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MÖSSBAUER STUDY OF RARE EARTH BONE UPTAKE
C. Kellershohn, J.N . Rimbert, D. Fortier, M. Maziere
To cite this version:
C. Kellershohn, J.N . Rimbert, D. Fortier, M. Maziere. MÖSSBAUER STUDY OF RARE EARTH BONE UPTAKE. Journal de Physique Colloques, 1979, 40 (C2), pp.C2-505-C2-507.
�10.1051/jphyscol:19792177�. �jpa-00218553�
lOURNAL DE PHYSIQUE
Colloque
C2,suppl&ment au n o
3,Tome
40,mars 1979, page
C2-505MOSSBAUER STUDY OF RARE EARTH BONE UPTAKE
It+ x I
C. K e l l e r s h o h n
.
J.N. Rimbert,
D. F o r t i e r and M. ~ a z i e r e +*Luboratoire de Biophysique, Facult6 de Mdden'ne Necker-Enfants-Malades, 156 rue de Vaugirard, 75015 Paris, Frmce.
'cormissariat
dL ' E n e ~ g i e Atomique, Ddpartement de BioZogie, Service Hospitalier Frdddric J o l i o t , H6pitaZ dlOrsay, 91406 Orsay, France.
REsum6.- L ' e x i s t e n c e d ' u n e f f e t Msssbauer d ' e m i s s i o n a p r e s f i x a t i o n d ' u n i o n t r i v a l e n t de t e r r e r a r e s u r l e s p a r t i c u l e s m i n e r a l e s de l ' o s , s o i t a p r S s a d s o r p t i o n " i n v i t r o " , s o i t a p r e s f i x a t i o n mdtabo- l i q u e " i n vivo", a Q t d m i s e e n Bvidence. L ' e t u d e d e s s p e c t r e s h y p e r f i n s o b t e n u s B 4,2K semble m o n t r e r que l ' i o n a d s o r b 6 s e t r o u v e au s e i n d ' u n e d o u b l e couche d e m o l 6 c u l e s d ' e a u d ' h y d r a t a t i o n d a n s un environnement d e g r o u p e s o x h y d r i l e s a n a l o g u e 2 l a s t r u c t u r e d ' u n h y d r o x i d e d e t e r r e r a r e .
A b s t r a c t . - The e x i s t e n c e of an e m i s s i o n ~ z s s b a u e r e f f e c t a f t e r u p t a k e t o a t r i v a l e n t i o n o f r a r e e a r t h on bone m i n e r a l p a r t i c l e s , e i t h e r by " i n v i t r o " a d s o r p t i o n o r a f t e r " i n v i v o " m e t a b o l i c u p t a k e , h a s been r e v e a l e d . S t u d y o f t h e h y p e r f i n e s p e c t r a o b t a i n e d a t 4.2K seems t o i n d i c a t e t h a t t h e a d s o r - bed i o n i s found w i t h i n two monolayers o f h y d r a t i o n w a t e r m o l e c u l e s i n a n e n v i r o n m e n t of h y d r o x y l g r o u p s s i m i l a r t o t h e s t r u c t u r e of a r a r e e a r t h h y d r o x i d e .
I n t r o d u c t i o n . - Rare e a r t h e l e m e n t s , a s w e l l a s t r a n - s u r a n i c e l e m e n t s , have an i m p o r t a n t p l a c e i n t h e f a m i l y o f "bone s e e k e r s " a l o n g w i t h a l k a l i n e e a r t h e l e m e n t s / 1 , 2 / . There a r e a p p a r e n t l y two forms o f bone u p t a k e of a l k a l i n e e a r t h s and r a r e e a r t h s : s u r f a c e a d s o r p t i o n on bone m i n e r a l p a r t i c l e s and i o n i c exchange. For t h e most p a r t , t h e f i r s t o c c u r s i n t h e c a s e o f r a r e e a r t h s and b o t h mechanisms o c c u r i n t h e c a s e o f a l k a l i n e e a r t h s / 3 , 4 / . We do n o t e x a c t l y know i n what form r a r e e a r t h s a r e f i x e d on t h e bone s u r f a c e . The c u r r e n t a s s u m p t i o n i s t h a t t h e y may a p p e a r a s h i g h l y i n s o l u b l e p h o s p h a t e s on t h e i n o r g a n i c bone s u r f a c e and t h a t t h e i r l o c a l i z a - t i o n mechanism may c o r r e s p o n d t o a d s o r p t i o n f o l l o w e d by a r e a c t i o n w i t h t h e p h o s p h a t e g r o u p s on t h e hy- d r o x y a p a t i t e s u r f a c e 151.
