Iffiion

CIgrI
Iffiion
lntroduction
Chapter 1
r.1
Chentstry of Ur.rtum
chdical !ro!.nis of stirid4 .xhibn vsiabL cb@t.istics Fuiths
notiHble di$ioilditid 6 obwcd b.twed light ond hervv a.tinid6
10
ttal
B@se of !€nial detocdirrdon oflorbit ls in liSbt* &tini.Lgs, 5t.leEoN &quirc
ilEedl nate ,nd tt t a.tinidcs &oodtat W.i.l .l@tuic ed nagtetic
p@perti6. h m.EbeB of fist hltf of &tinidc sdie vaLnc. .LcE!6 of ?t' 7P dd
otiLb .le 8!t 68rscd in chdicsl bondinS dog tith i|e 5J v6le@
eldros. Th. 5/cldns of e i.ohrql rrod bavc .! dtit l esdd mndrE ,=3
6d
ed rhcir Erclvilg s!.Gd .roud rbc neL{5 it cao.l to th. !F.d of liSb Ele.u!6 in
a elid @ q'po6cd lo b. Fnituy !h.r.d by .vc.y trotlr oryosilc lte $lid Du? !o
this fa.r tbc Fobdble rclc of l!* .l@tu6 in ch.Ei€al bolding b@G hiCL fte
rlbtivistic 4oti@ .nd th. cl6td4l6tu intdi.{ion of 5/cl4ue6 {ith a.b ott r
ed also wil[ othd olccmB idlucor. thc bondinS ftjl .nlr&rqislc pn?env of
&iinid6
i5
aposiblc,fda!ang.ofori&tion 3t
ei!
liSit r4ti!rda.
Th. dcneep of valde .l4roN fton 6d to 5/ obitds i!c@6 the .ucl4
*racdon in h4vid &tinid6. thi! i! thc |!en for the l@dlzdiot ofl.le.tros ed
h€@ llse @tiddes hale a sotuwhar mmionic division of oxidatid state.
As actinitlts
My
hav. diffeent oridltio! !l!la3, s.vcral
ligdd! cd
with actinidd. Codplcx6 ,nd conPoundr of etididA arl3i!
Actidd.s p6s hiS! c@rdin tion Dmb.6 wbd bo!.led
. lrgc idic aiz. of &tinftL.
. EiEicl-tto c efitity dE io +3 !o +6 foEsl dn86
Mi5!.n Nazii
PhD
Dis.rt tion
fm
@lplexcs
I uiqe chdistry.
i! codpls\es. This
chapter
htroduction
1
. AE ability ofa crqts nuD6€. of !tld@ shcl dbitab for bonding
Dlp@diDr upo.
$. fdor!
fom @bpl*s d.r:l€M
in
Iite ioric
ait ed
t[. Ionoei4 ddq
cblrg. of a.li!id6, th. tdd.ncv to
of th.
difi@t ori&do.
sta&s:
N4).Mo:')M* rMo:
Nucl.5 t clnoloSy is b!$d o! lrturnuy ecdrilg ..dio*rivc
t!.
dddts lik! l@id
El4ttolic lhielding of 5/
of &tid.!.s is !e cfrcidt bt cLdrco! of tu .!d ?P thd thal of 4t
eleroB of larthdi&s by thcir 6t ed 6p cLdrons. SPatial e4cNiotr of slorbids is
rh@f@ I{gd lbe tboe of 4J Lnth&id. otbitsls. A@rdi!8ly a sdEll .trdgy
umim
de!o6
is
fourtb eLmot of thc a.tinide saies.
difflMe is FB@i ir
clc.dolic @ofisMtioB
a a c6ult
r atilidar.
@nfigur*ions dd thgl
po$iblc for
tdt
1.13 Er|l-lG olunnlun
rlalt
Iv6
of is.rops of
of lvailability,
boiope!
d eplc
|
ufuim @ giv.o in Tablc l.l.
Misb.rr Ndn, PhD Dhs.rt tion
of 5l'7t'rd,l
5f "-'6d1?
choic. of ondldon stltes i3
Introduction
Chapter 1
Tonh 1.1
Half-liv6 of
U6jm
i$hD€6
1.1,4 Occllrtnce olu.rdum
lalf lif. of ufuiun i$toF dd is.topic 6rios cl)@pod lo ay 3Pei6c d of
ciitL thc age of .oith 6 be fr.d dlc ro i!. milut qudtity of Ddiun, Penr
ldly ev.rywheE in cti, soil eld wrllr I. EMich.d d.?.siB of u@iu t&t in
AGudia C'""n- Nuibia. Solrh Atric! &d USA 'z. U@iun do.$ not @u in
Th.
nantr itr iela&d stare..dF ir cists in
fm
of tu ond. (..8. pit hblcn.le)
dd
in a
fom of @dpLx sdt (c.8. cdtrotit ). rtc aEns! oi6!*id of !@im in t!€
c.nht st is .pForiMtely 2 p.rtr pd nilion. ft b .ls unifornly dis!.is.d in
sqt r, enadn its o@ftarid is alom 3.1 rglrr Gt- Ar sq.td is p|!gt i! a
Misb:n Nzzi. PhD
Dsrado!
Chapter
Introduction
1
o! thit pl,r!€r 6. .!tiF |lloul of uruiu pr6dl i! s e'&r B
6 Thu lh. (){td e the @logical $d
ahosr loOO iiG to t[.t of .arth's dt
piololgerl rew6 of lruiu Scidlsls N looling forwlrd ro fird I chctpet
t cbnolo$r fd the t@vdy of utldm Aod ()c.@. Olving to th* iniosios tnd
conid.ing irs dvirc!@ rl ire6.rs n ! .ssati.l io d.tdEinc umi@ la'15 in s
lESc quarlity
r.lj
Aqueoc
chotltlt
of
utuirE
Brcltt si6 of bydtobric dd @ldintdm Ee66 @Plic!r. tlc u@i@
ch.ni.ry in aq!.N Dcdi@ Ihw fa.td sult in thc fdlulion of pobodic is
und4 suitable cnviromnt'.
Thc @in hrdrolrtic products of uroyl
d
uo,llo/Jl,uo,f:
i@ @ ndiitr@Lrar conpl':g
suc!
a
uo,lovol\' 'ea.
1.1.6 Ey.lblFb
Tbc
ri.Nid
of
ufuiu
3alt3
in
aq@u elutia
M" + H,o e M(o )r'v
Rd6.
i!.
grh
by th. fouosirg
O
cqlrtio!.
l)
Cte86 oD mt l &d
cn6t of hydnlysis, TFld of Lldroly$ of Umiu!! $luti@
of poton in th.
iodic ndii afi6r
pEs6
+H'
is
of Dc$l i! cdled bldrclysis.
u* <uo:'<u+
N.!uE of th. Pl.dlct of ib. Ltdolyiic @.ti@ dlFr4r on odditia liL PB &d
r.dFln|rc of elurjo6. Srrdi6 q.rdi.8 tb. htd@lFi6 of |miu i6 i! .qEu
o.dim hav. b.a qondet d by vsioB c9.@h6. A wid. tug. of f@ul& lor
Mbb.h Nazlr,
PhD
Dl$ertadon
Chapter
Introduction
1
th. hydrcl'lc ?r.ducts of ufuiuD. d diffeent Pg ru94,
Hldrcly6ir or
ufuiu (I9
solsri@
Flducls
polrdic ipeis UtU(o1),11" e
upJOEI in ufuy' slutid
h8ve
b..n eport!.d.
u(on)'in fffi n P " ed
produed. PobEedc
hlvc ben mtion
iols U,oi ,
al
U
bie! pH
'oi
d by Suad '0
4d
Oplicd
irvesrigariN of u&yl ion slutioB Lad wood[cad.t al- to oncludc tbat diE€ric
sF.i6 e 6e hydFlyic prodrcts rt. Sls rat of bydolytic polt* ,.!ctio8
cEet€s difflculty in
.chiding .qlilibdum, Coft.qEnily, htdrolysed @mpdldr in
ufui@ elutioB cMot bc .*di&d by forcltio@Eic l'6u!!!mt!. Al!.
spec@oto@tric mthod c..trot difi.Mtiate tb. v{i.ty of h}dDlttic aPei.s ol
&y @iurn elution, Tbcs f!c16 e Elpo.sibL fd ircosbteav ir r.Frdng thc
b.havid
oa
UfuiM
in
elutioN.
1.1.7 dd.tioD 5!rre.
Th@ @ fou qidrtion
(Iv) ed (vD
e
tb.
Mt
umim (ID s. Erd
seiun i... (m). (m, (v) sod (\at) Andg lh.m
ID..q@u sluti@ of
ond.d@ 5t.r6 of
statcs or
slabL
'@i@
y ond'?cd !o (I\l) ond.dm 3raG, sith th.
Wal.r dd o{td btdrolytic
onFu&,
disptpni@a1!
El.e
ult im(v)
of hydotcn
i o @i!s(Iv)
.nd Orl) valo€ 3r!rB. E{E!!Ely skbl. and disF..d pdnicl€ of @irir. F@
in iFeous @Lx @ in +4 ondltior rtat $d wb.n thtu vdcne st tc ch!n86 into +6
ondadd 3nic, thly
te@ $l!bl.
in aqu@us mediud.nd thdforc, il
1.1-7.1
gqd
i!'! ei.L
sP@d
Uruiu
it .atilt slublc
in filsh w.td, Minc tat r sd
wala,
(\rD
u'
El@tFlnic Educdon of
Ue d U+ yi.ldr rld
colorftd solutid of
ofuiu
(Itr)
U' &d th.! flally ilto
u& . Thi! indier.r GralL r!t@ of +3 odolid st{. D€G!, i! pn d
U+ sluti@
,wbcn
Misbah NazL, PhD
dp6€{t (' .n, .sny 8ct oridizld inlo
Dl6.rEtion
Chapter
Introduction
1
renperarur my st bili4 riiv.L.t .r.r. of
p*sfitl idrcilg
agrdB. Crti*.Ioenphic
utui@ @) @DFUlds
otrnior c
bNe b@n us.d to study
t@iud i! slurioB
tahliqE
11,
Tttcsc
'.
tt12u+
t travalc s|at of u@iun vs 66l cportld by EphDib ad M.a.r in 1933
rr.
T!. most id..l .oordiori@ nuha fd utuim (m c.Epld6 is 8. In ehrjo6,
The
Ue f(fu cdplcB
b@i!g @rdirntid !umh.. of 8. IAc ford.ti@ of .n bte
cdpLx€ ol utuim h t€travddt 3t t .ltow! the du|ctior of the Gt l ios ftom
aq!@us solulioo, PrDtr MSnetic
sugCest thc
cooldin$on
lurb.r
ts.m@
studies
of
U*
coEplerca in
slutio!
of 9 t.
U'
Lr.73
Tb. oxo
io
of
umim
in
p6rd.Lot orid,alid stat
is i&ltitrGd
s
UO; .
A.ltlagh
dd .lir!.oponiooalet irto (M &d (vD oxrdaid !t!r.s of ur.riuD, yct
.rt6tllogaphic '6, polsogFpbic " rnd infilrd 3$di.s r! indicare rbar n is lrabL in a
pH tu8e of 2 to 4. lts elunon in DMSO ir El.tiv€lt strbL thd ir orh6 elE.ts'z
it is not $abl.
u-
1.1.7.4
Ihft
ir r htg! veirtio!
Uga(h bild
i!
st6.od.diltt of uoi' cadin tior coDd.r6.
