Millipede

A few cyanohydrins and ethers of cyanohydrins occur naturally One species of millipede stores benzaldehyde cyanohydrin along with an enzyme that catalyzes its cleavage to benzaldehyde and hydrogen cyanide m separate compartments above its legs When attacked the insect ejects a mixture of the cyanohydrin and the enzyme repelling the invader by spraying it with hydrogen cyanide... 

Indoor Pests cockroaches, fleas, flies, Hce, carpet beetles, clothes moths, silverfish, centipedes, millipedes, termites mice, rats mil dew... 

It is commercially prepared from benzaldehyde and hydrogen cyanide. Mandelonitrile is used by certain insects (tiger beedes, an African millipede) as a defense duid (38). After expelling the duid an enzyme catalyzes the conversion of mandelonitrile to benzaldehyde and HCN, which is usually fatal to the insect s enemy. 

The phylum Arthropoda includes the classes Diplopoda (millipedes), Chilopoda (centipedes), Crustacea (see Chapter 3), and Insecta (see Chapter 1). All luminous arthropods other than crustaceans are terrestrial, and not very many luminous millipedes and centipedes are known. The luminescence of millipedes is usually intracellular, whereas luminous centipedes discharge luminous secretion. Substantial chemical studies have been made only with the millipede Luminodesmus sequoiae and the centipede Orphaneus brevilabiatus, of which the latter is discussed in the Section 10.3. 

Fig. 10.2.1 The Sequoia millipede Luminodesmus sequoiae illuminated by a flashlight (left) and by ultraviolet light (right).

Davenport et al. (1952) were unsuccessful in their attempts to restore the luminescence of the filtered aqueous extract of Luminodesmus. Hastings and Davenport (1957) saw a weak luminescence in their filtered aqueous extracts made from the acetone powder of the millipedes. They found that the luminescence is dependent on pH, with an optimum at about pH 8.9, and that the light intensity could be increased by 10-30% by adding ATP. Hastings and Davenport also measured the luminescence spectrum of live animals, finding an emission peak at 495 nm. 

Fig. 10.2.2 Influence of the concentrations of ATP, Mg2-1- and Ca2+ on the maximum luminescence intensity of the photoprotein of the millipede Luminodestnus. The luminescence reaction was started by mixing a solution of the photoprotein (A280 0.3, 10 pi) with 2 ml of 10mM Tris-HCl buffer, pH 8.3, containing either 1 mM MgCb plus various concentrations of ATP or 0.05 mM ATP plus various concentrations Mg2+ or Ca2+. From Shimomura, 1981, with permission from the Federation of the European Biochemical Societies.

When H2O2 is a necessary component of a luminescence system, it can be removed by catalase. If a luminescence system involves superoxide anion, the light emission can be quenched by destroying O2 with superoxide dismutase (SOD). The ATP cofactor usually present in the fresh extracts of the fireflies and the millipede Luminodesmus can be used up by their spontaneous luminescence reactions, eventually resulting in dark (nonluminous) extracts containing a luciferase or photoprotein. The process is, however, accompanied by a corresponding loss in the amount of luciferin or photoprotein. The use of ATPase and the elimination of Mg2+ in the extract may prevent such a loss. 

Davenport, D., Wootton, T. M., and Cushing, J. E. (1952). The biology of the Sierra luminous millipede, Luminodesmus sequoiae Loomis and Davenport. Biol. Bull. 102 100-110. 

Kuse, M., et al. (2001). 7,8-Dihydropterin-6-carboxylic acid as light emitter of luminous millipede, Luminodesmus sequoiae. Bioorg. Med. Chem. Lett. 11 1037-1040. 

Shimomura, O. (1981). A new type of ATP-activated bioluminescent system in the millipede Luminodesmus sequoiae. FEBS Lett. 128 242-244. 

Cypridina bioluminescence, 66, 69 firefly bioluminescence, 16 Diphyes, 334 Diplocardia, 335 Diplocardia longa, 216, 235, 240 Diplocardia luciferin, 235-238, 340, 342 See Earthworm luciferin Diplocladon, 337 Diplopoda (Millipedes), 307 Diplotrema, 235 Diptera, 1, 2, 25... 

Several different types of photoprotein are presently known, for example the Ca2+-sensitive types found in various coelenter-ates (aequorin, obelin, mnemiopsin) and protozoa (thalassicolin) the peroxide-activation types found in scaleworm (polynoidin) and the clam Pholas (pholasin) and the ATP-activation type found in a Sequoia millipede Luminodesmus. 

Phylum Arthropoda Scorpions, spiders, crabs, insects, millipedes, centipedes... 

The production of HCN by animals is almost exclusively restricted to various arthropods 7 species of about 3000 species of centipedes 46 of 2500 species of polydesmid millipedes and 10 of 750,000 species of insects, including 3 species of beetles, 4 moths, and 3 butterflies (Duffey 1981). Millipedes — which are eaten frequently by toads and starlings — secrete cyanide for... 

Last but not least, a very intriguing terpenoid pyrrolidine alkaloid, poly-zonimine was milked from the millipede Polyzonium rosalbum (148). The structural formula of polyzonimine (118) is based on an X-ray crystallographic analysis of its perchlorate and by a total synthesis. 

Milli thousand, thousands thousand, thousandth millipede, millennium milli (symbol m) = factor of 10-3... 

Two classes of dendrobatid alkaloids have potential dietary sources. The first are the pyrrolizidine oximes (32), whose carbon skeleton is identical to that of nitropolyzonamine, an alkaloid from a small millipede (33). Indeed, raising the dendrobatid frog D. auratus in Panama on leaf-litter arthropods, gathered weekly, resulted in skin levels of the... 

Perhaps the most interesting arthropodan defensive compounds from the point of view of structural diversity are the alkaloids. While alkaloids had long been believed to arise only as a consequence of plant secondary metabolism, it has become apparent over the last few decades that arthropods are both prolific and innovative alkaloid chemists. The millipede Polyzonium rosalbum, once thought to secrete camphor (20), in fact gives off a camphoraceous/earthy aroma produced by the spirocyclic isoprenoid imine polyzonimine (21). 

In this discussion, we have restricted ourselves to the consideration of only a few examples of arthropod chemistry. From these alone, it is evident that insects synthesize defensive compounds by using all of the major biosynthetic pathways, producing acetogenins, simple aromatics and quinones, isoprenoids, and alkaloids. In addition, some of the millipedes, coccinellid beetles, and spiders we have studied utilize biosynthetic pathways that have yet to be characterized. 

Milling equipment, pilot plant, 18 732 Milling techniques, in large-scale pharmaceutical synthesis, 18 729 Millipedes, alkaloids in, 2 75 Millisecond catalytic cracking (MSCC) process, 11 685... 

---