lucia bonilla - tesis doctorado - fq.edu.uyriquim.fq.edu.uy/archive/files/c8bc46ec90d10a0da2c... ·...
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Transcript of lucia bonilla - tesis doctorado - fq.edu.uyriquim.fq.edu.uy/archive/files/c8bc46ec90d10a0da2c... ·...
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A
B
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14
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!
15
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% ,G! >;@AGB;I>! K;F?<;BG! ADFADED>@G! U>! >UDH=! MDBG>;EM=! <D! EDjGK;bGB;I>! D>! KG!M=<UKGB;I>! <D! KGE! ADEFUDE@GE! BDKUKGADE! G>@;a;>ZKGMG@=A;GE! C! G<GF@G@;HGE! mQPn8! ,=E!>;@A=GKTUD>=E! M=<UKG>! DK! ZD>=@;F=! ;>ZKGMG@=A;=! <D! MGBAIZGJ=E! C! >DU@AIZ;K=Ek! ADJUKG>! KG!GB@;H;<G<!<D!ZGB@=ADE!<D!@AG>EBA;FB;I>! ;>H=KUBAG<=E!D>!<;HDAE=E!FA=BDE=E!BDKUKGADE!mO`k!QLaQOnk! D\DABD>! DZDB@=E! BGA<;=FA=@DB@=ADE! <UAG>@D! KG! ;>\UA;G! F=A! ;ETUDM;G! ADFDAZUE;I>! =! DK!FADGB=><;B;=>GM;D>@=! ;ETUVM;B=!D>!M=<DK=E!<D! B=AGbI>!G;EKG<=k! C!M=<UKG>! KG!GB@;HGB;I>!<D! KGE! @DAM;>GB;=>DE!>DAH;=EGE!>=B;BDF@;HGE! GE=B;G<G! GK! DE@AVE! >;@A=a=:;<G@;H=! mPQk! OQk! QQk!Qcn8!,GE!FA=F;D<G<DE!<DEBA;F@GE!;>;B;GKMD>@D!D>!M=<DK=E!!"#$!)-%k!G<TU;A;DA=>!JAG>!F=@D>B;GK!S;=KIJ;B=!BUG><=!ED!<DM=E@AI!KG!E?>@DE;E!D><IJD>G!<D!>;@A=K?F;<=E!D>!B=><;B;=>DE!>=AMGKDE!C!ZAD>@D!G!DE@?MUK=E!FA=a;>ZKGMG@=A;=E!mPPk!PLk!PQk!Pck!OQk!QRac7n8!!! ,G! ;>ZKGMGB;I>! DE! U>G! B=MFKD\G! ADEFUDE@G! <DK! =AJG>;EM=! G! KG! FD>D@AGB;I>! <D! U>!GJD>@D!;>ZDBB;=E=!=!<Gj=!BDKUKGAk!B=>!DK!Z;>!ADM=HDA!DK!DE@?MUK=!<D!KG!;>\UA;G!GE?!B=M=!;>;B;GA!DK! FA=BDE=! >DBDEGA;=! FGAG! EG>GA! DK! @D\;<=! mc9n8! #E! U>! FA=BDE=! Z;E;=KIJ;B=! BA?@;B=! FGAG! DK!MG>@D>;M;D>@=!<D! KG!_DM=E@GE;Gk!FDA=!DE@N! @GMS;V>!GE=B;G<=!GK!<DEGAA=KK=!<D!>UMDA=EGE!FG@=K=J?GE! B=M=! KG! G@DA=EBKDA=E;E! =! DK! ;>ZGA@=! <D! M;=BGA<;=! mcPn8! ,=E! >DU@AIZ;K=Ek!M=>=B;@=EXMGBAIZGJ=Ek! FKGTUD@GE! C! BVKUKGE! D><=@DK;GKDEk! ADEF=><D>! G! KG! DE@;MUKGB;I>! F=A!GJ=>;E@GE! G<=F@G><=! U>! ZD>=@;F=! FA=a;>ZKGMG@=A;=! TUD! ED! BGAGB@DA;bG! F=A! !&! KG! M;JAGB;I>!BDKUKGA!_GB;G!DK!Z=B=!;>ZKGMG@=A;=k!!!&!KG!D:F=E;B;I>!<D!FA=@D?>GE!<D!EUFDAZ;B;D!eD\8l!EDKDB@;>GEf!TUD!ZGB;K;@G>!DK!ADBAU@GM;D>@=!<D!KDUB=B;@=E!_GB;G!DK!E;@;=!<D! ;>ZKGMGB;I>!F=A!G<_DE;I>!B=>!FKGTUD@GE!C!BVKUKGE!D><=@DK;GKDEk!!!!&!KG!FD>D@AGB;I>!<D!KGE!BVKUKGE!EG>JU?>DGE!G!@AGHVE!<D!KGE!FGAD<DE! HGEBUKGADE! mcLk! c^n8! (DBU><GA;GMD>@D! GK! BGMS;=! ZD>=@?F;B=k! KGE! BVKUKGE! GB@;HG<GE!K;SDAG>! MD<;G<=ADE! ;>ZKGMG@=A;=E! B=M=! KGE! B;@=TU;>GEk! TUD! ADJUKG>! KG! ADEFUDE@G!;>ZKGMG@=A;G8!%KJU>=E!<D!KGE!D>b;MGE!BUCG!D:FADE;I>!ED!;><UBD!D>!ADEFUDE@G!G!KG!GB@;HGB;I>!<D!JD>DE!;>ZKGMG@=A;=E!E=>!KG!0,%9k!0WY(a9k!&)(9k!C!KGE!&%/0Y!=:;<GEGE!e&):f8