*it! thc lfuyl ion Bualy .t .qunori.l positior I! l!. .qutorial pL!.
tbe
h6dy @.pt l@ pai6 of .l€cuoN fto6 ligods rnd b.h!re r.6 a lrwis
eid. }|o*.vd, &. to rligbr ..€arive chdga on qo ioN lth.td to lroiuo. it &a
umyl
!t
ions
qis
b.*. Howda,
@y qi$
lkbah Nrrr,
PhD
b.tai@
Coql.c
ufuiM (VD
in erlb.dnl F!l|g@l bipyriDidd dld h.r!!p&l tipt!.riidd
this
Dls!ft.non
is v.ry
iDAlq@t
of
Introduction
Chapter 1
g@ltlrics.
Th.
n$.r of
tisan ls, c@dinat
factos .!d cLladlg ibitrty of ligeds
r.l,t
lo.ic
It
d to
lmvl catid. dtF G on 3tdic
d
rlrti
inldlEtioa.bo!t fi. idic t?dii of ofuilnh !fuiM 6. im 5/ lev.l c tl|d by .leto6 cvd i! lh. pce@ of 6r' 6, @d
tu .d8y tev.ls,: hene n fib in to 2d iMer t.!sitio! tutal cbah. It s.ening of
s/ot'itsl redu6 th. larg. vdiati@ in ndii of u.ltrm iN wit! oridiatid srar..
CqsraltosBphic techiqu$ povid. thc
T.bte I
2
Ddiqra
t
bh
ionic
12
nitii ol ufuiM d it! vdo6 orda[oD s|!r6]
lonic Edii ot
dir.ant ordard s.r6
ot
lfuM
Pfr fr ldrfitrE-1F6fr .a6", t- o;fl
t.t.9 c@.dlolio! cr,,,,,r.r.y
umiu
of
u..!ium
!n gstcr ir @npeisa sith Fditioo ftrals of rb.
slE sln , hoe th. @din rio6 nuDbq rld DuEb.r of vrL@ cl6tu of ufuiM
i! ldgd. All of rh. f@ oxidation stlras of umiub (m, N, v, v0 hav. snolg
amacdd fq ligrds having nitl8E(! ox]€u &nd hdidd d @frliradl8 sirls. Tl.
shbitity of Ufuid ir its (Iv) dd OrD ondrdon sitrA b.ing higts, l!. t!q.! o!
lonic r.dii of
ion!
Ulsbah N.zlr, PhD Dk5€ddon
Chapter
Inuoduction
1
tb.n coordution prcpdties is nu.h n@ ubi$liou tba!
1.1,9.1
obplcrd
of
unai@
([)
Nlto&! dmr l&r.&
th@ i! s wi& rug€ of coryLG of ulsiM eith N.lo.o.ligcnds Th.v ilclude
Eurrll @@ or nultid.drL lig.nd! sh $ .,tl|Mir. Prio&v' s.coiddy dd
t.nidy mines- s(E qaEpL of coodilrtion c@Pontds of utrlim ([) st!
@ural liSnads liliog lillSld d . Ugating sPei. e
vxlNl4r,6 =Cl, a=r3: x = B. n=3,a.q, A,pr.,U|'\rud), dd
uct,(c ,cNrt .
s.vd.l conpld6 of |eim (A/) with oitreto &d,tils ligutb ravc bc'n
c'dilc{L Gclattly @dilldon nudas of 8 !o 12 rd u@ r0 (I9 @EPLics
rw obs.rv.d. C@dilatior of lit&& crn b. invasely af.d.d bv 304ic 6idtu@,
fdq.rnpf. U(oO.(r{tr). (n = llttl, dll; | =\4t.
Disproponionation of
umim (v) @npldcs ilto reiun GD tld
unnium (VD
@Epliclt s th. invatigltio! of lb* conPl.ra. s(m of the conlioari@ @nplq4
of p.ntN.ldt st c of l@i@ (Uxrrdd U(OA)j ) havc been i$rlt'd and sMi'd In
celdirllid nMbq!
tb.s @oplq6
the
Mostly unmm
(vI) @rpl€B i.vc
r!!8e
bc.tr
t@
6 ro 8
r-
cPottd owilg to dti! ir$ilitv TEle
dlqo udyl ion, UO?', is @Dly !$d rs !
sue
of
umiu
(vD
otio! fte
coqdi!$on Nd$6 or !fuiu (VI) compoudi ws found to b' 6 d 8' *itb
haaso l bip}trddrl d @tab€dral 8.@.trv ExaElI* of uranvl @dPlq$ @
AO2X\L.(X = Miaz,oR. NO1, RCO., L= Ntt pti@v' !'6nddv rnd t!'rtiatv
dic,
pyr
r=2-4).aaI
Misbai N.2lr,
PhD
Dlss&tion
'
lntoductior
Chapter 1
1.1.92
ltoqhon6 DoG lig.!d!
Uruiln
Ptdas pd*utul li8$ing
dod: thalfot!, uruiln @nPLi* sit!
Cb.Lti!8 !!!r
v..y
phos![i!. e
r',rr. = l, -9 t! -daahyl ptolPbim) atoncsldilts lh'
crryo!!&-U(rfl .)'(d'P) ald
UX,(dnPe\
ol
liged
@rdidtid
tx = Cl,Bt.CH). Hw.v't'
Mod.nilt liged,.ls fom conPlda {ilh 'miM Th'sc
c@rdilaid @EPou& 5! of Srat i!r.t$ t cs!. oI tb'ir 4Plica[6 i! 3]dh'lic
phdphinc P(Cflr): !
orgdone$lic chcdjsty of lmiu
6',
1.1,93 Oxts€o Donor UgDib
ligt!&
Ei.ty of ligrr.ls with 0rl€6 ddalinS 3ite c@drcl! wlh uani@ Tb*
of
i!du& oaptic Eoldlf4 sttodd6.nd tltorid's Atdougb rht coiopltc
A
f's in nu!$d
id'ntif'd but tb'v
't vai6 ft@
@adidlid nunb.t
tban udim(Iv) tld lndln(VD @Dlond! Ttc
si3cm! g catoayl*''
6 to 12, As orygd dodor ligand! @ tlqEal in difieM!
'
fd |bee
l$litv
uFu@
of
, hydrorid. d'' howltdgp
..600r|, tq@,
urdiuh (m)
sltd
lmi!d(\,) bw. ,lio
bcen
Pt66Ph|t
li8!nd5 i! viral
tu6 aviMdni.l Fint
of
vid a'
1.L9'{ E lides
(IIl N' v VD
umiufl ttftb @nPld.s di6t il.I 6c fou v'!oci6 of lmius
hith oiidrlid $n's
Crddrly lgends Pitb fludi& i@ bild stb 8di8 in its
*fth urltiu ios or loecr
Wlitc lige.ls conniting iodi& id is tiblv to codrli!'tt
g'd idpo'ta!@ i! idurrat
vaLmi6. ft. .ooPbis of r@iu {itb b'lid" hlt
cleDistv. Tbc ddpL! of h'sc comPlcs lr VOX"(i=231'
sd
srribetic
lao,x,)h (n=lto1)'M pF,(El' F5, 6
MLb.h Nrzir,
PhD
Dl$.nation
?:
r-2'
t{'
?' 8; r=3'
!4'
E 9i r=4'
Introduction
Chapter 1
FJ), v,UCl,(
F
x=1,
1r.95 Org.!.o.a.lllc
6,; r=2,
rd,6,
?i r=3.
vd
?' 8
9I i{ ,UDt,(El'Z\r4)
.
Cdpl.t
d!r!@.truic cooPLr.s t! I'E6t sith !U 6c didlrid !tLt of l@tum
blt ut!6i@ (Ivlds.lMlic ceFoldi r'. .odmo olStmct'tlic
66pdDd6 of u@iun Pliy . reb .6 looog.rdt |!d h.r..ot.roo3 c'nlFls in
Tboorb
qt i! polt@irjid
1.2
ud bydrls.rllid ntci@6 'r '
Cheolsby of AD|ro
ArI of th! 20
tigh E
e *!ia qtllrltiE .oli& i! tttir Po!! qlL ILtv n'vc
lt y e ilslublc i! GSlnic el!.d! tiL eron'' clldoforD
deino si&
lils Fintt
d.l .lt .
but
rdtt
$bblc
in
A4.ot!3 3olmid! of @i!o
tlra.
*iih
a?
Spod
uil of |nilo *rd i! .boM ia Figull l
sauct@ i! th. t trlst l dltr (!) .r!oo (CJ. enich i! ovd'dlv
th. 3rtrt!.
of
!
typic.l
cotd&rdt
Pivor of thi'
tond'd b rn
@i!o Srop .nd . dttoryl 8r$p Hv&ogo i! do b6<t'd lo thi3 dPt' cdto! Tb'
foull .ltity wticb i5 lid.d to O. .lptr eftod is ' vtatn' riac cbd4 csUcd R
Gl.! lDim 4id it3 ildividditt at Pll ? th!
gdp rnd ii tu tb. oF thrl
8iB
cstoiyl goup dilts
s
COO-.!d @ino g!l,p
e
@L.d. i! crtLd ! zeilcior
i/!!b.i
N.rlr, PiD DLs{t don
sr{'i. tld
tDi tlit
ddd
Chapter
Introduction
1
H,N
ffi \.-,"ffi"
tti@tr
lel
Cbslt[otloo
of
COOE
SEuctr of AEilo eid
.Dle.d&
D.p.ndilg on tlr. veabrliry of R 8rcup, dino rcidr diffd i! sizc. poldity, .[dge
.!d chdical Ea.tieity. B43e of tbi! l!!M @i!o &i& @ cL5sifi€d in vuious
wa}!. G.lenlly tbey de c.!.rpnz.d oi rbe b.st of Poladty of tte sid. chti6.
rhft @ for rW6
AccordinS to rhh .ribdoo
.
.
.
.
Nd-polr
dino &id3
Acidic
uiN
eids
Bdc sFiro &i.rs
Non
polr muO.I mino .d.r3
dino eidi do not po.lBr &y cbtg. tlat i! ehy
neltr.l h utre. No!-pold or brdrophob,c dino eid! ilclu&
grculs of th.s.
e
ssv
PoL.n utd a@no rcids
P.r.l
R
raiil
of @ino &itts.
.
ADilo lciG
. Irolc
eitl dryl
(havinC
cbain R
.y.lic sll'r.!ft)
Mlsbah Nazlr, PhDDissen don
th*
@i!o &iG
golPs..s. aLniE, vdir., l@i!. ed
Chapter
Intloduction
1
Mc|Ii@i!. (@ of tbe $in! contlitrirg @i!o &ids)
typtolld)
Arcoldc Diro &ids (lbdylrlrdiE .tni
Trylropbd hs thc lbiliry to
i
rin& The noGhonding d!.trons of th.
dy .lemphilc
bondjng with
laP
lv-}I gou
F.d eitb wal6 om{8!
such
3dir
aton in
of ib.
in&L
Detliolin my hvolv. ir
a @ld ios.
Polr @Ld uino rd&
Si& chai6 of
th4 ei@ &ils @
ctPlbL of
fmi.g
hldoSen bood wi|!
wid
A!6Bsi@ dd Slutloire e uidc dcrivtlivcs of dpdriic !.id .!d tht Dic &id
Flpe.tiv.ly. Eisl y pold nrctioMl troup, aElde, i: caP.blc of htdrerFr bond
rhdsh 0L rlulrdryl €rd9 (-srr ) or c'st ie is M lola i! cb8..ra' t hA
tb. abiliy ro lod *.!L E !o!G lhDug! tu qyg@ ed niEog.d .roG. ThdEfoE il
E€
is listcd
i!
this clas! of
dido &id!,
rxe by&oscn bond fmi!8 ability of hldsxyl SdPs of It1osie. ihl@jne &d
sis mfd l!.D tb. polar dnE.
dsiddilg
l2l3
'De
lhis
berllt of its dim
.!1l ..rborvl
f&l it b Plac.d in Pol{ dd und.rgEd EID'P' c.t tdv.