S i n c e bone m a t t e r i s a s o l i d s t r u c t u r e and s i n c e s e v e r a l r a r e e a r t h s p r o d u c e a n i m p o r t a n t Mzssbauer e f f e c t , we hope t o o b t a i n i n t e r e s t i n g i n f o r m a t i o n on t h e i r u p t a k e mechanism w i t h e m i s s i o n MEssbauer s p e c t r o m e t r y .
M a t e r i a l s and method.- We u s e d t h e 25.65keV t r a n s i - t i o n o f d y s p r o s i u m 161. E x p e r i m e n t s w e r e made on mice. A f t e r i r r a d i a t i n g 5 0 t o IOOmg o f Gd,O, w i t h a f l u x o f 2 . 5 x 1 0 ~ ' n . c m - ~ . s - ' f o r t h r e e d a y s , t h e l 6 ' ~ b produced was s e p a r a t e d from t h e Gd20, m a t r i x on a Dowex-50 exchange i o n r e s i n column 161, b e c a u s e g a d o l i n i u m i s t o x i c i n mice 171. C o n c e n t r a t e d i n a volume of 0.3m1, i t was i n j e c t e d i n t r a v e n o u s l y i n t o t h e t a i l s of t h e mice i n t h e form o f a n aqueous s o l u t i o n o f l 6 ' T ~ C I o r c h e l a t e l 6 ' ~ b HEDTA
( h y d r o x y e t h y l e n e d i a m i n e t e t r a c e t i c a c i d ) . T h r e e d a y s a f t e r i n j e c t i o n , t h e n.ice were s a c r i f i c e d and d i s - s e c t e d . T h e i r s k e l e t o n s were c u t i n t o f i n e p a r t i c l e s which were compressed i n t o p e l l e t s w i t h a d i a m e t e r
of 2cm and a t h i c k n e s s of 2.5mm. t h e r a d i o a c t i v i t y o f which may r e a c h 20mCi.
E m i s s i o n Mzssbauer s p e c t r a a r e p r o d u c e u s i n g s u c h a p e l l e t a s a s o u r c e a t room t e m p e r a t u r e o r a t h e l i u m t e m p e r a t u r e and a 50mg/cm2 Dy,O, p o l y c r y s t a l l i n e powder a s an a b s o r b e r a t room t e m p e r a t u r e . The v a l u e of 39cmls g i v e n by Wickman and Nowik I 8 1 f o r t h e s e p a r a t i o n between t h e two o u t e r l i n e s o f t h e Dy203 a b s o r p t i o n s p e c t r a a t 4.2K was used t o c a l i b r a t e t h e s p e c t r a o b t a i n e d a t h e l i u m t e m p e r a t u r e . R e s u l t s . - The e x i s t e n c e of a n e m i s s i o n Msssbauer s p e c t r u m a t room t e m p e r a t u r e h a s b e e n proved and i t s i m p o r t a n c e d i s c u s s e d i n p r e v i o u s p u b l i c a t i o n s whe- t h e r a f t e r " i n v i t r o " u p t a k e of I 6 ' ~ b o n bone 1 9 1 o r a f t e r " i n v i v o " m e t a b o l i c u p t a k e 1101. An e m i s s i o n