16
;><UBD! KG! E?>@DE;E! D><IJD>G! <D! >;@A=K?F;<=Ek! TUD! <;EM;>UCD>! KG! ADEFUDE@G! ;>ZKGMG@=A;G! C!ZGB;K;@G>!KG!ADE=KUB;I>!<D!KG!;>ZKGMGB;I>!mPcn8!,=E!>;@A=GKTUD>=E!<;EM;>UCD>!KG!D:FADE;I>!<D!&)(9! C! KG! EDBADB;I>! <D! KGE! B;@=TU;>GE! FA=a;>ZKGMG@=A;GE! ',aO! C! .&[v! D>! ADEFUDE@G! G!K;F=F=K;EGBNA;<=E! e,0(f! F=A! MDBG>;EM=E! ;><DFD><;D>@DE! <D! KG! Z=AMGB;I>! <D! h&)k! KG!GB@;HGB;I>! <DK! ADBDF@=A! 00%3�k! =! KG! ;><UBB;I>! D>! KG! D:FADE;I>! <D! KG! D>b;MG! G>@;a=:;<G>@D!_DM=! =:;JD>GEGa7! eY)a7f! mcOn8! .GMS;V>! ;>_;SD>! KG! G<_DE;I>! <D! K=E! M=>=B;@=E! GK! KDB_=!D><=@DK;GK! mcOnk! ;MF;<;D><=!KG!M;JAGB;I>!@AG>ED><=@DK;GK!_GB;G! KG! ?>@;MG!C!EU!<;ZDAD>B;GB;I>!_GB;G! MGBAIZGJ=E! MD<;G>@D! KG! ;>_;S;B;I>! <D! KGE! M=KVBUKGE! <D! G<_DE;I>! FADED>@DE! D>! KGE!BVKUKGE! D><=@DK;GKDE! GB@;HG<GE! eD\8l! 0aEDKDB@;>Gk! #aEDKDB@;>Gk! M=KVBUKG! <D! G<_DE;I>!;>@AGBDKUKGAa7k!=!2$%"a7f! mcOn8!%!M=<=!<D!D\DMFK=k!DK!<DA;HG<=!>;@AG<=!<DK!%%! ;MF;<;I!DK!D>EGMSKG\D!<D!KG!&):!C! KG!FA=<UBB;I>!<D!AG<;BGK!)9
ha!D>!U>!M=<DK=!G>;MGK!<D!;>ZKGMGB;I>!mcQn8! $=>! ADEFDB@=! G! K=E! MDBG>;EM=E! <D! GBB;I>! FA=FUDE@=E! FGAG! DE@GE! GB@;H;<G<DE! G>@;a;>ZKGMG@=A;GEk! ED! F=E@UKG! TUD! KG! M=<UKGB;I>! <D! KGE! BVKUKGE! FA=a;>ZKGMG@=A;GE! F=A!>;@A=GKTUD>=E! DE@N! MD<;G<Gk! GK! MD>=E! D>! FGA@Dk! F=A! KG! >;@A=GKTU;KGB;I>! <D! ZGB@=ADE! <D!@AG>EBA;FB;I>! >UBKDGA8! #K!&)9)%! C!&)9,%! GKTU;KG>! 00%3�! D>! U>! ADE;<U=! <D! B;E@D?>G! BA?@;BG!mPPnk!K=!BUGK!FA=SGSKDMD>@D!@;D>D!B=>EDBUD>B;GE!>=!E=K=!D>!K=E!FA=BDE=E!;>ZKGMG@=A;=E!E;>=!@GMS;V>! D>! KG! ADJUKGB;I>! <DK! SGKG>BD! D>DAJV@;B=! C! KG! G<;F=JV>DE;E! mPPk! ORn8! #K! ZGB@=A! <D!@AG>EBA;FB;I>!&[�1! @;D>D!U>! A=K! ;MF=A@G>@D!D>! KG! ADJUKGB;I>!<D! KG! EDBADB;I>!<D! B;@=TU;>GE!FA=a;>ZKGMG@=A;GEk! ZGB@=ADE! <D! BADB;M;D>@=k! M=KVBUKGE! <D! G<_DE;I>! C! FA=@D?>GE! <D! ZGED!GJU<G8! .GMS;V>! DE! ADJUKG<=! >DJG@;HGMD>@D! F=A! GKTU;KGB;I>! <D! ADE;<U=E! GK@GMD>@D!B=>EDAHG<=E! <D! B;E@D?>G! D>! KG! EUSU>;<G<! FO^! <D! U>;I>! G! %/&! mcOn8! #K! &)9,%! ;><UBD! KG!D:FADE;I>! <D! Y)a7! mcOk! cck! cRnk! TUD! @GMS;V>! DE! SKG>B=! FGAG! =@A=E! K?F;<=E! S;=GB@;H=E!<DA;HG<=E! <DK! %%k! B=M=! 7^<a0W]9! mR`n8! ,G! Y)a7!MD<;G! DHD>@=E! BKGHDE! D>! KGE! ADEFUDE@GE!B;@=FA=@DB@=AGE! <DED>BG<D>G<GE! <UAG>@D! KG! ;>ZKGMGB;I>8! ,G! ADJUKGB;I>! <D! KG! D:FADE;I>! <D!Y)a7!DE@N!MD<;G<G!F=A!DKDMD>@=E!