7/25/2019 Kataoka 1996
http://slidepdf.com/reader/full/kataoka-1996 1/16
E L S E V I E R
Journal of Chromatography A, 733 (1996) 19-34
JOURNAL OF
CHROMATOGRAPHYA
R ev i ew
Derivat izat ion react ions for the determinat ion of amines by
gas chromatography and their applicat ions in environmental
analysis
Hiroyuki K ataoka
Faculty of Pharmaceutical Sciences, Okayama University, Tsushima, O kayama 700, Japan
Abstra ct
T h e e n v i r o n m e n t a l a n a l y s i s o f a m i n e s i s i m p o r t a n t t o p r e s e r v e h u m a n h e a l t h b e c a u s e t h e s e c o m p o u n d s o f t e n
h a v e t o x i c ef f ec t s . G a s c h r o m a t o g r a p h y ( G C ) o f f r e e a m i n e s is g e n e r a l ly u n s a t i s fa c t o r y o w in g t o t h e a d s o r p t i o n a n d
d e c o m p o s i t i o n o f th e s o l u te s o n t h e c o l u m n . D e r i v a t i z a ti o n o f a m i n e s i s e m p l o y e d t o r e d u c e t h e p o l a r i ty a n d t o
i m p r o v e t h e G C p r o p e r t ie s . D e r i v a t i z a ti o n r e a c t io n s f o r t h e d e t e r m i n a t i o n o f a m i n e s b y G C a r e r e v i e w e d w i t h
respec t t o r eac t i v i t y , se l ec t i v i ty and sens i ti v i ty . The i r app l i ca t i ons t o t he de t e rm i na t i on o f i nd iv i dua l am i nes ,
a m m o n i a a n d N - n i t r o s a m i n e s i n v a r io u s e n v i r o n m e n t a l s a m p l e s a r e a l s o d e s c ri b e d .
Keywords
Review s; Derivatization, GC; Environ men tal analysis; Am ines; Amm onia; Nitrosamines
C o nt e nt s
1. I n tr od uc ti on . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20
1 .1. A mines f rom e nv i ronmen ta l sourc es . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20
1 .2. D e riva ti z at ion o f a mine s for gas c h roma tog ra phy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20
1 .3. O b je c tive a nd sc ope o f t he r e vie w . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 21
2 . D e rivat i z at ion re ac t ions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 21
2. 1. A cy l at i on . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 21
2. 2. S il yl at io n . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 23
2 .3 . D in it rophe ny la t ion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 24
2. 4. P e rm e th yl a ti o n . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 24
2 .5 . Sch if f ba se fo rma t ion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 25
2 .6 . C a rbama te fo rma t ion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 25
2 .7 . Su lphonamide fo rma t ion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 26
2 .8 . Phosphonamide fo rma t ion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 26
3. A pp li c a tions in e nv ironmen ta l a na ly s is . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 27
3 .1 . A l ipha t ic p r ima ry a nd se conda ry a mine s . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 28
3 .2 . A romat i c p r ima ry a nd se conda ry a mine s . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 29
3 .3 . Te r ti a ry a mine s . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 30
3 .4 . A m m on i a . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 30
3 .5 . N -N it r os a mi ne s . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 30
4. C on cl us i on s . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 31
A c kn o wl e d ge m en t . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 31
R ef er e nc es . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 32
0021-9673/96/ 32.00 ~ 1996 Else vier Science B.V. All rights reser ved
S S D I 0 0 2 1 - 9 6 7 3 ( 9 5 ) 0 0 7 2 6 - 1
7/25/2019 Kataoka 1996
http://slidepdf.com/reader/full/kataoka-1996 2/16
20
H. Kataoka / J . Chromatogr . A 733 1996) 19-3 4
1 . I n t r o d u c t i o n
1.1. Amines from environmental sources
A s e n v i r o n m e n t a l i s s u e s a n d g l o b a l e n v i r o n -
m e n t a l c h a n g e s a r e g e n e r a t i n g a n i n c r e a s i n g
a m o u n t o f a t t e n t i o n w o r l d - w i d e , t h e o c c u r r e n c e
a n d d e t e r m i n a t i o n o f a m i n e s h a v e r e c e i v e d a
g r e a t d e a l o f a tt e n t i o n i n r e c e n t y e a r s . T h e s e
a m i n e s o c c u r in a n u m b e r o f a m b i e n t e n v i r o n -
m e n t s s u c h a s a i r , w a t e r , s o i l a n d f o o d s , a n d a r e
a s o u r c e o f s e r io u s s o c i a l a n d h y g i e n ic p r o b l e m s
[ 1 ]
A l i p h a t i c a n d a r o m a t i c m o n o - , d i - a n d p o l y -
a m i n e s a r e n a t u r a l l y o c c u r r i n g c o m p o u n d s
f o r m e d a s m e t a b o l i c p r o d u c t s i n m i c ro o r g a n i s m s ,
p l an t s and an i m a l s , i n wh i ch t he p r i nc i pa l rou t es
o f a m i n e f o r m a t i o n i n c l u d e t h e d e c a r b o x y l a t i o n
o f a m i n o a c id s , a m i n a t i o n o f c a r b o n y l c o m -
p o u n d s a n d d e g r a d a t i o n o f n i t r o g e n -c o n t a i n in g
c o m p o u n d s [ 2 - 7 ] . T h e s e a m i n e s a r e a ls o w i d e l y
u s e d a s r a w m a t e r i a l s o r a t a n i n t e r m e d i a t e s t a g e
i n t h e m a n u f a c t u r e o f in d u s t ri a l c h e m i c a l s , e . g . ,
pes t i c i des , m ed i c i nes , d yes t u f f s , po l ym ers , ' s u r -
f ac t an t s , co s m et i c s and co r ro s i on i nh i b i t o r s
[1 ,8 ,9] .
T h e s e a m i n e s a r e d i s c h a r g e d i n t o t h e a t m o s -
p h e r e a n d w a t e r f r o m a n t h r o p o g e n i c s o u r c e s
s uch as ca t t l e f eeds and nea r l i ves t ock bu i l d i ngs
[10 -12 ] , was t e i nc i ne ra t i on [13 ] , s ewage t r ea t -
m en t [13 ,14 ] , au t om ob i l e exhaus t s [15 ] , c i ga re t t e
s m oke [16 -18 ] and va r i ous i ndus t r i e s [10 ,13 ,14 ,
1 9 - 2 1 ] . P r e s u m a b l y , a n a t u r a l b a c k g r o u n d l e v e l
o f am i nes a l s o ex i s t s o r i g i na t i ng f rom an i m a l
was t es and m i c rob i o l og i ca l ac t i v i t i e s [13 ] .
M a n y a m i n e s h a v e a n u n p l e a s a n t s m e l l a n d
a re haza rdous t o hea l t h , i . e . , a s s ens i t i ze r s and
i r r i t a n t s t o t h e s k i n , e y e , m u c o u s m e m b r a n e s
and r e s p i r a t o ry t r ac t [21 ,22 ] . S om e am i nes a re
a l s o s u s pec t ed t o be a l l e rgen i c [23 ] and m u t a -
gen i c o r ca rc i nogen i c [24 ] s ubs t ances owi ng t o
t h e i r t e n d e n c y f o r a d s o r p t i o n i n t i s s u e s . A m i n e s
a r e n o t o n l y t o x i c t h e m s e l v e s b u t c a n a l s o
b e c o m e t o x ic N - n i t r o s a m i n e s t h r o u g h c h e m i c a l
r eac t i ons w i t h n i t ro s a t i ng agen t s s uch as n i t r i t e
o r n i t r a t e [ 2 5 ] . R e c e n t d e v e l o p m e n t s i n e n v i r o n -
m e n t a l c a r c i n o g e n e s i s h a v e d e m o n s t r a t e d t h a t
N - n i t r o s a m i n e s a r e p o t e n t i a l l y c a r c i n o g e n i c s u b -
s t a n c e s t h a t l e a d t o a w i d e v a r i e t y o f t u m o u r s i n
m any an i m a l s [25 -27 ] . In gene ra l , t he n i t ro s a -
t i on o f am i nes occu r s i n t he hum an d i e t [25 ] , t he
e n v i r o n m e n t [ 28 ] a n d i n v i v o i n th e s t o m a c h o r
s m al l i n t e s t i ne o f exp er i m en t a l an i m a l s [29 -32 ] .
T h e r e a c t i o n o f n i tr o s a ti n g a g e n t s w i t h p r i m a r y
a m i n e s p r o d u c e s s h o r t - l i v e d a l k y l a t i n g s p e c i e s
t h a t r e a c t w i t h o t h e r c o m p o u n d s i n t h e m a t r i x t o
g e n e r a t e p r o d u c t s ( m a i n l y a l c o h o l s ) d e v o i d o f
t o x ic a c t iv i ty a t t h e r e l e v a n t c o n c e n t r a t i o n s . T h e
n i t r o sa t i o n o f s e c o n d a r y a m i n e s l e a d s t o th e
f o r m a t i o n o f s ta b l e N - n i t r o s a m i n e s w h i le t h a t o f
t e r t ia r y a m i n e s p r o d u c e s a r a n g e o f la b i le N -
n i t r o s o p r o d u c t s [ 3 3 ] . A l t h o u g h t h e r e a c t i o n
p a t h w a y s a r e u n c e r t a i n , i t h a s a l s o b e e n d e m o n -
s t r a t e d i n m o d e l e x p e r i m e n t s t h a t a m i n e s r e a c t
wi t h N O x and O H rad i ca l s i n a ir t o fo rm n i t ro s -
am i nes and n i t r am i nes [13 ,27 ,34 ] .
1.2. Derivatization of amines for gas
chromatography
G a s c h r o m a t o g r a p h y ( G C ) h a s b e e n w i d e l y
u s e d f o r a m i n e a n a l y s i s b e c a u s e o f i t s i n h e r e n t
advan t ages o f s i m p l i c i t y , h i gh r e s o l v i ng power ,
h i gh s ens i t i v i t y , s ho r t ana l y s i s t i m e and l ow cos t .
I n g e n e r a l , a m i n e s c a n b e s e p a r a t e d o n s t r o n g l y
bas i c s t a t i ona ry phas es a s t he i r f r ee fo rm s . The
s am p l es a re ana l y s ed a f t e r add i t i on o f a lka l i ,
e i t h e r b y d i r e c t i n j e c t i o n [ 3 5 - 4 2 ] o r b y t h e
h e a d s p a c e t e c h n i q u e [ 4 3 - 4 6 ] , o r t h e y a r e e x -
t r a c t e d i n t o a n o r g a n i c s o l v e n t b e f o r e a n a l y s i s
[ 4 7, 48 ] . D i r e c t o r h e a d s p a c e a n a l y s e s o f s a m p l e s
m i n i m i z e s a m p l e p r e p a r a t i o n , t h e r e b y r e d u c i n g
s a m p l e c o n t a m i n a t i o n . S e v e r a l p a c k e d c o l u m n s
d e a c t i v a t e d w i t h p o t a s s i u m h y d r o x i d e , t r i m e t h y l -
c h l o r o s i l a n e o r a m m o n i a i n t h e c a r r i e r g a s h a v e
b e e n u s e d f o r t h e d e t e r m i n a t i o n o f f r e e a m i n e s
[ 3 6, 4 2, 4 9] . H o w e v e r , m a n y o f t h e s e t e c h n i q u e s
a re l i m i t ed t o pa r t s pe r m i l l i on l eve l de t e rm i -
n a t i o n s . D e t e c t i o n l i m i t s c a n b e i m p r o v e d b y
c o n c e n t r a t i n g t h e a q u e o u s s a m p l e b e f o r e m e a -
s u r e m e n t o r b y u si n g a se l e c ti v e d e t e c t o r . F o r
t he fo rm er t echn i que , s t eam d i s t i l l a t i on [50 ] ,
vacuum d i s t i l l a t i on [51 ,52 ] , t r ea t m en t s w i t h ab -
s o rbe r co l um ns [53 ,54 ] o r S ep -P ak ca r t r i dges [12 ]
a n d m e m b r a n e d i f f u s i o n t e c h n i q u e s [ 5 5 - 5 7 ] h a v e
7/25/2019 Kataoka 1996
http://slidepdf.com/reader/full/kataoka-1996 3/16
H. Kataoka / J . Chromatogr . A 733 1996) 19-3 4
21
been inves t iga ted . F o r the l a s t t echn ique , n i t r o -
g e n - p h o s p h o r u s t h e r m i o n i c d e t e c t i o n ( N P D )
[12 ,37 ,39 ,44 ,47 ,55 ,56 ,58 ,59 ] , chemi lumines cen t
d e t e c t i o n ( C L D ) [ 43 ,5 2] a n d G C - m a s s s p e c -
t r o m e t r y ( G C - M S ) [4 1,4 6] h a v e b e e n i n ve s ti -
g a t e d . B y u s i n g t h e s e m e t h o d s , s u b - n a n o g r a m
d e t e c t i o n l i m i t s h a v e b e e n a c h i e v e d . H o w e v e r ,
t h e G C o f f r e e a m i n e s g e n e r a ll y h a s s o m e
i n h e r e n t p r o b l e m s r e l a t e d t o t h e d i ff ic u lt y i n
h a n d l i n g l o w - m o l e c u l a r -m a s s a m i n e s b e c a u s e o f
the i r h igh w a te r s o lub i l i ty and h igh vo la t i l i t y .
T h e r e f o r e , t h e s e a m i n e s a r e d i f fi c ul t t o e x t r a c t
f r o m w a t e r a n d a r e n o t e a s i l y c h r o m a t o g r a p h e d
o w i n g t o t h e i r p o l a r i t y . F u r t h e r m o r e , a m i n e s
t e n d t o b e a d s o r b e d a n d d e c o m p o s e d o n t h e
co lumns , and r ead i ly g ive t a i l ed e lu t ion peaks ,
g h o s t in g p h e n o m e n a a n d l o w d e t e c t o r s e n s it iv i ty
[ 6 0 -6 3 ] . T h e a d s o r p t i o n t e n d e n c y i n th e a n a -
ly t i ca l s y s tems , i . e . , i n s ample ves s e l s , i n j ec t ion
s ys tems , g la s s -w oo l and G C co lumns , i s in the
o r d e r p r i m a r y > s e c o n d a r y > t e r t ia r y a m i n e s ,
and i t is gene ra l ly mo re d i f f i cu l t t o ch rom ato -
g raph a l ipha t i c than a romat i c amines [64 ] .
