NMR Spectroscopt

S1ied.M!lllc,py i, 1he Jludy of lhe inli!ffil' lilll of e l.>.,11111n1g11e1ie l'lllllotiln \\.1lh n1UILOI',
Nuclear nngnetic resonnnce (NMR) l< • spocLroscap) t<clllniqll! 1vh.rh is oosal on ,1.,
int:er.tcti:t n of t.te. &imp le being ex:unincd with elixtrolill'l.gre.tic rw Ult.ion in the range
nf rudio fn,qwi>:a ( I• 1000MHz). Th ub~>l'bu pl.,..,nofcloc: 1ro111ag11:1icrodii1ion,
u., 1111nsnion cnersy A£ iJln~lc du, to 1hc hucnr1ion of• nwklur spin in the .<01111ilc
wi1h • nngnttic fi,U """' "'"ch tmt of 1lw, absoobed nidintlln al u 6',quciry.
AE ampk =-£ photon : IMo =In,= lld>.

TIE NMR e.xperime.nts will provite a brood ran~ of informatio n on a simp~ : in

pa1ticular lnw the NMR frequeirycan be used todaern:anc sLrocLu:a l and dynamical
dnui.
Cll1ssb1Uy. a mu, ting 1,an tie le posse5.41CS t1 ngular 1m1ncntum. The nucleus of an :uo m
cim be vi.smliud as "'rotn1i1tg'" :utl h:u. n spin nngulY 1mmentu1n/. 11V!' tmgnitude of
I.tr spil ~ m:,rnemum is giw!n il qwmwn rrednni:s by:

I, l/1/+III½ I = O. 112. I. 312.

where ~ i< Pbtrk's co 1"1ll tU h divided by 2a and / i< t he ,plu a ngubr mon.,utum

11uni11um llJlfflCr or 1hc '\<phi' ofd,c n1.d,o<. /I,"• quantlzcd t-<:Ol?J'oncnt.

lz= /rm m ;-/, ·--, 0, .... ,
whe.re mis the nugretic qm.mm mmbe.r wih 2/ +1 \a.bes.
Nuclei of all elerrenLs ure ronposed of prolOns (pl and ll!lt:ron., (n). both of whic h
111 \C .lip in / = I fl. Thus I.he ttol:11 IIUC'lcnr ~pin ~ 1Ji: swnof lh: spi1t11 of all thr nuc:lco1t~.

Tl-, qua,uum ,rel'ltmc.ni lnd1ica1CS tb:lt protons n1l.l newron.J pttlr l~) .upmutcly 1.1 nJ lhiu
L"\T:1\ 11.11lftrs of ci1.her li:i,-c :mo spt1 W'l1'J-br 1nonrnwm.

Spn Nucleon Descripiloo £mmplos

e,·en ruabe.i,; of botl1p :uxl n I 2C: (Jp. 6n
/ :0
160: Sp. 8n
<1dd numbcl"I of bo1It /I ul n 2H: Ip. In./-,,. 1
/ 2 n (lllCIJ!r)
108: Sp. 511. I = 3
0\-rnp (n) ruxl odd n (pl J3C: 6p. 1n. I= 112
I = 1111. (lnf i11e g,r)
23Nn: I Ip. 12n. I= 312

Dr. C. Kr1shn.a.iW1my
 NMR Spectroscopt

Cl1t11k:ull)\ if• rou11i11g pnrtkli! i1 charged, i gtll<l'II~ a nt1g,~tie d.,ali! whie h

cremes a tmgnetk fekl. 1lr dipole h:t"' a tllitgiletic momenL Associnli'd with ni.rtem·
spin a ngubr mJDE mum is tlr nucle:l.r angnetic moment µ which can inur..1.ct with a
1111g1~,r flnl::
,. - y /
\\.lll.!re y S dic rtn~-.tlogy.: ra1-,, ll o:,r,;ornt chruadcrislic of cooh 1tti!c.

Nuclear Spin in an Exlenul ~lagnrtic Field (:Uem:m EITecl)

Tlrre is m preferred ori:nu11ion ilr a rrognetic mom:o.L in die absl:JICI: of exLernal

fackls. In the ab.se i-x:c o( Dw, the na.gnctic momcnlJ o(uxlhrk:hwl 1u1Cle.i llR: nmdomly

orlc ~d and all lw"' c<Se 11 i•l!) the so ,no• 11:rgy. Applita11J110 fu n cxu:rnal magnc1kl
field 11!:JllO\'CS thi! mndomness. forcing Ll·.:i nuclei to align whh or against 1tr: di rec Lbn

of 8 11. 11ii.s Ch:mff! fm m a tnuliom state to 11.n ordered st1.ue is known as pohriz.o1D11
SLCh pobrimtion n-eans there is :i diffu reoce in the population of the wriom spin
Sllllcs. NMR sp,clro.wopy i11hrc, lm1>1hloll'I l.,ctwttn i>djacc ul nu:I.,.,. spin e rcrgy

.<1n1cs \d1e sckction rul: i. Am • "'11-

Ctn,~biUy, In 11\e prc.'i<e11Cc ofan aiernnl mag1101i: fitld n. 1l1e CIIC!g)' o(a m:,g1ie1ic
IIDLnel\l

µ depends oo is ori!otation n,lot;.,, 10 the li,kl:

Ee µ 0.

0•
·-••
•

Au ll 11i,I IUj1 di♦

- r 1nr.,-u,, --+
, 11 '!'(,t .._r-

••
whk.:h ti a mmimum when II~ nDg:nc1ic momcnl LI aligned pam llel 10th! m:1gnc1ic
fi.ekt 11nd a nn.dmum w lr n ii is ant ►p llr.sllel Prom the qrn 1uum nleCllrnlcn l
prospective. wbe.o a aucleu.s is introduced into a IDlgntlic fteld it, magnetic rm me Li.
will nllgn itself in 2 /+I a rlt'nt:tiors (number of valurs of Lhe m qu:iruwn nurrher}

uboul UICl ~ drecti.Jn or Bowhere tlr coorgy is IJiwu by.