<D!KG!ADEFUDE@G!G>@;=:;<G>@D!e%3#Ef!C!DE!F=E;SKD!TUD!K=E!>;@A=GKTUD>=E! ;><UbBG>! KG! D:FADE;I>! D>! Y)a7! F=A! ADJUKGB;I>! <D! 00%3�! =! &[�1! mcRn8! ,=E!>;@A=GKTUD>=E! @GMS;V>! ;>_;SD>! KG! EDjGK;bGB;I>! FA=a;>ZKGMG@=A;G! MD<;G<G! F=A! (.%.!e@AG>E<UB@=A!<D!EDjGK!C!GB@;HG<=A!<D!KG!@AG>EBA;FB;I>#P#3#ZGB@=A!<D!ADEFUDE@G!<D!ZGED!GJU<Gf!MD<;G>@D!KG!;><UBB;I>!<D!"%0!TU;>GEG!Z=EZG@GEGa7!e"%0qa7fk!U>G!Z=EZG@GEG!TUD!B=>@A;SUCD!G!KG!ADE=KUB;I>!<D!KG!;>ZKGMGB;I>!F=A!GK@DAGB;I>!<D!KG!@AG<UBB;I>!<DK!%3&M!G!FA=@D?>GE!mR7n8!,G! ;><UBB;I>!<D!"%0qa7!F=A!>;@A=GKTUD>=E!DE! ;><DFD><;D>@D!<D!KG!GB@;HGB;I>!<D!00%3�k! KG!K;SDAGB;I>!<D!h&)!C!<DK!FA=BDE=!<D!>@;A=GKTU;KGB;I>k!<DM=E@AG><=!TUD!D:;E@D>!MDBG>;EM=E!<D!GBB;I>!<D!K=E!>;@A=GKTUD>=E!Gi>!>=!;<D>@;Z;BG<=E8!
!
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17
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21
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22
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23
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24
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<D!&9k!ADEUEFD><;<GE!D>!MD@G>=Kk!C!G>GK;bG<GE!C!BUG>@;Z;BG<GE!F=A!,$a"(X"(!mQ7n8!!
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;=>DE! e5.3%0! 9```k! %FFK;D<! 1;=ECE@DMEX"/(! ($'#df! e[;JUAG! 7`%fk! B=>! U>G! ZUD>@D! <D!
;=>;bGB;I>!F=A!DKDB@A=EFAGC!G!FADE;I>!G@M=EZVA;BG!e#('a"(f8!0GAG!KG!;<D>@;Z;BGB;I>!<D!&)9%%!
C!DK!G>NK;E;E!<D!KG!MDbBKG!<D!ADGBB;I>!U@;K;bGM=E!K=E!E;JU;D>@DE!M=<=E!<D!DEBG>D=l!!&!57!EBG>l!
D>!DE@D!M=<=!ED!G>GK;bG>!KGE!ADKGB;=>DE!MGEGXBGAJG!eBCDf!<D!@=<=E!K=E!FA=<UB@=E!FADED>@DE!
D>! KG! E=KUB;I>!D>!DK! AG>J=!<D!BCD# EDKDBB;=>G<=o! !!&! D>_G>BD<!FA=<UB@! ;=>! EBG>! e#0'fl! DE@D!
M=<=! ED! U@;K;bG! FGAG! GUMD>@GA! KG! ED>E;S;K;<G<! C! JD>DAGA! U>! FG@AI>! BGAGB@DA?E@;B=! <D!
29
ZAGJMD>@GB;I>o! ED! EDKDBB;=>G! DK! ;=>! G! G>GK;bGA! D>! 57! C! ED! ZAGJMD>@G! D>! 59! MD<;G>@D!
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KG! @AGMFG! <D! ;=>DE! e5Pf! C! KUDJ=! ED! K;SDAG>! FGAG! EU! <D@DBB;I>o! !!!&! MUK@;FKD! ADGB@;=>!
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DEFDB@AIMD@A=!e"3"fk!=!ED! ;>CDB@GA=>!<;ADB@GMD>@D!D>!KG!ZUD>@D!G!U>!ZKU\=!<D!7`!µ,XM;>!
e57k!#0'f8!,G!BUG>@;Z;BGB;I>!<D!&)9%%!ED!ADGK;bI!F=A!,$!"(X"(!D>!M=<=!"3"!SUEBG><=!KG!
@AG>E;B;I>!BCD!PLcXP`7k!BGAGB@DA?E@;BG!<D! KG!FVA<;<G!>DU@AG!<DK!JAUF=!a&)9k!=!PLcXLOk!TUD!
FA=F=AB;=>G!MGC=A!ED>E;S;K;<G<8!(;DMFAD!ED!HDA;Z;BI!TUD!>=!_US;DAG!B=>@GM;>GB;I>!B=>!%%!
