FARMACIA, 2008, Vol.

LVI, 3
THE LANTHANIDES: PHYSICOCHEMICAL
PROPERTIES RELEVANT FOR THEIR
BIOMEDICAL APPLICATIONS
CARMEN MARIA STURZA
1
*, RICA BOSCENCU
2
, VERONICA NACEA
2
1
Arsmedica 150 Aurel Vlaicu str, Bucharest
2
University of Medicine and Pharmacy !arol "avila
"e#artament of $nor%anic !hemistry, & 'raian Vuia str, Bucharest
*corres#ondin% author( carmen)stur*a+arsmedica)ro
Abstract
Over the past ten years a resurgence ! "nterest "n the #anthan"$es che%"stry has
&een nt"ce$, espec"a##y "n the &"%e$"ca# app#"cat"ns ! these e#e%ents' In th"s rev"e( (e
try t $e%nstrate that !r the &"%e$"ca# app#"cat"ns ! #anthan"$es the"r spectra#,
%agnet"c an$ cr$"nat"ve prpert"es are essent"a#'
The #anthan"$es represent the #argest natura##y ccurr"ng grup ! e#e%ents "n the
per"$"c ta&#e' They are h"gh#y e#ectrps"t"ve an$ react"ve %eta#s' Spectra# an$ %agnet"c
prpert"es ! #anthan"$e "ns are re%ar)a&#e' The"r cr$"nat"n che%"stry "s c%p#"cate$,
espec"a##y "n s#ut"ns hav"ng nt (e## $e!"ne$ stereche%"stry an$ uncerta"n cr$"nat"n
nu%&ers' *(ever, the c%p#e+es ! #anthan"$es an$ even the #anthan"$e sa#ts are gett"ng
%re an$ %re app#"cat"ns "n &"#gy, &"che%"stry an$ %e$"c"ne'
The che#ates ! #anthan"$e "ns are use$ as #a&e#s "n !#urescent "%%unassays'
The para%agnet"c an$ #u%"nescent T&
,-
. phsphat"$y#ch#"ne.c%p#e+es are un"/ue
ev"$ence !r the cat"n phsph#"p"$ "nteract"n' 0ater.s#u&#e 1a
,-
an$ Eu
,-
c%p#e+es
are e!!ect"ve "n $etect"ng sugars neutra# env"rn%ent an$ g#yc#"p"$s an$ phsph#"p"$s as
(e##' 2urther%re, #"terature $ata sh( that s%e s"%p#e #anthan"$e sa#ts an$ c%p#e+es
e+h"&"t an ant"tu%ra# act"v"ty'
A## a&ve revea# the actua#"ty ! the su&3ect'
Rezumat
4n u#t"%"" 15 an" a e+"stat reven"re a "nteresu#u" pentru ch"%"a #antan"$e#r, 6n
spec"a# pentru ap#"ca7""#e &"%e$"ca#e a#e acestr e#e%ente' 4n acest re!erat 6ncerc8% s8
$e%nstr8% c8 prpr"et87"#e spectrscp"ce, %agnet"ce 9" cr$"nat"ve a#e #antan"$e#r sunt
esen7"a#e pentru ap#"ca7""#e #r &"%e$"ca#e'
1antan"$e#e repre:"nt8 cea %a" #arg8 grup8 $e e#e%ente natura#e $"n s"ste%u#
per"$"c' Sunt %eta#e !arte e#ectrp:"t"ve 9" react"ve'
;rpr"et87"#e spectrscp"ce 9" %agnet"ce a#e "n"#r #antan"$e#r sunt
re%arca&"#e' Ch"%"a #r cr$nat"v8 este c%p#"cat8, 6n spec"a# 6n s#u7"e, $e
sterech"%"e $"!"c"#8 9" $e nu%ere $e cr$"nare "ncerte' Cu tate acestea, c%p#ec9" a"
#antan"$e#r 9" ch"ar une#e s8rur" au $"n ce 6n ce %a" %u#te ap#"ca7"" 6n &"#g"e, &"ch"%"e 9"
%e$"c"n8' Che#a7" a" #antan"$e#r sunt ut"#":a7" ca %ar)er" 6n "%unteste &a:ate pe
!#urescen78' C%p#ec9"" para%agnet"c" 9" #u%"n"scen7" T&
,-
.!s!at"$"#ch#"na !er8 $va$a
"nterac7"e" cat"n" %eta#"c". !s!#"p"$e'
C%p#ec9"" s#u&"#" 6n ap8 a" 1a
,-
9" Eu
,-
per%"t "$ent"!"carea g#uc"$e#r 6n %e$"u
neutru ca 9" a unr g#"c#"p"$e 9" !s!#"p"$e'
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FARMACIA, 2008, Vol.LVI, 3
Ma" %u#t, $ate $"n #"teratur8 cn!"r%8 act"v"tatea ant"tu%ra#8 a unr s8rur"
s"%p#e 9" ch"ar c%&"na7"" c%p#e+e a#e #antan"$e#r'
Tate acestea re#ev8 actua#"tatea su&"ectu#u"'
#anthan"$es
phys"c.che%"ca# prpert"es
INTRODCTION
One ! the cn!us"ns assc"ate$ ("th the grup ! #anthan"$es "s
cnnecte$ t the ter%"n#gy' The ter% <rare earth= (as r"g"na##y use$ t
$escr"&e a#%st any natura##y ccurr"ng &ut un!a%"#"ar +"$e an$ unt"# a&ut
1>25 genera##y "nc#u$e$ a#s c%pun$s as ThO
2
an$ ZrO
2
' By that t"%e the
ter% &egan t &e app#"e$ t the e#e%ents the%se#ves rather than t the"r
+"$es, an$ a#s (as restr"cte$ t that grup ! e#e%ents (h"ch cu#$ n#y
&e separate$ !r% each ther ("th great $"!!"cu#ty ?1, 2@'
The #anthan"$es c%pr"se the #argest natura##y.ccurr"ng grup "n
the per"$"c ta&#e' They are &e#ng"ng t A.th per"$'
The !"rst e#e%ent ! the A.th per"$, Cs BZCDDE, has the e#ectrn"c
cn!"gurat"n ! Fe !r DG ! "ts e#ectrns an$ the #ast e#ectrn "s p#ace$ "n
