:chemistry / Q000494:pharmacology / Q000528:radiation effects; D006624:Hippocampus / Q000166:cytology; D007473:Ion Channels / Q000187:drug effects; D008027:Light; D008163:Luminescent Measurements; D009474:Neurons / Q000187:drug effects / Q000502:physiology / Q000528:radiation effects; D010782:Photolysis; D051381:Rats; D005680:gamma-Aminobutyric Acid / Q000737:chemistry / Q000494:pharmacology / Q000528:radiation effects
D000098:Acetophenones; D007473:Ion Channels; D018698:Glutamic Acid; D005680:gamma-Aminobutyric Acid; D001640:Bicuculline