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UNIVERSITATEA VASILE ALECSANDRI DIN BACU

FACULTATEA DE INGINERIE

SPECIALIZAREA

CoSAMIB

SPECTROSCOPIA 13C-RMN

MASTERAND,

Andreea BORTA

2013


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Cuprins

1. INTRODUCERE. GENERALIT I ..........................................................................3

2. SPECTROSCOPIA 13C- RMN..................................................................................... 4

Caracer!"!c! #$nda%ena&e......................................................................................... 5

Par!c$&ar!' ! ...........................................................................................................5

D(%en!! (r!ena!)e de a*ar! !e a "e%na&e&(r 13C...............................................................5

3. TE+NICA DE LUCRU 13C-RMN. DEPLASAREA C+IMIC.............................................6

. SPECTRE 13C-RMN. DECUPLAREA DE SPIN +ETERONUCLEAR...............................7

. APLICA II .............................................................................................................8

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1. INTRODUCERE. GENERALIT I

Sa!&!rea "r$c$r!! c(%*$/!&(r (ran!c! e"e ( *r(&e%' #rec)en' /! d!#!c!&' a c!%!e!(ran!ce #!e c' e"e )(ra de $n c(%*$" na$ra& "a$ $n *r(d$" ar!#!c!a&, de "!ne', "$ne%

*er%anen c(n#r$na4! c$ ne)(!a de a "a!&! "a$ a )er!#!ca "r$c$ra &$!. M$& !%* "!n$ra

*("!!&!ae de de%(n"rare a "r$c$r!! "e aa *e %e(de c!%!ce. Ace"ea c(n"a$, de re$&',5n ran"#(r%area "$"an4e! "$d!ae 5n c(%*$/! c$ %(&ec$&e %a! %!c! 6(*era4!e e#ec$a'ade"e(r! *r!n (7!dare8 a&e c'r(r "r$c$r! #$"e"er' "a!&!e aner!(r. 9n (r!ce ca ace"e (*era4!!"$n de("e! de &a(r!(a"e, n$ de *$4!ne (r! !%*&!c:nd %$nca *e er%en &$n a $n(r 5nre!ec!*e de c!%!/! e7*er!%ena4!. 9n *er!(ada %(dern' a c!%!e! (ran!ce 6a*r(7!%a!) $&!%a

;$%'ae de "ec(&8 "-a$ de)(&a 5n"' ( "er!e de %e(de #!!ce de !n)e"!are "r$c$ra&'"*ecr("c(*!a (*!c' 5n !n#rar(/$ 6IR8, /! $&ra)!(&e-)!!!& 6U$a"!$nan!%' a %e(de&(r #!!ce. R'%:ne, de"!$r, %$nca de!ner*reare a dae&(r "*ecra&e. Acea"a n$ %a! re*re!n', de %$&' )re%e, ( ac!)!ae c$caracer e7ce*4!(na&. D!%*(r!)' #ace *are d!n %e(de&e e7*er!%ena&e (!/n$!e, $!&!ae

*rac!c c(!d!an de c!%!"$& (ran!c!an %(dern. De aceea e"e !%*(ran' ( !n"r$!re 5n ace"d(%en!$ 5nc' d!n #ae&e !%*$r!! a&e "$d!$&$! c!%!e! (ran!ce. D!nre (ae %e(de&e #!!ce,re(nan ' %ane!c' n$c&ear' 6RMN8 e"e aceea care (#er' cea %a! (a' ! c(%*&e'

!n#(r%a !e "r$c$ra&' a"$*ra c(%*$ !&(r (ran!c!. S*re de("e!re de "*ecr("c(*!a IR, 5n RMN *rac!c (ae "e%na&e&e "$n !ner*rea!&e re&a!) $ (r, !ar "*re de("e!re de"*ecr("c(*!a e&ecr(n!c' %e(da RMN (#er' %$& %a! %$&e !n#(r%a !!. 9n !%* ce"*ecr("c(*!a IR "a$ ce&e de %a"' "$n *rea (ae 5n !n#(r%a !!, dec! re$ !ner*rea!&e, !arce&e U


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c8 n$c&!!! 5n care a: *r((n!! c: ! ne$r(n!! "$n *reena ! 5n n$%'r !%*ar ! a$ )a&(r!I !nre!I1F2F3 6e7!"a n$%a! a"e%enea n$c&!! "a!&! 2D, L!, 10B, 1N, 0


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!((*$&$! 13C (#era !n#(r%a !! cr$c!a&e de"*re !n"' ! "ce&e$& %(&ec$&ar a& $n$! c(%*$" (ran!c, deecarea ace"$!a *r!n RMN e"e de !%*(ran ' #$nda%ena&'.