the ; she##' S"%"#ar#y, the ne+t e#e%ent, Ba BZCDAE has t( e#ectrns "n the ;
she##' The !"rst %e%&er ! the D$ trans"t"n ser"es,
DH
1a, n( appears ("th
the e+pans"n ! penu#t"%ate she##' *(ever, a ne( phen%enn appears
("th the e+pans"n ! the O she## "n success"ve stages !r% 1I e#ectrns t
-2 e#ectrns' The !urteen ne( e#e%ents, &et(een ZC DI an$ H2 are ca##e$
#anthanns, #anthan"$es r rare earth' They are very s"%"#ar t ne anther'
Th"s "s a trans"t"n ser"es ("th"n anther trans"t"n ser"es are s
ca##e$ "nner trans"t"n ser"es'
The"r prpert"es are s s"%"#ar, that !r% 1H>G, (hen J'Ka$#"n
"s#ate$ <yttr"a= (h"ch he thught "t (as the +"$e ! a s"ng#e ne( e#e%ent,
unt"# 1>5H, (hen #utet"u% (as $"scvere$, near#y a hun$re$ c#a"%s (ere
%a$e !r the $"scvery ! e#e%ents &e#ng"ng t th"s grup'
!ENERAL PROPERTIES
The %eta#s are s"#very "n appearance Be+cept !r Eu an$ L&, (h"ch
are pa#e ye##(E an$ are rather s!t, &ut &ec%e har$er acrss the ser"es'
Mst ! the% e+"st "n %re than ne crysta##graph"c !r%'
The e#ectrn"c cn!"gurat"ns ! the !ree at%s are $eter%"ne$ n#y
("th $"!!"cu#ty &ecause ! the c%p#e+"ty ! the"r at%"c spectra, &ut "t "s
genera##y agree$ that they are near#y a## ?Fe@ G!
n
D$
5
As
2
' The e+cept"ns areM
71
FARMACIA, 2008, Vol.LVI, 3
1' Cer"u%, !r (h"ch the su$$en cntract"n an$ re$uct"n "n energy !
the G! r&"ta#s "%%e$"ate#y a!ter 1a "s nt yet su!!"c"ent t av"$
ccupancy ! the D$ r&"ta#N
2' Ka$#"n"u%, (h"ch re!#ects the sta&"#"ty ! the ha#!.!"##e$ G! she##,
G!
H
N
-' 1utet"u%, at (h"ch p"nt the she## has &een !"##e$, G!
1G
'
*(ever, n#y "n the case ! cer"u% th"s has any %ar)e$ e!!ect n
the che%"stry "n a/ueus s#ut"n, (h"ch "s ther("se $%"nate$ &y the ,-
+"$at"n state, !r (h"ch the cn!"gurat"n var"es regu#ar#y !r% G!
1
BCe
III
E
t G!
1G
B1u
III
E' It "s nta&#e that a regu#ar var"at"n "s !un$ !r any prperty
!r (h"ch th"s G!
n
cn!"gurat"n "s %a"nta"ne$ acrss the ser"es, (hereas the
var"at"n "n thse prpert"es !r (h"ch th"s cn!"gurat"n "s nt %a"nta"ne$
can &e h"gh#y "rregu#ar' Th"s "s "##ustrate$ $ra%at"ca##y "n s":e var"at"ns
&et(een 1,52O !r Ce
III
an$ 5,IA1 O !r 1u
III
' The ra$"" ! 1n
III
"ns $ecrease
regu#ar#y !r% 1a
III
B"nc#u$e$ !r c%p#etenessE t 1u
III
' Th"s <#anthan"$e
cntract"n= ccurs &ecause, a#thugh each "ncrease "n nuc#ear charge "s
e+act#y &a#ance$ &y a s"%u#taneus "ncrease "n e#ectrn"c charge, the
$"rect"na# character"st"cs ! the G! r&"ta#s cause the G!
n
e#ectrns t sh"e#$
the%se#ves an$ ther e#ectrn !r% nuc#ear charge n#y "%per!ect#y ?-@'
Thus, each un"t "ncrease "n nuc#ear charge pr$uces a net "ncrease
"n attract"n !r the (h#e e+tranuc#ear e#ectrn charge c#u$ an$ each "n
shr"n)s s#"ght#y "n c%par"sn ("th "ts pre$ecessr'
On the ther han$, a s"%"#ar vera## re$uct"n "s seen "n the %eta#
ra$"", &ut "rregu#ar'
A cntract"n resu#t"ng !r% the !"##"ng ! the G! e#ectrn she## "s
nt e+cept"na#' S"%"#ar cntract"ns ccur "n each r( ! the per"$"c ta&#e
an$, "n the $ &#c) !r "nstance, the "n"c ra$"" $ecrease !r% Sc
III
t Cu
III
,
an$ !r% L
III
t Ag
III
' The "%prtance ! the #anthan"$e cntract"n ar"ses
!r% "ts cnse/uencesM
1' the re$uct"n "n s":e !r% ne 1u
III
t the ne+t cu#$ %a)e the"r
separat"n pss"&#e, &ut the s%a##ness an$ regu#ar"ty ! the re$uct"n %a)es
the separat"n $"!!"cu#tN
2' &y the t"%e * "s reache$ the 1u
III
ra$"us, "t has &een
su!!"c"ent#y re$uce$ t &e a#%st "$ent"ca# t that ! L
III
N that "s (hy th"s
%uch #"ghter e#e%ent "s "nvar"a&#y assc"ate$ ("th the heav"er #anthan"$esN
-' the tta# #anthan"$e cntract"n "s ! a s"%"#ar %agn"tu$e t the
e+pans"n !un$ "n pass"ng !r% the !"rst t the secn$ trans"t"n ser"es, an$
(h"ch %"ght there!re have &een e+pecte$ t ccur a#s "n pass"ng !r%
secn$ t th"r$' The "nterp#at"n ! the #anthan"$es "n !act a#%st e+act#y
cance#s th"s ant"c"pate$ "ncrease ("th the resu#t that "n each grup !
