Radiochromic dye cyanides and the dosimetric characteristics of their dosimeters

0146-5724/88 $3 00+000 Pergamon Journals Ltd

Radlat Phys Chem Vol 31, Nos 4-6, pp 405-408, 1988 lnt J Radmt Appl lnstrum Part C

Pnnted m Great Britain

RADIOCHROMIC DYE CYANIDES AND THE DOSIMETRIC CHARACTERISTICS OF THEIR DOSIMETERS

Guan X i a n g r u i * , Li Kezhong*, Lt J i a n p i n g * , Tang Hongchun*, Li Weigang* and Zhu J t a n h u a n * * *Research Institute o f Chemical Defence P.O.Box * * B e i j i n g S h i y i n g R a d i a t i o n D e t e c t o r Works

1044-400 R e i j i n g ,

China

ABSTRACT

The new methods o f s y n t h e s i s and p u r i f i c a t i o n o f two r a d i o c h r o m i c l e u c o d y e s [ p a r a r o s a n i l i n e c y a n i d e (PR-CN) and h e x a h y d r o x y e t h y l p a r a r o s a n i l i n e cyanide(HPR-CN)] a r e o u t l i n e d . S t r u c t u r e and p u r i t y o f t h e p r o d u c t s have been c o n f i r m e d by e l e m e n t a r y a n a l y s i s , infrared spectrometry, ultraviolet spec t r o m e t r y , f i e l d d e s o r p t mass s p e c t r o m e t r y and t h i n l a y e r c h r o m a t o g r a p h y . Two l e u c o d y e s have been e v a l u a t e d and used i n s o l u t i o n d o s i m e t e r s , f i l m d o s i m e t e r s , o p t i c a l waveguide d o s i m e t e r s . KEYWORDS P a r a r o s a n i l i n e cyanide; hexahydroxyethyl p a r a r o s a niline cyanide; p r e p a r a t i o n of p a r a r o s a n i l i n e cyanide; p r e p a r a t i o n of hexahydroxyethyl p a r a r o s a n i l i n e cyanide; s o l u t i o n dosimeter of p a r a r o s a n i line cyanide; solution dosimeter of hexahydroxyethyl pa ra ros a niline cyanide; film dosimeter of p a r a r o s a n i l i n e cyanide; film dosimeter of hexahydroxyethyl p a r a r o s a n i l i n e cyanide; o p t i c a l waveguide d o s i m e t e r o f h e x a h y d r o x y e t h y l p a r a r o s a n i l i n e c y a n i d e ; r a d i o c h r o m i c dye c y a n i d e . INTRODUCTION Radtochromtc dose measurement on t h e b a s i s o f t r i a r y l m e t h a n e l e u c o c y a n i d e dyes was i n v e s t i g a t e d and developed by Mclaughlin and Far West Technology I n c o r p o r a t i o n [ F W T I n c l . The l e u c o c y a n i d e dyes and s o l u t i o n d o s i m e t e r s ( E l - a s s a y , 1982), f i l m d o s i m e t e r s (Humphreys, 1981) and o p t i c a l wavegutde d o s i m e t e r (Kronenherg, 1981) h a v e been used i n r a d i a t i o n dose measurement f o r q u a l i t y c o n t r o l i n various i n d u s t r i a l r a d i a t i o n processing; s t a n d a r d i z a t i o n of r a d i a t i o n dosimetry (Mclaughlin,1978); e l e c t r o n beam (Humpherys, 1979), p r o t o n ( H a s s e n , 1984), f a s t n e u t r o n (Kronenberg, 1982) and o t h e r n u c l e a r r a d i a t i o n d o s i m e t r y as w e l l a s measurement o f h i g h . r e s o l u t i o n dose d i s t r i b u t i o n ( H a s s e n , 198~). Because t h e l e u c o c y a n i d e d o s i m e t e r s have good d o s i m e t r t c c h a r a c t e r i s t i c s and convenience i n operation, i n order t o extend their usage, it is necessary to manufacture on a large scale at lower

costs.

