Assay of the enantiomers of 1,2-propanediol, 1,3-butanediol, 1,3-pentanediol, and the corresponding hydroxyacids by gas chromatography-mass spectrometry.
We developed gas chromatographic-mass spectrometric assays for the enantiomers of 1,2-propanediol, 1,3-butanediol, 1,3-pentanediol, and their corresponding hydroxyacids, lactate, beta-hydroxybutyrate, and beta-hydroxypentanoate (3-hydroxyvalerate) in biological fluids. The corresponding ketoacids, acetoacetate and beta-ketopentanoate, can be assayed simultaneously by pretreating the samples with NaB2H4. The assays involve spiking the samples with deuterated internal standards, deproteinization, ether extraction, and derivatization of the carboxyl groups with (R,S)-2-butanol/HCl and of the hydroxyl groups with chiral (S)-(+)-2-phenylbutyryl chloride. Mass spectrometric analysis is conducted under ammonia positive chemical ionization. We used these assays to follow the metabolism of diol enantiomers in dogs. For (R,S)-1,3-butanediol and (R,S)-1,3-pentanediol, the uptakes from dog plasma of the R and S enantiomer of each diol were identical. In contrast, the metabolism of (S)-1,2-propanediol was faster than that of (R)-1,2-propanediol. (R)-1,2-Propanediol is formed during acetone metabolism, while (R,S)-1,3-butanediol and (R,S)-1,3-pentanediol are potential nutrients. The assays developed will allow further investigations of the metabolisms of acetone, (R)-lactate, and artificial nutrients derived from the 1,3-butanediol and 1,3-pentanediol enantiomers.
Powers
L
L
Department of Nutrition, Case Western Reserve University, Cleveland, Ohio 44106.
Ciraolo
S T
ST
Agarwal
K C
KC
Kumar
A
A
Bomont
C
C
Soloviev
M V
MV
David
F
F
Desrochers
S
S
Brunengraber
H
H
D020155:3-Hydroxybutyric Acid; D000818:Animals; D001894:Borohydrides; D002072:Butylene Glycols / Q000097:blood* / Q000378:metabolism; D004285:Dogs; D008401:Gas Chromatography-Mass Spectrometry / Q000379:methods; D006018:Glycols / Q000097:blood* / Q000378:metabolism; D006880:Hydroxy Acids / Q000097:blood* / Q000378:metabolism; D006885:Hydroxybutyrates / Q000097:blood / Q000378:metabolism; D007202:Indicators and Reagents; D007773:Lactates / Q000097:blood / Q000378:metabolism; D019344:Lactic Acid; D010421:Pentanoic Acids / Q000097:blood / Q000378:metabolism; D019946:Propylene Glycol; D011409:Propylene Glycols / Q000097:blood* / Q000378:metabolism; D012680:Sensitivity and Specificity; D013237:Stereoisomerism; D013329:Structure-Activity Relationship
D001894:Borohydrides; D002072:Butylene Glycols; D006018:Glycols; D006880:Hydroxy Acids; D006885:Hydroxybutyrates; D007202:Indicators and Reagents; D007773:Lactates; D010421:Pentanoic Acids; D011409:Propylene Glycols; C013056:beta-hydroxyvaleric acid; C091257:1,3-pentanediol; D019344:Lactic Acid; C028491:1,3-butylene glycol; D019946:Propylene Glycol; C025364:sodium borohydride; D020155:3-Hydroxybutyric Acid