'De pold ldur! of Stdm is
gluF tld
Adrlh .ei!o rd.l5
pc.@
of tdditio.d COO"8 sn R tM,P in &idic
|niro &i& givq tb.d
siL ch.j! c..bdy'ic gdry e qljla h.!hE rhd
rh. o -COOfl @iay yd they @ !d.q!n ly eidic to l.@i! $ cllborvltr. io$ .I
reltrrl !H. &p.nic &id dd 8bt@i. &id e qdPl6 of tLi! s.t of @iN eids.
-idic naE
.
rdth.lr Nrlr,
Altlougb
PhD
6e
Dls.rEtio!
Introduction
Chapter 1
1.2.1.4
Baic rDlDo
&i&
Mino eids (hirtidi@, {rini@ ud ltsirc) !rv. !a po3itile cbg. !.u|.rl
pE. lx.cfor!, r!.y @ €p.bl. of fmiry i@ic boddt with eidic |Dioo @i.b,
'I!.e
uino goup .5 a sid. .bai! fc!t! cdjugst a.id (_,vlrj) by
a...ptir8 . potd nm wald. Si@ tbc ru&idino Sroup of {siiift is p.tu@dy
gjnidie
Eord.r.d 1lhFiologiel pH, it dc @t t t Fn i! eid-bcl. r!..liodl
6drai$ ibid.4L eidt chah dd is wc* ba!. i! Gnf. Al !H ? it b l0
Llsie
havilg
1r2
ID
Sysleolc
'Iable L3 sys@ic
lIlG ud chdidl
ra6
6d
Misbah Ndlr, Pho Dlssertadon
lodult
lo.noh.
of m
ol
@i!o.ciih
colt|M dirc eds
e
lsbulaEd
s
Chapter
Introduction
1
furl2I.3
N,I'IE
St6t@rc
sfsmrrAnc
olG od romula of uito *i&
FO&MUL/I
NAME
NH: -CH:.COOH
(clt,): -cE -cH: -cHr}l}],)-cooH
clt, - cH(|+rl). cooH
(cH,)) -cH - CH(NH,) - CpOH
cH, -cE, -cH{cH,).cH(M))
-
@OH
Pr-cr{r.CH(NH:)-COOH
HO-Pb
-Cri,.CHOtl:)-COOH
HO.CH: -CH(M,)
- CCTOH
HS.CHT -CH(NH)) - COOH
cHr -s. (ctr,), -cH(M:)-cpoE
Ph-NH-Cn=C-CH,
-
CI(NH,)-
COOE
NH - (CH 1)r . CH - COOH
cH, - cll(otl) - cH(M:) -cooH
HOOC.CH: -CHNH:)-COOH
H)N -CO-CHr -CH{NH,)-CEOH
Cn(Mlr). COOH
H)N -CO.(CHr), -CH(NH:)-COOE
HN - C(Nltr) - NH.(CH: r, -CHO1I,).
HOOC-(CH,):
-
COOH
HrN -(CH,), -CH(NH))'COOH
NH.CH = N _CH =C-CH: _CH(NHi).COOB
Misbah
Nau
lr, PhD
Dk*r{ation
Introduction
Chapter 1
r23
Sietwh@istlr
.rnlro rddr
of
Excpr glrdne, thc c-cdbon of
to
i! ftu
rI
thc
th. c-c{toD! ar. tnown
as
Mino
acids
$}rl@tric
ha tou diffftnt
or
ctdtd
greups .n&hcd
clrbts fte doL@la
diffd only in the spati.l aranS.mnt of lh.ir atot$, Thc st!@ieoers, Lisond dd
Di$M (Firs€ 1.2) @ njffi i6!8cs of .rch orhd Th.y @ abo .Mtiotrs, i ..
the noleculB c@ot be supcdnpoo.d or c&h otld. Thc PhFicd ploPati6 of
e@tiolEs
dir6{ioB
e
sn l
ftl@oc.l ap.n ft@ d!1 lh.y torfic pl@-Polariz.d light h oPp6iL
@ calcd odic.l
isi)!ts.{ n
R- C-H
I
I
cooH
cooH
Sl.r.oisoo.B of milo eidr
12.4 Abpholrtrc ortr$
of
rnl[o tdth
&i& n b..de of lt p86* of both *idic
(cstoryl) !!d bsic (aroino) greuP. Tt trith@ of dirc &id! io tb@ diff@t
The
ulbol'tic
ionizile
Misbah
nalue of.idjno
states depclds
Nadi
PtrD
o! lbc
Dis.rbtlon
PH of
$lutio!
Inboduction
Chapter 1
Thc
tt!..li6dal idic {d6
,1, N- CE
2
-
COOH
ofgbEin
e
H, N-
c
CE
t - COO' a It. N- CH. - COO'
At tbort D!trIptl bolb tt a@iro.td lqftoryl ItorF G i@izrd.!d
ddtfoc uilo .ci& d $ zei&rioos 6 dipols .p.cica. l!. i@l6tic Poid (pI) i.
6. pH.r qticl tt. dto|j io6 ir cLdricdly lcunl. Wba tt aio..ion iN dmcd
*i6 d ei4
coo- glop i! cdrt'r.d into Coott. Th. PH.l $'tict tD.
co@!adi6 of coo- rnd COOItrc.qul i! t&.sPrdr SiDit dt *h.i t[.
z*ioaion i, tiEf.d wilh I b.tc,tn. MtiSr@P b..oE d.Prctd.Ld. Tt pH !r
tD.
*nic[@6triol,of
bolh
]Vltj .!d Mtr.i..qod, rtpts. !?ran
d@i!o rld c+dory' gwF, i@iz&L gdF .! .Lo Pilgt i! tt tid.
.hrii6 of uilo eid!. Tb iclcctic !o ! of uino 3i& crn !. .do&(.d tlm
o.irrtrar, pra: lrdplturr.du.d ry r.E olt!! $tE q@!r.qutti@ (1.2.1 4)
Be.id.
Fo.
Dino &i.b *i& naurl lidc dda,
pr JPKq+ ern'%
0.2)
rd tur fd ridic.ni!o iirt
't
/2
Ad tc
Dolic
Pr
oioo -idt,
=@r4'+ Pk'L
&b.h N.dr,
o.3)
PhD
Dlarterlon
o4)
Introduction
Chapter 1
The subscipts I, 2
ll.5
3
Ef.r to d{arboxyl, a-milo .nd sid. chah ioniabL
A6ho.ddr !s.d .| U8.!!b b
Shqt d.sqiptio!
Esfu!
&d
is
sd rtwtrrs
givd b.low.yrl
t
6i!o
of
aN,
sreuPs,
rtud!
&ids u*d
$
coordidting age s
h
this
Gl$inc he tb. sibpldt sEu(,lq tlvils hy&o8d lron in pL.. of R grcup. Tbis
hydrcg@
@mt
rm
by pold .eino and
a
sood H-bo!d. Tb. elubiuty of
sl}lie
is
p.i@ily affat
qlloryl gNF. I i! r pold &d !!ch4€d aEilo
d
a.id.
tl
OH
I
NHz
fi8uE
r..'
SEucoE
ofcllrin.
l2J2 S.rin.
Hydrxyl Gthyl mi.ry (AOO{1-)is prsdt
s
a sid! chain io
sirc |!d thd.f@
it is me of th. @irc &id vitn hydoxyl Eup. This ltdoryl
8rcu! tu! ih. tbility to
fom hldrce.n bond with rlP solvdt waEr Eol6ul6i b.@ ir i! pol& in MhE.
Mlsb.h NadI, PhD Dis..tadon
lntroduction
Chapter 1
fitld 1.4
1.2J3 Clsbire
Cyst€inc
ud E thio
SEUnlE of
kine
r.
&d mltionine aE tbc .xa6pL! of sulphu @ aidry dino eid5.
chain of cF&ire
i, Uiol Gtby' (tlscli,-) ebda! th.I of E rhioniE
is
Sidc
tu6yl
.rbd(cltrscltlcll, -). ADilo &i& with sdphu @laid,g R grolps
@Dpris of both i.c. cbs r (ei!o ard ceboxlato) 4d clas b (6io.th{ a! !ubhi&)
.rby' rliol
clatrou of sutphu in Fethidirc 4 @PabL of fmitg bonds
wirh .t icrcphil€ lit o.r.l i@. Du. !o tne nd pol{ o.t@ or ruldydd(-Ju)
The non.bonding
goup of ctscilc, it
Tne
foo! v!2t bydDgd bdth eii! litlgd dd
tbE @rdjnati@ sir6 of cFciF alt
l.
2.
3.
Mblan N.zir,
PhD
Dt$.rtation
oxygcn
chapter
lntrodudion
1
otl
HrN:Ao"
i
\SH
fAeLs
StJuct& of clsteirc
o
uc'"-'--fog
NTL
ai8d.
1.25.d
SE!.tre of M.thidic
trirlidhe
dibsic moMaftdylic rcid. An inid@l. rrcuP, *'hich is . 6ve
h.ts@yclic Eoi.ry, occtpies tbc plae of R g!q! in tbis @ino aid, T!.
Eisridift is
'mbdld
r.6
!
ioiduole !rou! of htuidbe
is
taric i! .h@cld, But al tcur.l
PH
tb. ovd"il chaa!
FsitiE. b srt r 6. pl<a vrl@ of tn. ioi&zoL 8rouP of bistidine n
lrdolt .qu.l !o 6.0, wb.@, solution wiih plysiologic.l pH (?H = ?.4) @liaiN
ompdlrivcly hi8! @!@trlion of iEidrzole (bnic) ald iEidrzolid (&idic) fom
of R g@p of hisddi@. B'cl@ or seit t e it i3 !o. c@dercly ioniz.d !r PH ?. As
! nldt n pdfom 6 a buftr, It is .le ilvolrld in ..ttlytic elivitis of scrcEl
is sliS[tly
Misb.h Nr.lr, PhD
Dls.rt
don
lntroduction
Chapter 1
Th. I@ dtsinibr nrHioral BMp6
3-
Thc ptrolc dttoSpn atom of th.
4
Th. plddire !iEo€6
aro@
of
i! hi$di* c oFU.
of coddilaton witl
ioid@lc pur of thc ml@ule
lll. ioid,al. Fn
of
tt! nolede
o
dYf""
rh/
Nf,
r2j"5 AlEirfc .dd rnd gltrdic.dd
&d gutanic &ids Mt in catory' 8ro!P s sid€ cttin L.@ rh.y
didrborylic tMo@irc aod!. Tlcn ov@ll ch{ge .t PH ? it rcgativc Tb€y
g6s"[y tloM a 6p.fi!r. ed Sluladt! Gpctiltly
Aspanic
-)!.?@ 3ide.h.i! catoxrllc *id ton a
*t@ i! 6p6nic &id whib two E $/tu (-car -cd' -)c{to! atods $e
A silslc o.r[yLc c.rbd (- CIt:
pBmt bctwed
side
cb.i! clrbdylic rcid !!d o-.5rbo! i! gu!&nt
.
Allh@8i lh. rid. chrb ditEr,4 &id g@!s @ w&t a @nprF! to rnc
s -COOH Entte, yct th.$ @ .d.qulaly &idic to cxisl a cdboryhr!
srcups (- Coo-
J at
pH 7.
Mtsbal N.zii PhD Dtsertadon
I
ChaFter
lnEoduction
\^r*"'
OH NU
t&@ld sft.te
tia'rrr
1156
Sid!