Our l a b o r a t o r y has improved C h a l k l e y ' s ( 1 9 5 8 , 1 9 5 9 ) methods o f s y n t h e s i s and p u r i f i c a t i o n o f p a r a r o s a n i l l n e c y a n i d e (compound I ) and h e x a h y d r o x y e t h y l p a r a r o s a n i l l n e c y a n i d e (compound I I ) . Products w i t h h i g h p u r i t y , h i g h y i e l d and low c o s t s were o b t a i n e d . I n t h e p r o d u c t i o n on a l a r g e s c a l e , q u a l l t y and p r o p e r t i e s o f p r o d u c t s a r e c o n s i s t e n t and s t a b l e . Two leucodyes were e v a l u a t e d and used a s s o l u t i o n d o s i m e t e r s , f i l m d o s i m e t e r s and o p t i c a l wavegutde d o s i m e t e r s .

ROUTE AND TECHNOLOGY OF SYNTHSIS Pararosaniline base is dissolved by appropriate amount of dilute hydrochlorlc acid, soon afterwards excessive solutlon of potassium cyanide or sodium cyanide Is added to it, so that raw p a r a r o s a n ~

l l n e cyanide I s o b t a i n e d . Then t h i s p r o d u c t I s p u r i f i e d by s e l f d e s i g n e d p u r i f i c a t i o n d e v i c e , by which t h e p r o c e s s e s o f e x t r a c t i o n , c h r o m a t o g r a p h l c s e p e r a t l o n and r e c r y s t a l i z a t l o n a r e combined, b e i n g c a p a b l e o f p r o d u c t i o n on a l a r g e s c a l e . White c r y s t a l compound I i s o b t a i n e d . Compound I r e a c t s w i t h e p o x y e t h a n e a t 7 t o IO a r m . , y l e l d i ~ compound I f . By t h i s means t h e r e a c t i o n p e r i o d is shortened from 35 (Chalkley,1959) to 15 days. Equations are: 1.(HsN~--~-OH~'~N~-'~-CN+~

o+KCI

STRUCTURE IDENTIFICATION AND PURITY ANALYSIS PRODUCTS 1. P a r a r o s a n i l i n e Cyanide (compound I ) TABLE 1 P h y s i c a l P r o p e r t i e s |~hysical

state

meltin 8 point

405

llterature

value(liantzsh,1900)288_290 ~

I

GUAN XI~Gatn et al.

406

TABLE 2 R e s u l t s o f q u a n t i t a t i v e [

I calculate experimental

compound I

[

N=17"83% Nffil7.99%

Elementary Analysis [

C=76"43% C=76.44%

I

H=5"74% H=5.82%

I

C h a r a c t e r i s t i c f r e q u e n c i e s o f IR s p e c t r u m o f compoun~ I a r e a s f o l l o w s : yu~--3500c~L3200cm"#, vc~= 3200cn;L-2900cm'J,vc~f2200cm "j, ve:c=1600cm't, 1500cm-j, ~cu=1480cm'.L-14OOcm'l, ~ c s f g 6 0 c m ' L 8 0 0 c m"j. Which a r e i d e n t i c a l w i t h t h e o n e s by t h e o r e t i c a l c a l c u l a t i o n ( G u a n , 1 9 8 5 ) .

2. Compound "rI and Ftrr-40* TABLE ~ P h y s i c a l P r o p e r t i e s physical properties HPR--CN ¢~ound II ~-40

physical white

state

melting point

crystal

215--216"C 168-173"C

tiny blue p o w d e r

literature

value(Chalkley,1959)

