Synthesis and Characterization of Various Amino Acids Complexes ...

Synthesis and Characterization of 

Various Amino Acids Complexes by 

Different Analytical Techniques 

Raja Adi-t Sarfraz 

National Ceuter of Excellence in Analytical 

Chemistry, 

University ofSitrdh, Jamshoro - PAKISTAN 

June 2008

Synthesis and Characterization of 

Various Amino Acids Complexes by 

Different Analltical Techniques 

izVei al,/-i 

A t frz';' tu,sirkl b t6. ,Ul e$iq ,J Sn 4 i^ portialj,tfhrd J.r tfre 

d?Btu oJ aocr'/ ofefritosoptry in Chanirtr| 

Raja Adil Sarfraz 

National Center ofErcellence in Analytical 

Chemistry 

University ofSindh, Jamshoro - PAKISTAN 

June 2008

CERTIFICATE 

"Syntheals and Characte zation of Vadous Anino Aci& Comptgxo€ Using 

Different Analytical Techniiues" 

under my su;dance ed supeNision in thc labonlories of National Cenre of 

Excellence jn Analltical Ch€misFy, Univ€rsity of Sindh, Janshoro-Pakistan. 

His rcsearch work is original, irnovative and thesis is worrhy ofpreseniation io 

the University of Sindh for dre award of degree of Dodor of Philosophy in 

Chemhtry. 

This is to cenify that, Mi RAJA ADIL SARFRAZ s/o Raja Sr.frrz 

Akht.r has canied our his Res€arch and Experimental work on the topic 

(Prot Dr, Tasneem Gul Kirl) 

SupeIvisor 

Nation l Cfttc of Exellcne in Anal}lical 

Chemi$ry. Univ€siry oi Sindh, 

Jmshoo, Pali$an.

ACKNOWLEDGEMENTS 

I bow oy held b.foE AlEthq Ahh, The omnipotent thc onnipEs! lhe 

n.lciful, lh. nosl gtuiols, th€ @np4;or5lq rhe b.nefic.nt, who b tlE dln ..d only 

sole or d.ry *nowlcdgc dd wisdon sdo$€d to narLnd ud wno bbs*n m. wnh rh. 

ability 10 do ihis work sd g'nr MuhrDerd (Sellalldro Alaihe Waallm) wno gav. u 

th. spim ro 18. h is lnc blsing ol Alnigbry AId od Eir Pmp!.r (Sdhll.ho Alaib. 

Wasallmr fiar have enrbld me @ malc my eifotu d:uas. 

I rculd liLe to lllc this opportunfy to @v.y my @rdial gdnud. ud app@idjon 

b ny vodr, eleend, dd Ealol supeFief Pret Dr Tcrtren Cul Ksi, wnhoul vh@ 

@n51ol help, dF, inLGt .nd vi8ilDa sull$e, 

rhe @ntleton of tiis d6is would nor 

h.vc ben possible. I sm euy ind.bt d to ho fo hd .@omod.rivc atiirudc, lhoughl 

povoldns guida.ce, inh.r int lletl.l input, p.1i.M, symp.lh.tic bdt.vior dd 

adninhtrative dedure in Foviding m. all rhc f.ciliries r.qlircd 1o complere $b piece of 

I m !.ally indebt d to Prof. Di MuhuEad Iqbd 8n.r8.., Dn€ctor National 

Cote of Exellae in AMlydc.l Ch.oist y, Univdity of Sin

I d litcdlly ideh.d !o Di Nr.iD. M@oq and Di AEbcr Reh!. Solalgi lo! 

$eir inlpintion $d nolivatioh !o improve quali9 ofwo*,.cadaic vision dd broadei out 

lmk. I wuld likc b tnet ny felloss 6Fi.lly Mi Abdul Nlo, Mutubrd 8.lrl 

Arrin, DL Rrn. Shthid lqbtl, J.6il AnE.d B.lg, Oh{l.o Abb$ Ka bre, 

Dr. tllstr Im.a! Afridi! T.bni, ADFan M,L J.ndi, Sy.d Afal Sh.h, M. R.uf 

I(nakn.t, DL Mlbam A|.hrlr, T.[ir R|frq!., , N@r-!LHun, Di FrE! Nu 

T.lpur, A,Q. Shrh, N$rdl Jilb.tri, Mu@r Ahnsd Xid, Ibrm Brklsh and resl of my 

f.Uo*! for lhen assislae, go.d 6npst ntrlous bdavior, niadly lititud. dd keping 

€xceusr h@lthy dd conpetitive eolircnhent foi L@ing purpose in the 6.srch kbs 

My thdks e dtddcd ro my ucle Rti. Trqn Aimd, ny bdnd R.j. Ejo 

Ru, H.hmd Rra, Ab.d RM, H.$.! S..fn& Mohrh $rfnr 4 well $ ny ftGids 

N.jcm.l H.*!.!d M{ik MuhtDmrd Jht!!.t, 

Ano.g d. dministr.tive slafr of llle cqt r, I m hidly iod.b&d 10 Pir zi.-ud_dir, 

ML Athr.r Ali ViShio, Mi lEnr-ullliq &d Mr, Nar !!. 

Ar lasr b not thc l.!s! I @lly ac}jdlldge ed offd ny h.!rti6t gr.titude to tll 

menb.6 of ny lamily ap.cially, noiher, wifi, si$ors, lof deir great @nfi@, nonl 

spp.r! @p...rio., enouE8mol, .h 4d odd disluhec., D.ri6e, blrde od 

pnyetr lor my hcalih durin8 this *ork,

DEDICATION 

lfuis Eatcopors Is Adraatto ry lBebwt 

aarnts an[EEec'ut1t! rr., [edest cousit qfuia 

EjazQgzaforfris ttiring ont Sintere Effot* to 

gtafg frle $ucessfa[

Anino ai.ls @ t!. diftt uilof.v.ry kind of lifc ed e foud in aU O.living 

syneN. Tb6c have b.m involyed ir synlhdir o{ a lsgc Imbd of @mpouds with oB&ic 

atrd inorydic doieti6, both in-vito &d in-vivo. Th@ h6 bc.n cncNiv. lit€rare available 

on vdious derivative! of mim acids, like schifr bes, mides, .sleB elc. witl diflcrerLt 

bioloeic.l 6 w.U 6 inorganic .orDpouds. As fd 4 ihen inte@tion wilh cholesleFl, 2- 

m.tiyrE-hydroxyquinoline dd osiD (rclal) is @ncmed, linir.d mtk is ?vidd.ed by 

lireratun 6 @mprFd lo o$q @npoud.. lFp.ntio. ard @nPlete ch@tcriaion of 

miDo &ids 6mplex6 wilh lhe tyFs of cmpLxitg @gcnls: (i) 8-Hvdbxvquinaldi@ (ii) 

Cholesrml dd (iii) Trtuitio! m.lsl (osDid Il) vd @i.d out in lbe pan for Ph D. 

studi6, s d€sribed b.low. 

Amino Aci& Corplss of 

Abstract 

Part I 

'M.rlvl'&btdrcrrquirorit' 

Fou dino acidr (dpetic &i4 elui.Dic &i4 cvslei@ ed sin ) @npl*6 of 2_ 

malyl-E htdoxyquinolire wcre pr.psed bv a w on step BedE4 iwolvins ullrl eud 

sine

H,C 

N 

rrd'.turstcd-r.dl,}||lid. 

htn 

Adho A.ialr D.rtediv.t of Clohtetol 

Anim.oid ddivriits of ctobEol bv. llcadv t .a tvei"d tld dplov'd 

s lr{ mddrb &tidt dg.nic S.ldoti ([MOG!) (Yr 8!Dg .' tl'' 2qrl Dolto6 tb€s' 

slpouid. .ls t rG ba u!.d ftr d$S ddivtl od .ti!o tcdlot! Wc hs 

"i'b 

ryid6ir..I liDitd tind of E* dim &iG

o tl 

"4o 

N 

r.rn.dEtu P!qo..d nldEddd&i &!d 

P.ftm 

Arho A.ibcrrpbr. orornr (tr) 

cHr 

CH, 

Tb tF Nvd t if edwin dis sik 6d"c' of o.bi@ i" lo{ileF 

cyn!'Exrl-N{F>,ndy'dycir D.4dcara)chl (^) od todt|6Pct''GExrl-N'N{s} 

lt€rrrdoir.mido)Cll (') wt! svtthclizl, frllv 'r|ncraiEd Dd th @dovld tor 

ct dlo6.h6ll! Edtdd of ldG (9: a' p{56!tsd t'roc it 3 t@!bd rddE) Tt' 

erd.dznio of 004lo.6 w tri.d dt tv Acdlslio B wdr d |['lylid oabod!' 

ih.ir qydrl iiucnG wG ibt 6fE d !t i!8k 6tri x{|)t solFir BoG of dE 

mi@ odddd es! fqld lo .dlt4 tt' Ettt'ioo of t' FMd'd rdo6 to 

sdgd.d latG ft!{€h iwizniod of rb' Fidilv F!&'cd dtlb dcff! TIF 

Ed'rftL lrtmG3 tfr .dttd io ..CoiG intord{im d lL dtd$n @d tEb &'to's 

etiot dy irflGE t!. insdid of e Ddl cqn' win |!' sid'L @4 l!8' siol 

&. *r.divily of tb bd$g*t|64i E(hcdc

ft. d&dns :llrlMof A 'd 3. Dirpr@d 

ditoi(L! dM d rl' 40 % !..6.hlnY r.vd 

t

Tirlc 

t2 

1,3 

1.t 

1,7 

LE 

1,9 

Amino rcid( a Ligmds. 

Table of Cotrtcnts 

CEAPTER T 

AminoAcidsuscdinPEhtwdt,,,,..,,.,.,......,.,., ..... ., .,- 

CoDplqineRagms ........... 

Mdrl Conp.exes of Amjno Acid-tlF LiSlrds . . . 

Cdrlysis bl Ttusiuon Meirl Complcx*,,,.,.......... . 

Mctah"Ami@ acids Complq6 s Cataly$ fd Chdosleclivc 

HydftC€n-Tdsfe. Rcrtucli@ ofu8list d Orgeic CoDPouds . .... 

?h@aocuticd lmpoiare of meial Complcxa of mito @i.ls ..... - , 

Intc@don of Ruthoiurn AMc CoDplqcs wilh Asilo Acids dd P$tcis.. 

Llo Objeriv6of Predwo*. .. . 

Lll R.fem6. . 

vin 

iii 

t 

l0 

ll 

l3 

t7 

l8

3.t 

J.2 

3.3 

3,5 

CEAPTER 2 

Amino Acids Conpleres of 2-Methyl+hydroryquinolirc 

4.t hcqIucliotr...,.,,,...... 

4.2 Expqid@t,j............. 

CHAPTER 4 

Anino Acidt D.rivrriv6 of Chole€tcrol 

23 

32 

38 

42 

85 

E7

43 

4.1 

A.hoAdtL 

5.4 R.$lrr rd DiMioa,.,... 

d(bl|.(tr) 

9l 

lll 

lu 

12 

11,1 

u7 

130

d....................,.........,........Bdid!.'El*dd, 

ra,...................................,...Bbiiim 

|Dl,.,..,,,..,.......,..,..,...,-,....,..,ur. 

& Y.,......................,........... Bndri.ur 

qirh............................-2. rfy 

Oric................................... 

Abbrcvbdo[ rynbeb ued 

Cbl-.......-...:..-................-.(loLa.d 

O. ----.---.----------.O@ 

Ru..,........'......................,.rdnid 

An d.....................,..,.,.....r&dx 

cU--.........-.......*-..r........G[Fb 

r'16_*........._.........*,-,,.....xtatldlnr 

q/.,*,.,,...-........---.-...Crt to 

rrd|-..-*,-..--............------tr6bL. 

ah--'.--.-----....... ......euu 

Ar&.........--------..--.4itrirF 

s6--. -- - " 8'd!' 

vd....,,.....,.,,,........................,:.....Jdi!. 

ols 

/ 8.fM!ryFi!.ldtE

L 

4. 

5 

6. 

List of Original Publications 

SgrfruaR 4.. Kazi. T. C.lqb3l. S.. Atidi, H l. Jamali, M K, hlbmi, N md 

_Symhesis. S!ructure Dcleminalioo ed Chd*l*liv€ Catalltic Srudi6 otAnino 

Acids Compl€xes of Ostuidill) . 

(2008) ADDtied Orsamm€t llic ch.niatry, 22; l8?- l9zlmp.d rtdor 11 2241. 

sarlr.z.R. A., Kdi. T. G. Iqbal. S., Afiidl, H I,.tmali M. K Jalbdi, N and 

_Synrhesis and X-Ray SltucoEl StudiesofHalfSmdqich Amino Acids Complexes 

(U008)TurkhhJournalof Chemislry,l2i237-247 lhpsctFaclor106541. 

Other Publications 

Baig J.A.. K@i. T. G.. Atan. M B, Afridi. H I Kmdh'o, G A sailitz RA' 

li"J"arion or erenic i"a .Oc! Phyrio_chdical Pdmet'6 of Surf@ aid crosd 

Wakr ol Jarshoo. Pakisld-- 

C00e) Jonrnal of H,zrdod Mrterilh. ii PE$ (Ms Ref' No : HMMAT_D_ 

^dicle 

O8-01092). Inpacl Factor 12J37l 

Si!h. a Q.- Kazi. T.C.. Anif,, M B , Jotli M x.,Atidi tl'l'. Jrlboi. N ktidhm'C A B!ig'JA' 

i.'.',* .r ."r t'r''a. 3!..ntid dmtr ar.'Pnon spdon"v ra e 

"r*i-r-r 

d0si Food Ch?Di5'r.\ rr.r't15r ri5 lmD.d ftdor13l82l 

Kazi. T.C.. Atain. M B. Jmali. M K.. Afridi. H I _JalbaniN S'rfnl RA Baig 

::ii*.i.i"tii. oi "*ni" t"*ts in drinlins ster wirh lre biological spl€s or sk!' 

ijOost. s"i"""" "r rhe ror.r S ngirctm.tt do1: ta t a t 6tj t'itoten 2aa8 ta 0 t 3 

ABin. M.B.. Kazi.T.G.Jmali M.(..Afridi H l. aeigl l A' Shdn AQ Jalbani N ' 

'-oerenri."tion ol cenic l*ets in hr€ *ater, edim€ni, ed foodsluff fton eldted 

area olsindh, Pati$tnr .stimtion of

7. (ri. T,C.. Adn. M.B., Jddi, M.K...lalb€ni, N., Aftidi, H.1., S.rft.z, RA, Bai& 

,r.A..Shah.A.Q. 

_Asessm.ntoawad quaht ofpollded lak cing Dultivaiatc shtistical l6rsiqu4: 

(2009) E.otoricolog/ cnd Envirormot l S.f.t, 72 (2). pp. l0l -l09. Inttt 

rrclorl2,0l4l. 

8. ain. M,8.. K@i, T.C-..lmdi, M.K., Aiiidi, l|I-, Jalbdi, N, Srlft I' R-A, Baig, 

1,4.. Kandhro. G,A,, Memon, M.A. 

-Tine eving modifi.d BcR Fquoial cxtra.don p@.dm for lhe fii.lion of cd' 

Cr. Cu, Ni- Pb and ZD in sedimot sanpl.s of pollued la*e- 

(2008) Journrl of g@rdo!. M.r.ri.ls. 160 (l),pp 235-219 IEp..r Frctor 

12.13?1 

L Aain- M.8., Kei, T,G.. Jd.li, M.K.,.ldh..i, N., Atridi, H.l , Kddhb' G,A.' 

Ansan. R,,Sulw-R,A. 

_gazrdos imp.ct of toxic m.ltis on bba6o l4v5 sreM in ontaminaLd $il bv 

uhtuonic r.. i.d p*udontgc.non Vd r!mal. !ud) ' 

(2008)Journslof H.ardoutM.t.rid!. 155(l_2)-pp 2l6_224 lEp.clF.ctor 

12.1371. 

IO. Abin- M.B-. Kei, T.O , Jm.li, M K. Afndi, H.l , Jdbdi, N ' S'rfro R-A 

''Compari$n of DifieEnt Exllaciing App'@h* for Heavv M.lal Panidoning in 

(200s)Pcdosihcre. aihr.iiPre$ lnp..tFrctorl l.8l?l' 

r r Ar.irL M,B.. Kui, T.G,.loali, M K. Afddi, H,l, Baj& J A ldboi N, sh'b A Qii'i."rio" 

of physio- "r,"nica F@el.F of MNha LiI€ q'rcr ard |n€ir 

comDarison with otber global Published valuej 

(200b Prrhhn Jo!roilofA!.lvtisl & ENiolbe 'l Ch'Di(rv aniclc lD Pl* 

i2 Jrn.li. M K.. Krr-Tc. Araiq M B,Anidi Hl.J'lblriN-$rrEiA B'i3 r'a 

'- ii,i i'r"i..i"o', *;';"" ' "pdr. or@. sd bic*nnBbv vri* vdidi6 orsoBhum 

O00O Jourml of Usrdo$ Mrt.ri.l5 lts (2_3). PP 644 65I lbPlct Fidor 

l2.137l 

rr Krzi. LC rarba N r'mli MK A*idrHI K'ndhD cA sr{na 

R.^..\lrir. AO ars,r'R 

:i",.",*o, o". v."t, " *.tptlai$np:!orctmn{ Kidis Pd 'n6 

eooo)liotocicrt.I rcc lttotrr R6drch PP Ll2 Anicl?inPEs Inplcr 

Fcdorll.007l 

14 (rzL. LC,lalb.ii N, A h, M B,Jln.li M K,Aiidi H'l"str'na RA'Shrh A Q 

''*.''"..,.r"ostib*l*iâilTrcntconpoisborP*nbiirndimpon'dc's'*bv

l€*orhcna aromic 'bsQlloi speftn b' 

( oE Joumrl of Ru.dors Marcri.ls. . &d.L in Pl6i lEpacr F.ctor 

123371 

15. (aDdih. o.4.. K.r. T.C.. Afirdi, Hl., rd, 1,r.. Min, M.8., s.rfn& R.A" Sinjuddii. sy.d, N., 

'Elarudioiofior inS! ummdU ft aid r|leir R.l.!ioi rilh ltyrcid Ftrfttion in F.nrl. Coitoa 

{1003) Biolosical Trr.e El.ncntR6srch, pp. r-r0 Adicl. in PE$. Ibpr.l 

l6 Ka|'1 c.. ramdi. M K., Amin, M,B., Alr di. H I , Jrrb'ni, N.. srrlna R.4,, Anei R. 

'Eulodion orrn uhBmic eid disd 

0003)Joumll ofHl4rdo$ M.t.ri.b,. anicl. in Plls.IEplct Fr.ror 

l2J3?1. 

r7. Arhdi. H r - Kazi, T.c^ Krzi. N., rrmdi, M.K, ani., M.8.. Jllbsni, N.. s 

(|ndhm. c.A . Si.h. 4.Q,. Bri& J.a. 

'Po6$ium, circium. M.SicsiuA .!d Sodiun L.wh in Biologicll Sanpl.. orH$.n.nsiv. lid 

Nonhyp.tu3i{ DiibG M.nitus PnimB". 

{1003) Biolosic.l Tnce Elcm€ R6sEh.pp.l.19 in ft*.Iop.cl 

^nicl. 

blolo3icalnnP|6ordirbdE mdrLtus pd'.nc 

{ 00 Dirbel6 R64rch trd Cli.iql Ptrcti@,30 (2), ee 23G233 InFct Frclo. 

ll.823l 

sr'h. M.ioi. A.-u.. R.. Khindhrc, c a. 

'Distribuiior ^.a. of,inc. .orF dd id ii biorogi@l $pks of P'kisrii nvqdial i^rctid ( r3! 2id 

rrd h@n dr.L) pari.its md 6nhk- 

'nd (2000 clidci chini{ Acr.. 3se ( 1.2). pp r 14 l ie. lmp.cr rrcior 12.60l l 

20. K'i. T.O . M.noi, R . Attdi, tl I . rmrli, M.K.. 

'D.r.tr,in.rioi of.adniurn ^ ii {hol. blood od $dp h8n rmPres ofP'*iedi @r' lung €ner 

pdients by.ldorhdil .Mic .h6.arid s4brd 

itoo!) Sci.nc. ofth. Tot l Environndl, r3e (2_r) pt 2?0_275 lEpact F.ctor 

t2.l82j 

ll lqbd S, Kdz,.-.r .. Bhangcr M I. Aknld M Srrfmz. R.A. 

-D€r.rmindionof$l.nim @nlent In *Fred P.kisbr f@ds 

(200E) Intehrlion.lJouh.l of Food Sct !@.!d Tehtrolog/' 43 (2);139_345' 

Imprct Frclor 10,94ll 

^din, M B , Jllbri, r. s'd'4 F'A 

22. A6in, M.B.. K@i. T.G.. Janali, M.K , Jalbdi, N Aftidi' H I , strfmz' R A . shan, 

"D;temidlion of toxic elem.nls in mel. tissu.s of live fish spdi6 sing 

ullrasound-assiret t6eudodige$ioo by€LcEothe@l 5toruc abso4lioo

spocrophotom.lryi Opimiation sudy". 

(2007) Spet@copy lid.6, 40 (6), pp. 651-878. Inp&t F.c.or l0rl1. 

21. Anidi, Hl , (&i, rc.. l.mli, M.K, Kuj, G H., -^nin, M.8., ,.lbtni. N., shr. Ga., srrrrr4 R.^, 

"Ev.lurioi or bxic mbh in biolosical enpLs (slp hilr, blo.d Dd uiE) ofGl onlw{ tdby 

.r*irdh.'trl smic rtdd!.id S.ceftty". 

(t006)Toricoloo/.nd hd$tri.l tl€lrh, 22 (0). pp.rlr-3e3. Inpicl Ftctoi 

10.73r1 

]l r,mri.M.K-(Ei.rc.,hii.M.a..^Fidi,H.r..rrrb-i.N.-^drr,R-a 

jn. ffihrioi ol rdl .nd lxrdcbbl. havy mbh fi'on 'oil and domdi. *mg. .lude. md dEir 

rtr{d ro njz (za tuys L) PbB . 

00.6)Totcololiqt. ENn!!n..rdCtdittry.33(.),pp.61e632.Ibp.cl 

:1. Jalbaii.N.Kzi.T.c..Adin,B.M.J.nall,M r.,Afi idi.H.r,S.{r4R-^. 

_ApDlidion of fersil d6i9 ii dgrimidioi of uh?si6ir.n.r*htr of .lmi'm ir jui6 

(20a6) Tlhnt4 70 (2r p9 r07'r r., lmp..t F.ctor I!3741. 

?6, KdL TG. Anidi. H.1.. Jlnli. M.L, Kr4 O-H., An4 M.B, irlb|ni, N. s.tfts &A si&, GQ 

_Erer oful@ rsibtjon d $. d@ ofhavy .ldac in enifild Efc.ne m&irl ofhmb 

{2006) Jolhrl of Aoac hr.m.tio!.l 39 (t), pp. l.lo. r.16. lnp.ct rtdot 

n.5!9t.

Chapten* t

Irtroductior 

Chapter - 1 

Anino *i& de lh. foudrlioa sor. of life a ihcs @ $. b4ic @Ntitusa of all 

liling b.incs in $. fm of pbLin, *iich in tum @tni$b tundh.nl.l orgs syslens, 

m@16 {d r gal veiay of 64m6 lo ca|rltE all of UG br@hdiel radim @uirg 

in ou His. Our hair. nlils, husl.s, blmd, skin dd body nui&, all e. smlNd of o.ly 

t\dty mim eids of diffcMt qT6. Major Fnid 

of M food @nFis of dE s. 6ov. 

Mdon.d dino &ids, q, it is tn bqic rcquiMent fo! ou .xi!t@e- DuinS $e lal two 

.Lcrd.!, s athnllins d.lurnion in ln. fi.ld of mino edll|lhi6 ns b€n obw€d, 

chafflri2rd by e ouElsding eroslh of sdnciciLd chrndognphic cquipncnt dd . 

logdirhmic in@e of dF .mb.r of iddtified discs. Cmncrcial f.bricotio. oi n* 

itfudlrim ha ber riftd by $e lwlts of ttct |lplic.lion in cliricd di.grosis of 

@ino &id ap.lhi.s. It ha clely eu&d a \mw ball cffal . W. musl b. .w@ of the n*d 

l@ mcthodoloei.d sppmpial€rBs, shil. daling {iih ihe @Snilion of mho Eid 

.bmmalilia in th. field of publk h.dth. Ci6 b€los b lh. @FEidiw clNific.lion of 

mino .cids. which cov6 llmost all aBts of th.if cltr@lsisti.s.

Ch.rit rdor of^biro Adb 

MoloDiro DoroqrDoryllc ald. 

(i) tti$hdinlt dmim4id! 

yaun, I2knu, CIt lse, lla,n'l' dtA lpbst& 

(DôiF -id. $bdil|t d ri6 rnydo.rt Sr!.p 

'ftmDile dd s.de. 

(b) lrlnnic uim &id! 

Tylo'i!. ud Ph!|lyblxina 

(c ) E!.a!cy.& airo d& 

gididiE &d Trrptophq. 

MorDi|o .[..]toryli .dn 

&p..dc &id ed Clurmi. &id5! rhcy c .bo F*r B d.n tnidc., A4{.gic 

Db.n ry*.arrL.dd. 

A4inh. .rd LFiG 

S.bled|irld{ dtro..tdt 

C)*irc sd Merhi6i&,

ADim ..lL @rt irhS u idlo grelp 

Hydrut!relirc md Ptuli@. 

Tlc mino &id! qhich csot be st h.siad by rhc body @ ar.gorized a.sn.l 

di.o.cids $iich ircludc n rhidiE, phdy'ddie, thMiilc, ltuiE, iel.ucinc, l$iie, 

fyltophd, rdii., s4 i! @ly infdcy, nididin . How.v.r, &n of th. diio &idr re 

clrsificd a ndeti.l, od d b. syn$6isd d&lgrdsly by th. body s Fr 

Anim &i

i! eit seg6's 6gdn 0-tll|@2, 4-dinito bqE .) lal. 'Irtc @sor urdeac 

@nd€nslior Eelio Nilh tu€ Mino greup3 in @ld dd nildly .lkdin. $ludon, 

Ar th. @jdiry of di@ &ids do na Sow 6ogh (ry lb$Drim .l drc Nd 

Mv€ldgths (250 to 280 m} . di@t ealysis s4i not p6sibl.. Anothd pomisi.g 

tpFqh b ddiwrizr1iu of rh. oirc &id\ pbviding luit Uc rMing @npound, beloF 

e.ltsk, nt. liiedtu@ Gviff sho*Ed Ihat, a Nnba of&rirEtizi.g qgaB l@ cmptoyed 

fd tbe d.r.minari6 ofdino *idr itr biologic.l tluids. 

A fluooneFi. hetlod for d.tdniratio! of oho 4ids i. biologiol tluids w 

d.velop.d iI ou l.bo..toy, Faisly l5l. Daiw$atid % pafom.d with oxim in 

@idic ndi. after h.rtilg foi l0 ninutes ar ! ortrolled r.npRtr. (60oC} Ilc p.l. yellN 

l{lduds obt itEd, s@ na&d in difft.6r sp6t!6copic Fgios !r. *arc lagrhs dgq 

100 to 380m fo. qci6ti6 $'hil.dission int nsiti.s wft obswd !r 410 !o 480,n for 

dififfit &rivs'tiv6 of @ino eid5. It. pEpa.d €SGnl wd ! nd dc ed ws not 

E on d in li.f.nd Aiolhs *uk E oncd by ou crelp 16l, w Fhr.! wirh Mi.o.cids 

dcdvariv6 of niiltddi, e ihpovddts ii thc Fs.dw w3 mad. i! arldition ro mct l 

ioN $ch B zin , coDDd, cadnih, strDitium clc in rh. hi.o eid $lurio, Th.s. nerli 

ions fom . mnplq, *lich givc ! b3rhahMi. shift &d \e Elrriv.ly m@ 5r.bl.. 

Anino rclds as Llgrd! 

Thc lese sl. lppl'€liolr ofligeds rLrieed fron di.o rcids is a Dopuld subjet 

i. orSdoncr.llic .hcmisty 11. A rmbs of iqq n.r.l ios, srch s Cu':, Co", Mn*., 

Fc'1, etc. @npl*6 eirh mino sids i! ettich boib @tboxyl 6d olhd lroups, sh 6 -NH1 

b.l Jl|. e involvd, nsv. b.d rcponed Ior .bple:

s "-9--F 

E-9-N{l /N-fEl 

| ,q"i. I 

drr-o I o-

2-Mclhyl-8-ttydroxyquirolir. ole c.ll.d &HydroxtquiDldift, is a *ni...r:ralline 

$tid ( n. w- l59.l7r n. p- 7CC ) slubt. in bc@ne chlmfod, dha o..q@$ dlotine 

ed &idic elulion- walkci dd M€Ein l9l dcclaed a 10 bc un@dive lowads aluninun, 

dk ro $€iic hindrsc. of th€ nethyl gNp, which prvdr! rh. Egat motcul6 lo 

6lth.d6lly @rdidi.! rh. s.ll dMi.m i@. Tfte i6g6r B ued lor *turio of 

inLrLring ioa hefoE th. dtrsiio of.luminun ltol, ft h iletubte in wrt r, hosevd, 

dislv* 6ily i. no61of th. dgei. $lv.nq for indame, alohol, .thd, .hlorefom, rcelic 

&id dd doiltic hld@rto.. It is ,t$ dislwd @nptcr.tt in otlatis ed *ids ud h6 

ben usd, .xtcnsiwly, 6 chcllring lgeot *it\ difr@t hetlt ions ll l-r9. 

E-Itt.lturyqtboli@ (Oxtn ) 

Stn f E ollrydrorySliDldi* 

8-Hydbxyquinolitu (Oxin ), a whic cryn llire @nFurd wirh not.cut& wisht 

145.16 .nd i! imluble i. w.td blr dielc Epid,y i! mos of rh dgeic etrcn! lmh 6 

al@hol, ah.r, chloofom 6d mmi. hyd@a$ons. It is .lso diselv.d @adity in .cidic

It is also kroM s 8.qui.olinol (ontu) dd 

6 ch.lal'ng.gent in &.I)ricol chdistry, 

Il71,s e oallical i€!8.nt 

OH 

h6 ! phcnolic srcup which is 

It ws iiitially inlrcdu*d by 

Olin. fms Mpld6 wit[ n@ $s 60 neicls ard slts includin8 alk li mcLls 

U8-201, Divsl.nl and rimlent ndl ions rerct wilh oxi.. lo foft inn.r @bpleres wh.ci. 

ihe n t l ion is .edimt d !o thc ninog.n arom sd orygd aon d 2-pcnion sd 3- 

portionc F9et'rcb, lomrns suble 5-memb.Ed dngchelrk. 

The cholBt.bl is a scrcl, whiic crysnllinc powd.r with holsolr lomula C,H{O, 

M,P, 148-150'C, B.P. 360 'c ed nold na 186. Tne name cse lron thc cel qords, 

.roL- (bilc) ed r,.r.as ($li

\z\.\z* 

San

a us€d ESulsly a FEc.r.lls$ 1251. Il|e nd.t abn is . chiEt qt r ir .uch tyF ofh.tf- 

sodwich ompld4 wilh $@l€gged pido.3lool like Con ll1 ed i!v. rh. usthmelri.al 

chcla. ligld LL. b ddidon [o dorllq ligod X, eg, ! hliide. Th. re dirsrtuI6 

rM,Sc od SM,& lppd by dployi.g s @rioneically ple tiSod LL1, 6 of Sc 

vaiG nldi6 or chi!.I-lrlet t nrloim @pld6 lile I(!t@.)Ru(LL.)11 

ed I(ff.€M.)Ru.(LLrLlx(@O m6nyld., hdeethylb.Ene, b.nane, /{}md., 

LLr ) ndE l d oi@ic oedo@i€ly F!! chcbte tis..d, L ) mo,odar.l. ligdd or 

halide, x ) sion) h.w bd r.!on!4 de hwinS diro Fid .hctal6 Bo, 3ll od nuch lc$ 

eudi.s d Ehl.d .hiralnt-ner.t (IG.M.Fdnim @npt*.r. c.@6lty. nor ! tor is laFw! 

Eg&dilg rhc chdisr.y of osih @. @plq6 6pd!d L rlDe of d[oim ed 

im., a shM by lit stuF. Pl.rinum dd ruthoim @hptex.s havinr cheladng N,N- 

h.r@yclic ligodr tuh s, bipltidiE (!ity), plBd0Ntift On@), ed ph€nyl%- 

ttridim (azpy), have bu vid.ly iudie4 {xt ! &w hsc b6 Epon d to sio* eris6 

&riviry [32-!al. 

Crtily3i! by TrrNitior Mcrrt Conptcrc| 

A eralysr is lbl. to |eler& r rlt@odyrdh.tly Imisiblc r@rion by 

dffiing thc d.rgy b.rid, howa, it c60r supporr . ln.frodFhiquy prehibircd 

Eeiion. nrk purely, is a kin tic eif{i. In johe ces, th. spsj4 whi.h h cablrlio|y 

&rirc, @y mt h. th. @. @npound rh.r k iiFodr:ed to rhc r:aid niltuE 6 a €(.trc. 

Soie @nv6ions odd Gur 1o gdc@ lh. divc sFcics qhioh 6 bdng abour ih. 

otlrysis. B6id6! th€e mighr bc & indwdo pajod b€foe rh. cal,bthslty activ. sDei.s

cgins ro fibcdd a ! cltdyrl. Th s. de thc inponot fedoFs of ! .yclic P'd.ss rcga.dls 

of qhdld 6? sp€i6 r$ bcing a lEt@s.n6G q . hono8o6ur c.hllst ft@ b* be. 

e illfu in lEs€el! il rh. ,l.ld of qtsblis 6ing dsirior ml.l @pler.r d@ rlE 

1940s onwdd, The deidd for qrcni.d dd n@.tncienl i.d$uial p@esss Kqui..d a 

najor c.@h .xplosion ir strrh€tic .hehisrry to d4€lop ns syslen! wnich cd acr s 

..!aly$, Tne baic rdtim lh, orgo@adlic od @idinild cmpouns 6 ud.rgo 

e (s) oridtion md llduaiolr (b) lisud Epl&da! (c) inenion ad clinindid 

Mtioi ed (d) dirldiv. .dditior !d Eductirc .limin iion 

Metrb-Anlno Acid! complclcr r! C..rlyr.! for Chenorelectlve Eydmgen- 

Tr lfcr Reduction of U.lrtur.ted Org.nh Conpomd. 