A4.rtic &id
Stucdlr of Clumic acid
A4.rr8i!.
apo..tiE @t ia 6 di& gNp ald b€{u& of aid. @i.ty tlis
eid co fm r htdrcged b@d. At physioloSiel ps OH = 7.4) MC. lle
ctri!
ajlo
I.,
of
of
di{b gmp 6tu
b. Foro@t d &d b
ud.t!.rl
NHz
NHu
rir@.1.r0 StrdFof
Mlsb.lr Narir PhD
Dl*ri.d@
AlpeBsirc
Introduction
Chapter 1
125.7
ryrcC!.
dim rcid
is botrd.d to ttc qttrbon vi. t rcrbvl@ (-Ca'_)cbab TltsiE @ rod
hydrogd bodd by iE !t nolic gq|p- AFoa& ri.g ir sPoolibL ld lhc @-pol,
A
p!@l golp i! p(.gt !i
ir ttGirc' Ibc aronttic riry in lhi.
R Srou!
checi.r of tyNitrr. conv6.ly, PKa val@ of 10.1 indicaLs
of pbtrlic ring i! t (hat!c4 Flt un t high PH.
frlgrr
r.Il
SE&-tu!
thot lhe hvdreryl gbuP
ofT'l!.ile
r-2jr ladd.
h ldci!. iebolyl SroP it FE d s t
aclbyl
SrouP
i!
tbc sid.
.hab
is tbe
g'l!M (t){dto!
ti4oJ.I2
l,titbrl
Idt,
PhD
Dl$.dtion
sid. chai!
SEuct rc of
.!d lb.
of dE
lruoft
po€itim of buching
dino &id'
Chapter
Introduction
1
r.2.6 Conpludon
rDho rddt wlth
ol
dldr
Vdiou t!.hniq@s have b.4 dploy.d !o strdy c@ldination of Stycine witL
diff@t E tdt ed thlt fom.ti6 @!i6t5 of thc @D!Lxc! i! 1:l ed 1:2 M'
{
t
nti6 {@ r.pori.d. Rabdju .t .1. od BilEoodo ct d. i!v*!ig't'd 6!t
glyciF b a mnoddtaie licrld and cddi!.te! tluough its carboxylat' Sroup ch lhc
!
d
odd bald snrdi6 ol bSrd€c c al. 'r tld C.rfol. ct d 3rst d th' syrtb6is of
ch.lat€ @mpLx of umyl iotr witl glti& sz.to.nd GMtn''dmust'ated that a!
bv
pE
tlrline fo@
high pH &pmtootion
ro
d[ibil
both of
coryl*
&
@md.nt
bclte
lMy'
o..s ed a ch.hrc
t
sil
in ih.
f@
of
zwiuedN sbtre4' d
fomEd. Tnev Ntjccd
@dpld
'5
Urlenrd! cha&tltillca
i!
ite
8lt!i!'
qrdyl comPLx6'
umvl c.tion &d Slycin' * pH 3
i! Ue ab6dploa md barh6lFEic tbifr u altorPtio! p<jls'J
UV-VisibE spei$m of
shoqed
silb
6odi6tio! conpoud
of
sd Ni(E) conPl.xcs with tlvcine !ov'd
rh.r cfiri! vibratio! t6tdr lile C=O stra.hht, Itt,lc}jrg tld l'lvld
Moltre&hing beds @ affellrt by t!.tds ed thce btnd! @ shitkd to hiSnr
Tbe bfta.erl study of R(tr), Pd(tr), Cu(tr)
t!q@nci6 i! th. foUowiq od.r of Det
k
Ni(tr) < c\(D <Pd(tr)<ft(tr)
The $!.rching
f(@ @6t&ts of
The stta.ning bards of M,V
affffil
MO abo
in@!' i! t!' sinitt' 3€quE
&d rttoof sotu lEul conPlQG with 8lltirc @ grE!
Misbdr N.zlr. PhD Dlsrtadon
Introduction
Chapter 1
Tdbb
1,4
Sts.hiog be& of
lt\i
.nd MO of
fttd-glldn
@6pLx.s
tlc
uid.ot r. b.laviout of gyci@ esr cpon d .n.t thc sordy of h(trlglycin
@nplq. nE @mplex bs-lPtclyH)1x11(x is 6 h.lospn) exhibir5 c&boxvl
sE€tching
orhd
bdd at l?10 cmi ildiodlg unidiz.d
fm
of ornoryl
hd4 tts-tRcty):(NHJ,l$o*ld $ntchils b&dr
tk
gdP. O! rn.
1610
dr
fot it!
ioriz.d cnboxyl soup ir.
Sa@
ljtif d
d., by
ui4
su€€lst d thal owils to th. sinde
@.od. .r.
ligsnd. Ar pg 5
ed FkotioDeo. t chrqG' 'r,
sdu$F of sltti.., n @diIrr6 to ion a a
spe@pbotodEic
&d in aqu@u solltio! @L ntio of
idicat d lo b€ MLr. At pH
1.9,
1l
moL latio
fl)mlio!
tbc
@dPlq w5
of umyl"givci!.
@c6
HowcH, by inds!'rg pH ttc hydrclFt of ur&yl io! bl@k its @nplexalioa with
sie
ftr
Dte
- i/Iil
tlycilc ed thc
n
ion UO,L is Lrdy to de@e lhc altruEoo of th. catuoxylarc qith l!. GEt ior
slyciE,
and
spangi@.
l{lsbah N.zlr, PhD Oissen tion
c.tionic
or
8rcrP of
lntroduction
Chapter 1
ed
R.se@h of U
ir
ldy
strblc.
D@dy
s t {tt! to @nclud. th.l
As.ist ti.l C! (tr}!qi@ conpLr,
thc
codpLr of Cuz' wiih
b@usc of tle PE!c@ of
is lot suf6cidtly stablc !o b€ sMicd !o!.ntio@tric{Uy.
rpplicd ro u@yl @DpldB. sol@t
value of
fmtim c@talt
Th!
&
dtrsri@ drtod
valuc of
w
siuc
- ItAj
,
Sib d 8@dlity cd b.
@doycd ro cdord. 6.
umylsioc conplq wa etibacd
to
v7.1,{'2.
Brcod
&d srorg
botrdilg
i! sdPlc
!t
b6ad
of
siE
34@
m
'
lpccitrd
t!. fcDllion
of snus hvdd86
@rduGd wtb Al. (OHl, Ar'rr@Erc ad ,vBneEic
gflp w fNd to b. .t
Gpetivclr. Th. dff.l!@ b.rsa d6. vo vihatid
vibndon b@ds of clrboryl
1590
m ' rd lalo
b.!ds rl8o @r )
t
cE
l
bjSnd
rherhstof pN DL{- laire (145
cni).It
ws obsartd at 1250 .o '
pft iaiD .!d b @6PLx.d fom tith .l@l!M
h!.
ScidttB
invesdgar.d
borh
i!
csdiMiid
sh.tP
dd !!!tr8
Dcbavid of cyst
ic
OE
d.fdErdorbld
ald ndbioni!.
*ilt .
*it! ll Mt t{io ws obsv.d Biic sal/icol l! biiq6
3!ch s Tr. r6o1v.d IM i&h..d fl!d8..!6 !F<tocc.!v ed Uv-vtsiblc
sFcro!@y. A tl @rylq !F.i.3 qbicb i! piodled tt conPantiv.lv h8h
on dErnos of utuiub, involB tb. .ooidio.tid tbiouth €tloryln 8o!P i! s
U@yl cy5lEift @nptq
p,ototrlt
d
f@
rnd
-Sd
-NIi2 gMp.
Itis
sleiec d(B rct btw sinile
ti8.!d.dtio with.:$orlt g@9'
ine ooly lie.dng 8rouP. Tt &6o.Fion P!na! of ltmiuD(vlcvstciE stscD n Ps
dep.ldcrt.I! s pH 6tc of2 to 4 e iictd!! in !b6ory{i@ !va. oh6dvcd with a!
.hsorPtid
FoFni4
to
tb@ bving san
NLl
|o
it.l!& i!tt @edrnri@ of cysEie Tbd. w . b.rbd!rcDic ahilft rt PIt 2 .!d
3 *til. .t pH 4 e iicMirt ht?so.luooi. lhift of lblin .berytid perks ws
Msbzlr N@ir, PhD Dis.rN.don
Inuodudion
Chapter 1
l.ld !o lh. condci@ th,r 6lei6 wit! diffdot
3ioichiotutic rctal-prciod-liged 6ri6, hlvil8 tliffelcnt strstuE, rrc Prcdlcld.
Thc val@ of formlti@ @$8t for !fuyl cF€ine @Dplot *ith l;2:l
mtalproto!:li8|trd stio es .valur&{t 10 b. log P6 = 20.05 10 14 "
nodc.d.
'n6. crFitMld
d.ra
R!$d!hat studi.d ttc ataoBis of unniuD(VD c]'nPld wirh cvsIli& usoS
por.ndotutric tcciliq@ !tr'. b a @nPlq podeed this wav, the ntio of
'mvl
lrd cyst ift w6 fNd io b. 1:l .rd d[t c&iro ald tb€.lnorvl grcuF ..r a
@ntiDtilg goup6. Ifr.tld $ !oi!t .l out tbat lhe cootti@lion of sulPhu .!oD of
cysrcin. with dte ufuium catioo, in.@d tbe stlbilitv of ihc coDplq. conftry ro
O.a ,rradd Ml,c@pldd of lroilm wirh o.llioni@ ww oDs.d tt *a.
polos.d thrt h thqs. sp..i6 c.rboxyl .!d @i!o grouF
wh*s sulphu tloe not tat pet in cdili.adon t.
e
lbe bondi!8 ercuPr
@Bpl*.s of cyst!i!. wirh a vdicty of Nlal6 i! th.n
dird.nt si!r.s. ltF bindilg sit s of cyst irc, wtcn .tryldcd eih zilc (II) rnd
niclcl (ID i* hav. be! found o be dim rnd suulydtyl 8rcup! CdPlcxd of
U et
at, inv4tigat d lhe
cystein witlt l€ad (tr) hav! FlatiEly hi8! st bilily b.c$E of tid.otar! c.ordinario!
or
c,stcie i! the @DFur& e.
@Dpi*ltid of d@i@ (Itr) tiin Detbi@ine tugg€!.!
rr.
kol.don o( elid
LhnL lulpbu M6 i! not a coqd'@tug spei4 i! tha @DPoond
Crttr)-rcfiioni@ co6pr.r* {ith fmdt lc'(rtct)rl, lCt(OH\M.r)1H'o1 tlA
Po(.atioD€Lic study or
w
crd.d out.t ?H ?-9. -coo- &d -lvt,@ hc
cmdillrils s@!! b 6e.e cooplcxd 6i- ttre mtiou ot C,C\..6E1O td
Ic4oE)1@.t)(H,o),1
i.ld lolMa)l4,o)alb cmplex. Futnq iffils. in PH
predEd . @bpld witl rodarh [c'(MrXo[X/t'O\]'&d ult'@r.lv
tc4M.tXoH)JE,o)'l @4]td s.rii!.d. tcl(?,t ')rl is 'td'PuPl. i! @lou
mrhioninc .r ptt +5
Misb.h Nazn, PhD Dl$etudon
Chapter 1
I
ed
its
goftEy
is @nb.dral.