206_208Oc

TABLE~ Results of ~uantitative Elemantary Analysis Elemants

1~

compound I I lq¢T-40

H%

C%

9.69

7.27

66.44

9.45 8.94

6.94 8.29

65.11 64.45

C h a r a c t e r i s t i c f r e q u e n c i e s o f IR s p e c t r u m o f h e x a h y d r o x y e t h y l p a r a r o s a n i l i n e c y a n i d e a r e a s f o l l o w s : V~cx=360Ocm~--300Ocm'l, VcX=300Ocm~--2500cm"t, VciN=2250cm~, Vc:c=1620cm°J,1560c~/--1500cm'~ ~cm=1310cm~, --880cm'LS00cm"I. C h a r a c t e r i s t i c f r e q u e n c i e s o f compound I I a r e i d e n t i c a l w i t h t h o s e o f FgT-40( Guan,1985). ~ s a x o f band El o f E-'-~X* t r a n s i t i o n o f UV s p e c t r u m o f h e x a h y d r o x y e t h y l p a r a r o s a n i l l n e c y a n i d e i s 208 n m . ~ m a x o f band B i s 278 n m . ~ p m x o f band R o f n - - 4 ~ * t r a n s i t i o n i s 316 n ~ . The p o s i t i o n o f a b s o r p t i o n band o f compound I I a r e i d e n t i c a l w i t h t h o s e o f I ~ T - 4 0 ( G u a n , 1 9 8 5 ) . F i e l d d e s o r p t m a s s s p e c t r u m c a n d e t e r m i n e a c c u r a t e l y m o l e c u l a r w e i g h t o f compound I I and FWT-40. Two p e a k s c o r r e s o n d i n g t o t h e h i g h e r m o l e c u l a r w e i g h t , 666 and 710, a r e d i s p l a y e d i n t h e s p e c t r u m o f FgT-40, b u t i t does n o t show i n t h e c a s e o f compound I f . The r e s u l t s p r o v e t h a t compound I I p o s s e s s e s h i g h e r p u r i t y t h a n FgT--40. s78

tO0

I O0-

in

j~

6e

el

~0

+

°I

i

Fig.l.Pleld

d e s o r p t m a s s s p e c t r u m o f compound I I

Thin layer The r e s u l t s

c h r o m a t o g r a p h y shows one s p o t formed by compound I T , b u t two s p o t s formed by FgT-40. p r o v e t h a t compound I I p o s s e s s e s h i g h e r p u r i t y t h a n FWT-40.

Fig.2.F~

d e s o r p t mass s p e c t r u m o f FgT-J40

F i g . 3 . ( 1 ) TLC o f 0 - 6 h y d r o x y e t h y l p a r a r o s a n i l l n e (2) TLC o f FWT-40 (3) TLC o f compound I I ~TNT-/40 i s t h e t r a d e m a r k o f HPR--CH p r o d u c e d by FgT I n c . .

cyanide

6th I n t e r n a t i o n a l M e e t i n g o n R a c h a U o n P r o c e s s i n g

407

DOSIMETEIC CHARACTERISTICS OF TWO LEUCODYES

I. Solution dosimeter Leucodyes are dissolved in polar solvents and used in determination of radiation dose. Compound I and compound II are used to prepare solution dosimeter. Such as: ( 1 ) DNSO s o l u t i o n dosimeter and 20% a c e t i c a c i d a q u e o u s s o l u t i o n dosimeter containing 0 . 5 mg c o m p o u n d I r e s p e c t i v e l y ; (2) mixture of triethylphosphate (TEP) a n d DgSO s o l u t i o n dosimeter containing 2 ~ / c o m p o u n d I I o r 2 ni~ FWT-40. Fig. 4 shows that peak value of absorption s p e c t r u m o f DHSO s o l u t i o n dosimeter and 20£ acetic acid aqueous solution d o s i m e t e r o f 0 . 5 -el c o m p o u n d I a r e 5 5 6 nm a n d 5 4 2 nm r e s p e c t i v e l y . Fig. 5 shows that the sensitivity and linearity o f DHSO s o l u t i o n d o s i m e t e r i s much b e t t e r than that of 20£ acetic acid aqueous solution dosimeter. Fig.4 and 5 indicate the effect of polar solvents on the characteristics of dose response. $ .

b

P

> i-

t

u~ z

I

n < u

u

P

& o

o

! I

s

i

Fig.4.Absorption spectrum of D~O solution dosimeter (a) and 21~ acetic acid aqueous solution dosimeter (b) containzng 0.5 ~ compound I respectively

