In 1200 B.C., a blue-purple dye known as Tyrian purple and/or royal purple, became a highly-valued commercial item throughout Asia Minor. It was produced by shellfish of the murex family, but the formula was kept secret for centuries.
God commanded Moses to require Jews to use this dye to color the edges of their shawls so that they could recognize the dawn and start their morning prayers. The dye was reported to be worth more than silver. Cleopatra had requested Anthony give her dye instead of pearls.
Tyrian purple was first produced by ancient Phoenicians (whose name means “purple people”) and exported to various Mediterranean ports. Pliny the Elder, in his ninth book of Naturalis Historia, described the preparation of the dye.
The dye is obtained from the mucous secretion from the murex shellfish hypobranchial gland (Muicidae family). The shellfish glands are incubated for three days in seawater and then boiled, and the insolubles are removed. The murex glands contain both the organic substrate and enzymes for production of the dye.
Tyrian purple was synthesized by Franz Sachs and Richard Kempf in 1903 and identified by Paul Friedlander in 1909 to be 6,6′-dibromoindigo (13). Archeologists have identified dye production sites that contain large quantities of murex shells. The production of the indigo dye represents a very early biotech project using an enzymatic process to produce a valuable product. The next report on an enzymatic halogenation reaction, about 3000 years later, was the paper Shaw and I published on the detection of a chlorinating enzyme in C. fumago cells (14).
We detected chloroperoxidase (CPO) activity in our first experiments using crude extracts prepared from C. fumago. In these early experiments, we incubated 36Cl with potential precursors of caldariomycin and examined the incubation mixtures for a 36Cl-labeled organic compound. We identified δ-chlorolevulinic acid as a product formed from β-ketoadipic acid in these crude reaction mixtures (15, 16). Subsequent work at Harvard established the peroxidative nature of the halogenation reaction (17), and work on CPO continued upon my move to the University of Illinois in 1960.
—written by the late Dr. Lowell P. “Bad-dad” Hager, former head of biochemistry at the University of Illinois