D e r i v a t i z a t i o n i s a p o p u l a r m e t h o d f o r o v e r -
c o m i n g t h e a b o v e p r o b l e m s . D e r i v a t i z a t i o n
m e t h o d s h a v e b e e n e m p l o y e d to r e d u c e t h e
p o l a r i t y o f t h e a m i n o g r o u p a n d t o i m p r o v e G C
prope r t i e s . D er iva t i za t ion r eac t ions , o f t en se lec -
t i v e f o r a m i n e t y p e ( p r i m a r y , s e c o n d a r y , t e r -
t i a r y ) , h a v e a l s o b e e n u s e d t o i m p r o v e t h e
d e t e c t i o n a n d s e p a r a t i o n o f t h e s e a m i n e s . M a n y
d e r i v a t i z a t i o n r e a g e n t s f o r G C a n a l y s e s o f
a m i n e s b y f l a m e i o n i z a t i o n d e t e c t i o n ( F I D ) ,
e l e c t r o n - c a p t u r e d e t e c t i o n ( E C D ) , f l am e p h o to -
m e t r i c d et e c t io n ( F P D ) , N P D , C L D w i th a
m o d i f i e d t h e r m a l e n e r g y a n a l y s e r ( T E A ) a n d
G C - M S w i th s e l e ct e d -i o n m o n i t o r in g ( S IM )
have been inves t iga ted . A cy la t ion , s i ly l a t ion ,
d i n i t r o p h e n y l a t i o n a n d t h e f o r m a t i o n o f d i f fe r e n t
c o n d e n s a t i o n p r o d u c t s ( S c h i f f b a s e ) a r e c o m m o n
p r o c e d u r e s . F u r t h e r m o r e , p e r m e t h y l a ti o n a n d
t h e f o r m a t i o n o f c a r b a m a t e s , s u l p h o n a m i d e s a n d
p h o s p h o n a m i d e s h a v e a l s o b e e n i n v e s t i g a t e d .
T h e s e d e r i v a t i z a t i o n r e a c t i o n s a r e d e s c r i b e d i n
de ta i l i n th i s pape r . Chemica l de r iva t i za t ions o f
amines and the i r app l i ca t ions in G C have a l s o
b e e n r e v i e w e d b y M a a n d L a d a s [ 65 ], K n a p p
[66] , Drozd [67] and Blau and Halket [68] .
1.3 . Objective an d scope o f the review
This r ev iew is conce rned w i th the u t i l i za t ion o f
chemica l de r iva t i za t ion and G C ana lys i s f o r the
d e t e r m i n a t i o n o f a m i n e s i n e n v i r o n m e n t a l s a m -
p les . The r ev iew cons i s t s o f f o l low ing tw o main
par t s . I n the f i r s t pa r t (S ec t ion 2 ) , gene ra l
a s p e ct s o f t h e d e r i v a t i z a ti o n o f a m i n o g r o u p s f o r
G C a n a l y s i s a r e s u r v e y e d a c c o r d i n g t o t h e i r
r e a c t i o n t y p e . I n t h e s e c o n d p a r t ( S e c t i o n 3 ) ,
app l i ca t ions o f the de r iva t i za t ion r eac t ions in
e n v i r o n m e n t a l a n a l y s i s a r e c o n s i d e r e d a c c o r d i n g
t o t h e a m i n e t y p e . T h e r e v i e w c o v e r s n o t o n l y
a l ip h a t ic a n d a r o m a t i c p r i m a r y , s e c o n d a r y a n d
t e r t i a r y a m i n e s b u t a l s o a m m o n i a a n d N - n i t r o s -
a m i n e s , w h i c h o f t e n o c c u r i n v a r i o u s e n v i r o n -
m e n t s a s v e r y t o x ic c o m p o u n d s . O n t h e o t h e r
h a n d , b i o g e n i c a m i n e s s u c h a s c a t e c h o l a m i n e s ,
p h e n y l e t h y l a m i n e a n d i n d o l a l k y l a m i n e s , c a r c i n o -
g e n i c h e t e ro c y c l i c a m i n e s a n d o t h e r n i t r o g e n -
c o n t a i n i n g c o m p o u n d s a r e n o t c o v e r e d .
2 . D e r i v a t i z a t i o n r e a c t i o n s
T h e G C o f f r e e a m i n e s , w i t h o u t s p e c ia l m o d i -
f i ca t ion to the co lu mn , i s uns a t i s f ac to ry ow ing to
t h e a d s o r p t i o n a n d d e c o m p o s i t i o n o f t h e s o l u t e ,
r e s u l t ing in peak t a i l ing and lo s s es . D er iva t i za -
t io n o f a m i n e s m a y b e e m p l o y e d n o t o n l y t o
r e d u c e t h e p o l a r i t y b u t a l s o t o i m p r o v e t h e
vo la t i l i t y , s e l ec t iv i ty , s ens i t iv i ty and s epa ra t ion
o f t h e s e a m i n e s . T h e c o m m o n l y u s e d d e r iv a t iz a -
t ion r eac t ions fo r G C ana lys i s o f amines a r e
l is ted in Table 1 .
2 .1 . Acy la t ion
A c y l a t i o n is o n e o f t h e m o s t p o p u l a r d e r i -
v a t i z a t i o n r e a c t i o n s f o r p r i m a r y a n d s e c o n d a r y
amines , and th i s i s top o f the l i s t o f ava i l ab le
methods in Tab le 1 . A c id anhydr ides [16 ,17 ,
64 ,69 -80 ] , acy l ch lo r ides [74 ,75 ,81 -83 ] ,
acyl imidazoles [84 ,85] and acylamides [86 ,87]
have be en us ed as acy la t ing r eag en t s (F ig . 1 ) .
T h e s e r e a g e n t s e a s i l y r e a c t w i t h a m i n o g r o u p s
u n d e r m i l d r e a c t i o n c o n d i t i o n s . M a n y o f t h e m
7/25/2019 Kataoka 1996
http://slidepdf.com/reader/full/kataoka-1996 4/16
22 H. Kataoka / J . Chromatogr . A 733 1996) 19-3 4
T a b l e 1
D e r i v a t i z a t i o n r e a c t i o n s f o r g a s c h r o m a t o g r a p h i c d e t e r m i n a t i o n o f a m i n e s
Reagen t Am i ne t ypea Detect ionb Ref .
(detection limit)
Acylation
Trifluoroacetic anhydride P , S , A I (4-5 ng), E (30 pg), M (1 ng)
Pentafluoropropionic anhydride P , S N (4-20 pg), E, M (1 ng)
Hexafluorobutyric anhydride P , S N (4-20 pg), E (0 .1-6 pg), M (1 ng)
Chloro- or d ichloroacetic anhydride P E (0 .2-1 .5 ng), M (1 ng)
Trichloroacetyl chlor ide P, S E (0. 2-2 ng)
Pentafluorobenzoyl chloride P , S N (0 .1 rig), E (10 pg)
Heptafluorobutylimidazole P, S E (0.3 -0.4 ng)
N-Methylbis(trifluoroacetamide) P, S I (80 ng), M (1 ng)
Silylation
N,O-Bis(trimethylsilyl)trifluoroacetamide P, S M (4- 20 pg)
N-MethyI-N- tert.-butyldimethylsilyl)acetamide P, S M
Pentattuorophenyldimethylsilyl reag ents P, S I (5 ng), E (5 pg)
Dinitrophenylation
2,4-Dini t rofluorobenzene P , S I (1-2 ng), E (20 pg), M (0 .3- 4 ng)
2,4-Dini t robenzenesulphon ic acid P , S , A I (50-100ng)
Permethylation
F orm am i de -sod i um bo rohyd r i de P , S N (0 .1 ng )
Schiff base formation
Benza ldehyde P I (60 ng)
Furfural P I
2-Thiophe nealdehyde P S
Pentafluorobenz aldehyde P E (20 pg), M (5 ng)
Dime thylformam ide dimethyl acetal P , A S (25 pg)
Carbamate formation
Diethylpyrocarb onate P , A I
Ethyl chloroform ate P , S , T I , N (3-10 pg), M (1 .5 pg)
Isobutyl chloroform ate P , S I , N (3-20 pg), S (40 pg), M (2 pg)
Amy l chloroform ate P , S I
2,2,2-Trifluoroethyl chloro form ate P, S N (10 lag), M (10 pg)
Pentafluorobenzyl chloroformate P , S , T E (3 pg)
Sulphonamide formation
Benzene sulphonyl chloride P , S , A S (6-25 pg), C (60 pg), M (5-30 pg)
p-Toluen esulphony l chloride S I (10 ng), M (45 pg)
Phosphoamide formation
Dimethyl th iophosphinic chloride P N (0 .5 pg)
Di m e t hy l t h i ophospho ry lchloride P, S I, P
Diethyl th iophosphory l chloride P , S , N P (3-15 pg)
[69-74,128]
[16,17,64,69-781
I69,73-77,79,80]
[73, 74]
[741
[74,81-83]
[84,851
[54,86,87]
[881
[891
[901
[91-96]
[97-99]
[lOO, lOl]
[61]
[103]
[lO41
[105-1081
[109,1291
[1101
[112-114,119]
II13,115,1161
[1111
[117]
[120]
[33,60,62,122-
126,128,129]
[63,127]
[13Ol
[131,134]
[18,132,133]
a p = primary amine; S = secondary amine; T = tert iary am ine; A = a mmonia; N = ni t rosamine.
b I = F ID ; N = NP D; S = F P D (S m ode) ; P = F P D (P m ode) ; E = ECD; C = CLD; M = GC-M S -S IM .
a l so r e a c t w i t h h y d r o x y l , p h e n o l a n d t h i o l g r o u p s
[ 6 5 - 6 8 ] .
I n t h e r e a c t i o n s o f a m i n e s w i t h a c i d a n -
h y d r i d e s a n d a c y l c h l o r i d e s , i t i s u s u a l l y n e c e s -
s a r y t o r e m o v e e x c e s s r e a g e n t a n d b y - p r o d u c t
a c i d , b e c a u s e t h e s e c o m p o u n d s d a m a g e t h e G C
c o l u m n . T h e s e r e a g e n t s a r e o f t e n u s e d w i t h
b a s e s s u c h a s p y r i d i n e , t r i m e t h y l a m i n e a n d t r i -
e t h y l a m i n e , w h i c h n o t o n l y a re e x c e l l en t s o l v e n ts
b u t a l s o a c t a s c a t a ly s t s t o p r o m o t e s m o o t h
r e a c t i o n s a n d a s a c c e p t o r s f o r b y - p r o d u c t a c i d s .
O n t h e o t h e r h a n d , t h e d e r i v a t iv e s p r e p a r e d w i t h
7/25/2019 Kataoka 1996
http://slidepdf.com/reader/full/kataoka-1996 5/16
H. Kataoka / J. Chromatogr. A 733 1996) 19-3 4
23
a. Acid anhydride
R > m~ R C O > o
+ ~ R /N-CO W '~ + R CO O H
R' R CO R'
R -CH3, CF~, C2Fs, C=F7
b. Acyl chloride
R : ~ N H + R C OC l ~ R : > N - C O R + HCI
R' R '
~: F ,NO2
R : -CH3 , -C (CH~)~ ,-CCI3, -~F , ~ -N O 2 , - ~
F F N O z
c. Acyl imidazole
R ~ N H , = k
CO-N.. .~ N - - - - - - I~ R )N-CO R
+ H N . ~ ~
R ' R '
R : -C Ha, CF~ , C2F5, C~F7
d. Acyl amide
R : > N H + R C O > N - C H ~ ' - - - - -~ ' - R : > N - C O R + R C O N H C H +
R ' R CO R '
R : -CF3
F i g . 1 . A c y l a t i o n o f p r i m a r y a n d s e c o n d a r y a m i n e s . R =
a l k y l o r a ry l ; R ' = h y d r o g e n , a l k y l o r a r y l.
a c y l i m i d a z o l e s c a n n o r m a l l y b e a n a l y s e d w i t h o u t
r e m o v a l o f e x c e s s r e a g e n t a n d b y - p r o d u c t i m i d a-
z o l e . A c y l i m i d a z o l e s h a v e b e e n u s e d i n t h e
de r i va t i za t i on o f s om e d rugs [84,85 ]. N-M et hy l -
b i s ( t r i fl u o r o a c e t a m i d e ) ( M B T F A ) i s v e r y v o l a ti le
a n d b y - p r o d u c t N - m e t h y l tr i fl u o r o a c e ta m i d e d o e s
n o t c a u s e c o l u m n d a m a g e . M B T F A c a n b e
us e fu l fo r N-s e l ec t i ve acy l a t i on a f t e r t r i m e t hy l -
s i l y l a t i o n o f h y d r o x y a m i n o c o m p o u n d s [ 8 6 ] .
A m o n g t h e s e a c y l a t i n g r e a g e n t s , f l u o r i n a t e d
c o m p o u n d s a r e w i d e l y u s e d t o i n tr o d u c e e l e c-
t r o n - c a p t u r i n g p r o p e r t i e s . E C D g i v es a g re a t ly
e n h a n c e d r e s p o n s e t o h a l o g e n a t e d d e r i v a t i v e s ,
and t he s ens i t i v i t y o f de t ec t i on i nc reas es i n t he
o rd e r F < C 1 < B r < I. Ho w ev er , vo l a t i li t y and
s t ab i l i t y t end t o dec l i ne i n t h i s o rde r , s o t ha t
f l u o r o d e r i v a t i v e s a r e t h e m o s t w i d e l y u s e d i n
p rac t i ce . A l t houg h f l uo r i na t ed acy l de r i va t i ves
a r e m o r e v o l a t i l e t h a n t h e c o r r e s p o n d i n g n o n -
f l uo r i na t ed acy l de r i va t i ves , t he re i s gene ra l l y
l i t t l e d i f f e rence i n r e t en t i on t i m es fo r t r i f l uo ro -
a c e t y l ( T F A ) v e r s u s p e n t a f l u o r o p r o p i o n y l ( P F P )
a n d h e p t a f l u o r o b u t y r y l ( H F B ) d e r i v a t i v e s . T h e
E C D r e s p o n s e g e n e r a l l y i n c r e a s e s w i t h i n c r e a s -
i ng f l uo r i ne con t en t . Mono- , d i - and t r i ch l o ro -
a c e t y l d e r i v a t i v e s a l s o p o s s e s s h i g h e r E C D r e -
s p o n s e s , b u t p e n t a f l u o r o b e n z o y l ( P F B ) d e r i v a -
t i ves pos s es s sti ll h i ghe r E C D res pon s es . T he
E C D r e s p o n s e s f o r c h l o r o a n d f l u o r o d e r i v a t i v e s
o f a n i l i n e s h a v e b e e n c o m p a r e d b y L e e [ 7 3 ] .