Or. C. Kr1shn.a.iW2my
 NM R Spectroscopt

£.. =µ>. Ho =yhfflBo

For an/ = 1/2 m.1elell\ llr ·re are only two orientati:ms for Lhe n111gu!lt momert µ: I )
n b \\er energy orkmlntion ptr.t.llel to 8 11 whh a m:,,gnelic qwut um numle'r m = 112
oficn ref<rred 10 l1ll Lhc o s pin slDI< ard 2) a high:r cncrgy anli•panaU.1 oricrcotun
whh m • - la re"rrcd 10 •s ,rep 1!pin stntc, For •n I= I nucleus then, are thn.'C
1,oS-.sib~ tn!ntntlOn.~ ilr 1he nugft!lk ll'klUlCl\l. ll"CSC itnte."' ore lnlllll'llted bdo\Y

-' -' ..
r, 1~
'\
... -.I r, • \
I

I
I
P, 0
I
,.. 0

I I I
,,,
/ m,·z ,,. ..... ,,,
- -
l)lrttrlrmul quu,ncy}tio11 ,f 1/w "'''""'' #t01M1#0111 I' m lht ""'lftldl,·J1rldfor- ,a,dcf """ l •l/i mftl
I

Applitd
NoMrl

..ro ..
m>gn011c &lid
m: -, I

...
w
..
·--- ma • i
'
Ent'R,.V krrrl sdttMU for u m1dt!us ,p,a q,,n,.tlln 11u111hrr Y.t

'i'nm<ition Froquondes
Wli:n Lbr imgnetic frdi is applied tlE nucleus begins to precess aboUl u o"'n axis of
spi, witl1 aqiubr llcqucncy (w) "'th urit.s ofmditr&s«ond citie d urnor &cquc,c y.
Tl., frequency ot whic h 1>n>lnn precc.'""'' is dlm:tly proportrmal IO the 1treng1h of
opplied fllllgreti:: f1eld. Suo ngcr the mogr1'Lic fi,,ld tlr higher 1lr ru1cofprece.<.,i>11
Tlr angul:Y frequency of an N"MR mmsiLDn is norec-ommonly wrilen as: whi: h is
llx, Lormor eqw1im.

Or. C. Kr1shn.a.iW2my
 NMR Spectroscopt

I {J](J C yl3o
Gynxm!J!etic mtio = 2xµlhl
V =y8(1/2lt
lirv- yBo

l ,• 211v l
0

..., ½ I
I
I
-

,
....... I I
~_.,.,.....
....,___,-.-
~I.
- •
(a} A tq> ptttessiug lo the ean'lh"s gni, iation.al fie Id; (b) lhe pcecessi:111 of a. spu•1u1g 11.~leus
rcsulli.J'IS ftoo11tt i.ntlue1re er an a.wittl n1ag:nel.ic fie kl
lloltmmm Sliitktics

ltt the l'""cna, or 11 11 cxw-nol ffillQIICtic field. dtffcrcmt uw kmr ,pu, -'llllt-< (with
differcn1 \-alua of m) 111 ~ difl'c~m c rorgies. TI1t c1l!.rgy difference iJ J>mponio tll t 10
Bo. At. tbermtll equilibrium. these st11es will n ko ""'" diffuem popubtions. Llrir rntio
gi-.n by 1h< Bolzmann '-"JWtion:

,v1,,,1, = e -iM l.t Tl

¥v,01,
Ntu,t, ttnl Mo~d.. l'<'Specti\e popibion., or the uppu :md IJ,vcr s1>il """"·
6£-=:Eb'J!b-Ei-- tbe energy d.ifaerr:e between tJr twostues,
k tll! llobmnoo conslllnl an! Tdl! ob,;oillc ~hire.

In the upptied imgnctic f10 lls, tlr difference bct,..,cn nuck:o r spin o.ncri;y """"' tJ,.£ i•
nuch snull<r dnn kT. ••~>lying lh:tl Nt,.. l< only '"">' •IGhtly b, ®'CS, of Nt..,.,
For 1H in• 9.4 Te.,ti r.,ld (400 MHz) 11,n 300 K on: obtui,u a popubuon rn ti>

,\~a)liV(Jl) of l.()0006<1, i.,., i,r oar millio n spins in tlr ~pe r p ,;:an, tlrre ore one

mllllon an! si'Cly• ilur in the b--.r e rergy a smli!! II ii the e,i:ess 64 spins tbot

l1l!IIX) tll 101he NMR expllrimen aal rnm te the net m:IJ!lll.1imtlon M., To summarize.

Or. C. Kr1shn.a.iW2my
 NMR Spectroscopt

1he iirger B. s 1he if~aler I h~energy d1rr~r~nee !1£ bl111.!en IIi, levell •nil 1he lilrlj.lr
ll(' A£ tlr rmre excess popta.01 e.:d.'i.t'> in the km-e.r ene.tgy stale.
TLE excCM nl.lC'l!i arc llr one tb.1t allow us to obscnc reso 11Hre. When tie 60MH z
mdlation is applied IL,., , o n ly in h a:u Lron., llion upw•nl bul ol,o sil111Jbala uun.,hun
dow11"~rd. If populn1lo1~ of the upper 111111 hwer s,00,5 bcc,,mc ,.,.,,1) cquol '""
ob.,;e r"' no re1 signul Th is siu.aion fl co llcd satumtf,ut. o,~ must be! cnn,.ful 1.,,
avoid saturati m when pe.rbming an NMR experime.DL
Nudc;u- SpiD Belll:mtion
Relnud.Nm pro«ss in,·ohres mo 111dii.1lh"'t' lna.n sition by whk:h a ouc~l1S in 1111
0

lJPl>er t.n.tlKition J tnte nilllm.Y 10 the kmcr spin s talt.

OIi
The process that brings Ille •Jin hock lo lbemul •cptibbriurn is cnlled rebxolkns

II decays du< IO three dislm efkll:

L. Spio-Lauitt (or Long"uoml) Relwrntioo. Tl

Mee ha n1lm involves a 1~ 1 ttamkr o( energy from ipin .sy.slcm to surmurd ing11. 10

rc,:su~>IL<h ll<>l1znwnn dl,11ibulon. Tiic 1cr111 refer. IO 1hc fr11n10 ""rt of m:ilocult
ro111ainlng tbt. prece.s...!ilng n uc~i AU these nn krules untler!J) Lrn11.d:11ioml rouu.l011al
ruxl ,1bratiui:tl motion ord posses magnetl" propertes giving ruE 10 snnll magnetic
field in 1J,e bun. Wben somll nngn,ti: field applied md11:es transition in porlicrulur
prccc..oing nudd fro m upper IO lower Sllllc . TIIC energy fro m 11tls tmn.,iLion l1
u·un11rerrcd 10 the co 1rp o1'C 11 of lh: b t1l:e tu tddl1io1al u1uu'-11_N)1\lll ard , 1brutfom1 I

t~ne1·gy. Tok rmim:i.itu 1.he crcu of rudcl ln Lill" lower rrrrgy strue~
Sp[o-Laulce relnlon co n be denoied by T l and it is a m,e1,,urc or a\O:rag< lifetime of
the nucli!i in the higher e.nergy smte. TI,e Lime TI is depe.ndcnl on the g)romignetic

rnllo of "'"'"""1! nuclei.

2. S1il11,Spln (or Tru1t<.-enrc) R, la,.,.tkm, T2

In whic h rnu1u,I e_;,,c Ill nge l)f spins by two precessing nir lei Inc b~ proximity 10 o ,...,
rulOJJier. With ea.c.h processing nucleus. Lil! re is n.n nssoc iued nl!!gne1 ic fie.Id ro1.a1.ing
perpendicrul:tr 10 the main liekl. If this small nngnetic fie kl ls ,mme a< is n,quired to
in.I uce transmn in the 11:1.glibouring pm101~ Ll1tn mutual excho ngc of ipin lnltc pltw:c.

