Iffiion
Transcription
Iffiion
CIgrI Iffiion lntroduction Chapter 1 r.1 Chentstry of Ur.rtum chdical !ro!.nis of stirid4 .xhibn vsiabL [email protected] 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<itrGd 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 [email protected]! 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$6 or !fuiu (VI) compoudi ws found to b' 6 d 8' *itb haaso l bip}trddrl d @tab€dral [email protected] ExaElI* of uranvl @dPlq$ @ 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 [email protected] 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$M (Firs€ 1.2) @ njffi i6!8cs of .rch orhd Th.y @ abo .Mtiotrs, i .. the noleculB c@ot be supcdnpoo.d or c&h otld. Thc PhFicd ploPati6 of e@tiolEs dir6{ioB e sn l [email protected] ap.n ft@ d!1 lh.y torfic [email protected] light h oPp6iL @ calcd odic.l isi)!ts.{ n R- C-H I I cooH cooH Sl.r.oisoo.B of milo eidr 12.4 Abpholrtrc ortr$ 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 [email protected] 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 [email protected] 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)[email protected])(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@ [email protected] 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* [email protected] 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 [email protected] 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 $6d!e. l.llsbah N,rlr, PhD of a slltid @w Dis.Gtior Inboduction Chapter 1 inFs..t ..d oth.. GUor! r.16). ft. dio of ltrE lttdbc lo the .rm9olit d rh<.6|@ is €qurl to 6. mlc Fa.ri6 of &. corylq lddly fan d ? Molc fix@ Lr6 _uatl lvr) MoL ntio plot of a conPLx 0.5) c Co@nlatid of . oEdd [email protected]. Ir,oal MLb.I N.rir, Rrto(L PhD Disrt don - chapter C Introduction 1 = Totd .lal$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 [email protected] f.ld of sFcifc BFcl *[ o$4, Tbis sp€drc6.opy inv.sdgaB ih. chsfuEristic vibr.tio@lba!d! of ct nic.l gNps. ODly thoe viblatidal Eoder 4 n€g@cy, arotu ID@ with l.li{Bh l{.rir, PhD Dls.Edon !o Introduction Chapter 1 IR &tive t!!t d alcEtid iovolve in dipolc tt]lear VibntioMl mo.Ls @ dect d l foB 2. bteldoDic 3. Mes O{!d 5!ast5) of the aroDl concened 80rh ftEqrdcy of yibr.rion .rd absorytid tend.cy e Ntrlt d by iDar ald iltctfulcubr.tre6. SFfd p{@.ia! wh a pcition ald eidn of a b.!d 4d [email protected] of absorprion olfd rhe prdiction about sid. chain struct@ lJr.r B.hrviNr of dd irr @i@ rclds io btnr.d Ngion Thc !h6oDti@ bchlviou of .d@ @idi i! Ile infilt d F8i@ !a betr .Iei!.d a *€[ as in !olu!@ forfil Sodi6 of IR iF.t" of ani@ a.i& ald Elst d c@posds i! aqu.!$ 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 &[email protected] 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 [email protected] 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 [email protected] @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 [email protected][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) [email protected] 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 [email protected].,|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