H o w e v e r , c h l o r o a c e t y l a n d P F B d e r i v a t i v e s t e n d
t o be l e ss vo l a t i l e than t he s m a l l e r pe r f l uo roa cy l
de r i va t i ves , and t he r e ac t i ons o f l owe r a l i pha t i c
a m i n e s w i t h P F B - C L g i v e w h i t e , c u r d y p r e c i p i -
t a t e s , w h i c h m a y b e t h e h y d r o c h l o r i d e s o f
am i nes , s o tha t t hes e r eac t i on s a re no t quan t i t a -
t i ve [10 ] . A l t hough de r i va t i ves con t a i n i ng a n i t ro
g r o u p a r e a l s o s e n s i t i v e t o E C D , t h e y a r e g e n e r -
a l l y m uch l e s s vo l a t i l e , and t end t o g i ve t a i l i ng
c h r o m a t o g r a p h i c p e a k s , s o t h a t t h e i r u s e i n G C
ana l y s i s i s l i m i ted . O n t he o t he r hand , N P D ,
wh i ch i s ve ry s pec i f i c t o n i t rogen and phos pho rus
c o m p o u n d s , h a s b e e n w i d e l y u s e d t o d e t e c t
p i cog ram l eve l s o f am i nes . Th e d e t ec t i on l i m i ts
o f acy l de r i va t i ves depend es s en t i a l l y on t he
n i t ro g e n c o n t e n t o f th e d e r i v a ti v e s w h e n u s i ng
N P D . A l t h o u g h G C - M S - S I M is a l so sp e ci fi c a n d
s ens i t i ve t o each am i ne , t he s ens i t i v i t y o f t h i s
d e t e c t i o n m e t h o d is g e n e r a l ly l o w e r t h a n t h a t o f
E C D a n d N P D ( T a b l e 1 ) .
2.2. Silylation
T h e a m i n o g r o u p i s n o t v e r y r e a c t i v e t o
s i l y l a t i ng r eagen t s , and i t s conver s i on i n t o a s i l y l
der ivat ive i s d i f f i cu l t . By us ing s t ronger s i ly la t -
i ng r eagen t s and ca t a l y s t s , however , t he s i l y l
d e r i v a ti v e s o f a m i n e s c a n b e p r e p a r e d . N , O -
B i s ( t r i m e t h y l s i l y l ) a c e t a m i d e ( B S A ) , N , O - b i s ( t r i -
m e t h y l s i l y l ) t r i f l u o r o a c e t a m i d e ( B S T F A ) [ 8 8 ] ,
N-methyl-N- tert-butyldimethylsilyl )trifluoroacet-
a m i d e ( M T B S T F A ) [ 8 9 ] a n d p e n t a f l u o r o p h e n y l -
d i m e t hy l s i l y l ( f l ophem es y l ) r eagen t s [90 ] have
bee n u s ed as si l y la t i ng r eage n t s (F i g . 2 ) . The s e
r e a g e n t s r e a c t n o t o n l y w i t h a m i n o g r o u p s b u t
a l s o h y d r o x y l a n d c a r b o x y l g r o u p s u n d e r a n h y d r -
o u s r e a c t io n c o n d i t i o n s . T h e e a s e o f r e a c t io n
wi t h t hes e , r eagen t s i s gene ra l l y i n t he o rd e r
a l coho l s > phen o l s > ca rboxy l i c ac i d s > am i nes >
am i des , and i t i s h i ghe r fo r p r i m ary t han s ec -
o n d a r y a m i n e s . T h e a d d i t io n o f t r i m e t h y l c h l o r o -
s i l ane a s a ca t a l y s t w i l l gene ra l l y ens u re t he
e f f ec t i ve de r i va t i za t i on o f am i no g roup s .
7/25/2019 Kataoka 1996
http://slidepdf.com/reader/full/kataoka-1996 6/16
24
H . K a t a o k a / J . C h r o m a t o g r . A 7 3 3 1 9 9 6 ) 1 9 - 3 4
a. TrimethylMlylat ion
O-Si(CH=)s R: -CH3 BSA
I
R-C=N-S i (CH=)3 -CF = BS TF A
b. tert .Buty ldimethylsi ly lat ion
CH= CH=
(CH=)~C-S I~N-C-CF~ MTBSTFA
I
II
CH~ 0
c . P e n t a f l uorophe ny l d i me t hy IMl y la t i on
F)_.~__~ (~H R:-N H, FloPh em esylam ine
F-~ \ /~ - -~ | -RF)~FH 3 -N C = H s)=F l o p h e m e s y l d i e t h y l a m i J e
-CI Flophemesyl
c h l o r i d e
F i g . 2 . S i l y l a ti n g r e a g e n t s f o r p r i m a r y a n d s e c o n d a r y a m i n e s .
In t r ime thy l s i ly l a t ion , BS TF A i s a pow er fu l
r e a g e n t c o m p a r e d w i th B S A , a n d t h e b y - p r o d u c t
o f the r eagen t i s vo la t i l e , s o tha t i t does no t
i n t e r f e r e i n a n a l y s i s . H o w e v e r , t h e N - t r i m e t h y l -
s il yl ( T M S ) d e r i v a ti v e s p r o d u c e d b y t h e r e a c t i o n
w i t h t h e s e r e a g e n t s a r e u n s t a b l e t o m o i s t u r e . A n
a d d i t i o n a l p r o b l e m i n t h e s i l y l a t i o n o f a m i n e s
a r i s es f rom the pos s ib i l i ty o f r ep lac ing bo th
p r o t o n s i n p r i m a r y a m i n e s , r e s u l t i n g i n t h e
f o r m a t i o n o f m o n o - a n d d i -T M S p r o d u c t s . O n
t h e o t h e r h a n d , t h e N-tert.-butyldimethylsilyl t-
B D M S ) d e r i v a t i v e s p r o d u c e d b y t h e r e a c t i o n
w i t h M T B S T F A a r e a b o u t
1 0 4
t i m e s m o r e s t a b le
t o h y d r o l y s i s t h a n t h e c o r r e s p o n d i n g T M S d e -
r iva t ives , becaus e the bu lky tert.-butyl g r o u p o f
the t -BD M S der iva t ive p ro tec t s the s i ly l g roup
f r o m m o i s t u r e . T h e s e n s i t i v i t y o f t - B D M S d e -
r iva t ives i s 10 and 100 t imes h ighe r fo r mono- t -
B D M S a n d d i - t - B D M S d e r i v a t i v e s , r e s p e c t i v e l y ,
t h a n t h a t o f T M S d e r i v a t i v e s [8 9]. F l o p h e m e s y l
r eagen t s a l s o r eac t w i th a l coho l s , pheno l s , ca r -
b o x y l i c a c i d s a n d a m i n e s , a n d t h e f l o p h e m e s y l
d e r i v a t i v e s a r e s e n s i t i v e t o E C D . T h e s e q u e n c e
o f s i l y l d o n o r p o w e r o f r e a g e n t s i n p y r i d i n e
s o l u t i o n is f l o p h e m e s y l a m i n e > f l o p h e m e s y l
c h l o r i d e > f l o p h e n e s y l d i e t h y l a m i d e .
2.3. Dinitrophenylation
D i n i t r o p h e n y l a t i o n , w h i c h c a n b e p e r f o r m e d
i n a q u e o u s m e d i a , i s u s e d f o r t h e d e r i v a t i z a t i o n
o f p r i m a r y a n d s e c o n d a r y a m i n e s . 2 , 4 - D i n i t r o -
f l u o r o b e n z e n e ( D N F B ) [ 9 1 -9 6 ] a n d 2 , 4 -d i n i-
t r o b e n z e n e s u l p h o n i c a c id ( D N B S ) [ 9 7 -9 9 ] h a v e
b e e n u s e d a s d i n i t r o p h e n y l a t i n g r e a g e n t s ( F i g .
3 ) . D i n i t r o p h e n y l ( D N P ) d e r i v a t i v e s p r o d u c e d
by r eac t ion w i th thes e r eagen t s a r e s ens i t ive to
E C D a n d t h e y a r e p a r t i c u l a r l y s u i t a b l e f o r l o w -
m o l e c u l a r - m a s s a m i n e s t h a t h a v e i n c o n v e n i e n t l y
s h o r t r e t e n t i o n t i m e s . A l t h o u g h t h e r e a c t i o n
p r o c e d u r e w i t h D N F B i s s i m p l e , t h i s r e a g e n t
i r r i ta t e s the s k in and occas iona l ly caus es a l -
l e rgen ic de rm atos es [60] . D N B S i s w a te r s o lub le
a n d t h e r e s u l t i n g D N P d e r i v a t i v e s o f a m i n e s a r e
s o lub le in o rgan ic s o lven t s . There fo re , t he de -
r iva t ives can be eas i ly s epa ra ted f rom exces s o f
r eagen t by s o lven t ex t r ac t ion a f t e r de r iva t i za -
t i o n . A n o t h e r i m p o r t a n t a d v a n t a g e o f D N B S is
i ts g r ea te r s pec i f i c ity fo r the am ino g roup ,
w h e r e a s D N F B r e a c t s w i t h t h i o l , i m i d a z o l e a n d
h y d r o x y l g r o u p s a l o n g w it h a m i n o g r o u p s . H o w -
e v e r , D N B S g e n e r a l l y r e a c t s m o r e s l o w l y t h a n
d o e s D N F B , s o t h a t l o n g e r r e a c t i o n t i m e s o r
m o r e s t r o n g l y a l k a l i n e c o n d i t i o n s m a y b e r e -
q u i r e d t o c o m p l e t e t h e r e a c t i o n .
2.4. Permethylation
P e r m e t h y l a t i o n , w h i c h c o n v e r t s p r i m a r y a n d
s e c o n d a r y a m i n e s i n t o t e r t ia r y a m i n e s , c a n b e
p e r f o r m e d i n a q u e o u s s o l u t i o n u s i n g f o r m a l d e -
h y d e - s o d i u m b o r o h y d r i d e an d h a s b e e n a p p li e d
to the de te rmina t ion o f po lyamines [100 ,101 ] .
P e r m e t h y l d e r i v a t i v e s e l i m i n a t e t h e p o l a r N H
g r o u p s b u t r e t a i n t h e t r o u b l e s o m e a d s o r p t i v e
p r o p e r t i e s o f t e r t i a r y a m i n e s .
R~>NH + F NO= ~-~ R~>N NO2
D N F B
+ HF
O=N O=N
R~>NH + H03 NO , ~-~ ~N NO2
R R
D N B S
H2S03
F i g . 3 . D i n i t r o p h e n y l a t i o n o f p r i m a r y a n d s e c o n d a r y a m i n e s .
R = a l k y l o r a r y l ; R ' = h y d r o g e n , a l k y l o r a r y l .
7/25/2019 Kataoka 1996
http://slidepdf.com/reader/full/kataoka-1996 7/16
H . K a t a o k a / J . C h r o m a t o g r . A 7 3 3 1 9 9 6 ) 1 9 - 3 4 25
2.5. Schiff base formation
S c h i f f b a s e - t y p e r e a c t i o n s a r e e m p l o y e d t o
c o n d e n s e p r i m a r y a m i n e s w i t h a c a r b o n y l c o m -
pound (F ig . 4a ) . A ce tone , 1 ,1 ,1 - t r i f luo roace -
t o n e , m e t h y l i s o b u ty l k e t o n e , c y c l o p e n t a n o n e ,
c y c l o h e x a n o n e a n d c y c l o h e p t a n o n e h a v e b e e n
us ed fo r a s e r i e s o f long -cha in and a l i cyc l i c
m o n o a m i n e s , a l i p h a t i c d i a m i n e s a n d a r o m a t i c
am ines [69,102 ]. Be nza ldeh yde [61 ], f u r fu ra l
[1 03 ], 2 - t h i o p h e n e a l d e h y d e [ 1 0 4 ] a n d p e n t a -
f l u o r o b e n z a l d e h y d e ( P F B A ) [ 1 05 - 10 8 ] h a v e a l so
b e e n u s e d f o r l o w - m o l e c u l a r - m a s s a m i n e s . T h e
c o n d e n s a t i o n r e a c t i o n s w i t h t h e s e r e a g e n t s
p r o c e e d r a p i d l y i n a q u e o u s m e d i u m ( u s u a l l y a n
a l c o h o l o r a c e t i c a c i d ) a t r o o m t e m p e r a t u r e o r
o n w a r m i n g , a n d S c h i f f b a s e s a r e o b t a i n a b l e i n
g o o d y i e l d s . T h e s e c a r b o n y l r e a g e n t s a r e s e l e c -
t i v e t o p r i m a r y a m i n e s , a n d t h e b y - p r o d u c t w a t e r
d o e s n o t u n d e r g o s e c o n d a r y r e a c ti o n s in t h e
r eac t ion s ys tems invo lved . H ow ever , exces s r e -
agen t s , w h ich o f t en d i s tu rb the amine ana lys i s ,
h a v e t o b e r e m o v e d i n a s e p a r a t e c l e a n - u p s t e p .