,11

•

Fig.5.Curve o f d o s e r e s p o n s e o f DHSO s o l u t i o n dosimeter (a) and 20~ acetic acid aqueous solution dosimeter (b) containing 0 . 5 mH c o m p o u n d I r e s p e c t i v e l y

Fig. 6 shows the backgrounds of unirradiated solution d o s i m e t e r made o f I ~ S 0 ,TEP a n d c o m p o u n d I I ( a ) i s much l o w e r t h a n t h a t o f FWT-40 ( b ) a t t h e o p t i c a l w a v e l e n g t h f r o m 3 4 0 nm t o 5 0 0 nm. F i g . 7 shows that sensitivity of irradiated solution d o s i m e t e r made o f I~ISO, TEP a n d c o m p o u n d I I ( a ) i s a b o u t 6% h i g h e r t h a n t h a t o f 1~T--40 ( b ) . The p e a k v a l v e o f a b s o r p t i o n s p e c t r u m i s 6 0 5 um. F i g . 6 and 7 prove that the compound II possesses higher purity thanFWr-440.

lnf~

ion

'~nl~

, Goll

I "/nn

~

I

I f~lf~

w a v e l e n g t h (r~a) Fig.6.Comparison of backgrounds between compound II and Ftrr-40 Solution: DHS0 a n d TEP m i x t u r e ( 1 : 1 b y ~ c . )

~tnfl

w a v e l e n g t h (rim) Fig.7.Comparison of sensitivities between c o m p o u n d I I a n d FWT--40 o f 2 mM c o m p o u n d I I ( a ) o r FWT-40 ( b )

2. Film dosimeter Polyvinyl butyral (PVB) f i l m d o s i m e t e r i s made o f c o m p o u n d I a n d c o m p o u n d I I . and curves of dose response of the dosimeter are identical with those reported nfi1-Burgos,1983; HiUer,1984).

_

L

:

Absorption spectrum in references (Bue-

.

:

,

:

;

ii

I 4~.0

Fig.S.bbsorptlon spectrum ter of compound I

o f PVB f i l m

dosime-

/ 500

1 60U

Fig.9.Absorption s p e c t r u m o f PVB f i l m meter of compound II

I 70O

dosi-

408

GUAN XIANGRUI et o/

The p e a k v a l v e s o f a b s o r p t i o n s p e c t r u m o f PVB f i l m d o s i m e t e r o f compound I and compound I I a r e 550 am and 600 nm r e s p e c t i v e l y . F i g . I 0 shows t h a t l l n e a r l t y r a n g e o f c u r v e s of dos e r e s p o n s e o f PVB f i l m d o s i m e t e r s of compound I and compound I I a r e IOL-IOIGY.

/

0.; Dc~ S60.m

a

la

le

! 10 3

i

,

,

to t

! 1° 5

F i g . l O . C u r v e s o f dose r e s p o n s e of: PVB f i l m dos i me t e r s o f compound I ( a ) and compound I I (b) 3. O p t i c a l w a v e g u i d e d o s i m e t e r The s e n s i t i v i t y o f o p t i c a l w a v e g u i d e d o s i m e t e r o f compound I I i s much h i g h e r t h a n t h a t o f FWT--70* w h i c h h a s t h e same s o l v e n t s and t h e same c o n c e n t r a t i o n o f l e u c o d y e s . The new t y p e OWG-86 i s much more s e n s i t i v e t h a n FWT--70. A b s o r p t i o n s p e c t r u m and c u r v e s o f dos e r e s p o n s e o f 0WG-86 a r e r e p o r t e d by Zhmw~ ] ~ l h ~ a ( 1 9 8 7 ) . The r e s u l t s a l s o p r o v e t h a t compound I I p o s s e s s e s h i g h e r p u r i t y t h a n F~r--40. CONCLUSION Our l a b o r a t o r y h a s improved t h e s y n t h e s i s and p u r i f i c a t i o n me t hods of p a r a r o s a n i l i n e c y a n i d e and h e x a h y d r o x y e t h y l p a r a r o s a n i l i n e c y a n i d e . The s t r u c t u r e s of t h e p r o d u c t s h a v e be e n i d e n t i f i e d and t h e p u r i t y h a s b e e n a n a l y s e d . The r e s u l t s show t h a t compound I I p o s s e s s e s h i g h e r p u r i t y t h a n PWT-40. Two l e u c o d y e s h a v e b e e n p r e p a r e d on a l a r g e s c a l e and u s e d a s s o l u t i o n dosimeter, film dosimeter and o p t i c a l w a v e g u i d e d o s i m e t e r . V a r i o u s d o s i m e t e r s made o f our l e u c o d y e s s a t i s f y a l l t h e r e q u i r m e n t s f o r r a d i a t i o n dose m e a s u r e m e n t .

