Latia luciferin

Properties of Latia luciferin. Latia luciferin is a highly hydrophobic, fat-soluble compound, and volatile under vacuum. It is a colorless liquid, with an absorption maximum at 207nm (s approx. 13,700 Fig. 6.1.2). The chemical structure of Latia luciferin has been determined to be 1 (C15H24O2), an enol formate of a terpene aldehyde 3 (Fig. 6.1.3 Shimomura and Johnson, 1968b). The enol formate group of Latia luciferin is unstable the luciferin is spontaneously hydrolyzed... 

Fig. 6.1.2 Absorption spectra of Latia luciferin (1), the product of catalytic hydrogenation (2), the product of ammonolysis (3), and the product of hydrolysis (4), all in ethanol at the same molar concentration (89 pM). Latia luciferin has an e value of 13,700 at 207nm, and a bioluminescence activity of approximately 7.6x 1015 photons/mg. From Shimomura and Johnson, 1968b, with permission from the American Chemical Society.

Fig. 6.1.3 Bioluminescence reaction of Latia and the hydrolysis of Latia luciferin.

Fig. 6.1.5 Fluorescence spectra of the purple protein (1-4) and the luminescence spectrum measured with Latia luciferin, luciferase and the purple protein (5 Xmax 536 nm). Excitation spectra (1) and (2) were measured with emission at 630 nm and 565 nm, respectively. Emission spectra (3) and (4) were measured with excitation at 285 nm and 380 nm, respectively. From Shimomura and Johnson, 1968c, with permission from the American Chemical Society.

Fig. 6.1.6 Effect of the purple protein on the luminescence of Latia luciferin (0.16 jxg) plus Latia luciferase (A280,icm 1.2, 10 pi) in 5 ml of 5mM sodium phosphate buffer, pH 6.8. The amounts of the purple protein solution ( 280,1 cm 0.6) used 20 pi (curve 1), 5 pi (curve 2), 1 pi (curve 3), 0.5 pi (curve 4), 0.2 pi (curve 5), and none (curve 6). From Shimomura and Johnson, 1968c, with permission from the American Chemical Society.

Kojima et al. (2000a) that the purified luciferase exhibited a luciferin-luciferase reaction with Latia luciferin without any cofactor. Nevertheless, the purple protein is a conspicuous presence in the live organisms and it is highly likely that it enhances the bioluminescence of Latia in nature. 

The quantum yield of Latia luciferin is surprisingly low. When an optimum concentration of purple protein was used together with luciferase, the quantum yield was 0.0030 at 25°C, and 0.0068 at 8°C (Shimomura and Johnson, 1968c). When 1 mM ascorbate and an optimum concentration of NADH ( 0.25 mM) were added, the quantum yield was 0.009 at 25°C (Shimomura et al., 1972). 

The reaction scheme of Latia bioluminescence. Based on the structures of luciferin 1 (Ln) and the product of luminescence reaction 2 (OxLn), it was proposed that the luciferase-catalyzed luminescence reaction of Latia luciferin in the presence of the purple protein results in the formation of 2 moles of formic acid, as shown in the scheme A (Shimomura and Johnson, 1968c). However, when the luminescence reaction was carried out in a medium containing ascorbate and NADH (in addition to the purple protein) to increase the quantum yield, it was found that only one mole of formic acid was produced accompanied... 

Kojima, S., et al. (2000b). Bioluminescence activity of Latia luciferin analogs. Tetrahedron Lett. 41 4409 1413. 

Nakatsubo, F., Kishi, Y., and Goto, T. (1970). Synthesis and stereochemistry of Latia luciferin. Tetrahedron Lett., pp. 381-382. 

Shimomura, O., and Johnson, F. H. (1968b). The structure of Latia luciferin. Biochemistry 7 1734-1738. 

Quantula (Dyakia), 180, 334 Quantum yield, xvi, 361, 362 aequorin, 104, 106, 110 aldehydes in bacterial bioluminescence, 36, 41 Chaetopterus photoprotein, 224 coelenterazine, 85, 143, 149 Cypridina luciferin, 69-71 definition, xvi, 361 Diplocardia bioluminescence, 242 firefly luciferin, 12 fluorescent compound F, 73 Latia luciferin, 190 pholasin, 197 PMs, 286... 

FMNH2 requirement in bacterial luminescence Crystallization of Cypridina luciferin Crystallization of firefly luciferin Cypridina luciferin in fishes the first cross reaction discovered Structure of firefly luciferin Discovery of aequorin and GFP (green fluorescent protein) Structure of Cypridina luciferin Concept of photoprotein Structure of Latia luciferin Dioxetanone mechanism proposed in firefly and Cypridina luminescence... 

Certain Schiff bases, i.e. 122, were synthesized as model compounds for Latia luciferin. This compound exhibits strong blue chemiluminescence ( max 385 nm) on oxidation with oxygen in DMSO/potassium t.-butylate, the main products being acetone and 2-formamido pyridine 124. The mechanism suggested by Me Capra and Wrigglesworth includes the concerted bond cleavage of a dioxetane derivative 123. 

Nigaki alcohol (18) has been identified by spectroscopic and chemical means as a constituent of Picrasma ailanthoides Planchon. Latia luciferin (19) has been synthesized in a stereoselective manner. A key step in this synthesis involves the addition of lithium dimethylcuprate to an enol phosphate derived from a 8-keto-ester to form an a,/3-unsaturated ester. Dehydro-/8-ionilideneacetic acid (20), an important intermediate in the synthesis of abscisic acid, has been prepared, as have the two nor-abscisic acid derivatives (21). The metabolite (22) of abscisic acid has been identified in the seeds of Robinia pseudacacia... 

Synthesis of a luciferin. Latia luciferin (4), the specific substrate for the luciferase system of l.citi nerit aides, has been synthesized in three steps from dihydro-/3-iononc (I). Reaction of (I) with dimethyloxosulfonium methylide, both... 

Latia luciferin (94) was isolated from limpetsand the structure was confirmed by synthesis.The stereochemistry of the enol ester double bond... 

---