Or. C. Kr1shn.a.iW2my
 NMR Spectroscopt

Th~ slnm,M Ile lifo lin,e o &n i!il Md 111 I nuellous m 1he higher ,11m~ In oiler word~
it invol\Cs tlr tr.1n.-.fer ofeoergy from otr ni.rleus to tlr C>Lher. Th&loss oftmn.~\Crse
nmgna izzuion is cbnructe.rized by:,.~ constall. denotal by T2. cn.lltd the spin•sp in
or lnum'CrK rmultl)n t.in:c

J, T he nmgn<tk ll<ld i< oo1 p,rfc ctly u nlrom, Nuclei In d ifferent paru or ti,:
.,, rn1>r inc«s nt slightly dirrcn,m freq uc "' le, a id !!<1 ou, of phu'"' with one oooLher,

d,e_reby gr.,du:llly decrea.<iq;: die oet OJ;J!jli!Li7.ltion ofth, sample,

NI\IIR instrumentation:

Hl 4 ii1iC.: ~c-
- -def

I. Somple holler: Oas. rube ,.,d, 8, 5 c m mg ond 0,3otn i11 diun:1<r

2, Permanent 11.igne1: It provides honngeneo111 niognoLlc f1<U at 60- 100
MHz

3, M DgreLi: CQ ~L!i; TI~ coils lndll('e nugr»:ti: frekt wlie.n ~ment flows

lhrough irem.
4. S"'~cp gcnc111 1o r: To pmcha:c Llwt equal ::m»u1•. of 111.1g.nrti: f.eU pa~

lhrough d,: "'"~' kl.

S, R:uliofn,q lll r>: y ,ransim,er: A rndo U'llnsn1iuer coll that 1>roduce a , 1., ,1
J)O\\ffl~ puke of radio W:l\Y...\.

6. Radiofreq L1?1r y n,c-,iver: A rad i, recciv,r coil thru deLoc ts rndi>frequencies

c1ijled ;u rue.lei relax ID II lower e11crgy le\C'l

Dr. C. Kr1shn.a.iW2my P>ijO 7

 NMR Spectroscopt

7. Rtl\11 001 systeire A Cllft1llllcr 11,11 ru!li~ and rtoord 111.' d:lm.
FOURIER TRANSFORMS

A Fourier tmnsimn ti anopera.t:ion whic h con\erts fmrLMJM from tim~ 10 f.reqLC1x: y

domain,. An in"'"'• Pouric:r tra111form (Irr ) con"'ns from ,1., frcquca: y domain 10
ll~ 1i no donult.

NM.R ClruiCll Shih

• llie clltuical s hift ii Uie [)}QSDXl on llr ii scale (111 ppm) 11bcre die peak l!CCW'S.

(ur<Juenc)' of "P"~' • fr~1cy or 1<Crt<t1tt!) •

10
~JleellOlll<ltt h<qn<llC) 111 lit

Clrmi:ol shill =5 = dkton,.., of peak fmm TMS. In Hz

spectrorna..,. (requmcy in MHz JlJlffl
• Thcrc are two m,jor lactors tl1'II inlu!ncc chcnicd sliis:
I. OcJhodding due to reduced e1',1ra,1 den;il.y (duo e1<cuunoia1Iv,: a101111)
2. Ankoll'Opy due 10 111ngni.1i, li:lli b'l!nt.'11llcd by a bonds
TIJbl, ofch, 111/cn/ 1/1/fl,

I I
- c-.1 t:=c-y-H
lH
9 H'-
/c- c.._
H
-y-x 6H
K-v- -i-r-H
HJ,0
H "
"•' I
H X• O.S,
QY lu1lo1,n
' 4=H
l>,1U)lw
arff)k• k
all) hr «
:ulja«•• t.
UIMr11tfll

l3 - t.O
-
1.S - 6.5 ,~ - .U
... ~~

5.0 - ?.5 ----

J.0- l.S
c-1 ,·bcut.)1

~-1..0 LS-0
U U - 10 II 6.0-5.0 F >Cl >Br >i 1• >l • >1°
H 10.~ - t.5 H 53 - U o,.o. Jo
N J.0 - 1.0
(pp1n)
Tulra Me 1l!yJSilane (TMS) as a ~ren,ire con1'<"1Dd

~H, I. All 12 nuclei or iu hydrogens are equn'lllerL so l1

H.C- j-CH, sDDWJ only one shurp NMR signt1l wbi,h se""'' "" •
fM, rtfcn:1" poilL

Or. C. Kr1shn.a.iW2my
 NMR Spectroscopt

2. IL, hydro~n 5ig1111L1 llfl f><fOI' 01 higher fial! 1ln11 do imll IH Mig11nl1 iJI otb!r org11nie
oompolJlds. th"' nnki~ it easy to lde1tify ~r Tht S peak.
3. TMS is ioorL so il doe:s not react with Lno~ organic compoulli.s. arxl it is bw
boii1g and cun be r<n10,•cd Cl..\iy at I.he cntl or" mc1.JU.tc:nJ;t"ri.
SIik- klll\l and o ,.1deklh,.; or prntun<:
A bur< pro1on. wl,:n o;<po!<ed IO mdl,frequoncy flq" it• ,pin from low..- to higher

eoergy le\-e.L Ho\\evcr. aJE the protons do 001 fJJp the.ir .spin at sank! .spplied field
l:,ecaug of !heir energy depend upon tlle che mica! en,iroom:nL 17iu i.\ d IE 10 illluce
r.,tl may Cll'P""" or l'Cini,rce dr opph,d (,:ti.

Wlrn 1J,e applied •Ill lildua:d lieu, reinforce• snullcr field mu>'I be applied w Oil'
Llr 1i1nton. Su.oh • pro1on k uld ID be dcshleilcd :1ld oboened n1,run, down field.
On tlr other hull when the fieU oppos., u strong,r f.,ld mi,;t be appW The proton
~ ,.,w.sm,ilcd oo:l observed :a ,mre up li,tl.

appl•d ft.W

l•l I<)
Sh--ld•d ...,.__.,_
&IN ,.,oton o..lMfdtd protoa
~Mfort•wleh Oppo~wkh
-dlloW 1pollftdn.M

Und<r an applied magn<'llc li!ld. ciculntlng cliruons in ti., e rctron cbud produce a
<mall oppo.<ing mognc ti: f.,ld. ultiimtely decreasing tlE effa:: Live nng,,,lic field leh
by Lhe pmlOn. ,Wiling Lhe signal lo LIE righl (or 11p/',../dl. Thls cli,ct in whkh the
el,c1,u n cbud ·shields" the proion rroni 1hc "tlphod mag11:1k: fie ti ;,. called ,.,.,,,,