RMN-$& a de)en! #'r' 5nd(!a&' en!ca cea %a! *$ern!c' *enr$ caracer!area"r$c$r!&(r, "$d!! de "ere(c!%!e ! de c(n#(r%a !e a n(!&(r %(&ec$&e (ran!ce ! acea"a

da(r!' 5n "*ec!a& ce&(r re! *ara%er!1. De*&a"area c!%!c'2. S$*ra#a a *!c$r!&(r3. C(n"ane&e de c$*&a;

Caracteristici fundamentale

1. de*&a"area c!%!c' a !((*$&$! 13C "e e7*r!%' e7ac &a #e& ca "! *enr$ 1+, ad!c' 5n*.*.%F

2. d(%en!$& de )ar!a !e a& de*&a"'r!&(r c!%!ce *enr$ 13C e"e %$& %a! &arF3. de*&a"'r!&e c!%!ce a&e n$c&e$&$! !((*$&$! 13C "e da$ *r!n ra*(rare #a ' de ace&a

"andard ca ! 5n ca$& 1+ RMN de*&a"area c!%!c' a n$c&e$&$! 13C 5n era%e!&"!&an 6TMS8e"e c(n"!dera' 0.

Particularit i

1. de(arece n$c&e$& !((*$&$! 13C de)(&' c$*&a;e de("e! de *$ern!ce c$n$c&e$& !((*$&$! 1+ 6de (rd!n$& ec!&(r de +8, "*ecre&e 13C RMN *( #! e7re% dec(%*&!cae, "e%na&e&e a*'r:nd "$ #(r%' de c$are,r!*&e "a$ d$&eF

2. 5n "c(*$& "!%*&!#!c'r!! %a;(re a "*ecre&(r 13C-RMN e"e ce& %a! ade"ea*re#era' 5nre!"rarea ace"(ra *r!n en!c! "*ec!a&e care "$*r!%' rea&!area c$*&a;e&(r 13C-1+a"#e& 5nc: "e%na&e&e 13C "' a*ar' #'r' e7ce* !e "$ #(r%' de "!n&e !

Domenii orientative de apari ie a

semnalelor 13C

C+3 0-3 **%FC+2 1-0 **%FC+ 2-0 **%F

C+2Br 20-0 **%FC+2C& 2-0 **%FC+2N+2 3-0 **%FC+2O+ 0- **%F-CKC- -@0 **%FCKC 100-10 **%F

Ar(%a!c! 110-1 **%FC O 1@0-220 **%F

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3. TEHNICA DE LUCRU 13C-RMN. DEPLASAREA CHIMIC

Penr$ "*ecr("c(*!a 13C-RMN "e #(&("e"c "(&)en ! an(ran!c! ca + 2OF D2OF +2SO"a$ "(&)en ! (ran!c! ce c(n !n d(ar 1 - 2 !*$r! de a(%! de car(n d!#er! !, de (!ce! ( "(&)en !! de$era ! ca CDC& 3F CD2C&2F CDF 6D3C82COF 6D3C82SO. 9nr$c: (ae a*arae&e

%(derne #(&("e"c *enr$ anc(rare #rec)en a n$c&ee&(r de de$er!$, dac' "(&)en$& a&e" n$e"e de$era %!"c!!&, "e%na&$& de re#er!na e"e de (!ce! ce& a& era%e!&"!&an$&$!, "andard!nern $!&!a ! 5n "*ecr("c(*!a 1+-RMN.

