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This Chapter reports an overview of the historical development of bioluminescence (BL) and chemiluminescence (CL), starting with the primitive understanding of natural light emission phenomena from BL terrestrial and marine animals and fungi. At that time BL was just described as a fascinating unexplained natural phenomenon and was limited to terms of magic and superstition.

In the course of the Centuries, paralleling the development of other scientific fields, methodological study of BL and CL began, ultimately leading to the exponential growth of knowledge in the last century and half or so. After the first experiments in the late 1800s, the mechanisms of light emission from firefly and marine animals were fully defined in the early 1900s, taking advantage of the background of natural sciences and the advent of the modern chemistry. Again in the late 1800s, the term CL was introduced and in the following years many new CL molecules were synthesised, also modifying the structures of natural BL substrates.

In recent years CL and BL have become fundamental tools in molecular biology and related sciences. In particular, bioanalytical chemistry has greatly benefitted from implementation of CL and BL in a variety of analytical methodologies, such as amplified coupled enzymatic reactions, immunoassays, nucleic acid-based assays, in vivo molecular imaging, cell-based biosensors and in general molecular biology techniques.

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