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+@;K;bGM=E!FGAG!DKK=!U>G!B=KUM>G!$7c!EDM;aFADFGAG@;HG!e^!�Mk!7`MM!:!9^BMk!+K@AGEF_DAD!
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ZIAM;B=!`8`^zf!C!1!eGBD@=>;@A;K=XNB;<=!ZIAM;B=!`8`^!zf!D>!KGE!E;JU;D>@DE!B=><;B;=>DEl!P^!z!1!
e`! G! 7`!M;>fk! 7``!z!1! e7`! G! P^!M;>fk! P^!z!1! eP^! G! L^!M;>f! mQ7n! G! U>! ZKU\=! <D! 9!M,XM;>8!
'>CDB@GM=E!_GE@G!7!MJ!<D!&)9%%!FUA=!F=A!B=AA;<G!C!KGE!SG><GE!B=>!MN:;M=!<D!GSE=ASG>B;G!
G!9QL!>M!ZUDA=>!B=KDB@G<GE!G!KG!EGK;<G!<DK!Y0,$!D>!_D:G>=X;E=FA=FG>=KXNB;<=!GBV@;B=!FGAG!
ADGK;bGA! U>G! D:@AGBB;I>! K;F?<;BG! F=A! _D:G>=8! '<D>@;Z;BGM=E! K=E! ;EIMDA=E! FADED>@DE! D>! BG<G!
SG><G!B=KDB@G<G!F=A!57!EBG>!=FDAG><=!D>!DK!M=<=!<D!;=>;bGB;I>!F=E;@;H=!D>!FADED>B;G!<D!
GBD@G@=! <D! K;@;=! ^! M"8! #>! FADED>B;G! <D! K;@;=k! ED! SK=TUDG! U>G! BGAJG! F=E;@;HG! D>! DK! JAUF=!
BGAS=:;K=! <DK! >;@A=GKTUD>=! K=! TUD! ZGH=ADBD! KG! ZAGJMD>@GB;I>! <D! KG!M=KVBUKG! G! @AGHVE! <DK!
D>KGBD! ;>EG@UAG<=! $a$! <=><D! ED! D>BUD>@AG! DK! JAUF=! a&)9k! JD>DAG><=! ZAGJMD>@=E! <D!BCD!
BGAGB@DA?E@;BG!FGAG!BG<G!;EIMDA=!F=E;B;=>GK!F=E;SKD!mQ7n8!
!
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FDAI:;<=!<D!_;<AIJD>=!eY9)9fk!&k&k&rk&ra@D@AGMD@;KaZD>;KD>D<;GM;>G!e."0/fk!SGED!.3'�"%k!
Z=EZG@=! <D! E=<;=k! C! ZD>=K! <D! (;JMG! $_DM;BGKEo! 0W#9EA! <D! $GCMG>! $_DM;BGKE8! ,=E!
30
>;@A=GKTUD>=E! &)9)%! C! &)9,%! E=>! U>G! <=>GB;I>! <DK! /A8! 1AUBD! [ADDMG>! e+>;HDAE;@C! =Z!
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ED!DHGKUI!U@;K;bG><=!U>!=:?MD@A=!e)3)1)3)(!)9gf!G!PQ!t$!D>!GM=A@;JUG<=A!Z=EZG@=!^`!M"k!
FY!Q8L8!,G!MDbBKG!<D!ADGBB;I>!<D!9!M,!B=>@D>?G!0WY(a7!e9^!>"f!=!9!e7``!>"fk!ZD>=K!e^``!
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31
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32
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33
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34
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35
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36
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1;=ECE@DMEX"/(!($'#df!e[;JUAG!7`%f8!#K!%%!ED!B=>BD>@AG!C!ADEUDKHD!F=A!,$!!C!@;D>D!U>!FG@AI>!
<D! ZAGJMD>@GB;I>! BGAGB@DA?E@;B=! TUD! FDAM;@D! B=>Z;AMGA! EU! ;<D>@;<G<! D>! DK! M=<=! "3"!
eMUK@;FKD! ADGB@;=>!M=>;@=A;>Jf! E;JU;D><=! KG! FVA<;<G! >DU@AG! <DK! JAUF=! a&)9! eBCD! PLcXP`7o!
BCD!PLcXLOf!e[;JUAG!7`1f8!0GAG!KG!BUG>@;Z;BGB;I>!B=>E@AU;M=E!BUAHGE!<D!BGK;SAGB;I>!B=M=!ED!
MUDE@AG!D>!KG!Z;JUAG!7`$8!!
!
d>S>S% % <K*$1$I,)$G-%&"3%+"-&$1$"-*(%&"%+",))$G-%
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Z=AMGB;I>!<D!FA=<UB@=!MD>=A!GK!7`zk!<D!KG!BUGK!ED!=S@;D>D>!GFA=:;MG<GMD>@D!`8^!MJ!<D!
&)9%%!G!FGA@;A!<D!Q^!MJ!;>;B;GKDE!<D!%%8#+>=!<D!K=E!=S\D@;H=E!<D!DE@D!@AGSG\=!ZUD!=F@;M;bGA!
KGE!B=><;B;=>DE!<D!@AGSG\=!FGAG!GUMD>@GA!DK!AD><;M;D>@=!<D!Z=AMGB;I>!<D!&)9%%8!.GK!B=M=!
