| {dollar}sp{lcub}13{rcub}{dollar}C enriched coelenterazines (4a-c){dollar}sp1{dollar} were incorporated into apoaequorin and the functional part of the labeled aequorins was investigated by {dollar}sp{lcub}13{rcub}{dollar}C NMR spectroscopy. The results indicated that the oxygen atom is attached to the C-2 carbon of coelenterazine in aequorin.; Two coelenterazine analogues (26a){dollar}sp2{dollar} and (32b){dollar}sp3{dollar} were prepared and successfully incorporated into apoaequorin, affording new semi-synthetic a- and e-aequorins, respectively. e-Aequorin displayed 4 times faster luminescence compared to native aequorin and a biomodal fluoresence spectrum ({dollar}lambda{dollar} = 405 and 465 nm). The ratio of the peak intensities was (Ca{dollar}sp{lcub}2+{rcub}{dollar}) -dependent in the range pCa = 5-7, thus providing an improved tool for absolute (Ca{dollar}sp{lcub}2+{rcub}{dollar}) determination.; The euphausiid bioluminescent system was investigated and the gross structures of two chlorophyll related bile-pigments, compound F (58){dollar}sp4{dollar} and oxy-F (57a){dollar}sp5{dollar}, have been elucidated on the basis of spectroscopic data and characterization of degradation products (2){dollar}sp6{dollar}, (16b){dollar}sp7{dollar}, and (62c){dollar}sp8{dollar}. The structures 2, 16b and 62c were established by synthesis. ftn{dollar}sp1{dollar}See p.26 in dissertation for illustration. {dollar}sp2{dollar}See p.39. {dollar}sp3{dollar}See p.50. {dollar}sp4{dollar}See p.181. {dollar}sp5{dollar}See p.181. {dollar}sp6{dollar}See p.145. {dollar}sp7{dollar}See p.151. {dollar}sp8{dollar}See p.185. |