,1/nmngnrtlc 1hltltll11g.
$il'~e II~ m:ignetic field .su·e.ngth di:uues Lhe e1,a-gy sepamLion o( tbe spin sa.au:.s. und
lerce I.be radio freq "' rc y or I.be resonance, the structur:,J factors mean !hat di ffere oc
types of nuc:l<i wiR occ11· ,11 diff<l"-nl chemical shifts. Thi< l, wl11 t mike.< NM Rso
ll(cful ror KrUl'lu.rc de t.ennhunion: otherwise u.U ntrlci would huvc 1..be stnic cl~ mi cul
Or. C. Kr1shn.a.iW2my
 NMR Spectroscopt

.~lift. SOIi\! lff1)01\Jllll fllf llll'.! U!i!lld.?:

• ixlucti,e ,ti,cu by cl,ctroreg:ai-.e groups

• 1mgrc1ic :mi;orropy lo" fidd lujlhfield

dow,i field up field
dc.Jucldcd •lucklcd
hil'h fttque-n<:y lo\.\. frcqucnC')'
,,.~., a I ppml ••uall o ( PJ)UI)

1o;e7.
I•

::,-4 >l ia6

7
Faciots aff,cting c.be nical sli.ft:

Ekclrolll.'g athity,
M's 1J1a1an: 0113dl<'d 10 1110>1:c elodmnci.;:,1ivc a10m, cxpo:ricncc highcrch:mcolshil\s.

Ek!.c11uncp11-.c ut.om.i; nl-io rcmo,c elccLro 1..: fro in the electronc Dud. which dccn:u11es
1he ir de1u ty arrl resuh1 in las .sbElding~ he 1r:e Ucm:;,negative a101ns a~ said to
de.<ltidd the pm10n ,rd c,use it to have• higher chemical s hill. movinll iuo the 1,fi
(or dow1rfi,/J).

OL1F CH:ICI OOlt CH:ll CIUOO C IJ.I Sl~lol OOU

<.21> l.05 .2.69 2.19 0.911 O.l o.o

Tl,i magnitudr of tit< D,sl,1,/d~ ell,ct, b1>1"'''"- mpld.ly decrenses M tbt dl<1011CC

between dr proton and ek!ctJ1ll1cg3th-e ntom i:rrreascs..

OL18r CH30l20l211t CH30l20l2CH1Br

2,69wcn l. 66ppn l .06l'l'm 0.9lppm

Mnb'llcllt Ankc,tropy
M.ug1rti: nnkocn,py me.nns 1h11 1here l1 n no 1l-- unli>rm n.'llgncLlc field. Electrol'li in 1t
sy.s1:em.s ((!.g. aromati:s, ahres. :t.ll:ynes, carbonyls. t'lt:.) interact with tlr npplied
ft;,ld which ialuce.<, nmgJ>ellc field that c, uses tlr anisotropy. As a resull the neorby
noclill wilJc;,peri:occ three fclch: the nppli:d r..,u. the J.biokllng field cl tile 111lcocc
Dr. C. Kr1shn.a.iW1my P"!l• I 0
 NM R Spectroscopt

cl!oiro1K. and 1he. fl! Id due 111 th! • sy,;,~m. O..i1tndmg on ,tic 1iosi1ion a f 1h, nuelell<
in L11i< tlurd feld. II cinbe eith<rshiekkd (s1mU.r6)or,deshicldcd(brger3), which
implies llut dr eoergy requrcd iT. and tl1: frequency of the nbsorptbn ,.,i] chan!J!.

FI.O Ira - tho ll!)Pliod Id<! C, •iro •

/ •-ltldlntN, reglon(~to,hl:la,,g)

/ .c. Anlsdrq,it indJced ""'9"ffl' -

'\• >-- - di.etothonladdra.,l.....,olll-api
....

I . ,,.,...,.,• ., bS\lll!re

Field htllq-od ,,..h -od WI a•'9•

10,g<r te4dnltlar•nceq,.Mstl0-dr1Q)

~ \+?
-A ~ +- _H ~-

,-1~- ' . 5-7 """' 6•&-IOR'lft

-•-df,g-
SChlmd ic dlg,n .. lhiddrg -
Tht •
ta com""'" pl oy;llfflO
fftl · -OWlleldlng. . -
Rffll«tnbe --.ldl,o-a lho ch!mlc>I alU, h nd
doltliel~lr,gI n : - l I 11>IC61 tj I - .-e 111o l l ow,
Addle a nd ExchWlb'< uble pro tom

Acidic b)dmgem: Son]C oflhe !0<1shielded pro1om are tills, u11J1Clrd ID corboxylw;

uci:1 nt l O ID l 2 ppm.

BoLb
-~- i ,,•
re..son:mce tuxl electro ncgaivity effect or OX)'!?D wlhdmw electrons fi"om the
proLon.

Or. C. Kr1shn.a.iW2my P"!l• 11

 NMR Spectroscopt

Hydmg•n bonding 011d f\!~••hli- prolo11s:

Pm10 1,; tin! con exhibi1 h:ydmg,n borlllng (-OH & -NH) hnve e:<tr,mely ,•,rilblc

ub"3rption posili:rns over a wid• 111D3'. T l., more hydro!!'• bo 11iing 1oke pb:e tho
onrc dcshltUal n proton blXlOIDC!I. The nnvwi1 of H• bo 11ll11g i, clcpend, on
m 1r.en1nuion and lCm1,era,l\ff, The more tnnccntnl e d~ .wh11Dn rrorc nw,lcc ule
001110 huo collll,~ u,.i h)'llmg,n bond. A1 ltlgJ.,, dUutlon no h)dmg<n bonding

occurs.

~ vuluc ti d.wll!' sdttion o( -OH «cun Ill 0.3-1 .0 ppm

6 vu.Jue at bJsho- C'Onccntmtlon cxc1n aa 4.0-5.0 ri,111.