S e l e c t i v e a n d s e n s i t i v e m e t h o d s b a s e d o n t h e
f o r m a t i o n o f s u l p h u r a n d f l u o r i n e - c o n t a i n i n g
S c h i f f b a s e s o f p r i m a r y a m i n e s h a v e b e e n d e -
v e l o p e d f o r G C w i t h F P D [ 1 0 4] a n d E C D [1 05 ],
r e s pec t ive ly . A l though the s ens i t iv i ty o f F P D i s
m u c h h i g h e r t h a n t h a t o f F I D f o r t h e d e r iv a t i v es
o f t h e
Cl- C 4
amines , the s ens i t iv i t i e s fo r the
d e r i v a t i v e s o f t h e C 5 - C 7 a m i n e s a r e s i m i la r
I104].
F u r t h e r m o r e , d i m e t h yl f o rm a m i d e ( D M F )
d ia lky l ace ta l f o rm s a S ch i f f bas e - typ e de r iva t ive
w i th p r imary amines [109 ] (F ig . 4b ) , bu t th i s
r e a g e n t a l so r e a c t s w i t h c a r b o x y l g r o u p s o f f a t t y
a c i d s a n d a m i n o a c i d s t o g i v e t h e c o r r e s p o n d i n g
es ters .
2.6. Carbamate ormation
C a r b a m a t e d e r i v a ti v e s , g e n e r a l l y m a d e b y
S c h o t t e n - B u a m a n n - t y p e p r o c e d u r e s , a r e u s e fu l
f o r t h e d e t e r m i n a t i o n o f p r i m a r y , s e c o n d a r y a n d
t e r ti a r y am i n e s. D i e t h yl p y r o c a r b o n a t e ( D E P C )
[110] and a lky l ch lo ro f o rm ates [111 -118] have
been us ed as r eagen t s fo r th i s pu rpos e (F ig . 5 ) .
T h e r e a c t i o n o f a m i n e s w i t h t h e s e r e a g e n t s c a n
b e e a s i l y p e r f o r m e d i n a q u e o u s a l k a l i n e m e d i a
a n d t h e r e s u l t i n g c a r b a m a t e d e r i v a t i v e s h a v e
g o o d G C p r o p e r t ie s . A l k y l c h l o r o f o r m a t e s r e a c t
w i th pheno l , t h io l and imidazo le g roups a long
w i th amino g roups . A s s how n in Tab le 1 , t he
c a r b a m a t e d e r i v a t iv e s f r o m p r i m a r y a n d s e c o n -
da ry amines a r e s e l ec t ive ly and s ens i t ive ly de -
t e r m i n e d b y G C - N P D [1 13 ,1 14 ,1 17 ], G C - F P D
[115], G C -M S [113 ,116,117 ] and G C -E C D
[120] . O n the o the r hand , t e r t i a ry amines , w h ich
t e n d t o g i v e t a i l i n g p e a k s o n c h r o m a t o g r a m s
o w i n g t o t h e i r p o l a r n a t u r e , c a n b e a l s o c o n -
v e r t e d i n t o c a r b a m a t e d e r i v a t i v e s w i t h a l k y l
ch lo ro fo rmate a f t e r dea lky la t ion [119 ,120 ] .
T r e a t m e n t w i t h a n a l k y l c h l o r o f o r m a t e c a n d i s-
a~ ie thylpyrocarbonate
C2H=OCO R
R/~NH-- + ~O ~ ~N-C OOC zH= + CO= + CzHsOH
R' CzH=OCO R'
a. Carbon)t l comrou nd
R' R'
R- NH2 + O =C ( ~ R- N=C<~ +
R R
R': alkyl or aryl group; R': h ydrogen, alkyl or aryl roup
H=O
b. Dimethylformarnide dialkyl acetal
R ' % H N<~CH3 R .N=CH.N<CH~
R-NH2 + -
R'O CH3 CH~
R': alkyl
roup
+ 2 R 'O H
Fig . 4 . Sch i f f base - type con densa t ion r eac t ions o f p r imary
and secondary amines .
b. Alkyl ch lo ro fo rmate
R~>NH + R OCOCI ~ R~>N-COOR + HCl
R' R'
R ': -C=H=, CH=CH(CH=)=, C=H~=, CH2CF~
~)N + R OCOCI ~ R ~>N-COOR + R Cl
R
R': -CH= F
F F
Fig . 5 . Ca rbamate fo rma t ion f rom p r imary , s econdary and
t e r ti a r y a mi n e s. R = a l k y l o r a r y l ; R ' =h y d r o g e n , a l k yl o r
aryl .
7/25/2019 Kataoka 1996
http://slidepdf.com/reader/full/kataoka-1996 8/16
26 H. Kataoka / J . Chromatogr. A 733 1996) 19- 34
p lace the s ma l l e s t o f the a lky l g roups to the
n i t rogen , pa r t i cu la r ly i f i t i s a me thy l g roup , to
f o r m a c a r b a m a t e ( F i g . 5 b ) . T h i s r e a c t i o n
p r o c e e d s i n t h e p r e s e n c e o f b a s e c a t a ly s t so d i u m
c a r b o n a t e , b u t t h e y i e l d is g e n e r a l l y l o w . T h e
c a r b a m a t e d e r i v a t i v e s o b t a i n e d f r o m t e r t i a r y
a m i n e s b y r e a c t i o n w i t h p e n t a f l u o r o b e n z y l c h l o -
r o f o r m a t e s a r e s e n s i t i v e l y d e t e r m i n e d b y G C -
ECD [120] .
2.7. Sulphonamide ormation
A s r e p o r t e d b y H i n s b e r g [ 12 1] , t h e r e a c t i o n o f
amines w i th s u lphony l ch lo r ide i s u s e fu l f o r the
s e p a r a t i o n a n d i d e n t i f i c a t i o n o f a m i n e t y p e ,
b e c a u s e s u l p h o n a m i d e s d e r i v e d f r o m p r i m a r y
amines a r e s o lub le in a lka l ine s o lu t ion and thos e
f r o m s e c o n d a r y a m i n e s a r e i n s o l u b l e , a n d s i n c e
te r t i a ry amines do no t r eac t (F ig . 6 ) . Th i s
r e a c t i o n e a s i l y p r o c e e d s i n a q u e o u s a l k a l i n e
m e d i a a t r o o m t e m p e r a t u r e . B e n z e n e s u l p h o n y l
ch lo r id e (BS C) [33 ,60 ,63 ,122 -126] a nd p -
to lue nes u lpho ny l ch lo r ide [63 ,127 ] have been
u s e d f o r t h e s e l e c t i v e d e t e r m i n a t i o n o f l o w - m o -
l e c u l a r - m a s s p r i m a r y a n d s e c o n d a r y a m i n e s .
A f t e r b e n z e n e s u l p h o n y l a t i o n o f a m i n e s , b e n -
z e n e s u l p h o n y l ( B S ) d e r i v a t i v e s o f s e c o n d a r y
a m i n e s a r e c o m p l e t e l y e x t r a c t e d i n to n - h e x a n e i n
50% po tas s ium hydrox ide . - -22 .5% methano l s o lu -
t i o n , a n d r e m a i n i n g B S d e r i v a t i v e s o f p r i m a r y
a m i n e s i n t h e a q u e o u s l a y e r a r e e x t r a c t e d i n t o
d ie thy l e the r under ac id ic cond i t ions [125 ] .
T h e s e B S d e r i v a t i v e s c a n b e s e l ec t iv e l y a n d
s e n s it i v e ly d e t e r m i n e d b y G C - F P D [ 12 5,1 26 ]
lhlma~nmtae
R -N H= O S O , C , ~ O S O , N H R N aO H~y S O ~ N F ~ N a
Secondary al~e
R > N H + O I O = C I ~ O S O = N ( ~ N aO II D- I ns o lu b le
Tertiary amine
i ~ N O S O , C I ~
N o r e a c t i o n
Fig . 6 . Sepa ra t ion and iden t i f i ca t ion o f p r imary , s econdary
and t e r t i a ry amines by Hinsb e rg ' s me th od . R , R ' , R = a iky l
o r a ry l .
( Fi g. 7) , G C - N P D [ 1 2 7 ] a n d G C - C L D w i th
mo d i f i ed T E A [33 ,62 ].
T h e B S d e r i v a t iv e s o f p ri m a r y a m i n e s c a n a l so
b e d e t e r m i n e d b y G C - E C D , t h e s e d e r iv a t iv e s
s u b s eq u e n t ly b e i n g c o n v e r t e d i nt o t h e i r N - T F A -
N -BS de r iva t ives by the r eac t ion w i th t r i f luo ro -
a c e t i c a n h y d r i d e ( T F A A ) [ 1 2 8 ] . T h i s m e t h o d i s
s e lec t ive and s ens i t ive to p r imary amines , be -
c a u s e t h e B S d e r i v a ti v e s o f s e c o n d a r y a m i n e s d o
n o t r e a c t w it h T F A A .
F u r t h e r m o r e , a m m o n i a i s c o n v e r t e d i n t o i t s
B S - d i m e t h y l a m i n o m e t h y l e n e d e r iv a t iv e b y a
c o n v e n i e n t p r o c e d u r e i n v o l v i n g b e n z e n e s u l -
p h o n y l a t i o n w i t h B S C a n d s u b s e q u e n t r e a c t i o n
w i t h d i m e t h y l f o r m a m i d e d i m e t h y l a c e t a l , a n d is
d e t e r m i n e d b y G C - F P D [1 29 ]. T h i s r e a c t i o n is
b a s e d o n c o m b i n a t i o n w i t h b o t h b e n z e n e s u l -
phon y la t ion (F ig . 6 ) and S ch i f f bas e - ty pe con -
dens a t ion (F ig . 4b ) .
2.8. Phosphonamide ormation
P r i m a r y a l i p h a t i c a n d a r o m a t i c a m i n e s r e a c t
w i t h d i m e t h y l t h i o p h o s p h i n i c c h l o r i d e in t h e p r e s -
e n c e o f e x c e s s o f t r i e t h y l a m i n e t o g i v e t h e
c o r r e s p o n d i n g N - d i m e t h y l t h i o p h o s p h i n i c a m i d e s ,
w h i c h a r e d e t e r m i n e d b y G C - N P D [ 13 0] . A l -
thoug h th i s m e th od i s h igh ly s ens i t ive , the p r e pa -
r a t ion o f the de r iva t ive r equ i r es a l eng thy p ro -
c e d u r e a n d a n h y d r o u s c o n d i t io n s . O n t h e o t h e r
h a n d , t h e r e a c t i o n o f t h e a m i n o g r o u p w i t h
d i a l k y l t h i o p h o s p h o r y l c h l o r i d e s c a n b e p e r -
f o r m e d r a p i d l y i n a q u e o u s a l k a l i n e m e d i a [ 1 8 ,
131 -134] . A l though thes e r eagen t s eas i ly r eac t
w i t h b o t h p r i m a r y a n d s e c o n d a r y a m i n e s , t h e
N - P b o n d o f t h e p h o s p h o r u s a m i d e is n o t a s
s ta b le a s t h e N - C a n d N - S b o n d s o f t h e a b o v e
der iva t ives . By us ing thes e r eagen t s , a s e l ec t ive
a n d s e n s i t i v e m e t h o d f o r t h e d e t e r m i n a t i o n o f
al iphat ic [18,132,133] and a rom at ic [134] am ines
b y G C - F P D h a s b e e n d e v e l op e d .
I n p a r t i c u l a r , s e c o n d a r y a m i n e s c a n b e s e l e c -
t i v e l y c o n v e r t e d i n t o t h e i r N - d i e t h y l t h i o p h o s -
p h o r y l ( D E T P ) d e r i v a t i v e s w i t h d i e t h y l c h l o r o -
t h i o p ho s p h a te ( D E C T P ) a f t e r t r e a t m e n t w i t h o -
p h t h a l d i a l d e h y d e ( O P A ) , b e c a u s e O P A r e a c t
o n l y w i t h p r i m a r y a m i n o g r o u p s ( F i g . 8 ) . A s
s how n in F ig . 9 , p r imary amines a r e a l s o de r iva -
7/25/2019 Kataoka 1996
http://slidepdf.com/reader/full/kataoka-1996 9/16
H. Kataok a / J. Chromatogr . A 733 1996) 19-3 4 27
2
A)
/ 3
4
1 2 1 3
14
S )
15
16
R e t e n t i o n t i m e m i n )
F ig . 7 . Gas chromatograms ob ta ined f rom benzenesu lphony l
d e r i v a ti v e s o f A ) p r im a r y a n d B ) s e c on d a ry a m in e s . G C
c o n d i t i o n s : c o l u m n , DB- 1 1 5 m × 0 .5 3 m m I . D . , 1 . 5 / z m f i lm
thickness) ; colu mn temperature, programm ed at 10°C /min
from 120 to 280°C; in ject ion and detector temperatures,
290°C; n i t rogen f low- ra te , l0 m l /m in ; de tec to r , f lame pho to -
met r ic S mode) . Each peak represen ts 2 ng o f amines.
Peaks: 1 = methylamine; 2 = ethylamine; 3 = isopropylamine;
4 = n-propylamine; 5 = isobutylamine; 6 = n-butylamine; 7 =
isoamylamine, 8 = n-amylamine; 9= hexylam ine; 10=
cyclohexylamine; 11 =heptylamine; 12= benzylamine; 13=
octylamine; 14=/3-phenylethylamine; 15=dimethylamine;
16 = diethylamine; 17 = dipropylamine ; 18 = pyrrolidine;
19 = morpholine; 20 = piperidine; 21 = dibutylamine; 22 =
hexamethyleneimine; 23 = N-methylbenzylamine.