72
FARMACIA, 2008, Vol.LVI, 3
trans"t"n e#e%ents the secn$ an$ th"r$ %e%&ers have very s"%"#ar s":es
an$ prpert"es' Re$+ prcesses, (h"ch ! neces"ty enta"# a change "n the
ccupancy ! the G! she##, vary "n very "rregu#ar %anner acrss the ser"es'
The use ! ther%$"na%"c $ata BGE !!ers the "n":at"n energ"es' The
su$$en !a##s ! the th"r$ "n":at"n energy at K$ an$ 1u re!#ect the ease ("th
(h"ch these e#e%ents !r% K$
-,
B!
H
E

an$ 1u
-,
B!
1G
E'
CHEMICAL REACTIVITY
The #anthan"$es are h"gh#y e#ectrps"t"ve an$ react"ve %eta#s'
0"th the e+cept"n ! L&, the"r react"v"ty apparent#y $epen$s n the"r s":e,
s that Eu, (h"ch has the #argest %eta# ra$"us, "s the %st react"ve ?2, D@'
Treat%ent ("th (ater y"e#$s hy$rus +"$es, an$ the %eta#s
$"ss#ve rap"$#y "n $"#ute ac"$s, even "n the c#$, t g"ve a/ueus s#ut"ns
! 1n
III
sa#ts' The great &u#) ! #anthan"$e che%"stry "s ! the ,- +"$at"n
state, (here, &ecause ! the #arge s":es ! the 1n
III
"ns, the &n$"ng "s
pre$%"nant#y "n"c an$ the cat"ns are the typ"ca# ca#ss.a ac"$s'
A nu%&er ! tren$s cnnecte$ ("th the "n"c ra$"" are nt"cea&#e
acrss the ser"esN sa#ts &ec%e s%e(hat #ess "n"c as the 1n
III
ra$"us
$ecreasesN re$uce$ "n"c character "n the hy$r+"$e "%p#"es a re$uct"n "n
a#)a#"ne prpert"es an$, at the en$ ! the ser"es, L&BO*E
-
an$ 1uBO*E
-
,
thugh un$u&te$#y %a"n#y a#)a#"ne, can ("th $"!!"cu#ty &e s#ve$ "n ht
cncentrate$ NaO*' ;ara##e#"ng th"s change, the ?1nB*
2
OE
,
@
-,
"ns are
su&3ect t an "ncreas"ng ten$ency t hy$r#yse, an$ hy$r#ys"s can n#y &e
prevente$ &y us"ng "ncreas"ng#y ac"$"c s#ut"ns'
*(ever, s#u&"#"ty cannt &e s"%p#y re#ate$ t the cat"n ra$"us'
N cns"stent tren$s are apparent "n a/ueus, r !r that %atter nna/ueus,
s#ut"ns, &ut an e%p"r"ca# $"st"nct"n can !ten &e %a$e &et(een the #"ghter
<cer"u%= #anthan"$es an$ the heav"er <yttr"u%= #anthan"$es' Thus +a#ates,
$u&#e su#!ates an$ $u&#e n"trates ! the !r%er, are rather #ess s#u&#e an$
&as"c n"trates %re s#u&#e than thse ! the #atter' The $"!!erences are &y n
%eans sharp, &ut c#ass"ca# separat"n prce$ures $epen$e$ n the%'
A#thugh #anthan"$e che%"stry "s $%"nate$ &y the ,- +"$at"n
state, an$ a nu%&er ! &"nary c%pun$s (h"ch stens"&#y "nv#ve 1n
II
are
actua##y &etter !r%u#ate$ as "nv#v"ng 1n
III
("th an e#ectrn "n a $e#ca#":e$
cn$uct"n &an$, genu"ne +"$at"n states ! ,2 an$ ,G can &e &ta"ne$'
Ce
IV
an$ Eu
II
are sta&#e "n (ater an$ are strng#y +"$":"ng an$ strng#y
re$uc"ng respect"ve#y' T&
IV
presu%a&#y (es "ts e+"stence t the sta&"#"ty !
the G!
H
cn!"gurat"n'
73
FARMACIA, 2008, Vol.LVI, 3
The sta&"#":"ng e!!ects ! ha#! an$ c%p#ete#y !"##e$ she##s can &e
s"%"#ar#y "nv)e$ t e+p#a"n the ccurrence ! the $"va#ent state "n Eu
II
BG!
H
E
an$ L&
II
BG!
1G
E'
SPECTRAL PROPERTIES
The e#ectrn"c cn!"gurat"ns ! the #anthan"$es are $escr"&e$ &y
us"ng the Russe##.Saun$ers cup#"ng sche%e' Va#ues ! the /uantu%
nu%&ers S an$ 1 crrespn$"ng t the #(est energy are &ta"ne$ "n the
cnvent"na# %anner ?-, D, A@'
Because ! #anthan"$es G! e#ectrns, "ns are #arge#y &urr"e$ "n the
"nner cre, they are e!!ect"ve#y sh"e#$e$ !r% the"r che%"ca# env"rn%ent'
As a resu#t, the sp"n.r&"t cup#"ng "s %uch #arger than the crysta# !"e#$
B2555 c%
.1
c%pare$ t 155 c%
.1
E an$ %ust &e cns"$ere$ !"rst' Nte that
th"s "s prec"se#y the reverse ! the s"tuat"n "n the $.&#c) e#e%ents, (here
the $ e#ectrns are e+pse$ $"rect#y t the "n!#uence ! ne"gh&ur"ng grups
an$ the crysta# !"e#$ "s there!re %uch greater than the sp"n.r&"t cup#"ng'
E#ectrn"c a&srpt"n spectra are pr$uce$ (hen e#ectr%agnet"c
ra$"at"n pr%tes the "ns !r% the"r grun$ state t e+c"te$ states' 2r the
#anthan"$es the %st c%%n ! such trans"t"n "nv#ve the e+c"te$ states
(h"ch are e"ther c%pnents ! the grun$ ter% r e#se &e#ng t e+c"te$
states, (h"ch ar"se !r% the sa%e G!