R.dudiM is c of $. Dosl .gti.l ud vslubl. @di6 '! draic str$Bis. 

Alilroldr reductio of e isht d 6nc1io.il sreup, with nunfta ds.nrr s b. tri.d 

out aily, sleclive Eduction of o.e frctidlity in th. pEM€ of such olh€r tunctiondl 

Sroups th l6t ddaSe to the hsitiv. elnFnE of a Eol@uI., h8s b€n a frEqu.nl 

dil.|tfu in o4uic t!dr6i' Thdfft, d4.lop|trat of sLcdve nild ed cmci.ri 

FdEing arct! still minr e e of ima@ inr.rgt Ur!d{ hild c@dnios. 

onvdliod ny{lroSatrid pr&s aldmuSh frlquotly od6 sLdive Edu.tion, il 

n*ssit !.s ! speial s.t o{ appdotu!, sd h also asiat.d wi$ $e usul risk! of usi.g 

tydrcsd s6. Cabbtic hydbgenatioD tesfcr pe6s povide f6ibl. alh.tiv€ lo n 

Siving e'..!d qpain nld qp.dia.y &d rvoiding sh diedtdbg6 Dd .itri The 

pcliom e ecncolly F.fm.d with a hydrcgd e@. .@np..lng a c.t lt5! for 

.mpk a ndd @plq. HydroSq-lrosfcr Educlions edjons of unshdr.d 6.gdic 

t0

$b3l!d6 clldlz.d by naal e ofboth selt Fa.ricsl ed tuidodtat edrh I3q. P@tical 

npctus sis fton $e fa.t thlr srch typ. of re&tions @ sy to slnlh*iz on lege sl. d 

lhcc is no n.€d to hak us ofg high htdregd p6sw or 10 ftploy uDsaf€ Gducing !g.!ts. 

FDn lhe ftndd.nt ! vie*loin! idlction cid3 rgrdiigus$Eld deoic.ubsrlabs 

pl.y d iDpqrsr relc fa rhc odets.rding of honogdes c.&lrlic |srimi 

pEdoniMtly for lhc f..lo6 *hich cdFd rhc *l6ivity of . pI!.*. 

Phrrnrceutic.l hpo.hme ofM€til CoDpl€Ie! olAmiro Acid3 

Tbugh mosl of th. rcvd drugs @ ebon-b.&d, $d h a gre{ing rdtiz.tion tn r 

vdiN i.!!l iom @ involvcd ir n tud life pl1Bs dd {ul ih.F is a g@r lep€ for the 

n r.l+as.d design of rh.aFnic agcits 1361. M.frl cMpl.x6, wirh d.ir eid. sreaun of 

coddin rion gonltrics, cddi,Etion .mbGR, rh€nDdtndic &d tiraic Dcf@6 for 

ligdd .roru, and i! a fd @3 Fnox &nviq, offd i* hehsjsN of .qi@ which &. not 

wajlable with o.gdic @npoDnds. Gsc6lly, the @6bined .fen ofnalur. ofth. mel'l ion 

with ns oridrilion dLte sd lh. nunb€r bd ttp6 of bod.d ligdds, nsy exqr . sisnificut 

infllde on lh€ biologiel adivity/.clvni€s of a n!.d @pld [37, 3a]. An uodGtandins 

dd ho* rll tb* &.106.trdt b'olqicd acrivity n.y h.lp ro {hsiF m.rd mtl.x6 virh 

defiDit ncdicin l pbpqtie Th€ bro.d EBtuD 

of ditrr.lhiologi.d ..rivin6 ddgsl 

plari.un conplex.s I39,.lI 6 well a lhe clinicd sue* of plarinudl) die(m)be 

@mplexes. e,g. chplatin, s dlitu€r dogs of.r e dc.lldl illuslr.tion for this Doint. 

Alrhough platjnm @nplcb @ now dLnsively dploy.d fo rhe can@r tErnmt rhe 

ircrc of dne cisr *, $c toisos sidefds of ckpldir sd rh.l&k of divny of 

plllinum @mpdDds ag.irut oo. 9!6 ofc€|@ @ dE nain pbblens which h.v.lo b. 

ll

oE@D. [41], Ihis prcvidq dr sole of dotirdlon lor lh. qrh of sri6c.r acriviry 

mmg otnq m.als @dPl.x.s. 

Orgeomctallic clFnisry hc d*lot d r@idly in th. eoDd half of ihe 2oth mrlry 

l42l ud bicdg'|Mddli. .hdbEy 16 b6 .r.blkhing ir$lf tw, s e 6hti.l 

bm.h or th. subj6t 1431. Priicnlsly, ore&omebtlic mpl.i€, offe sEjt pordnal s 

stcmd aSatl duc to thc ldge vaicry of si ctlc dd bo.ding mods rhet ft uiqE io 

Ercn dough ti5. fs s)sladic eforc h!@ ben n.d. fm ddigiing orgeonddtic 

onplqes @r@ing dino eid. d.rivalivs, s thq4.!ri. agdts l.tst46l. tl s b pcibty 

due ro th. NmpIid thd bioloCy ad dgdometallic chdisFy aE Dutualty insmpalibl., 

c my dgeher.llic ot|!@nds e eririw 10 dygen ed f,?r.r. N4id!.16s, 'ts@h 

duins iI. rs1 dccad., 6leidty by Kopi Albsro la4, Fi3[ IaEl dd .,&ua f9l, h6 

e$ablished rhlr rl* pbblds cd b. conEoll.4 Finforcing lhal oig&onddlic druss cs 

b. pFpard. The orssom.ialtic rehndim.99h cohprd, j..., tTc(MBr)6f &tBr 5 2_ 

b.thoxy-2-nclylpmpyl isyeid.), h6 ba eidely ur.d for ny@ldial D.rision 

ndioimein8 l!01. Ar peh! sm. orhd l.chrcrim ed dEnih(t) Ei@toryt @nplffi 

e hoing explor€d fq oth.r Ddioim8iDg .tpticarionr for odioilmuoilF6py. Md sd 

@-*qk6shovrdd rurlaiMc€$onyt@nDlexcs,fddmpt.,[R(co)rctGlyci.ale)], 

@ b. u!€d a CGEl6ing tulml6 id viw, thu supF.$i.g qgd sER ridion ed 

shieldins r(sca &oh .poprosis dd ish@ic injlry Isll. 

It is.lso wonb nadonirg thal esdic rioxid. (As{, wa t&hchcd @htly, wirh 

m&k bL cliri..l su@s for the ft.ln il of &ur. ponrllo.rric lokmia, IS2l, L nt. 

liq, AMiqlD is n.tnyk d by m.s oa ondriE ddilion l!di@s" ro nonG dd 

\2

dim.tnybed ma.bolir6, brtinS mdlyl$ms &id, nctbylaluic eid, dihe$ytdsinic 

*id, od din rhyldinous aid. Swh orgeom€t llic merabolires @ @nridercd ro con$ibute 

a thq4cu$c .gcn! iD vim l5!1. N$@t bio-noteut6, @nt inirg netal+e.bon bonds have 

ba Epoftd 10 di4 !oo, bchyl@tEtmin (nerhr-Bl2) n. wctt

streng inluae of 3ulfusntlining him &id! on th. .hmisny of plrinuE drugs sr 

inE*.lluls !4t, 6paidly, lh.ir involvmql in Fsislar@ m@hdiss ed dcloxincadoh 

I59l- PDLi. Nbsflt s ray .l$ pl.y a pan in $G meh&is or@rio rtr Ru0D @. 

.dplcs, kcrring irvid rh. posibiliry rhn dll|6im @ rEple imn b poleins. h M 

obwed rh* (r6-Bip)R(a)clllPF.l @.r! a bil tlqty wirh rh. $lnr@iiinins 6ho 

eid Lc'rlch€ in !qu@E etutior at r,II 2-5, 3lO K, sd a not{ hrio I : 2 onty o.bour 

50% @nplaion I()!. Roaiois rq.d ro involv. .quadon, b€ins the ti6t stcp le.ding to 

iniial fofrario of I : I adducr, ilblgh subsriluiion of Milr by O,bound or S.boud 

cts!.i.e Tw di.Gl@ Mpl.G hlvc alb ben iddriGd 6 pbducrt ton thc sctio. 

Tnce 6. fim thc lo$ of ch.Lr.d crhttm.diuiE, @uiline d. or reo cooneting sites 

ofcye.in noleul6. Thc nr?i.d clud.r g@p (Bi!) Ru) 6.te pdd!..4 speilly ar 

highq coDqtudos of cyslein.. Cysr.ine erioB me supper.d by 50 mM elulion of 

uidn/mmonim lo€tal. in 100 mM NaCl d Mlh pH 5, iDdiating lnal ,SH may nor in, 

4tlurc Ru(ll)q.ffie onFlnds in @lls d iD btood pl6o." edity. Simildty, inlemction 

vith maiioitu scdr lo bc mp..riivdy qald. Not D@ fia 2?% of I(16- 

Bip)R(q)CUtPF6l rs.Ld .1 m iliri.l pII of 5.7 ana rbod 48 h .r tenFltlF, 310 K wirh 

Lndhionin€ (r -tr/hi!0. eivin8 ris @ j6 one adducl kI6-8iD lu{dIL.M.rH-St: . Ir 

@nt studi.s, meingly feile onddid of thc sulfu of gtuhnion G-l-ch-L-CysCIy) 

{6 notic.d ro giv. Nlfo.to @nplex6, AppMtly, $oine Eadity dhpts..d rudenium- 

boud sulfoaro liseds. ThcrcfoE, th@ roy b. r.dor mtolted palnmys for the 

dhd'ri@ of DNA by gl&rhione inr.dcdial6- chtnhi@ is $@ in @lts !r very shdl

Olns po$ibL binding 3it s n.y .le b. an ibur.d io hisridir. Fsidues, for rurhdiun 

.fu @plq6 withii por.iB. Th.EfoE, rh. @.ri@ of L-ni$idinc with I(16- 

Bip)R(s)ClllPF6l ir aqu.@ eluid vs d$ hlrsig.tcd .r 3 t O K. Tnis c&ri@ is rinc- 

coosuning, dd nnishB t*o iMaic L-His .dd@ls boud by iDirilaL, I(16- 

Bip)tu(mlcNFLHirl:' dd (rt6,Bip)Ru{e.X}!d-L-Hclr*. Ar auilibrib ons!,ni of o.t4 

mM w6 6thlish.d @nsidering both ih€ ism6, for lhe @tior betrcGn a4uatd ftohtGs, 

(rd-Bip)R(dxH1o)l! ad $. L,His. Complien of$h Elu. sjrh L. ncthionitu (0.j4 

nlM) ed L{ysr.iic (0.60 nM) $gg.sLd rhx tn i q..rior ofrh. (r.-Bip)Ru(.nrt' fo, 

th* hjm *ids d@s.d in th. ont r L4ylliF > LM.rnionin. > LHjsridinc. Radio6 

or t(f-Bip)Ru(en)clllPFdl wi0! rtE h@ Ft in .,r@hrch. c !s de cldied Frl. 

Cltochon. c ha e .xpos€d Qlis33) .l@gwirh a hidda hislidirc 6id& (Hit6)_ 

ElelrolpFy m6s sperom.trt ealysis show.d thar in both trielhyl!@orim !.daL bufr.r 

bH 7.q od waro (!ti 8.7), fronoorhoal.d cri@hrene c poducr w4 elct, fomel. 

inSilc ofr.n-fold ftold dB of (taBip)R(6)CUlPF6l. ICP-AES Atulysk shord thaL 

clr@hFnc c *a rolhasEd uFo 5AZ. 2D [H, lsN] NMR dar. dnibir.d th,| thc 

lnhaiM @mpld6 wF bood.d !o dE MnD rEnitru (e ?0e,4) 8d .lboxyld. gout 

(@ 3094), Elha th& hinidine cidu6 of cr{4hl1fu c. l6ill fth my b. alriblred io de 

stedc @nslr.irts appli€d on tn 6insle .ddin tion sit of {( n6-Bip)R(.n)l} noity by d. 

On fi€ anlrary. X{ay cryst llognthic ddysG fo. lhc ene-tuthenimszyn 

@mPhx (t'4ym)Ru(lyszyn.)CLl, dcpicted ihat rulhdiun is bonded sledively lo N ol 

the inid&|. rirg, gssisr.d with Hhl5. lo.r.d .! rhe porein surf&. [6]1, Ruthddio. 

stre.ts diddy rh. Maini.g .nzt@ srudla. Tlc bindd! el*rivity of ( 16€ym)RuCL) 

I5

eith ltsrin. dd th. .rt llzing crplbility of RuoI) Nn. @plq6 iowds ldsfd 

hydreC.n.lion F.rioB Fqos.d rhd dtn.{iu cmptq* of prot in nay pmvid. , be for 

rh. Mtiosh.tivc |nifci.l madl@4m6

l , sitlmr, s, E., BoF, A., Roitm, E : TIE histidit iquim.nr of ib. infont, 

P.diars, 11, ?86 0 963} 

2. H. Als (.i1.),'P.rdcL cliiicd Bioch.nisry" d Edilion, Hdnmm M.dicd Bookr. 

22 Bdtu lodo, (1988). 

3. M. Sak ly, " Fon DNA to pioLir" Publis!.d bv M.4iuatr PB lld- Lodd, 

0980). 

4, W. R. Todd, H, S, Mas@ ed J. T Vd, "Ten A@t Bidhdistv"' Tlrc 

Madld Cohfot Colli4 MaiilL! Linii€n , lddo! ' F2?2, (1960) 

5. Gli. Xei, T Iqhr, ed z .H Z.ini,, J Chan soc PaL"2, t44'(t980)' 

6. G. H. Ka1 r. Iqb.t, sd z. H Zlidi, , C,.t S" Pat 2, 50' (1980)- 

?, K, S.vdin, R Bcrgs sd W.Becl.ary,e C en lnt Ed 31' 1634'(1998)' 

E. M. S. S.hitd, Th6B of Ph.D, 'stoichim.lic Studi* of 6trPlcx6 of Oiin' with 

tulnirc &d HistidiF uing Flbohenic ard cmp!'drve Aialtcal tcrhodt" 

Univ. of sindi (1994) 

9. L,L. Mditrdd ., X. w.ltd, l,t l. Eng clch,ltuL Dd.15'381(1944) 

lO. R J. Htr.k atd J L Wdg{l,1nal.Cbn"2l'l520'(r956t 

I l. R. C. w.s! H.ndbok of chnttrv dd Phvsi6 , 6f Ed cRC PBs Inc B@ 

Rdon, nNd! U S. A,0987) 

12. z. Hdzbdhd, L. D.vis, M. Ko6l sd L, Su'na Hddbook ofo4aic Rogol! in 

Inorgpnic Aralvsis', Elis Ho$oo4 chi.h'$d U K, (1976) 

t7

13, F- P, Dwya dd D. !. Mill6 "Cldd4 Agdts dtd M.ld CheLr6", Acldcni' PEss, 

NN Yodq (1964). 

14. w. D..lohnston &d F. Frci*t, /&l chh"..lcta lr'201'(1954) 

15, A. J, Ddning $d L P. R.nlNd:|.J ch.n Soc Datd tL'1259,0940, 

16. H. SchuSlr. D E- Cdn M L BoM, L E' S@n Tin Stotr' K Bonftdq F 

Thmss D- D Ald, P. R- lsthd, M Msktl. K- H Thdps'C ooig 'l8N 

CIem. ll9, l0, 11 16 (2107) 

lt. R Bdg, 'oxin sd ir. Dqi!.nw." J Pmld ch2n lli'118'\r927)' 

lE, T. Yoshidutt, Frcldi$'z€itsckin Or Aml''!$he choi' 307 (5)' l?8' O98l ) 

19. I- P. Pn l'P., Cr€'i.z, x44, s6 2?l' 0955) 

20. RG- Holtimha4 vol I r' BonB wonh's' Lndo|! F25' (1954)' 

21. klmq & MuG Iv,' Polboh K sinkcl K Rohl c' Btck w ClEn E"r'JlEii2l 

r518, 

22. R. Fish .id CJd6, Ogmbi'i6 2t' 2166' (2003)' 

23. (a) F 106lxf E Tt6csanvi.J ds@fla Clc^'Ztl'63'0982) 

(b) D-4. LAdls, D J. Molt*r'I Otsonotut ctEh 2To' l2l (1981) 

G) M N*ar.w5, H. Nd6 dd K wd@b'' c,j'r' I"a 5& l9l (1985)' 

(d)A, Saitoh, K ,A.cniwa, K. Tet*t {d T- J Monnob 04: Chtn 65' 4221' 

(2000). 

!8

24. (a) a, Md, H, ohlo, H. N raK Tetkr ed S ltuue ' Sy'l" 563(1991)' 

(b)M.t. Bur8r.Etc, M colbdo, J- Estin@h' F Galirdo, B Gdit_v'rdlgo' s-v' 

Ltis,MJ.Vi.d. Lnat &@ bt ' a'1' 6891' (2003) 

2J TN-ls ttTltltt &rl sl. Mutthahi, C'€t xa' 9t' 259' (198)' 

?6. R,Noyori dd S Htshigwhi,Acc ClEn. Rts.10'91'lt91) 

27. H,BrMq,tdt Orya@Nt C/st lt' 151,0980)' 

28. H.R':'mr, -l,8a CLn' lll' naE $9991, ItAa- C'Pm' L'! Ed ' tE ll94' 

(199). 

29. H.BNn r.Ev J liorg Ch.^.,905,e@l\ 

30. K. Sdsit! R Bdgt ed W.B..l. tng* Ctts,ll0' 1122 (1998 

31. D- Cs@., M P.lsrr! 6d L. A c'o' Ev J ltu'a- Chtr.2239'Q@2) 

32- a,H. cld.rs, H (@ijnrL At. Sp.tq J.C H'sd! D D' Vos dd 

CIEd.,19,2966, (2000) 

33- K, S.vsit! R A.rss. l W.Bak'1'A$ Cla6 ht U 37'16i4'(l99aJ' 

' 

Rcdijk rmtg 

34. R. k!na, M. Mads, K Polbon, ( Sonkcl, C Robl sd \ll'Bsk"Chen Eo J 

2,ltl8,0990. 

15. E. Bidchini, M FD.ni' M G@idi, A Pt@ini &d PoLtt\t' orgoM"allic'r2' 

375!,(1991). 

16 M. j, Cls|-, C@td C/tn X.t .216,209 t20O1) 

l9

37. Z, Guo ed P, J, Sadld,,{ n84. Ch.n., !t1t E'"]f.1512. (199) 

3E. z Gw nd t .t. sldLt, ,1.'v. to's. cr.t, a9, 183, (20@). 

19, M. J. cf.e sd J. D. Hael!.L, Blotndg. C,.n ,2,187 '(1973) 

{I R- D. ttfBdo.h dd I. ?GDy., I'r. )trch llLrst rt$l tnwl. ,' 4t6, (1965). 

41. H. n[ Pincto !d J. H. Sch@s.l Gn3 ), r]dn'. Nd Ydls (196). 

a2. t.tttl{r'n, P@ lppl. Ckr,73,209, (2001). 

43. R H. Filh dd G. tit'tM, OryawLlr.,r,"2tc'6.o{o3r. 

14. c, El$h.nbreich 6d A. s.la, Or8oonet lli*: s dci* intoductid, vCH' 

weinhcin, 2!d e.h., (1992). 

45, P. Ko_Pf-lvtuid ed H Ko-Pf, 5vln l Cotnpoudr in Ca|E Thapv' S P f icld 

Cn ict pm & HaI,Iat&",9. t09'(1994). 

16. G, hqa! A, v6sic G.rd t. S. Bl!!a,,rd Ci rt X.r.' 24' 361, (193)' 

4?. R. Altdto, R. S.!ibli, n- w.ih.l, U, Abrm ed A. P S.hubi*r'C@rt! Ch'n Rd' 

901, 190,0999). 

18. E.Fith, Co@d. cL.m Rd., 56e, 185' ( 1999). 

49, F.IrBidolM S.lt!.i4 S. Tq td G ho&r C"t tr' J '1'2289'(2001)' 

20

50. R- Albdro, in CodPr.hdsivc C@rdiNlid Chsisry ll, Vol. 5; E C. Cdst bl. dd 

J. R. Dilwortn @ds), Elevi4, Amstf

6a F. Wq, , D.{r ,. rL Eid d F. I $dE J tor h's! CldL r|' l'? 

2@5. 

63. L w. McI-, K FlihqE,A- Itulb' T.1,. HuF M' vddr4 r' w-q; 

M II w.Idtrfr!, d P. J. Sd.., Cinx Cddr' l?&' elp')' 

64. C.lr.lbmr.dd T. R w!4 cx.t sto r.v.' 34 337' (']00+ 

65. D.B.G$d&,Ct td c[- x.r. llrs' 190' (199I 

66. rL 8d ! !r, K BL66.dw. s" sb.ldthL'rFry cJ$t,L,4 35' 340' 2o@' 

6t & E AiEJ. qmhlll" a- ridi., X. r'ti, R- E ricit' Ir ct'n' P' 

rd D. L Jon ]l' &. J c,@, s, l6ta(]xE). 

' sdl

Chepter -2

Anlno Acids Det rmi!.uoD 

Literatu?e Review 

Cfupter - 2 

sevdl exeu.nt piss tsarding the pi.ciPl6 3d mdnodoloSics for 

dcr.min.tion of ni.o &i& n ve b€n publilh.d in $e Pad- lnFrtst Gl4$t li&ntlltc 

b.ing sllmiz.d h.c, E8.tdt dim *irb dctariMli@ i' wi6$ ntrriG 6 sll a 

sFdEais ol di.o &i& @pler6 whicn mav Prvide 

good odhtio with vdk repon'd 

Ai d. djotity of eirc &id! do nol show $diciat UV absotpdon ar usu6l 

srrcldgds (250 lo 280 d} a diret o.ltsis doe mt *n ro b' posibl' A n@ 

pMising atp@h is d.rivltizltior of thc dino &ids grliig suiublc lblorbins @npou'd' 

prior 6 the selsation. Th. lieraturc Eview indhand tha! srqil dcrivatizing r"genl {@ 

.mploy.n for lh. d.€miElid ofdim ai& i. biologcal nuids. 

A flul)m.tic frdltod for ddminatid of dim @& h bioloSrdl fllids ha ba 

d.v.lop€.!in N hbontory bv (Kdi d.l, !980) I1l. Daivoliatio! M !'rfom'd silh 

oxine in &idic n dia aft.r h@ting lO minuLs !t @nsoll€d l€mFdulq 60'C The palc 

y.llow todDcls obbin.d werc n6urd in difl.rol spetrDsoopic ESioNi 300 b 380nn lor 

crcnario. *h.@. 4lO b 480 fd disid for diffGisn &riYtrivd of Dim eids Th' 

Fpon€d Mg.nl ws na dd s rcr cFn d de sbF in liLdtlc 

2t

Ano$6 worL Egon d bv us (Kdi .t.l- 1980) I2l, q3 rcltt€d wilh mino eids 

dqivaiv6 of ni.hy.lrin,6 ioptovfldls i. th. F!.€dd 

}:s had' in addhioi b nelal 

iohs sch s zinc, 6pp€r, sdmiuD, stonliun.lc in th' dirc 4id elution Thesc n€t'l 

ions fofted ! @nplos *trich 8.ve a barh@hromic shift ed wd Flaivelv noE sbble The 

cbjmabgm ws stF €d wirh niihvdi. @ntuine $'* io6' lhc @lour'd sPols w 

rcsined for Dp lo six weks, wh.Es iinhvddi @lou M stabl' for abod onlv onc hour' 

Slill sorh.. fludom.tic ssateg 6 d*lop€d in ou llboEtond (K@i et al 

l98t) I!1, fd 3.p8ation ofAl (ltt) id tu t mixtut @rriniis A(nD, Fc (tll) ed cu0l) 

ions by co-p@ipnlring ion ed @pF ions ss deir 2-dcilvl-8_hvdrcxvquinlinal6 dd 

sub*q@l pdipir,tion of slhinun'8{ui.oliD& nie pEcipitat€d tlumibum clFlare $6 

.xrr&tcd in orgeic ltyd .rd qutitdiE .stimdio ss thd @nplishsd 

Dd@inati@ of mino &ids. pwnt in $' n€mns of ins4B wa achided bv thet 

.tenvdiation with n phnahnce2, 3iic$boxtldchv'le follo*€d bv op6 tubuld liquid 

cnlM.bg6phy dalysn (0.16 .1 al., ! 990) lal. Anq dqivdiztio' the iobl volM' bede 

appd:imd.ly 25.1. I ? mirc eids w@ detmi.ed bv ihis ndnod 

Ior q@iitttive der.minsti@ of mho *i&, morher n'lhodoloe/ s E oned bv 

{od6 4d Jorge@n, 1990) Iq. inrctvins dEn d'rirttizlion win nllhthdde2 s- 

dicdbonldchyd.. Hy{trolris of4 fnol (f.mto hol.) of proi'in rs p"fodcd bv using a 

ers-pne m.lhod dd scbzcd bv opd $bule liquid chmnaiograPhv' quoitaivelv l4 

dino &ids E€ malyz.d wi$dt ev interfd@' 

Fluoon.itlc d.tcminldon of nino acids utilizihg a copper 0I) "t'lvzing reagenl 

*6 F.fm€d (Hisak@ d .1., l99l) t6l. Arino &ids edant'd rhe coPpd (ll) car'l'z€d 

oxidanm of di2-pyridyl k.ronc hrdmc (DPK!0 to fm ' nuoMt @mpound Dre to 

24

ihis cnt@c.d efrer of dlllysit vaiou sino eids ould be deial.d bv tlow inje'tion 

Malysis. The dele tiot linn ws h$ thm 2 pnol (picohoh) 

Sehi, md N@ys6my @ied o ! srudv for qw.ching ctf.cl of chlorin€ in 

polynEld aM{ic hydm.rton, (Sehi, ed Ndve.sM}' 192) I7l Numbs of 

polyud* Maric hyd@bon no!€ulcs *@ dislv.d in ncrhsol ed inv6ligded Ior 

$.ir fluo6.nc. qudching bv chbnic. Exrcndv €mcie.t qumching m ob6fled 

b.lwa the 0uobpho!. &d the quenchei, with inc*ing chlori.. @nccntatio' The 

6(tinss

m dd .nission 45oin. [tv.loted nethod s suNtutlv lpPlicd ro lne salvsis of 

tl'proPha in a D@led huma eNn. 

Dctcdinario of tliPhlric 6ino &lb in sdn ws sicd oul bv HILC wilh 

fllmn ric da.dor, 6ins @-i@biliz.d dztm Fcror (Nobddhi et al ' l9' 0ll' A 

sinpl€ dd s.lstile merSod v$ pEseit€d for dc d.1emi.ati6 of alPnetic dino eids in 

*M by HPLC, wnh d.tddon bv cinrobil'ed llein' dehvdegd&&uci'e 

dehydd8@ by po51 olum r@tion sd nu@m€r€r' TIF *Ptntion s &hidcd bv 

n $t ODS @lunn *nh .Mion *i1h ph$ph . bufd (!tl ?0) The svstem 8!vc x'@ 

6p6e sd detetioh lini$ al I +2M ld.h. 

Flrconetu d.tdni..tior of tFtlionirc 6 &hid'd bv oxire (Kui '1 al ' 1994) 

Il2t. MalFnire M @f,d.ns.d with oxin. uDdq low ldpF$t al 6d in aq@us D'di4 

The Ou@$fll peduct ws studied tpdronuoronelri@llv as w'll 6 bv oin'r dd,tical 

rehniquas. The d.retion limil ofmdionin. ws *hi4'd dds !o nnol ld'l 

A tludoneuj. studv of naPhlhalcnc2,lnicabqvtldchvd' (NDA) s a Fhrial 

dedvalizing ssql for $c fluoromeEio d.telid of min4 ed nho &ids in $e Drcsene 

of payclod.rrinw@ wLd (Aninuddin dd Mill6, |994) lrll Exp€'indr'tl condilio6 

including pH of $e ncdim. l* optjniad fd th' flndid of rh' flunsl NDA- 

ChonarognPnic da@indion of dino &i& w4 Gpon'd b, (Aninuddin dd 

Milh, l99a) lr4. A P.Ecd'pne HILC pF.!dE, 6ing a flwlge 

lined for th. sinsle sd qldtitaliv€ {tetemi.clio ofda@ hounB of mino rcids in lhc ng/L 

6gp, by pEslMh d.riv.tizltion si$ mPhh.loe'2,lnic{bo*ldehvde l was obseNed 

in4 nl@s..G {t€r..don of thc d.tivlris hls tdv&tsg6 ova rhc Uvn'rdion svffi 

26

ne ndhod @ b. us.d for $e Egid deimindio. of mino &ids in dplcx hiological 

A. mi@ eid Ddvsis ba3.d 6 dciilarjzdion of dirc &idt with 

ph.nylielhidynai. w6 rpon d (loin., 1994) {r5l H}dtulvz'd PFt'io or P'prrd* 

denvarizcd qnh cited E!$nl sd eFration of 6. rcsuti'8 Phtnvlthiocebmvl 

w6 ddmincd bY F.6.dthe HllC. 

mino tcids 

Fluoon tic dctedio. of d.tsvl 6iDo &ids bv ptct now @ll in liquid 

.honatogdphy ws also rcPoftd (Trt uchi Md Miw4 1995) U6l 

Fluonmetiic d'r*tion 

vith p&t d flq elt hG b..n .ppli.d io d!fttl dito 4ids in liquid chmMlogrphv a'd8 

mvdtioEl si4 @lums (4 5 nn i.d). ft. sc Packing 6 for 6' *p'!{im @ruE M 

u€d in 6x L5 nm id cylindri@l flow @U, qhd doly6 w* d'tecled in the pF!'n@ oftne 

d.tiody pne. Born Flr h.ieht md p.!& e5 of mlt16 inc@n Nnh in'6'ng 

er€dtion owing b fcusing dd wircmdld .trats of rh' snridev phe' loding b 

dm.lic imProv.n nt in th. ssitivitv lor @ltt* 'luli4 llE It ts bd obs'Ned tnat' 

on{hmn lluorcn tic dctctid inpmred thc qsilivitv in bo$ ist?tic gndial 'llton 

fl@l!$.E ohucdor of doDstl oino -ids bv bovif sff albuoin (BsA) s 

nobil. Phs. ldditire in nicb_6lm liquid cluotutogathv q$ Fpoi'n Gtlcuchi dd 

Mi*., l9t) tl?|. The .fr6t or a.etoniril. dd BSA c@'naa$ons o tn' siE,d intensitv 

od rddtio h.havio6 oadrdvl dirc rcidt wc dmin€d bt osing,

signal cnhdccm.lt by o.olumn Iluorcm.lric derction in ctadiett 'lution of d$/ 

mino eids in liquid chFn.ro8rapnv h6 be..aft.d out bv Grkdchi dd Miwa' l9t) 

IlSl. Ft@maric {hcclio. in lhe p!!$e of .5:tari6{v Phe ws tppli'd !o sddidr 

.lurion of d.ntyl die &ids in liquid chomtoSrlphv- A l-5 nn d qunz tub' p&k'd 

' 

$ith rh€ s. datcdals 6 the rPd.tion @luin M dplov'd for $' no* @ll 

conv.ntionalsiz. @lumns see @ploy.d Thc pe6,li h.i8]t of s'l)tcs incrc$ed Nilh 

i@ing ercntion owing lo fausins ed mvnomdtd ed4!t of thc sttdonary pbe' 

leding to inprovddts i. ssitiviiv, *ttich B po.ouced fq ealtr"ludng l.re TrF 

low dt. glrdihq $. la4p. lhe inpmv.mdr i! sitivnv 3'hia€d Dcr'ajo linils w@ 

inpmwn by ! f&tor ofnp to 51 bv fllorcddrc det*ti@ usins $' prk'd ltow cll' 

comp&ed with thoe achi.ved 6ing a @nmon .mPlv flow 4u 

Deleminarion of mino &i& sd eino $ge bv dcivlti4tio! widt 6 

dinoguindylN+'dbrt5@ininid/c&b@e (AQC) follo*€d bt hid p"roIllne 

liquid chm.bgnphy (HPLC) with ouq.3@e derM, 6 rcpon'd (Diu cl al 1996) 

Il9l. A n.thod for th. dei@lizltim of dino &ids with lhe cit'd @npolnd (AQc)' for th' 

N of HPLC *6 lcsrcd Repodlcibility, lii.ditv dd limits of detdion rcE simih lo 

those ohain.d wilh olhd melhods, ech s lhe @phdal'ld'hvds dd 9_ 

n@Enyln.rhoxycdhontlchldi.L icthods. 

Thc n lhod dcv.l@ for ddmindon ofddiE *6 cpon'd eliB bv us (Kdi 

eta1.,1997) 1201. R.elioi oltldin€{ilh oxin undB onlol ldp@turc al60 "c fot l0 min 

Ms €tu1cd, ft. nuoMt Pmduct {6 obbincd ud debren al lB 330 'h dd }'h 420 

m by tuoiiE.try. M.ihod m be agpli.d fot d.t mination ofal$inc in biologictl fluids' 

2E

sm. mino sid5 glycine *dinq vdin. dd lcucine s* d.tdld lluometnsllv 

sd sloichimedc rtudy M @i.d out using oth.t salt, i€l tetniqucs (Kui elal . 1998) 

I21!, oxine (&hy&oxyquiioli..) m us.n s cohPlexi.g @g.nt R.tclion of ori'e Nnh 

mino & s h6 bd .di.d dl uder low r@p€dtw al 60 "C fo 30 ninules. conPlexes 

w spear.ly d.Bl'd lluobndisuy ar tm nolc l.v.l Mcthod s be tppli'n for 

dcr.didid of sino &ids in biolosicd flli& 

chonalogiiphic heh.vior of m.tal .onplcxcs *ith 3_hvdoxvquinolin€. 5{hlore3_ 

hydoxyquinolin., .nd 5,Tnichloo-8-hydrcxyquinolin in the ev..s.d phe svdem wa 

studi.d (Nagad {d tshftb, 198) P2l, $ing mcro.iEile_war.r E lhc nobile pte Th' K 

vllB of ttre nc6l E-hydro\tquimlirc @otl4* d4@s€d lilh itcding ohls of thc 

nodilier d.FndinS on ihc stsgth of Flsitv 

paMetd TlE K' v.lu.s. d€temin'd 

.xpsinst lly, cs be alalcd to th€ polsitv pltd.tds of oigdic hodifies Ior $ivd'nt 

met t ids, blr nor for ddothLnt od diul.nt iotu. 

a sinpl. &d ssidE ey mood fd d!. q@tiariv. damhltion of t)tsine i' 

blood spl. h6 b@n dcvcloPed (Clawilot .t d ,1998) 1231. a volum. of 0 2 nL of pl6ma 

is us.d .ier depbtinianion wilh tichlorc4.d. acid, lbe prcdu.t *6 ualtzed E1 2'u 460 

nn dd l,b 570 m 0udi@Eicaly, Th€ lin@ d.po&ne ofth' nuoc@e sk'al oith' 

qrsirc @nqsdid *ithin th. Msc of 2_60 uglnl, M obs'd' qith high speificiiv, 

accua.y dd EF0d!.ibiliry. 