S*ecr$& RMN e"e c$ra a"(r !e! de ener!e rad!a' 6rad!a !! e&ecr(%ane!ce8 de c're n$c&ee&e *r(e!, 5n #$nc !e de c:%*$& %ane!c a*&!ca 65n ca$& a&e!a;$&$! de c:%*8 "a$5n #$nc !e de #rec)en a 65n ca$& a&e!a;$&$! de #rec)en '8. 9n %(%en$& *&a"'r!! *r(e! 5n c:%*$& %ane!c, c!rc$&a !a e&ecr(n!&(r de &ea$r' e"e %(d!#!ca', 5n "en"$& c', 5nc(n#(r%!ae c$ *r!nc!*!$& ac !$n!! ! reac !$n!!, e! 5nce* "' "e %! e a"#e& 5nc: "' eneree $n c:%* %ane!c (*$" ca "en" c:%*$&$! e7er!(r. A*are a"#e& $n e#ec de ecranare

d!a%ane!ca, care d!%!n$eaa c:%*$& e7er!(r ce *'r$nde *:n' &a n$c&e$& re"*ec!). Acea"'ecranare e"e de"!$r #(are %!c', ea a!n:nd &a *r((n! %a7!%$% 10 %!&!(n!%! d!n )a&(areaa"(&$' a c:%*$&$!. 9n %(d e)!den ecranarea d!a%ane!c' e"e *r(*(r!(na&' c$ den$%!reade e&ecr(n! d!n ;$r$& n$c&e$&$! re"*ec!), den"!aea c(nd!!(na' de an$ra;$& c!%!c, dee#ece&e ar''(are "a$ re"*!n'(are de e&ecr(n! ec. La cre erea 6de"!$r c$ )a&(r! #(are%!c! 8 a c:%*$&$! e7er!(r, )(r a*'rea *e r:nd "e%na&e *enr$ d!#er!e !*$r! de n$c&ee, 5n#$nc !e de rad$& &(r de ecranare. E"en a %e(de! RMN ! "en"!!&!aea e! c(n"a$ (c%a! "e"!area ! d!#eren !erea 5nre n$c&!! de ace&a ! #e& 6de e7e%*&$ *r((n!8 a)and ecranar! d!#er!e. Inr-$n "*ecr$ RMN n$c&ee&e %a! *$ern!c ecranae da$ "e%na&e &a c:%* %a! %are

6re"*ec!) #rec)ena %a! %!ca !n ca$& a&e!a;$&$! de #rec)ena8 c(%*ara!) c$ n$c&ee&e %a!*$!n ecranae.

D!#eren a )a&(r!&(r c:%*$r!&(r %ane!ce de re(nan ' 6&a a&e!a;$& de c:%*8 "a$ a #rec)en e&(r de re(nan ' 6&a a&e!a;$& de #rec)en '8 5n #$nc !e de )ec!n'' !&e "r$c$ra&e "e n$%e"e deplasare ci!ica. De*&a"area c!%!c' !nd!c' dec! *(! !a d!n "*ecr$& a "e%na&$&$!#!ec'r$! n$c&e$. Ea *(ae #! de#!n!' 5n %(d a"(&$ *r!n e7*r!%area %'r!%!! c:%*$&$! "a$#rec)en e!. Ace" %(d de e7*r!%are n$ e"e $!&!a 5n *rac!c' d!n ca$a c' e& ar #! !nc(%(d ! ar de*!nde de a*ara. Se rec$re de aceea &a e7*r!%area de*&a"'r!! c!%!ce ca d!#eren are&a!)' de ecranare a n$c&e$&$! 5n ra*(r c$ $n "andard. D$*' c$% "-a a%!n! ! %a! "$"

"andard$& $$a& e"e de ce&e %a! %$&e (r!, a: *enr$ 1+-RMN c: ! *enr$ 13C-RMN,era%e!&"!&an$& 6C+38S! 6*re"c$ra TMS8, care are $n "e%na& $n!c 6a& ce&(r *ar$ a(%! decar(n, re"*ec!) a& ce&(r 12 *r((n! ec!)a&en!8 ce a*are &a e7re%!aea de c:%* %ane!c%a7!% a "*ecr$&$! 6n$c&ee #(are ecranae8. TMS "e d!(&)a de (!ce! 5n *r(' 6"andard!nern8 #!!nd !ner d!n *$nc de )edere a& reac!)!' !! c!%!ce ! #(are )(&a!&, e& "e *(ae 5nde*ara $ (r (da' c$ "(&)en$&, *er%! :nd rec$*erarea *r(e! *rac!c *$re. 9n ca$& "*ecre&(r 13C-RMN de*&a"'r!&e c!%!ce a$ )a&(r! %$& d!#er!e 6d13C0-220 **%, !n enera&8.

