The plasma levels of free oxysterols (7-ketocholesterol; 7 alpha-hydroxy-,7
beta-hydroxy-, 25-hydroxy-, and 27-hydroxycholesterol; and 5 alpha,6 alpha
-epoxycholestanol) in patients with diabetes mellitus and hypercholesterole
mia were determined using gas chromatography-mass spectrometry with selecti
ve ion monitoring. We studied 39 patients with diabetes mellitus, 20 nondia
betic patients with hypercholesterolemia, and 37 normal controls. Plasma ch
olesterol levels in diabetic and hypercholesterolemic patients showed no st
atistical difference. Plasma 7-ketocholesterol was significantly higher in
patients with diabetes (31.6 +/- 2.8 ng/mL) or hypercholesterolemia (52.3 /- 5.9) than in the control group (22.4 +/- 1.2). The increased plasma chol
esterol can be regarded as an oxidation substrate for the oxidant stress an
d the higher absolute levels of oxysterols in hypercholesterolemic plasma c
ompared with the control plasma. This difference disappeared when 7-ketocho
lesterol was expressed in proportion to total cholesterol. The oxidizabilit
y of plasma cholesterol was evaluated by comparing the increased ratio of 7
-ketocholesterol after CuSO4 oxidation to the ratio before. We demonstrated
that the patients with diabetes showed increased oxidizability (77.5%) com
pared with the control (36.6%) or hyperlipemic group (45.3%), which is like
ly due to the lower amounts of alpha-tocopherol in the diabetics. Measureme
nt of oxysterols may serve as a marker for in vivo oxidized lipoproteins in
diabetes and hyperlipemia.