A sdsniv€ HPLC merhod dev.lop.d, for the det@ihadon of anino &ids wiih pe' 

@llm flu@$oc d.rivaizlion wiih @bs.le'9_vl-@tvl chlorid. *s cported (Ms ct 

al., l99s) I2.{. S.pdtion or mino eid dqi{liv6 *6 achi.v'd on ! Pcbt! eha cr 

29

@lutr. fte ndhod d.sib.d is als $iitblc lor lhc dalvs's of Mino eids in biologi@l 

A *.sitiv. liquid .hremabgaphic mdhodoloSv for del.mination of mino eids 

with pllgllm fllorcslt@ d.riEti?tid with sidoFN_s.tvl chlorid' @ d'Elopql 

by (Mao d !l-, l99E) 1251. Anino eid ddivdic v@ eluted in 'o minut's wftn sdd 

dprc

Cbol*teroLAriro Ad& Compldg 

Litdture ounts veious *dples of intFction ben|a: mino lcids and choleslerol 

ii-vito (Abuj.nab dd AbduFalin, 2OO4) ltsl s wetl 6 in_vivo (Yu Fdg et al, 2006) 

1291. Arprire is lh. eino &id which p.rfon3 weEl bdn-halnv frn*tjons D'la 

suggcsr.d 6a. orginin. hsy f&ilibte r€sulliion of cholMl l*lt {tuhh cl '1 , 1987) l'01 

Mor€ovq, egininc scds lo work 6 6 n.lutal blood lhi.ocr by d@sing plat'l'l 

lggEsllior h,lscbohn.blenic inditiduls (wolf et al-, 1997) l3ll 

11 aho msint'ins th' 

cls!.ty of bl@d v.sk via etioxid4t tdivilv L_Alsininc d$, t b'lid€d ro bc tn' 

pe@r for niEic oxi{h. th.'[ is a ncsg.r, iNolv.d h d @v of phvsiolosicd etf41s 

wnbin ihe vscule sy$cn (BodeBdgd ct .1.' 196) [32]' Nitic oxid', ' gd nold!r'' 

mal€s its way i.io *lb ed Egulales thet tunctios dd ai{b to conuol blood pdsurc' $at 

B us.d by rn. bodt b l@p blood r.sk cxp dod lcning tn h{r 10 @lL'i sumci"t 

oxlgd Gs@t c al., 195) 1331. ckonic &d &uE ldminitdion of th' esinin' wa 

found lo impnve mdothelial nnctioning in sinal/living mod.ls of 't!@sclsosk ed 

hr!.dol€n€ol€mia (Ptln r .t al, 1983) t34t. li.t4ed leukoctlt tdhdion s obs'ry'd 

in ibbits fed enn did having hieh chol.stftl, which *s woid'd bv L_ dg'nin' 

$ppldqtatio.. Plt'rclcll 6lq Eon htFchol.sr.reldic plridE (Yu Fdg d a! 2006) 

l29l !d! f!@ Ebbits.xhibitede inprcv.dtcnd.lcvtoasgrcsde, in vito (T$ 'r al l994) 

l!31. Il w6 slablishcd t[.t L-egini.e, $. substr.k fot ddog.no$ NO syllhe, rcveG's 

rht inlwe{t pltt l.l sgg.gdion of htFrchol6|mlcmia i'_vilto' ihpliB thar rcdu'cd 

bio.v.il.bility d Foductio of No is @n@ed wirh nvPcFhol6|slcnia_induc'd 

thhmbodbolic pto6s.s B6id6! L_rBinin. al$ orhmcs 4dodeliMn'pqd'nt 

.I

Eedilddd for lm$ *ith dhdelmsis cd h$erhol'sr@l'da Who 8gi'ire is 

adninisldcd to Patidi5 .1 lhc b.8iming of h.!n dis@, n sloPs thc diease ion lo 8ei 

vo* sd l6ens ch6r pri. in addition to iiplovins clini4l svmPtobs r ms v'h 

ddiotells di99 (Cl&t$n d ol., l9%) 136l- Thc utlitjtid of glul'din' in spns nat 

o6Pond to NO Fodu.tio 

I37,3E1. 

(Belloff ed JdIc, 1999 ed MuQhy dd Newsholm'' 1997) 

Md6vc, th@ 4ids . clatim bdrq th' dio of enti'l mino &idt to nm- 

6smtid dino 4ids in plMa dd choletcrcl la'I. 6 plr$t ldcls of 6*ntial Mino 

eids s.F fou.d to be i.clg$d in hr!€llipid&mi€ Padeits (Abu-Jslaab tnd Qan4 ' 198?) 

1391, h w6 shoM $41 in nuru sbjeds ht?@hohreoLmic dids prcduc'd coNid'nll' 

.hmgd in Ae dino eid @nmnations of pt$m {Cdich 'r tl l9?0) 1401 fi!' Esults of 

pEviolsly epon d study shosed lhal $se w.$ a @relation foi f'lding lhe ssntial dino 

&ids lo cholesr.ol lev.l in nbbn dd 61(M.hgoub &d AbuJa)lab' 1987 dd AbuJtyab 

ed Q!tu , | 9s7 ) 1a1,421. R.6t tlsh thd.d lhor f"ding th' rsls {ftn cholcshl lor 

aboul fiv. Fonths atPEciablv in@as.d tn. dgiDite o ett in th' tidn€v whil' it nctrlv' 

depl.t d frc Sldanin. @nrclrs of the kidn.v ed th' livs tissu6 in the r'!t'd dinal 

sroups (Ab!j.!ya! 4d Abdutrshin d.1.2004) ll(|l- Sod l!*eh6 susgcncd the 

posilivc .ff4rs of glddi.. (Houdiik er al , 1998 sd ldin' ct 

'1 1994) 144451int'dd'd 

by hi8lEr sginine Foduclion in the kidn.vs ofEts (Houdijk d al l994) 146l' dd inhunes 

d *ll (Holdijt .t 61., | 99s) ll'{L nflc., rh.d mv he a EldionshiP b''w rh' cholcsLml 

inscnion 6d glutamine in $. livcr ed i' dt kidmv md ulrin&lv wilh dsinin' Podlcrion 

At nomal physiological onditids. ghtaninc d a m"ssenti'l mino eid lt Na 

'xis1s 

asMcrl th.l, md.r .iEmsrlcd of inces.d dMd, dtdo!6os Slurmin' prcvis'oB

nly beon. a Esrdini.g f&!or fo. nenbolic Foc6s; lherefor, gluldit' is smdin's 

considdd 6 a condidonally dslial mi.o &id (Abcouw€r et al ' 1996 dd Luv et rl ' 

1990)[47,rE1. 

Anino ei& ddivadv6 of choLsl4ol h.v. *nlv ben 3vnth.si4d dd ftplovcd 

6 !o* ml*!l& kidt orsEic seldoF (LMocs) (d al.,) t29l- 

Metll Ccr.lylis by Amim Aci& ComPlercs 

Rh, Pd, P! Ru dd sinild tresition n.lds hav. ben *id.lv ued a c'ralvsls for a 

vdiery of ml@ts tusfmati@ (McMm sd Hurchingi 2004 sd B6tF ed &gn'' 

2O0l ) I19J0l. A nunbd of hmog*s csralvsB have bei deiiv'd ftud lllsnion mcttl 

@npl.x6 (Reerz, 2004 dd Brcn, 2OO5) 151521, b@!s lhev d iholght s d i emediat€ 

of @lions. car.lyz.d bt n.(aj. 

fte *od 'nydogoation" is u!€d fd t .ndi6l @tion *fiich involvd the 

iDo.Fdri@ of orc o. norc hyilreCo ltdns 1o dte Frd*(t of lhe @tion The 

ch.noFl€.:ri,. hyddgcnatim Miar.d rn ! ptrliculd {bon'@bo' doble bond in 

@mpouds having e.al of lben hs b.d a hdd job in sri$dic orldonetdlic dd 

oedic cnemislry (Chaloid d ,1., 194) 1531. 

Hydmg6-t6.sfd ttducoc rsdi6 of ustulr€d orgsic subnEEs. €alllvz'd 

by n lal e of tunddcnral ed el€lr p@ticd intonee. I'rDli4l iNpndo6 dise fod 

th€ slily ihrl such typr ofre&rions e fesiblc fot @mnercial scal' svndesis &s ihere is no 

n€ed b mdc us. of hlzrrdous r€ducing rg.nis d high hvdo!'n p6s@ Frcft 1he 

tunddobt vi.qoin! ftd@tion of usmm.d dedic @npomds h'lF to unde66d rhc 

honosa@6 eLl'4ic cdio6, prqlosinstlv of fi. 'a66 lhat @nttol tl€ spditcitv of ' 

33

pr@ss, Oul of diffa..i Edu.ibl€ subsldl.s of much inpoid.e' o' p'uoeluBlcd ketones 

N th*, contdnine bolh, @bo.yl 8rcuP 6 Mll $ C{ bond Ti' abilirv of rcducing' 

$le.rirly, on gtuuP o.ly (!&tioldly lh. fomr) *niL bving lhc otlEr o* M['t4 is ! 

dimc![ job in dgeic s]nl66is, FEdminl|rlv fd U. f(mari@ of ag@hniel md 

Dhm@ulicd prcduct' The l}esf€r hvdo8.nslioD of o Fsotdtcd reics in the 

pt€sce of alcohols is pencidrlv catalv&d bv !.ry r@ irssiliot-n'lal @nplcx's wilh 

tu! 03, Hi, zr, 4d lr .tc (E$ed€ba d .l, 1992 dd Fmeni 'r d , 193) [54'55l vav 

linit d nmbd of 6hpl.G of Hf, zr, ed lr, @ GPod.d to "rrv olr dE ch'tusldiw 

c5b\,tic Edrctiot of$. qrhoryl C@P which is difflcui 10 Ed@ s @6p't!d with th' 

doubl€ bond (fn ni cr aL 1988 ad N*so ct al., 1988) [s6' s,]. 

G.n.duy, not mucb is known about $e ch@ifrv eQ4i'llv, thc ch'noel4tiw 

@blytc a.tiviq ofosmim @. ohplcxes 6 conpeed to thoe oftuthdiud dd iron A 

eplon d by licElw Plahm ard rul|loium @6pl€x6 of N,N_hcroclclic lileds ' e_ 

biprlrdinc, thdslhdlinc ed phqvl@tlndic wc sfidi'd ro a l{8"xtcnt Oiovalora 

d al-. l9t, Blmint .l ct., 196 od veld.B .t sI 2000) Iss 601. 

Tt. ldgc ede dtplications of ligdds dciivcd frd mino aids h ' PoPuld subj61 

in orgdomcLllic chcFisry (Sevetin at d, l99E) 16ll M€t l @nPl** vilh Mino &id- 

type lig.ndt sho*cd .ppticatim morly in bio-inde,ric cl*ninrv c g ' lor lhe !'prid's 

sFrhsh (Kdnd d al-. l9e6) l6tl or bici.oedic nodeh (Fistt 

't al-' 2003) {6'l 

Honoscnous .ne$sletive @talttb n.rhods enldc'd bv nds of lrdsilion merar 

conplexes have bn poled einciot m..ns to get kcv ors&ic mol*ulcs conlaining high 

oplioll puity. Thc .xplohlion lor syndetrio sutportins ligdds c"tblc of trmsfeding 

chialiry b $c ultimst dgmic @btound tlEn b€ones a 6hdldcnol is* in cablvsis' 

34

Anino eids dons virh tn ir d.dvadvs ttFsl s Momicdl dd 4ilv obtai'able solp 

of chiial ligeds, ed rh. lit4frft pDvid* nnmus crdpld of bdog'n@6 

..etiosleciive pm6s eldtud by dd.foino @d onplcx6 (Sdioh et al ' 2000) 

t5.ll. None$el6s, honogclous fldd@lcclitc qlalvs|s having ahino &id mid's as 

li8&ds, lomd $ f.r e le (Malkov.t al, 2003) 1651. It. at ltlic pbsFctivc oi 

ru$..iun @nptq6 wilh cead lo orgdic tvnthsis is w[ @gniz.d (Nd' et al ' 198) 

F51., Hlr-sd*ich (rc'!w) n niM(tl) @nPlexs @ usd nlqEnrlv 6 p6a1!ly3r' 

(Noyoried tt6higlchi, 199?) 1571. ln such $EleeJFd piso_st@lgpc half{ddwicb 

@mpLx.q ih. n tll lbe b.ins a cnid qLr i! surcurlcd bv t halide ligmd X sd 

dorhs 6srmdi6l chct.lc liged lL' Th. rs dia*don G Ss& md xMt lr* 

obr.in.d by sing d .nsdomdi.ally puF (foi quPle of "t ontieur.lid) ligod LL' 

(BMis, 1980, 199,2001) 168-701. Sev@l $udi6 on chid-ar'mdal conpleres ofthe lvp' 

t(F@.)Ru{LL.)Llx ed t(il6.€m)Ru(Ll,r)Ll 

(.m. @cPd'ds to Mmq 

hMclhylbe6., p.ync.., m6nvl*, LL' ), ndoddtd! lirad or btlide' x, dion) 

&d dimic or neuu.l .nedomsislly poE chd.t€ lieand, L ) h!v. so idr b*' reponed, 

roSdns wirh oino a.id ch.htes (sddin .l sl , 1998 ed cm6. .t al ' 2002) l?1' 721 ild 

v.ry @ studi6 d tlc osim an log:es ns b6! caist oll 1o d.r. 

l5

L C,H, Kdi. T.lqbal. ddZ,A ZAidi, J Chen Soc Pak,2' 144,0940) 

2. C, H, Kui, T- Iqbal. dd Z.H, Z.idi, J Chsn So. Pat,2'50,(rgaq 

3. G. H- Kui , L G. t

16. T. Tdleuhi md T. Mira. Ktunatosvf, 16 t81 (t99st 

I ?, T .T.Lerxli od T. Miw\ ChmatogtuPltia , 4, 162 (1995)- 

r8. T. Takerhi ad T. Miwa ch@togi, 11, 152 (1995)- 

r9. .t- Did, J- U. Llibqi!, ed F.Broto.PtiA,J Chotutosr1 1r9O)' I19096). 

20. T. G. Xdi, M. M. h! S. W. Shah, dd O H. rwi, "l Stnd Uni'-. 29, rM 11997). 

21. T. C. Kui, S. w. Shth, sd O. H, Xei, Sdl (,y. tird, II'1250998). 

22, Y. Nogoe dd T. Isnid^, J Liq. Chntu,,rl,103\199U 

2J. v. B. Chuilov, A.v. Lychl@vskii, sd S V Kond, J ,{rPl tP..t, 61 384 ( 1998) 

24. Y. L Me, F. X. Ju, O. Q. Yu &d Z. Q. Cu, Crth C,tt Z?'' 9' 285 098) 

25. Y. L Me, F. x. Jm, O. Q. Yo. !d Z, Q. Cu, Crtn Cr.n L.t- 9,666(199& 

26. K. Statr, K tlab6e. S. Saltli, M, M!.d! 6d K Z!ns!, A.4l I Sci , rt 1091 (1999) 

27. M. D, Ga!es.y. ed J. t, Adon Bi@..l ChtukatoSr , 13' 172 (.1999) 

28. Abujttyab, AHurnhim ,'Ih. 6k &tenttfc ol th. Asrciatio, oJ.o|eea ol Phamacv 

in ttu ttub Woi.l, Ciru EpPt, D.c,2004 

29, L. Y@soe, L, K.jqim& L. Jin& P .lu.xix F Xuli, 8d v fee., L@shti. 22 

oo,7016, (2006). 

30. K. L Konh C. Ka.t 4d tt. M. Foq,v',r LP ,t., at 5, {198?) 

11

3l. A. woli C. Zalpor, c Tneilrci.r.JAmCo cardiol , 29, 479. (1997). 

32, S.M. BodeB6gq, R.H. Bdga, H Allt , D H.iMel D Tsika, A Celuig ' K 

Al.xsdd, dd J. C Fr$[cn, Crttllariol., vol. 94, 85, (196) . 

33. P. L.l@! B. D.noldbe , $dRqrn L'\, CUn E p Erped.tu ' 1?(7)' 1009. ( l99t 

l r. R, M. J- Palna, D. s. A.hbn, d S. Mo*rd!, lv,r@ , l3!, 664 0 9tl). 

15. P.S. Ts, G. Th.ilftid, A, H. Singo, L. L.K. r-Ns, dd !.P coJ&.. Anqiotekl 

lhtuhb' L4, , 1529.ll994J. 

36. P, Clsten. M. R, Admi A J Pow€, A E. Do.ald, R Mccttdie, J. Robin$n, S N' 

Mccdhy, A. K€dL D.S, C!l.mqi.r. sd , F D€dfiel4 J C/fi INst ' 91' 1949. 

(196). 

17. c. F. B.lloss ed B- M. Jafic, ./S'zs x4, t6 (2), 213' O99) 

lE. C. Mu.phy, sd P- Neaholn , Bio.lea So. fruN'2s AJ.404' (1997 ). 

19. A.R.{bu-J.t}ab dd KU. Q![!t,6a(2 & 3),263,098?). 

40, J.D. O&ich, G, Baj@o, udRE Ol*n,am J Cltn Nut" 23, 1626' (1970) 

4l . A. M.ngoub Md A.R. AbrJ.Wan, Noition R.sarch .1l1J 77l. (1987 ) 

42. A.R. Abu-Jatyb. K. Qaod\ snd A E.shardi, Sci. R6.' tte.lsi Res ' 15 1391 ' 

o98?). 

a3- Abujry'€b dd AtdurEhin, nr 6th S.i.rtif. of ' Aswidion af ethe' ol 

Pharwy in th. Arun Vdd, Citu EAF.D4 e@4). 

41. A. P. J. Houdijli. E, R. rjNbug.n J Jde,aal,.IMer,352.772.(1998)

45. S. A.l3irc, s. K. N!6, C- is Ming, C. Yu! ad ltt- Dorosz-GBn4nknlos/' 

106, r69E,0994} 

a6. H, P, J. Hou{tijlq P. A. M, !s lswa! T. Tdlinlq JPE I J P@tur E ttrol Nut 

18, 422, 094). 

4?, S. F, Ab..uw, B P. BoiL, lxl w W souba, ,ry, 4d cmpoa, Botton l,sA' 

353,0996). 

48. lM. L*ay, D.w Wilmore,,v x.t, al,29' (190). 

49. P, McMonldGJ Hurcnings Ci.t So..,I?v 33' loE (200)' 

50. .IJ. B.d@ dd Mx. G!sD. 14 clca. k5 '!'1%'12@4). 

51. M:f.N.aa Prcc Natl. lodd &r U S ,{.i i01' 5? 16 (2dX)' 

52. B.Bri\/ng#. CId, It'L U.2005r14:6ar6- 

53. P.A. Chlon6, MI. Er@las'iF.l(n.ftLA' otu' IlowaereN lt'htgtnztion' 

Kll|rE Doderq Ncha|rd! (1991). 

54. M, A, Esr.N.la4 M P.Oeia, A M LoP@ bd L. A Oto' Otgpwnetalll$, ll' 702' 

0992). 

55. E.F.frdlN v. Guldi, M.tui,OdChin ztal '123't66,(r93)' 

56, E, Fs.tli, J. K!Ss, R. SFghnc,lt, M. t GEziei, C/su Soc DaltdTrM 941' 

09E8). 

39

5?. T. Nateq S. Uhsq Y.Kiio, Y- l3hii, M J. Oe.w\ Ot8 Cr,.t.' 53. 1762, ( | 96E) 

58. o. Nolatov.. J. (aprlova, o. vtua. PM ve vlie! J- Reedijlq v Bdbe 

Riochehhnt, a4, 12J69, (t995) 

59. M,J. BlMinl, H E g.tldn& s (6ta!oul6, B Krcbt, J R'cdijk 'lDrg C"t' 

31619. 0996). 

60. A,H. v.tdes, H Kooins, A.L SPek, J G' H@noor, D De vos J Rcdijlq 

ch.h. !9,2W, (2vt0). 

6l- K, Sd.rh,R. Bsgs,Ii.B,c*'An4a CIcn t's En 31'l6t1(1998) 

'erg 

62. R xrlhd, M. M|tlru K. Polbom, K Sihk'I, C Robl'W B'ck'Chtn Et J 2' 

l5l8 (1996), 

63. R. Fish, G J.oud, Og@fttalliein,2r66'2co] 

6,r. (t) F. J@, E.Tnidnvi' J OrE!tuda Chen t'l'63'/J942) 

O) D A. kidld, D J Molns,J Or8'@t Chtn 210'r2l'{r984)' 

(c) M Naktsa*, H Ntko, K Wal!'lbe Cist ktt 5s' 391 O98t 

(d)S Colmo' A Menldi, M Spldo ' L Cslla' M Cullo[i' J CtEn 9E' 

P{t:rTM.1l'(1987)' 

(.) A. s.i!oh, K. Achist K TstI!,T Mqimb'J O|& C/ct ; 65' 422? (2000) 

65. (6),{.Mori,H Ohno H Nin4 ( T$!ka, S Inoue' sy'l€n 563' (1991) 

(b)Ml BuBuei., M. collado, J Es'orjhucla' F G'lindo' E Cdit_verdlso Sv 

Liis,M.! ''li..nr', Tetrulzdtun Lert i 't', 6891' (2001)' 

(.) A-V. M.lko!, J.B Hdd, P K@vst''Cfun Connun l94a'Qno3)' 

66. T.Ns!.,H Tat.va S I M!8hshi, Ci€t' it ' 9E' 259' 0998)

dt R. Ioro.i S. Hdildi, "nn-ro,nr,rrO, 

6{ EBn!E,,ad. OrEln Cln,r4Ul,O9&} 

59. E arEl.f, ,a,!tt cr.', rU, t21{199). at{.B- Clrh.' tttLEA' 3a' 1194' 

(199). 

?0. g.BdDn,lt[ J lhdt Cx.',905, (l00l). 

71. K S.\i.in, P. B.rrt' v.i,r,''Aigd. Cl^'llo'l?t (l994tt'1,s* Cbi-Ir' 

Er,t,l6t,G9N). 

72. D. ceod.,lr- P.Lrdd., LA.oto\fu. J Iw&cl@,',r,g'6frtl,' 

at

Chrphr - 3

Cfi.apter- 3 

ADino Acids Compleres of 2-Methyl+hydroryquinolitre 

Sumrlrry 

Four mino &ids (spanic sid. glur@ic eid' cvst ine dd srinc) @splexes of2' 

nerhyl-8-hydDxyqlinolin. \@ PtpaEd by t ns one st ! n thod involving Utd ou'd 

6si!t d 6dgJ !r 60-?0 "C foltosld bv lncir cMPlcL 'hdctdi2'tion rhougt 

sp€tospic, de1Md ed lhmal stlFis tdhtiqud, Al 6' ndtion'd @hniqc 

@nfm.d th. syn$.sis of $. @hpleG Lid s of dddrion (LOD) of lhc @Plex6 w'E 

.ls obi.ined by lsing spelro0@rom.t6, whicn eft found lo mo n6l' (nn4 bvcl 

Glut Dic rcid b reag.ht 6d spartic &id !o age'l noL talio s foud 10 b€ I 13' shil€ in 

$e .6. of seline dd cysteine ool. Elio b *tablisncd 6 I :2 

Amino &i& e lh. disct lt uit of elcry hnd of lifc sd @ fouod in dll tb' liing 

systdr. A nunbd of ncthods hav. bM dqelop'd in plsl for qMr ativ' d well 6 

qulnlrive d.t minction of dirc eids in d'ft.Mr n!Fi6 tl-9l Vqv 'ficid! m'thods of 

Diro &ids m.ltsis hav. ben d*loP.

Erp.ribertrl 

IctEn n|.iio., CheEh.h ..d Gbsrd u.d 

Spctlfl!@m.iric darysn vs 6i.d our bt usinS Pdtin Eln r LS-45 

sp{Eoflooomet.r, W}ilc Shimtzdu DT-30 B ln.md d.lvza .quitpcd win DGC'10 

lh.mobaloq R-123 T nulticbdnel t.cordd ws 6.d 10 Fcord th.dal cury.s in a slsE 

olN: f,owing at a @ oa50 numi.-t|l NMR sP€ft l* obbin.d 3,! 300 K on ! BNLcr 

I{lO FI spc.rrom.rn, b, lsing SiMe4 s i eml 3tddttd. InfE !d S€lra vft @rded wilh 

a NimLt 5700 FT-IR sPecrophotohele! in lhe reg. 4O0o'40O cmr, Eln.nlal ealvsis (C 

H. N) s@ psfom.d by Bing . Flsh Mod EA I I 12 dalva. h cxpqinc'tal Pt*$ all 

glsla !.ed wE of pyEr 4d q6 vtsb.d *ith NiEc rid sd Cho@ hil:tlE' 

followed by distill.d dd deioniadwalercstenv.lv 

Anal}li4l Gad. MERCK' dd FLUr'Ao btdds or chtriels rm u$n in all 

datrsis. Dcioni2.d *€ls B lsd dudne tbc qholc dFindtlt sd' Amino acids splc 

oblaned fro6 BDrf ch.niclL Lld P@le Ended. 

G.r.nl Sydh.tic Pm.dlF for ADi.o .cid! D.rtvriiv6 nr cf,oldl€rcI 

o.l M sloct eluliG of.ll dino acids u*d \@ Pitfdld in 4uous ned'c' 

wh€c6, O.l M 2-ndhyl.8-hldroxvquimline solutioo rc E 

paEn in 

'theol 

25 nl ofe&h 

of 0.1 M @ino &ids $lutions Y@ ratd in lo0 dl sepa'de fl6tl follow'd by d 'qual 

slu. ofo.l M 2-h.0vl-8+vdrcxvquiDoli.. ellton Th' tla*r *w thd pltc€d in th' 

eni@tor &d @t€n ar t@n r.mFBtuG fd 15 Minutcs Oil whn' crtdab ofprcdocc w'ft 

obtlioed wiih ti.ld 

norc the 85% it 3ll 6cs, $lv.nls r@ made lo daPodi€ in ultrlonic 

blrh at dbiqt r.mFdluE. Thc dsivdir6 obEin d *w 'ash'n $rie with 0 l mM HCI 

!d NIOH and fin.lly with ultra pE wdd, dricd sd $otd al 25'C iI d6iccotor' for 

4l

Fluomm.tdc Study 

Results aod Dbcussiotr 

Th. mjoiry of oim eids do mr exnibil nlollge acivitv, trvplophd b'ing the 

.xc.ption. t1E codplqB of fou mino eids @.ly.vsti.q glllanic &id' 4p,nic a.id 

sd sinc with 8-hydoxyquinoliE (Oxine) dd 2-melhvl 8_hvdroxvquinoline (8-hvdroxv 

qriruldii.) *4 trtd.d ed subj*,r.d io tll@n t'c dalvst for omP@tiE studi.s 

comp€dive [@l!gs@ inld3ity @lrl of c$LitF8nvdox]quiBldin. with cvs&b63- 

hrdoxyqlimli* @mdd e. sivo itr T.bL l, thiL rg!r. I (.) 3d r (b) iidicai' thc 

€ellls in gbphic.l fon for cy3l€in @npld6 ll m obss'd thtt' cvst€in' snow'd 

llighd n!o6dc. intensitt witn E-hvdoxrquinoli.e 6 conps'd lo thal of 8' 

T.blc | (.). Conpdliv. sdv ol fllor€s4m id.nsir) of cvstone _8_ hldbx)quinoline 

@;pbr with cysGb. _8-hldbxvquin.ldh. compl'x 

0.2 

5 1.5 l?3 lll 

(a) rE 375 m, rh alo m 

6) ra 360 in,lh 440 M 

r08 

t3l 

130 

t35

At l& 375. 360 m .rd la43l,, rl40 d rlE r*t nts &hy(|lqyquilotin , 8- 

hydroxxuiiddim Dd cFt iE sh.*td m fwtlsE ..riviry, 

Cylr.iF8{ydrxrguiiddirr od ctc.ictiydd)quitutirc $o,!d rtc adiviiy ar 

ri 35O n', rd 3?5 D, od flur@te a 445 d lrd a3O b eni|c F( lroichir*rric 

i.v.stigarion, difr€cnr Erio of @gcft *s rddld in c@pLring nalrix s l: l, l:2, l:3, 1.4, 

l:5 sd e d, ft *{. c,b$rrcd rltd d l:3 moh Elio cmplq sltowd nuinun ttuotgen€ 

inL$ily, F.DL r 6), *iiL.l highk 6r.|riioo, d4|qs i. rh. inidiry of @[dd 

w.. obw.d s 3hM in FlglE I, delta ln rb. i dsity B p6t bly dE !o qudning 

,t5

tl3 t (a! ttE {6r dqdr..ald..' Er*-r. idq|\ 

E +dar $,h'daa c ot-!, OdG, AaiddE

AD 

r60 

1@ 

140 

1m 

81@ 

d, 

4 

6 0 

&. t OI C@Fniw sdtdy of f,wB.@ idosit, of cts.i* {'lrydqvquioldiE 

@mplq sith qsici@ -&hydoxyquimlie conpl* 

t:3 

ExpctrlMlll ed thotdicd d.lelion limns ol lhd Blv sFlhdisd .mPleG 

w4 found 1o b€ 2.0xlor rtul / nl, 2-0xlo 5 pnol / nl dd 4.!(lor |lnol / nl dd 2.0x lO' 

Th. Fsulls de 3lnnwiz€d in T.blc I (b). For detetion lin of @npl'x dilTd'ht 

exFrimatal Ddu.td of ins Such !s hsdwidrh for ex'naion dd 

di$ion. g.in $d ditlti@ f&ror of dlbtq Fig.n 2 indicdld $e .ffccl of lhe PH d 

nu@s{xci 6sityof nqlypi.Pddonptd6,whichwsoptinizedbd*6Iand5 It 

s obsd.

T l. l. (b) h4tior LiEits or C}3l.l!. Cond.E 

Sr. E! 

t0 l0 

2, (B) l0 l0 57 33 

3. (c) .20 {0 5t0 95 

(D) m t00 95 

Itd.cnon Lihits E{Gimtul = 2,0 x I 0- u movml 

Thocricd = ,l.lrlor r nol/nl 

B w = B..d width & IlU s.lc difradotr 

o s -007srCvsine /l00ml=001M 

0.s ml or di;; $lui@ k dild.d uP b 25 ml _ (A1 2x Io_ M 

sbichion.tic @mDonrion | :l cysldnc '8_hvrtoxvquhddrn' 

5 mlofAJtobl= (Brzrlor.M 5 ml ofB/50 rl _ 

,mtofc/romt= (D)2xt0,M 

I 

2.05 

2 

195 

t.35 

t,8 

7.15 

l.:5 

1.75 

d 

lJ60 

FICuE 2. Effed of PH oi flNteae inL$itv of Cvn3inc @mPlq6' 

48 

(C ) 2xlo'lvl 

192 

335 

5.25

Thc @mpsitiv€ study of 0uoFslxM 'tLntitv of glutldic eid @npkxcs ws 

indic.td in rrbk r(.), qniL $. twlls it gnpniol fm @ rcPt*nt d in firuE 3 (.) 

Dd rigrE 3 O) fd eillhic &id @nplffi clllanic did-8'hvdot]quin ldinc ed 

gluramic scid-Mrdoxyquinolin. sho*ld lhe ..livity d lE! 345, 

TrbL 2(.) C@Dlr{ivc $udy of nu()lMt intqdty of elutcnic &id'E_ lvdrextluinolinc 

conpldwith glubnicaoid-8-hydoryquinaldimconPlq 

Si 

I l:l 0.2 o.2 m 

2 l:2 0.2 85 

l l:3 0.2 0-6 148 |l0 

(a) r& 335 nn, 16 425 nn 

O) ,!d 145 .n , 16 435m 

o) 

0,2 0.8 t44 t07 

1:5 0.2 1,0 105 

oi-i,-lll, .lls nm ed l€n 425 43t m 'h' G!@ts 3-hvdoxtquinolin' 8_ 

hldrcxyquinaldin ud gluhnic *id sho*.d m flsll3ne "l'wv 

le 315 rd fluq.slE@ .t lh 425 nn d'l ''h 435 m, 6p@ri*lv Difr4't Eli6 of 

.dplding rasdl vw.dd.d fq doichioodic inv'siSalion s d*qib.d 'bo* thc 

6ulLs d sumndiz.d in T.bl. 2 (r).

E. 

c-o 

f: eQ 

h. 

eo 

eQ 

rtln 3 (.)! Fluo$i.dt sp6t! or glutdic &id cmplffi, G- Sld{Ec ..i4 o.8j'e' 

Qui.rldirc. Ex - Ercildio!. *$elenglt, Em, - Enisio W3rclotgh 

120 

o 

+GrEdc d.}orl, +Orbrrc r:*l+qtddaE 

12 1:3 

rigun 3 OI CodF..liw 3trdy of fls.6&e ilt 6itv of Gtdt@c ocii ofrpbG 

d.l@li@ linits l@ f@d 10 bc 2.Oxl0r xnol / nt od 4 2xl0t F ol / Dt t!6pe'tiElv' 

Tte @fts tt gis in T.bL t O). FiltE 4 shN lhe pE .fi"t @ [|s|lgM 

50

Si E! FsD (!)v 

(A) l0 t0 92 0t 0.1 

2. (B) t0 l0 210 50 0.5 

L (c) 20 124 0.2 

(D) 20 

Debtion Limils ErP.rinfllal = 

Thddiol = 4lil0_ 

B. w = Bdd *idth & FSD = Flll slc dfian@ 

'10 

540 85 

o2 

l120 

tlor p nol/nl 

115 02 

o. s = 0.089c ddmic &id /l00nl00lM 

0.5 bl of qi;;l slutioi n dih.d uD ro 25 nl = (A) 2x l0'M 

Sroichione;c @mDdnio l:3 clut nic eid -Chvdtirvquimldin? 