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4. SPECTRE 13C-RMN. DECUPLAREA DE SPIN

HETERONUCLEAR

9n ca$& "*ecre&(r 13C-RMN, re$!e a)$ 5n )edere c' &$cr:nd c$ a$nden e&en$c&eare 6@,@J C c$ I0 "! 1,1J 13C8 c$*&a;e&e C - C "$n *rac!c !n)!!!&e, c'c!

*r(a!&!aea a*ar! !e! a d(! a(%! 13C )ec!n! e"e ne&!;a!&'. Ace" #a* *(ae #! c(n"!dera (#er!c!' *(r!)!re a a$nden e&(r na$ra&e, c'c! dac' n$c&!d$& 13C c$ I d!#er! de er( ar #! #("

*red(%!nan, c$*&a;e&e C - C d!n (r!ce caen' ar #! #'c$ !%*("!!& de !ner*rea "*ecre&e 13C-RMN. Pe de a&' *are, ( a$nden ' ! %a! %!c' a !((*$&$! 13C ar #! "c'$ "en"!!&!aea%e(de! "$ &!%!a ad%!"!!&'. R'%:n de &$a 5n c(n"!dera !e c$*&a;e&e 1+ - 13C, care c(%*&!c'5n rea&!ae "*ecre&e 13C-RMN, dar care "$n de (!ce! (a& e&!%!nae *r!n ceea ce "e n$%e"edec$*&are de "*!n eer(n$c&eara *r!n (%(. Ten!ca $$a&' de dec$*&are eer(n$c&ear'c(n"' 5n !rad!erea c(nc(%!en', *e de(*are c$ #rec)en a c(re"*$n'(are e7c!'r!! n$c&ee&(r13C, ! *e de a&a *are c$ ( #rec)en ' %(d$&a' de dec$*&are, c(re"*$n'(are *r((n!&(r )61+8 &a 2000 Oe, c$ ( &ar!%e de %(d$&are de 1000 +. E#ec$& e"e ec!)a&en c$ !rad!erea"!%$&an' a $$r(r *r((n!&(r c$ #rec)en e&e &(r c(re"*$n'(are.

9n "*ecr$ "e ("er)' *e de(*are ( !nen"!#!care a &!n!!&(r, *r!n r$*area "e%na&e&(rda(r!e ace&$!a ! car(n, *e de a&a *are ( !nen"!#!care "$*&!%enar' c(n"!dera!&' 6*:n' &a30J8 da(r!' e#ec$&$! O)era$"er n$c&ear 6EON8. 9n e"en ', ace" e#ec c(n"' 5n!n#&$en area #a)(ra!&' a *(*$&a !e! "*!n!&(r car(n$&$! *r!n dec$*&area ace"$!a de *r((n!! c$ care #$"e"e c$*&a. Odaa c$ dec$*&area eer(n$c&eara "e *!erde 5n"' !n#(r%a !a "r$c$ra&'

*r!)!nd n$%'r$& *r((n!&(r &ea ! de #!ecare car(n. D!n #er!c!re e7!"' *("!!&!aea de re'"!rea ace"e! !n#(r%a !!, e#ec$:nd$-"e &a d(r!n ', d$*' ce "e 5nre!"rea' "*ecr$& n(r%a& dec$*&a, $n "*ecr$ *ar !a& dec$*&a 6(## re"(nance8 care %en !ne d(ar ( %!c' *are d!n c$*&a;e&e *r((n!&(r d!rec &ea ! 6( #rac!$ne d!n 1C+8 e&!%!nand ce&e&a&e c$*&a;e 62C+F3C+ ec.8. 9n a"e%enea "*ecre, car(n!! r$*e&(r %e!& a*ar "$ #(r%' de c$adr$*&e ! c$!nen"!' ! 1331, car(n!! r$*e&(r C+ 2 "$ #(r%a de r!*&e ! c$ !nen"!' ! 121, car(n!! r$*e&(r C+ "$ #(r%' de d$&e ! c$ !nen"!' ! 11 !ar car(n!! ce n$ "$n &ea ! de a(%! de !dr(en a*ar ne"c!nda !. Ace"e dae "e n(ea' $ne(r! *e "*ecre&e 13C-RMN *$&!cae, "$#(r%a >6C+38 6C+28 d6C+8, ! "6C8, n(a a&'$r! de #!ecare "e%na& 6>-c$areF -r!*&eF d-d$&eF "-"!n&e8. O !%*(ran' de("e!' ( *re!n' "*ecr("c(*!a 13C-RMN *enr$ "$d!$&c(%*$ !&(r ar(%a!c! 6!n "*ec!a& *(&!c!c&!c!8 c$ "ce&e car(c!c&!c "a$ eer(c!c&!c. Laa"e%enea c(%*$ !, c$*&a;e&e %$&!*&e +-+ n$ *er%! e&$c!darea "*ecre&(r 1+-RMNF deaceea "*ecre&e 13C-RMN r'%:n "!n$re&e care ad$c !n#(r%a !! "r$c$ra&e. 9n "c(*$& ar!$!r!!"e%na&e&(r 13C-RMN *( #! $!&!ae "! a&e %e(de c$% ar #!