Id'
vt'
calcular.d
rot
3.73
ft@
is
rc ,t-Crbond in rlis
ntroduction
coDrler
sd
rbe
BM6,
lh. fumrion conrtaln or comdcxd ol zi.c sith clycire .!d
tulhiode 8iB did.le thlt ihc hlding goqps ar! siDild i! bo{t rh. c@pld6
Compdisor or
dd rb6egruFe -NH2ard -COO
d
study
ieral.d corqoulds
@,
lik
lPtCll(M.H)1, IPtCt(MaXNHl)l
.d
tPrcl(xlrr )(M"{)lCl tiv6 dc cvii€nc. 6.r tlE lis{d i! tt & @Eplcx4 ir bold
to
mul
tbftugh amilo srd rhio nh..
gqp6
tot-
Difr.rclt ealtlical &cbniqu6 (polasgnphic, pot ntio@tdc, colduct@ric Dd
rpelrlploroGEi. bdlods) @fm rh. fo.urid of @6pler6 of @pp.r (r) wnn
detbiolie in l:l &d l:2 D.tal !o ligrad trtios c. Mci[iolirc actr s a bidArlte
ligdd in th. f@nti@ of ttce cdptexcs. Convetuly, McA'rlifie er sl @ suggatcd
ilc tcdmtatc @tE of Ferhi@i!. with wio6 ft$ls i! thci. divalc.t stlre, Itc
co@dindion
sit6 in .opF E.tbioid coepl.s,
culMa)1lg,O)1,
of suur
h
the sildy of
hN.&n disv.r.d
noti.ed $, sn@ $dicd
Ed$ll
C!(,t
.rxtt,O)l
rtrd
ilt E ii@
rhMeh NlltR teh!iq6. SFctd .vidd6 ir
io bc
airoga dd ox'?d
ct d. shoaed thc ch.],adn8 b.hlviour of
and
!o
hbtidin vi, th. @ino
ed inid.zoL
Tolled
srculs in Cu (tr).hhridine conpLx 'm. ConE!ry b thar Cohn .nd
Epod.d th. carbonyl .!d iEidazolc lrouF of hisridi!. !r! @di!ad4
h it' @opls sith M{tr) ''. U .r .1. cehd.d A@ rh.ir r$!rcb tbar ditu
g@up ed prdditr. liEogcn of iniddolc grcup @ the ligatirS sites of hiltidirc ld
sites
rs.
Cu (tr), Ni (tr) &d UryD
e tas-plane in sEEr,r ard t!.t the two lirtoga
abB ir t[* 6bpl*r ut s Ugrdag spe.io. The carbqyl gup of
IP(bjlo:l .!d lR{his-s),f'
Mtsb.h
Ndli
PtD Di.s.rtadon
Chapter
I
Inhodudion
lPdhisorl @mgler i! iooi4d md h.ne shos lR bdr.b
th. othd hdd
indicir.s &,r
do6 lot
tlk
ir
tR(hist-tD1lr' conplcr,
tbc carboryl
Irdp
is lor iooiz.<L
Hisridi4 ..ts .. a idd.niaL ligad
Rc (V)
rld
vihlti@d brnd
I! boll
of lhe
l:100 cmr .
{
t7tl0
oi
tu'
coqLx6 or}ld .ton
16,
p.n i! @ptcx.tion
ro.tll o t8!nd ratio pith
i!.
ar 1625
d.t
@Dlla\ who biicd ritb
l:l
l ion. Thc th@ biodilg sitat in tnis @npld
@
rb c fmilg
a
crnd)tilc ard iDidaalex. Tb. 6.ri@ of ti5tidic tith
Rc OX, (OrP4 Xi[.:J) in ! 6iio of 2:1 Gpeliv.ly yiclds a corpld rith a fotlula
lsdnc4 or)!!n lrod
of
IR.O(r-[,i),]- b t!, @hpla
ard tbe othd k lf, X-bid€otaL
lwo
eios lrc eng.8€d orc b x,
lV,
eior '6.
Eistidilc fo.lbr lT.(colllirlconpld by i.plaolg lhio
ITc(Co),ltfidth.t)1. I! tttu .dpLx, hisridi@ @rdi@t i l!Fu8!
ab6
rnd @c
ortgd
lrd
@rid.nt t
.lhd frln
two niuoto
'd.
*@ dploy.d to s..t th. sbichio@ty of cldnim dd
ziB @E9ldc. wit histidinc .q1l!. codpl.g q@ f@.d to b. C?(Aatt)? dd
Pohmgnptic t cbniqB
zr(Itirt)r. Th.ir ovdau fomltid coBt
bg
r, - 12.3 Bp@drcry
I!
aq@s d.diu rnd in pE
ols
ws fMd to be
= 11.10
5, th! conpL*6 of ircd (IU) with elut
3pcdophoton Eic dd pocolioMic t .t!iCu.s
^
tr
dd
I@).
$pa!tar! show.d th. sroiclriomerry of ML:, Th4* c@plq.s
ICd(A'pE)NOt)
log
v4
Mt
sodi.d
ed
tbstn
t
@npbr ot Cd(tr) with !tP.na!.
Flrld i! enich . 5iDsl. ,IoE of crdDid id
e.i}llalinc i! illre
It i5
a
f@ orysp! notu of
c{boxylst &d thF! oryS@ st@! of .i!|t*, Nido&tr of milo grcuP it pfotobtted
Mlsbah Nazir PhD Di!..rtsdon
bilds with
Chapter
ed lot
I
Introduction
involv€d in
@dbation. Icd(rrp)l @nPl.x
is al6o
fm.d
tNt at high PH
val@ &d tbll nitroSd of @im Sroup i! lhi! spei. als b.b3vo .s a coodhtitg
ln !h. cmplqnion or Cx (tr) .!d Ni(tr) ioa wilt $p:Egin ., dilo ed
csrboxyh& lrouF ecr€ fMd to b€ thc binding sita &d mi& srouP ofth.ligald
ws lor ilvolvcd in tb. cddi!.tid 5r.
1.3
Ch.mirtry ofTartrric sdd snd Glut lic acid
ed
Slubric &id @ c8&i. @Epoolds
cpc*arld in Fig@s 1.13 ud 1 l4 Sivcn b.lN.
Tura.ic &id
oft
&d lll.n steoGs @
o
"\AA*
ooH
rk@r.lJ
Stuct!& ofTdt{ic rcid
oo
so,jJox
r'{s!4.l.L
Misbah
Nat.,
PhD
Dlsedtion
Stuctule
of Glurnic a.id
chapter
Inhoduction
1
t rrdic rcid b $rBftlric i! @tift. Tne hydrcxyl od cdboryl goups
of rhk &id 4 p!!@t i! diff@lt plo6.nd @D!!i& of disinilt 8loreEy.Ihe
iifrEd spetrlo of t{taic eid nach* wit! lta of alipbatic dohols dd
Molccule of
caftoiylic eids. Th. vib.nionrt
@ thcir
ft.$@i6 of Ofl,
Cfl
ed C =oCtqs d.F!d
g.lNtnc shNpa'6.
6!'l.!ts of d.t l @bpldB of tlrt !c &id bav. b@
nethodr. Th* vale3 w@ als @tn$Ed will lho3! of
valu4 of &idiiy .!d lhbility
adm.red by pot ntiomEic
it€ BFnic &id .!d e$ @oclud.d thd @tal i6 bind via diloxy'ic gNp of
tdtliic &id wbiL h ce of arp0rtic a.id carboayl d w.[ a @in ercup. @
ilvohrd td c@dilrdo! with d.I ioB. Tailric acid do.s lor fm Eiddiir.
ch€hL @dplq ud h@e, th. drrl i@ is poorly rbicld.d. A! .6ult n.ral i6s of
th.s @Dpl*s c& ad6go slbdtitDtion ra.tioB, Stability of @EpLrcs of lniadc
eid w6 fourd
t<,
b. in tb. foUowirg odq 'ro:
Mrt'
'rC NIttR rndie
> Cblr >
Cr*>
b2'
otr $olutioE eitb so@ otha
D:O&lutio! w$ @deGd.
I}
!F.[rl!n
o.r.l ioc ald tdt.ic &id
idicar€d lbc
fmtior
ol
di@
in
in
cd.
ed olest n (\,1). Fuihd ro tnat in a $lutior conldlias bott
th* @d!, a dir.d diM i5 d!,IEGd "I. T.ps@d de fdld dircd diffi of
dtinonr'(Itr) sd 6ajc (m) duins htu r.s@h "'.
of nolybd@u (\rD
cl!fur.li.d
by vadous
nnse of 356G34{D
a-' is d
Mctd guunte dihydroinab hFraies w.I! synrh*iad &d
&rlylid |anliqB. ftc brlod bsld I . t!qu.&y
ildicatio! of pBd@ of byddyl goup of watd nolaule in glut ra! @bpLx6.
As}lu.tic ud 3rnmEic $r!t hilg iilquelris fq c.t!oxyl.& ioB i. th6.
coepLrG w@ fNld !o b. in r nrse of 163G1610
aEd8.
dif{@
Mirbai Ne.li
PhD
of
th4 te! tEqercie
Di$rt do.
d-'
&d
143G1390
m
I
.
Th.
6 210 .D ', which lhos ndo.t rErr
Inrodnction
Chapter 1
b.havior of th.
.!d
1.95
litdd- Th. Fd v.lu6
sD..iivcly. Tte
of thcF cmpdid!
3.10 BM
diaEagnaic mturc
l.4
or
8l!tdi& @Dd.rcs
v.lB &rnNt!r.
of cobalt
e
@tth.dFl tEtctE atd
!'3.
Chemlslry ol VitsmtDs \tith reference to NlcotiDlc
ntu
dd oicl.l
rdd
q dein
(Fr8@ Ll5) is hdidin -3carborylic &id. lt @ bc lFtbaiz.d by ondadon of d@tirc vith poternt oidniry
TIE chcEicd
of ni@tioic &id (NA)
E?aie, ssh a tuojng dric d.id
or
pougoarc
'ta,
otl
"'-*^"
Ik@ l.r5
In
aqu@us @lutio|! tri@tiaic
('NHC,E POO'ft
i.
Il
@
n6.
Ni@tinic &id
eid i F*dt in
Lhs tso sir6 fq @!diuti@
with
il.9 zwinerioiic fom
o.r.l ios.
Tb?y
@:
Ptddift ring litrog@
a.r botb
a nmod.nul. s r.U d
bid€nrar., lig&dr r'7.
L cepld.s of d@dnic eid !fuyl r@u&, chldidq
nitJar! ed sulpba!! wF lqfotud by AIuj! et al. by uliog ilfilr.d sFdroscopic
tcchriqE- U6bn d c.rnoxl bedt v (COO )in @yl-d.ltiric aid @plcx of l:2
Chl@Edzati@ of solid st
Mltb.I Nuir,
PhD
Di$.rErion
lntroduction
Chapter 1
mdination Ho*cv.r, tLe ina@d spetrun
.xhibit! . si8lifi@t Eallocdon of pyidilc tilg tinddoN i! rhc 6npld lt t 4
Gvid€ne of @Dplqdio! of ddtid€ &id witb u@yl io! thDuS! nidoS.n aton of
irs pylidire dn8. Monmic h.xa @!d[atcd sttuctud of @mpLx6 of ulayl
Mt
Frio, erclude thc relal to oxygcr
s@ ob!d.d. Wh.$5" u@yl nitrar. ed
rrt.