R-NH2
Primary
~ , , C H O
a m i n e
-',e.,.~-CH
R ) N H
R '
S e co n d a ry
a m i n e
R-N
~:- ~ S
(No reaction)
CzHsO II
>p-cJ
CaHsO
(No reaction)
s
R I I 0C2H5
R,~N P ~OCzH5
Fig . 8 . Se lec t ive de r iva t i za t ion o f p r imary and secondary
amines wi th o -ph tha ld ia ldehyde and d ie thy l th iophosphory l
ch lo r ide . R , R 1= a lky l o r a ry l .
t iz e d w i th D E C T P w i th o u t O P A p r e t r e a t m e n t
a n d d e te c t e d b y G C - F P D , b u t t h e y a r e n o t
d e t e c t e d a t al l w i th O P A p r e t r e a t m e n t . O n t h e
o t h e r h a n d , s e c o n d a r y a m i n e s a r e d e t e c t e d i r r e -
s p e c ti v e o f O P A p r e t r e a t m e n t , b e c a u s e t h e s e
a m i n e s d o no t re a c t w i th O P A . A r o m a t i c a m i n e s
a r e d e t e c t e d a s si ng le a n d s y m m e t r i c a l p e a k s b y
c a p i ll a ry G C b a s e d o n t h e p r e p a r a t i o n o f N -
d i m e t h y l t h i o p h o s p h o r y l d e r i v a ti v e s o f a m i n e s
( F ig . 1 0) . I n t h e s e m e t h o d s , e x c e s s r e a g e n t s ,
w h i c h d is t u r b th e d e t e r m i n a t i o n o f l o w - m o l e c u -
l a r -m a s s a m i n e s , a r e r e m o v e d b y t h e r e a c t io n
w i t h c y s t e ic a c id b e f o r e s o l v e n t e x t r a c t i o n o f th e
d e r i v a t i v e s , b e c a u s e t h e d i a l k y l t h i o p h o s p h o r y l
d e r i v a t i v e o f c y s t e i c a c id is n o t e x t r a c t e d .
F u r t h e r m o r e , t h e s e r e a c t io n s h a v e b e e n a p -
p l i e d t o t h e d e t e r m i n a t i o n o f N - n i t r o s a m i n e s ,
t h e s e a m i n e s b e i n g d e n i t r o s a t e d w i t h h y d r o -
b r o m i c a c i d t o p r o d u c e t h e c o r r e s p o n d i n g s e c -
o n d a r y a m i n e s a n d t h e n d e r i v a t i z e d w i t h
D E C T P [ 1 8 ] .
3. Appl icat ions in environmental analys is
E v i d e n c e f o r t h e p o t e n t i a l h e a l t h h a z a r d s o f
a m i n e s h a s b e e n p r e s e n t e d [ 2 1 - 2 4 , 1 3 5 ,1 3 6 ] .
A m i n e s f r o m e n v i r o n m e n t a l s o u r c e s c a n b e to x ic
t h e m s e l v e s o r, m o r e o f t e n , s o m e o f t h e m c a n
b e c o m e t ox i c N - n i t r o s a m i n e s t h r o u g h c h e m i c a l
r e a c t i o n s w i t h n i t r i te , n i t r a t e , N O x o r O H r a d i -
c a l s i n t h e e n v i r o n m e n t . I t is t h e r e f o r e i m p o r t a n t
t o d e t e r m i n e t h e c o n c e n t r a t i o n l e v e ls o f t h e s e
c o m p o u n d s i n t h e e n v i r o n m e n t . I n t h i s s e c t i o n ,
t h e G C o f a m m o n i a a n d N - n i t ro s a m i n e s , w h i ch
7/25/2019 Kataoka 1996
http://slidepdf.com/reader/full/kataoka-1996 10/16
28
8 1
A ) 7
H. Kataoka / J . Chromatogr . A 733 1996) 19- 34
B ) C )
13
12
9
_A
6 ,i
14
i i
b 4 12 h lz 0 4
Reten t ion t im e m in)
o )
1718
19
~12 2 3
12
18
2 3
,° //I
l | |
4 8 12
F i g. 9 . G a s c h r o m a t o g r a m s o b t a i n e d f r o m N - d i e t h y l th i o p h o s p h o r y l d e r i v at i v e s o f p r i m a r y a n d s e c o n d a r y a m i n e s . ( A ) P r i m a r y
a m i n e s ; ( B ) p r i m a r y a m i n e s p r e t r e a t e d w i t h O P A ; ( C ) s e c o n d a r y am i n e s ; ( D ) s e c o n d a r y a m i n e s p r e t r e a t e d w i t h O P A . G C
c o n d i t i o n s: c o l u m n , D B - 1 7 0 1 ( 1 5 m x 0 . 5 3 m m I . D . , 1 . 0 / z m f il m t h i c k ne s s ) ; c o l u m n t e m p e r a t u r e , p r o g r a m m e d a t 1 0 ° C / m i n f r o m
1 00 t o 2 6 0° C ; i n j e c t i o n a n d d e t e c t o r t e m p e r a t u r e s , 2 8 & C ; n i t r o g e n f lo w - r a te , 1 0 m l / m i n ; d e t e c t o r , f l a m e p h o t o m e t e r ( P m o d e ) .
E a c h p e a k r e p r e s e n t s 2 0 p m o l o f a m i n e s . P e a k s : 1 = m e t h y l a m i n e ; 2 = e t h y l a m i n e ; 3 = p r o p y l a m i n e ; 4 = i s o b u t y l a m i n e ; 5 = n -
b u t y l a m i n e ; 6 = i s o a m y l a m i n e ; 7 = n - a m y l a m i n e ; 8 = h e x y l a m i n e ; 9 = c y c l o h e x y l a m i n e ; 1 0 = h e p t y l a m i n e ; 1 1 = o c t y l a m i n e ; 1 2 =
b e n z y la m i n e ; 1 3 = / 3 - p h e n y l e th y l a m i n e ; 1 4 = d i m e t h y l a m i n e ; 1 5 = d i e t h y l a m i n e ; 1 6 = d i p r o p y l a m i n e ; 1 7 = p y r r o l i d i n e ; 1 8 =
p i p e r i d i n e ; 1 9 = m o r p h o l i n e ; 2 0 = d i b u t y l a m i n e ; 2 1 = h e x a m e t h y l e n e i m i n e ; 2 2 = N - m e t h y l c y c l o h e x y l a m i n e ; 23 = N - m e t h y l b e n z y l -
a m i n e . R e p r o d u c e d f r o m R e f . [ 1 3 2 ] .
o f t e n o c c u r i n v a r i o u s e n v i r o n m e n t s , a r e a l s o
d e s c r i b e d a l o n g w i t h i n d i v i d u a l a m i n e t y p e s .
3.I. Aliphatic primary and secondary amines
L o w - m o l e c u l a r - m a s s a l i p h a t i c a m i n e s c a u s e
u n p l e a s a n t o d o u r s d u e t o t h e d e c a y o f f o o d s a n d
f i s h , a n d a r e h a z a r d o u s t o h u m a n h e a l t h . T h e s e
a m i n e s a r e a l s o e m i t t e d f r o m t h e l i v i n g e n v i r o n -
m e n t a n d v a r i o u s i n d u s t r i e s . S e c o n d a r y a m i n e s
s u c h a s d i m e t h y l a m i n e a n d p y r r o l i d i n e a r e p a r -
t i c u l a r l y i m p o r t a n t , b e c a u s e t h e y a r e b r o a d l y
d i s t r i b u t e d i n v a r io u s e n v i r o n m e n t s a s p r e c u r s o r s
o f c a r c i n o g e n i c N - n i t r o s a m i n e s .
A l t h o u g h G C d e t e r m i n a t i o n s o f a l ip h a t ic p r i-
m a r y a n d s e c o n d a r y a m i n e s h a v e b e e n c a r r i e d
ou t i n a i r [12 ,40 ,43 ,56 ] , c i ga re t t e s m oke [18 ] ,
wa t e r [56 ,58 ,60 ,71 ,96 ,107 ] and s o i l [60 ] , m any o f
t h e s e m e t h o d s h a v e b e e n u s e d f o r f r e e a m i n e s
[12 ,40 ,42 ,43 ,46 ,55 ,56 ,58 ] . In pa r t i cu l a r , t h e t r ace
d e t e r m i n a t i o n o f lo w - m o l e c u l a r - m a s s a l i p h a ti c
a m i n e s i n a i r h a s b e e n p e r f o r m e d w i t h n i t r o g e n -
s e l e c t i v e d e t e c t i o n m e t h o d s s u c h a s N P D , C L D
a n d G C - M S b y d ir e c t i n je c t io n o r t h e h e a d s p a c e
t e c h n i q u e . O n t h e o t h e r h a n d , d e r i v a t i z a t i o n
m e t h o d s h a v e a l s o b e e n u s e d i n w a t e r a n d s o i l
s a m p l e s [ 6 0 , 7 1 , 9 6 , 1 0 7 ] , b e c a u s e t h e s e s a m p l e s
c a n n o t b e d i r e c t l y a n a l y s e d .
N e u r a t h e t a l . [ 7 1 ] r e p o r t e d t h e d e t e r m i n a t i o n
o f 40 p r im a r y a n d s e c o n d a r y a m i n e s a s th e i r
t r i f l u o r o a c e t a m i d e s i n s u r f a c e w a t e r s f r o m r i v e r s
a n d s w a m p s b y G C - F I D . H i g h c o n te n ts o f C 1 -
C 3 a l ip h a t ic a m i n e s a r e f o u n d i n t h e s e s a m p l e s ,
b u t t h e c o n t e n t s o f s e c o n d a r y a m i n e s a r e g e n e r -
7/25/2019 Kataoka 1996
http://slidepdf.com/reader/full/kataoka-1996 11/16
H. K ataoka / J. Chroma togr. A 733 1996) 19-34
29
5
3
9
4 \
6 4 .
6
R e t e n t i o n t im e m i n )
Fig. 10. Gas ch rom ato gra m obtained from N- di-
methylthiophosphoryl derivatives of arom atic amines. GC
conditions: colum n, DB -17 (15 m × 0.25 mm I.D., 0.25 /.~m
film thickness); colum n temperature, programmed at 10°C/
rain from 180 to 220°C; injection and detector tem peratures,
260°C; he liu m flow-rate, 1 ml/min; splitting ratio, 5 0:1;
detector, flam e ionization. Ea ch peak represents 5 ng of
amines. Peaks: 1 = aniline; 2 = o-toluidine; 3 = m-toluidine +
o-ethylaniline; 4=2,5-dim ethylaniline; 5=p-toluidine; 6=
2,4-dimethylaniline; 7 =m -ethylaniline; 8 = 2,3-dimethyl-
aniline; 9 = p-ethylaniline.
a l l y b e l o w 1 5 p p b . K o g a e t a l . [9 6] r e p o r t e d t h e
d e t e r m i n a t i o n o f t r a c e a m o a u n t s o f tw e l v e a li -
p h a t i c p r i m a r y a n d s e c o n d a r y a m i n e s a s t h e i r
D N P d e r i v a t i v e s i n w a t e r s f r o m s e w a g e a n d
r i v e rs b y G C - M S . B y u si n g t h is m e t h o d , l o w -
m o l e c u l a r - m a s s a l i p h a t i c a m i n e s i n w a t e r s a m -
p l e s c a n b e d e t e r m i n e d i n t h e r a n g e 1 - 3 p p b .
A v e r y a n d J u n k [ 1 07 ] r e p o r t e d t h e d e t e r m i n a -
t i o n o f t r a c e a m o u n t s o f s e v e n a l ip h a t ic p r i m a r y
a m i n e s i n t a p a n d r i v e r w a t e r s a n d w a t e r f r o m o il
s h a le p r o c e s s in g b y G C - M S b a s e d o n S c h i f f b a s e
f o r m a t i o n w i t h P F B A . T h i s m e t h o d is s p e ci f ic
f o r p r i m a r y a m i n e s a n d t h e d e t e c t i o n l i m i t is 1 0
p p b w i t h n o s a m p l e t r a n s f e r s o r m a n i p u l a t i o n s
b e i n g n e c e s s a r y f o r s a m p l e v o l u m e s o f 0 . 5 m l .
T e r a s h i e t a l. [ 60 ] r e p o r t e d t h e d e t e r m i n a t i o n o f
e i g h t p r i m a r y a n d s e c o n d a r y a m i n e s i n r i v e r
w a t e r , s ea w a t e r an d s e a s e d i m e n t b y G C - M S -
S I M b a s e d o n d i s ti l la t i on o f t h e s a m p l e u n d e r
a l k a l i n e c o n d i t i o n s a n d s u b s e q u e n t b e n z e n e s u l -
p h o n y l a t i o n . I n t h i s m e t h o d , t h e d e t e c t i o n l i m i t s
o f a m i n e s i n w a t e r a n d s e d i m e n t a r e 0 . 0 2 - 2 a n d
0 . 5 - 5 0 p p m , r e s p e c t i v e l y . K a t a o k a e t a l . [ 1 8 ]
r e p o r t e d t h e d e t e r m i n a t i o n o f s e c o n d a r y a m i n e s
a s t h e i r D E T P d e r i v a t i v e s i n c i g a r e t t e s m o k e b y
G C - F P D . T h i s m e t h o d i s s e l e c ti v e a n d s e n s it i v e
t o s e c o n d a r y a m i n e s , a n d t h e d e t e c t i o n l i m i ts o f
a m i n e s a r e 0 . 0 5 - 0 . 2 p m o l . B y u s i n g t h is m e t h o d ,
i t w a s c o n f i r m e d t h a t d i m e t h y l a m i n e , p y r -
r o l id i n e , p i p e r id i n e a n d m o r p h o l i n e o c c u r i n
m a i n - a n d s i d e s t r e a m s m o k e s o f c i g a r e tt e s , a n d
t h e c o n t e n t s o f t h e s e a m i n e s i n s i d e s t r e a m s m o k e
a r e v e r y hi g h c o m p a r e d w i t h t h o s e i n m a i n -
s t r e a m s m o k e .
3 .2 . A r o m a t i c p r i m a r y a n d se c o n d a r y a m i n e s
A r o m a t i c a m i n e s s u c h a s a n i l i n e a n d i t s c h l o r i -
n a t e d a n a l o g u e s , p h e n y l e n e d i a m i n e a n d d i -
p h e n y l a m i n e a r e u s e d i n t h e m a n u f a c t u r e o f
c a r b a m a t e a n d u r e t h a n e p e s t i c i d e s , d y e s t u f f s ,
c o s m e t i c s a n d m e d i c i n e s . T h e s e a m i n e s a r e a l s o
e m p l o y e d in t h e r u b b e r i n d u s t r y a s a n t i o x i d a n t s
a n d a n t i o z o n a n t s [ 1 3 8 ] a n d a s c o m p o n e n t s i n
e p o x y a n d p o l y u r e t h a n e p o l y m e r s [ 13 9] . T h e
t o x i c i t y o f t h e s e a m i n e s t o m a m m a l s a n d f i s h i s
w e l l e s t a b l i s h e d [ 1 4 0 ,1 4 1 ]. M o s t o f t h e m a r e n o t
o n l y p o i s o n o u s t h e m s e l v e s b u t a l so m a y b e
c o n v e r t e d i n t o c a r c i n o g e n s s u c h a s N - n i t r o s o
c o m p o u n d s , n a p h t h y l a m i n e s , s u b s t i t u t e d p h e n y l -
a m i n e s o r b e n z i d i n e a n a l o g u e s [ 1 4 2 - 1 4 4 ].