a) %arcarea c$ 13C-RMN !%(' !, *r!n "!ne', 5n *(! !! "*ec!#!ce ! ("er)area "e%na&e&(r care cre"c 5n !nen"!aeF

b) de$erarea, *r!n "!ne', c$ %arcarea $n(r *(! !! "*ec!#!ce "a$ *r!n "c!% !((*!c a&&e'$r!! C-+. Tre$!e %en !(na c' 5nr$c: de$er!$& are "*!n n$c&ear 6I18 "e%na&$&CDC&3 !n "*ecr$& 13C-RMN e"e $n r!*&e c$ !nen"!' !&e 111 6"c!ndarea !n 2I1&!n!!8F

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9n "*ecre&e 13C-RMN dec$*&ae eer(n$c&ear *r!n (%( de c$*&a;e c$ *r((n!, c$*&a;e&e c$de$er(n! r'%:n nea#ecae d!n ca$a "c!nd'r!! &!n!!&(r c(re"*$n'(are car(n!&(r ce "$nde$era ! ! d!n ca$a a"en e! e#ec$&$! O)era$"er n$c&ear, "e%na&e&e r$*e&(r CD, CD 2"a$CD3"e d!"!n !%ed!a 5n ra*(r c$ ace&ea ! r$*e nede$erae, *r!n !nen"!aea %$& %a! %!ca

a "e%na&e&(r car(n!&(r de$era!. 9n $r%a de$er'r!!, "e%na&e&e car(n!&(r ce *(ar' de$er!$d!"*ar *rac!c c(%*&e, !ar ce&e a&e car(n!&(r 5n)ec!na ! c$ ace !a "$n d!%!n$ae da(r!a c$*&a;e&(r &a d!"ana. Un a)ana; c(n"!dera!& a& "*ecre&(r 13C-RMN #a ' de "*ecre&e 1+-RMN 5& c(n"!$!e #a*$& c' d(ar *r!%e&e *( !den!#!ca r$*e&e &!*"!e de !dr(en c$% "$nr$*a ce(n!c', n!r!&, e"er car(7!&!c. Preen a ace"(r r$*e *(ae #! c(n#!r%a' de "*ecre&eIR, dar "e !e c' $ne(r! !nen"!aea a"(r !e! IR *enr$ r$*a CN e"e a: de %!c' 5nc: d(ar "*ecre&e 13C-RMN r'%:n 5n ace"e ca$r! $n d!an("!c "r$c$ra& "!$r.

. APLICA II

9n "!nea (ran!c'- e&$c!darea "r$c$r!! c(%*$!&(r (ran!c! ! deer%!narea "ere(c!%!e! ! c(n#(r%a!e! ace"(ra

9 n c!%!a "$"ane&(r na$ra&e-deer%!narea "r$c$r!! ! "ere(c!%!e! d!#er! !&(r c(%*(nen! (!n$! d$*'!(&area "! *$r!#!carea #rac!$n!&(r

9n ana&!a a%e"ec$r!&(r- ana&!a ca&!a!)' ! can!a!)' a a%e"ec$r!&(r de "$"an e (ran!ce

9n "$d!$& *(&!%er!&(r-ana&!a $n!'!&(r de %(n(%er ! deer%!narea "r$c$r!!

ANALI?A CALITATI

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