@Dloulds of D@ttuc rid &t ct!.eddarcO in urur
cNdit .!d sulpllL wit
st
re c@dina,tjotr
ni@tinic &id
May ol! r llqrchcs pcn Lt d rbat tlF orly bindiig 3ilc of !i@ti!ic &id eith
udiun (vl) is its cdboxylic glup "t rte. Act et al. I'r Eport d tbfl dE ro th€
stqic hind.q@ th. chclat rioS doet not fom ald th€ crloryl oxyg.n is ihe oDly
Grat.@tradidic @ al$ prs.at
li@tiric &id coDpl.I (fq cx@de
t!. fdbatid @tutlrts of t|ruiud
r,8 & tug* fron 2 to 9) ta "'.
in
(VI) ald
sdr. ot lareir tlsc&h of R diEtr cr .1. dro sulpoi tb. @idinalioa of
udiln O'I) ed li@tiric lcid drcugh tle c.rnoxyl gm!p. I!. pH o!s. of 2 ro 4
tlc f@ti@ of cb.lat dlr is aor fesibL. A6 . qult of dr! pcirior of lirorcD i!
a @lc.'de or !i@tini. &i4 rtc .l4Ecr.tic rcputsioo bdr@ -Xn; ed UOl. is
nininizcd. Mo@vd. I[e niroS.n of pyridinc !i!g, owing b irs mcsomdic ed
Th.
deEolic efrcG, sl,rbilis
tbe
c@pld
12.
El.cilolic tatls, sF.td pdseaB ed @grcric mtMrs q* u!.d !o ilvBtiSal.
tbc i arctioa of .jcorinic a.id wirb dlrririd oetals *.tyl@to!d6 of fi$t rew of
p..iodic iablc. In @balt, nict l ed @pP.r omplei€s of tri.orilic &id, t[e
@rdinatior i! via ptddi!. rilg nilloSln. ltee @EplqB @ mid.$nllim in
s'|lte and
@dy bsollblc i! dt&ic 6olraa. Irr@
vitr.tid be.ls
of
.dtoxyl
netal-(tr) @ryleloMre3.
l,l
is
!o E@t bt stiftilg of
grcup v (coo_ I of ni@tinic &id aftd cosptcxarion wirh
milc lh. inted
isb.h Nuir, PhD DlsserEdon
ab.oati@ beds of prFidie .ins of
Chapter
lntroduction
1
sitniftall pdnlblrid Ia. cosid.Bblc poitiE lhito
licodlic &id dnibit
a
&€otptio! bddr of
v(C:C) !!d v(Carv)
ligsd
is a sign of
Mono&drt
.ing
@ldiotid
binding of licotinic &id
Bult! i! th. s[inj!8
(
1,312 L133
v
(c - o)
od
of th. li8ed
ofv(c-t)
ritl
ard lrridi@
in the
.i!g of ucoEplard
E rlls rbrugh njftg@ atom of irs
wii! @tpd via it' niro&n .tc,D of pFidbe
bldb A@ lJ24
d
I
ro tiShd Atqueo.y
.' r ,, No .tisnl$ae w.r otad.d h rh€ inniEd ba!& of v (C - O) .
6
(o.a ) . whil.
B d oicoe of @dialrion of ni@tini. &id with cr
(tr) eral, v,(coo )gq. EdsfolD.d tom 1428
d_t
ro a torcr
tlqeey
of
Unid.dar. @orililati@ b.rE!.n Mg (tr) lnd qrboxyt trelp (-COO_)
is..nftE
d
\lc-o)
i...l40t) @-\ ta.
by inGR
sE
tchilg
vihdioDrr bsds
1.5
fd
R
!t
!640, l45n4to &d 1385 .,-'. No
rh. ilter&'li@ of Mg (tr) 6d plddi@ ring nitoS.r w@
filqu@ie$,
T.cbDlqu€s u3€d
for Oe
chalrct rlzrtion
of
sflrth.dzed
compleres
l5.l
W-Vhlbt
SFotroc@py
Ul. of s!6d!3copy i! $ic!ri6c 6.{r!! h.tps to FdoE i. d?6 ilrBrisatioos
Eht tl to ltos &rl @l@le ed e..tliniry rheir squ@e in vei* conpould!.
Th. tuld!|mrrt Firciplc of stEforcopic t dDiquc tuolva alwd rhe abi[ty of
Ylstai N:di
PhD
Di$rEdon
lntroduction
Chapter 1
eh
chedi.rl sFci6 to ob6ort !.d c6it
ndi'ri6
of sFcmc
3rEroscopic .imimriod @npdition of chceical sp€iB
.d
b. nr.d wi$ hrrlt
d& 3 cdP.r.d
!o
otM ch@icd PI.c.dNr
iouti!., I.lius spc.Eosopic t@lr .mble
'n
lad io 3twturd 6i3rioc-
u
lo obt in viol
s@itivity .nd &.1fty, in a shon
cnploy.d
tbar
uv.L.AL rbasl
ft.r
infmtion
@lartr sp€.fosoPy @d tht idi{.d sP..ltod@py
lnd Uv-vtiblc spe6s@py a$ alug tb.d ljv-vtuiblc aPeFa e gpidly Lss
r'
rhe sfi?r€d sFcE but qlldralv. .!aly!h ce bc Pcrtomqd aily
@ Fvcral h.!ch6 of
"Erdrcd
EI6E@i. trNitioft in .
.idic.l sleiB die beue
of th. abdpli@ of ligbt bv
oolecds in ulraviold ald viliblc r.gio6. Ttu @jor cbMct .istic f4tu!.i or
.!6orydo. 3p..f!n e it5 sbnpc, lt p.ir mrcbnSih (X- ) !d dt F3l hcitlt d
molll qtirctid @ricidt (€) 'x.
Ab6oatid of radiatiN by ml6u&s in $lutioN i5 vcry wfrtl itr dalrtidl
appUdtic Fi@iprUt i! o.. of kt! @ldl6- By uiug B.a-rdbai he
@rcenuadon of ey unhoM lohtior @ b. deimin d- ChromoPhG i! I
rrr
@l@L ord lberptid ar a q,pi6l qv€l@8o &d wi6 di3titrgus[Ds sEErstI
lJ.Ll
n[oL nlio mdlod
Molc .atio m.thod or nold 6tio ncitod is orc of tbe vanols m$od!, vhich
us.d to
d.{mie lb. Elio of tigod lo Ml in . c@PLx b
e.lldc.l
l!.
oth.r
concentratjotr of
irci6
is
MolG Etio @tbod
i!
i3
tcpt
oilt
nt ald
tbir trihod ltE
.@4t!don of
wi.d '4.
tu
b! .Eploy.d
ro
dderEjdc the $.bility
co$t!
of 6 comPlq
ligrld !o dd iu (d vie r@) @Lr
the lolution, r1l. sbaiSh liE ponim of thc plor .E qtdPohr.d dll th.y
by plonilg
6tio
.ilhd retd q lig&d
e
$6d!e.
l.llsbah N,rlr, PhD
of a
slltid @w
Dis.Gtior
Inboduction
Chapter 1
inFs..t ..d oth.. GUor! r.16). ft. dio of ltrE lttdbc lo the .rm9olit d
rh<.6|@ is €qurl to 6. mlc Fa.ri6 of &. corylq lddly fan d
?
Molc
fix@
Lr6
_uatl
lvr)
MoL ntio plot of
a
conPLx
0.5)
c
Co@nlatid of . oEdd f@D.d.
Ir,oal
MLb.I N.rir,
Rrto(L
PhD
Disrt
don
-
chapter
C
Introduction
1
=
Totd .lal$icrl onMtrtioD of
n t l or lrgald (ebicl
b held
Lwr=eF
o.6)
If
lMl=q-Iw)
0.7)
txl=cx -lI4(l
o.E)
lb.n su!5.iuirg fd Ir4{1 fim
cqordoa (1.6)
i! Gq!.!id O.n .td
rMtzq-l-lc
txl= c"
For
lt.
cn
r!)
1;-
F
o9
0.10)
didl .qldon
lMl+IxleIMxl
Ih. .qoililii@ cdl6r it
Mlsb.h N.rlr, PhD
Di$.odon
0.ll)
(1.8) yi.lds
Introduction
Chapter 1
_-
tMxl
IMIIx)
wh@ Cr
a.d
l%^r
l.
0.12)
ln^),I,.W*Y)
ond Cx
@ tl€ &rl}d.al .onenirarioB of nad dd ligald sP@tively
r i5 t!! statility .6tdt r'.
15.1.2
Elct
otric
b.IlhloB b ddnldB
Elddodagnaic tidialioB is th.
|4
ulF.violet, visibl. .nd
innli.d rcgio6 @
.b&l!cd by adini& sluti@. A la4. ouEber of ab$rPti@ Frb in tbc lisiblc
m8. @ b.cN of rhc sharp 6to6 of actiud. solutios This diltirguisnilg
I.ruc
of acriride solurioN s of Iran
SEols
hlt
IlEtltt gle
i.
'z.
oe of 6. chd!.terislic ofl<t dds of litlt &tiddd.
1t.
thcn lh. lhlity ro pdricipat ia bo4diog *it! adjoiai.S alos
idizidg ability is
This fcanE giv.s
imEsl dotrg sicnts$
of cl@toDic
Elclrodc t
a
luiiioN
.uldc b.t'g
o!6.i€d io a.tilid.s @:
sr35t @..st lelrr6 or d*'r-rt"
ugllrr
Envit!'wlt docs lot aftct l[.* t aiii6 .nd Eldivcly .{row .bsFion
b&ds @ obrain d- Thc rrdirioN bet@! 5F5l Lttls ed bv 6.
sbsorFio! of el.ctomgDeti. adiati@ ir ult.avioLt visible @d n@
EgioB. Th.y @
sully l4ort Jorbid,ls tmsiriou d
!uH.ll.
tbcy involtc otbit2ls
co.s.q@dy th. trlsiti@ Po$ibility b
iltdsity of abudiotr bdds it nor d!c!.
of sinibr
intded
less
dd th.
Th. eMcy lcv.b in this O?. of Edsilioo cs b. turrlc. sPlit bclse of tbe
.fid of h!a!d 6cld ed eilotit t intF&l|oB. I! sluti@ sDeEa @r or
Mlsb.h Nazlr, PbD Dis.rEtion
Introduction
Chapter 1
tbe lsitiod. @
wel
ii
@pi.d
and
not
,-n-t
*p@r.!,
d.
oiry so@ of th. @qsy l€Eb w!i.h
lhow bdds with higb rFolutron.
Elctt@ict rLifeo6 Dstv@ 51.!d 6d.r..Ar
Tle trdrition betwcn 5/dd 6d ldels @
t!.m thar of
5F5t
As
e
. 6ult h!6d
Lr&
mF eBitiv.
ah6dFi@ b6n&
ro tb€
e
tumuldings
nctic.d
ed !o
pcdictios Fgarding th. shuche cm b. b.<L eir[ ecufuy,
iii
EL.foric
llg!
hBidd b..'a
5f
@.tg' Lr.l .rd orblt b
of
..rylsils
16.
Th* r.eiri6
@ itrIhe.€d by rh. latu! of ligdd!. Ltdd's clcd.@ic
confic@tios d.termin thc lroblbility of trdsitios, Envircnmntal f&tqs
.lso aff.d itee t6r5ili6. Ilc ab.dpli@ b.!ds ot||ricl by t!4 E nsiti@
e hom !s .l@t on rallfs d cb4e aelf.r uaciliN. Th. poeitio6 of
thes. bod! deFnd on coddimtinS ligdd ItE. b&d! e Elativcly jlicN
EdiniG ir uli.viola .nd yisab rlgioG. Th.
bridt colorcd lotuti@ of eti.i&s @ minly d@ to lhc!. alsqptiod btlds.
Ev@ tbo[g! thc .L.[mic daitios b.two 5/- 6d lcvcls c
@mpar.tiv.ly E@ irGB rld th* ud!iti@, ,Et tt@ 8@d& f.6
@bb b.cue of lhc .b!or!Lio. of ddiatiou in ululviol.r egioo '.