n
cn!"gurat"n as the grun$ ter%' In
e"ther case, the trans"t"ns there!re "nv#ve n#y a re$"str"&ut"n !
e#ectrns ("th"n the G! r&"ta#s B"'e' !P! trans"t"nsE an$ s are r&"ta##y
!r&"$$en, 3ust #")e $P$ trans"t"ns' In the case ! the #atter, the ru#e "s
part"a##y re#a+e$ &y a %echan"s% (h"ch $epen$s n the e!!ect ! the crysta#
!"e#$ "n $"strt"ng the sy%%etry ! the %eta# "n' *(ever, "t has a#rea$y
&een p"nte$ ut that crysta# !"e#$ e!!ects are very %uch s%a##er "n the case
! 1n
III
"ns an$ they cannt there!re pr$uce the sa%e re#a+at"n ! the
se#ect"n ru#e' Cnse/uent#y, the c#urs ! 1n
III
c%pun$s are usua##y #ess
"ntense'
A !urther cnse/uence ! the re#at"ve#y s%a## e!!ect ! the crysta#
!"e#$ "s that the energ"es ! the e#ectrn"c states are n#y s#"ght#y a!!ecte$ &y
the nature ! the #"gan$s r &y ther%a# v"&rat"ns, an$ s the a&srpt"n
&an$s are very %uch sharper than thse !r $P$ trans"t"ns' Because !
th"s, they prv"$e an use!u# %eans ! character":"ng, an$ /uant"tat"ve#y
est"%at"ng, 1n
III
"ns' ?H, I@'
Neverthe#ess, crysta# !"e#$s cannt &e c%p#ete#y "gnre$' The
"ntens"t"es ! a nu%&er ! &an$s B<hypersens"t"ve= &an$sE sh( a $"st"nct
$epen$ence n the actua# cr$"nate$ #"gan$s' A#s, "n the sa%e (ay that
crysta# !"e#$s #"!t s%e ! the r&"ta# $egeneracy B2- , 1E ! the ter%s ! $
n
74
FARMACIA, 2008, Vol.LVI, 3
"ns, s they #"!t s%e ! the 2. , 1 $egeneracy ! the states ! !
n
"ns,
thugh "n th"s case n#y &y the r$er ! 155c%
.1
' Th"s pr$uces a !"ne
structure "n s%e &an$s ! 1n
III
spectra'
Ce
III
an$ T&
III
are e+cept"na# "n prv"$"ng B"n the u#trav"#etE &an$s
! apprec"a&#y h"gher "ntens"ty than usua#' The reasn "s that the part"cu#ar
trans"t"ns "nv#ve$ are ! the type G!
n
PG!
n.1
D$
1
, an$ s are nt r&"ta##y
!r&"$$en' These 2 "ns have 1 e#ectrn %re than an e%pty ! she## an$ 1
e#ectrn %re than a ha#!.!u## ! she##, respect"ve#y, an$ the pr%t"n ! th"s
e+tra e#ectrn "s there&y eas"er than !r ther "ns'
S%, Qy &ut %re spec"!"ca##y Eu an$ T& have e+c"te$ states (h"ch
are n#y s#"ght#y #(er "n energy than the e+c"te$ states ! typ"ca# #"gan$s' I!
the e#ectrns n the #"gan$ are e+c"te$, the pss"&"#"ty there!re e+"sts that,
"nstea$ ! !a##"ng &ac) t the grun$ state ! the #"gan$, they %"ght pass !"rst
t the e+c"te$ state ! the 1n
III
an$ then !a## t the %eta# grun$ state,
e%"tt"ng ra$"at"n ! character"st"c !re/uency "n $"ng s B!#urescence r,
%re genera##y, #u%"nescenceE' E+c"tat"n &y UV #"ght pr$uces
#u%"nescence spectra, (h"ch g"ves "n!r%at"n a&ut the $nr at%s an$
c.r$"nat"n sy%%etry ?I@'
MA!NETIC PROPERTIES
The #anthan"$es are trans"t"n %eta#s'
The %agnet"c %%ents ! the trans"t"n %eta#s "ns are assu%e$ t
&e $ue t e#ectrn sp"n n#yN as the r&"ta#s ccup"e$ &y unpa"re$ e#ectrns
are near the per"pher"es ! the "ns, "t "s genera##y suppse$ that the r&"ta#
angu#ar %%enta are /uenche$ &y e+terna# !"e#$s ?-, D@'
2r% the very h"gh va#ues ! the %agnet"c %%ents !r T&
,-
, Qy
-,
,
*
-,
an$ Er
,-
, "t "s c#ear that at #east !r these "ns the r&"ta# cntr"&ut"ns
%ust &e ta)en "nt accunt' S"nce the Gf /uantu% she##s are (e## sh"e#$e$
!r% uts"$e !"e#$s &y the e#ectrns ! the nCD an$ nCA /uantu% she##s, th"s
"s a reasna&#e cnc#us"n'
It "s a#s c#ear that there "s a %"n"%u% va#ue !r the %agnet"c
%%ent ! tr"va#ent "ns such as ;&
-,
, S%
-,
an$ Eu
-,
' Agree%ent &et(een
&serve$ an$ ca#cu#ate$ va#ues "s g$, e+cept !r S%
,-
an$ Eu
-,
'
The %agn"tu$e ! the separat"n &et(een the a$3acent states ! a
ter% "n$"cates the strength ! the sp"n.r&"t cup#"ng, an$ "n a## cases,
e+cept S%
,-
an$ Eu
-,
, "t "s su!!"c"ent t ren$er the !"rst e+c"te$ state ! the
1n
,-
ther%a##y "naccess"&#e, an$ s the %agnet"c prpert"es are $eter%"ne$
n#y &y the"r grun$ state'
75
FARMACIA, 2008, Vol.LVI, 3
Tab"e I
Magnet"c prpert"es an$ c#urs ! 1n
III
"ns "n hy$rate$ sa#ts
1n Unpa"re$
e#ectrns
Krun$
state
C#ur /
e
R BM
%0.1. 2 13
/
e
R BM
O&serve$
Ce 1BG!