H R R
I I I

Free (dilute) H-Bond (Cona,rumtcd)

Pro101°' aux .hed 10 clootruncp1hc ;ato m wllh knlC pair 1,u;:h a.s oxy~n'nitrogen cu n

undttgo r.1pid chc:n1lcul c..:lunge. T ltH L,, 1lt: ycan be tmn<iel'rcd ....,idly from 01»
mlecue u, :unrrer :md n.re: a.ltd exchangeable pmeoa,.
► Rapid ex.dnn~ CIUSeS spil decoupling

► Spin c1ca, up ling I; fowd in HNMR or nlcohob. a.mine:., and c'"1>o,yli,, oc id<.
11., •it:r"'k of ()1-1 & NH pmions nrc tnnn..Uy un<pl1 111\l bmnd.
► &rog,d:J,,g & •cl,alf&t!Ubl~ Proums. Pn>tom tb:it unde rl:J> ~id d emicnl

=lnng, can be easily deiecred by replacing the co cq,o,md by D,O. The

prowm ""' rapidly repbcal by de utc,riwn ond tie prolo o sigmls dirnppear
6-om lhc spcc:tru"'

-CH-011 Cll-0D 1100 Dcul.-roum c:.,chBngc

Other types or ,xcl11111ge: TAUfOMERLSM

Mok!cues whose suuc1LO'es differ mukedly in the m:a.~"-e-menLor 11totm.. butexfi L in
equilibriwn ulh one 11 1ntl£r :tre called I11 u1omeo . Ttr mosl comtmn type of

Dr. C. Kr1shn.a.iW1my P"!l• 12

 NM R Spectroscopt

IBUIOlllflUffl 8 Ke10-e11nl llllllilmeri, m ill ,vltleb 111! ,peeie., differ mamfy by 1he
posit.on of a h)dmgen atom

I, 3-di:amonyl compoull'.ls an, capC1ble or exhibiting ket.o-e11>I U1u10merism and Ll"

equiiniwn iil,oin Lliecool i11m due 10 fommti:rn ofillraDlll:cuwr hydro9!D borxl.
E.-.umple b- I. 3-dK:orbon)f is 11cetyl ore101,c,
H
o/ '-o
I _,,c,
c...._ I
1
CH, ~ Cllj

....H

Tie pro1on ,pe,;iru,11 or aceiyl aceionc , 111w, O-H pmk 01 very for down f,eU 01 6 •
IS.S ppm a, "'"'U ,u ti" vlirylic C-H pro1on n16 • S.S ppm. Al., the >!tong CH, pcnks
from eool ilnrs a.nd compam ii with the much "cku CH1 peuk from the k.a o ilrm.
Aoo nou, !Int the CH, pellk nt 3.6 ppm is \\'l'llk. It concludes that the enol i>rm

prcdomiJDtes ii tli.4i cquiibrium.

!I lI AlI
I

I
I

- -
Dr. C. Kr1shn.a.iW1my P"!l• D
 NMR Spectroscopt

Vlllflll'• IBlllnnYrkm:
¼lence tau10me.rism L~ intr.umlec-uhr I1Hll'C in whkh tnuuome rs rapidly 1Dli!rronvcI1

wilb ore :tmlhec but lite ttoomeric lbrms di&r priocipolly by the position of
a>VJieJt bonds ra1trr ~un by llr pc>.<itiorL< of prc,1om.
E.S111t1plc b- . . _ 111®111\Ct~m is Bulvnkmc.
Tl., pr01on NMR • pec 11u1111 of Bullvolcnc 111 bw l<lt1'<'mtUre (holow -8S"Cl consls1<
of i>ur COR1Jle., mulLq>let., As the 1empera1ure i, rus,d Lhe rnuhiplcts bmodon urd

1m1ee cbH:r 10g,:lher. Al +110'C, !he entire :;pcrlllllll cons_ilt, of one sbup single!.

Thl'i behavior II doe II> Bu Uva~nr re:tn'llll~'- tJrough .sedes of L~o111eru..1.tbn known
'" Cope l\'OrTOngcmc m. 11,c posiliom bbol<d I ard? arc- port ofo cycloproponc ring
in o ne .su,acture bul in the ~flf ~Lructure, po.sJ1ion 2 is pun or dou.blt bond. If this
reormn:J!mell is n:peutal ill tlntev-ery bond boromes in,olved, oil 10 h)'WtllJ'l!i in
Bullwere llil b<c:otre equ,unt.
I
•
I

l ,
j

SPIN-SPIN Spli~:
Spooni generally huvc 1>Cllks tint nppenr i11 chJ11ers dll! 10 coupli,.; (sc:ulnr.
sphh,pin. J •oupllng) with ncighborin~ pro1on!i. Cauplin~ 11ri.<es bccall!C 11,:

nmgr-et ic fcld o( o<ijnce11 !YOIDM infloc 1ccs 1he: fte:IJ nhu ll'W! pro1on cxper-N: rw:es.

Eoc h type of proton .se 11Ses the nud>er or cq u:iw.Jiert protmM on the next arbon tHo m
whCb i. is bonded 11nd its resot..irri- pe:ik is spli iuo fr»-L) co1rpooeli.
This pbemmemn is calledSpu►,pin •plitLingard 010 be expla ined cmpori01Uy hy Lhe
(»>I ) nAc.
11 + IR111<

,-\,; J)l'Otom on 11 cn.rbon utom upcri!ncc LI~ nngnttic f.eld or 1,rowns on adJ1-1Cent

carbon nioms tresignul for n p:nicubr proton will be ,plit by ~,ese prolOns itto " +I
peaks wlr!rc n k the nurrbcr of adj.,cert proL0 11'.
E.<tllllj>lc: I. I. 2-trk:bbrocthrnc.
Or. C. Kr1shn.a.iW2my P"!l• 14
 NMR Spectroscopt

1b u1rlasm1rl tie i1n11lica11011111(1hi~ fiPsl eo,isrlu 1he effec1 1he - CH W"'-1' ha., 011
the ndj,,celi -CJ-13. T he melhine -CB con ndopt 1wo olignme1Ls wilh respect to Lhe

ttpplcd fioll. As • result. !he signal fo r the adjac:clll nrlhyl -CfD is split into •
doul>lcL two lu,cs or ,qw.l io1c111ity rntlo I ~ , Now con,klcr LIil clb:1 1h: - 0 13
i!J'l"'I' Im on 11>, n1ijnoc 1u - C l l T hc 1110 thyl -CHI pro1011< J11,-. 8 P""-"hlc
oombitntb11, with res1>ccl to th<, appltod flek:I. o nly i>ur or which in tmgnetlcu lly
distinct. The resulting sign:tl ir !he odjace 11 metbaoe -CB is split into• qwrll!L 4

litic-s of irumily r.JLi:l I :3:3: I.

t •I
I
'- f"t_,c
t , _tJ
_

Tl~ rel31i,ie mte.n.'dLlcs or tlr hne.s in ii coupling pane.rn i; given by :i binomial

e.xpaffiDl of de equation
(x+I l"
wltm: n is the 1t111ibor or B mrl:i

or n101·c con,-eni: mly by PM1::1rs trinngk!. I 1'1h'l1u:.tl tt.50111 ,~c• art split dlC to
rol4)llng. with n t.djnre 11 IH't'iora. The number of lines in a cou1:,ling pm.Illa is glve n,
11 gereral by 1n/ + I for rouping wi.h 11 ~>•1 / rud,i

Dr. C. Kr1shn.a.iW2my P~e l S

 NMR Spectroscopt

a• D I slJcltr ConO,:urutlnn 1',.. a.tr.