ACKNOWLEDGEMENT

R e s e a r c h I n s t i t u t e of Atomic Energy S c i e n c e o f Ch i na and I n s t i t u t e o f R a d i o l o g i c a l M e d i c i n e o f B e i j i n g a s w e l l a s B e i J i n g S h t y i n g R a d i a t i o n D e t e c t o r Works ha ve e v a l u a t e d two l e u c o d y e s . P r o f e s s o r Zha Z i y i n g , Wang J i n q i , Shen Wenxou and Sun Cunpu ha ve o f f e r e d v a l u a b l e s u g g e s t i o n s . Me would l i k e t o e x p r e s s our a c k n o w l e d g e m e n t s i n c e r e l y . REFERENCES B u e n f i l B u r g o s , k . E. and o t h e r s ( 1 9 8 3 ) . R a d i a t . P h y s . Cham. 22~ 3, 523. C h a l k l e y , L. ( 1 9 5 8 ) . U.S. 2 , 8 2 9 , 1 4 9 ; ( 1 9 5 9 ) . U.S. 2 , 8 7 7 , 1 6 9 . E l - a s s a y , N. B. and o t h e r s ( 1 9 8 2 ) . I n t . J . A p p I . R a d i a t . I s o t o p e s . 33, 641. Guan X i a n g r u i and o t h e r s ( 1 9 8 5 ) . J o u r n a l o f I n s t i t u t e o f C h e m i c a l D e fe nc e 2, 22. H a n s s e n , J . W. and o t h e r s ( 1 9 8 4 ) . R a d i a t . P h y s . C h w . 23~ 455. H a n t z s h , A. and o t h e r s ( 1 9 0 0 ) . C h w . B e t . 306. H a s s e a , J . W. and o t h e r s ( 1 9 8 4 ) . R a d i a t . Res. 97, 1" Eumpherys, K. C. and o t h e r s ( 1 9 7 9 ) . 1EEE T r a n s . N u c l . S c i . HS-26, 1, 1784. Humpherys, K. C. and o t h e r s ( 1 9 8 1 ) . IEEE T r a n s . N u c l . S c i . NS--28~ 1797. K r o n e n b e r 8 , S. ( 1 9 8 2 ) . AD-A 117308. K r o n e n b e r g , S. and o t h e r s ( 1 9 8 1 ) . S u c l . I n s t r . Meth. 190, 363. M c l a u g h l i n , W. L. ( 1 9 7 8 ) . " N a t i o n a l and i n t e ~ t i o ~ l s t a n d a r d i z a t i o n o f r a d i a t i o n d o s i m a t r y " V.1, IAKA 89. M i l l e r , A. ( 1 9 8 4 ) . IAEA-~J~ECDOC 321. Zhang Yuhua and o t h e r s ( 1 9 8 7 ) . C h a r a c t e r i s t i c s o f Newly D e v e l o p e d Model OWO 86 R a d i o c h r a m i c O p t i c a l Waveguide (OWG) Dosxmeter(~T~ge~r~e4 tQ ~ ~ ~4~J

* O p t i c a l waveguxde d o s i m e t e r c o n t a i n i n g FWT-40 made i n FWT I n c .

i s named FWT--?O.