1
E
2
4
DR2
C#ur#ess 2'DG 2'-.2'D
;r 2BG!
2
E
-
5
G
Kreen -'DI -'G.-'A
N$ -BG!
-
E
G
$
>R2
1"#ac -'A2 -'D.-'A
;% GBG!
G
E
D
$
G
;"n) 2'AI .
S% DBG!
D
E
A
5
DR2
Le##( 5'ID 1'G.1'H
BSE
Eu ABG!
A
E
H
4
5
Very pa#e p"n) 5 -'-.-'D
BSE
K$ HBG!
H
E
I
6
HR2
C#ur#ess H'>G H'>.I'5
T& ABG!
I
E
H
4
A
Very pa#e p"n) >'H2 >'D.>'I
Qy DBG!
>
E
A
5
1DR2
Le##( 15'AD 15'G.15'A
* GBG!
15
E
D
$
I
Le##( 15'A5 15'G.15'H
Er -BG!
11
E
G
$
1DR2
Rse.p"n) >'DI >'G.>'A
T% 2BG!
12
E
-
5
A
;a#e green H'DA H'1.H'D
L& 1BG!
1-
E
2
4
HR2
C#ur#ess G'DG G'-.G'>
1u 5BG!
1G
E
1
6
0
C#ur#ess 5 5
S These are the va#ues ! /e at r% te%perature' The va#ues !a## (hen the te%perature "s
re$uce$'
The h"gh.sp"n para%agnet"s% an$ #ng e#ectrn"c re#a+at"n t"%e
! K$
-,
have %a$e "t pre.e%"nent a%ng cntrast agents !r %agnet"c
resnance "%ag"ng ?>, 15@'
In a$$"t"n, para%agnet"c prpert"es ! #anthan"$e c%p#e+es are !
great "%prtance'
COORDINATION CAPACITY
Over the past years there has &een a great "nterest "n the che%"stry
! #anthan"$e c%p#e+es "n s#ut"n "n genera# an$ "n a/ueus s#ut"n "n
part"cu#ar'
Cr$nat"n che%"stry ! #anthan"$es "s /u"te $"!!erent !r% that
! the $.trans"t"n %eta#s ?12, H@'
Cr$"nat"n nu%&er "s genera##y h"gh an$ stereche%"str"es, &e"ng
$eter%"ne$ #arge#y &y the re/u"re%ents ! the #"gan$s an$ #ac)"ng the
$"rect"na# cntra"nts ! cva#ency, "s !re/uent#y nt (e## $e!"ne$ an$ the
c%p#e+es are #a&"#e'
Thus, "n sp"te ! ("$esprea$ pprtun"t"es !r "s%er"s%, there
appears t &e n cn!"r%e$ e+a%p#e ! a #anthan"$e c%p#e+ e+"st"ng "n
%re than ne %#ecu#ar arrange%ent' 2urther%re, n#y strng#y
c%p#e+"ng B"'e' usua##y che#at"ngE #"gan$s #ea$ t pr$ucts (h"ch can &e
76
FARMACIA, 2008, Vol.LVI, 3
"s#ate$ !r% a/ueus s#ut"n, an$ the c%parat"ve tenac"ty ! the s%a##
*
2
O %#ecu#e c%%n#y #ea$s t "ts "nc#us"n, !ten ("th cnse/uent
uncerta"nty t the cr$"nat"n nu%&er "nv#ve$' Th"s "s nt t say that
ther types ! c%p#e+ cannt &e &ta"ne$, &ut c%p#e+es ("th uncharge$
%n$entate #"gan$s, r #"gan$s ("th $nr at%s ther than O, %ust
usua##y &e prepare$ "n the a&sence ! (ater'
1anthan"$es, &th "n crysta##"ne c%p#e+es as (e## as "n s#ut"ns,
sh( var"a&#e cr$"nat"n nu%&er BAT'12E, "n (h"ch C'N' > "s the %st
pre$%"nant'
Cr$"nat"n nu%&ers &e#( A are !un$ n#y ("th very &u#)y
#"gan$s an$ even the cr$"nat"n nu%&er ! A "tse#! "s unusua#, H, I an$ >
&e"ng %re character"st"c'
Cr$"nat"n nu%&ers ! 15 an$ ver re/u"re che#at"ng #"gan$s
("th s%a## <&"tes=, such as NO
-
.
r SO
G
2.
, an$ are cn!"ne$ t c%pun$s !
the #arger, #"ghter #anthan"$es'
The stereche%"str"es /ute$, espec"a##y !r h"gh cr$"nat"n
nu%&ers, are "$ea#":e$ an$ "n %st cases apprec"a&#e $"strt"ns are "n !act
!un$'
DISCSSIONS
The %st "nterest"ng reve#at"n ! the "%prtance ! the che%"ca#
#anthan"$es "ns prpert"es B"n"c ra$"us, re$+ prpert"es, cr$"nat"n
capac"tyE "s !!er"ng &y the cancer $%a"n B1-E
1anthan"$es are cnsu%"ng React"ve O+ygen Spec"es BROSE,
(h"ch are %a"n#y +ygen $er"ve$ !ree ra$"ca#s an$ per+"$es, &e"ng the
%e$"atrs ! a nu%&er ! $egenerat"ve $"seases' The <ant"+"$ants= are
e+ce##ent su&strances use$ as $rugs !r the treat%ent ! $egenerat"ve
$"seases'
Tcpher#, ascr&ates an$ a nu%&er ! ther rgan"c c%pun$s
are cns"$ere$ as c%pnents ! such $rugs $ue t the"r prperty sh(n
t(ar$s ROS "n$uce$ $egenerat"ve $"seases' 1anthan"$es are cns"$ere$ !
h"gh ptent"a# &ecause ! the"r "nherent ant"+"$ant prpert"es ?12@ 1"u et' a#'
?1G@ !un$ 1aC#
-
e!!ect"ve "n "nh"&"t"ng s"#"ca "n$uce$ #"p"$ per+"$at"n !
