Paralytic Shellfish Poison: Viii. Some Chemical and Physical Properties of Purified Clam and Mussel Poisons

Abstract

Mild reduction of purified clam and mussel poisons with hydrogen yielded a ~lo~ltoxic dihydro derivative. The poisons and the dihydro derivative showed 110 absorption in the ultraviolet but all absorbed in the infrared a t 3, 6, and 9 h. Mild oxidation of the poisons in all<aline solutio~l produced rlo~ltoxic products with strong absorption in the ultraviolet. Preliminary studies 011 oxidation with permansanate or periodate and oil hyclrolysis with acid yieldecl only small fragments s~~c h as g~ianidopropionic acid, urea, guanidine, ammoriia, and carbon dioxide. Titration of the poisons and the dihydro derivatives showed pK, values a t 8.1 and 11.5. The two poisons appear to be similar in their chemical and physical properties.

Paralytic Shellfish Poisons

“…The structure of the resulting amino purine derivative (16) was established by synthesis (38). This degradation confirmed the presence of two guanidinium groups in the saxitoxin molecule, a hypothesis previously based on the observation that permanganate oxidation of saxitoxin afforded fragments such as guanidopropionic acid (17), urea, carbon dioxide and ammonia (36). In 1971, RAPOPORT'S group proposed structure (18) for saxitoxin on the basis of the degradation studies and 1 H-NMR data (37).…”

“…The molecular formula of amorphous saxitoxin dihydrochloride was first proposed as ClOH17N704· 2 Hel by elemental analysis (20,36). Fourteen years later a question arose regarding the appropriateness of the formula (37).…”

“…Scheme II. Degradation and lBO-exchange reactions of saxitoxin Saxitoxin (1) was found to be extremely unstable under alkaline conditions in the presence of oxygen, a reaction leading to the formation of a fluorescent degradation product (36). RAPOPORT'S group oxidized saxitoxin (1) with NaOH-H202' and obtained a fluorescent product (15) [A-max 324 nm (21,000), 236 (12,800)] in high yield (38).…”

Two toxins from a poisonous sample of mussels Mytilus edulis

“…Seven, 1958 (Sommer, et al, 1937). The poison from these mussels has been purified and is almost certainly identical to saxitoxin, the paralytic shellfish poison from the Alaskan butterclam Saxidomus giganteus (Schantz et al, 1961 ;Schantz, 1967 (Needler, 1949 ;Prakash, 1963). Attempts to use standard saxitoxin purification procedures to extract the poison from Bay of Fundy scallops failed (Schantz, 1960 andpersonal communication, 1968) and therefore it seemed likely that G. tamarensis produced a type of paralytic shellfish poison that was different from saxitoxin.…”

Neutralization of shellfish poison by chemical disinfectants

“…Products such as guanidopropionic acid, urea, ammonia, carhon dioxide, and guanidine were isolated and identified by Schantz at al. 7 when the poison was treated with periodate and permanganate or strong acid hydrolysis.…”