638
Arch Toxicol (2007) 81:627–639
Jakubowski EM, McGuire JM, Evans RA, Edwards JL, Hulet
SW, Benton BJ, Forster JS, Burnett DC, Muse WT, Matson
K, Crouse CL, Mioduszewski RJ, Thomson SA (2004) Quan-
titation of Xuoride ion released sarin in red blood cell sam-
ples by gas chromatography-chemical ionization mass
spectrometry using isotope dilution and large-volume injec-
tion. J Anal Toxicol 28:357–363
Kitas EA, Perich JW, Tregear GW, Johns RB (1990) Synthesis of
phosphotyrosine-containing peptides. 3. Synthesis of H-Pro-
Tyr(P)-Val-OH via dimethylphosphate protection and the
use of improved deprotection procedures. J Org Chem
55:4181–4187
samples from casualties that have received medical
treatment. The opportunities to undertake assess-
ments ex vivo were constrained by the experimental
design of the guinea pig studies, which had a diVerent
primary purpose, the outcome of which will be pub-
lished elsewhere.
Acknowledgments Biomedical Sciences Department, Dstl,
Porton Down for guinea pig samples and to N. Bailey and E. Gos-
den, Dstl, Porton Down for cholinesterase determinations.
Means GE, Wu HL (1979) The reactive tyrosine residue of hu-
man serum albumin: characterization of its reaction with di-
isopropylXuorophosphate. Arch Biochem Biophys 194:526–
530
References
Murachi T (1963) A general reaction of diisopropylphosphoXuo-
ridate with proteins without direct eVect on enzymic activi-
ties. Biochim Biophys Acta 71:239–241
Nagao M, Takatori T, Matsuda Y, Nakajima M, Iwase H, Iwadate
K (1997) DeWnitive evidence for the acute sarin poisoning
diagnosis in the Tokyo subway. Toxicol Appl Pharmacol
144:198–203
Nigg HN, Knaak JB (2000) Blood cholinesterases as biomarkers
of organophosphorus pesticide exposure. Rev Environ Con-
tam Toxicol 163:29–112
Noort D, Black RM (2005) Methods for the retrospective detec-
tion of exposure toxic scheduled chemicals. Part B: mass
spectrometric and immunochemical analysis of covalent ad-
ducts to proteins and DNA. In: Mesilaakso M (ed) Chemical
weapons convention chemicals analysis (sample collection,
preparation and analytical methods). Wiley, Chichester,
pp 433–451
Noort D, Hulst AG, Platenburg DHJM, Polhuijs M, Benschop
HP (1998) Quantitative analysis of O-isopropyl methylphos-
phonic acid in serum samples of Japanese citizens allegedly
exposed to sarin: estimation of internal dosage. Arch Toxicol
72:671–675
Noort D, Benschop HP, Black RM (2002) Biomonitoring of
exposure to chemical warfare agents: a review. Toxicol Appl
Pharmacol 184:116–126
Noort D, Fidder A, Hulst AG, WoolWt AR, Ash D, Barr JR
(2004) Retrospective detection of exposure to sulfur mus-
tard: improvements on an assay for liquid chromatography-
tandem mass spectrometry analysis of albumin/sulfur mus-
tard adducts. J Anal Toxicol 28:333–338
Peeples ES, Schopfer LM, Duysen EG, Spaulding R, Voelker T,
Thompson CM, Lockridge O (2005) Albumin, a new biomar-
ker of organophosphorus toxicant exposure, identiWed by
mass spectrometry. Toxicol Sci 83:303–312
Adams TK, Capacio BR, Smith JR, Whalley CED, Korte WD
(2004) The application of the Xuoride reactivation process to
the detection of sarin and soman nerve agent exposures in
biological samples. Drug Chem Toxicol 27:77–91
Bechtold WE, Willis JK, Sun JD, GriYth WC, Reddy TV (1992)
Biological markers of exposure to benzene: S-phenylcysteine
in albumin. Carcinogenesis 13:1217–1220
Black RM, Noort D (2005) Methods for the retrospective detec-
tion of exposure toxic scheduled chemicals. Part A: analysis
of free metabolites. In: Mesilaakso M (ed) Chemical weap-
ons convention chemicals analysis (Sample collection, prep-
aration and analytical methods). Wiley, Chichester, pp 403–
431
Black RM, Clarke RJ, Read RW, Reid MTJ (1994) Application
of gas chromatography-mass spectrometry and gas chroma-
tography-tandem mass spectrometry to the analysis of chem-
ical warfare samples, found to contain residues of the nerve
agent sarin, sulphur mustard and their degradation products.
J Chromatogr A 662:301–321
Black RM, Harrison JM, Read RW (1999) The interaction of
sarin and soman with plasma proteins: the identiWcation of a
novel phosphonylation site. Arch Toxicol 73:123–126
Briseno-Roa L, Hill J, Notman S, Sellars D, Smith AP, Timperley
CM, Wetherell J, Williams NH, Williams GR, Fersht AR,
GriYths AD (2006) Analogues with Xuorescent leaving
groups for screening and selection of enzymes that eYciently
hydrolyze organophosphorus nerve agents. J Med Chem
49:246–255
Bryant PJR, Ford-Moore AH, Perry BJ, Wardrop AWH,
Watkins TF (1960) The preparation and physical properties
of isopropyl methylphosphonoXuoridate (sarin). J Chem Soc
1553–1555
Degenhardt CEAM, Pleijsier K, Van der Schans MJ, Langenberg
JP, Preston KE, Solano MI, Maggio VL, Barr JR (2004)
Improvements of the Xuoride reactivation method for the
veriWcation of nerve agent exposure. J Anal Toxicol 28:364–
371
Ellman GL, Courtney KD, Anders V, Featherstone RM (1961) A
new and rapid colorometric determination of acetylcholines-
terase activity. Biochem Pharmacol 7:88–95
Polhuijs M, Langenberg JP, Benschop HP (1997) New method
for retrospective detection of exposure to organophosphorus
anticholinesterases: application to alleged victims of Japa-
nese terrorists. Toxicol Appl Pharmacol 146:156–161
Riches J, Morton I, Read RW, Black RM (2005) The trace anal-
ysis of alkyl alkylphosphonic acids in urine using gas chroma-
tography-ion trap negative ion tandem mass spectrometry.
J Chromatogr B 816:251–258
Schopfer LM, Champion MC, Tamblyn N, Thompson CM, Lock-
ridge O (2005) Characteristic mass spectral fragments of the
organophosphorus agent FP-biotin and FP-biotinylated pep-
tides from trypsin and bovine albumin (Tyr410). Anal Bio-
chem 345:122–132
Fidder A, Noort D, Hulst AG, De Ruiter R, Van der Schans MJ,
Benschop HP, Langenberg JP (2002) Retrospective detec-
tion of exposure to organophosphorus anti-cholinesterases:
mass spectrometric analysis of phosphylated human butyr-
ylcholinesterase. Chem Res Toxicol 15:582–590
Jakubowski EM, Heykamp LS, Durst HD, Thomson SA (2001)
Preliminary studies in the formation of ethyl methylphos-
phonoXuoridate from rat and human serum exposed to VX
and treated with Xuoride ion. Anal Lett 34:727–737
Tsuchihashi H, Katagi M, Nishikawa M, Tatsuno M (1998) Iden-
tiWcation of metabolites of nerve agent VX in serum col-
lected from a victim. J Anal Toxicol 22:383–388
123