;;i;;;,;;i---:-id;i"ioiv i^roie,56;'t -,c, 2rr0'M 

= (D) 2rtotM 

t,.,, 

FiglE ,1. EfrGd of PH on nu@M4 irtensitv of dd.nic 

5l 

eid MPI'x6

Tt @DFrali* ladt of nur6c. in Gny of aFdic &id @npl.G is 

qnibit d in T.!b 3 (.1 FiFE 5 (t) ald Ft E 5 O} Asr..tic -id-& 

hyd.oxyquin ldia .!d !t!.rtic r.i4&ltydroxyquimliE ompki6 slbred llE divily .l 

fis ! (.1. Fls€o.G 39.ct. ot Nt.rrtc ed dpLx.t E\'- EKifio $rc|'icrh' 

E; - hBid w.El6Sth A. sFnic rd Oorir- qqu'mtdtE 

20 

20 

+A.dtbd4dlr +A.Fdc*da{iEbr 

rig 5 (b). ConFotivc a[dt of fluordenc. id.$it of 4sFltk *id{dtuldr'e Pilh 

l€" 3?5m rd fl@tlslce d I e a]O m .nd ltu 450 tt! 6!.cav.lt Ef'ct of pH on 

n!q!s.€M irtendy of sFnic .3id cdnpldcs is dlgib.d it Film 6' 

52

Trble .1, (.) Comp.d'E sEdy b.il{6 fluollsol in@snv of t9'ni aid 8_ 

hJ doxyqu inoline @mplcx qith a9.tl ic .cid-8'h) dr.xvquin al dinc @sp lex 

rtuoa*e t"t^* 

Sr. 

(!D 

l:l 0,2 0.2 

2 lt2 0.2 0.4 9l 48 

3 l:l 0.2 0,6 IE5 n 

G) 

0-2 0.8 180 

5 l:5 0.2 L0 175 50 

(.) le 350 in! 1€' 410 nn 

(b) l.e 375 ns. i.h 450 m 

Ar rE l5O. !75 ii 4d i6' 430 450nn th. dnsls 8nvdrxvquinolin' 

E-hydoryquimldine md lst nic *id shord m fludt$ne *awv 

Exp.rinentd sd lh@t*i€l d'L'lion linir of &eptnic did -8'hvd'otvquiitldinc 

conplcx wF Ioutds to b. 2.oxloi Pmol / ol ed 't 5xl0' rnol / il cspcdiv'lv Thc 

rcsufts ee givm in Ttbl. 3 (b). Th' €fcct of pH on fluoEsdce intcnsirv of wlv PFpatd 

ofrpleies of dtlnic lcid h indiqt€d in Fgorc 6 

(u 

36

7 

r.95 

1.35 

r.3 

l.?t 

: 

!.25 3.5 3.15 I (23 45 475 5.25 5,5 

Fi& 6. EtI@t of pH on nu@s@e intffitv of $?trtic *id @h9ld6' 

T.bl€ 3. (b) D.tdtioh Linil of Complex 

Si 

E.'IT 

E@ 

I l0 l0 180 0l 0.2 

2. 

(B) 

3. (c) 20 

(D) 20 

20t 

425 

l =2xlo' lrhol/ dl 

Thdr.licat = 7.5xl0r unol/hl 

-ExDdjn€nt 

f1* = 

"-o *,u, o tto = ,"ll s&le dift&tion 

Slti#i 'i',pibi ' o. , ,* **rc .cid /r o0 dr=o 0r M 

i.ii'i*.ii -.p"'it- 

0l 

t5 

l5 

3o 

n 

t5s 

3t8 

t:l *r*k ed -8'nvdoxvquniidin' 

:ilirhtl:[l"l';",1- "n';s 1r;ifo'iil.,j z,ro"v 

i doia5ont= (D) 2xloiM 

54 

TSD 

0t 

o2 

!:L 

OJ 

OJ 

ol

ng. E {r): Fl@cac.c .P.cm of !.nE compleai 

En-EDi'sion Wawl€n8lh Sa4m, o{xie, Qqoit rdift 

Er=Eeiliid *wlaBr\ 

Th. mpuM of nuoElqe @iivitv of sin Mplqd with oxint dd 

qui din. is dai.r.d ii r.br a (r) dd llslB t (r,b). Th. &rivitv of *dn'{- 

hldoxyquinddin. &d sin+8_hydbxyquimltlin. @9lqd w* obs€fttd al l^ 365nm 

l,& 340nm ud tluoesne tl 16, 430In .nd 2{. 450nF 6Fcriv'lv, lh' rcslLe @ 8'v'n 

i. r.b|e 4 {.} Expdin.nt l 6d tlEr.licd d.i4do linits of sdn' @npl'B l@ foud 

!o be 2,Ox I0r Fftol / nl dd 6.5110r Fnol / nl EsP{tilclv ft' 4ults at giv'n in T'bl€ 4 

(b). Figu.. 9 indb.l.d inc cfi.d of pH on nuotlsne inlasnv of erif,' -8' 

hyddxyquinltdinc @npls 

55

FE E (bl cdlFrlt € lody of alst3&@ ideNrv orsi'. .@ddca 

Td. a (.) Conpa!.liv. dudy bctcE 0udts6t int Nrlv of si,p8_hvddvquimlinc 

conpl.xqith srine -8-hydexyquinaldin.cohPlex. 

Si 

-F1@.Inkmttt (b) 

0.2 0l 12 

2 t-.2 0.2 t52 l0l 

.l 0.2 0.6 r45 

0.2 0.8 195 l,lO 

5 lr5 0.2 t.0 190 l3? 

(a) l,E 365 nm, 7'8" 410 m 

O)ra r,()nn, r6a50 m 

Ar l& 350, 375 m dd 16 430,45onn 0r pdlrds 8-hvdoxvquirclirc' 3- 

htdnxyquinrldift dd sift CE*d m fluor*d. -r'etv

Trbl. a. O) Del.ctio Linn or conplq 

Sr, 

FSD 

l0 l0 0l 0.2 

2. (B) t0 l0 22 o.l 

L (c) l0 l0 170 55 0.2 

(D) 20 42 20 0.1 

210 60 0.5 

D.te.tioD Linitt Exq.tituttt = 

TlEidical = 6.5x10{ 

d1* = 

"-o to* o ,ro = ,ull s.de dif&etion 

970 

Orqi!.l $lulrotr (o S) = o.r3ls *rb. /t00tl = 0 01M 

0.5 nl ofdigiml ellnid is dilut d uP to 25 nl = (A) 2x l0'M 

Sloichion.llic 6npci$on I rl sirc -&hv&oxvqlinaldin' 5 ml of A/50 nl = (B) 2x l0'M, 

5ntofE 50nl = (c) 2xlo'lvl, 5 .1 o66756 n1= 1o; uxtotV 

2.16 

2.15 

2.t4 

2.13 

i z.tt 

2.0E 

2,01 

2.06 

2.05 

pH 

ll5 

t00 

2.5 2.75 3 1,25 ).5 3.75 4 4.23 45 475 5 525 5s 

Figla 9: Th. efid of pH on fl@Es{re inL6itv of erin' conpl'x's

TGA / DTA Sludie. 

A4rnic Acid-2-Mdhy'-Cqydreryqrilolirs Conpld 

Th. TGA / DTA nudi.s *.8 csied our for all lbe four uino &cids cooplex.s of 2' 

m.t'yl-8-hydbxyquinoline (Q!inaldin.), Dm.ly, 6p.njc rcid, glnLmic &id, cvsiein. dd 

srinc. ThcnogMs of mino .cids, 2-D.rhyl8-hvdrexvquinolitc sd their r'sp'ch!' 

@npld.s w.E nanipulat d .Id d66ib.d in lhe following litus Thmol cvf,L or sPanic 

&id, lh. EaBat Md ils complcx hs ben |bulat n i. I.bL '- 

T.ble5. Item.lAnalv3isofA$MicAcid_2-Mcihvl-8-Htdmxyquinolin€ 

TG DTA tG v" DTA 

I I 

2 

2 

3 

- I 

2 

I 

2 

90 

190 

220 

260 

4@ 

2r0 

230 

ll0 

24r) 

29tt 

10 

220 

210 

80 

2t0 

260 

680 

230 

260 

200 

230 

560 

q) 

210 

TndogD of 2-n.thv!8-hvdoxvquiNlinc 

'l t:: 

sr.p wcighl lo$ (W L = lo{p/o) st a i.nPdlue ds€ of 90-210 'C 

(Quiiddine) ws obscry'd to h6!e on' 

and u cDdofi'mic 

DTA (Oifr.Mi.l lr]mat Analvlis) P.al with Mpd'$E tuse 60-80 "c Possiblv for 

hcltinr dd solh6 exo$mic DTA Flt fd d@@p6nid d c lldpd$c @se of 1901 

2lO'C, aspttdc eid h$ lhc *.ighr los n@s, @Gtotdi4 to r'openrlE tu9"! 220- 

2@ 'c, 260-400 'c .nd 400'680'c Fsiblv for cooH (w L '14 = 33v')' ctlrN (wL 4? 

5E 

33 

v 

,j 

59 

l3 

'j 

12E 

1) 

':' 

- 

Boiling

(wL. a4 - l3%) Bp€rivcly. Mo@vd, il rl9 sno*d 

= l4%) ed fd s.dd coOH 8rdp 

@ ddotlmic DTA pal *ith t sp.r.t!. mgc 210-230 oC Fsibly fd m.hing ed 

dofid cxofimic on. for dccdpcitio !r . tdipalluE tu8. of 23G260 'C- Th. s?lnic 

&id - 8- qlin ldiic @nphx sto*ql . mplccly difr@r pltr.m of rhh.l d.nrs in its 

thhoSrM virh thE widt los sl!g6 d t dprrN tus.s, I 10-200 'C, 24&280 'C .nd 

29G560 'c p.sibly for trandts of c! HD N, o2 (w.1. 32E = 59 %), Cr Hr Or (w.1. ?3 = 

13 %) ed CmHrNl (W.L. 157 = 28 %). Ti. DTA Uamlnn di&rccd rwo Deks bo$ 

.rdorhmic si6 hpa E Mg.r ?&90 oC sd 22G270 oC which na, h. t @nsqee 

of ts d.co.rposnio s.tr. Moev6, thc d.conF nion Fran of @npl.x Einfo6 drc 

l:3 dol r.rio of Mino eid ro dgat ia this c.s.- 

Glut ntc rcld Conpler 

nc th6n l bdlviu of glutmic &id.lons wiu @s.nt ed irt mplcx h$ ben 

d.picld in FtrE l0 sd T!b& 6. Olui.nic $id a shoM to lo* $,hol. of irs *ight in 2 

strs6 wi|n rqnF !c @s6 23G120.c sd 32G520'C omsrondins to qs.qN (w.1. 

| 0l - ?0 %) ud Cq (w.1. aa = 30 %) lspetiv.ly. TN DTA Fk' *w .l$ obwad ror 

slurahic eid in thc tdFlnr ds.s or l9Gr0 'c (.idothmic) lrd 4,(l'ss0 'c 

(do.lEmic) Dosibly fd $! *F€nt ddnD6irid 4qts. Thc @nrlq !!o cxhibit d two 

wighr lo$ 3r.F.r 190-170 "C rd 37G550 .C s*.ptibly @ftrporldin! ro CD Htr N: O. 

(w.L. l?2 = 65 %), ud CD Htr N: (w.1. 198 = 35 %) 6p6rircly. Te DT p6er 94 

fouid wirh LnF..tE rs6 l5G2?5 "C (ddoth.mic) ud 510{:10'C (.xodEmic) 

pGsibly for boiling &d fiml d.conFsirio ofrh. @npoud. Th. denposirio Frl.n of 

Slubmic &id @mpl.x al$ a!r6 ro l:3 mla r.do of 6im aid io €96r. 

59

E.; A I d i! 

533t 

Po 

I ;r 

E -=; 

60 

2. 

EF 

6rr 5; 

6- 

!9!: 

I 

,,t Fl 

ts 

6 

3 

€ 

ia|| Ia I lr 

3 i. 

E6+ 

3

(.r-..-ld (r5cd.+rFqdir- 

r|. lc Dsrslta ,iorilt 6. 6cn4 hfivldr of gl'eic .oi4 rqd .!d 

Irbr - 2 - U.ary+rynqqnbdb. C.lt|td 

rt tb@l dlrdr d !h. .t q elt Fld !d its oooda i.r ha 

d.d.!d ilt r U dd.mrild b T.r,f ?..It cis ooqtd d...qo... h tF 

d.F a f04..a!l oci.g tm 20t 0o 250 .C h. Cr Bu N q (w.L 2il - I Xt d 

L.o|ld m Ew 2r0 ro 550 .C tu C,o R N, (W.1. IJS ! al %). Tm DTA !.rk w.$ 

obG$d d t6rt.6r& ms!.! 25E-290 rc (t|@ttmtc) posibly for aot rlidiod art 

l*s/o t{r5{0 .C (ad.rbnic) e. nd dcoqodid. On th. ..h- tD4 shc b 

.&o rbh trD rdsh loc . F[ .| rm mA Fb, Ed @q-E nar. Ft 

dfrrn it 225-26t "q 269t{I} .C t s|lntc of C2 H6r.L q(wl- 60 - jt 

X) dd @()I| (Vr.|5 = 12 ta) tq..dv.l, d IIIA t .k E ot-r,!d d dF 

26t3q) .C (.sdaDic) nd 43J-5ltO .C (..d.Odi.) S. p6th hoih,t !d 

dmpdtdo .te.cdrcly. 

6l

q 

s 

sa!, 

{,32 

5. 

I rs8 

EI 

Fi!P 

-9 lYF 

E!-Z 

:F a 

!: e 

62 

8a6 

!q 

!J9!9 xt3 

''E ! 

|,t :-r 

9

€.t-a+lydq{qr5- 

t; n.Ihqm-oftg&6..nltd.tnaofEila E sld ri oddd 

s!r*b. -, - lt Olr|+rydl.ryqlb.lr. C.rd.n 

ftqdl b6.de .rhlb:d Ir crn tB rd drir 6qk ir dslt d !.tos b 

T.[.]lrlt nll.AlDdrt ri. tktrl cv6r. d E ot6r$d t ! ft.tt 

.loE Edod ELd.r 

63

t I 

: 

Eer 

er 

*; 

-9 r 

,P1 

9?! xi3 

rl 

!s 

cy.bln -l-Hyddyqlln.ldrn 

Er, rr.lbdg6 ioils 6. tmd bd|vlott ofct!.i.., t!.8d |!d oorytoc 

hfi|I.d Spc.lr!.cAh (R) Sidy 

LbL 9 oG.p@d! ro dE cdD.rd'.! drdy of in6ed !}..td hod.tttFn ltt 

of ctlt iF&hlddyqsinolie ed cynchcE.lrydroryqdaddie c.qlitc. A bldlt du6 

ro -NIl go||p of c)r.h. i 3300 6'! E .tD.(al &. L c.qldnid. I E otst&d 

|td, r t.rd b-d e,ilcl E F€.d.3130 sr i! rt t .'t.f et!rd.., s D. f@d 

in r[. 

"d. 

of c.ql4 dt io tihdo of 6.. {oorl .b tt @pL.dioo of 

cato(tic gqp oforn i!. vin 8+]d!oq/$hddh. rt |@brdld 1700, !750 6d 

u00 @' rr.(. virudird sllus, hNd I|d |! die cpedv.ly w@ oblctEd ln lhe 

q.dr of coopLd, 6ir do!*d S. i.blv.itd of (+o) qtoyl tD.li@l 8Mp ir 

coqlqrbc Ai ftgr Fid .!gt@ lny !.t idi e4d i! ttqtr of thc 6rPld 

itrdi.dg d!€!a dfnd oAlaic 

65

Tlbl. q Infred rpst al b6nd $ignn nls fot 8-nydoxlquinaldine, cy3tcin. ed 

cyd.in.-8-hydoxyquinaldio.@plex. 

Sr. &hydrcry{uJrrldh. 

.1300 

2 ll.t0 

a2a 

2350 

5 1780 

r7t0 

1700 

E 1620 

9 1600 

l0 1570 

ll l5l0 

l2 1460 

ll l42t 

l4 1400 

t5 l160 

l6 tt20 

l7 t250 

IE It90 

l9 I140 

20 lll0 

2l 1050 

22 950 

2l 910 

900 

25 870 

26 840 

27 8{Xt 

2a 750 

730 

l0 700 

3l 5t0 

J2 510 

(s) - 'nons, (u) = -edin , (-) = idh O) = brcan a"d (') = No baha 

6a

T.th l0 hdisr€d th.6dpr6rivc nudy ofint Fd sp.ctal bed $riSnidt of 

!.iirc, E-Htdbxtqlinaldh€ ard sinc -8-HydrexyquiEldine mpld, A bmd.t 3740 

6' wc .tr.tcd due to @lplqrid of -N}|, 8ro!p of mim &id (sim). It w 

ob.iv.d dn ! bi!.d bord B l'..ar .I 33O or in th. +d[r of dgdl, b..m6 

diepodrd inrbcstc.n of @oplq dr& to @Dld.lin, Beds t 1720,1701,, 1650 ad 

1620 m' *w vi{Izd sug ed ddiun c.p.dnery i! .!. r.dr of.oddcr 94 

Nt llwlt i. Eg.r. s w.ll .! in sii. ,p.ctr, $4 w be& indid. lh. 

@nplcxdion, ComFEdrc shdy of ipel!. of 6irc @i4 @gst sd is Bpeaiv. 

@mpl.,r, indi..&i lhe pEme of lqin+&hydroxtquinaldi!. @n!'Lx wid! d.n d.finn 

61

.th 10, hnlr.d s!€t"lb€d Nignn.nli fd 8-Hydtuyquinaldhe, S.ri* &d si..- 

8-hydoryquin.ldinc onplex. 

Si &hydrotyqgli.ldln. 

3740 

2 J.tm 

l 1080 

2940 

5 2120 

6 2600 

2t4o 

3 tt20 

9 2t20 

l0 1720 

ll 1700 

t2 1650 

t3 1620 

1600 

l5 t515 

l6 t560 

l1 l5l0 

IE 1500 

l9 1,160 

20 l4l5 

2l IJ60 

22 l3l0 

23 t280 

24 t240 

l7 400 

26 55 

27 ll15 

28 1020 

29 920 

30 900 

3l E5o 

32 770 

ll 750 

t4 710 

l5 650 

l6 550 

rqr: (3) = stdg, (n) = n.dim , (v) = ec!& O) - b@d dd (') - No b€td 

68

ibh U indi€i.rl th. Erutt! of i.tutld !p.{dil b{d stignndt of 6Plnic eid, 

8{yd&xyquimldir. aid spartic sid-E-hyduyquli.ldin. @mpLx. A bbd .t 33OO m l 

due oH gdp of Bg.rt *s .ppaild in !pc.l!. of E.hlddoyquilrldie wa nol 

vi$.lizcd ii e6L! ofconpLx, it is indlc.t d tld, d C-E Position whft hytoxyl €roup 

M .itacn 4 dle cobplstion tl*6 pl4. Two !.* budr w@ |pFaFd .t 3150 dd 

3o5o d' dF to lomrdon of! w hond b.t!r@ r..i6t tnd dilo gDup, whic[ ir 

$pportins th. fmalid of . trc* -NH- bdd h.t$M 4tnirc &id dd d$t'l @ 

mplddim A w Dcd |9Fr.d in $. 3p..crD of @Ddq I | 220 d ' dE to s. 

@ .1n8. in d. 3ostuF of Fg6t ed q.dc &id. C@F!dE lardy of +€.t of 

di@ &iG sg!.1od n! E D..dE codDl.r' indiccd thc Fgag 

trdolnuidldia Mda widt lhdr d.frn! dDo.ltid. 

59 

of Gpndc sd+

.bk1l. tntdcd sp@t6t bard Nirnncn$ for 8-Hldsrrllimldirc, Aspsic e'd ard 

Aspltlic.cid.8-hydrcxyquimldin conphx 

Si &hydreryDqyilrldi!. 

3300 

2 3150 

l 1050 

2980 

5 2120 

6 2@ 

2321) 

8 2120 

1620 

l0 r575 

ll 1500 

l2 l{60 

tl t4l5 

1390 

l5 I t50 

l6 l3l5 

t7 1280 

t8 t2@ 

l9 l22A 

20 ll90 

2l I170 

22 l160 

t070 

24 l0l0 

25 950 

26 900 

27 870 

830 

29 820 

.10 7E0 

3I 

32 730 

33 ?t0 

6E0 

@ 

l6 580 

37 540 

Keys: G) = rttons. (n) = m.d um, (w) = vsk, O) = b'oad dd ( - )=No bdid 

70

T.U. 12 indics.d th. nsultt obt incd by bt i.d ry..tlsopy of glu&nic @id, 

&htdnxyquin ldim ed Cht nh &id{t}'dDxtquinddinc 6nplq, ft B o6s.d 

|[r, r tod .t 3300 d'' irdd in ry.d. of agat d& to u't ri@ of ta 4tl gNp 

of &hy.lroxyquinridine w rct vhu.lized in .!4t . of @nplq dw to @npLutid. A 

B t!!d ws.ppald d 3O8O 6'r i" *pla!p..n dG to br.g. of-NH-SDot witt 

mgcnr. A iw bdd .pp€r6

Trbl. lt" hfnrcd spd..l tqd \sigMors fd &hydexyquiMldinc, glut mic &id 4d 

sh.mic eid+hydsxyquh.ldi.. mpl* 

Si 

I ll00 

2 3080 

3 2980 

2520 

5 2Jt0 

2120 

1 1860 

8 1600 

9 1575 

l0 l560 

t500 

t2 t460 

B 1405 

|]60 

l5 ll l0 

l6 l29o 

l? t26o 

t8 t220 

l9 1160 

20 1080 

2l ld20 

22 980 

940 

24 870 

25 850 

830 

27 110 

28 ?50 

29 730 

30 650 

It 550 

400 

(s) - rnon& (n) = h.au". (e) =aak 6) = bt&t a,d (')'No bcid 

12

Nuclar Mas.ttc Re3oD.ncc Sp..trorcopic (NMR) siudy 

NMR sady E ffi.d o'n for tlE mirc eids @mpl.x6 of &hydreiyquimldi@. 

Cyslein conplex shoed sDe chembal siitu in dos net csion rd $ne w.rc also 

nor.d in up 6eld duc to prorc a$ch.d b 6..liDhadc c.6o chth dd sfth mmatc 

nngs E+atively. s shoM in TrbL 13- Son. pqk5 w.E obw.d in th. Mg. of8.l2 

pprn to 6,99 ppn wift ditrq.it inrcgnl sl@i drc to @na!c polo.s of @Bplex. While 

. pet ar 4,42 ppn silh inr.gil int $ity of2.l2 B dE b ln. pdloD diGdv alarEd 

with nitroS€n Elon linln |(lwa $. nolcule of r!8.r 8-hvdoxvquinaldin., The 

chdiol shift rpp€rd .t 5,43 pFn uilh intcrnl inlasiq of2.0l d!. to thiol CSH-) 

Ptllon ofcys.in.. A psk ob@.d tl 3.lO Pfln with in|gdl inl.Nnv of 4,32, show.d th. 

an@hn nt of dethylae polots. Wtih .hdi4l snitu appq..d ot 2 ?0 ad 2 69 Ppm 

wih idcgral irhsity of5.2l ed 6,10 Esleiirclt duc r. maivl grcuP protds of3-

Trbl. 13. Nucl6 n.grElic EsMe sp.!t..i b{d ssi8M€nt! for Cyst in€ -8_ 

Hlddyquin.ldic @mplq. 

8,12 4.31 

2 117 4_22 

3 7.42 4.ll 

7.15 4_l I 

2 6.99 4.12 

Remrld / Ch.Diol rhltu 

chdi@l shitu or 8-Hydroxlquin ldit. md.tiding 

(2"5H) 

3 442 2.t2 Du. ro -NH. ptun of @pld (l Hl. 

.1.t0 4_32 D!. to ethylca. (cHr) ptolotr or@npld (2D 

5 1.10 6.21 

2.69 6-10 

PbtoB of n lhyl grcup (CH, oI8- 

ProloB of 2d mernyl lroup (Clit of 8- 

5.4J 2.01 Du.to sH- poton or cYst in (1t0 

R6uls oI th. trcton nule Mgn.tic reem€ of erinc'8'hvdrexvqd"ldine 

G suntuizld in r.bb ll. Chdi

T.bL ld Nlcld masrdic l!$@e spd:l bdd siSDndb for erie lhydbxyquinddinc 

@nplq. 

8.12 

2 1.92 4,ll 

l 1.69 2.0 

4.12 

5 152 4.05 

?.10 2.02 

7 rt.l0 2,0 

Chdictl sbin5 of 8-Hydoxlquiitdin. @n !c ring 

(2x5n). 

chmicd dlin of-NH- Drotd (110 

3.?8 2.05 6-" ro cs- pro* of o.ptax tt H). 

2,65 6,0 

'Forons 

ot ncrtryl grup fcH, of &Hvdmxvquinaldin€ 

Gro. 

l0 2.62 6.10 iffisf7 m"d'yl so.p (crt,) .f 8- 

Hvdrcxyquin.ldift (3}{)ll 

259 ,1,10 G oifiitar tcttzl poton of sirc tztt) 

l2 1.55 6.20 -fi;iditrin of -oH. soup of erine (l H) 

Vhil€ a Fk sl 4 lO P!|tr wih i cgdlinBhv of 2'0 sa ob*fl'd due to pbton 

atb.hed ro nitrog.n tum of mino sd! A Pat at 3 ?8 pps wirh 2 05 int'gral intensiiv 

shos th. proton !tl..h.d b alithalb @bon of @nPl*' Wtih t€a}l with inegr'l 

inr.nsitt of 6.0 ed 6.lO Bpetirctv, tl 2.65 !t

8,21,8.0, 7-?8, t.?5 ed 7,O ppm wi$ int eEl int$sity of4.0,410,4,05,4.11 ad 405 

rsldtisly du. io protds diddy linlcd ro mn tic rines- $/hilc ! Flt 6 4.7 ppm with 

inr.gnl inrhsity of 2-O rypa.n 

nirrog€n aion of the anplei, Chmiel shift 6t 4 

due to $e ch@ical ditu of proton di@dv .n2.n d with 

,10 ppn wilh inlegal intcnsitv of 2.05 is 

du. ro po(m lnlohed with diPnstic wbon. A Fd( * 2.90 PPm wd obsded Pilh 

inr.gd int rjry of 4.45, adv4:tcs rh. arllch@r'r of nahvlde Polo' anod'd p€r 

sE ob*d.d.r 4.0 ppfr si$ inlegnl intasity of 2 0 de b . Poron .ll!.hed to fre 

hydoxyl group of 6p6rtic eid, 

Trbk 15, Nucle ntg!.ric ltsde 3petd b.!d 6i9n@ls for aptnic &id-8' 

htdFxtqui.aldin. @hpld. 

5 

8.2r 4.0 

E.0 

4.05 

7.75 4.1I 

4.05 

Ch.nical shitu of 8-Hydrcxvqui.aldi* polons 

(2x5r0- 

2.0 ch.ni@-i-shi ft of -NH- poton t H) 

' 

2.05 Dc b {H' probn of cmPtq { I tD 

3 2.10 pror.i difi6-OH grcuP of 6p.nic eid ( lH) 

9 2.10 6.10 Protons ofEethyl guP (CHt ol8- 

tlvdDrrcuinaldin. (3H). 

l0 ).28 6.l5 I;6;;i-ndhrl eoup (cHt of 6- 

Hydrcxyquimldin. (31t. 

ll 2.90 4.45 flb ndhrld {cH2) Foton orastanic &id (2}0 

f.hk 16 indiclr.d ihc chmiol 3hitu of protd NMR of slot'nic eid-8' 

hydroxyqri.aldine conpl.x ln @npl.x sp.clta.h.nical shii:s v'E obseped * 3 03' 

?,90, 7.20 dd 7.I4 pPh with if,tcelll iniensilv of 4.0' 8 10. 4.1 I ed 4 05 rcspEtivtlv du'

o Plotms di@{y linLd wnh entdc tuchus. A Fak .t 4.0 ppm I .pF4d in 

onplex spcda wifi i .8ral int.!si9 of 2-0 dE io pdon ttl4h.d wilh mino grcup. 

wnib ch.nial shift al l,O ppn with incgtl inteosity of2.05 due to Prcion ar&h.d wnh 

teniary orbon. a shin d 2.87 pPtn Pnh integ.al inl€nsitv of 2 0 is dlc b a prcron afiached 

b fie hydDxyl gtup of glMic &id- Whil. lhc ch@icrl shitu .t 2.?2 sd 2.7 pPtr 

*ith 4.lO ed 4.05 6p..livcly de to h.lhyl grcut potoN !d!.h.d wih dnatic o85 

T.bl€ i6, NEla naEr.ir. rcs'Ee speftl bmd dsignmots for Glutlnic acid_8- 

Hydoxyquinaldin. @nthx 

I 8.01 4.00 

2 

l 

790 

1.20 

8.t0 

4.|l 

1.t4 4.05 

5 4.00 2.01 

l_00 2.05 

Chmic.l shitu of E-Hldoryquiddie pblons 

(2x5H). 

ahml;l $t6;i-NH- edon (lI{} 

Dk b{H- poton or @Pl.x (rHr' 

2.81 l;b. fr;:oH- g..,p of slumic 

"f-"f 

4id i I tl 

2.12 4.t0 6t tu;i;6yt s".p{cHJ or &Hvd$tvquidtdi,e 

2.10 4_05 

GH), 

E6; of 

(cHr) of 8' 

l0 

ll 

2.98 

2.a1 

4.37 

Hydroxycuimldine(3H). 

ffi;-."tlybre (cH2) poio$ of glltanic &id (2H) 

5;6F ..tl'yl* (cH2) pbbs of glubt eid 

(2H). 

-F€drytsb.P 

M.i. SpetmE tric Study ot Antro ftlds - &hydnryqrimldin' 

Syntn6ianl dino &ids @dPl.x6 of 2-n'rtvl_8-hvdroxvquinolinc (8_ 

tydrortquina8ii.), wc nudi.d bv ns sPelMdry b 6nfin lheir shcrucs Th' 

noldle ion D..ls in .ll tlE cls mfmed lhe fodarjon oftdg'i F 

- 

d@ts nott ovd

thc ovedl e4mdiElio. p.um of th. edpl.x.s v6 in aetdd@ $ilh poposd 

nolduld srtucrc 6 is didmt fion tn n sp@tra Ok r3-rD. Ir|c n6r saikinc rsturc 

oI all thc @trrptd.s w6 rrFir sLbility, B indi..red by th. tLds aiu.dan@ Tn. be 

p€lt in all ce ws lh. sd i.e. | 58, for 2-m.rhyl8-htdFxtllinolhc noi.lt, d.pnv.d 

of hy&oxyl Foion which indi6r6 $. binding Point b.tei thc nrc agoB Th. 

mldute {eigllt of nol4lt id @tfimed rh. @iddsdm follo*.d bv fodarion of 

pr.drcts Th€ orhd pronin.nt Flk includ. (Chti.ll = m/4 r42) dd (c{rlrNor = n'lui 

I ?4) in all th. sy.tn€siz.d @nPlex* s shos b.low in Ft& lll?. 

2-M.thyl-8-hydroxyqulloline- s€rtne CoDplcr 

Th. Gultl ol nN sMy fd 2-n.tlvl'&nvdrcxtquimlitu (8'bvdmxxuinaldiro 

@mplex of sin n.* bcn lhom in Fig, 13 (.' b). The noldld ion pel qd 

obtlindl *ilh high abudde, i-e 2t % whicb ws indic.tor for erbilrlv of lh' @npoud 

Ih be F3lg d ndlion d above, wG of 8+vdloxvquinaldine moi'tv in all or th' 

@nplds. olhd Fonitfll pars w@ mequene of botn 8'hvdtoxvquimldi" ed 

mino &id 6 *cll d of coGpondins prcd@l li.gnenLtion, '-g" (clorLN = ivzi 142)' 

(crc&No1= nyz; l?4) (CDEltN:or = rtzj 233), dd (crHn N3o' = nVzi 391) with 

abundsoc {vo), 70, 53, 57 dd 25 icap4tivelv 

78

toLcd.? ron Fr..rq ao3 I 2t t( 

Ft ll* Mrr8 A.d@ of 2d..b!,1-E+rdnyquimliF - giE cmDLi 

4... P..tq lSa r t(|0 tl 

It 13.; ProF..d Erso.dioo p.!!rn fa 2-o.ry-Cn$mEq'rimli& - silr 

79 

l7a!&|r 

I

2-Mclhyl+hydroxyquidolir. -.3p.!tic rca CorpLr 

Tt 8!..1ic &id cdnpbl or 8-ildoxyquialdiE thoq&d @lcsi.r io Ft {i{! 

la % ahDdlr. l4l .rd . s!bl. tugreit (Cott Nq - n/a 174) ofFodEr wirl {7 yd 

abud8e OIt r& dd lab). Asrortic &id (CagrNO.- da 130) im w.s ds oh.in.d 

wilh sood rhlrd.e (26 %I 

Fk,la.r Pr.po!.d tr3@did pt@ fd 2-rldDl.S,dydoxyquimllc q.!ic &id c.opla 

rE, la5; [,B lp6fD of2-Ecityt+bydilxyquidlc rrp.rtc r'd cor4ld 

EO

2-M.tty!&hydmryqrtrolin - glubDi .cA CorpLr 

Th. ml@ld ioi Flt for glul.tnic rcid cmpLx of &I|l/doxyquiilldnE w 

obr.in d with 9.0 '/o .bundlnG ad &!snc (C,0n!Nq = n/4 174) Mrh 5l ./' 

ab'Dd're (rb. r5r .d l5b). 