& s s b a u e r s p e c t r u m h a s a l s o b e e n r e v e a l e d a t room t e m p e r a t u r e by u s i n g t h e whole body of a mouse a s a s o u r c e a f t e r m e t a b o l i c u p t a k e o f r a r e e a r t h I l l / . However, t h e i n f o r m a t i o n o b t a i n e d on t h e e n v i r o n m e n t of t h e r a r e e a r t h atom i s q u i t e l i m i t e d b e c a u s e o f t h e e x c e p t i o n a l w i d t h due t o t h e r e l a x a t i o n e f f e c t s of t h e s i n g l e e x p e r i m e n t a l l 6 ' D ~ Mzssbauer l i n e a t room t e m p e r a t u r e 1121. On t h e o t h e r hand, t h e hyper- f i n e s t r u c t u r e o f a Dy p a r a m a g n e t i c compound, r e v e a - l e d a t h e l i u m t e m p e r a t u r e , depends on t h e n a t u r e o f t h i s compound and a n e x a m i n a t i o n o f t h e c o r r e s p o n - d i n g MGssbauer s p e c t r u m may p r o v i d e more a c c u r a t e
Article published online by EDP Sciences and available at http://dx.doi.org/10.1051/jphyscol:19792177
c2-506
JOURNAL DE PHYSIQUEi n f o r m a t i o n on t h e s t r u c t u r e i n w h i c h t h e r a r e e a r t h atom i s i n v o l v e d .
Figure I a r e p r e s e n t s t h e Dy203 a b s o r p t i o n spectrum a t 4.2K w i t h t h e source a t room temperature c o n s t i - t u t e d b y t h e lbl'Tb i n t h e i r r a d i a t e d Gd203 m a t r i x . Figures I b , c and d r e s p e c t i v e l y r e p r e s e n t t h e e m i s s i o n s p e c t r a a t 4.2K o f 16'Tb i n t h e i r r a d i a t e d Gd,03 m a t r i x , i n a n o n - r a d i o a c t i v e Gd(OH)3.H20 ma- t r i x and i n a n o n - r a d i o a c t i v e GdP0,.Sll,H2O m a t r i x , w i t h t h e absorber a t room t e m p e r a t u r e c o n s t i t u t e d by 50mg/cm2 o f Dy20,.
F i g . 1: a ) A b s o r p t i o n M k s b a u e r spectrum o f Dy,O a t 4.2K. Source : 16'Tb i n i r r a d i a t e d
G ~ , o ,
a t room t e m p e r a t u r e .
b ) Emission Mzssbauer specirum o f l 6 ' T b i n i r r a d i a t e d Gd,O, a t 4.2K. Absorber : Dy,03 a t room t e m p e r a t u r e .
C ) Emission M'irssbauer spectrum o f 16'Tb i n Gd(0H) ,.H20 a t 4.2K. Absorber : Dy,03 a t room t e m p e r a t u r e .
d ) Emission M'irssbauer spectrum o f 1 6 ' ~ b i n GdP0,.5, ,H,O a t 4.2K. Absorber : Dy,03 a t room Cemperature
.
Figures 2 a , b and c compare t h e e m i s s i o n s p e c t r a o b t a i n e d a t 4.2K f o r 1 6 ' ~ b r e s p e c t i v e l y i n Gd(0H) ,.H20, f i x e d " i n v i t r o " on bone powder / 8 / and f i x e d m e t a b o l i c a l l y " i n v i v o " .
D i s c u s s i o n . - The a b s o r p t i o n and e m i s s i o n s p e c t r a of f i g u r e s 1 a and b a r e i n a way s y m m e t r i c a l . However, t h e i r a s p e c t i s t h o r o u g h l y d i f f e r e n t because o f i m p o r t a n t phenomena o f r e l a x a t i o n which are probably due t o i r r a d i a t i o n damage and which a f f e c t t h e emis- s i o n spectrum o f 1 6 ' ~ b i n t h e i r r a d i a t e d Gd203 m a t r i x . However, we should n o t e t h e s i m i l a r i t y o f
t h e s e p a r a t i o n between t h e o u t e r l i n e s o f t h e two s p e c t r a . The e m i s s i o n s p e c t r a o f 16'l'b i n Gd(OH),.