ED!<;EBU@;I!D>!KG!;>@A=<UBB;I>k!DK!h&)9!DE!U>!;>;B;G<=A!;MF=A@G>@D!<D!KG!=:;<GB;I>!K;F?<;BGk!C!KG!
FADHGKD>B;G!<D! KGE!ADGBB;=>DE!<D!>;@A=JD>GB;I>!F=A!E=SAD! KGE!<D!=:;<GB;I>!<D! K=E!AG<;BGKDE!
K;F?<;B=E! Z=AMG<=E! <DFD><D! FA;>B;FGKMD>@D! <D! KG! B=>BD>@AGB;I>! <D! )9! D>! DK! MD<;=! <D!
ADGBB;I>! m7^^k! 7QRn8! #>! DE@D! ED>@;<=! DK! ! FA;MDA! BGMS;=! D>! DK! FA=@=B=K=! <D! E?>@DE;E! ZUD!
<;EM;>U;A!KG!@D>E;I>!<D!)9!D>!DK!MD<;=!<D!ADGBB;I>8!0GAG!DKK=!SGAS=@DGM=E!KG!MDbBKG!<D!%%!C!
&)9a!D:@D>EGMD>@D!B=>!%AJI>k!C! KG!EDKKGM=E!B=>!U>!EDF@=!<D!J=MG!FADH;=!G!KG!G<;B;I>!<DK!
NB;<=8! .GMS;V>! DHGKUGM=E! DK! DZDB@=! <DK! DEBGKG<=! e:9k! :P! C! :Lfk! <DK! E=KHD>@D! <D! ADGBB;I>!
U@;K;bG<=!e_D:G>=!HE8!GBD@=>;@A;K=fk!C!<DK!NB;<=!DMFKDG<=!eNB;<=!BK=A_?<A;B=!B=>BD>@AG<=!HE8!
NB;<=!EUKZiA;B=!B=>BD>@AG<=f8!$UG><=!DEBGKGM=E!GK!<=SKD!eDK!H=KUMD>!9:k!M=KDE!<D!ADGB@;H=E!
9:k! C! @;DMF=! <D! ADGBB;I>! 9:f! C! U@;K;bGM=E! Y9()L! B=>BD>@AG<=! B=M=! NB;<=k! K=JAGM=E!
GUMD>@GA!^!HDBDE!KG!DZ;B;D>B;G!<D!>;@AGB;I>!<D!%%!e[;JUAG!77f8!%<DMNEk!FUE;M=E!G!FU>@=!U>G!
BA=MG@=JAGZ?G!D>!B=KUM>G!U@;K;bG><=!E?K;BG!B=M=!ZGED!DE@GB;=>GA;G!FGAG!KG!FUA;Z;BGB;I>!<D!!
40
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XIC of -MRM (5 pairs): 348,200/46,100 Da from Sample 4 (ii 1/100) of Data220... Max. 1170,0 cps.
0,5 1,0 1,5 2,0 2,5 3,0 3,5 4,0 4,5Time, min
0
100
200
300
400
500
600
700
800
900
1000
1100
1170
In
te
ns
it
y, c
ps
1,45
3,51
2,702,06 4,932,921,730,10 2,622,370,64 1,96 4,073,34
! A
!B
!C
2$O/+,% SU>% :-_3$#$#% K(+% NY% &"% P<T::>% a:b! #K! B=>@A=K! <D! FUADbG! GE?! B=M=! KG! BUG>@;Z;BGB;I>! <DK! &)9%%! ED!ADGK;bG>!F=A!ESI-MS y LC- ESI-MS/MS utilizando un QTRAP2000.%a9b!#K!&)9%%!ED!<D@DB@G!F=A!,$!"(X"(!D>!DK!M=<=!<D! ;=>;bGB;I>!>DJG@;H=!F=A!"3"!E;JU;D><=! KG!FVA<;<G!>DU@AG!<DK!JAUF=!>;@A=! eBCD!PLcXP`7f8! '>EDA@=l!FGAG!B=>Z;AMGA!KG!;<D>@;<G<!<DK!FA=<UB@=!ED!G>GK;bG!D>!DK!M=<=!#0'!eD>_G>BD<!FA=<UB@!;=>f!EDKDBB;=>G><=!DK!;I>! FGAD>@GK! eBCD! PLcf! FGAG! =S@D>DA! DK! FG@AI>! <D! ZAGJMD>@GB;I>! BGAGB@DA?E@;B=! <D! &)9%%k! <=><D! E;DMFAD!DE@N>! FADED>@DE! K=E! ZAGJMD>@=E# BCD! P`7! C! 9^Q8! a7b! #K! FA=<UB@=! FUA=! ED! BUG>@;Z;BG! U@;K;bG><=! %%EF! eBCD!P77X9OQf! B=M=! DE@N><GA! ;>@DA>=! C! %%! B=M=! DE@N><GA! D:@DA>=! eBCD# P`PX9^Rf8! 0GAG! B=>E@AU;A! KG! BUAHG! <D!BGK;SAGB;I>k! ED! Z;\G! KG! B=>BD>@AGB;I>!<D!DE@N><GA! ;>@DA>=!C! ED!U@;K;bG>! B=>BD>@AGB;=>DE! BADB;D>@DE!<D!%%8! (D!JAGZ;BG! KG! ADKGB;I>! <D! NADGE! FGAG! KGE! @AG>E;B;=>DE! G<DBUG<GE! D>! ZU>B;I>! <D! KG! ADKGB;I>! <D! B=>BD>@AGB;I>!B=AADEF=><;D>@Dk!C!ED!;>@AGF=KG>!KGE!NADGE!=S@D>;<GE!FGAG!DK!&)9%%!eBCD!PLcXP`7f8!!