.!d inrclw t[.
rhddptiotr of
r5l lltntid SEetltFDt
U*
ot iinutd (IR) or vibntional sp.rEoscopy h valuabL for lle andFis of a
c!@icrl cmFdd '1'. In spors !o d *iUrd!8 .Lc!@l8D.dc f.ld of sFcifc
BFcl
*[
o$4, Tbis sp€drc6.opy inv.sdgaB ih.
chsfuEristic vibr.tio@lba!d! of ct nic.l gNps. ODly thoe viblatidal Eoder 4
n€g@cy, arotu ID@ with
l.li{Bh l{.rir,
PhD
Dls.Edon
!o
Introduction
Chapter 1
IR &tive
t!!t
d alcEtid
iovolve
in dipolc
tt]lear
VibntioMl mo.Ls @ dect d
l
foB
2. bteldoDic
3.
Mes
O{!d
5!ast5)
of the aroDl concened
80rh ftEqrdcy of yibr.rion .rd absorytid tend.cy e Ntrlt d by iDar ald
iltctfulcubr.tre6. SFfd p{@.ia! wh a pcition ald eidn of a b.!d 4d
c@fii.ieft of absorprion olfd rhe prdiction about sid. chain struct@
lJr.r
B.hrviNr
of
dd
irr
@i@ rclds io btnr.d Ngion
Thc !h6oDti@ bchlviou of
.d@ @idi i! Ile infilt d F8i@ !a betr
.Iei!.d
a *€[ as in !olu!@ forfil Sodi6 of IR iF.t" of ani@ a.i& ald
Elst d c@posds i! aqu.!$ solutro! by Edsau lcld to tt corclulio! tha,t dino
4ids qisr ir t[c i@ic $ar6 &d m6@ d. distiogulhiag n!qu@i.. of - l{}rr'ed
both in solid rtat!
Oo th. b6i3 of s?eftd@pic anldid
.
Iae
d{ino -ids, i! slid
poilts distr
.
s
srar.
ed
in lqucod solution
Amino acids a.quirc chd@ilristic Aequclcies
Gcncraly drc rEucntF of
.!.epB
Mlsb$ N.zk,
PhD
t
lt
then i.@lccric
dipol$ ioN.
- Ml t!9!@i6 i! - ntj
vuic
o! ui@ 4i&, fouopilt @trclBiN w@
i@ snic!
dsiro
E be! t
Dlsenadon
L!
rcid
to stDdy
wind
@ b.
t!.
th.n
ot -coo-
diF|I
wrift.d
IR sFcda of
a
i@jc
ud
chlaLr.
RcE(NH;)coo'.
di@ !dd5 u(4 .!d il
lntroduction
Chapter 1
ws mric.d rbd rhs.
hted
is
Fgion of 1600
loriquc B.dblalc. i!
d{
rb. b.havid of
uim &i& ir
to 1300 cu -' . Int{pretation of sp€Fa of m6t of thc
isid.6is cgio! s[owcd 5ix scdcnl .b6orFid balds (Lblc
sN q@piioB {@ rbo no{.d to thrs coGistley i! sp.cl6
@npdrd5
Howvd,
TtbL
I.S
Ab6orltioo b.blviou i! lot
flErioEl .rdd4 !': r'!
b.sid.s
thc
14.
1.5).
Comon sbloation bu.ls of milo sid6
si8!in@!y afl-Gd
by
l!.
pr6dcc of 3ulPhu d ottd
Ddtorylic m|]lmiN -id,
idiz.d caibdyl ald -
Mlsb:h N.zii PhD Dls.nadon
]!ltj
stow c4tony' !h6ot?ti@
.b{dptioc '''. Similely diMino{.lboxytc
Chapter
IntroductioD
1
sidr ilustral. Ae - Mt:
.hsolptioa
buG otlE
64 trtl of Eprt&dadv. dim
eid. T!. leryth of carbo! chri! ?r*Dt b.tw4n - /vA: tnd - COOIT 8rcuPs d€3
trot ioduce ey rff4t m th. djpols fm of tbe$ sFci.t. ConplicltioN in thc 16G
spedM dis by th. p@@ of lr@[lic .ine d l[. dino
&ids but Fpt nyl ddire, qsin Dd si4il! codpouds @e oDt to be cffectiv.ly
1500
d-' rgid
15.21
of
lDf.r.d sp..la
of
diDo &ld @[pld..
C = O grlup. ehilc b€bving
ward of crysirniatio!
d
6 nd{oddiD.tidg
8roup, @y
fom H-bond with ltE
rcigbbod4 eole.d., @ @y b. ec6&y botdcd
b O.
oet l of adjent @npld. Ac@rdiryly coordiulio !!d intcmol@ul4 lntqactioor
!ffd 6e vibdtion t frequdci$ of -COO r{. Thc s.P@li@ betwd 3yon.Eic
(v, -COO-) &d dtisrln ni. (v- -COO-) tlu.bilg vihlri@d nEqucfty or
cdtoryl Erup d!. to tbc bonding of iL dboxylic 8!oo! i. Lrger a @nPlnd to
fre€ s!ar.. Ir c@rdin$ld carbdyl gNps C = O sEdchjng vikatioN bdtb .pp.d al
16@1640
''.
A tuBc of ret l .@plcx6 h8 b@
stilizd
to 6!d
o
rne cfic.r of
br.hgd
seLhilg tlqerci* of -COO_ in both hyrl$tql ald
artydrcN c.ystllinc 6aar., Ar in.@. in antis]riEEic frlqudciq ed. deGas.
in symdtic n Cencns {@ obs.rvcd dd $. i.peali@ h.tw@ the two
!{.
fiecudci.s in@s i! th. folowing ofltd of nctds
bolding
.d.oodbador
Ni (tr) <
on
zi
(tr) < cu (D) <
c!
(tr) < Pd
(n .P(u) < ct (ru)
Evd thougn ther @ sevcral ex@ptioi! to rhis s6qw€, bu1 uuaUy tt e Bults
spdify rtlt th. out@G of c@rdinatjon is th. mt inportdt 6pan fd the
6tiE!ti@ of tq@ncy odd i! ! speifi.d ptFicat rtdq As thc @rdi.atim of
Mtsb.h
Idir,
PhD
Dl$ert don
lntroduction
Chapter 1
gmP wit[ maal strcn8thtr, thc arymmr.ic ch@td
it|.t!.g. rLnc tle at E ilqMcy ddd d€noisdare e itlcr4ilg irr.r&lid of
oryg.n a1on of
Il b mt
6y
-coo-
fie stFnsth of rctd
ro conlcr
and
oiEotd bdd fim tlE oldct of
fitqudcy of -lvt,vibFdon bcrdt bda@ Alcudiat of -,vtt, @ dtdcly
rcsponsivc !o the effet of int€mol4uls intc@tion At tt Egion of low.r
&.q@.ct v M-Nand v M-Ovibdtion h€!d5 @ id.d to disB lr-Oard
M-X
of nLl onPlexca {ilh @ino &ids
slElchirg forc. c@t.'!ts e dtc! l.g tbe bd of
bond su.nSrh.'nE exuimtion
iDdicates tbar thc
,t-O
@ b. stlt d t[tt os_i6ol|6 shry
nG bards in the infi&td tSid the tbe E6$isot!6 Cis-ism ctlibil5 t*o
librarionit banG for elch lt -N .nd ], -O in the low filqEdy Egion, whjle lh.
Conlidding tE sylueuy of ! ch@ical 6p.ci.s it
trs-isM
s[oes ju3
oc
fd.&!
oI
l[e
Eoda rd.
d.pFto.itim
Th. lrrcrgrh of ibe M -
lv bod beo@
dd d
a
M-Nof lle cddidt d -NH1 gNp ir de$l.omPl*6
mv.d
!o
r.sj
Mai.euc s!6c.pdbl!ry '!a
Esulr of lhb v
hislc posirioa 'o
snongd du. to tle eff@t of
it
''.
$3
Duc !o the .LcEic.l chdS$, rogn.tisn is a chdrddiltic of
.ll hsr.ddi Aiob'
. louft of d4lic cbdgc .!d tidfoE, rna$.ri$ it I
lnjvmal ph.noFenon. fte nagnedc fi.ld in d aton is prodoc.d dw to in.
ddbririoD of sDi! ud orlrld @Imts Flattl wirh th. Doti@ of cl6Els Th.
mgmtic prcp.nid of ey Mt rid e bdds of 6. oseSMdat of olnftd ed
besic
6il
of
rl
md..i!b,
is
Misb.h a,ldir, PhD Dl$.rtatioa
lntroduction
Chapter 1
3pin
na€!.tic !|]o|@ts of its MtdtutinS
lool
fd
chdet riAiion
thc
of sub6taldr.
'lo@.
Mlgnctic
FoF i6 @
a valoabL
M!$etic prcp.ni.s of lubst&q cd b.*anin d by lh. alplcation of. @gn tic
fi.lddd.vdu.tionof lh.indrEld@8!.ii2!ri@iatt 3ubck!c!$.
I!
nl
gcn
EASDctic
auspiibility of a Eldial i! tesdcd a
a
nDcti@ of its
*ithq
o.l3)
pheE
Li,
de
.N
sc€Ptibiliry of tb. cdPould
lu.@ribil,ty orthe @mpound b Elr&d
to tbe
x, =x.w/z
vhd
is
pa
1532 cui.'s
In'
ul
v.igh
fmd!
of thc conPoud dd Z is th. flrnb.r of rh. Dolcg
weigbt of dE coEpoDd,
15
Tbemd Eolion of MgDarc
@ngm
Folr slsePnbililv, X,
0.14)
Mw is thc nolccular
of de brgr.ric
ed P i5 th. ddsitv. Th. ms
nJns
h6. t
nde@y lo on
lobtt
th!
m@ s, tbdfoe,
nodnB of Fri@llaic sb.tars utda
u applicd DgD.lic 6.Lt. At losa tenpdtd|B th. ltr&1 of thcmd mtioo tlss4
rd consequdtly rh. obsdcd pdba$ctic Els..pobility of. EAt rial ilcFas€s.
o!pc.
rh.
Cuie
h* crpliirs
s
Misbah l{azri, PhD
of tlE Mgrcti.
th. Flati@hip of &.
Dl$.n
don
6B.Fibility of a !.r@8!.ti.
subsra@
chapter
Introduction
1
x,=%
(r.r5)
.Graa! rbich i! tlc cb.Ei.dsic of tbc @4lcx .!d r it tlc
l.mFEfutg Thc plor of ilF irvme Dold na8rcuc sNceptibilitv ed llnPnte
giB r s6ig[t lie vith . tloP .qurr to lIC. tb. t LrioNhiP b.tu@ Cwie @BLnt
Wld.
C is th. Cuic
and .fr@tiv.
*PEsed
Mgretic Donnt ltd, (lunbd of uPairc l .lettom) or
by the
a
conpoud is
folovilg .qu&on.
Fd ={8,(rI,'I -(8c)q =815(5+ll!4
=t,'r+2'lq tl 16)
vi$ no dbitd conEibunon to the
Erg!.lic 6ondq S is lhc !a'!t nl spi! q@om dnb.. ed n h tb. lMbd of lnc
whm l-alxta's f&tor, g!2
uPfur.d crfEos E @
ft.
abov.
.Surli6
0 for an
3Fm
'...
daton
J = 72
or ion
,
rmm s tle sPi!4ly fomuL' b6a!$ i! ltn dFsdon n
is
fq !F na$.tic moNnt
. @oplci @ b. d.laDi!.d aeqdilglv.
is 6sum.d thar only dE ddhon 3pin is lcsponsibl.
lurib.r ol unpair.d
dedw
'.