/r/ 

\"\ 

Ft 15+ PropGd figtrhtnior t len for 2-E rhyl&ttdroxtluiFli* - gt|lsic {td 

Im 

I 

Fig l5b. Me sp6tu ol2-E.tiyl-&hy

2.Mcahyt+tydmryqlirolir. -cF!.lnc CoDphr 

Moldi! iod lql of cyr.iE dhpLx s oa(rid virt l5 % rhurc (FE! 

16. .trd l6b), *t ch B lBr rho rhlt of si* .mpld Th. lcy ft..gndtrs i.c, (ch&N 

= rta 142), (cbtl.No, - da 174), (cnHD&Og = da 249! .!d (C'H:iN'ors - dz: 

40t) ',@ oh.iftd with rburdrtrc (yo) 85 lt 44 %, 43 r/o ad 19'l' Bpetiv.b. (fl& 

floh.d.r kr P-r, arr - ra !| 

D!, l6.i Pnfc.d firgm.dio Fnd fa 2rdlr-8-ltydbxrgttitbtia cys.iF 

fi9. r6h Ms 3Fcru of 2-ndlryl{.tydDxyqubolift - crn ire c@dd 

82 

t

Rotir c.s 

L 

3. 

5. 

6. 

G}l rad, T. Iq6.l, .nd zJt Z.idi J Ci.d Jo. P4t" 2, 144, (1980) 

G rr Kd, T. hb.l ltd z n Z.ili J Ch.e $. ?e,\$,!9|or. 

G. H. Kei , T. O. K.:i od s. A. An, ?,r4 Cr4r, { !0, (198t 

D. ir. On6 Dd lv. Jo4Frd\,l,ul Cr.t, 6', 1580, 0990) 

M. D O.t6, & a, CooF, dd J, w. Jdrlrldl, -ld. Ci.t , 6r, I57?, (190) 

lv! Hi!.ba! s. l(4c, Y. Kyoto srd H. s.tM, r!4. Cb"o.. .Ltt 5l' 3638, 

091) 

?. l{ sd , dd & Notd$rtrx lttdta., 111.85,(192). 

E. rL Iiala S. Fujii S onnli ltd M. ltLl$tldtiltr,rd' rttl RaJaP"[992). 

9. tI E liz.n ed T. Odt,I Hrtflttu,,@ r.,t .Jq. l3,rr'(19'2). 

ro. lt riaf.. !|d T. Y.jiEa ri.l Pt@ attllJaP,16't06,11993t. 

I l. K. Nobuto6bi, O. Yd

15- O.B.trin, lbrlrd. rEL3126t0994) 

f6. l.ftrdcti rdt Mh,., rtu6ecs6.,rGltt,(t9r. 

l?. T.Llorhi rd't Mr! cltuttdogaiia, 10'162, ll95t. 

f8. T. T.lqEti !d T,ll,fw., cfuotttotogt , 11,152,(1995r. 

19. r. r|iu, J- U. Lfihqi.- rd F.Btt,'+,ngJ. Ct'wtust.t n9 O) l 19' 0996). 

2t, T. G Krri, M, l( h, s, w. sbd, dd o, H. (!i,l Jlrr4 [l,'t' 29' | 0a' o97). 

2t. Yuqirlg Li Kdqil|g Liq liig Li!, Iwi. ?68, Xuli Fdg' md Yu f$9, 

l@srdt, 22 06; 7016, (2006) 

ta

Chapter - 4

Amitro Acids Derivrtives of Cholcsterol 

Chnp*r - 4 

Ani.o acids have bd itvolved in sttih6it of exti.mely ltSe nlhbq of 

@hpoDd! ein o.sdic .nd ino4aic noi.ri6, horh in-virro 'd ir'viYo [l'1. Thd hG 

b..n €xt nri v. Iite .tue av.i lsble on vdious d.iiv!1iv.s of m ino aids, like Sch i,f b6es. 

bid€s' csrc6 !.c, with diffdtu biologi@l MPood.. As fr s lheir inleddion silh 

choLsLol i.-litrc nd in-vivo is @nMsd, limiLd wik is did.nced bv lit nrr a 

conped with cihd smpolnds. 

Exdpld of inL@don b@H miro &ids sd cholcsLbl in-viEo (AbujaDab 

ed AbdulEhin, 2004) lrl s well s in-vivo (Yu Fsg €t al,2006) Itl @ avtiltble in 

ln€hturc. Aqininc is d Mino &id which swes mDv h.ln'tiddlv o.tions. Dala 

$Bg.*s thrr dgi.in (Ars) n.y si3b 6nol cnol*r@l ld.ls (Kohb a tl' 198?) [31 

Mo@vo, ArB app.G 1o a16 6 g@d bl@d lhidd bv Flu.ing pl.tcl.t aggEgltioi in 

hFdhol.$colcnic huid. (wolf d !t, 1997) lrl 

blood Gels lhftulh mriorid.nl lcliviti€ L-Arg it al$ a Pelns 

lr nav also @nsdc ihe flexibilitv of 

of niEic oxide s 

odogdow ms.nger nolanl. conemed with . vddv oi endoth.lium-medidted 

physiologicd .fi&$ (BodeBogs d al, l9%) E- NiErc oxid. is a ga mlaulc which 

t*ftt6 c.lh ed Egulal6 lheir fuclio.s, od .le helps ro dhl blood trcs@. 

wnicn lhc body udlias 10 k..P blood v6sel3 apedcd, auowing the hed 10 3.1oodgh 

orygd (h@t .t .1, t95) l5l. Acul€ dd chsnic ldninisiBrid of L'At8 uG @a!dt 

85

!o iipov. ehdoth.lial tuftdd in min.l nod.ls for h}lerchol6leol€dia ed 

rn@l.Dsis (PdJtrd cr .1, l9E3) ltl. 

Amino &ids d.iivltiv6 ofcnol6l.ol hsv. Emdy bccn 3rrth.lized hd emplov.d 

s low nol-uld *idr desic B.ldds 0Jr.{OGs) (et al,) lrl. Hd w. Glqt $. timild 

kind of Miho eids dsivatives of.holestqol PcAared by s verv @lomiol dd tine 

eving natodolog dw.lop.d in ou labqddics. 

Elp.rimert l 

Sdmts wc ddcd bef@ u$ od *d srocd da nol€ula si.vd dd !.&r 

nitog.n, lH NMR splctra s.F Mo.ded al 100 K on . Boka 300 FT sPdtbnct !, bv 

usirg SM.. 6 nnm.l crd.rd. hn@d V€L w obt in d with . Ni@l€t t?00 f-rlR 

sr*ttuDhoton ter in the @gc 4o0o-400 cmr. Elnolll &dvs.s (c, H, N) wft 

Frfomd by uing a Flssh Mod. EA ll12 s.lyd. Th. flmll$.@ malls w6 

6i.n o by Perkin Elm4 Ls-4t sp.ctonuobnerer sd lhdtul d.lysis rc don. bv 

Shinrduu DT-30 B th.m.l dalya. 

ln qpdinot l Fc$ ||l gl6sd us.d s@ of tyex od PIFE, Thcv w 

Mhed with Niltic &id &d Cnodic &id hixtuE, follow.d by dinill.d dd d.ionized 

wo&r 6p@liEly. Chcbiel sd @cqls we of dalt'liczl gdde obt3incd fob 

MERCK sd FtUv'A .henicak wd us.d in arl d.lysis Deio.iz.d wl€r wds us.d 

dring th. *nolc.ilcrisdr.l mr|. Anito sids smpt. obrrin€d lion BDH chcm'c.ls 

86

Geftnl Synatealc Proedure for AmiDo .ci& Ihrtv.riv6 olcholestcrol 

0 I M stock elutions of all uioo eids uen wd. pGpded in aqu@u n'dia, 

e,t.@, 0.1 M chol6l@l ehio B pE n d in aerd. 25 nl of @h of 0.1 M 

dino &ids studons NcE taLn it IOO hl spe.te flasls folloqed bv b eq!.I volum. of 

O.l M choLdol elulion. Thc [.*s ww lho Placcd in th. eniebr ed tared !t lo@ 

tmpc6$r. fd l5 Minut s. WhiL oysr.ls ofpoduct wd obLined with vield noE lhs 

stP/. in all @i elvsts wN m.d. lo d.porde in !lt&sni. b.lh at mbiat 

&mp.6r@. Th. &rivltiws obui.cd w. uth€d lti€ wiri 0l hM HCI ad N.OH 

sd fin.lly sirh lltra puc wat€r. dri.d sd sloftd .l 25'C in ddiccator' ior 

Syltbe.i!of Chol.s.eml.lr.lmt (AbDileDcriv.tiveof Choldterel) 

A 25 nl solltio! of Boc-aldine (4,?5 x lO' g o lM) in !d wG 6dded lo 25 ml 

choLsLol slution (9.65 x lor g, O IM) in . IOO ml f,lsk This d6t thd w pla'd in 

eniclror Md r.!td al mh t mpcr.tE fd 15 hinulB bv utteund .nog}. Mritc 

crysuh of pFducts wd€ obbin d witn 8l% yi.ld. Solvdls ue madc to 4apoEl i' 

ulr@nic bdh .1 obi6i MF!i)E. Ttc d.dvltit obEi..d {a *6h.d lllrie with 0 l 

nM HCI dd NaOH ed nnally wnn uk. Purc 

il6icc{o., for ch@t rizlid. 

w.ter, dtied md $oted al 25'C i. 

Ehnerrrr Arrbir; cakd (%) for csftrNo, (474.00): c ?8?2, E 1123, N 1.06; 

food: C ?9.lZg 10,68,N2.76. 

FI-IR (cd')t 3a?5 NH), 29a5, 2860 (cE) l7l9 (-c-o), 1246 (_c-o)

Strlhgn ofchok t.rel crd.i..lc 

Abolr 25 nl, Eplicst slddord ofB@.cyst ine(3.05x l0r&0l M)*eet kei in 

*p.nr. flrsk, *nicn lF rhd lddcd to 25 ml of cbol6r@l $l'nion (9-65 r lO'9 O.l 

1"0 in a 100 ml Aask follN.d by lhe mc p@.d@ e ncltion d .bove, lhe producr 

ELbdt l A!.rye4 @lcd (%) ftr crHJ,Nqs (4re.0o): c ?3.57, s 10.5q N 2.E5. S 

6.55; fomd: C ?2,02, g 11.10,N2.97,S5.q4. 

Fr-rR (..r): 3418 (NF), 294 t, 2867 (CS) 1744 {-C{), 124? (-C-O). 

Str6.b ofciokrt ml..Ai n.L 

A 25 ml oq!@us elutio ol Boc{ginii (6,85 x l0r g, O.l lO M added to 25 ml 

cno|6lhl elution (9.55 x l0rg, O.l NO in a IOO nl ns{ lh. Ptoduct yi.ld w6 80 % 

Ele6..hl A!.lyrili elcd (%) fd c€Hd,4or (5.2 00): c 73.@, E 10,77, N 10-32; rouhd: 

C ?2,66, I19.9,r, N 10.54. 

FT-IR (cD ): 3a36, 34?5 (NE), 2938. 2862 (CE) 1743 (.GO), 1252 {-c-o) 

Syr.l6b of CloL&ml sidr. 

A 25 nl {alc. s{usus solulio. of Bcsc.ine (5 15 x lOr g,o.lM) m tdded to 

25 ml chol6teol (9.65 x lO ig, O.I M) slution in ! 100 nl fl.slq $e product }leld ws 82 

Ebb. rl Amlyrbi €lcd (%) for ciH3,No! (73 m): c ?6.06, E I0 85, N 2 96; found: C 

?5.6?, E ll.O2,N 1.01. 

FI-IR (cr ): 3439 (IE), 2937, 23tl (cs) l?45 (.c=O), 125? (-c'o). 

8E

Syrrtgh olcbol€t rJl r.lb@!i!.i. 

Ar lqucc $lurion of Be-ncrhioirc (625 r lO' & 

O IM) ss.ddcd to 25 ml 

cbol*Lrcl (9,65 tr 10i8, O.I M) solltion in a 100 ml fllsk lhe p'oduct vicld *a 8l 5 % 

ELo.rr.l adFb; cdcd (%) fd clH&No€ (517.00): c 74.21 E 10.? I, N 2 r0' S 6 19; 

found: C 74.22, g 9.87, N 3.04, S 6,91, 

FT-IR (cD )r 1455 (NE), 2941, 2865 (CE) I74l CC=o), 1256 tC'O)- 

SyrrL6i' ot Chok r.ryl v.lb.r€ 

An 25 nl aquous elutio ofBoc-v.lin (5 45 x l0r& o.lM)usadd.dto25 nl 

chol.srftl {9-65 r lcre, o.l lvo etnion in t 100 mt llsts lhc pFdud vi.ld vB E2 % 

ELn.ltd arrb{b; calcd (%) lor c,HsNq (.sr'00)r c 79.12, g I I 4l, N 2 88i fdud: c 

80.32, B t 0.78, N 2,64. 

FTrR &oi): 34.44 (Ns), 2942, 2855 (C{) 1740 (-C-o)' 1256 ('c'o) 

S}llhBir ol Caokd.ryl l€tci!.r. 

A 25 nl aqu@6 elulion of Ba-ldcitu (5 80 x lO | & 0 lM) s add'd lo 25 ml 

chol€stercl (9.65 x lO re, O.I lO sluion in a I OO nl fl6k, th. product vicld w$ 82 %' 

cholBr.ryl lacidt.i qhd (v") for caHdrq (19t 0o): c 79 30, E I I 49' N 2 80r found: 

c 79.98, H 11,27,N2.62, 

FT"rR (chr): 3446 (Ng), 2940, 2864 (CIr) 1742 (4-O)' 1256 (-C-O) 

89

R€sults and Discursio! 

Fluor.lconc.Studl.6olAntuoAcld!Dcriv.dverof Cboldtercl 

Tte di.o &i& sldlld fo. tEet lrudy ec nm nsre..t, whiL cnobst .ol 

dbq.d mnin l flu{)|!!.dg &dvity. B'n ftn &dvdiB h& 3ignifi6t lettede 

.ltivig .r dirad .rcitaris 0a) ud mi$ir (rd *N.lcngns. Th. Hlts @ 

ChoL.tcml 

Cholest bl show.d a vcry wc.k Fat .t e .rcibtion wvd.tgth of 341 m dd 

dtsion qsl.ngn 365 d sith 9,6 inrd3ity (It r). ni! flu@sltd activnv of 

choLddl d, b. arr.ihidl to . dnubl. 

rb.r nbffi sp.cltln of choLiteret b@d Fent i! cvololEte ri.s or tlt 

90

Aolm AcXr D.dvrtiv.. ofchol.st rol 

ALtri!. i! @[DG@.!im ei4 it stos 6 tlE€sd.dirity.lc, bqt 

sn@ ft L 4rtvnird sith cholc.rdol,ln. c[.k*ry' .lEidlr 3to*r 6. frdt3 .icc 

&rivily dc&it lidqElogtb (r.Jof225 @ od @i!iouEldsdr(ltu)3J0tu 

(Fi4) lnd wi6 20 % inhsity, dlhasb tb. ts!..ce in 6!'ily is loe, ht iiehs tlu 

Fi& I nuoirsc.nG spel'un ofcholcateryt ddtulc- 

chotlderyt sinn sho$tdllE flur*6* !tt&337 m dd l&452 m, TIE 

tlbrq.dc. i.tatlit of gtriE d6iE!iv. it Egld lho olhd siD..'& i . E5 %OE 

ro l* Fn ofd!.|f,d d hy&qyl gtue of.aitc, fE; ! 

9I

na,3, nr* tda.addtl si- 

Ctd*rt rdidi* E d b bl! lirhidt, iG.7t r d U22t d 

dli3.or,ttbrrnrrl|. ridlr'a,a 

n

Clol.ddyl sgi.id. B ob66ed b h.E 75 % nlg!s..@ idaaity .l l& 343 

nn rrd 1b453 rd. s gvar ir r.bb I .nd rt; 5. 

rts 5. FL|ec .!.cdtr orctoLcatl .rgur.L 

Cb6tr'yl ctttcird! B t Fldtcl witt t 7t % flFr!3dE r! Poc' 

nn.td r&'35a M €8O 

E&6 ttElM lp.slD orchokra, ordrd. 

9! 

n l& 2'

Tb. *ilrlid .nd .nisiod wlcrgths foi Cnol..ldyl v.liidc M! 324 tr .!d 

6a3 m 6p61iE!, Fldaingd irn siy of 5l % 

Fig. 6, n@ic. ipocltu of Ch.i.$ayl di6L 

IrbL:1 Flls€s.cre Studrd ofchol.sterol !d i$ &riwtills wilh Abim Acids 

s.No 

t.9 .l4l i65 09 00 

2l 225 150 .20.00 

3.2 .]17 452 85.00 

4.3 225 3r() 75.00 

54 3,t.] 45.] m.m 

6.5 l.!€hl 3rl 4t7 59.m 

7.6 230 65 ?3.00 

E.a 324 643 5l.m 

Not : Asim eids shos D nulscdc etivilv .l tb6. mrcl@gtlE

Thern'rl Amblis IIGA / DTA studi€t 

Ibe TCA (Tlemog.viftenic ealysis)/ DTA (Dif&Mtid Tnmal Analvsis) s$dies 

scre csi€d oul oi the 3ix mino &ids, i . alanine, ndnionine, &ginin'' valine' cvsleine od 

serine md $.n d.rilativ.s ofchol.slerol Thedoerms of Mino a'ids' chol'sreol $d rheir 

espdtivo d.nvaiv.s {.rc msiplltLd od desrib.d in $' following pdoSrapbs 

Chol.steryt rlatrimte 

Themal .vetts of sl$ir.. .holdqol ed its d'iivati!' have bs' sdEdiz'd in 

T.bl. 2. chol€*.rcIwhich t the onlv Elgd for all detiveriB' ils th.mog@ sho*3lhsl 

whoh *eight (w L = 386 (n.w) = I OO9/o) ws lost in one st'p tl ' leftPedue re8' of 2s0_ 

130 'C, md e .ndoih.dic DTA (Diftd'ni.l ft@al Andvsis) Pe'k qs obeded *ith 

tenp.r.tltc dgc 240-280 oC po$iblv for volalilialion' Aldin' de t6 a single weighl 

los steg oGponding 10 tcnp.itlu€ tug',240-320 oC Moftov'i it also sbo*ed one 

odolh.mic DTA p.al< lith t'mPd'@ dg' 220_280 'c' most probablv for 

de@np6irio.. The cholst ryl alsi@l' showed a diffcent paddn of th'mal 'v€'h w'th 

leignt bs of 64 o/. ii . singl. sl@ * Ld!@l@ tug'' 150190'c Dossiblv for C FH8NOI 

ftlgnal of derivltive (W-L. lo3 = 64 %) Th' DTA lh'dogrm of detiladve 

'ridcnced 

sinel. endolhmic p€st wih t mPcratue dge lO+140 oC wnich m'v b' a oonsequene of 

I

T.bl.:2 TGA / DTA Srudi6 ofcho!6lDlddre d.tivdive (Chol6tcrvl tl$intL) 

cht. 

TGA DTA tT.'c F.T.'c IG DTA 

I 

I 

I 

2t0 

240 

240 

220 

lt0 

100 

Cholgteryl Dethionimte 

330 

280 

J20 

280 

190 

l,l0 

100 386 

73 

.t0l 

Melting 

Th. tn fral hcluviN of mcthionN d@g sih cholda'l tnd iis dawtit chol'Gvl 

n thioninrlc is thoM i. T.bL 3. M.lhioirc M shom t' !e *tFl' of il5 wi3ht in ' 

singL *ep widt ! tug. oft mPcotE iion 2lo.c b 3fl 'c An Gndodmic DTA p€k 

6 d$ obwcd for sernioin' in $' tcnPqd@ de' of 23&260 'C 

posibl! fot 

o.lting. Chol.i.ryl hd|i@imrq the pFduct' 'rhibikd t*o wient ls skgcs d 22t280 

"C dd loG37o 'C, pobablv cot6pondins ro c,Hrr (w L- 369 = 

? l %) dd c5Hdots 

(W-L. 148 = 29 v") rspdislv Trc ddolh@ic DTA P'!ts w@ tte f@d *irh 

rmFrdlr Mgd I IOJ4O "C sd 21G250 'C Fsiblv 

96 

for ndrbs ed fintt d@nPcoo

Ttbl. 3. TGA / DTA studid ofcnobsrol-n€Oioni* ddiv.tvc (chohn ryl n.lhioni@c) 

TG DT lr.'c FT..C 

ch!, I 250 

240 

I 

2 

I 

2 

210 

210 

225 

300 

Il0 

2t0 

330 

280 

360 

2@ 

280 

370 

250 

tm 186 

!00 113 

29 

1l 

148 

369 

DTA 

Ef. 

Mclling 

CTHTNO:S 

Thc thtul salFis of sinc aldg *ith dgot dd ils dqivtdw hs ben daictcd 

in dd rlnmoz.d in T.bL a. Th. sinc &riv&e d.lmpos in i*o n"s d tcnpdl@ 

dSrng lion 255 to 3lO 'C fd Crlls (Wt 169 = ?S %) dd s@nd mc ion 3t0 b 550 

'C for Cil.NOr (WL lO4 = 22 v')' Two ddolhmi' DTA P'{t5 w ob$d& 5r 

hFr.1@ @s6, 89_128 'C Flsibtv for vol.ritiatjo dd b'tsd 54G580 'C for n$l 

d.sbpcnion o. de othd ho4 e!in' h6 tl$ shoM I*o wcigh tos s wll s M DTA 

F.{G- B$ 1dnp.6lw MEps weF ditrffir vizi 225'268 "C 268'500 "C fd wishr l(,s 

of C:ll6NO (WL 60 = 5s %) dd COOH (V L a5 = 42 %) Es?ctiv'lv ed DTA Flrs 

pcF obefl.d at Fg.s 265_300 'C (qolhdic) dd 43t5OO "C (ddolhmic) for pcsiblc 

boiling and d@nposhioD rcsPei'*lv

.U.4. rCA / DTA Slvdi.s of Chol.stbl-sdiDe dqivdne (Chol6Grt I sinarc) 

TG DTA n.'c F,r.'c DTA 

chl, I 250 

240 

Sa.chl. 

I 

2 

2 

2 

I 

2 

Chol.3teryl cysteinlt 

225 

263 

265 

4t5 

255 

350 

89 

,180 

t30 

280 

268 

500 

300 

500 

ll0 

550 

123 

100 t86 

58 

42 

78 

22 

60 

)69 

104 

Melting 

Th.m.l .gl3 of cyskin., choLs:r.ml md ils deiurirc hN. b.a Mndiz.d in 

T.6L 5, Cystei.. hs nro rcighr lGs sleps, coftspondiog to tenp€mrurc mgq 220-2?2 oC 

&d 280.610 oC for CTILNS (W.L. 76 - 63 %) ad COOH (W.L.44 = j7 %). MoFovci, it 

ha d$ dDM ore c.dolhhic DTA pe* *irh ldnplbtu tug. 210,270 .C, posibly due 

to dmposhid. It. chol€nayl crs.i@ sno$d . difi.mt paicm of thqnal dor, 

*.ighr los, 19 %, 43 % od 20 % pmbabty for CIHD C,,+t, ad CjH6NqS .r tatrp€atuE 

mg4, llc2!0 "C,26G320.C ed 32O4tO !C. Th. DTA tnmogm *jdac.d nvo 

Pcab. & e.do$enic sith rchpddue i&go 60-80 oC prcbably for meldng sd dorher ohe 

posibly rordedmpo$rion or hp.@E trge of 22c)?O o. 

98

T.t te 5. TGA / DTA StldiB of Chol.slroky$.ine ddivsrive (Chol6t rvl c)stcidlc) 

TG DTA lr.oc rr:c l,LW DT.E. 

chl. 250 

240 

cvn 

Syrchl. 

cbol.lt ryl rrgtrh.tc 

2 

l 

2 

220 

280 

210 

260 

12t 

60 

220 

330 

280 

272 

610 

270 

210 

320 

410 

80 

210 

l0o 186 

6t 

37 

l9 

43 

20 

1t3 

256 

t20 

Exo, 

Melting 

C?tl.NS 

cooH 

crHr 

crri.Nqs 

'IrE $mal b.hatiou of .rginiic along Bith chol*teol sd i$ ddErive, 

cnokst ryl dginin.te is stoM in lrbL 6. Argi.in lon veighl in two stcPs, filst 49 vq ed 

rh.n 5l %. An s*loihmh DT,{ per s de obs.d fd 4giiine cl LmFrstw, 190- 

220 'C possibly for n.liing. chohst ryl egininate, th. ploducl .xnibit d two reiglt lo$ 

n F, n 135-260 'C ed 260-400 "C, prlt6bly @dEqotdine to CTHBN. (lV.L l29 = 24 %) 

dd CrHaq (W,L.413 = ?6 %) Fspetivdy. T*o ddothmic DTA p.ck ssc als f@nd 

widr tcnFiturc tugq lt0-130 oC md 195-230'C posibly for ftlling lnd nn.l 

d@mposnion of thc 6mpoud. 

99

T.bl. 6. TGA / DTA Studies of Chol6lrol{ginin dsisiivc (cholest rvl dgiiinate) 

chl. 

ars. I 

2 

Arg{hl 

rG DTA Ir."c Fr.'c DTA 

I 

2 

250 

240 

150 

2t0 

190 

t35 

2@ 

lm 

195 

330 

280 

2\0 

5?0 

220 

26/J 

130 

230 

100 .tE6 

5l 

24 

76 

86 

8? crH:O 

119 

4t3 

Tte th.mll ealysis of valinc alon8 wilt @g.nt dd its dqivarive ha bcd 

5ummdrz€d in Trbl..7 Thc valin. denvdir. d6mposes in Mo eepr d ledpritoE EginS 

ii.n 2OO to 290 "C for ClHr (WL. I 13 = 23 %) md 5.@d m liod 290 to 175 "C aor 

CTHaNO: (W,L. 172 = 7? %). Tm cndotnmic DTA Flks 96 obed€d.t tenFdrrc 

Mgs, 105-125 'C bd 21G260 'C Fsibly for rcl.dlidid sd 6..1 d@nposilion. On 

th. orhs had, Bli.c hs shou dly o. wi8ht lN pel sd c DTA peL 

T.bl. 7, TGA / D rA Sordi6 of Chol.tul-vrline (Chol6E t I vclin&) 

chl. 

TG DTA lT, "c FI. M.W. DTT. 

I 

I 

I 

2 

250 

u0 

t50 

'l0 

2gJ 

290 

105 

210 

llo 

280 

2t0 

150 

291) 

315 

t25 

2@ 

100 386 

100 l16 

l0o 

lt3 

372

Mrss 3F.trcnclric ttudy ofrmino rcit! - choldt nl derivttivs 

Thc F€potd mino &id5 dair2li!6 of cnobsreol, w.t. studied bv nas 

3D4hn lry to @nfim lhen snuc$c. Tn tulddd ior FsIs 

in all lh. cs .dvocaled 

rle lomalion of k8.1 products. not ovd lh. ovenll fEgm.nlalion plnd of derivatives 

s in E ordoe airh dE pmpo*d mdqle srudtt s L aidat nod then speh (Fig 

7'll) ed Tables (&12). The nost slriking fc6$r. ofd. d.rivaliv6 w.s lheir slabililv, $ 

id,i6!cd by tlE elttivc abud{e it aU of$. sPetr& ThG b& pdt in.ll c.s sG lhe 

sMe i.c. 385. cholcatercl noiety d.prived of hydoxyl ptoto s'tlich indic,rd $. bindi.C 

Doi b.tla th. teo Mgob, is .|onolic grcop of chol.rL6l. Iria mlsld qcie,it or 

holeculd ion oifim.d the cond4elion followd by fodltion ofprcducts 

CholgtreLctNr.b. d.riv.tivc (Chobr€ryl crt iut ) 

Thc Esult oi m6 stidy foi Chold.bl ddivaiiv. ol clsrein. hale ben summei4

T.bL: t Cbolc{.yl cy{GiMre 

120 w Crlt il'l (Cl}l6irqs) 

2t4 57 276 croHrollQs 

275 211 caHrs 

169 86 r20 

J8J lo0 t04 

426 5E 51 

456 t6 J3 cnH$NO! 

aE9 38 0 Clnt'NO$ 

T 

Prepd.d .tnctnE ofcLoh.i.ryl qi.iut 

t02 

I 

cHt 

cH'

F g. 7. Mss sp.doneoic atudica of cholBt ryl cysteinat 

Cto|..rFt{ltli!. ddtu.itu. (C!or.r.ryl .Lliut ) 

Thc mss study of Chole$eryl aldinat sho* ihc aidila patt€d a nenlio.ed 

lbort, t shoM in Fq 8 (Irtb 9). Md*ule id Ft *a obt itt d sftn 30 % .bud.ne, 

agaii showing g@d ndiliiy, 

T.bL: 9 Chd6lryl aleiml. 

51 65 400 

88 t5 

t0? ?E lt0 crHr 

2tt a4 

275 90 132 

369 8t 88 

3Et 100 12 

426 OE 29 

442 

451 t0 

l0l 

I3

426=l,E1( 

M.l Peak=457 3E5'10o% 

PrcF..d 'trD.tuE ofctole$crrl 'r.nM. 

Fb. & Mrs spetoDctric sndica ofcholei.ryl .leiDr. 

l0l 

361-05% 

cHt 

cH" 

27Wr

Cl.ldr.oHcqi@ d.riutiE(Ch.L.ic!yl Lrci..a.) 

Molculd ior oal of laaiE (}|ivdiE B obltid rilh 15 % tbd.hnce 

(Fig 9), $,Ucn @ 16 thd thos of bodr .borc rcdioFd c|s. Bcid6, b&{ pai

I 

iE 9.M6+..rr!n ric sbdi*ofch6l.n ryl l@in!r. 

Clol6ahlr.iliolL. .lqtu.dv. (CloLt ryl D.ilhi.rt ) 

Ttblc 11 od Ft l0 show rh. Ea lpc{tomcfi. 6uhs ftr cholcs.ryl 

n llioriNi.. Thc ndslj io. p€t( ir |l 16 % .lrdlM lq.l dd hoF pqlq ir de m. 

T.bL U, Chdddyl m.rii@iEtc 

13 54 

87 25 410 crH"NOr 

143 48 369 CrHroNO:S 

2t3 5l 3U 

275 88 242 

169 90 t30 

.t85 100 t12 

426 06 9l 

456 26 6l 

517 l6 

t06

4fi=26o4 

426-06% 

Pr.Doied mE!& of ctolcldyl tn.rlidiEtc 

!- 

3E5{0(Ir 

Fi& l(L Mas sp@trorcnt atdie ofchot.srryt D.rhioind. 

to7 

cH. 

CH, 

nFagt

Cnobtnlsir. d.tta.ttE (CroL.o..yl xrt!.t ) 

Th€ sire d*idrirc of chol.s&rol sbwd nole'ir id pet ei& 30 % 

.b'D(br l*l .rd t srblc frls@t (C,rLq = 126) of Fod',t 'ni 65 % $iDrbc. 

sdi* (Clr6NOJ = 104) id sar .ko obr.ircd *i6 niin .hDd.@ (J6ta) 

Grbb 12, F!. ). 

T.d. ra Cbol6rdl sii,le 

lo. Psk %l euity 

73 

104 

2lx 

275 

3t1 

385 

4$ 

473 

32 

43 

56 

52 

93 

90 

100 

65 

30 

l" 

Protord sdEtG ofcboler.ryl sidr. 

433 

400 

w 

2& 

198 

120 

EE 

47 

l7 0 

426=65% !85-lm* 

t08 

@ 

ctto, 

c,rLNo, 

cdrrrNG 

353-90'( 

cHt 

cHt 

275=93%

. I l. Ms +€.tonet b sdi6 of ctoLe.rrl tai t 

r09

. Abujryylb, AbduL.nin, It 6th sci.t*tfu of L twr rq ot@tw.s oJPt@ndr 

i, ttE lnt vt4 Ci@ Fj{Jr,.D.f,(2W4). 

2, L, YMgeg L. kiqhl& L, li!g, P. Jdiq F. Xdi, sd Y. F48., t&gmun, 22 

0o, ?016. (2000. 

3. K. t, Kohls, C. Ki6, dd H, M, Fox,,{dr&p tu.35,5,0987), 

4, A. wolf, c. zdDou, O ltdlwiq,J lrco cardLl.29,a19,lr991). 

5. S,l't BodcBo3c, &H. BolFr, tl, Alft, D, H.itEI, D. Tsittl a Cptzig, K, 

AldDda, dd J. C Frolid, ClEdrli@' rcI, 9!, E5, 096) . 

6. P. f.u!"! B. D.notmb.,ll,iBallGl.',Cun Eq ttta.tuN" 1t(7I1009, O99t 

7. R M, J. Palrnr, D. S. A56tdr !|d s, Mdc.d4l/4rw' 33i1. 664, 0983). 

8. P,s, T$, G. Ti.ilm.id, A, }l Sirgcr, L. LK, rag, nd tP. Cd.c" ltuiMlr 

fl@nb., tul, 1529, (1994r. 

9. P, Clst$t! M. R. ad.D!, A. J, Powc, A, E, Doi.ld, R, Mccr.din J- Robin$|! sN. 

Mccedrn A, Kcel! D.S. Ccl6n.jd, &il J. F. D.tfi.ld. J Cti, Lwst.,91,1949, 

0996). 