41
&)9%%8!,GE!<;MD>E;=>DE!<D!KG!B=KUM>G!U@;K;bG<G!e9O!:!P!
BMf! FDAM;@D>! U>G! JAG>! E;DMSAG! <D! FA=<UB@=! <D!
ADGBB;I>!e_GE@G!7!J!GFA=:;MG<GMD>@Dfk!F=A!K=!BUGK!ZUD!
B=>HD>;D>@D!ADGK;bGA!C!\U>@GA!HGA;GE!E?>@DE;E!D>!FGAGKDK=!
B=>! KGE!B=><;B;=>DE!=F@;M;bG<GE8!#K!UE=!<D! KG!B=KUM>G!
FDAM;@;I! FUA;Z;BGA! @=<=! DK! FA=<UB@=! =S@D>;<=! D>! U>G!
E=KG!;>E@G>B;G!C!<D!MG>DAG!MUC!DB=>IM;BG!ADEFDB@=!GK!
UE=! <D! .,$! FADFGAG@;HG8! 0=A! =@AG! FGA@Dk! DE@GM=E!
F=>;D><=! G! FU>@=! KG! >;@AGB;I>! <D! %%! F=A!
>;@A=EDKD>GB;I>k! U>! MV@=<=! TUD! _G! E;<=! ADF=A@G<=!
FADH;GMD>@D! D>! KG! E?>@DE;E! <D! >;@A=GKTUD>=Ek! C! TUD!
FADED>@G! KG! HD>@G\G! <D!=S@D>DA! U>! ;EIMDA=!DEFDB?Z;B=!
B=>! U>! GK@=! AD><;M;D>@=! mc`n8! ,=E! D:FDA;MD>@=E! G!
BGAJ=!<D!KG!/AG8!2;AJ;>;G!,IFDb!_G>!FDAM;@;<=!E;>@D@;bGA!
U>G! MDbBKG! <DK! ;EIMDA=! >;@A=GKTUD>=! Oa&)9%%! C! <DK!
>;@A=GKBG>=!^a&)9%%8!
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80'0&! 9! #*,/8+)#&! (1-#:+)(.()0$,0! 5;;! )<! .0!
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KG!MDbBKG!<D!ADGBB;I>!DE@N!B=>E@;@U?<=!F=A!U>G!MDbBKG!
<D! ;EIMDA=E!F=E;B;=>GKDEk!<=><D!DK!JAUF=! a&)9!FUD<D!
U>;AED! G! <;ZDAD>@DE! BD>@A=E! ;>EG@UAG<=E8! 3DF=A@GM=E! FADH;GMD>@D! KG! EDFGAGB;I>! F=A! 30a
Y0,$! <D! P! F;B=Ek! <=><D! ED! ADEUDKHD>! 9! ;EIMDA=E! eRa! C! 7La!&)9%%fk!M;D>@AGE! TUD! K=E! <=E!
ADE@G>@DE!B=aDKUCD>!e79a!C!7^a!&)9%%f!mQ7nk!D>!U>!MV@=<=!TUD!DE!SUD>=!<DE<D!DK!FU>@=!<D!
H;E@G!G>GK?@;B=!FDA=!MUC!;>DZ;BGb!FGAG!KG!FUA;Z;BGB;I>!C!B=>BD>@AGB;I>!<D!;EIMDA=E8!0=A!@G>@=!
>=E!FKG>@DGM=E!B=M=!=S\D@;H=!G>GK;bGA!C!FUA;Z;BGA!KG!MDbBKG!;E=MVA;BG!=S@D>;<G!G!FGA@;A!<DK!
>UDH=!FA=@=B=K=!<D!E?>@DE;E!D>!MD<;=!NB;<=8##
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_D:G>=! B=>! &)9a! D>! MD<;=! NB;<=8! (D!
Z=AMG>! U>G! EDA;D! <D! FA=<UB@=E!
=:;<G<=E! C! >;@AG<=Ek! <D! <=><D! ED!
FUA;Z;BG! F=E@DA;=AMD>@D! DK! &)9%%! F=A!
.,$! =! BA=MG@=JAGZ?G! D>! B=KUM>G8! 0GAG!
GUMD>@GA!DK!AD><;M;D>@=!<D!KG!ADGBB;I>!
DHGKUGM=E! F=A! .,$! G>GK?@;BG! DK! DZDB@=!
<Dl!DKK!DEBGKG<=!e:7k!:9!C!:Pfk!DK!E=KHD>@D!
<D! ADGBB;I>! e_D:G>=! $1,! GBD@=>;@A;K=fk! C!
DK! NB;<=! U@;K;bG<=! eY$K! O&! $1,! NB;<=!
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&)9%%! ED! ADEUDKHD>! FGAB;GKMD>@D! F=A! Y0,$! B=>! <D@DBB;I>! D>! DK! +2! e9QL! >Mf8! 0GAG! EU! FUA;Z;BGB;I>! ED!