#ung %acrphagus an$ s%a##er ! s%e ther #anthan"$e ch#r"$es "nh"&"te$
#"p"$ per+"$at"n "n rat #ung'
In !act, "t (as !un$ that a#%st a## #anthan"$es c%pun$s,
espec"a##y ch#r"$es, are /u"te e!!ect"ve "n "nh"&"t"ng *
2
O
2
%e$"ate$
per+"$at"n ! #"ps%es ?1D@'
77
FARMACIA, 2008, Vol.LVI, 3
Tab"e II
In"c ra$"us ! #anthan"$e BIIIE "ns
In"c ra$"us
BCN AE
S'O' III BA
5
E
Ce ;r N$ ;% S% Eu K$
1'52 5'>> 5'>I- 5'>H 5'>DI 5'>GH 5'>-I
1(er #anthan"$es
In"c ra$"us
BCN AE
S'O' III BA
5
E
T& Qy * Er T% L& 1u
5'>2- 5'>12 5'>51 5'I> 5'II 5'IAI 5'IA1
*"gher #anthan"$es
0hen tert&uty# hy$rper+"$e (as use$ t %e$"ate the
per+"$at"n, #(er #anthan"$es "nh"&"te$ (h"#e the h"gher #anthan"$es
pr%te$ per+"$at"n' Interest"ng#y, 1nBIIIE #st react"v"ty ! per+"$es
(hen they (ere &un$ t %e%&rane'
The #anthan"$e "nh"&"t"ng ROS strng#y "nv#ves the"r +yph"#"c"tyN
&ecause ! the ava"#a&"#"ty ! +ygen &"n$"ng s"tes n these !ree ra$"ca#s,
they are e+ce##ent targets !r 1n BIIIE cr$"nat"n' Th"s causes #anthan"$e t
p#ay the r#e ! ROS scavenger, there!re present"ng g$ ptent"a# !r
#anthan"$es as !uture $rugs'
The "nv#ve%ent ! #anthan"$e "n ROS re%va# "s /u"te $"!!erent
!r% the "nh"&"t"n ! ROS &y rgan"c c%pun$s #")e tcpher#,
ascr&ate, etc'
Mst ! the rgan"c ant"+"$ants scavenge !ree ra$"ca#s &y s"ng#e
e#ectrn e+change ("th ra$"ca#s an$ thus trans!r% the%se#ves "nt ra$"ca#s
hence act"ng as <pr+"$ants='
1n
-,
eas"#y "nteracts ("th e"ther !ree ra$"ca#s r per+"$es, &ut "s nt
trans!r%e$ as ra$"ca#s'
In a$$"t"n ("th the ant"+"$ant e!!ect, $"srgan":at"n "n the
cyts)e#etn "s a phen%enn ! c%%n ccurrence "n tu%ur ce##s an$
apptt"c s":e$ ce##s' M"crtu&u#es ! the cyts)e#etn un$erg sta&"#":at"n
an$ repa"r an$ th"s ccurs $ur"ng the act"n ! s%e ant"cancer $rugs #")e
ta+#' Qep#y%er"sat"n ! the cyts)e#etn "s ne ! the %st re#evant steps
"n the appts"s prcess'
1anthan"$e c%pun$s have &een sh(n t "n!#uence the sta&"#"ty
! %"crtu&u#es ?1A, 1H@, %"+e$ #anthan"$e c%pun$s ?1A@ "ncreas"ng the
a%unt ! r$er#"ness ! %"crtu&u#es "n ;AMCI2 ce##s'
Other sc"ent"sts ?1H@ !un$ $"!!erent #anthan"$es sh("ng $"!!erent
&ehav"urs an$ th"s (as ascr"&e$ t the s"%"#ar"ty ! 1n BIIIE pre$%"nant#y
("th Ca
2,
r the s"%"#ar"ty ! 1n BIIIE ("th Mg
2,
'
78
FARMACIA, 2008, Vol.LVI, 3
Is true that 1n
-,
"s very s"%"#ar t Ca
2,
"n aspects #")e s!tness,
cva#ence ten$ency an$ re$+ prpert"es' 1n
,-
an$ Ca
2,
"ns are strng
1e("s ac"$s, have a #( cva#ence ten$ency an$ neg#"g"&#e re$+ prpert"es'
Tab"e III
;rpert"es ! Ca
2,
an$ 1n
-,
;rperty Ca BIIE 1n BIIIE
E#ectrn"c
cn!"gurat"ns ! "ns
?Ar@ ?Fe@
Cr$"nat"n nu%&er A.12
A r H !avure$
A.12
I r > !avure$
Cr$"nat"n ge%etry *"gh#y !#e+"&#e *"gh#y !#e+"&#e
Qnr at% pre!erence S 5UNUS 5UNUS
In"c ra$"us BA
5
E 1'55.1'1I BC'N' A.>E 5'IA.1'22 BC'N' A.>E
Type ! &n$"ng Essent"a##y e#ectrstat"c Essent"a##y e#ectrstat"c
*y$rat"n nu%&er A I r >
0ater e+change rate
cnstant Bs
.1
E
D'15
I
D'15
H
Q"!!us"n ce!!"c"ent 1'-G 1'-5
Crysta# !"e#$ sta&"#":at"n Nne Neg#"g"&#e
SCa
,2
an$ 1n
-,
are c#ass a acceptrs r hard ac"$sN !r% %st sta&#e c%p#e+es ("th
#"gan$s cnta"n"ng N, O r 2 $nr at%s'
Ca
2,
"n (as !un$ t $esta&"#":e %"crtu&u#es, cntrary t Mg
2,
'
The #(er #anthan"$es &ehave$ %re #")e Ca
2,