10, R M, J. Pqlmq, D, S, tuhton, sd S, Moncrd4 xata,, 333, 664, 0983). 

lt0

Chapter - 5

SunD.ry 

ADiDo Acids Complerca of OsniuD (tr) 

Cfrapter - 5 

Tl| $o i@l h.lf ridqich mirc eidt mpLr6 of Mim ia los(n6f 

cymxrl-N{tuhhdylglFirc ncltyLsr)Clrl (A) od [O{rttp.ys4x(l-N,N{s} 

plE yl.L.itfuido)cll (B) *d 3Ft[6iz.d. tully chteiz.d cd dEr aryloy.d ror 

d.relcdrc rlductio of kdofts (9; q, F@!e!.l.d lcioB & 3 s.turdld k!ron6) . th. 

cl!..cciatid of MpLr6 w! cdi.d ot by +..ti@Dic d wll a tDlyliql mdnods, 

$.n ryn l 3rn (G qw dm dfmd by rirgl. cryird xdy ddy3i! Both of lhc 

osim @hptq6 Pw fou

Introducrion 

Rn. Pd, Pt, Ru od simil& tresnion nctals hN. b.a wid.ly usd 6 @l!s1e for r 

raicry of noldr.r tusfomdions [,21. A imba of honogcns c.r.lJ6i. hav. b4. 

d.dv.d t!6 'm'rid n r.l mpl.x$ t!,11, bc.u* fty e dolglrt 6 d ii|erediat of 

ldions" c.bltzed by n t l- 

CEnmUy, Dor mu.h is know .ho!r lhc chmisr.y, 6pdi.llt tn€ cndoeldtive 

olal}lic !.tivity of osinm @.. @mpl*s a @npar.d 10 th* of iron od dlhmiud as 

cvid€oced by litdatm. Rutn niln sd phtinum @npl.x.s ofN,N-hetnoyclic lisods, .,9,. 

biprridine ibipy), phmrbDlh (!h.r) dd ph.nyl@pyddin€ (azry). peE srudied ro . 

nr ldlr scale .ppli@ti6s of ligeds ddild non miio &ids is a Fpul& subj..t 

in or8Eone&llio chmistry [8], Mcrd @hpl.rcs @nming mino &id-ryp.ligdds h.v. 

shoM rpdi6i@ mosdy ir bieinog$h chdistry, c.C., in d. sy.th6h ofFFid6l9l 

tr bicinorcrnic nod.L [rq. 

Out of difrdt nduciblc subsd6 of huct inpotune, q, Fds.r!r.r.d reloGs 

d th@, coDr.iring borh. cdbonyl gMp 6 w.ll a C{ bond. nie.bility of reduing, 

el@tively, one Crcup only (raniculdly lh. fom.r) *hile lqving the othd one unalledd. is a 

ditticut job ii orSsic s)ttn.sis, prcdoninmily fd lh€ lomdid of aSrochmicrl dd 

phm*ulical producrs. Thc Lasfcr hydrog.lation of a, p-uneturat€d k loh$ i. the 

prcsde of ol@hols is pmficicntly c$rlyzcd by !.ry lee lrmsnioh-nelal omplex.s trilh 

Ru, Os, Hi Zr, sd lr cr..rr Vcry liniL! nunbd ofosdd.s ofHl Zr, dd Ir, e Eponld 

b €rry od lh. dmo$ldirc caldytic Gdlcrion of$..lhonyl gbup vlicn is diiiculr !o 

Edm 6 ompdld *id lhe dobl. bo.d,r: 

It2

h pr6.nr $rdi.q w illu{ra.d l|r. synlhBis, ch!.|('ai2,tid, dE +6!ospic 

dd x-6y sdlcuc rn lrsis a sll s dffilc.dE c{rl}dc hyd6g.n tr&.fc .biliq of 

nfo w h.lf-sdwich Miu0D omek*d otdtd by sii8 (RlDhciyldycin ndnyl 

.d.r (Ll) sd (slphdrlddinmi& (rl) 6 lis8&. Ami66 !.ri!ity dd funh4 

.!t lytic bdt.vbr otdE qotud mpl.i.s i3 rl|dd.y in ou LtoraoriB. 

Erp.rlD.r.l 

All oldE reidr l4 6in od u!d6 &y ni!o8!o e sP[at, airg srrtdld 

S.hL.t tch.hc. Solva ! w .tri.d b.f@ @ .nd tha EE stdrd oq rcleulu 

3i.G, utda nirioga, koron NMR sp..m wG tetdcd i 300 K d . Bruka 300 FT 

sp.dromcL, by cinS tdr.n.rnykiL* !s iiEn l r&d.td. Intltd +.dr *d ohrii.d 

wilh . Ni@la 5700 FHR T.clroplE1o|na.r 

in d. tu8c 40{0-600 on. Elmdl.l dlris 

(c, E N,s) g* *ticvcd by Bins . Flsh Mod. EA I I l2 6dy&. In. cr.$t usiont 

he tan .mircd by s.r lhuid dmn roirqly d . PdldFEloa Sirn. 38 g$ 

chmdogr.Fh Biir .ithr . CP-Sil4 Ca widdo.. dPllltry @lutr (25 n x 0.t3 hn i.d.) 

or. SuFIow l0 vi.h+d! ..pill.ry ollm (30 m X 0.?5 m i.d.). TIE lldid 

pbdu.r!. otlHwi$, wF id.oti6.d by GC-MS 6int ! Hdl.n- Piltd 5971 A tus 

dct .td @pLd with | 5E901 | s$ chDrdosr4h on e sP255 .9il|!ly dw (25 m X l 

pn). ft. ddtimdiqlly puE s-ph.iylddii. di& (HL2.HCI) rd (R!9h6ylslycii. 

n.rhyl6r. (Ll.Hcl) w4 prr[a.d rm Aldti.h, wh.B to{}cynd)chh M 

rEFrld fotlil4. E orEd n.rlEd'r. Aerod6@ (Fluk )udcydoh.x,te( ldncn) 

wa! cFDloy.d a @iv.d, 

3

Preprrrllotr ofthe OS(ID conplerei 

lor(lcFcymelex K rN-Ll)cl,l (A) 

200 mg (:0.9 mmol) of hydrcchlodd. fotr ofligtud (Ll.Hcl) dd I00 ms (:0.9 

mmol) ofl-AUOK w€e mix.d in 40 nl of.thdol lt ebi..t t npa"lE, .-Fl,r. ra |n.n 

!d

IlM solulioo obtaincd m iho Etigq.r.d at 4'C to @ll*t breM prismtic crys!.ls. A 

tunhd yi.ld of slid (o@9. powds), aQd filtlatio!! w6.caliEd by mixing $e nolhet 

liq@r *ith di.thyl cth.i Yicld: 262 mg (?5%), M,p.: 241-2,15 'C. 

I H NMR (CDTOD): fr.jor 

diat @m$ d 1.25 (4 3H, p{yner., 3iHH = Ttlz), 1.34 (d, 3H, F.ynoq 3J}lH = 7Hz), 

2.08 Gbr, lH, NIt, 2.l l G, 3H, p{ymde), 2.44 (n, 2H, cHt, 2.73 (n, lH. Fcrmcnc), 3.10 

(dd, lH, CH(B2)NH,,2.IHfi = 4.3H2), 5.54 (d, lH, Fynqq3JHH = 6Hz), s-53 (d, lH. F 

cyn tu, 3JHH = 5-8 tl2). 6,14 (4 ltl. p.yncn., 3rHH = 5.8tlz), 6.48(4 lH, p.ynd., 

SJHH = 6Hz), 7.32-7.09 (h, 7H, ?h + NH,} dind di6t@na d Ll6 (d, 3H, p€ymde, 

3IHH = 6-9Hz). 5.20 (dbr, 2H, p{}T€.e, 3.tHH = 5.7H2), 5.41 (dbr, 2H, Fcyna.. 3.tHH = 

a,?Hz), An.l, €lo fd CrettlclN:ooilaHo: c,42-89; H. 4.93i N, 526%- found: C, 

42.65; H, 4,?4; N, 5.41% lR 32E8-l120 (NH), 158(c{ didc), 

Sirgl. crysrlB of A dd B w lixcd on gl$s lib.6 b @llea X-ay ditrtacio. 

d.ra on 6 Brukq- Si.mos SMART AXS 1000 set wiih CCD d.l€€td. by gdPhite 

non@hromar.d Mo k Bdidion (x,= 0,710654), De olLctior d.tlils w.e si c$td b 

ddcrd dinr@ = 5.0 @, fEh6 onelcd = 2424, (Mplae 3Dh.e node), Fr nu. ih. 

= 30 s, oscill6lion rF 0.300'. Crysl.i ddy v6 fou'd itsigili{t in botn ffi. Ddr 

Eduction .ondidds @c.s, d = 0.70 ed 0,90A fd A dd B, Fspeclively, by $e SAINT 

p&k!8.r' &d dab ln6 w.rc.o@l€d by $. SADABSIr p6

Fin d wirh Esed loitl ion-hydro€ei lloms, *ila% hydog.n tr@s 9@ b@ugh in 

gom.lriolly @lculated p6itions, d.luding oi.. sd mide hydoSens, s'6ich w.rc b be 

fomd by Foun€r mps dd tho Gnn.d i$rcpicauy. A panlt @upicd (halo wau molecule 

m.l6 up th. ltmcEic uit for B. Conpl@ sfucnie of I E dsluor.d by Fl&k s 

paDs.rcr - - O.ll'0, ultimaic haps wcG indistinclilc, Cmbridge Crysbllographic 

Dar,beL' f&iliies Nere utiliz.d for slnctlE dieussion. Tn. rdulll @ Mneiz.n in 

Eydret ! td.sf.r rsclion!: 

O.O5 hDol ofD E add.d 10 5 nl of iepop.ml ed thd $lni@ wG k.Pr ar the 

d6iFd tdpdaI!rc (Mn llmpoee d 70'C) in l|)dn6u! A 5 nl (50 mhol) iepbpMl 

eluioi of$e rdon€ {B ihci added ed Bno one hou, a 5 hl (0.1 mdol, ll ns) 

iepopdol $luim of |-B!OK w6 nmher add.d. Aftq d odEr hou of @tion a liftle 

ndim oa th. r*14r eldion *s rlka o! quocn d with {.t ., dtur.d by dihe$ll 

€ths, €lu.d vi6 a short silic. colum wilh dinciiyl .lher ed thd tinolly !a &llyzEd bv 

GC. 

Resnlt! md discussion 

tos(!4,tneic)Cl,l: 

in s ansouchlo@{od hi*tlc *a nrd. ro E&t wi$ 

Ll.Hcl .r mn ronpatuE fomins @npLx,{ (S.hMe l).Ihc larid E qdjcd ont 

udc. cxlr.nely dry @ndnions to pr€val lh. hydtolysis of rh. ndnyksEr goup' 

assi .d with lieed, A wls islgl€d ed obtai!.d 6 a Powd.r witn bomish colour, 

!t6

ed B foud ro haw s psqd@teiralEdrd g6nclry, *t@ Mim I smdd.d by 

two chlori

Fig 1. ThG mleule strlcte of , with orc a|m-rDbdira schan., Di3pllenot 

clliFoi& e (hlm at tn. ,10 % Fohabihy b!cl. 

Tt .xr..ircmt condirioG for HLz E cti@ *idllG{pcrn E)Clrh c dE 

mq td th. romrd@ orcmpld t (SclffiE 2)!! we for r 

H,f 

NHr l/2[oe(Fcrm(nc[],], 

troll ( ll( li 

S.[.r.: 2 Syr{hcB of lte tjrll-$dqch OsiF\o, Coq|q B. 

F_ 

I 

Hl-t\cr 

o/YNH, 

(Y 

Thc comptd E r@, b stallc in IIE iolil st te lrd ir oFn air elutim. Thc ligdd 

.rlibiri t bi& ir. h.hvic, boddirg to lh. nrdrt vis rh di& rd mirc nirtugEn 

Itt

atohs, The omplexatior ws conpleted 

no.o d.pbid.lioi of th. nitogd ir N,N 

tr 

Fig l. Th. mleuls iilciG of & wilh rh. ddMub€ing ehf,e. Displrcodr 

ellip$ids e dEm al th. 40 .,4 probsbility ld.l. 

Th. lH NMR .vid.ned ihe p|ene of t@ dir*@n6 (* Sdion r); !t !D@ 

r.rt nniF they wcrc in.3:l i*io, Ths, witn lh€ exisld@ of d .mlidedqlly puc 

ligdd, bolh diate@m6 R&S. bd So,Sc .hdge in ihe pEsnt cde having an Sc 

@nfi$sd@. A silong s[dching hqnd of th. Mide C=O goup w6 ob*fud al | 575 cn I in 

lR stehn *ie6 th. slcting of rh. MiE tonds &is e low l$ldion 6ard in the 

lt9

$c X-ny dift& on dslysis of . singl. crystsl of B ltIlin.d at 5 'C fon . 

chlmfom eluion, indi.rLd th. din M of both di.sr4on6. 'Ilc X-Ey ulysis of B 

show.n lhlt L2 mint in d it3 @nfigwdion wilh 3Lcogcdic @bon .tom, Connty b liged 

Ll, Th. pEee of tvo diEl.om.6 i! $. sG c.yd.l hc .lddy b€.n ob&ded fo! 

rurhdid, ! onloci of osiM, in R(!6en.)(LL)cl qlc @adq.s 4 EPon d in th. 

|n.r.nN. b th. n.jdly of th.n &.b *ith th. ttF of MtLs of gddl fomul. [M(IG 

p

In both of $* c6, th. Osmiun ooordinaion w6 t Fal'edr.l, by t king inio 

.@unt lhe dini. dd didic nih8.n alons of lh. li8ed, tn chlorire od thc sodaric 

@ft (Cy) of lhe p.ynd. being rh. founi li8dd, ln bo0! @, d. co.rdinltioD to lh. 

Minic gMt s6 foud ecrter rhr t F nidic donor, Tt!..hcldim of 12, havi4 hi@B.n 

dod lrotr lo Os, Fodu..d . fe tudt Ed d.lalion ring, @niaining bne dgl.s N- os - 

N = 76.5(3)' boih i. A. dd 81, wh.B th. Esi of @rdi.atio. usl6 on Os e bigg.t ihm 

thc Mlolpu s6 in Ar. Tn dnv.e.b$lulc amg.n .t of lh€ nelal in both Al dd Bl 

qus6 e ulik ondtalim of rhc Os -al bond @npe.tively 10 the c€rbo!'hydrego bond 

of thc chiral .dbon .lon (for Ai sd Br,C2 od C2l, Bpelively} Bolh bonds wcre dially 

otiolfd with reged to the chehti4 rings, .x@pllhey v@ in e1i €onnguElion in B'. md 

sy. in A'. The p{ynoe wG @Bbtly c@rdi..Ld wdn rh. n lhyl sd oriqtding 1o lh. 

chldrc ligatrd [CI€ll- Osl{tl = -20.6(9t, Cl6 - Cl] = 3.55(l) A ; Cl5-.3'L 

Os2{D = -23.5(9)'C35 - CD = 3.56(l) Al. Cocrysrdli2ti@ 6f diafud Ar dd 

B. 6ulr€d ir a dins qirh s@mcEy of a invsLd pi@$ooL in $hich A' od B' s4 

!ssi.Ld by . noHryslatlosrsphic o9.6Iion initding t 6ter of inv.6ion. ir od.r lh.i llle 

Nmrdc A{yb4 noidiB h. posniorc! pdllcl m optciL sides El.rive 10 ih. n.lal 

atons. It ws sugg€sl€d $ar de stlbility of inv.n.d Pi4o-stool tggnitio. g@netry wa $. 

bdis of lh. appbprialE @!nen e of diasteFonss @cryslalliz,lion for Os(IGrene)XYZ 

ryp. ohpleresr, hdins eldsooeg.tivc X sd Y, Th. invdion opdtio. w6 n6esry to 

g.nebre.ont!.l3 betsem cmpl.n nt!ry groups on A' od B': C29_--ol = 142(l), Clo 

02 = 3-37(l), Nl- -- CD = 3-491(8). ud N3 - -Cll=3482(8)A 

cryslullogEghic opd.rid Bo*5 mid lh. n ttl e.ras oflhc A' !' din6 to Sir 

noleu!6 oppGic chid'ty on lhc hcr.ls, 

t2l 

Such a no._ 

the tso

Ncvenhelds, b€cous of th€.ndtidcnqlly pu€ L2, ihe stmne,try ftl3tio.6uld 

.ot b. cxpdded to lhe wnoG nolaule pai!, ho*ad i w6 resui€t€d b th. eiral cor.. 

within dF d.fin€d limit for tn chisl cdbo6, Ihc 6!0 @npl€x6: ScSc sd RcSc wcc ii 

cloe @nr..! virh Osl --- Os2 = 5,I (4O.OO3) A, CF Oe 09 Cy = r8O, od Cy, OF 

Os = lll', vîch !* quit. distiEriw ulu6 for ech t t tt6n!. Thc olh6 shodcn Os - 

Os @r&ls w g@6 rhd 6.(10,002) A. IrE ms i di.g l€ln *s tL build u! 

of th. crtslrl Nhi&.nd E3.h dialEmd s a pafi of rhc helix of ealoSous motarld 

duc 1o E stmg nydrcgen beds (T.bl. 3). Both hcli*s A sd B wft g€n@lfn vi.lh.4l 

symh.rry operlior. with pilch (c) = 14,572(l) A (Fi8. 4), bavihs opposite hddedD6s. I.il- 

hud.d foi A ed nght-hmded for B, Tn. h.lix hdd.&€$ ws diJsred by merll 

co.figuBtion ir $ch a wy lhat all th. .hloiin. ligeds snrck outeid€ th. m6 of lhc 

ch.iN, The inrra4hah p4ling of L2 s th. lin. of d.n@dio. b6ei rhc lfo 

dir!.ffiic h.!i6 A. dd 8.. H.li6 in rh. crylral. 

122

T.H. a, crys!.| d.i. rd *udrE .lucid.tio fa A &d E. 

C l9H25ClNo2os lcl9tl25ClN2OOsl2 

.0.5tro 

560.00 

10t4.00 

0.71059 0.7t069 

PI 14l 

9.?090(9) 21.55t(r) 

b(A) 9.?69E(9) 

t0?650) 14.72r(rJ 

9?.515(2) 

9 (') 97.4t2Q) 

'r (') r05.0r(2) 

965.920t 8 reqr) 

z 2 3 

1.6t54 l_425 

abirprio c..fnciot lm ' t.095 0.90? 

F (000) 440 J595 

0Rsg. fd&l!@lletior(') l9!3031 t.5l-,24.01 

Rcflerior oll*r.d 0 > 2 sigm) B59l 16800 

D.rtE t6inttpam.&n 525(//,240 59flq44o 

1.3036 l.l7l 

FinalR indies II > 2d (l)1 R'-0.0210, wR:=0.051I Rr{,0361, 

0&=o.99El 

81185 

Rr{.02rO, w&=0.055 | &{.0539, 

vR:{.1202 

dF memuivminhm o1E514159 0.9tr43t0 

l2l 

B

i .dat d in 3!ch ! wy, tn@urn (u irv.n.d pi$o-s@l lilc) dihds, F3irion.d sr @h 9oo 

tun of thc hcli( rtlr @h h.lir wa smuid.d by fou opp.'ir. gF of h.ties. pa.ked ii 

Tn pdpontion of O(ll) cohpl.xB @.t ining othd eino eidr ligsds with $. 

ain to idpo!. th. .n$1iosl..1ivity of lh. hydogd t.Nfn El.tion s w€tl s $.ir 

dlicscr &dvny is .u@ndy h.ing ci.d our ii N l.boBtory. 

Cb.noieLctiv. HydrogeD-Tr.mf.1 R.ducttor ol Ketor.. Crt lyz.d by 

Compl.r A 

IX. @mpound5 el6r.d ir p|gar w.t fd hydsgd-resf.r Educrio. sist d by 

lh. mplq6 A lrd B *@ (i) t ioi6 (9 d, Fhsllrd.d tdoc vi2 d[id +t2 & ] 

3rodr.d t loc; .fl.i6 l-3) sd (ii).ldchrd6 (dEi* t3-lJ). Thc !*ri@ w di.d 

oul by .nplolng pDp..-2nl &d cycloD.nt rFl bcin8 hldrc8d donoE s *tl s $lvdrs. 

Thc ddim &c losnd to b. r lid. fasr6 ii lhe lene of fomd, posibty, due ro ln. 

ler innibning .ller of rdon. a @Dacd io cyclofabDot rhs o ntidl, h. .vapod.d 

d.l.vLd L0!6or @nd idr (EoPC), Botn r[. onpl.x6 A.nd B 9@ lEy sbbt. ed 

! nhbq ofc$.lytic ctrlB o bc adidld by Fhrging rhc sy(.m win $b6r.!c s wll 

Acycli. a, p-$etud&d ldacs Qd Edrc.d wirh deldr ..b]riic &iivity io givc 

@londing sl'u.r.d k ron6 which \@ Onh.r rdued to s.rudld dohok (dri6 

l,6r,ll & 12 in T!bl. 2). As a8!,tl! cyclic d, p-utu nlrA&d kcro.6! rh. poducts yi.td 

obbin d bt th. Edmtio of eDll.r cy.lic ebsml!! with hi.imln of $c!ic hindde 

eund th. Educibl. gblps (.nEiB 2 & 4 in Tlbte 2), vu nlch hi8hd rhs tho* of wirh 

lego sia dd sldic hi.&ee, Crloh.xcnon. giv.s ! hixtuE of Edlciio poducts pnh 

124

C{ od C=O but upon th. hindde of C=C boad G.tri.s 5,6 &10 it Tlbh 2) thc 

us.turred al@hol *a pEf.nhly fom.n. s.tudLd lcro!6 l@ rh€ mjor plducls in rh. 

ceof fiw mmberd rings (dni6 4 & l0), 

T.U. 2. Htdroeo-Tdrfd R.d'&dd Cddyzd by A 

(L) (%l 

7 l6 0 

2 88 0 88 0 

3 0 35 

2 60 35 0 

5 9 20 0 20 0 

3-Melhyl-2- 5 to 0 30 

7 2 90 22 68 

5 60 l5 0 

100 80 20 

IO 3-Mcthyl-2- 5 ll 

tl 5 90 10 20 

l2 90 88 0 

t3 65 l5 50 

t00 2u 80 0 

It 5 55 

As fd a ihe reducrio of aldchyd6 is @@h.d, intBtinglx n w6 pqfofred 

sKtully (aai6 t3-l5, Tsbk 2) by a sni.h k, ro dE b.s of or tnNl.de. qnn re 

b.l8viM by Os.od. hrlf sd*ich @hdd' 

125

Ci.b6d€tiv. Eydnsd-Tlrllf.r R.d!.rior ol IGto!6 C.l.ry4d by E 

The hydsgofi!$fr ild!.rion of b..zylid@loE wt dalyz.d 6y a uith 

hid c.tal)iic divity dd ftir ch.'twl.aiviry, lh. tujd produd b.ing rlE ots?ondins 

unsltm&d al@hol othd orc

W. havc also t!i.d to siudy in emc d.sil th€ .ffet ol6e dFinhlrl @nditions o. 

lnc cdlllric &rivirt of B in rh. Educio of bdzylid66cc'@. Th. rM nydogcn do.or 

us€d, Fopd-241 or cyclopdreol, h.lh oflhd shoB.d $rc liniltiN- PEPa.24l 6 

dehydr.Sdat d durirg lha @1i@ 10 givc eadc which, lit eyclic k lon.s, et5 silh B 

in s dispbponionltio! E&nm,.NiDg slov, id!6ibl. d@liv.lion of tn cllllyst 

T.bk J. Eydrcid-Trltfd Reddior Crt ly4d !y a. 

(r) (%) 

9t 9l 0 

2 100 0 100 

3 8? 87 

90 l0 60 0 

5 l2 0 0 t2 

l-M.ihyl-2- l0 l5 

1 2 95 l2 5 78 

I 22, 68 0 

9 2 96 l0 

IO 3-M.thyl-2. 2t 23 0 

ll 8 71 17 0 0 

t2 91 88 

2 5J 5 50 0 

t4 l 35 85 0 

t5 5 0 0 

This tt?c of d.&tivation 

fas! but in rh. *. whee B G 

wirh $b3r.t. r.ducrion and, 

vs not woni Eddoning when tie subslrlt Educlion ws 

l€s a.riv., d@ivadon of de cat lFt ould b. mp.ritiv€ 

h6c., o iD@hplae @v.6i@ wB *hidcd. Bln 

121

fa*i dngly. ctrloFrrimnc, ac{uiFd by oxid.don of cy.lopd'dol did not poien rh. 

stalysi on (h. oihd nMd, lhe k.tdE *ticn fomcd m mt vololil. (6 wE rtu4 dd 

fay @mp.t *ith th€ slbsuale for @odimlion to osiun in tne 6N of th. catalFis 

'I.lrb osiun calalys (B), lil€ A is ale vcry 5t bl.; a nuber of @nscutiv. e ons 

cd b. fficd out Ning the s.ft c.rdlst with to coEid.nble deqy of aclitily. To lhc b.n 

of ou bowLdg€, no othd @iun omplq hs hen cpod.d $ fa.lo sl6ti4lv ot llz 

th. hydFgotusfd redudio of a, F{ns$d.d k ron6 ro .llylic llohols ro sh m 

Two .ovel h.lf-sdwich Os(lI) compl.l* h.!i.g ligeds d.rivodved nom amino 

eid *.c strth.si4d. cndzclsized ed €stcd $ catdysls for.hmosel*dv. tducdon of 

*l6t d a, Fun$tuded k too6, Within @npl.x B, @rynnlli?,rion of th. nvo 

dissi@ffi RGS. dd ScSc *s (|lttann. h.vbg ligdd (Shhdyltlui.sid. shich 

r@k pl4 tlFugh d inrcn d pieo-lrool lilc dind l:]md, Thc scric dd cld.uic 

posirion in $. oordinatio srhee of lhc cddysts A & B appaEd a poP.rlv dcsi$.d b 

flvour ih. rnuction of the @bonyl grcup of d, F-unsturaild k€{ond hlvio8 bulk, 

suhtitu.ots grcups st lhe C{ doubL hond, Th. rcduclior of lhe C=C bond wa ob*ded 

whcn .nhd $ a, Fusllrdlld kdo.. qs nor srdi@lly hindqld or th. c=o cdbon on 

b.$ . bllkt subiitmt. Th* @npl.x6 l* found 6 good c,t l'5lr fr th. el6tiv. 

Ed@tid of lreoEr.d ors&ic ebsElr.s. Thit oFns ! quir. p@iting {d lara.lv ncw 

t28

I P. McMom sd G..1. Hutchines. Cn?u. So.,, /t?!. 33, 108, i200). 

2 .,J, Beclq .d M.R. Gage. Ac.- ch.n, ,..t,,31,198. {20(/). 

t lrLT_ Rft'', PM. Nai. 1e4 S.i. U. S A,t 101,5116 (2@4). 

4 B.BEir,Angd Cheh., Iin! Ed.2005i4, 6816, 

5 Novatov. O, KcpdkoE J, vm O, ve vli€{ PM, Redtk J, Brot c V. 

Biefu nitiy l995t ta. 12369 - 

6 O. Nordova, J, K.s!.rkov., O. Vdn, P.[4 vs Vli.l,,. R*dijk V. Bmbe 

Bi@hedhtry, 34, 12369, (r995J, 

7 A.H, vcld6, H. K@ijnd, A,L, SFk,, J,G. lLsm! D. D. Vs, J- Rc€dijk /mfg. 

Chen 9,2*5,(2400). 

8 K. S€vdin, R. Bsgs, W. B.€lg ,tn4.e. Clen. ht. Ed, a1' 1634 Q99q. 

9 R. kil,n.r. M, Maus, K. Polbon, K, SUnk l, C. Robl, W. B.ck, Chzn. Eu. J., 2, 

rJr8o996). 

l0 R Fish, G, ,!oc'j' &a@retalics,22,2166,2@1. 

lr (a) M. O@imi, C. Nedin, A. Vrd, F, Z4obini,l .r,, Ch.d, S@. rr2' 9\90, 

(1990)_ 

O) R.L. Chowduri, J.E. Bekr€ll, J. Ckn. SOC-, Clen. Connun, 1063,(1991). 

(c) M. A't@s M.A. E€h.ls, FJ. knoz, J.A. Lopcz. U. Mctq, L.1. Ob, 

Wmd. H, Znorg" ,&.8: Cr.r., 31,, 288, (l9l). 

(d) M.A, Endcl.r, L.A. Oro, C , Vtl.tu, O'ZMdallics, 1992, ll, (3362r. 

129

(e) M.A. Eidel!!" M.P. Gai4 A.M. Ltp.1L,A. gn., Organowtalli.s, 11,702, 

(D E, Fdeti, N.V. culali, M- G@i^| A@. chin- ztal,.l2t, 166, (1993). 

l2 (a) A. Md, H. Oino, n. Nitq K TE*r, S,ImE, Sytea 563, (l9l). 

O) M.l. Bur!!cr., M. ColLdo, J- Esrihelc, F. Gdlindo, E- Ce;.-V.rduso, S.v. 

Ltis,rt.t. vian. Tenal&ro" Let1., i aa, 5891, (2003). 

(c) A-V, Milkov, J.B. lr&d, P. K@orsly, ClEn. C.nnun., l9aE, \2003) 

13 (a) A, M.Clsi., L.A. Drcsl, J.l. L.89., J ,,l', Crzt. Sd., 98, 4150. 0 t6). 

o) P. NlJ|fu, D,A. PhipF., t44 Chld, act .,11,L19 L20,11916). 

(c) Y. rla, l,org. Clen.,26,2454, (1981). 

14 s.Y. He, Y.A. Kim, Ltere&on,60,2441 ,lm04). 

15 w.s. sheldrick, S. Hab,1tutg. chtn../cta,l&93, \19 ). 

16 (a) H. Btuind, M. W.h.r, M. Z$.1, C@r.l CIE^ xs , 2t2,l,(763)- 

(b) H. Btund, M. wchs. M. Z$cl,'t, Zwl\ A,sN. Ch.n. ld. Ed., 12, 1859- 

(2003). 

l7 R. (lnfur. M. M!m3. R. Begs, K, Polbon, K. Sunlel. D. Wa8nd, W. Bek, CiPt 

&.. 1261959,093). 

| 3 H- B':md. T. Nculi6f, B ,Noter, Eut. J, !tu,g. Clcn., 1877, (l99aJ 

19 D. zucocci., E, Clot, A. M4hioni, .v€p J crez., 29, 430. (2005), 

20 (a) I.M. Plsld, P. vNilo, A. Adolf|g,ch.n. cdnth.2M6, (2002). 

(b) I-M. Ps1d, P. v.slila A. Addfls, Cr.r. ,r. 7, 9, 4031. (2001). 

(c) A- Bogcvi!, l.M. Pslor, A. Ado|a$n, cr!'. Eo. r. !0, 294, (2004). 

t30

S||pponing Informltlons 

CrFrcll,ograpblc I orm.tior lils (ClFs) for conplcl A. 

lIlt_rlqELdjolrnl t'pliedorgluEbllicclEnisir/ 

jubl otu_ldhd_'r'4 LA &rn'1 

j$l co'd_ruld_lddBs 

NcEAc, sindh.Univ., 

jublcotu_auihd_.Flil Bjaldrlwna@sh.ilon 

-}Ubl_cotu_dhdjborc\421i22-277 \!79 

J$l_onrc_.dhd fd 192- 022-21715& 

$bt-.!nu_Mc 

jrbl rnhd_ri&s 

# T1r climi..l, crJd.lloeEpnic a c)eqi'Mtn dlr 

_audir_cdri@_Dxrh.d SHEIXL9T 

clFni€l_lm._tFlandic 

_ctffii@l_nDc_omon ? 

cbonicd m.llinalDi.l ? 

_cnmi@l_fmula,mi.ty ? 

ch.miql fmul!_r@'Cl9 ID5 CD N 02 03' 

_.nenc.l_f@ulr_r.ighr 560.03 

ah o!._ryhbl 

tu t,9. ddnDdd 

_alon_ryp._sl-disFBid r.al 

_dm_l}?._sal disFsi6_ims 

tu ryp._sca!_$ue 

CC0.00330,C$16 lntenurion lTablesVolCT.bl.!4,2,6,3@d6l L4' 

H H 0.00m 0 0C00 ll1qMrioMl Tabl6 vol C T.blc, 1.2,6.3 aid 6.1,I 4 

N N 0.0061 0.m33 lnt m.lional T.b16 vol C Trbl4 1.2.6.3 ard 6.1.1.4 

o o 0.0106 0.0060 Intfuiond Trnb vol c T.blB 4.2.6.3 od 6.1.1.4 

cl cl o.l,(aa 0,158J 'lnicmiidEl T.bl6 vol c Tdl6 4.2.6.3 ri 5.1.1.,1 

os ot 1.259r 0.$6l b|.didEl T.tl6 vol c Td 6 4-2.6.3 Dd 6. L 1.,1 

l3r

_synmdy_ell_slnin! f icliric 

s)m.ry sp.4lDup_Me_H-M P-l 

_synn !t_.quvJ$_a_r'2 

_€ll rgic alDh 97.615(?) 

_c.ll_sgl.lMtu lot.Ool9(2) 

_el_llr.l|llllM_bFuE293(2) 

_@I_t@dt_cfla_a.d ? 

? 

_4u 

_ell'ffindr_tlEt 'Blmt'rls!_nin _nu? 

_*pd_qstl decnplid pri$s 

_cxprlcilsrsl_colou bbwn 

.xprl'crJsr.l_3ia_ns 0.25 

_cxprl cgsol !i4_hid 0,2t 

.xDd srsr.l-si4_hii 0.18 

_.rl(r_d).Ll_&6it 'lE ? 

_dFl_cFrd_ddi9_di6n L526 

.xFl cyer.l_dsi9_ndnod rd ll'6uEd 

_crqrl_dlo'fl _@mcid._mu l.0ll3 

dptl .b6dpl_corcdion_t'?€'synneiy-El.nd 

':Ellllmnls 

_cxprl ahborDlcmolion_T_min 0.78e12 I 

_ox!d at o4 c4c{on_T_tw Lom 

_.xp!_aboetl'@s_d.Gik 

Gddinsro!.dldl8ispl*uf.dindES{D BSF.L4p 

'| 

_di6!_mbidt_tnFtfu 293(2) 

_difi n_rldiano._swl.qrh 0.?1069 

_diftn rdidid_9F MoK\t 

_diiin_,ti{iod sde $Ff@ ssl.d trbd 

-di6n-r.didio_m*rmtu 3lpbjc 

di6tr-tElm.d_dcvie_$lr tsrut raxs ccD difilchdd 

difnn m6lMdl ndhod\e se' 

132

_diftn dd.@ t@_'sl_ll@ 8.2 

_diltr c.trddis nmbd? 

_difFn_3ratn!,5_i'tcPal_@ur ? 

_difin sbilrds-irk l_riB. I 

_dift ._tud.rd! de.y_% ? 