Thc qbilrl botjon of cletD! ,dnd lhc NclN giv6 ri$
nosMt rnd thel.foE
F,,!
wb.F L ir
= tS
th€
rbc
bial Ea8redc
moG ps
1r(s + l) + I{I + 1)p,l'
$6ns
nuolq fd
tu ejven
t<r
otbit
l
and
th.t
tueedc
by
(1.17)
@ ato6 ehich d.6!ca tbe
ollit l @tribution
r.533 l4rsDettc propdds of lfui@
c[acr.r of !.linid.s tltc dPdiDdt t vttG
lovlr lhd t[c v.lu* *dtun:d by ltlcs of Rus]l'
It is no[ @y io dcolhd i]e ba8!.tic
of tugn.ric nomcnts
{bb:l
Nadi
PhD
e
DisdEtior
Chapter
sludd:
couplils
Introduction
1
Cdrplin& This is
amge@
bondiry, !o sotu
b.cie
of uSdd ficld cffet .!d &6ci@y of lhn
ln vi.w of th. fact thit
d.gE, lig.nds
ft
5/.n .sy lcv.ls @ insltEd
ody @!.osibL lor tbc
d..@
in
covalst
in magneii.
lruyl .i!"re 6d uDnous oxalr.te in solid riate wF studlcd
by Be .nd BlE. W.dEkind &d l{uit p.rfomEd Men tc sodi6 or ondes of
l@i@ rt @biqt llmFatur.. Suctlmith .!ti@tcd na$etic susllibititiA rzlus
of UCl. . UO, &d U(Sq), !t veiN aryqrtes. Maendi. ptop.ni6 or q!.s
slutrons of Umium h.ving its wiou oid|lid slAIe (m, Iv md VD have b..n
Magldic proFrties ol
d.t min
d tbrcugh
nodinc'rioc b cnuy
EtM.
rs
of EDTA hd bcd Plldict b, usirg
r'
Fotor NMR sFcr.o!.opy ud rbe valq. ws oburat d ro bc 3ol BM.
Mr$dic mmnt of umim(m
@mpound
1,5.4 Th8ort of Cyclic Volblmerfy
Ele.rn hmial
@tio6 hlE ben eid.ly sndi.d lhmSh
cyclic
voliimdc
rehniqu., Applications of this llchdquc pcnain to thmodynMic ed kin tic 3$dieg
of r.dox @6@. Ay y.rying thc val6 of s@ rat of poLltid, kjnetic infdonion
Fgedht
lhe
Ei.! of
Me6od.
fd
.lct mioing
the .14[ode pro.4sd u.d.r itrvqlig.lion
6
b. obtailcd
ih. ha@g!@s detoo $dsfd rd. 6nsr.nts w@
dedib.d by Nichol&tr and Klingls d al- tlE @h.!is of ! r@ri@ @ b.
sugie.stcd usiag ihb info@ti6. R.dox polntial of m el@tt!.cliY. spei.s dd dt
.fret of D.dia o. ih. .L.to! trefd Mdio! @ bc apidy sMi.d by tpPllmS di!
Ar .lerectivc ap€ie i! Fdued d didiz.d d tne su.f.e of e .l4r'od. by
aplytry rpprclnac potential. The pot ntial of r sortinS clcdrcd. L s&.d
[ne.ny dd for this. ciallrd& poi@ld wdvc fom is ued (Figlt Ll7)- Th.
Misb.h
Naii
PhD
Dlserration
Chapter
iosEu@nt
lntroduction
1
drsc
rb. cbaled
i! cued $ a csdt
voh.dnoem {cwDl-pot ntial Plol) b
Ft nfrl swP
ald
a
cvclic
c@nt d.rdd! on th.
rbc cldtod. s'da€ dd tlc r& of rh.
obrrin
nov.t@r of s! .16{oocriv. sPeiB towsds
cl@tro!
!.
of
The
ri3
F!!fd r@tid
lig&& d thc oxidariodEdudio!
pot nri.l of thc mc|!l ions in mDplcrcd @nfigMtios hfodt'lid .bdt thc
cletro.hdicd bchviq of d. D.t l @optcr @ b. u.d fd *lari6 of .n
Cyclic
loLoeay
b.lpr to
.rtlut
tlc
!flal
of
ondirinSag. todrilttinrheiltdncditr.ondrtio!shr.of lhe@td@mpLx'!e
cleitod. is c6ied @r duing tltit Pr!.€!& Th. ee
voltag. M.hcs V1fion initi.l Vr Gigd 1 17) .nd th. rcft!8.
Cyclilg of p.r.adEt of
Fv@d whd
sftpt b{.L
to
tne
y'. Th!
d
is
d.o tdtrEd 6
nissE.l..l7
Equnion (1.18)
FpEsk
lhc cyclic
ctllc Eiuedlr sv. eol|lm.try
voliaS.
ss
of
v3
ti@ tnph.
t[. rclt
(1.18)
Mbb.lr Ndlr,
PhD
Dlsnt
don
t
.
Introduction
Chapter 1
wlE
.
v is
A typicd
th. s@ nte,
I i. the seir.ting
potatial E i! th. inlial pollltinl &d
volhtl@t@ fd . rcvGibl. !i!sl€ .lecEd tmsfd @tid
t
ir
is sbon ia
i."'
3
I
E
!.
FtzE r.tE
Fofldd
ltoduq
swclp
R
who
the
!.{
A tr?ical crrlic
a! oddi?ld
spdi6.
)o+.is
r!d!.d,
toliamm8lu.
0.19)
tbc oridi4d speci6, prcdlc.d
a!
sa4p, Sndurly &6 EdE.d to E&trDt.
(r.20)
'rhc
rcvdibL
Mtb.h Ndli
E<lox cnenicd €lcrron h6 foUowing
PhD
Dksertsdon
ch.ra.tditj6
Esult of
fward
Chapter 1
L
Intlodudion
Th. *pMtiod ofpc*lor.nrial
M=E,
2.
It
EF
vdB
-52hv
positio! ofrh. p€&lor.nriab is nor
3. Th. p€ak clenr drio
25.Cis
(l,21)
a
tulctioa of
su !e.
is cqud to 1.
(t.72)
4.
P.rk
(lllrtrc &! diBdy
pFponiooat ro l[c aqurc r@rs of the !c&
re1
o.23)
Rdox c@pLs wh6. peik scpfadon i!@.r6 wirt Oc $& 6r.
Evasiblc @pl6 1@16r
r54l EL.tod.Dll.rr
ot
u
N
r.ded .s qu6i
E
Tcnd.@y of uraryl @rdilalion coE{Eud! to rEd.@ io &t@ou and don
eluti@
ta
aqu6
tuin
d atd nrhrisD! for .l@rocb.niol @lduct of rhc
@Dpld.! haE b@ Eporr{t ,a'&. Oa uout ot rlc vsiors oxid.tid !t r.s (IIIvD of udiu, irs.lerr@hctuicrl b€havi@ i! .tiv.6e dd G gE.tly irfludrc.d by
bc.!
its.oordioriormrircn4'o.
Arotu pB6t in sbtioB afre.t lLe fodDt
por.ndal vil@
fd U'rua
c@plc ia I
rcdox porrnti6l valu€s. Thc foqnrl
mrd Hclqsohrioo
is 4_631
rclr *trd.rs.
i! I mla llcltbE vdE is {.640 rclr ASlmE.oluri@ of rmiu elr ud.rSo
&id rc&tioo osing to bldrolysis p|oe' ft. Fre ot hydrclrsi! rcadion irdr$6
in
Mlsb.l N.rir,
PhD
Di$.ir.do.
Chapter 1
Introduction
u'<uo1< u*
I!
nolar eidic mcdiun Ue ior htdrclys! lo ene
dt
dr
dd ir bay
i! i[ghi &idic eturic. U! peipirri..
of sioB rire F-, tDldd lo;.,
Fll'Mic
odpounb
ELc'rFh.nic.l proFni6 of
UCl.
produ@
olr by t[e ddiioo
iI N,N{iedyro@id. d diErhtt sdJon.i.
srvdrs w@ obw.d 6iae polo@gr.p[it r€.h!iqu6. Teo Eductio! Fjb, om for
tdudioa of utuim(Iv) ro uaaiM(Itr) ed rb. !@nd for lllc €ducnon of
@iM(lII) b l@im(o) on<ltlioa *ne 'o. o! r!. oth€r hud, Malry ct aj.
obs.d the tductior wrB thrcu8! cyclic volr.DEliric aMy ot UCl. i,
t t ahydtuir@
tci.,
'@-
X
ws popos.d itrr
rh*
!e.rs @
be!&
of tlc r<lrcrio! of
ditudc sF.i6 (U,Cl;) dd Ucr;. As . coo€queacc of 0E€ Edox
UAr
.-
1) UCI:
It.24)
vct,+Wct.ev2ct; +vcL
0.25)
+
wh.ca, Uct
is produccd dtroudr tnc
tudoos
u{t; +a ev,cl:
vacti +Ugt;
eyct;
Mlsbai Nzif, PhD Dirs.rtation
(t.2n)
+vct,
(1.27)
r.dioN
Chapter 1
Introduction
Esp€.tircly. Utuiuncv) @rali(dibdhyl sulfoxid.) in din tbyl sulforide r.dued
by showing rhe r.ducrio! F*s, Th.$c F.ts s@ dign€d o rb. rldudiod of
@iud(Iv)
lU(d,E
utuih(Iu), .ede(m of umihGD havils vdiou srnctuFs ftoD
@npoud ed ufuiu(Ill) ro u&iuD(O) Esp@tiv.ly r'.
!o
)rl'
Expdibclt see
dian. IAeNd,l., !o urniu(V) in DMSO
solv.nr haviry Ol mol{ of TBAP s & elariolyt . gowcv€r, no rdor
Far wa
obwcd dti.g crtlic volrablEq of rhis @Dpound i! a poErri.l @!. of _0.q25 to
+0.975 V uilg Platinu so*ing .lerod.
'4.
abo
Fdod.d
ro
oicelet&d. .!d naljr@ ddeic.eLctDd. *@
PhtinuD
u!.<t ro ilvstiaa&
rb. clatreh.mic.l mrurc of Cp,UCt. Ths! sMi.s shoeed th^r Cp,uct .Widly
Edu..dba6tlblesp.ci.5, Cp,UCl-.
sstiDabd to
Thc diftusion
coc6cic vatucof Cr,UCt w6
b.O.0+0.D.,5.or/s. rt rs.lso o!6.ry.d U.r Cp:UCi ondizs
ro
b( tbn speia is tur stlbL dd @&rgo djsprcpduonltr@ eaoo, A,
ECE Eehdiro ws poposed for tbis Ea.rioa. Ib@ ws !o Mjo, shinilg of
Cpj{./Cl',
se n&. Th. nrio ofcotbodic p€ak
cuft.t !o thrr of rlodic *!s l4s rio I bu! ir iEtlss Mrh e iDctte in s@ d€,
Howcvcr, u i!l.M Flarituhip *s p!!qt b.twc.D thc par cllMl
d.sny ed
su n1.. Consid..ing lh.e BulB e ECE @heis for rhis l*tion *4 put
oxidation
Fab of
ChUCI
e
2CP lvct',
Cr'rUCl with rhe vuiation in
C\UCI'
+.'
(t,28'
+ cp\uct + cP,ucll'
Owirg !o sbon [fc spe ed Epid
ueim
(VI) @bpound produ@d
Irrlsb.n Nrzir PhD Dis.@doD
etion i!
(t.29)
etutior !o cirnodr
ia tb. dpqi@nr ws dct .r.! ItI,
Intrducioa
Chapter 1
Utttlhttrb.-h.fi!8@6td.d.d.,|to*r'SDldrcdt 6ad
tuD d.l.c.e b o6.b.d. dt @l i6. tL F..dd,r ot rwio
bo m.|!oitm.oo! d .!dd}.(DjL tz.
IrD.b Ndrr, PiD
DiarEttlo
P.!.52