B=KDB@GA=>!KGE!SG><GE!7!C!9!C!ED!D:@AG\DA=>!D>!_D:G>=l;E=FA=FG>=KlGBV@;B=!eP`l9`l9f8!a9b!,GE!MUDE@AGE!ED!ADa
;>CDB@GA=>!D>!KGE!M;EMGE!B=><;B;=>DE!FGAG!B=>Z;AMGA!KG!FUADbG8!a7b!$=>Z;AMGM=E!KG!;<D>@;<G<!<D!KGE!MUDE@AGE!
C! <D@DAM;>GM=E! KG! F=E;B;I>! <DK! JAUF=! �&)9! F=A! DE@U<;=E! <D! "(X"(! B=>! ,;9p! D>! DK! M=<=! <D! ;=>;bGB;I>!
F=E;@;HG8!
43
#K!G>NK;E;E!<D!&)9%%!F=A!Y0,$!D>!ZGED!ADHDAEG!e30aY0,$f!B=>!<D@DBB;I>!G!9QL!>M!FDAM;@;I!
<;E@;>JU;A!BUG@A=!F;B=E!FGAB;GKMD>@D!ADEUDK@=Ek!>=!FADED>@DE!D>!DK!SKG>B=!<D!MD@G>=K!e[;JUAG!
79%f8!$=KDB@GM=E!K=E!F;B=E!G!KG!EGK;<G!<DK!Y0,$!ADGK;bG><=!U>G!D:@AGBB;I>!B=>!_D:G>=k!B=M=!
ED!<DEBA;SD!D>! KG! EDBB;I>!D:FDA;MD>@GK8!$UG><=! K=E!F;B=E! B=KDB@G<=E! ZUDA=>! ADa;>CDB@G<=E!
=SEDAHGM=E!TUD!EIK=!FU<;M=E!G;EKGA!G!KGE!DEFDB;DE!7!C!9!e[;JUAG!791fk!M;D>@AGE!TUD!K=E!=@A=E!
F;B=E! >=! FU<;DA=>! ADE=KHDAED8! 0GAG! ;<D>@;Z;BGA! K=E! ;EIMDA=E! FADED>@DE! G>GK;bGM=E! KGE!
MUDE@AGE! F=A! "(! ZAGJMD>@G><=! B=>! K;@;=k! TUD! SK=TUDG! KG! BGAJG! F=E;@;HG! D>! DK! D:@ADM=!
BGAS=:;K=! C! <D@DAM;>G! TUD! K=E! ;=>DE! ED! ZAGJMD>@D>! G! @AGHDE! <DK! <=SKD! D>KGBD! <=><D! ED!
D>BUD>@AG! DK! JAUF=! a&)9k! E;D><=! ZNB;K! FAD<DB;A! KG! BCD! FGAG! K=E! <;ZDAD>@DE! ZAGJMD>@=E!
DEFDAG<=E!<D! GBUDA<=!G! KGE! F=E;B;=>DE!TUD!FUD<D!G<=F@GA! DK! a&)9! D>! KG! BG<D>G! mQ7n8! ,GE!
DEFDB;DE! 7! C! 9! B=AADEF=><;DA=>! G! K=E! ;EIMDA=E! 77a! C! 7La&)9%%k! ADEFDB@;HGMD>@D! e[;JUAG!
79$f!eKG!B=MF=E;B;I>!<D!KG!MDbBKG!D>@DAG!<D!&)9%%!ZUD!<D!Ok!ck!Rk!77!C!7La&)9%%f8!.AGE!DK!
G>NK;E;E!G>GK?@;B=!<D!KG!MDbBKG!;E=MVA;BGk!FUA;Z;BGM=E!K=E!;EIMDA=E!77!C!7La&)9%%!U@;K;bG><=!
U>G!B=KUM>G!$7c!EDM;aFADFGAG@;HGk!B=M=!ED!<D@GKKG!D>!KG!MD@=<=K=J?G8!!
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K?F;<=E!S;=GB@;H=E!<D!JAG>!;MF=A@G>B;G!Z;E;=KIJ;BG!B=M=!KGE!0WEk!@A=MS=:G>=Ek!KDUB=@A;D>=E!=!
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44
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FUA;Z;BGB;I>!<D!KG!D>b;MGk!F=A!K=!BUGK!FGAG!K=E!D:FDA;MD>@=E!!"#$!)-%!B=>!0WY(a7!C!9!KG!GF=a
FA=@D?>G! ZUD! ADB=>E@;@U?<G! B=>! [DPpa00'dk! B=M=! ED! <D@GKKG! D>! KG! EDBB;I>! D:FDA;MD>@GK8!
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Z=AMGB;I>!<DK!FA=<UB@=!<D!<DBG;M;D>@=!<D!0WY9k!KG!FA=E@JKG><;>G!0W#9!eGB@;H;<G<!$)df8!
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GB=MFGjG! <D! U>! BGMS;=! <D! B=K=A! TUD! ED!
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DK!H;E;SKD! e[;JUAG!7P%f8!,G!GB@;H;<G<!$)d!ZUD!
DE@U<;G<G! F=A! =:;MD@A?Gk! K=! BUGK! @GMS;V>!
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DE! DK! i>;B=k! D>! DK! DE@U<;=! <D! KG! GB@;H;<G<!