_dilftD_EflG_nubd l3t9l 

,difin_Bfl6_av_R_.qui{lcns 0.0130 

_diftn FflB * ltMlh.d 0.0202 

_didrn_Fr^_linh_h_oin.l3 

_di6n Efs lsn h-'d 13 

-diifn_En6_lihn_l_nin nl 

_di6n En6 l'mir-k_lu l] 

_difEn_Eds linir l minJ1 

_diit!_el^_linir_l_nq I 5 

Enm-th.r._hiD I.94 

_diih 

_diFn rnG lhd_nq 30.33 

_EnN tGholddpBi6>2tigrs0) 

_mF inLild.-collelio 

SAINTT 9ax, AE Dcted Intgdid! si.Ms Adltr,cal itu.nls 

INc., Madisn wi!c63i4 USA 

_@FninsElLrc6im.ni 

SAINT: sAx Ad Dd..ror hi.sdjd! sim A4bric.l irst@od 

INC.. M.nisor! x/i@iG USA- 

_c@piinldrh Fdldid 

SAINT: sAx, AE D.t4ld lincgltio4 sism AMltli6l istm.na 

INC., M.disdr WisBi!1, USA, 

sA.DAas smd Ad D.rdd Ab6drtd cotdd sofr*e. 

ShcldicrC., 1996, Unisity of tun€E4 Gmoy. 

_cmrdiiLsl,rr@_sldi6 

BuL M.C., Cddli, M' C.Nzj.! s-, 

CMreq G., GiMtrzzo, C., Polid6i. G. 

& spagna. R (2001), J. Appl. C4Bt. - 34 523-t26. 

omNrim sMR Fliem.nt sHFLxL97 (Sh.l'ln( loal' 

@i.dr-L*'*d;$pt"* or'.e J rn wrrid! (tmlgla le97r 

_@pdingltublidjd_dqial 

PAR5r - M Nliklli, i. appl. CrFtllo€r. lt5, 28, 659 

t3l

R.6l1@d of Fr^ alajd ALL ERdiG. TtF wighLd R-htu ,R lxl 

eoodnc$ ol6t S @ brs.d d F^2 , 6$qdoml R.liclon R e bs.d 

on F, ri$ F !.i io do for n.gativ. F 21 Ih. rhEshold expEsid of 

F^2^ > 23i9!(F^2^) k 6.d oly for olcul.dns R-leol6Gt) dc. ud i! 

nor El.vdl lo llE choie of a,Lcli@ fd Efr.d.n! R-fa.ls bas.d 

dF2 @ diricdly rbotr t*ia 6lalE 6 d6. ba.d d F,4d Rfd6 

b6.d d aLL de vill h. .En I'eF. 

Eine_ls lEktue felu_Gf Fs4d 

E6rc]s_wiEhtiil$h.m. c.lc 

_r.f m_L_*.ightnldcbi13 

.d. Fl{\s^2'{Fo^2 XO.0l07P}2"+0.r]33Pl rlEa hFo^2+2Fc2^):' 

tu_siB_eluial'if, ,.y diGt 

,h siB sldjm 56d&tdi6lip 

-.lom_sirlr_el\td_hydqms g@m 

rcnn.Jr_hydrcscn_ft otncil oircd 

_rt6@_b_c{idio 

metFd non. 

_nfm_1tr_didim @f? 

_Efi*_ls_nmhd refla 52t2 

-r6*_li_n@bqJntu6 213 

_Efrn.J3_n@hd ltsid 0 

Eie_k_R_f&ror_,ll 0.0210 

_d6.e_ls_R_fad3 0.0210 

E6*_ls_wR_f!c1or_Ef 0,05t1 

Ef E_k_rR_ficidlr 0.053,1 

Efrft ltlo.d!B_of_6t_df 1.033 

Ffie_k_|toin d_S_dl L0t3 

E6*_k_shiUru ru 0.001 

E6n.h$i $ na0.0o0 

don_sit_U_ie-d,.qdv 

_arod_lir._stmdy 

mDltiplic y 

_dd_3it Enmd'.lllAr 

_tu_riE_disd.da embly 

03G0.l6365s02)0.03100(12)0.34336,t(10) 0.02594(4)Umi I 

cll Cl {.063414) 4.03014(5) 0.6?134{4) 0.01954(9) Udi I 1 d . 

ctz cl 0 I2m?({l 0.15?34(4) 0.332(4J 0.01612(9) uei I I d . . 

N ti0223t7(r4J0.l4rrEl6)0.6'r3t{ill,o.0lt5(3)uDi I I d.. 

ol o04J1to(r41010r54(16)0.{1137(l21o.o{qr)udi | | d.. 

134

02 O 0,1189204) 0,13415( l3) 0..1915701) 0.0112(3) Uui I I d. 

C I C 0.3675306) 0 1538( l7) 0.@,15304) 0.031 (3) Uoi I I d . 

Hl H 0.37{3 0.0563 05783 0037 Uiio I I c.lc R . . 

c2 c 0J9?9(17) 0.23170(17) 0.70523(l,r) 0-032(l) Uoi I I d . 

C3 C 0.6225(2) 0.18?(2) 0.70.t92{18) 0,0a29(4) UDi I I d... 

H3 H 0.6227 0. 1037 0.6459 0,052 Uiso I I cd. R . . 

cir c 0.7460(2) 0.253(3) 0.?915(2) 0.0551t) U&i l l d.. . 

H4 H 0,8295 0,2237 0.7900 0.068 Uilo I I ..lc R , , 

c5 c 0.74s9(2) 0.3725i3) 0.3791(2) 0.m0(5J Usi I I d... 

H5 H 0,8291 0.4198 0,9180 0Ot2 Uiso I I cdc R , , 

c6 c 0.6235(2) 0.,uft(2) 0,83 t64t9) 0-0515(5) Udi I t d . , . 

H6 H 0.62,|l) 0.-195,10.9413 0.052 Uie I I c.lc R . . 

C? C 049909(19) 0.3479{19) 0.?9112(1?) 0.0t9t(.1) Uoi I I d . 

H? H 0.4t65 0.3792 0.79t2 0.01'7 (Ie I I c.l. R , . 

C8 C 0.1325707)0229&(13) 0.4399204)0.0138(3)Uoi I I d. 

C9 C 0,J276(3) 0.41 l8(2) 0,38823(19) 0.053X5) Uei I I d . . . 

H9A H 0.4233 0.4313 0,3637 0,031 Uis I I calc R . , 

H9B H 0.1049 0.t007 0.4103 0 031 Ui$ I I alc R 

H9CH0.25990.l55OO.3l5l0.03LUisl I 4lcR.. 

C10C0.2979(110.0415(2)0,98988(15)0.03?s(4)Uui I I 

Cll C 0.3792(11o.ml I (13) 0.39366(15) o.Orlq!) Uoi I 

Hll H O,a7)2 0.0627 0.8986 0,0!tt Uno t t qlcR., 

c I2 c 0 12l3l ( l7) -0.0928108) 0.78e06(l t 0.0rJ2(, UMi 

Ill2 H0.1767 4.10170.72570.040ttso I I cdc R., 

clt c 0,18453( l3) -0.189560 8) 0.7?849(17) 0,0368{r) Usi r 

C l4 C 0.10457(19) 4. 16736( l9) O 87743( | 3) 0.0.05(,t) Umi 

Hl,tB0,0ll0i.x95087ll0.M9Ui!. I I c.teR.. 

c l s c 0.I53E2) 4.05@(2) 0,9803(16) 0.0,ot(,r) Uoj I I d. -. 

H l5 H 0.1036 4.0,151 |.0435 0.0,t9 Uio I I c.lc R . . 

cl6coJ535(2)0.1653(t) 1.0972.r(r?) 0.0555(5) Uoi l r d... 

H l6a H 0.1766 0.1108 1.1744 0.081 LJiso I I cd. R . . 

Hl6B l{0 2303 0.21116 L1062 0 031Uie I I .d. R.. 

H16C H 0.4333 0.2302 L0302 0.033 Ui$ I I crlc R . . 

c r 7 c 0. 12112) i.3129(2) 0.653?(2) 0.0508(5) Usi r l d... 

HI7 H 0.0135 4.3446 0,6637 0,061 Uis I I cdc { . , 

cl8 c 0.l54El) -or?49(!) 0.54112) 0.064.(6) Uui r r d . . . 

Hl Sa H 0.1202 4.19,12 0.t266 0.097 Ui$ I I cdc R , , 

Hl8B l{ 0.10?0 4lJtl 0.i1757 0.097 tt$ I I .dc R . . 

Ht8CH0.573{.15090.5,1220.c'7Ub. I I.rlcR.. 

CI9C0.r844{4)4.416t(l)0.6939(3)0.09r1(10)UDi I I d... 

H l9A H 02379 -0,4066 0,7071 0.137 Uis I I *lo R , . 

H l98 H 0.1451 .0.5175 0.6315 0.137 Ui$ r l .rlc R . . 

H l9C H 0.I530 4.46J0 0,77?2 0,I17 Uis I I .!lc R . 

HlNH0.l56(2)0.103(2)0.533(2)0.0,1-4(5)Ui$ | I d,,, 

ll2N H O-r42) 0-229(2) o6?a(2) 0.1X5(5) Uie I I d . . , 

135

Os0,02451(6)0.03135(7)0.02422{6)0.0031E4)0.00650(1)0.00993(5) 

c I r 0,0274( r 8) o.o.r8(2) 0.0179(2) 0.00?s9( 17) 0.0m630 4) 0,0046?0 6) 

cr2 0.017(2) 0 0t54209) 0.o381(2) 0.ms29(r 5) 0-m309(15) 0.01424{16) 

N 0.0?616) O04r 9(8) 0.0270(6) 0.01 16(5) 0.0067(r) 0.0030(6) 

or 0 01s(?)0.0592(9)0.0324(6)0,0 0(6)0.0154(5)0.016(6) 

02 0.05 r 3(7) 0.0406(6) 0,0320(6) 0,00915) 0,0121(5) 0.0039(5) 

c I 0,03 r 9(7) 0,031(8) 0.0284( 7) 0.006 (6) 0.009(6) 0.0076(6) 

c2 0.0300(7) 0.0175(8) 0.0239(, 0,01 14{6) 0.0065(0 om5(6) 

ct 0.041(9) 0.0513(r 0) 0.0ro7(9) 0.01 r2.i3) 0.012(, 0.0r30G) 

c4 0.0350(9) 0.082(lo 0.053(1 2) 0.0233(11) 0.006(3) 0.022100) 

cs 0.040{10) 0,07ur 5) 0.0s0502) 0.0r370 D {.m90(9) 0.00r 5o0) 

c6 0.055(12) 0.0464(1 0) 0.041 800) 0.0004(3) 0.0002(3) 0.0027(9) 

c? 0,0380(9) 0.040E9) 0.040s(9) 0.003q7) 0.007(?) o.0l 16(7) 

c3 0.0105(7) 0.0179(8) 00263(7) 0.0048(6) 0.m13(6) 0.0m(6) 

c9 0.069{r l) 00506(l D 0.or,1r 0 0) 0.0209(9) 0.0108(9) 0.0136(10) 

clo 0.or3(9) 0.052 r(r 0) 0.0258(7) 0.012(?) 0.0{v5(6) 0.027(3) 

c l r 0.02917) 0.0.162{9) 0.03 l ?(7) 0.0 r 40(7) 0.0rx 7(6) 0.01? (7) 

c r 2 0.034(3) 0.0105(3) 0.0323(7) 0.0120(6) 0.01 r 0(6) 0.01 so(7) 

c r 3 0,0333(3) 0,0321(3) 0.0.t43(9) 0.0r26(' 0.0099(7) 0.0142(7) 

cl4 0.033r{9) 0,042(9) 0.0509(r 0) 0.m4{3) 0-0r l{7) 0.0r4q'7) 

Cl5 0.M63(9) 0.0582(t I ) 0.033J(8) 0.0251{8) 0,019,(7) 0.029(8) 

c l5 0.06ry1t 0.0?59(r 4) 0,0106(9) 40or(9) 4.m,|r(8) 0.036(l D 

cr7 0,050(r l)0,036(9)0.063Er3)0.m320)0,0rlo(9)0.010q3) 

c l8 0375?06) 0.0573(1 3) 0.050( 12) .0.00890 0) 0.0012( I D 0,01t( 12) 

cl9 0.11q3) 0-or33( r3) 0 094{2) 0.@5?or) 0007(2) 0.0,{05(16) 

All .s!s (*cepr rh. .sd in rh. ditEdnl sel. bdwcn No Ls. plet 

G 6i@d uing tlc fi 6vri.F Mix TIE ell 6ds e t}n 

inro @d i.djvi.hdly ir $. 6lim,ri@ of6ds in di*m€s, ad6 

od bid arsl6 c@ldift bdwn 6& in€ll F@d6 & d{y 

scd wh.d ln.y e &nn.d by c.)tlrl !]!mdy. An lpFdjool (iseDic) 

lFarndt df ell $dr L s.d lor 61itutins esds iildlviu Ls. plG. 

lpon-hqi_aion_,itc_lib.l_l 

lc@_b..d ibm ric-hn l 2 

l6m_bond_si&_synmety 2 

OrN2.165(lr).? 

OrCl42.l69X16). ? 

OsC112.l3elil6). ? 

t36

03 C10 2.2032(15) . ? 

os cu xal r9(4) , ? 

o c[ 2.4206(.r) . ? 

NCI t,4!?809).? 

or c3l.l92(2),? 

02ct t,323(2) - ? 

o2c9 t,44442t.1 

cl c2l,5l4(2), ? 

cr c8 1.527(2) . ? 

c2 c? t.3E3(2) . ? 

c2 cl r,38t{2). ? 

c3 c4 |.330(3) , ? 

c4 c5 1,166(r) . ? 

c5 c6 1.37,r€) . ? 

c6 c7 l,388€) , ? 

cloclr 1.,rcso),? 

cr0cl5l.42(r).? 

c10cr6lJ93(r).? 

cll c12l.41(2).? 

cr2 clt |Ao212) . I 

cr3 cla t,,123{2) . ? 

clt crr 1.5r0(3), ? 

cl4c15l.339(t, ? 

cr?cl8l.'l(!). ? 

cuct91.5rq3).? 

-3d_!gL-.1dr-!ib-lrb.l-l 

lm_D8l€ e_sir._tD.L2 

lm_ugle_llom_.iE Lb.l-l 

_lFoi'r_sd€ !iG-3F rdy-l 

lm-ucle_riE_ryoety-l 

Cl2OtN9r.lr(6),. ? 

c12 O. C1,16?.52(5) . . ? 

N03CIa r'r9,8(?).. ? 

Cl2 Orcll33,l(6).. ? 

N03CII lm.8a(6). - ? 

cl403Cll ?9iq5). . ? 

Cl2O!Cll37.66(6).. ? 

No3Cl3l13.6(6),.? 

clr o. Cll 63.63{5) . . ? 

N Os C l5 16?.00(6) . - ? 

cl,r03ct5l?.r3(7).. ? 

cl1 or Cl5 67.4(6) . . ? 

cl, orc1563,38(?).. ? 

cr2o3cr0 6{,3q6),.? 

l3?

cl4 os cro 67,80(7) , , ? 

cll O!clo 37,39(6) , , ? 

cll O. c1O 8l,5.{?) , . ? 

cl5 oi clo l?.r2{7). . ! 

c I2 Or cu l&.86(s) - . ? 

N03CD8r,69(a).? 

Cla O. CD 126.33(5) . . ? 

Cll OsCl2l10,09(5)..? 

Cl3 O! Cl2 164,6?(5) , . ? 

crt03cox,T(5)..? 

cl0OBcl233.33(t.,? 

cl2o3cl t2,r.8E5).. ? 

N Ot Cn 31.614) - . ? 

cr403clr 89,3?(5) , . ? 

cll Os cll 162.67(5),, ? 

crt03ol q.4Es).-? 

cl503CI lll.22(5),.? 

cl0O!cll 147,73(5), . ? 

cD6Clt 8t.21{r5).. ? 

ClNO.l2lo(10)..? 

c8 02 c9 rl5,9El4)., ? 

NCI C2 r.92{11). - ? 

NCr C8ll3,6r0t.. ? 

c2cl c3 106,6(12)., ? 

c7c2c3ll9,t(ro-. ? 

q, c2 cl 12260(15) . , ? 

c3 c2cl ]]8.2J05)., ? 

c4 c3 c2 120.44(13) , , ? 

c5 ca cl 120,0,(19) . . ? 

or c5 c6120.!(19). ? 

cs c6 c7 120,(2) . . ? 

c2 ct c5 I t9.96(17) . , ? 

or c802l2t.r(r5),, ? 

or cScl 122.2?06)., ? 

(/2c8cr 11126(13)., ? 

crl clocr511832(t6)..? 

clr cl0cl6121.09(13),.? 

crrcrocl6 l20-55(16)..? 

cr5 cl0 o. 70.70(9) , . ? 

cr6cr0osl28.66(r2)..? 

cloclr cr2 r!).3705).. ? 

crocr1Gt2.20(9),, t 

c 12 cl I o. 69,98(9) . . ? 

cr3crzcll r2r.32(15).-? 

cBcr20372.!3(9)-. ? 

clt cl206 71,8(9),, ? 

cl2Cllo.l163(15),.? 

ct2ct3 clt !22lEl6)..? 

cr4cr3cr7 121.0r06),,? 

l.l8

c14 c13 03 70.25(9). . ? 

cl7Cl3 os Itl.lJ03)..? 

cr5 cr4crt 122.16(t6).. ? 

cltCl4Os 72.29(10).. ? 

cll cr,r037r.6{9)., ? 

cr4cl5 clo rm-s(15)..? 

cl3cr7cl8|13.36(l?)..? 

c13 Cr7Cl9 r07.74(19).. ? 

cr3cl7cl9l10.9(2).. ? 

llon_loFion_aron-lil.-loh.l-l 

6id_!ton_dt labd-2 

-3.m 

ls_bid_tu_lic Lncl_3 

-3cm hion-.loh-3ilc-lab.l,4 

lm_hid-siL-tmdY-l 

-3m dion-5i&-sYnm.tY,2 

l!om_toBion_siG,syMety-3 

ls bid_sit_lYm.tr -a 

Cl6Cl0OrCl2ll,59(l?).... ? 

co03Ncr 12620(13)....? 

OrNcl c2 -40.4(t7).. -. ? 

ldn_hbdvl_tu-!ic_lab.l_D 

3.m_hbod_alon_ir_lt!€l-H 

l.on_hbond,iLn-ril._lrb€l-A 

l!.rn-hb.nd-dillm-DH 

-3m hM-dtuE-HA 

lloo_bbond-disu@-DA 

l@ hbond_bgl._DHA 

l$-hbd|d_liE rYnn*,-A 

N HrN Crr 0.87(?)2.77(2r r 5r68{lt 1.5.r(17)2-556 

c15 H15ct20.93 2.92 3-590(18) 12912-557 

_ditth,t@drd t*rior-d.n-@ 0.902 

GilB-dEu-tull 10 33 

-difi_n 

nifiin t@r.d ftdi@-rh.r-tu110 902 

_rcft N did-d6iry-m* 0.a81 

_Efr ne_ditr_dmsily_fr in -0.455 

_Ef nc-ditr-d.Giq-N 0 05 J 

t39

Cry.trlhSr.phichfonmtiotr F .s(CIF3) torConDtctB 

I'rt|_Eqld.drcn'l Appliod o4.!malt,c chmE y 

la_M .sor M. R a $!tru 

rubl @e_lLttr 4.Jt'4dhrtu:@sdd 

jub|.co@ |fr Dhom re:{r:-rr?|]79 

]Du_@ 'dB_nx 

{It dHi..i, EFnirortgti rd..saie.t da 

d.niql_fddh sm CI9 1f25.50 O N2 Ol_25 or 

_dbial_fdhuL rliilr 1054.0{ 

-|Ml}'.-d-di'dsid-ol 

_em q!._d_disdrid 0rs 

c c 0.0033 00016 r,hldond Trbla vot c T*,t6 4.2.6.t hd 6.r.l.a 

H H o 0000 0!000lMridll Tibt6 vot c Tr!t6 {:.5.t Dd 6.r.r.{ 

N X o 0061 0!03r jnbdid.l T.bt6 vot c T.t|6 a.2.6.t rnd 6.r. 13 

o o 0.0106 0.0060 Inhddd Trbl6 vol c Tr!t6 4.2,6,3 rd 6.1.1 4! 

cr cr 0.r434 0 r53J ,rncnlidrl T,btd vot c Tiht.,4,2,6,3 dd 6.1 L4 

-''Mdy'cclgiryF|gond 

srMay_lFEl&up_M._II-M I 4f 

140

stm.dr'-.q!ivls,a-42 

eu-iBu'ld EnFnw2er(2) 

ell_'']..3'l'qM nrE_u!.d ? 

..d|-IE'ffi:6dt-rjn? 

_dd_crni_d*nptd F!4 

os.l-c'':bl-dtrny-M? 

.rr{_ortldtriry_dtnn t.r23 

_.41_sFr.l_ddi9 iah.d nd 'Eu.d 

_4pd_:h3orn_.0.fn.id_n 0.905 

_dpd_.belpr_.o@id T-din 0.143u7 

sd_de.t_ddioi r ox 1.000 

.ad_.bu-n_rc_d..il" 

rBrlins b tc.d@ impldM.d in dE sA.D Bs pcbs. 

: 

dift!-btd-6n!.l@ 2e3(4 

-diftu 

.d is wdaudr 0J1069 

_diftn_ndidjd rrF MoKu 

diltln ndidion-su@ fiFfq! *rl!d r!h. 

dirft '_ndiri6_mcl't!@ 3rrhic 

dinn dM:d.vie-lyF t'lllr 

dfrr_roffi!_n.lod 1* @ 

diltn-dddd-d-f$l-,'ld ll 

dilnn_rddt0_i'lhl_qM ? 

_difft !_6nd..d! i!@rl_ritr ? 

-di'fu-'rnd,d!6y-%? 

t4l

_difirn EfB rv_R_.ldvilsa 0 0375 

_din-. rcni. .v_dsfur/'dr 0.01 9r 

_dift.r EnB finir h dn-26 

_dii*i_rc38-linir h tu26 

_ditln_dB-rinh_k iin,26 

-diit'l-EfB.Iihn-k.lu26 

-diffin 

Ef6_$a_tu 23:9 

_riE_d,Ehdd_.q....id >2'isn{D 

s M: s,lx, Aa Dde bl.a'rjo4 si@ An lrrAl id!1|l'd 

njc',M,di4*r.ffi4us^' 

S.,!NT: s^)q A^. I)dd. hrsnid, sitll4 Andyd..l ilfu. 

rNc. M.diq wied4 usa. 

SAINI: sd, Ar. D@q Ltsdion, sidd ,ln|lrrid itum 

INC,, Madilon, vl&sii, UsA. 

SADAIS: Sid.o tua tj.dd Ab$lDdm cl,@id soit*ft, 

Sn.l4i.l c., l996. Onsitrofcclir3q cftay. 

-@nFdnL@-soludd 

Buri M C,, C$dli, M.. Ciroitrii 8., c|ffi, 

G., 6ir.@, C,, Poliddi. c 

& sFgq L (?00D. r. 

^!rl. crys. . 3., 52.r'5x. 

.odq!inl

_cfir L_widtr&sdE* olc 

'cdc Fr 4v^2^(Fo^2^!10,06 r0Pr2421.50er4 slm F-{ro"z}rr.r"t3 

6m .i@_$ldimlinu] did 

_ed 5i6_!.1{id r6dry dildrD 

_@ id_!.r'bd_hr6.FB sdi 

16r|s|'}db!gjffid'in,d 

_[6ft L_rD._@_d.rik nak ll D (re33), Ad CBi. A3q 3763t1' 

E6rbd.MFrd(-o.r(4 

_a6n. L 'mbd Fni.59m 

Efrn.k'nmbcllm.641o 

E6beh'nhbc.ffirjfug 

_Efr rr *R ndd ifo.r2ft 

k-wR_rd.rj 0.9916 

-rcfim 

-rcfin.lsl@dgs-o'-fr1-'dl'l7l 

-ErE 

k-fifi$-no 0.001 

_lbn_sit_rrrm.try nulriDlicig 

06r o3 0.63$0G) 0.06e53(l) 0.5e1 l0o 0.0re4{2) usi r I d. 

c cr0.63r5(1q0.m439(10)0.6tr(2)0.05lanu.rr l I d... 

or o 0 772(3) 0.t2le(3) 0.324(6) 0.055O) uai I I d... 

o'wo0.51l5(rD{.0?56(10)0l0t0(140.r70(e)ULo0r0 I dP . 

Nr N 0.745r(' aoD(r) 0fe63(7) 0.044(2) uai r l dD.. 

N2N0.649q1)ol3l2(3)0.6760(7)0.0a4)uai I I dD. 

cl c 0.73ee(4) 0.1 Ie(4) 0.x4{e) 0.050(, uoi I I d . . . 

c2c0.6e (ral5ero0.r3e3{400t3(2)urir I d .. 

cl c0.66lel5) 0 r 301.) 0.t!?0(t0) 0.0?2G) uei I I d.. 

HrA H 0.6904 0 1967 0.i6t2 0.037 Uih I I calc R . . 

H3s H0 6163 0.11030.30970337Uis I r .5lc R .. 

c. c 0.62t70) 0.135.{1} 0.1!0(5) 0.07eO) uai I I d a . 

c5 c 017011) o.rt|(.) 0.L77(O 0.12(5) Ir-i I I d c 

H'H0,552!0'l$e0'l]1|0.152!lFl]€lcR.. 

c6 c 0.54o(3) 0.03e0(6) 0,e0eo(3) 0,r43(t) uhi I ' dc.. 

H5 H 0.5013 0.0164 0.9007 0 172 uis l r ..rc R . 

c7 c 0.1676(6) 0 04e(o 0.962r@ o.r4'(7) ud ' r dc.. 

t4l

Hr H 0.5472 0.m02 0.990. 0.169 ue r I oic i . . 

c3 c0.62516)0,052(3)0.975(6)0.16r(9)Udi r I dO., 

tu H 0,6411 0.0?57 l.0r r | 0.202 uis l 1c.r. R.. 

o c 0.6562(r) 0.0e5l(1) 0.e3r3(6) 0.10 (.) udi I tdo . 

ros0.69'0.0e709.2r0r2ruist loicR.. 

cl0 c 0.6eer(1) 0.0or(.) 0.4r4e(t) 0o50G) uuj I I d... 

Hro H 0.699r -1).0341 0 4t39 0.05r uiso I I crlc R . . 

cr c 0.6466(4) 0.03361t 0.16ee(e) 0,055G) uei 1 l d . . 

cr2 c 0.6163{4) 0.D3?({) 0..6313) 0,05 (3) uhj I I d . . . 

crr c 0.6e7(4) 0.1?.q.) 0..74(r) 0.04e(r ud ' rd... 

firrB0.5%r 0.r5r201780.059uilo I I qtcR. 

c 14 c 0.7506(.1) 0.0e63(t 03333(3) 0.050(3) uri I td . 

c15 c 0.7503(4) 0.035r(5) 03el6i3) 0.0rq3) usi I td... 

Hrs s 0.7&o 0.0161 0.5025 0.062 uie I r drc R . . 

cr6 c 0.e30(4) {.00oq4) 0_46o(t0) 0.0630) uei | | d . . . 

rr6a H 0.539r.00r340,rtr40.095 uho r rqrcR., 

cr7 c 0.r.r7(4) 0.r29(6) 0.4e3(e) 0.07r(4) ulr r rd... 

clt c 0.7te4(O 0.1e045) 0.5re2{12) 0.0e3O) uDi I I d . . 

HrsA H 0.710e 0.2035 01691 0.r40uis r r.rrc R., 

Hr38g033{50.20610.12740.t40Uis1 1c,lcR.. 

Hr3CH0,r3l 0.194r0.J7a3 0.l,r0uis I l €rcR.. 

clecal.4(r0.lr3e(r0)0..152{r6)0.17411)ud r I d... 

ti2N?8064r(3)0.r66e(lt065r(4)0.0401?)uilol ldD.. 

srroH0.6te(2)0.r1{r)0.?0qs)0.040(7)uiso r I d D.. 

HlNr tl0.Trl(16)0.06(r)0.71r(t)0.0{q4ui$ I I dD.. 

G2 G 0.311e'{t {.07000{r) 0.76601(3) 0.03er(1 urn I I d . . 

cr2cr 0ffr?700)-0.0055(10)06633(?0.050(7)usi' I d.. 

02 o 0.7333{3) -0ller(r) 0.5rle(6)0,053(2) udi I I c,.. 

Nl N 0.7$qt4.otlnt0er6(4001J(D !fl I I dD.. 

M N 0.1516{r) { rr12{t 03Nr t{r 0.04{2) ubj I ldD. 

c24 c 0.7617(3) i.r 16r{0 0.5er(e} 0.0.5(?) uai I ld .. 

c2l c 0.323?lt 4.r 335(3) 0.5e.45) 0.047rir3) umi I r d . . . 

ml H0 3.139-01r310J4920.057Uie 1 I elc R. . 

c?2 c 0..33q1) -0.te6.(t) 0.54e5(e) 0.07(t usj I I d.,. 

H2,rrH0.lr05]t.rg?l0.a9r90.015 Uie I I olcR.. 

Hz1BHo.tt?|{2AaojcL0.0c5Uisl loLR.. 

c2rc0D2?G){?14414)0.526r(6)00e(1)uri I t dc. 

c14c0.e25(t{.ll0l(4)0.4706(3)0 )9r{rr)udi | | dc.. 

cr5 c 0.er07(r) {.re57(6) 0 4eqr 0) 0,r(2) ud I l da.. 

ri25 H r,002r i r27 0.a rr2 o.ler ui!. r r Elc R . . 

c26 c I 0ot(3) .0.2.n(6) 0..t 4{r0) 0.lero r) U,i I I d G 

I]25Hr.0396ir56a0.47040l3rUi$l lel.R. 

c27 c 0,969{4) n.27ee(4) 0.5403(3) 0 Da1nUd r r dc.. 

m7Ho.93a?4.3133 0.56360.166Ui5 I I €rcR.. 

c2r c 0.el.e(4) { 2643(r) 0j6r(4 0.r r3(o rbi r r d a 

c2ec0mqt{.007s(1)0374(r)0.056(3)ufli I I d .. 

E9H0.N0t1 0.03150 3635 0.063Uko I l.,lcR .

c30 c 0.756r(t {.035(.)0.r6.4qe)0 06r(, udi | | d. . 

H30 H 0,7230 .0.0r 53 0.3541 0 073 Uiro I I .nc R . 

c3l c 0.75J6(t .0.0e6r(4) 0,37 l0(e) 0 r5a1t uri I I d... 

ca2 c 0.3010) { r?3 (4) 0ir63(o 0,056(3) u$i l r d . 

c13 c 0.3515(1) { 0e?1{1) 0.3c55(r) 0.0rq, uuj r l d . 

Hr3 B 0.1913 i.r r r4 0.904.4 0.060 uiio I r €]cR . 

c]4c0.35r(ti.03r7(4)0.3err(00.0,1r)u&i r I d... 

c5 c o.er 16() i.mro 0re5i(' D 0.0r(4) uui I I d . 

ca6 c 0.7006(t { 1264(3) d.35r7( lo) 0 073(4) uDi r 

ctc0.7076(t{.1e01t0.343e(14)0.0e6(l)uei | | d... 

cIc0.6610().0 rrr9(7)0e4r?.(14)0 r:rrDLrsi I Ld 

Hl3^H0Ot6{ rrr009lMo.traUihI I€hr . 

Hrrc H 0.d7u 4.133t 0.9rr 0.13a !i$ I t qlc R . . 

HrN3 X 0.71r207) 4,066(3) 0 632(r) 0.04(7) Di$ r I d D.. 

HrN4 H 0.r3r.407) -0.r r 13) 0.6600) 0.040{n uis r r dD.. 

H2N4 H 0.16(1 4.16q2) 0.725(4) 0n.q7) uiso I I dD.. 

orl 0$3(4) 0or50(4) 0,0lae(6) 0 002(0 { 0032(4) 0,0o4rc) 

o r 0.050q r ) 0.04030 2) 0.0620(1e) 0.00170 3) 0.001?0 3) 4.0.311 l0) 

or 0or7(! 0.0621,! 0.076{n 4.0r?{r) 4.02e(t 4.006(, 

Nr o.0r(.) 0n50(5) 0.052{6) 0.007(5) {.0r0(4) 0.0or11) 

rE 0.0440 0.034{4) 0 053(6) 4.0{40 0.m4(t) 0.mt(3) 

c r 0 040(5) 0.042(5) 0,06r(7) -0.003(5) .0n8(5 ) -0.00e{r) 

c, 0.047(.) 0.036(4) 0.07qo -0.00e(4) {,0041) 4.004t 

cr 0.070(6) 0.05(6) 0.0e0(e) .oj]?{o a.0r3(6) 0.0r0(t 

cl 0.07{n 0.03eo a06e(5) 4 0240 oi't(t 4.m16) 

c5 0.0e6(r0) 0.r30(r t 0. r01r0) -0.0fl 0 D 0.0r(3) {.0r (r 0) 

c5 0.1270 2) 0 22(2) 0Or2(r0) 4 0?qr r ) 0.047(e) -0.0r1(r3) 

c7 0.112( r4) 0 134{r 7) 0.016{10) .0.0r 5(r0) 0.064{10) .0.074114) 

c3 0.34(3) 0.0er(10) 0.077(e) o 02(3) 0.01004) 0 00q r4) 

cr 0.r?0(r0) 0 0,031r) i.0.r(7) 0.0047) 0.016(r) 

cro 0 063(6) 0.05r(o '0r(e) 0.03r{o {.00\5) 0.m4(5) 0.0ltr} 

cI 0.042(t 0.064(7) 0.05no {.006(6) i.0r15) 0.002(t 

c1? 0.0q6) 0 047(6) 0 050(3) 0 00r(r) -0 00(61 03116) 

cr3 0.06r(6) 0.043(t 0o3e(6) 0.00e(r) {.006(51 -0.004t 

c14 o.0.qr) 0.074{7) 0.0r4{o 0.00q5) 0.006(4) {.0r3(r) 

crs 0.0,r2{t 0.o71o) 0.0.10(4 i.003(t 0.m2(.) 0.00r(t 

cr6 0.06l(6) 0.043(' 0.07(e) {.0r 6(6).0104{6) 0.0r (t 

cl7 0.0r (6) 0.r0(e) 0.060(e) 0.005(4 0.0046) { 037(6) 

145

c r3 0. r00l9r 0 03E9r 0 o92{t rJ 0 6l(9) 4.02(9) {.lx2n 

cre0.0ez ta:q?)0 l7(r,4.06]{19,0.0?di1; jmir;, 

Gr 0.0r7qo 0 ovq.) 0.0.6r(o 0.00?et4 | {.00rri4r o mi? L 

;i f #i11'i;: l'!fr illfjil:ll $%*li f ,ggTj,, ". **' " 

xr o.orzl o.ootrr o.orqo aoorro o.ooqo o.ooerir 

v o.or

t47

le_&3h_#.r@y-t 

_lr.m-dd.-ft_rrfrey 3 

l,a

t49

l@_Eid_e,tE_lrbd_l 

ldn_6io_@-3ic-Lhd 2 

le baid-6-dc-Lbcl-3 

150

ls_hid_M_siF_hb.r_a 

ls_bnr_d! .y.!6y I 

l4_bim_jE .ynn6t-2 

l@-djm-!ie-s}nil&y_3 

ler_6id_d._rinMy 4 

c16c'l orl o1 20.(r.. .. ? 

c35 C34 Or2 cI2 -21.5(9) . . . ? 

ls-hbdd-@ !ib-rrb..l-D 

ls_hled_@ ,nb-bld-H 

lM-bbdd-ltb-3ynn.'y.A 

Nl HrNl cl2 0.e6(2) 2,65(1) 3.490(r) 147(5) . 

rr ErNr ol 0-e6(4 2rq3) r]rr(9 r6qo , 

c29 ro9 or 093 2.52 t.aa{12) 1596 - 

cr0H10020.932.473,3r703) 153.6. 