A l t h o u g h t h e G C d e t e r m i n a t i o n s o f a r o m a t i c
7/25/2019 Kataoka 1996
http://slidepdf.com/reader/full/kataoka-1996 12/16
30
H. Kataoka / J. Chromatogr. A 733 1996) 19- 34
a m i n e s h a v e b e e n c a r r i e d o u t i n v a r i o u s e n -
v i ronm en t a l s am p l es s uch as a i r [78 ] , c i ga re t t e
s m oke [16 ,17 ,134 ] and was t e wa t e r [59 ,134 ] ,
m o s t o f t h e s e m e t h o d s a r e b a s e d o n t h e d e -
r i va t i za t i on o f am i nes w i t h an ac i d anhyd r i de .
S k a r p i n g e t a l . [ 7 8 ] r e p o r t e d t h e d e t e r m i n a t i o n
o f a n i li n e a n d r e l a t e d a r o m a t i c a m i n e s i n w o r k -
p l a c e ai r b y G C - N P D . A i r s a m p le s a r e c o ll e c te d
i n a l ka l i ne e t hano l s o l u t i ons and t he am i nes a re
c o n v e r t e d i n t o t h e c o r r e s p o n d i n g P F P a m i d e s b y
a n e x t r a c t i v e a c y l a t i o n p r o c e d u r e . T h e d e t e c t i o n
l i m i t o f t h i s m e t hod i s abou t 40 -80 fm o l . P i e rac -
c in i a n d c o - w o r k e r s [ 1 6 ,1 7 ] r e p o r t e d t h e d e t e r m i -
n a t i o n o f s e v e n t e e n p r i m a r y a r o m a t i c a m i n e s a s
t h e i r P F P a m i d e s i n c i g a r e t t e s m o k e a n d i n d o o r
a ir b y G C - M S - S I M . C i g a r e tt e i s s m o k e d in a
l a b o r a t o r y - m a d e s m o k i n g m a c h i n e a n d t h e
a m i n e s i n t h e m a i n - a n d s i d e s t r e a m s m o k e s a r e
t r ap pe d i n d i l u te hyd roc h l o r i c ac i d . I t was con -
f i r m e d t h a t s i d e s t r e a m s m o k e c o n t a i n s t o t a l
l e v e l s o f a r o m a t i c a m i n e s a b o u t 5 0 - 6 0 t i m e s
h i g h e r t h a n t h o s e o f m a i n s t r e a m s m o k e , a n d
s o m e a r o m a t i c a m i n e s i n a m b i e n t a i r s u c h a s
o f f ic e s a n d h o u s e s m a y b e d e r i v e d f r o m c o n s i d e r -
a b l e c o n t a m i n a t i o n o f a r o m a t i c a m i n e s i n s id e -
s t r e a m s m o k e .
3.3. Tertiary amines
L o w - m o l e c u l a r - m a s s a l i p h a t i c t e r t i a r y a m i n e s
a re i m p or t an t a s i ndus t r ia l r aw m at e r i a l s , and
have an unp l eas an t s m e l l and h i gh t ox i c i t y . In
p a r t i c u la r , t r i m e t h y l a m i n e i s f o u n d i n a n u m b e r
o f a m b i e n t e n v i r o n m e n t s [ 4 1 ,4 5 , 56 , 1 45 , 1 46 ] , a n d
i s a s s oc i a t ed wi t h t he f i s h odou r s ym drom e [147 ] .
D e t e r m i n a t i o n s o f a li p h a ti c t e r t ia r y a m i n e s
h a v e b e e n c a r r i e d o u t i n a i r [ 4 1 , 5 6 ] , w a t e r s f r o m
i ndus t r i a l was t e , s ewage o r r a i n [45 ,56 ,145 ,146 ]
a n d r i v e r b o t t o m s e d i m e n t s [ 45 ] b y G C - F I D ,
G C - N P D a n d G C - M S . H o w e v e r , m o s t o f t he se
m e t h o d s h a v e b e e n a p p l i e d t o f r e e a m i n e s , a n d
n o m e t h o d u s i n g d e r i v a t i z a t i o n f o r e n v i r o n m e n -
t a l a n a l y s i s h a s b e e n r e p o r t e d .
3.4. Ammonia
A m m o n i a a r i s e s m a i n l y f r o m n a t u r a l s o u r c e s
b y d e c o m p o s i t i o n o f o rg a n i c m a t t e r c o n t a i n i n g
n i t r o g e n a n d f r o m m a n u f a c t u r i n g p r o c e s s f o r
i ndus t r ia l chem i ca l s [148] . Am m on i a i s t he
p r i n c i p a l a t m o s p h e r i c b a s e r e s p o n s i b l e f o r
a e r o s o l f o r m a t i o n a n d t h e n e u t r a l iz a t i o n o f at -
m os pher i c ac i d i t y [149 ] . There fo re , t he de t e rm i -
n a t i o n o f a m m o n i a i n th e a t m o s p h e r e is i m -
p o r t a n t i n st u d i e s o f s m o g a n d a c i d r a i n f o r m a -
t i on . Am m oni a i s an i r r i t an t t o t he s k i n , r e s p i r a -
t o r y t r ac t a n d m u c o u s m e m b r a n e s . H i g h e r a m -
m o n i a l e v e l s a r e t h e r e f o r e b e c o m i n g a h y g i e n i c
p r o b l e m i n i n d o o r e n v i r o n m e n t s w h e r e i n d u s t r i a l
ope ra t i ons s uch as r e f r i ge ra t i on o r f e r t i l i ze r
m a n u f a c t u r e a r e c a r r i e d o u t . T h e s h o r t - t e r m
e x p o s u r e l i m i t f o r o c c u p a t i o n a l e x p o s u r e t o
a m m o n i a is a t im e - w e i g h t e d a v e r a g e o f 3 5 p p m
over a 15 - ra i n pe r i od , and ye t t he l ower l i m i t o f
h u m a n p e r c e p t i o n i s 5 3 p p m [ 1 5 0 ] . W a t e r p o l l u -
t i o n b y a m m o n i a o f t e n h a s a t o x i c i n f l u e n c e o n
aqua t i c s pec i es .
A l t h o u g h G C d e t e r m i n a ti o n s o f a m m o n i a
h a v e b e e n c a r r i e d o u t i n a i r [ 4 0 , 4 3 ] a n d w a t e r
[ 5 8, 71 ,1 2 9 ] s a m p l e s , m a n y o f t h e s e m e t h o d s
h a v e b e e n u s e d f o r f r e e a m m o n i a b y d i r e c t
i n j e c t i o n o r t h e h e a d s p a c e t e c h n i q u e . H o w e v e r ,
m o s t o f t h e s e m e t h o d s g i ve p e a k t a il in g o w i n g t o
t h e p o l a r i ty o f a m m o n i a . N e u r a t h e t a l. [ 7 1]
r e p o r t e d t h e s i m u l t a n e o u s d e t e r m i n a t i o n o f a m -
m o n i a a n d p r i m a r y a n d s e c o n d a r y a m i n e s i n
s u r f a c e w a t e r s f r o m r i v e r s a n d s w a m p s . A m -
m o n i a i s d e t e r m i n e d a s t r i f lu o r o a c e t a m i d e b y
G C - F I D a n d i t s c o n t e n t s i n t h e s e s a m p l e s a r e i n
t h e r a n g e 3 0 - 7 0 0 p p m . O n t h e o t h e r h a n d ,
K a t a o k a e t a l . [ 1 2 9 ] r e p o r t e d t h e d e t e r m i n a t i o n
o f a m m o n i a i n r i v e r, l a k e , s e a , s e w a g e a n d p o o l
w a t e r s a m p l e s . S i n c e t h e b e n z e n e s u l p h o n a m i d e
d e r i ve d f r o m a m m o n i a b y b e n z e n e s u l p h o n y la -
t i o n o v e r l a p s th e B S d e r i v a t i v e o f m e t h y l a m i n e
on t he ch rom at og ram [126 ] , i t i s add i t i ona l l y
c o n v e r t e d i n t o i t s d i m e t h y l a m i n o m e t h y l e n e d e -
r i v a t i v e w i t h D M F d i m e t h y l a c e t a l , a n d t h e n
d e t e r m i n e d b y G C - F P D . B y us in g th is m e t h o d ,
a m m o n i a i n e n v i r o n m e n t a l s a m p l e s c a n b e s e l e c -
t i ve l y and s ens i t i ve l y ana l y s ed as a s i ng l e and
s ym m et r i ca l peak , and t he de t ec t i on l i m i t i s
abou t 25 pg .
3.5. N-Nitrosamines
I t i s w e l l k n o w n t h a t N - n i t r o s a m a i n e s a r e
p o t e n t m u t a g e n i c a n d c a r c i n o g e n i c c o m p o u n d s
7/25/2019 Kataoka 1996
http://slidepdf.com/reader/full/kataoka-1996 13/16
H. Kataok a / J . Chromatogr . A 733 1996) 19-3 4 31
i n h u m a n a n d l a b o r a t o r y a n i m a l s , a n d a r e w i d e l y
d i s t r ib u t e d i n v a r i o u s h u m a n e n v i r o n m e n t s . N -
N i t r o s a m i n e s a r e f o u n d i n f o o d s t u f f s [ 2 5 , 1 5 1 -
155 ] , d r i nk i ng wa t e r [156 ] and va r i ous env i ron -
m e n t a l s o u r c e s [ 2 9 ,1 5 7 ], s u c h a s r u b b e r p r o d u c t s
[158 -165 ] , d rug fo rm u l a t i ons [166 ,167 ] , he r -
b i c i d e f o r m u l a t i o n s [ 1 6 8 ] , t o b a c c o a n d t o b a c c o
s m oke [18 ,28 ,169 -175 ] and i ndoo r [176 ] and
o u t d o o r [ 1 7 7 , 1 7 8 ] e n v i r o n m e n t s . T h e o c c u r r e n c e
o f N - n i t r o s a m i n e s i n b a b y b o t t l e r u b b e r n i p p l e s
and pac i f i e r s i s o f s pec i a l conce rn becaus e t r aces
o f t hes e am i nes m ay m i g ra t e i n t o i n fan t s a li va
d u r i n g s u c k i n g , a n d t h e n b e i n g e s t e d . T h e N -
n i t r o s a m i n e s i n e n v i r o n m e n t a l t o b a c c o s m o k e , t o
w h i c h b o t h s m o k e r s a n d n o n - s m o k e r s a r e e x -
p o s e d , h a v e r e c e i v e d a g r e a t d e a l o f a t te n t i o n a s
a s ou rce o f i ndoo r po l l u t i ons . Th e t o i x i c i ty o f
N - n i t r o s a m i n e s c a n b e m a n i f e s t e d e v e n a t a l o w
l e v e l ( ~ g / k g ) . T h e r e f o r e , a s e n s i t i v e m e t h o d f o r
t he de t e rm i na t i on o f t hes e am i nes is e s s en t i a l.
G C d e t e r m i n a t i o n s o f N - n i t r o s a m i n e s i n e n -
v i r o n m e n t a l s a m p l e s h a v e b e e n c a r r i e d o u t i n
rubber n i pp l es and pac i f i e r s [162 -164 ] and
c i g a r e t t e s m o k e s a m p l e s [ 1 8 , 2 8 , 1 6 9 - 1 7 5 ] . I n
m o s t o f th e m , N - n i t r o s a m i n e s a r e d i re c t ly d e -
t e r m i n e d a s t h e f r e e f o r m s b y G C - T E A , b a s e d
o n t h e d e t e c t i o n o f c h e m i l u m i n e s c e n c e e m i t t e d
f r o m a r e a c t i o n b e t w e e n r e l e a s e d N O r a d i c a l s
a n d o z o n e a f t er t he r m a l c l e a v ag e o f t h e N - N O
b o n d i n N - n i t r o s o c o m p o u n d s . A l t h o u g h G C -
T E A i s s ens i t ive and s pec i fi c fo r N-n i t ro s o com -
pounds , i t i s ve ry expens i ve . Ka t aoka e t a l . [ 18 ]
r e p o r t e d t h e d e t e r m i n a t i o n o f s e v e n N - n i tr o s -
a m i n e s b y G C - F P D . T h e m e t h o d i s b a s e d o n
d e n i t r o s a t i o n w i t h h y d r o b r o m i c a c i d t o p r o d u c e
t h e c o r r e s p o n d i n g s e c o n d a r y a m i n e s a n d s u b -
s e q u e n t d i e t h y l t h io p h o s p h o r y l a t i o n o f s e c o n d a r y
a m i n e s . B y u s i n g t h i s m e t h o d , i t w a s c o n f i r m e d
t h a t N - n i t r o s o d i m e t h y l a m i n e , N - n i t r o s o p y r r o l i -
d i n e a n d N - n i t r o s o p i p e r i d i n e o c c u r i n m a i n - a n d
s i d e s t r e a m s m o k e o f c i g a r e tt e s .
G C d e t e r m i n a t i o n o f fr e e a m i n e s i s g e n e r a l l y
u n s a t i s f a c t o r y o w i n g t o t h e a d s o r p t i o n a n d d e -
c o m p o s i t io n o f t h e s o lu t e o n t h e c o l u m n , r e -
s u i t i ng i n peak t a i l i ng and l o s s es . There fo re , a
w i d e v a r i e ty o f d e r i v a ti z a t io n r e a c t io n s , s u r v e y e d
i n t h i s r e v i e w , h a v e b e e n e m p l o y e d t o r e d u c e t h e
p o l a r it y , t o im p r o v e t h e G C s e p a r a t i o n o f c o m -
p o u n d s a n d t o i n c r e a s e b o t h t h e s e l e c t i v i t y a n d
s e n si ti v it y o f G C d e t e c t i o n . S o m e p o t e n t i a l p r o b -
l e m s w i t h d e r i v a t i z a t i o n p r o c e d u r e s i n c l u d e t h e
f o r m a t i o n o f u n w a n t e d d e r i v a ti v e s , t h e p r e s e n c e
o f u n c h a n g e d d e r i v a t i z a t io n r e a g e n t s a n d a r e -
q u i r e m e n t f o r n o n - a q u e o u s r e a c t i o n c o n d i t i o n s .