I l .....le, A r
.....
•• l

--:
• ·J I 3
2
3
I
I ........
AB
AB,
I 1:1
I :?:J

..··•, I I
s
4
10
6
10
4
~
I
I ..
'""'"'
..., -
AB,

AB,
IJ:l:1
1)16)1:1
1:HO.l<U:1
11i" seres is C1111:d Pascals lmligE AB. II '6:1 ~:tS,6:f

aJIJPLL'I G CO.'I S1'ANT Ul

Tio: couplmg corg111111 J i< • nr o.<u1,: of ,p:iclns btt,«,cn in,Jlviduol pcuk.< of
nublplo tJ.
► Coupling coi><lllnr is independent of fold strength o r opemlJJlg tieq..,ncy of
N'MR.
► h is corwtnm 111:d cxpressai ii term11 of He.nz (Hzl
► •J. n: ir,11:urcs I he l'llllttr of bontls ~ro'4!h wt.ch I Ill i1ll!mc1ion oa:u"'

► Coupling bc1wecn .~ me nuc:l,I l\l'C cnlll"d fl>nlllnud.:nr c;o1,1p1ing ~ hcreus

couplllg bct\\een Lhr difermt mmk,i ru~ hi2.roro:lettr coupling.

T lr magruude of oo ~liui:; conswn depends on the number of inh!nerung bo ,xl<

between the t\W atom'i o r group lh;i.t inte rnCL V-.uious ftclor influe 1r e the 51.re.nglh of

b1lcmcti>n bcl~cn two nuclci bul in g,mcml

'J >~J> 'J .•

Or. C. Kr1shn.a.iW2my P"!l• I 6

 NMR Spectroscopt

NoC.._.,,lld
Hy~ c-{-c-H _L4_
J

J l._
1
Twoa,ui,lod
Hydrogens - ~C_~b_J......_~ATod«
H
~-c_...
H

0 11,pling th~h difTo l'Cnl bond< • n- gh-. n

Spin-s pin ro~ lng over o re bood 'J
Cicmi•d 5pu>spin co~ing 'J
Vi:il:11 sph-lp&n coupling IJ
Lo11j\-rani,, •pin-•ph couping

Factors alfrcling s im-spio < ~

Spio-sp in coupling co1>slll 1l1S are m t ensy 10 predict tbooretkcully. am depelll on u
11.md)t!r ofbc.'IOrs:

I) 11)1,ndQ.oti>n or u., ""''"' ""'IV<:d , , the ro~lng:

II) bood on::J<s;

iii) dhodml nngles:

iv) C • C bolll r.ngU,:

~ >Uhs11ucnl elkclS

Or. C. Kr1shn.a.iW2my P"!l• 17

 NMR Spectroscopt

Chart ",-uupllna w"'lllll

Slrv:ctural f ype 3 CH•l Stntdur• I TfYPtt 3 CHL)

i<-{-<c>--{--+< m "d 11to 19

(1.1!'lleu 1r1 • "9'id
,c1, ., 0,1• ...,..,, I "
H,C-CH1..Jt

H,C
Hot :~"
\
7 0>12

~H•< 5 l07 ,'c:=t!-.. o., ti> J

H,C
\ H
~-c."-
' '
2tll 12
(cl.p1r,c;, .,.....,i,1 .....,. /~-H )U, 11
X V tfl4tl'o•~-· ...... ,, \ (1i•~•ntl, _.,_..t --,1,)

-i-< o,,.,, -i-<.C:-1' 2t11J

M H
"
)/'
I ri
12 to 1,
(ffl1.1tt b•;i,.,_,,____, O'" rl
o 6tol
m 1tol
O OU> l

1J -Spin-,;pin coupling: (o n, bond)

A 0 110 hood couping oa:urs whm • si11;1! bond lits two ,pi, ucti-., nu:l,i

00
'J• Gemiml spin-spin rotq>ling: IT"° b<11d)
C.-Jmi:W couping between protom tu.lllChcd 10 sanr centrul 1.110m

:.- Ocniial cou1,lb1g li~'Olccs n,clrnr-cEctronk: ,pil coup&,g ns • tt"'1n.< of

tmnutiting spin hbnn:uion from one f'I.IC~"' to lhc olllt!l'.

, Th;, oimu11 of 1wo bonl coyplng depl!!lds Dllllly QD ll,o !-1- C- !-I boll!

~ - tlE i1ilucooe of a ond ~ subsliuerus and lhe hybrili7.ation of !be

carbon.
:.- Oc,m;,1 couplilg ln,rc..,... u II>: ung~ hood argl, dccrca,cc,

H
H H

oo I
~JliHz
·'J .V,cinal spin-,;piu -<:oupling:

Or. C. Kr1shn.a.iW2my P"!l• 18

 NMR Spectroscopt

The SJ)in or Oh)drog, 11 IIL£1flli in one C-H bond is t~uplfd Ill , ~ !iplM of 3dJlli!elll
C Hbmds.

Thrco-bond • !Cina! coupllni

ln tJtl'i coupling nock! ar spin inforrm Wn is tmnsferred vb Lhe small am:, um of

p;irall:I olbilal owrllp ~llll elUILS bc1wam adjllcem C·Hbood orbuls.

TIM 0tb1tal1 telwal:t)'

~ave eorne tlotwtyt
cw.,t,&p T'l'll1 ov•U• p
ltilt'tf•n tc>Jr, lnfOffflll.,O,n
trom on. CH bond to s,-.
fh.• CC bol\d tt
ortnogonal to
uw CH oono1 _ _ _..,
°'""'
The mug1u1u:lc of 1hc co'l?llng rons111 ru hclw<cn '"'l l odjucc111 C-H bonds dcpo1•l;
dlree1 ly on th! dihedral a.ng1' " be twee n Llr 1wo bo a:b. TI,e mogniloo, or Lhe
splitting ba·we:eo two h)'d ro~n is greates t when a = OU or 180° :tad is snnU w ll!n

(t = 90'.

••O'flldlvltw} • • 110' (tnd .,.,_,

0/r,
r
lllt « no ~•fll? Wtltlfl
Ol'tlW. .,. pe,pencta .,. a
MIMIAUIA OVEl'UJ' MA)(fMUIA CJo/EAlAP

Th, dilrdr.,J angl, ( o.) dep,nd,na,. the Knrplls eqmli>n:

, ,J,.r-A +Bcos a + Cros2 u

Or. C. Kr1shn.a.iW2my P~e l fJ

 NMR Spectroscopt

whci'O c, b lhc dU.,dral angk btlwccn lilt IWO C- H \-0: IOl'l, and.<\, B alll Can:
ro1>11J1nL< with cntpiriell I values i>r h)dmCU l'l,ons bun:I ID be A = 7 Hz. B = - 1 Hz and
C:5 H7.

