Kataoka 1996

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

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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

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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

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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

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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


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 .

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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


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 -

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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


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 -

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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

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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

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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 .

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32


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