A m i n e s i n e n v i r o n m e n t a l s a m p l e s a n d i n d u s t r i a l
p r o c e s s s t r e a m s a r e u s u a l l y f o u n d i n a q u e o u s
s o l u t i ons excep t fo r a i r s am p l es , and a re o f t en a t
t r ace l eve l s . Th ere f o re , i t i s des i r a b l e t ha t t hes e
a m i n e s c a n b e d e r i v a t i z e d i n a q u e o u s s o l u t i o n
a n d b e s e n s i ti v e ly d e t e c t e d . O f t h e d e r i v a ti z a t io n
reac t i ons p res en t ed i n t h i s r ev i ew, acy l a t i on and
s i l y l a t i o n u s u a l l a y r e q u i r e a n h y d r o u s r e a c t i o n
c o n d i t i o n s b e c a u s e t h e d e r i v a t i z a t i o n r e a g e n t s
a r e v e r y s e n s i t i v e t o m o i s t u r e a n d a r e h y d r o -
l y s ed . On t he o t he r hand , d i n i t ro -
p h e n y l a t i o n , p e r m e t h y l a t i o n a n d t h e f o r m a t i o n
o f S c h i ff b a s e s , c a r b a m a t e s , s u l p h o n a m i d e s a n d
p h o s p h o n a m i d e s c a n b e g e n e r a l l y p e r f o r m e d i n
aqueous s o l u t i on . F o r ob t a i n i ng h i gh s ens i t i v i t y
and s e l ec t i v i t y , n i t rogen - s e l ec t i ve de t ec t i on
( N P D ) , n i t r o s a m i n e - s p e c i f i c d e t e c t i o n ( T E A )
a n d G C - M S h a v e b e e n u s e d . I n a d d i t i o n , t h e
c o n v e r s i o n s o f a m i n e s i n t o f l u o r i n a t e d d e r i v a t iv e
t o i n t r o d u c e a n E C D r e s p o n s e a n d i n t o s u l p h u r
a n d p h o s p h o r u s d e r i v a t i v e s t o i n t r o d u c e a n F P D
r e s p o n s e h a v e b e e n d e v i s e d f o r t h e s e p u r p o s e s .
A l t ho ugh t he u t i li t y o f de r i va t i za t i on i n am i ne
de t e rm i na t i ons by GC i s c l ea r , i t s app l i ca t i on t o
env i ronm en t a l ana l y s i s i s no t s o we l l known .
There fo re , i t i s hoped t ha t t h i s r ev i ew wi l l be
us e fu l fo r fu r t he r app l i ca t i ons o f de r i va t i za t i on i n
t h e G C d e t e r m i n a t i o n o f e n v i r o n m e n t a l a m i n e s .
4. Conclusions
M o n i t o r i n g a m i n e s i n v a r i o u s e n v i r o n m e n t s i s
i m p o r t a n t t o p r e s e r v e h u m a n h e a lt h b e c a u s e
t h e s e c o m p o u n d s o f t e n h a v e t o x i c e f f e c t s . T h e
Acknowledgement
T h e a u t h o r i s g r a t e f u l to P r o f e s s o r M a s a m i
M a k i t a o f O k a y a m a U n i v e r s i t y f o r h i s e n c o u r -
a g e m e n t .
7/25/2019 Kataoka 1996
http://slidepdf.com/reader/full/kataoka-1996 14/16
32
H . K a t a o k a / J . C h r o m a t o g r . A 7 3 3 1 9 9 6 ) 1 9 - 3 4
R e f e re nce s
[1 ] H.A.H. Bi l l ie t , in E . Hef tmann (Ed i to r) , Chromatog-
raphy , 5 th ed i t ion , Par t B : App l icat ions (Journal o f
Chrom atography L ib rary , Vo l . 51B), E lsev ier , A m-
sterd am , 1992, p . B583.
[2] G.R. Seaman, J. Bacteriol. , 80 (1960) 830.
[3] M. Richardson, Phytochemistry, 5 (1966) 23.
[4 ] J .A. Budd and C.P . Spencer , Mar . B io l . , 2 (1968) 92 .
[5 ] S . Lowis , M.A. Eastwood and W.G. Brydon , Br . J .
Nutr. , 54 (1985) 43.
[6] D.J .B . Da Pon te , J .P . Roozen and W. P i ln ik , J . Food
Technol. , 21 (1986) 33.
[7] S .H. Zeisel and K .A. D a Costa , Cance r Res . , 86
(1986) 6136.
[8] O. Kirk , Encycloped ia o f Chemical Techno logy , Vol . 2 ,
W iley-I nters cien ee, New York, 1978, 3rd ed. , p . 272.
[9] M.S. Reisch, Chem. Eng. News, 66 (1988) 7.
]10 ] A . R . M o s i e r , C . E . A n d re an d F . G , V ie t s, E n v i ro n .
Sci. Technol. 7 (1973) 642.
[11 ] G . L . H u tch in so n , A . R . M o s i e r an d C . E . A n d re , J .
Env iron . Qual . , 11 (1982) 288 .
[12] K. Kuwata , E . Ak iya ma, Y. Yamazak i , H . Yamasak i ,
Y. Kuge and Y. Kiso , Anal . Chem. , 55 (1983) 2199 .
[13] B .J . F in layson-P i t t s and J .N. P i t t s , Atmosp her ic
Chem ist ry , Wiley -In ters cience, New York , 1986 , p .
561.
[14] S .E . Ma naha n , E nv iro nm enta l Chem ist ry , Lewis ,
1990, 4th ed., p. 422.
[15] S .H. Ca d le , P .A. Mulawa, E nv iron . Sci. Techno l . , 14
(1980) 718.
[16] G. P ieraccin i , F . Lucer i and G, Monet i , Rap id Com-
mun . Mass Spect rom. , 6 (1992) 406 .
[17] F . Lucer i , G . P ieraccin i , G . M oret i and E D olara ,
Toxicol. Ind. Health , 9 (1993) 405.
[18] H. Kataoka , S . Sh indoh and M . Maki ta , J . Chroma-
togr. A, 723 (1996) 93.
[19] A. Mil ler , R .A . Scan lan , J .S . Lee and L .M. L ibbcy , J .
Agric . Food Chem. , 20 (1972) 709 .
[20] S . Fusel l i, S . Ce rqu ig l in i and E . C h iacch ier in i , Ch im .
Ind. , 60 (1978) 711.
[21] L . Bel in , U . Wass , G . Audunsson and L . Math iasson ,
Br. J. Med. , 40 (1983) 251.
[22] C . -X. Ga o , I .S . K ru l l and T . Traino r , J. Chrom atogr .
Sci., 28 (1990) 102.
[23] G. Bi t tersoh l and H. Hebere , Z. Ges. Hyg . Grenzgeb . ,
24 (1978) 529.
[24] M. Dalene, T . Lundh and L . Math iasson , J . Chroma-
togr., 322 (1985) 169.
[25] A.R . Tr icker and R . P reu ssm ann , Mutat . Res . , 259
(1991) 277.
[26] M. S i t t ing , Haza rdous and Tox ic Effects o f Indust r ia l
Chemicals , Noyes Data , New Jersey , 1979 , p . 27 .
[27 ] M . C . B o w m an , H an d b o o k o f C arc in o g en s an d H aza rd -
ous Substances , Marcel Dekker , New York , 1982 .
[28] A.R . T r icker and R . P reussm ann , Cl in . Invest . , 70
(1992) 283.
[29] S.S. Mir uish, Toxicol. Ap pl. Phar ma col. , 31 (1975)
325.
[30 ] G . B . N eu ra th , M . D u en g ar , F . G . P e in , D . A m b ro s iu s
and O . Schre iber , Food Cosmet . Tox ico l . , 15 (1977)
275.
[31] B . Sp iegelhalder and R . P reussmann , Carcinogenesis ,
6 (1985) 545.
[32] W.R. L ich t and M.W. Deen , Carcinogenesis , 9 (1988)
2227.
[33] B . P fundstein , A .R. Tr icker , E . Theobald , B .
Sp iegelhalder and R . P reussmann , Food Chem. Tox i-
col., 29 (1991) 733.
[34] P .L . Hans t , J .W. Spence and M . Mil ler , Env iron . Sci .
Techno l . , 11 (1977)403 .
[35 ] J .J . F ran k en , C . V id a l -M ad ja r an d G . G u io ch o n , A n a l .
Chem. , 43 (1971)2034 .
[36] A. D iCorcia , R . Samperi and C . Sever in i , J . Chrom a-
togr., 170 (1979) 325.
[37] M. Dalen e, L . M ath iasson and J .A. Jonsson , J . Chro-
matogr. , 207 (1981) 37.
[38] D.S. Treybig, J. Chromatogr. Sci. , 21 (1983) 310.
[39] G, Aud unss on and L . M ath iasson , J . Chrom atogr . , 261
(1983) 253.
[40] G. Aud unss on and L . M ath iasson , J . Chrom atogr . , 315
(1984) 299.
[41] T . Fu j i i and T . Ki ta i , Anal . Chem. , 59 (1987) 379 .
[42] M. Mohnke, B . Schmid t , R . Schmid t , J .C . Bu i j ten and
Ph. Mussche, J. Chromatogr. A, 667 (1994) 334.
[43] N. Kash ih i ra , K . Makino , K. Kir i ta and Y. Watanabe,
J. Chromatogr. , 239 (1982) 617.
[44] S . Lowis , M.A . Eastwo od and W.G. Brydon , J .
Chromatogr. , 278 (1983) 139.
[45] A.Q. Zhang , S .C . Mitchel l , R . Ayesh and R.L . Smith ,
J. Chromatogr. , 584 (1992) 141.
[46] T , Tsuk ioka, H . Ozaw a and T . Murak ami, J . Chrom a-
togr., 642 (1993) 395.
[47] R . I .P . Mart in , J .M. Franco , P . Mol is t and J .M. Gal-
lardo, I nt. J. Foo d Sci. Tec hnol . , 22 (1987) 509.
[48] T . Lundh , B . S tah lbom and B. Aksson , In t . Arch .
Occup . Env iron . Heal th , 44 (1991) 81 .
[49] L . M ath iasson and P . Lovkv is t , J . Chrom atogr . , 217
(1981) 177.
[50] J . J . R ichard and G.A. Junk , Anal . Chem. , 56 (1984)
1625.
[51 ] J .A . L een h ee r , T . I . N o y es an d H . A . S tu b e r , E n v i ro n .
Sci. Technol. , 16 (1982) 714.
[52] C . L ee a nd B.L . Olson , Org . Ge ochem . , 6 (1984) 259.
[53] C .D. Chriswel l and J .S . F r i tz , J . Chrom atogr . , 136
(1977) 371.
[54] J .S . Smith and J .M. Han raha n , J . Chrom atogr . , 193
(1980) 271.
[55] L . Gro nber g , P. Loukv is t and J .A. Jonsson , Chromato -
graphia, 33 (1992) 77.
[56] L . G ronbe rg , P. Loukv is t and J .A. Jonsson , C hemo-
sphere, 24 (1992) 1533.
[57] B . L indegard , J .A. Jonsson and L . Math iasson , J .
Chromatogr. , 573 (1992) 191.
[58] X. -H. Yang , C . Lee and M,I . Scran ton , Ana l . Chem . ,
65 (1993) 572.
[59] R .M. Rigg in , T .F . Co le and S . B i l le ts , Ana l . Chem. ,
55 (1983) 1862.
7/25/2019 Kataoka 1996
http://slidepdf.com/reader/full/kataoka-1996 15/16
H . K a t a o k a / J . C h r o m a t o g r. A 7 3 3 1 9 96 ) 1 9 - 3 4
33
[60] A. Terash i , Y. Han ada, A. K ido an d R. Sh inohara , J .
Chromatogr. , 503 (1990) 369.
[61] Y. Hoshika, J. Chromatogr. , 115 (1975) 596.
[62] B . P fundstein , A .R. Tr icker and R . P ressm ann , J .
Chromatogr. , 539 (1991) 141.
[63] K.A . daCosta , T . J . Vrbanac and S .H. Z eisel , A nal .
Biochem., 187 (t990) 234.
[64] M. Dale ne a nd G. Skarp ing , J . Chromatogr . , 331
(1985) 321.
[65] T .S . M a and A.S . L adas , Organ ic Fu nct iona l Gro up
Analysis by Gas Chromatography , Academic Press ,
New York, 1976, p. 76.
[66 ] D . R . K n ap p , H an d b o o k o f A n a ly t i ca l D er iv a t i za ti o n
Reac t ions , Wiley -In terscience, New York , 1979 , p . 65 .
[67] J . Drozd , Chem ical Der ivat izat ion in Gas Chromatog-
raphy , E lsev ier , Amsterdam, 1981 , p . 97 .
[68] K. Blau and J . Halke t , Han dboo k o f Der ivat ives fo r
Chrom atography , Wiley , Ch ichester , 2nd ed . , 1993 .
[69 ] W . J . A . V an d en H eu v e l , W . L . G a rd in e r an d E . C .
Homing , Anal . Chem. , 36 (1964) 1550 .
[70] W.J. Irvin e and M.J. Soxby, J. C hrom atog r. , 43 (1969)
129.
[7 1 ] G . B . N eu ra th , M . D u n g er , F . G . P e in , D . A m b ro s iu s
and O. Schreiber , Food Cosmet . Tox ico l . , 15 (1977)
275.
[72] R .T . Cou t ts , E .E . Harges heimer , F .M. Pasu t to and
G.B . Ba ker, J. Chro ma togr. Sci., 19 (1981) 151.
[73] H.-B. Lee, J. Chromatogr. , 457 (1988) 267.
[74 ] D . H . M . L au an d G . L . H en d er so n , J . C h ro m ato g r . ,
129 (1976) 329.