1l ti

10 ,o

• •
'.ll;H,l 0 8

' '
2 I

0
•

The kllrplu, n:la1lon, hl1> ntikes pcri,ct <e1'"' ucronling ID 1hc Dime model Wh, n 1hc
lwo adj:u:c11 C-H bonds.,.., orthogonal 1here , J.,utl ho minimal orbillil O\'erbp whh
liLLE: or oospin internc L..->n bet\\"'tt:D the e.lectroJ:5 in trese orbit.a l". As :a resuh nuclear

spin inilnmtion is CDL Lm..llmlll1ed ::trd 111111=0, When I.be two bolDS :a.re p:m:tllel or
11111q,nrallc1 dE a.,~lng co.nsuan .slaukJ lt,vc SJl%11CSI nuptilld c l J1a,= J1U.l.

f.)~ltJrs idlutndng lhe no1t11HOOr or JJ 11u

• DIINlml on~
• llon:1 l,q;Lh (Rec)
• the ,-a1!me •l\:r o, an:l lh
• flectmrx:gativhy or any slb.sliueru auucl~d to lhe:curbnn atorm.

Or. C. Kr1shn.a.iW2my P"!l• 2 0

 NMR Spectroscopt

H H
'c-<_
eiledt~ e:tee o

Long-range spin-spin coupling (•J, 11 ::! 4 )

long•ran~ ro~ling ore tl:nse tha1 in,·olvc ,mn, th:in throe bonds. It II common in
ll)',•Wnli wth o.lybc h)diugcn, ammJlic oonvoundi and l'.I r~iJ bic..1d~ 5)'51.crm.
Allylit spQling " oo,e,·,'Cd i1 ron1,0111,b • uch a< fellowing:

H II

R-g.;-<X
l

IIAXAMUM INTfl\AICTION t.t.,IMUM1Ht8'ACTION

CllEIIUCAL SHIFT REAGl~fl'S:

Smnelimu 60 MHz spcctrwns of an organic cou.,oustl :ire unrezl:i>lc b«-::nue the
chc1111c•I shifts of scvcra I gm~• of pro101t, arc •U "''Y simllor. In •u:h • ca«:, uII of
1he l)l'Oton resonnoce OCCll'll in lie .saff'W! (U'CO 0(1hc spec(tulll ond oflcn peaks ove1·L11>
so exu,,,si\el)' lh:ll individunl pe:b Md ., pfu Ling Clll'lllll be extr11t1ed.

Ooe waytoo,--ercoJW Lhl.~ proble:m is lO l5e spectrorreaer that operates at a. freq1.r 1x: y
hl81"'r llnn 60 MHz. But u1doing the this spcctr.1 con cleonly ;cpurJo,d nnd "'"'lvcd

Dr. C. Kr1shn.a.iW1my P"!l•2 t

 NMR Spectroscopt

llm 1Jie <11tond order ef'Q,c1 dR!lpjlel!l'j ,11 llight!r felil and 1l,i 1 nuny SplflrLI or~
simplified ID Int order <pocll'll 11 300 MHz.

Another way i< to lfi C drmical s hift "'"&"'CS ,Dows u rnpil :ull relatively

b>Cspen<k,. m::1111 of resot,u'l! P'lnwlly overlappilg ndtipl.:L<.

Tll.! Ctc nical <hifl n:ugenu are Orj?nll: ro 1111>le•cs ofpllfUnlUgnctic rurc ••nh mctnl,
fro m 1hc bntlunklc .<erles. \Vbcn sirh ,m 1u l co,~leus ore udded 10 tho con,pourd
whose speru-um s deu,rmloed. there will be pmi>uod sbift in Lhe re.'IOnance positions

or various goups or prolOos. The direc1irn of shift(~ ricld or down field) depellls
on \\11i:.h ~ml is being LWCd.
;. Cosq,lcxe5 of curo;p1wn. erbium. 1hulium and )11c.-rbium .s hift ~sorurrc lo
IOW<I' 6dd.
► Cocq,Jens of cerium. pniseodymlwn. neodyu:i.um. samnrium. ae.rbium and
bolnium slitl resornn,e ID ligler lie.Id.

or Il>C lantlullllC>I. Europium h "'"'' COllllllO,~y u<cd ITl!tol 'l\vo of b, ...ldely llW:d
a,111p1<,u,s are ti<-(dlplva'lomc1honwo) e urt~>lum and trl, - (6. 6. 7. 7. 8, 8.

8-lr 1• Alluro-2. 2-dlme Lliyl-l. 5-octtned o naLel e!D'Ophun. AbbreviJlll,s "' Eu (dp ml.1
and Eu (i>d)J

Tlc se bi111h..nile1 complcxe> pn,dirc s-pc<tra l s lnvUf.,mion In 1hc NMR ,pectrum of

nny ron-.,ouill with • reb thely b0<i: pulr of ekcuons which cun coorduuie with

Eu". Aide~. ketones, at:ohols. tliol;, eLlr.rs and an10e8 ol inla'llcL

Or. C. Kr1shn.a.iW2my P"!l• 2 2

 NMR Spectroscopt

2 Bo T Eu(dpm)j -

TI,: wmllll o( ,<hil • ,i"'n group o( pmtlllls •"l'cricnce< <lcpc1KL< on

I. TI,c Jktatl<'C oe,p.,n,1<1g 11-, ncud and du1 ,,,..,~ of Ill" ""\$
2. The conccntn11.bn of lh< shil rCllg<JI it 111' solu.i)tL

Firsl<0rdcr and Sccood'()rdcr Spectm:

F'in:t c1 nlcr SIM'ctra. SN:md ord~r g)N'l.ra.
S1,cclm ,-hi.,h etuuvt cxpbln d,: ,pll1l11g
S1,ec1ni d111 con be 1110~,~•d b)' u<lng ~')n1 11L'IT&, i1~Mitie.s lllYi 11JJ1"ber of penk.s

n+l rule orosmpi, gn,phic!I ODJ!)5il
arc 5'li! ID h<, Fir.SL onler s pectra_
In Om order <pec1n1 d1tn k h~
c.lrmra.l sliA di'i!renre l>elw'l?'en two
set\ of 1:ucE:i
ob.,,,.\ed ot'idrr gn,phl:al ~ nor ,,,. l
rue and reqms maLlrnttical :unlys~
,mnly b)' a>n:puter arc sail 101><, S«ond
onler s pcctm.
ln stcond ocder <pectnl die d6~rre ,1
clx-mic::tl mill between 1wo mr.~i M\e
=rly equi,'llle111 drmi:nl s1-ili but are 001

em<11y i<le1tical
Tl,: nu, of MJ is lw'i;t (> 10) 1111d Tir ra, of Au/J is small 1111d llltlr\jly

'"'"kly an..,l,d i, first order spa:cr.,. coupled In fir.i order spcaru.