N2 n2N? or 0,9!{4 l.r$) at6(l l) l6q4 3-554 

N. rEN4 o' 0.9(4 rrlt2 ..ql l) l6{q.-655 

_dfitn_o@&d-ftdi6-d'@ ts ln00 

-dfin_rltn-dd-fill 2319 

-diftn_trl*r.d 

nrdd-dd tul l-000 

_cnm_drfi-dr!fr y-d 0,909 

_F F_djtr .Ldty-hit 4 306 

ndr-difi-dajly d ort 

I

Conclusion 

PEDadion dd @npl.le €hd.cldiation of uino @ids conplex€s with the. 

g?.s of cdplqing €ag.nt$ (i) E-4drxyqnidldine (iD cholcsi@l &d (iiD 

Tdsition m.ut {cmi@ II) wE 6i€d out involving dlr. $ud Nsisted eneigv al 

60-?0'c, in th@ ptils. I'lE ch@ct rizltion oflh€ Papared odpouds m cdied oul 

by sp@troscopic (NM& Fr-lR and fl@@o@} CHNS' d6s sp@tDn'llic dd 

th€ftal dalysis t6hDqu4. Amino &ids (6Ptrtic acid. elut{tri. acid, c}dcine 4d 

sinc) @DDl.x$ of 2-methyl_8-hydoxyquinoline *.rc pEPsd bv a nev on€ sl€p 

Dedod. follovt

Puhtrieations

Re5earah Artide 

Synthesis, structure determination and 

ciemoselective catalytic studies of amino acids 

complexes of osmium(ll) 

Raia A. Sai{r!z", T.sneem G. X lr, Shahld lqb.lb, Hr$an l. Afrldl', 

M;h.mnadKJrm.lir u3r.lJ.lb.nir dM.8.Ar.in' 

ft Midh r{6tumAdrk{ddrLfr k lo4t6dr'f'u1{+"ttoryrtb

^|!6fu!d6l.d#rso|'qs(hicsb!4hm 

t ;;;;!;;;;. ?5., '." 

ri:i.s;#fJ"l: ; Tfl?r'::J;ji':"x tl*"r;;T:J l;:r."-ri;'j:"':l'jT; 

*"iii#rrdv,.mn,r, *'d.*dknq oskds a' - o or' cffi ' G4 M nte'q *' @ i 

ffi Lffi tr;l':*-* o"u - yH;: fr #ifff#ffi Trr jry:i1i 

04-|M r--o'4rr4d'- @l' -:1: 

'e'.r ronorth.o{r)cdDr.!.' :l1tTf[,:"^,Hy.lT,r"X.:..1: 

ro{rc,.qnd) {arx{r)trr) (A) h $e urNcx pxt4e rrr bidretk d stteoe{ Fchqs5 

nry*,ff mi:+s*ry**'ft ###;"HS5Fi#"LdfI 

:#".:"i*"JJffia{'il:l:1x#.il"l.n #"g,T'#T"'";T# 11illn'; 

:'"*H,v,I-itr*$*xY,l:"1rflfl: ;; ;;;.L',J* d f' c."-* c"rh"-i 

t a*'1ra :"';; ;T:lf;:':,ftf :::;l'S#"i11Jl'"i:: 

*ffi'#fi tr'sitrilifiij'tr *'infit;"ffi"'::tri;n':1f ;il 

:';T,1ll$'"'i",f;:.il:"%"i'1';;1-;"fi s;';-';y.;;r.".i:.T":î".T,:.:i'"'J[ 

; Hil#]1,ir",#,TFig*.,,,*ii f,fl,rm :T.*..*tttr:;lr:lrtr, 

#**$tt-'*i$,ffiE ii* g;E;*69*n:r'";":t-:rr 

loc$r3!6,lrlN,/vsKltrz&o t'l 

^rqdi or I ! nq (o 6 mno I or Hu'Hc 

d iB,ok *" d"d*d. rod d " 

tun ti t mLJ d lo!&{rmro,} o 

-*fuI5'cobdi'4l'wltsllffioyfl|(^G 

Hlftilr:i*'r"n1 :fl 'nl"*'r,'s'.'l;$ 

r r- = T Nn rs G, lrtdftro rrs = T rin r @B H Nh, 

u i-i r. rx og*t. x t^ u o.i r 

r:: i1 Lx !1fl,it. 5;.1rfl :i 11"".fi ;fr 

;rzr@ln,H.Pr + NBr, .r- d"l 

ffi. lf ;il$]1iL'i 3i.-trT#'i; 1'ffi 

*'i":?'H# "* ;J:'i#^s.T.*:-:::l: 

ll{ht@{&rdtlldn'v:c 

(rylr! u&b*brbrd 

r#trfl+:l :i *fl #Ylllff;"H"tr: 

tr:#*l:**T,ffi:lffiil:il; 

T*'jilr*:*::'J'#."'*.:f;:H:il:l-TT"T" 

Hffi :lJ f ','tr* l"E.lfi :ilf lJ*;:; 

ffi':#'"H'#dHi:#H#x*iT 

*ri:Jfr :H.ll'#y"'l*?dr",..,"''.,",,.,, 

Htr*#rffi,:flSex"lH*l 

ro*+tlff ig*fillffi ','ft --{'*i 

"#''.TiiH:H3'1":ffi1'" Hu rcdro wnt 

t6!]@Kr,L e 6. eft ror 'e 6 

+"tory-*,acmmupr:

H 

lrhm!]lJlor^ft!@pbn@'Ls 

; *dr*.a.,..rd-. tu rrg,d *id6 " "*"-" 

ttl1e'bd|4b*rd'E4hdlftid.Il4 

*i66ffih.d'e60..6 

Hd ;d.arq dddi, h tu mdodqd 

q iiiid&4d ft eas*or m@ffi nY. 

-,;d"*,. r, P," rrr-d ,h" '"" db 

}:tr"l*"tril,ffiT ilI'f'r#::s# 

-#H*15'}1[i :TH:H:j' Jl'#'* 

#':ff;*H:l#1$ffif ni.trtr; 

b! d'Ed s (dfrlusd d $! {rce'n' dtui dF 

;i:T:fl f lliiili#5f,fi #::#sll:.ffi ; 

tunmuE.6tuoj.drdd&Fd.@ 

'|'vnl'fuclF4fun'e6Fd|fikbp€t@ 

ffiHd#*,d&{ll1#i'i#r 

cldotL

MgH.."-. 

ffiffiijl#' #{trffi 

iH3 s*'Ti,-:):r?"ff lli: Lr#',] jli:'i* 

'iriah' Nn ontd 6 bY e.P*t 

ffiff*imi{*r#l,*tri 

iffiffiiifffi 

-i*,a"ry o g* *"'Fd"g tu"w ft*' -- 

;tuntu Eecd b sr:nd l.* 15%' ii 

"- 

rd rr i r:d. ll & odk 4t 

'9id5 

*r'{.-i-(.*'br.-n*-'h* 

O 

t4 

5.*i#.lffi f"fl ;f.*r"ili, fi XtrJ: 

ffiffiffiffiffi 

',lJ'ffiH':m:#;** 

onn6d.df|l'dqn'.Biands6n.'rMd' 

--+-;i ffiro 

iffiffi i*T#lip.#{.*:'fl ,i-T 

tqpsto:ohsE"rs-' ua 

^laoq-^'aaouwo:

him Fdsdtrlc of onnrfi0 

19 

ffi 

ffi#ffffiffi 

illitlit#ffi'ffia'i#j 

*ffi 

,'toa--do-d2'dlo fficuowsanta Fm*alkr.".4""*v.e

fubi@obdn d t odd.dd orqdoFsn.(.! d 

;;"d'.d!6t-d"od'r'."4'.'e.*nbto-,*' 

id 6nrh 6r ws rdmd $d nav.ohFe*hh & suttn:c 

ft ddqm obtr 6L rtu 

^ ! q stric . nqhF d 

G*|*€doi!6ib!F'dmddigtr'*db|y'w 

idb$ddddyoi:dMv.ros.b6t 

e'6nim.4bMbd@ndFl'@ftltly 

dbl&lvdqNili'|.dlfud&,knwdd 

k6s b dtrk ll.ohdr s lud ai dd 

w!'dll.@'(Md

Sy'nthesis and X-Ray Structural Studies of Amino 

Acids Half Sandwich Complexes of Osmium(Il) 

R'j! ^d s^R!R zi ft....E c x^zl, sbbid !QB^L. s.ru ldu ^}RIDI, 

Mob@.d X, JAM LI. Nmrt JAI,B]|j{I ed Moh.Mt Bilrl RÎN 

Ne6.t Ce ol E drM $ A$\ha! C'@!rry, U$BA| ot Sin,]r, 

Jmte,76030, PAI(iS?AN 

. Nit: d@dt]lartuastuit @n 

ftc ere &d 6hpld..f Gdultr), i.q lor(rcPcttut(tt N_(!&) perytld E hvr 

d6rcu (^) d l6("dl,

Enecl ofultrrsound Agititios or the Rel€rse oflle€vy ELmentJ 

ir Cenifed Referenca Materi.sl of Hum.! Ealr (CnM BCR 397) 

tuf,sl@.dturotu 

!ie'!yds64,c.fEdlFn^dndch'!l|lfu?60'0'Mfu 

And'ld|osNbd|*il.gl.!dd.s. 

lh/tbdft'lt.|'..,llioic|By..'m| 

oroicd,6,rntr)hdfi'*rrs 

flb3.r iuM E{crtr 33l) 

rh. c.muriy aumu.l tu4 €el dtu 

'|!€ tun 

cobn.l li6nF.r cdu!ry. 

cdEedi|,1....r8h!d!..Fe 

n. rl E rrd frr h r-lr[€ riar.d. rn. 

.n.o'o|dil.Mh.bad*|dhlnhgo| 

d.ldlr rlc|. F4i.&.r nrl*d 

urloilc.ttrElEi.bttc@'nhb 

hh.nhv.!edd.ol.6hnli.o'!E 

ifr.ror or hdv i*{. ns cir Eci rt ri 

hun|iEbhjr.4|i.riqfilh.!lyfu 

rociekb! [ndrydrr teld.dtr fi.d!.d 

dddS-hn drd'g'!.db.bhd 

&!d6d'td.i |iGfilEf, s'd *:b 

hrr..'rp* cu d a h bd'- rd di!-bvd 

d!.N5ri8{brnrtr..& 

d,dPa6d-tu!'ad!tud 

Mr.u#.p.o*v w-opw 

dtrld.d.'tgdbz4cdtB'^4dcu 

E.a. rr tr !0e d.5tl tt frrr'd 

t*.d..drn'..t .cdit'd6id'.d 

=-G-;ffir!.ffi#E-E 

lMr@.ffii"dFtub'i6e 

I hr dc od'.bor F"w. ui a M d tu 

-tu- tu $dd bE b mhd tr 

si.s'cr,'ld&diFdidros 

hi*dffiibdlFd!bd 

Idh|dogd,!iB 

lElGecddt.nlbcdlqdd. 

J;d ffi eEh FEq (nd), 

sh3 dDr. @di fiqiq 64d b tu! d 

b-dkendrîdbdlhme 

dr).ir tu & iffi 

ti4irt h Ftu 

.r ld r, s i!.hd 'isb dird6 de eb.r 

!d.rd{b!b4Ei*6qdIG(2I 

Hoffi. tu tltnrF; oa tue.red ot 

dspbrb|Ffu!u!rcd!]!e|@b 

s|.d.l&Fdtdle!!.'dEd| 

e o E6r 

@d!oby&xd$duddahfud ''doFd 

&E'd6ord4!hllnb'iFkrafu 

lfu*Ed{ddqsdPdc&tP1J 

bl tu bddd ffiEjrt tu bb u 4rq d 

Mdlne'rlrdardn.!d.6r'6 

{'rrq & i!! id M d iistu sd q'i. 

tuftr@tuL@!{dod@@@ 

'.dim 

ddoiddrdld!6blncddBflE. 

d|Fnd*E6&b!@Fho 

u-d co oI a rflhdd!!q& m&!*v! 

.no.i!!dqbb4declqdbi 

fuoflldLl@ui'qdpbd 

tuid3@tu&tar$dtu 

&lbrD&q|

cryidr o rryk r tur tulP. M 

Issn m$'0l0 rii'/r9ra drb 

D.i€rmin|tion of Todc EleD€nb h Mulcle 

Tissucs of Fivc ltlb Sp€ti€8 Uslng 

Ultrasound-Asslsl€d Ps€dodg€6tion by 

Ehcrmthermtl At ntc AbaorPdon 

Specrrophotonetry: Opttmizdion StldJ 

MotoDrd 3. A16, T.eo G' IOd, 

Mded.d r J.r.l! fiEd J oi, {-! l- lrrHl 

rrt. a- sr'lna rd Abdol O sh.n 

c.i6olEsdhiihdyndoEliq'U'ioilyofsid' 

Afu:AnDd.dn'idtr'fuL&d 

6brekdso'itfufthsb!yoJbd|li$dF'eF 

hrusDl^n|efuArl,d 

"-;it, ,@ s oi.ron '* (sD $Dr 

m oflrbloc t.i m, itii id (^tr d 'd:r ddd d tu (^2) i,E 

e&Er@dJsDbtuse 

4|] uod'ooprt&!s 

d;br d$ddd EM ..!d Dou: @odd' e! 

..ndktdtud rdr*Etu'r'dhvcrFitrdd€dc'r 

ddil!!ffir'EoM'nrort*ooj 

qFdtrgxi!fuljafuEdby0xFoFldUsDifud.dtddj 

dMd;d(ctl @d.€'.ft 

k.isd,cbb2006'ec*dl]1trr0 .ffi.flr4|fuhdyu 

r*fuEDiEr''cy@

original adicle 

Datalmlnation of lelenlum oontc l 

sblbld I{t lrt T@ Gul xrd,: uheDd r4h€l Bn !€a': Mubem rlthul & R{r Adll s&tuzr 

1M;d 'Md(!t$'!@dnada9!4dL4|cfu 

G- db.i.*. hnB o 

t tod t o.e tu lcctt 5 p@t6' ta tu) 

t loct.d P.kr.tlnl food. 

aumE turc b iBgEd ..Il€n etiium (9) lod3' rh' 't@dd 

' orb; s.@o6tcrso i, $. rdort.sb tk dlF M *!dlEni 

EiLd|W6{ldqa!H,n|!d..dd,dildi|kP'io'diMi 

..,iJ r, r"i.i, * -""" ". t" 

; N.d r-d, * -'*.it *i ' 

dibb ror TsC ii P*nrd iddt 

l.'sc.di'i&|d!|d 

S.l.truo (S.) B D *id'l lre.Lm.n' 'q!rd d 

nrll |ldnB bv uiErt ,nd bdftn! ror h! M( 

rwhB or liJi ud irnno. S. ba b€! dp.d c . 

EFr ru*ids' *t dffiq guboF Pa' 

;{de *hrhonkol.rheo\iddioi pl@ d aDuru 

L€L (Coho & Aqt!, re94. sund., r99.) b! rcaeng 

l'dhydtoFdid.@b|dp..@gbo|olE 

m' s.l.nooror.nr .nd o'hd s. f,.ubtB htv. 

be@ FNj! osos ,o 'har qul bk i' iroG 

totuL 'ir.i!E.rc or rdl', rd tdw Fc 

dusder.fi* (tuYnrd, :000) 

iiobd r tlill in 

;Ln.mE 6 hft b@ idauLd d& (RrYm 

zooo|'fulfuNo[l'q6d.D6d6toit'idqiLLi! 

'i0 

",illlTLil,ll;",'-**-.,"""..."*. 

- bdi'n. *hit d.6o.B or s. hr bcD rood b b 

.*6aEd *iri r.uhbdordst., iftludi4 rdbd 

d'n! 4 4r r934r 4Mr (Clr* z 4r, ls6) a'dro 

"*iu d'** d,rd':r.' oI. reri). ririr di-* 

'Bd&krud('|991'Tly|olda]'|9cn.infu. 

;non @idroE 

Hrv ;d6ror rHolh & sdtr, 199\' * MbY 

Eur.Ei Utoi @uLi6 bE ilfd.d rd i!!G 

dnr tudiod or e @ib' 'n roodr ir 'n. b r ,sn. 

Eturu!! n ur 'formnuo&d dr*s (anhu & 

Ne, 1996J 38.d m d* r.D.a D-iY omo'r 

b,sMbdil.dMlomFexdunlq 

rood! b rd4q I fdLa. 6 .iop6 rid 

bv Fiinc md npshr s+n.h '3truxunl r.ddt (Robdrn 

lt3t s. E pr4n' iD,Pt'tdbk uous s M.rcnr 

ro.& LL cmrda qona qurF aruq nuE 

fruu'full(Arudr/d'1006'Mcxrugh'on&Ma'r5' 

- 

;; d"q :rbn* (RDA' tloM 

20001 td -'u''a.d s. L tl tsg F drv for rdul Ir'. mirmum v 

@D;nutm, ruY b. dridrd molcn b 

"b.b l0_?0 4 F dry rb' a 

!Md.d !ry G6m4 Adi! squ 'du! N!h' 

'nd 

uon Asdrud, (RdNd lrhd f Ndrio' huk. 

loltr *hlc mDdb hc]. L{l klr ,ddtr tr *r r 

.e r F (l|v (loM. 106) A! tu rD& M 

nrftd lRaEr[ !000), n 'u$.t! ri. nPontr' oI 

|Mr d@irbo or TsC in food emthr lMrhr 

dh ., ,l , l00l) Md EU ddF hE * odrY 

ifflt b.lor RDA 8!'d.lins rh. @r rolor 6r v h 

B 6D'u tr 4u'.d to ekul.L rb. dtiv @B 

i^D[. err @6m.dhg drilY dtu4 @c. 

deE dr4 d rlr e6g'rPhd odtn (?ddia r00rr' 

obnB $d e. rcnudlkd bv biLrcmpqion nd ph 

irodye a c/., romr s.r.'M s'i.hh pll$' d bO 

Fdm f..& i. .eg3, MB (tuF d c/ rF

ffi 

ETSEVIER 

Av.]|'bbonh.n0w'sh€d|tsddn 

:;' scienceDire€t 

Distribution of zinc, copper and iron in biological samples of Pakistani 

myocqrdial infarction (ls! 2nd atrd 3rd heart attack) Patients and controls 

ferm Cul KM r', Hass Lds Atdi'. Naved Ku h, Vohdonad Khs lmli 

Mobmnad Bil.t AFi!', Raja Adil sarfie'. Nlet Jdb&i ', Rlhe Ansi 

Atdul Qadir Shrh', At .q-u- Rclll@ Mqe!', Gbuld Abta (!ttdl@ ' 

allr€bb.i)d6.tq6n& 

.*1.^r,."1-i'*""r*'bt*'o @dtsqbbq6kddEd 

mdd! d (r4 @d d 6d k rd$, 

ir,u,ri'tit"r-rqa*m tmMFds("dd.t'rrdc6EFarer)d'1 Hdvg.*rd*bB 

uobdqr4r.,E!,tldbvdh 

;tu* *d;hd- ft or & 

""*! 'dtr 

i'6odw E 6&! bv e hb'd 

!.-dc"; *ib o.$\d'r! 

-eft"lddi.lldb=od 

c-ll* o*qlr*utooMEsldsv^niduBdd 

^dnqt!Fq@ 

ei6 lrl. r1'. dddorrMt of rddKko!6 &Fd otr I 

bd.E bdag p(cidl|mrbry limll uditl'Dbq 

Jld |eild iHaE dhhic I1l. rE tut e 

b.iig tuai,'lly @Fird a .ldd dnjlh of $. 

lcurt ds. (cD) 

ahhgn rbd ir d !dg{y . dn* 

Aip bdwa d. &fhFE orcvD 8d E dd6b 

r@, h is lsprlyblia.n dd 9ft of'lh (or ! FOm 

vrtuo'i heabjd!$!m { 4d 

de&hnqk-akus'.6RG 

FotMlry, rlE ell po!!.g bisl'tv .raEiht pddE 

Eh6is iEludiis rditrillB *b a c-rGtbl 

crh@ 9@, slutrdi4 ild drr_btu3 tot63 

3u.h c ttud.nia .dloPladid t 

dlsE.s ruDoand. dnh!6. (MisoD), coprFzinc 

r@td. dj!I]& lcFzdoDl *l.E?r 3hdspm 

@i,c& (GSH-P:) in i@!i'nis ry qd& I4l 

^Dli*ndlbi'di4nlioidmcd 

*cullle or rE ndr.d.iiducd iijry 

dilHol.ffi'lbh€r4I.dd 

Ellid dv t d*b.hd *a 

ft.djd iijry dy Et (51. wto r 

rln odE $bdm. ! d* ,i! of inhry 

dn bk d 6.!$oDeI! dise 16l 

" 

"

a 

E 

I 

a 

i 

I 

a'i'c.'i.ot e E*dtu t c,'n,,a, od.-D.c 2ooq sa(.), d*r2 oltlg 

The corrclation oftotal and erlfact ble h..vv Betar! 

from 6oil .ad domesdc s€wage tludg€ and rh€ii 

trar3f.r to matz. (zea ,nsi,s L.) Prants 

I\d I' JA.I\,!AU, T. G. KAZII M. B' ARAIN' II' I' AFRID!, 

N- JAI.BANI, & R S. ADIL 

Nr*n t ctu r! F'.!xlM n A/$..t ct@i'ry s' u"'En\t tMhdl' M'@ 

(Raiua 6 fdjivry 2.,4 F;ea zs tpa zdb h f'dka 22 1s m) 

i?-Ji '".*"a 

t. -uL" -a nn@ orbsw "*! ciMr tu$ 

;i:;;;F; -;;* *;d -' n bd "d dn-'dn-i'".*t.g 

dffi;;;;;H,!r,;;*,,t.d 

L-Jiit" ui'i.- t *o ;t dr u mqi rd Plr nudn 

'*ob& "* ni'd dt Pd 

:Jl#J"J'."r"-*.",avu*,edt'M,.@l*s*'d.eD"d 

ffitrffis#ffiffiTsH, 

iGilfi *ii'a*; ;"*i u* & 6n' M o'-cu cd rd M'.r* 

ffiti. ii-"-..'r,a..a* 

^r 

**Ji J ti u co ru.at* rd d n.i,! pb!! Gtrr) tud d p*to 

ilfrii#;" "a :ron.ucac"L'"dc@-?o' 'dtd 3r'' 

i'iiiii r .,c..jr*??. -a d::{pats " wi'd'' 

i,.iiili*1"- i.;';.-t eut *.* d b't 46d-Dws-rd"'d' '*" n @n@ $d 

,-- lJJ- a i.r- .*. m "'* 

(@dn tu4 Laas, ar, rat. |da 4t'4n44h tuq ntu' d4to tus 

T!. rDDlouon or wB ddi. (blooldr ro FruhEl )md ha b'coe omnon 

;-ad 

' 

Rqcl,!. oI48 duds b lgrdlDr rrtrd R 

".-.;"1'* 'r'. p.. Giiyi-J*;;u.-"p-*u. '; -*d.po*xo-.,r,'et- 

, :f.;-tr**r.l";":n$;ffi1ffiffi'*"*

ELSEVIER 

Etratugtion of statur of to:dc metals in biolotical Bampler 

of diabetes mellih|e paticntg 

Ha!!d hran Afidi", Ta3n.n cut kzi'r, Nau€€d xdzi t1, 

r,4hMtuil r'an ta,,iali", tul,nD't,d Md Arait', 

Nsot roDani',,.n d Alnld laig', raid Adi S.tdr' 

r!.dd tu ltdh 6 turtddl cirurr lhllmt 45h4 /.,&q 7e!0. hr@! 

!!4u 6tu'dyd&i.d !/ kds4hbqllrd 

fo6thi@b.!!&4@ 

Dd4&bl'datr'adl'lnE(!@dy 

desh.d|ddb.:!ct@lrd!dtF2 

fuidldd{&dfu'.ffi 

&bl&ddrbDfurdcihs&eb&rd4dd 

.hd, kd (!b),.tu (dt ri |!t.r (t) h @qd ruPb {v* &d 

unsddrb)dFbMr.l|etuFrsdFdB*q0!-!o 

ded+ll|fuEdj&d@rllddjdh.tirdstd4 b' ea d ! rd re+bd 

rdddFdfudd'dd|@nq 

!! .']rd !' do6tu * dd d!E6 al.d d !d4el@ ntu! 

vdsd6dE4'@.jo!6on!y 

Bdsbdrhq. d@ d @{tuhdffi Ftur MFdb 

lqd'rt-!(r

ffi 

EI,SEVIER 

':;;'sci",tceDirec Earardour 

trdat.riak 

Hazadous impact of toxic metals on tobacco leaves 

grown in contaminated soil by ultrasonic assisted 

pseudo-digestion: Multivaria@ stldy 

Mobromad B.lal Anin. T6ncn Gul K&i I, MobMad Khstr Jan li, 

Nu!i. Ialbali. Hrls Inm Afridi. Ghulm Atta KtldhD, 

R!hr@ Arsi, nlb Adil $tte 

drd,fu',@^b 

!w@+n6wd 

tubs(.{ndh@@ L).r/.uu'r$[drdtuff trdcl€s!.brcdlddrru!,006{dd}d 

@.ErAj'^@9&dfuFtdtEruldlqd6i9l4 

eE-b;,r*b-qtubdKdFdiFtu 

d!.d/'jFm 

@.'e-*qdbroudednuds' 

êtdtu'FtudnFer 

".i;..dMetustutu*de 

d e;.d d&'@d !r 

"-tuldb 

""d 

.,ldbrdFq 

Er!'rd dil..s dii|& 6m s. hioroiqr d- 

4.lB ot ini|]sdd apom b MmB dc 

(diMtinciPsj!.lq*|'.he'r.ddbypyBy.' 

'@Fr 

dshdrharldtui.ldhlsn4Toa.@@r.bd. 

s.tl@i, nuE!.nic 6d .nin !.'nc 

adtli ol6heco dot n s BEtrd 

n ni. hioroict d d'd'iar *d rohism d d d 

Ihraidit'G@n.d$n'o...dnfI'@n''.&P 

@le atud'ctrk&r^nirrdd 

''.r.nB tt.a l1cd 

Mdl .r0y pftF$i.d, h! r iilh h 

hlF@d,4 sility b dtur e'mrr. dd blfu 

bln kr* o.haq 'dls ft6 sr5Il al Incadr&s' 

@cofsl.hr.,ntii.igecddd 

suidlc&oraiMt turl5l. 

ltu'letoft..qd.lliid&.tHgk*b 

g'ff ii ul6nmii&d $$ bq!1 md orl's ruin' 

plt"ci*10fu!oilEH.|'.lvlcbl 

fadlbd4''li.dbcq,Tdj.dd 

cN& d.l&'is.nd dE ro inhal.to 

rfrm dE iu6dd.rftlis udqddk gfln t @trlm' 

urd iil! x w irBidy i,r.qqn d rht of nu.rt 

'4.r. by Drnr &p6& oi rh. ph$iHbadc 

lFcir. od bil t6,?l Ii B b@ lorog tu r fd d6rde 

6'fuo!b,dBdEld4td 

cudd6dfL4!@}o&lb!: 

d I3l ldt€i smok'

vs&nEîi@Hd4drHd!, iLrt 

Evrluation of toxic mctals in biological samples (scdp hair, blood 

and urine) of ste€l mill workerc by electrothermrl atomic ab6orptioo 

spectronetry 

Hasen I ffndi TrIlren O Xri, Moh.Dbad K J.@[. Gln H Xri, Mob.fun d B Ahin, 

Nurd Jarbmi Ghdd Q She dd R.i. A Sarfar 

can4 of Ewthno b tnottiat ctffiitry Lhivtut ol sir',dj', tMk,o 76434, Pdkhlu 

rh. ddmidnion of roric ndalr in ![c bioropel aopld dr hm.n b.i43 n In eldd d'nsl 

crhint prcdm Thi! nudy aiftd ro rs* rh. posibh i.n')re or.trwo 

prtddlon ft'14 (pw) .!d qudiry 6!10l wkai (QcD oI a lcr oi! .n DL rbrd 4d 

srdhtic or Pb. Cd. Ni dd Cr 

biolqi€l rddd (bl@d. udiftil slp h,ir .npht fmb rld naddl.wft^ id rbtion ro 

@n6k-d u&ipo*d h.arrhy sbid! oath. nne is. sbu!. aftd ?FiErmd *ith nirft dd 

hldms! Fuidq rb. snpr6 ftc dtdtd ur . d**e. o\,.{, rd ror .MPesr Purtdcr 

s:* rnd6 e.c dissr.d by rb. @lqnod s rid djFrid d6od. Tb. sd6 dir6td 

{d $bjdLd b 3nrbiG furc dffi .!oario! lrdlmdy (aFAAs). 

'n 

i mtidl r&84 $ch & dfuion lini(t, slib'.rioD 

rans(t, .ef,cy lnd rdisid', wn ludi.d Qurli'y @nrnt foi th.$ pr.c.d 

wirb €dii.d hpl! ot [llJM hii( udne bd vh.l. blmd. Th. rsdt indi{k rbar th. l.wr of 

lad, .Dd nrLl i! elD h.i( blood da Uin. ':dhiu 

sDLt trd nFi6.dly bjshd in b.tr' 

sDlF or aFs€d s*di (Qw .nd rW tl& rhc .i ln. on@h Tt p6sibl. omdiotr or 

rbs .Lh6B pith rb. dioroe ofdi$ ir di$a.d. Tb. rl!6 lhd rh. 

inpmwtuits iD {orkphe vdtildioi ud Ddulnd h}Eem 'el6 p'rdi6 % 

(q dk ottu obntptba qd@@r; btood: drct wph\ xdt 

Hd.n bion nilodlg for bnc n r,is F rinuBro 

@iw@osid.nt'hstrmton$ tn .fionb adue 

rhc uiccrilirrt ir hellh risl as*sne inc@ss. 

Tt. pdDry so.l of bidonnod!8 nudid E ro 

.v.lur. huMn *pos& by cdprring lhc n.a- 

3urd con6tnrio6 ofroric .ld.rts witb tboe ol 

olbl goupr or with tt6bE-bacd back 

gFund ul!.r. Thu6, iD rh. ass$m.m ol bealrh 

risk, th. *nowle4. ol Ef.Etre valus (RVt in 

hud. ti3su.s and fluids Fovidd . n.di4ful 

iBighr into rb? qbr of rh. *p.surc ed n of 

fun'lD6bl inp.tu!6 in mvnm$nbr pollD. 

rior contol. A nunb.r of hert ncials rs *dl as 

dur fm.s .nd ga*s ae loud i. th.s worrirg

AUTIIOR'S PROOF 

Potnrlln, Cddun, !,!.g!.Cum, |rd Sodun Iwd! 

ir Elolodcrl S.mpl€6 ol ElTerrllrtu€ 

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of rh. irdy s b cqr. e 

u (cr), 'rd i*laid (Mtt dd &did 

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(Nr), ih biorosicd a'ry16 (qhol 

ldr lEurjtu r€rtuc@ 

N b iatu-as 

bGEldydMdIldbk

ELSE\'IER 

Determinadon of cadmlum ln whote blood end scalP hait 

salnple3 of Palistani trale lung ca[cer PadenE by 

electrothermal atomic absorption EPeclromebr 

T'G (ozr', ,dR. M.nont, rr.I. Atidit, M.K Jamelil, rt8. At itrr, N,albanil, R-A sartaz 

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hbddotdeDqHbN 

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EI.SEVIER 

':i;'scienceDirect Talanta 

Application of factorial design iD optimization of ultrasonic_assisted 

exfaction of aluminum in juices aDd soft driDks 

bbd;ra^tuLd,-+rd 

N8rat Jalbei, Ta$eE O. Lzi'. Bild M. Amin, M K ,@rli, 

Hsse L Anidi. R.A. Sefte 

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il EISEVIER 

1;' ftienceDirect 

A multivariate study: Variation in uptake of ftace and toxic 

elements by various varielies of Soryhum bicolor L. 

Mohrlunad Khs tahsli t, Tasnem Gol Kazi *, Mohmad Baldl Arain | , 

Ha$an Inru AnldiI, NBnt tslblDi '. P.rjr Adil S.rfilz', Jm@l Alm.d Baig 

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T!.ta.i.iddr6o{ din!6! te $dg.d.&@ 

N |l!E han Nrd by i@ t€ahar ,Illt F@ 

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23 Nl Pb .d Zn iI $dltn€tri t.bpk! of poluled lrk 

24 M,B. AEinr. T.G. K&ir'. M.K..ttd.lir, lll Aftidir,N. Jalbei' R A sdfit'',J-A B'ig' 

26 rc.nlGof cxcclhnein@lrti..lChdistrvUnirFitvolsindh Jothoo'Ptri$r' 

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4o 

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high dic[@l flcior $d slow Mo$l nc [l]

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Fld h.l|4Gffd.dtsnl|ddod 

lssessment of water quality of polluted lake using multivariate stalistical 

Fchniques: A cese stuoy 

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Synthesis and Characterization of Various Amino Acids Complexes ...

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