[95] D.E . Bradway and T . Shafik , J . Chrom atogr . Sci . , 15
(1977) 322.
[76] S . Skarp ing , L . Re nm an and B.E .E . Sm ith , J . Chroma-
togr., 267 (1983) 315.
[77] S . Skarp ing , L . Re nm an and M . Dale ne, J . Chrom a-
togr., 270 (1983) 207.
[78] S . Skarp ing , L . Renman , C . Sango , L . Math iasson and
M. Dalene, J . Chromatogr . , 346 (1985) 191 .
[79] S . Skarp ing , B .E .F . Smith and M. Dalene, J . Chroma-
togr., 303 (1984) 89.
[80] M. Dalene, G. Skarp ing and T . Brorson , J . Chroma-
togr., 516 (1990) 405.
[81] A.C . Moffat , E .C . Hom ing , S .B . Ma t in and M.
Row land , J . C hrom atogr . , 66 (1972) 255.
[82 ] A . R . M o s i e r, C . E . A n d re an d F . G . V ie ts , E n v i ro n .
Sci. Technol. , 7 (1973) 642.
[83] F .T . Delbeke and M. Debacker , J . Chromatogr . , 237
(1982) 344.
[84] C .P. Qu ar ter ma n , M.J . Kend al l and P .S . Jack , J .
Chromatogr. , 183 (1980) 92.
[85] L .M. Roso-Le e, M.J . E ache, F . Bochner , W .D.
Hooper and J .H. Tyrer , J . Chromatogr . , 183 (1980)
175.
[86] M. Donike, J. Chromatogr. , 78 (1973) 273.
[87] M.S . Lelowx, E .G . D e Jong and R.A .A. Maes, J .
Chromatogr . , 488 (1989) 357 .
[88] C . Drouet t -Coasso lo , C . Auber t , P . Coasso lo and J .P .
Cano , J . Chromatogr . , 487 (1989) 295 .
[89] M.A .D. Ibanez , M. Chesseb euf-Pach iu and P. Pad ieu ,
J. Chromatogr. , 488 (1989) 237.
[90] A.J . F rancis , E .D. Morgan and C.F . Poo les , J . Chro-
matogr. , 161 (1978) 111.
[91] E .W. Day , T , Go lab and J .R . Koons, Anal . Chem. , 38
(1966) 1053.
[92] T. W alle, Ac ta Pha rm. Suec. , 5 (1968) 367.
[93] S .W. Gu nne r and R.C.O . B r ien , J . Assoc. Off . Ana l .
Chem., 52 (1969) 1200.
[94] R .E . Weston and B.B. Wheals , A nalyst , 95 (1970) 680 .
[95] M.D. So loman , W.E . Perei ra and A.M . Duff ie ld ,
Anal. Lett . , 4 (1971) 301.
[96] M. K oga, T . Ak iya ma and R . Sh inohara , Bunsek i
Kagaku, 30 (1980) 745.
[97] A.D . Smith and J .B . Jepson , Ana l . B iochem. , 18
(1967) 36.
[98] Y. Ish i toya, S . Baba and I . Has h imoto . C l in . Ch im .
Acta, 46 (1973) 55.
[99] S . Baba, I . Hash im oto a nd Y. Ish i toya, J . Chrom a-
togr., 88 (1974) 373.
[100] A.G . G ium anin i , G . Ch iavar i and F . Scarpon i , Anal .
Chem., 48 (1976) 484.
[101] M. Dalena, T . Lundh and L . Math iasson , J . Chroma-
togr., 322 (1985) 169.
[102] L . Johans son and J . Vessmann , J . Chrom atogr . , 239
(1982) 323.
[103] L. Maros, Acta Chim. Hung. , 121 (1986) 339.
[104] Y. Hoshika, J. Chromatogr. , 136 (1977) 253.
[105] Y. Hoshika, Anal. Chem., 49 (1977) 541.
[106] S .P . J indal , T . Lu tz an d T .B. Cooper , J . Ch romatog r . ,
221 (1980) 301.
[107] M.J . Avery and G.A. Junk , Anal . Chem. , 57 (1985)
790.
[108] M.J . A very and G .A. Junk , J . C hromatog r . , 420
(1987) 379.
[109] M. Scoggins, J. Chromatogr. Sci. , 13 (1975) 146.
[110] T. Gejvall , J. Chromatogr. , 90 (1974) 157.
[111] M. Maki ta , S . Yam amoto , K. Ik eda, T . Sam ej ima and
Y. Ohnish i, Ya kuga ku Zass hi, 97 (1977) 304.
[112] S . Yam amoto , H. I tano , H. K ataoka a nd M. Maki ta , J .
Agric. Food Chem., 30 (1982) 435.
[113] G. Skarp ing , T . Bel lande r and L . Math iasson , J .
Chromatogr. , 370 (1986) 245.
[114] G. Skarp ing , M. Dalene, T . Brorson , J .F . Sandst rom,
C. Sango and A. T i l jande r , J . Chrom atogr . , 479 (1989)
125.
[115] H. Kataoka, Y. Imamura, H. Tanaka and M. Maki ta ,
J. Pharm. Biomed. Annal. , 11 (1993) 963.
[116] T . Lundh and B. A kesson , J . C hromatog r . , 617 (1993)
191.
[117] M. Dalene, G. Skarp ing and H. T inne rberg , J . Chro-
matogr. B, 656 (1994) 319.
[118] J . Vessman , P . Har tv ig a nd M . M olander , Ana l . Let t . ,
6 (1973) 699.
[119] P. Hartvig and J. Vessman, Anal. Lett . , 7 (1974) 223.
[120] P . Har tv ig , K . -E . Kar lsson , L . Johansson and C.
Lindberg, J. Chromatogr. , 121 (1976) 235.
[121] O. Hinsberg , Chem. Ber . , 23 (1890)2962 .
7/25/2019 Kataoka 1996
http://slidepdf.com/reader/full/kataoka-1996 16/16
34
H . K a t a o k a / J . C h r o m a t o g r . A 7 3 3 1 9 9 6 ) 1 9 - 3 4
[122] T . Hamano , A, Hasegawa, K. Tanaka and Y. Matsuk i ,
J. Chromatogr. , 179 (1979) 346.
[123] T . Ham ano , Y. Mitsuhash i and Y. Matsuk i , J . Chroma-
togr., 190 (1980) 462.
[124] T . Ha ma no , Y. M itsuhash i and Y. Matsuk i , Agric .
Biol. Chem., 45 (1981) 2237.
[125] S . Ohru i , H . Kataoka, Y. Miyamoto , K. Ohtsuka and
M. M aki ta , B unsek i Kagaku , 40 (1991) 119.
[126] H. Kataoka, S . Ohru i , Y. Miyamoto and M. Maki ta ,
Biomed . Chromatogr . , 6 (1992) 251 .
[127] G.M. S inger and W. L i j insky , J . Agric . Fo od Chem . ,
24 (1976) 550.
[128] Y. Miyamoto , H. Kataoka, S . Ohru i and M. Maki ta ,
Bunse k i Kagaku , 43 (1994) 1113 .
[129] H. Kataoka, S . Ohru i , A . Kanemoto and M. Maki ta ,
J . Chromatogr . , 633 (1993)311 .
[130] K. Jacob , C . Fa lkne r and W.Vog t , J . Chromatogr . , 167
(1978) 67.
[131] H. Kataoka, K. Nagao , N. Nabesh ima, M. Kiyama and
M. Makita, , i . Chromatogr. , 626 (1992) 239.
[132] H. Kataoka, M. Eda and M. Maki ta , B iomed . Chro-
matogr. , 7 (1993) 129.
[133] H. K ataoka, S . Sh indoh and M . Maki ta , J . Chroma -
togr. A, 695 (1995) 142.
[134] H. K ataoka, K. K i j ima and M. Maki ta , in p reparat ion .
[135] J . Pepys, C .A. P icker ing and W.G. Loud on , Cl in .
Allergy, 2 (1972) 189.
[136] R .E . Bru baker , H . , I. Ju r anko , D .B. Smith and G.J .
Beck, , i . Occup. Med. , 21 (1979) 688.
[137] S . Lain and M. Chan-Yeung , Am. Rev . Resp ir . Dis . ,
121 (1980) 151.
[138] L . Parm egg ian i (Ed i to r) , Encycloped ia o f Occupat ion-
al Heal th an d Safety , Vo l . 1 , In terna t iona l Lab our
Office, Geneva, 1983.
[139] G.D . C lay ton and F .E . Clay ton (Ed i to rs) , Pa t ty ' s
Indust r ia l Hyg iene and Tox ico logy , Vo l . 28 , Wiley -
Inters cien ce, New York, 1981.
[140] J .M. Son tag (Ed i to r ) , Carcinogens in Indu st ry and the
Env iron me nt , Marce l Dek ker , New York, 1981 .
[141] F .S .H. A bra m and I .R . S ims, Water Res . , 16 (1982)
1309.
[142] E. R inde and W. Troll , , i. Natl . Ca nce r Inst. , 55 (1975)
181.
[143] J.P. Seiler, Mutat. Res. , 58 (1977) 353.
[144] R .F . S t raub , R .D. Voyksner and J .T . Keever , A nal .
Chem., 65 (1993) 2131.
[145] M.F . P rokopeva , N .Kh . Tadzh ieva, T .V. S i lkna and
L.D. Glazunova, Zh . Anal . Kh im. , 37 (1982) 930 .
[146] E .L . S elyu t ina and Yu .Y a.Vinn ikov , Zh . A nal . K h im. ,
43 (1988) 2060.
[147] A.Q . Zh ang , S .C . Mitchel l , R . Ayesh and R.L . S mith ,
J. Chromatogr. , 584 (1992) 141.
[148] M. L ipp ma nn an d R.B. Sch les inger, Chem ical Con-
t am in a t io n i n t h e H u m an E n v i ro n m en t , O x fo rd U n i -
versity Press, New York, 1979.
[149] S .H. Cad le , R . ,I . Coun tess and N.A . Kel ly , Atm os.
Environ. , 16 (1982) 2501.
[150] S.J. West, S. Ozaw a, K . Seiler, S.S.S. Ta n and W.
Simon , Anal . Chem. , 64 (1992) 533 .
[151] J.H. Hotchkiss, Cancer Surv. , 8 (1989) 295.
[152] K. T akatsuk i and T . Kikuch i , ,i . Chromatogr . , 508
(1990) 357.
[153] R .A . Scan lan , J ,F . Bar bour and C. I . Chappel , , i .
Agric. Food Chem., 38 (1990) 442.
[154] A,R . Tr icker , B . P fundstein , E . The obald and R.
Preussmann , Food Chem. Tox ico l . 29 (1991) 729 .
[155] J .W. Pens abene and W. F idd ler , J. Assoc. Off . A nal .
Chem., 77 (1994) 981.
[156] W .I . Kimoto , C . J . Doo ley an d W. F idd ler , W ater Re s . ,
15 (1981) 1099.
[157] A.R . Tr icker , B . Sp iegelhalder and R . P reu ssm ann ,
Cancer Serv. , 8 (1989) 251.
[158] D.C. Have ry and T . Fazio , Food C hem. Tox ico l . , 20
(1982) 939.
[159] B . -G. Osterdah l , Food Chem. T ox ico l . , 21 (1983) 755 .
[160] H.C. Thom pson , S .M. Bi l ledeau , B .J . Mil ler , E .B .
Ha nsen and J .P . F re em an , J . Tox ico l . Env iron . Heal th ,
13 (1984) 615.
[161] N.P . Sen , S .C . K ushwaha , S .W. Seaman and S .G .
Clar kson , J. Agric. Food Chem ., 33 (1985) 428.
[162] S .M. Bi l ledeau , H.C. Thom pson and B.J . Mil ler , J .
Assoc. Off . Anal . Chem. , 69 (1986) 31 .
[163] J . I . Gray and M.A . S tachiw, J . Assoc. Off . Ana l .
Chem., 70 (1987) 64.
[164] N.P . Sen , S .W. Seam en an d S .C . K ushwaha, J . Assoc.
Off . Anal . Chem. , 70 (1987) 434 .
[165] D. Hjdasz, Rubber World (1992) 15 .
[166] B .A . D awso n and R.C . Lawrence , J . Assoc. Off .
Anal . Chem. , 70 (1987) 554 .
[167] L.B. Niclse n and S. Lings, Me d. Hyp oth. , 42 (1994)
265.
[168] R .R . Scharfe and C.C . McLe nagham , J . Assoc. Off .
Anal . Chem. , 72 (1989) 508 .
[16 9] K . O . B ru n n em an n , L . Yu an d D . H o f fm an n , C an ce r
Res., 37 (1977) 3218.
[170] D. Hoffm ann , J .D. Ada ms, K.D. Br unn em an and S .S .
Hech t , Cancer Res . , 39 (1979) 2505 .
[171] K.D. B runn em ann , W. F ink and F . Mose r , Onco logy ,
37 (1980) 217.
[172] C . Ruh l , J .D . Adam s and D. Hoffm an , J . A nal .
Toxicol., 4 (1980) 255.
[173] R . Truha u t , N .P . L ich , M. Castegnaro , M.C. Bou rgade
and C. Ma rt in , J . Cancer Res . Onco l . , 108 (1984) 157.
[174] W.S. Caldw ell and ,I .M. C onn er, , i. Assoc . Off. A na l.
Chem., 73 (1990) 783.
[175] A.R. Tr icker , C . Di t r ich and R. P reussm ann , Carcino-
genesis, 12 (1991) 257.
[176] K.D. B runn em ann , . I.D . Adam s, D.P .S . Ho an d D.
Hoffm ann , P roc. 4 th Jo in t Conf . Sen sing o f Env iro n-
m en ta l P o l lu t an t s , A m . C h em . S o c ., W ash in g ton , D C ,
1978, p. 876.
[177] E .D . Pel l izzar i , J .E . Bunch , J .T . Bursey , R .E . Berk -
ley , E . Sawick i and K. Krost , Anal . Let t . , 9 (1976)
579.
[178] D.H. F ine, D.P . Roun beh le r , E . Sawick i, K . Krost and
G.A. DeMarrais , Anal . Let t . , 9 (1976) 579 .
Top Related