~I- J -lh
I .... I ~ ....
Stn..,.....,.,11... _ _ _,,.
\\.,,l coupling. ftnt-ordu SJ)«U'I
(.l>IJ l.irgc) U1fJ •nwll

Or. C. Kr1shn.a.iW2my P"!lo23

 NMR Spectroscopt

PROTON-DIOCOIJPLED 1.IC Sfl£CTRA

Prolo ndecoupling is nccorq>lislrd in Lile process of determining a 13CN~f Rspe<-trum
by simuh:mt011<ly irrudintiag •ll of th, pm tons in the 1ml« ulc ,vilh • brood mn!J! of
frequencies in the proper runge. for th~ • sCOJol 1unal,,le radiofrcqucncy !,"'1>:n11or
tho decoupler b Uffll. l1'1'11dl•lc>n coWIC5 the ;>moon< 10 be""'" .,,,,..,.,u and they
111w:l<1l\O rapil upwnrd nnd dow,_rd 1rnn,ltbr11 among nil LI" 1»S<hle , pin su,ies,

Tlr..se rapif lr.lnsiuo11." decoupk any spin~spin inrerx:Lion betwee.n tllic b)'WOge.n and
~Ill "C tu:k:i being oilsen--ed. The C1rbo11 nucleus :scosn only one a,=gc spin state
i>r the auacred h)drogcn.'i rJtbcr limn h\tO o r nnrc distixt spin .!ii 111c.s~

•
OFF-lilllONANCE DEOOOPUNG
Tbe decoo.pling i,clmque tmt i< 11<ed to obtain l)picll proton decoo.plod spectra 111,
the udvJn •BC thot all pC:Jk!i become •inglcts. U11for1unately much useful i11fomo11v11
~ 111111 are .1111w: tr.d lo a p~1a:ubr CQrbon is b.s1 wh:n curhon
number of h)'dmg,m_

~iocrrn on, d<Couplcd. /I ronp romldng technlqU" olle.d off.resonair< da:oupllng

can o £ten pt>\'ide multit>E L inforauti:m while keep.mg the spec Lrwn re:Jatkely s.inµ le

in nppear:ure.
Till o[f..t'CJOmocc dccouplol !l)l'Clrum rctnlus l11: COl.l)lmg bctwttn the carbon olom

Or. C. Kr1shn.a.iW2my P"!l• 2 4

 NMR Spectroscopt

nnd d Ll'i'Ct1y nnru: led [ll'IIIOIU bll efi!(1i1e ly r, lffl\l!J 11>! coupll11g btl"ttn Ille Clll'bou
mxl 1mn- rem:>1e protons. Th! nt-1 rule can be used to deu.-rmir.e whetlrr 11 given

curbon l1lOIII has three, ~""- one or no b)drogen; ollllclrd.

111 1hl, 1echnique. the frcqu,rc y of ,ero1d radlofn:q..,n::y 1m11s111h1er (cloco~1ler) Is
""' either up fold or dnwn field. FLrthcr more in off.rc.1<>mn:e deooo.pllng lie ()O\\~r
of 1hc dceoo.plng oscillmo r k hell b w 10 avoU <ot'1'~"' decou1>li1g.
Co,,.iler the otr-re.sonance deroo.pl,d spectra of l-pmpt100l (CH; Cli?CfuOHJ. 11,e

-CH1 prll!ll0Sspli1 imo uj)leuas ntl rules ioce iDtaroon ii directly aw:bed IO 1wo
pro101u and dXff. ti no couping bctwecn 01J-r r Uloms.
l JIV'®'
II

-"{-11 HI

In CH; group spli 1110 qwu,., pe:,k due to ~11-.c prollln5 cfu:c~ atwd,od ID Clrbon

- -
-
-
Or. C. Kr1shn.a.iW2my P~t,25
 NM R Spectroscopt

NUCLEAR O\/ERHAUSt:R ENHANCEM lrNT (NOEi

\Vlrn a pu10n decoL4Jk!d spectm were recorded the in~nsiLies of many of 1.tr c-nrbon
resonaoces irrre:i..~ sign.ificut.ly obove lhose obsen1!d in a pt>IDn oouplcd
c.<pcrimcm. Corbon ntoms wkh h)dm!l' ll ntoms dircc1ly nunchcd arc enhanced the
nu9 und 1~ cnb.trrcmem inr:reaies &1$ n"Dte hydrogen i.t 1111 uc lc t1. Thi.s effect is
k1ll>\V1\ as nucl:ur overhl1U$CI' efface :md the <leg.rec of mcrentc! i11 the sigrnl K ca ltcd
die wdear o,·u luuBer e lib:uremenl (NOE).

Tb: NOE elra is heleronu:l::ar operating be1ween 11\0 dissimilar a1nms. Both alOms
C.l; hfbil spins ;ud 11.n: NMR aclhc. \Vhen one of tw1> dUTercnl l )t>CS of ntoms i.s
l11'1tdlJi1od. wldlc 1hc NMR spoc1rum of the o Lll'r l)llC l, dcuirmincd •nd If 1hc
ime 1l'i i1 ics: of ob$C.r\Cd i.e. nonimulin1.ed ntom ch:lngc indic1uc t.nlnn:crrent ha.'i
occurred. The effect t"n l\ be clt.re:r p.:,sitive o r ncgnti\e. T h! nia:<lmum cntnrrement
lin t can be ollR'rvcd is gi\'"en by~ rel:monship

Wll'rc Ya II 1hc 1mg11CIO~Tlc l'llll> or 1he nucleus being irntdiulod and y... l• Ille
nugretogync rntio or tlr 11.JC.r:l.5 obse.ned
Signal enba.na!~ct due ID NOE is :in exnmple of cross pol:aJi1.ation in which a
polw·iznt..i>n or lh: 1pin .state in ore l)pe of nuclcm c.,.us,es u pobu:imtion or lbc spin
.st.me In another nu;:l•lL't, Herc. when Lt~ hydmgcni in 1hc n'IJk:culc W't irmdi.i.tcd. Lhcy
l::.ect111~ uurmed 1.u1tl mta.m a di.'\lrlbullon or ~pins ve,·y dl!W!rc11 fro m lhcll'
oqulllbrlum , .., .There""' nnrespin.< tlnn nomul in LIE cxc i cd s=. Due 10 this
inre.rncti>n of spin dipoles llhc spins of the camon nod,i sense Ll,c spin imbahncc of
the hydrogon nuclei ond begin IO odj1a t tl•m1so 1,,.,, ID• new equUib rium , .., Llllll has
rm rc .spins in 11Y: bwcr .sUllt . Thi., mcnrnsc ofpopublion In the '°"'ff spin stotc of
cnrbon inc""-"" d,e h1cn.~ ty oflhc NMR signal
In a 111-omn &:couples I 3C .sp«rrum Lile total NOE i>r :i gh-e ncu.rbon me.rem.es us Lhe
1111nbe.r ofrearby hydrogen n:reases. 1lie iru.•Jl<ity oflhe signal asSUDli:s lhe order.

CH,>CHz> CR >C

Or. C. Kr1shn.a.iW2my P"!l• 2<,