H,O and GdP0,.51,,H20 a r e q u i t e s i m i l a r due t o t h e major r o l e o f t h e D ~ i o n s t r u c t u r e i n h y p e r f i n e ~ +
~ Z s s b a u e r s p e c t r a o f d y s p r o s i u m compounds. Nonethe-
l e s s , t h e y are somewhat d i f f e r e n t due t o t h e d i f f e - rence o f t h e i o n e n v i r o n m e n t , which i s n o t t h e same, e s p e c i a l l y i n terms o f t h e s e p a r a t i o n between t h e two o u t e r l i n e s .
I I
+XI +20 +lo 0 -10 4 -30
VELOCITY (cm.5-1)
Fig.2: a ) Emission ~ S s s b a u e r spectrum o f I 6 l T b i n Gd(0H) ,.H,o a t 4.2K. Absorber : Dy,O, a t room t e m p e r a t u r e .
b) Emission M'irssbauer spectrum o f l 6 'l'b f i x e d
" i n v i t r o " on bone powder. Absorber : Dy,03 a t room t e m p e r a t u r e .
C ) Emission ~ S s s b a u e r spectrum o f l 6 ' T b f i x e d m e t a b o l i c a l l y " i n v i v o " on bone. Absorber:
Dy203 a t room t e m p e r a t u r e .
However, w i t h i n t h e l i m i t s o f e x p e r i m e n t a l a c c u r a c y , t h e s p e c t r a o f f i g u r e s 2 a , b and c are q u i t e s i m i - l a r i n t e r m o f e i t h e r t h e i r a s p e c t o r t h e p o s i t i o n o f t h e l i n e s , e s p e c i a l l y t h e s e p a r a t i o n between t h e o u t e r l i n e s . I t c o n s e q u e n t l y seems t h a t t h e i o n o f r a r e e a r t h f i x e d on t h e bone i s l o c a t e d i n an e n v i - ronment o f h y d r o x y l groups s i m i l a r t o t h a t o f Gd 3+
i n Gd(OH)3.H20. Two f a c t s s u p p o r t s u c h a f i n d i n g :
.
t h e t r i v a l e n t i o n s o f r a r e e a r t h have a g r e a t t e n - dency t o be h y d r o l y z e d f o l l o w i n g , f o r example, t h e r e a c t i o n M ~ + + H*& MOH,++ ~ + / 4 / ;.
i t i s a c c e p t e d t h a t i n a n a q u e o u s s o l u t i o n two monolayers of h y d r a t i o n w a t e r e x i s t on t h e s u r f a c e o f t h e h y d r o x y a p a t i t e c r y s t a l / l 3 / .I n s h o r t , t h e s t u d y of t h e e m i s s i o n Msssbauer s p e c - t r a o f a r a r e e a r t h i o n , s u c h ~ y ~ + , seems t o show t h a t , a f t e r e i t h e r " i n v i t r o " a d s o r p t i o n on t h e s u r f a c e o f bone m i n e r a l p a r t i c l e s o r " i n v i v o " meta- b o l i c u p t a k e , t h e i o n i s found i n t h e two m o n o l a y e r s o f t h e h y d r a t i o n w a t e r o f t h e h y d r o x y a p a t i t e c r y s - t a l i n a n environment o f h y d r o x y l g r o u p s . Although d i s t i n c t , t h e e m i s s i o n s p e c t r a o f 1 6 ' ~ b i n
Gd(0H) ,.H,O and i n GdPO* .5,/,H,O a r e s u f f i c i e n t l y c l o s e s o t h a t t h e a s s u m p t i o n a c c o r d i n g t o which t h e bone s u r f a c e i o n i s bound t o t h e h y d r o x y a p a t i t e p h o s p h a t e g r o u p s c a n n o t be r e j e c t e d .
Acknowledgments.- T h i s work was p a r t l y s u p p o r t e d by t h e " F o n d a t i o n p o u r l a Recherche MGdicale F r a n s a i s e "
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