, &ecause ! the"r
#arger s":e an$ hence the prpens"ty ! e+h"&"t"ng re#at"ve#y h"gher
cr$"nat"n nu%&er'
*eav"er #anthan"$es #")e T&, Qy, *, &e"ng s%a##er "n s":e, &ehave
%re #")e Mg
2,
, hav"ng a greater ptent"a# !r strengthen"ng the
%"crtu&u#es ?1-@'
A#s, 1n
-,
, (hen a$%"n"stere$ "n h"gh $ses, &ehaves #")e Mg
2,
supprt"ng the assc"at"n ! tu&u#"n' *(ever, (hen a$%"n"stere$ "n h"gh
$ses, the 1n
-,
"nter!eres ("th the asse%&#y &y $"strt"ng the prte"n
cn!r%at"n, a#ter"ng crss#"n)"ng an$ cnse/uent#y $esta&"#":"ng the
p#y%ers'
The c%p#e+es ! #anthan"$es are gett"ng %re an$ %re
app#"cat"ns "n cancer therapy, espec"a##y thse $er"ve$ !r% p#y
Ba%"ncar&+"#"cE ac"$s' The !r%at"n cnstants ! these che#ates are ! the
r$er ! 15
25
t 15
2D
, (h"ch ena&#es the% t re%a"n "ntact (h"#e $"!!us"ng
"nt e+trace##u#ar spaces ("th rap"$ c#earance thrugh )"$neys' Que t the
h"gh ther%$yna%"c sta&"#"ty an$ e+tre%e )"net"c "nertness ! these p#y
79
FARMACIA, 2008, Vol.LVI, 3
Ba%"ncar&+y#atesE ! 1n BIIIE, the "ntact e+cret"n ennances, there&y
#(er"ng cns"$era&#y the &$y retent"n ! che#ate$ 1n BIIIE c%p#e+es
?1I, 1>@'
The &"n$"ng s"tes ! the &"#g"ca# su&strate (h"ch are pre!erre$ &y
1n BIIIE !r c%p#e+at"n "nv#ve $nr s"tes OV2UC#UNUS' The "nherent
strng +yph"#"c"ty ! the #anthan"$e causes the "nteract"n, pre!erre$
&"n$"ng s"tes &e"ngM COO*, O* Bphen#"cE, O* Bhy$r+y#"cE, O Bcar&ny#E,
N Ba%"n, "%"$, "%"nE, S Bsu#phy$r"#E' N"trgen su#phur $nr s"tes ! the
&"%#ecu#es a#s enter "nt c%p#e+at"n, (hen 1n BIIIE un$erges
che#at"n' The #a&"#"ty ! the #anthan"$e c%p#e+es, the"r strng
+yph"#"c"ty, the very !ast e+change react"n, the nn$"rect"na#"ty ! the
#"gan$ &n$ an$ vary"ng cr$"nat"n nu%&er, a## cntr"&ute t(ar$s the
#anthan"$e "nteract"n ("th &"%#ecu#es'
The "n"c s":e ! 1n BIIIE var"es !r% ne #anthan"$e t antherN "n
a$$"t"n, the "n"c s":e ! a part"cu#ar #anthan"$e "n var"es s"gn"!"cant#y
("th the cr$"nat"n nu%&er'
S%a##er s":e ! che#at"ng &"%#ecu#ar #"gan$ can even su"t #arger
#anthan"$es, ("th #(ere$ cr$"nat"n nu%&er an$ can !r% sta&#e che#ates
("th #arger &"%#ecu#es' Th"s can e+p#a"n the $"!!erent cr$"nat"ng p(er
Ban$ a#s the"r &"#g"ca# &ehav"urE ! $"!!erent #anthan"$es un$er $"!!erent
phys"#g"ca# cn$"t"ns'
It "s c#ear that ver the past years B25.2AE there has &een a great
"nterest "n the che%"stry ! #anthan"$es, "n a/ueus s#ut"n "n part"cu#ar'
The prpert"es ! the #anthan"$es "ns "n a/ueus s#ut"n are ! a great
"%prtance, nt n#y sc"ent"!"ca##y &ut a#s &"#g"ca##y an$ %e$"ca##y'
REFERENCES
1' A'W'Kschne"$er an$ 1' Eyr"ng X*an$&) ! the ;hys"cs an$
Che%"stry ! Rare Earths, 1>HI, v# I , Nrth.*##an$, A%ster$a%
2' N'N'Kreen($ an$ A'Earnsha(XChe%"stry ! the E#e%ents,
secn$ e$"t"n, E#sev"er, 255A, 122H.12G>
-' J' ;' Quran$ an$ B' Quran$ XIntr$uct"n t a$vance$ Inrgan"c
Che%"stry, 1>H2, 1ng%an Krup 1TQ, 1n$n, 11>H.125-
G' Q'A'Jhnsn . ;r"nc"p#es ! 1anthan"$e Che%"stry, . )!hem) 7d)
1>I5, DH, GHD.GHH
D' S'Cttn . 1anthan"$es an$ Act"n"$es, O+!r$ Un"vers"ty ;ress,
1>>1
A' Qu%"tru Neg"u . Ch"%"a cuant"c8 a c%&"na7""#r c%p#e+e,
E$"tura Tehn"c8, Bucure9t", 2555
80
FARMACIA, 2008, Vol.LVI, 3
H' 2'A'*art X C%prehens"ve Cr$"nat"n Che%"stry, v#' -,
;erga%n, O+!r$, 1>IH
