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Identification of 11-HETE and 15-HETE as major products of the platelet COX-1 enzyme Background: Prostaglandins (PGs) and hydroxyeicosatetraeinoic acids (HETEs) are synthesized from arachidonic acid (AA), which is released from the membrane phospholipids of cells through the activity of cytosolic phospholipase A2 α (cPLA2 α). In platelets AA is metabolised through the enzymes cyclooxygenase-1 (COX-1) and 12-lipoxygenase (12-LOX) leading to the production of a range of eicosanoids. We have determined the enzyme sources of the major prostanoid and HETE products released by platelets following activation by selective platelet agonists and investigated whether anti-platelet therapy might affect the production of these eicosanoids. Methods: Blood was collected into lepirudin (250µg/ml) by venepuncture from healthy volunteers (n=4). Intact blood and platelet rich plasma (PRP), obtained by centrifugation of blood (175 x g for 15 min), was incubated with collagen (30µg/ml), TRAP-6 (30µM) or vehicle, in a platelet aggregometer (1,2,3) with stirring (1200rpm; 37°C). Both blood and PRP were pre-treated with aspirin (100µM), the P2Y12 receptor blocker, prasugrel (0.03%DMSO; 3µM), aspirin+prasugrel or vehicle and incubated for 30min at 37°C. Plasmas were then separated by centrifugation (12000rpm) for 1 min at 4ºC and stored at -80ºC. The levels of prostanoids and HETEs were determined by LC/MS/MS analysis. Results: Stimulation of blood or PRP with collagen or TRAP-6 (Table 1) caused large, >100 times, increases in the levels of thromboxane (TX) A2, prostaglandin (PG) E2, and PGD2, and similar increases in 11-, 12-, and 15-HETE. Aspirin inhibited the production of TXA2, PGE2 and PGD2, as well as inhibiting the productions of 11-HETE and 15-HETE, but not 12-HETE, in both PRP and blood. The levels of 12-HETE were reduced by aspirin and prasugrel used in combination (*p<0.05), consistent with these drugs inhibiting the processes of platelet activation but not directly inhibiting platelet 12-LOX. (Data shown as mean±SEM; ANOVA with Dunnett test vs vehicle). Prasugrel alone did not alter the levels of eicosanoids compared to vehicle treatment (data not shown). Table 1. Eicosanoid production (ng/ml) in PRP and whole blood stimulated with collagen or TRAP6 (*P<0.05 vs vehicle)
Conclusions: In blood activated by exposure to collagen or TRAP-6 platelets are the main source of both prostanoids and HETEs. Aspirin abolished the production of not only prostanoids, but also 11-HETE and 15-HETE. This identifies 11-HETE and 15-HETE as major COX-1 products in platelets. (1) Born G. V. R., Nature, 194: 927, 1962. (2) O’Brien J. R, J Clin Path, 15:452, 1962. (3) Jennings L.K., McCabe M., Platelets (ed. Alan D. Michelson) Ch. 26:495, 2007.
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