I' N' Sa&&at"n", M' Kuar$"g#" an$ J'M'1ehn . 1u%"nescent #anthan"$e
c%p#e+es as phtche%"ca# supra%#ecu#ar $ev"ces, !oord) !hem)
8ev), 1>>-, 12-,1.2, 251.22I
>' I'W'*e%%"#a, T'Stah#&erg, ;'Mttva%'.<B"ana#yt"ca# App#"cat"ns
! 1a&e#"ng Tehn#g"es=, 0a##ac Oy, Tur)a, 1>>D
15' K'Math"s. "n <Rare Earths= ;uche an$ ;' Car BE$s'E, E$"tr"a#
C%p#utence, S'A'Ma$r"$ 1>>I, 2ID
11' M' F 1", 2'L Zhang, J' Z' N", ,,E!!ect ! #anthan"$e "ns n the
phase &ehav"r ! $"pa#%"ty#phsphat"$y#ch#"ne %u#t"#a%e##ar
#"ps%es=, .) $nor%anic Biochem'1>>G, D-, 1->.1G>
12' 2'Arnau$.Neu, S#ut"n che%"stry ! #anthan"$e %acrcyc#"c
c%p#e+es, !hem)6oc)8ev#, 1>>G, 2-, 2-D.2G1
1-' N'M Su$h"n$ra, M'A Kagnan", I'M' Qev", R'S'Shu)#a. B"#g"ca#
an$ C#"n"ca# Aspects ! 1anthan"$e Cr$"nat"n C%pun$s,
Bioinor%anic !hemistry and A##lication, 255G, 2, -.GN 1DD.1>2
1G' F' 1"u, R' 1", J'Chen, R' 1", W' 0ang, E!!ects ! 1a, Ce, L an$ T&
"ns n 2ree Ra$"ca# Me$"ate$ ;er+"$at"n ! *u%an Erythrcyte
Me%&rane, .ournal of rare earths, 2555, 1I, BGE, -2D.-2I
1D' W'0ang , R'1", L'Cheng an$ V' Zhu, 1anthan"$es.the !uture $rugs,
!oord)!hem)8ev 1>>>, 1>5, 2>H.-5I
1A' L'L' Sng, L'Z' Fu, B"#g"ca# e!!ects ! rare earth prte"n
c%p#e+esM "n!#uence ! #anthan"$e "ns Eu
-,,
T&
-,
n secn$ary
structure ! ca#%$u#"ns. Bios#ectrosco#y, 1>>>, D, BAE, -H1.-HH
1H' C'St, ;'*'R$r"gues an$ O' Mnaster", Ca#c"u% an$ ga$#"n"u%
"ns st"%u#ate the KT;ase act"v"ty ! pur"!"e$ ch"c)en &ra"n tu&u#"n
thrugh a cn!r%at"na# change, Biochemistry, 1>>A, -D B25E,
A--H.A-GG
1I' S'N'M"sra an$ W'Jhn, Q"!!erence an$ C%parat"ve A&srpt"n
Spectra an$ 1"gan$ Me$"ate$ ;seu$hypersens"t"v"ty !r G!.G!
Trans"t"ns ! ;rB###E an$ N$B###E . App#'Spectrsc'Rev' 1>>-, 2I,
2ID.-2D
1>' S'N'M"sra, K Ra%chan$r"ah, M'A Kagnan", M'In$"ra$ev" an$ S'
Shu)#a, A&srpt"n Spectra# Stu$"es Inv#v"ng Gf.Gf Trans"t"ns as
Structura# ;r&e "n Che%"ca# an$ B"che%"ca# React"ns an$
C%ps"t"na# Qepen$ence ! Intens"ty ;ara%eters . A##l)
6#ectrosc) 8ev), 255-, 2-, G--.G>-
81
FARMACIA, 2008, Vol.LVI, 3
25' M'I#"e, Q'C#tuc, Q'Ba#a#au, R'Bscencu, Q'1'Bacn", Ana#ys"s !
2#urescence. Scatter"ng !r Certa"n Nuc#eprte"n Ter&"u% che#ate
c%p#e+es. 8evista de !himie, 255D, DAB12E, 122A.-2
21' M'I#"e,V'2ugaru, Q'1'Bacn", Q'Ba#a#au, R'Bscencu, 2#urescence
Resnance Energy Trans!er an$ 1"ght Scatter"ng Stu$y !
Irrevers"&#e QNA Cn!r%at"na# Change "n the ;resence ! a
Ter&"u Che#ate .8evista de !himie, 255D, DABGE, -DD.I
22' O'A#ptur) et a#', 1anthan"$e c%p#e+es as !#urescent "n$"catrs !r
neutra# sugars an$ cancer &"%ar)ers, ;NAS, 255A, 2A, >HDA.>HA5
2-' F'F"a, J';'*ausha#ter an$ K'0 2ar"s, Upcnvers"n !r% a/ueus
phase #anthan"$e che#ates .-ett)9#t' 255D, -5B1-E, 1AHG.1AHA
2G' I'Wstva, K'M%e)v,T'T:anva an$ M'Wara"vanva .Synthes"s,
Character":at"n an$ Cytt+"c Act"v"ty ! Ne( 1anthanu%
C%p#e+es ! B"s XCu%ar"nes . Bioinor%anic !hemistry and
A##lications, 255A, 1.>
2D' S';'Ba&a"#v, 1anthan"$e para%agnet"c pr&es !r NMR
spectrscp"c stu$"es ! %#ecu#ar cn!r%at"na# $yna%"cs "n
s#ut"n, J)Pro%) :ucl) Ma%n) 8eson) 6#ectrosc', 255I, v#' D2, 1.21
2A' 0'W'0ng, F' Zhu, 0'F' 0ng.Synthes"s, structure, react"v"ty an$
pht#u%"n"scence ! #anthan"$eBIIIE %nprphyr"nate
c%p#e+es=, !oordination !hemistry 8evie;s, 255H, 2D1, 2-IA.
2->>
82