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MGAB=! <D! U>G! FGEG>@?G! <D! ;>HDE@;JGB;I>! D>!
DK! KGS=AG@=A;=! <DK! /A8! ,8]8! "GA>D@@!
e2G><DAS;K@! '>E@;@U@D! =Z! $_DM;BGK! 1;=K=JC8!
+>;HDAE;@C! =Z! 2G><DAS;K@! a! "D<;BGK! (B_==Kk!
.&k! ##++fk! TUD! FDAM;@;I! F=>DA! G! FU>@=! D>!
>UDE@A=! KGS=AG@=A;=! KG! <D@DAM;>GB;I>! <D! KG!
GB@;H;<G<! $)d! F=A! ,$! "(X"(k! E;JU;D><=! KG!
Z=AMGB;I>! <D! 0W#9! eFA=<UB@=! DE@GSKD! <DK!
<DBG;M;D>@=! D>! MD<;=! GBU=E=! <D! 0WY9f8!
/DS;<=! G! KG! FADED>B;G! <D! U>! JAUF=! NB;<=! a
$))Y!eBGAS=:?K;B=f!K;SAD!D>!0W#9k!DK!;I>!m"a
Yna! TUD! ED! =S@;D>D! F=A! #('! DE! MUC!
GSU><G>@D! m7Q`n8! (U! ZAGJMD>@GB;I>!
BGAGB@DA?E@;BG!FA=<UBD!DK! ;I>!<DA;HG<=!<D! KG!
FVA<;<G! <D! <=E! M=KVBUKGE! <D! GJUG! C! U>G!
M=KVBUKG! <D! a$)9! eBCD! P^7X9Q7f! e[;JUAG!
7P$f8!0=A!DE@G! AGbI>k!U>G!<D! KGE!FA;>B;FGKDE!
HD>@G\GE! <D! DE@D! FA=@=B=K=! ZUD! U>! JAG>!
GUMD>@=!D>!KG!ED>E;S;K;<G<!ADEFDB@=!GK!UE=!<D!=:;MD@A?G!D>!KG!<D@DAM;>GB;I>!<D!KG!GB@;H;<G<!
$)dk!C!DE@=!EDAN!ADKDHG>@D!FGAG!>UDE@A=!@AGSG\=k!B=M=!ED!HDAN!MNE!G<DKG>@D8!!
! ,G! Z;JUAG! 7L!MUDE@AG! DK! DETUDMG!JD>DAGK! <D! ADGBB;=>DE! BG@GK;bG<GE!F=A! 0WY(! C! K=E!
;>@DAMD<;GA;=E! ;>H=KUBAG<=E! D>! K=E! MV@=<=E! <D! <D@DAM;>GB;I>! <D! GB@;H;<G<! D>b;MN@;BG!
U@;K;bG<=E!F=A!>=E=@A=E8!!
!
d>T>S>T%%6J")*(%&"%3,%&(#$#%
!
! 0A;MDA=! DHGKUGM=E! KG! M=<UKGB;I>! <D! KG! GB@;H;<G<! D>b;MN@;BG! D>! ZU>B;I>! <D! KG!
B=>BD>@AGB;I>8!J%!34566!+$@+*+B!%(!(',+8+.(.!K4L!0$!()*(&!+&#A#-)(&!.0!%(!0$M+)(!e[;JUAG!
7^%f8!,G!i>;BG!ADZDAD>B;G!D>!KG!K;@DAG@UAG!G!U>!;>_;S;<=A!<D!KG!GB@;H;<G<!0)d!D>!0WY(!DE!FGAG!
2$O/+,% Sc>% '"*"+1$-,)$G-% &"% 3,% ,)*$F$&,&%
"-I$1_*$),% &"% 5Z?Y>% #K! B=>EUM=! <D! )9! DE! U>G!
MD<;<G! <;ADB@G! <D! KG! GB@;H;<G<! $)dk! M;D>@AGE!
TUD! DK! ."0/! DE! U>G! MD<;<G! ;><;ADB@G! <D! KG!
GB@;H;<G<! 0)d! CG! TUD! DK! ."0/! GB@iG! B=M=! B=a
EUE@AG@=! AD<UB@=A! BD<;D><=! DKDB@A=>DE! G! K=E!
B=MFUDE@=E! '! C! ''! <UAG>@D! KG! ADJD>DAGB;I>! <DK!
_DM=!ZVAA;B=k!C!=:;<N><=ED!G!U>!B=MFUDE@=!GbUK!
B=>! MN:;M=! <D! GSE=ASG>B;G! G! O77>M8! ,G!
Z=AMGB;I>!<D!0W#9!DE!U>G!MD<;<G!;><;ADB@G!<D!KG!
GB@;H;<G<! $)dk! TUD! FA=F=AB;=>G! MUB_G! MGC=A!
ED>E;S;K;<G<!ADEFDB@=!G!KG!=:;MD@A?G8!
46
DK!ADEHDAG@A=Kk!U>!FA=<UB@=!>G@UAGK!<D!=A;JD>!HDJD@GK!TUD!GB@iG!B=M=!B=aEUE@AG@=!AD<UB@=A!
<UAG>@D! DK! B;BK=! BG@GK?@;B=! <D! KG! GB@;H;<G<! 0)d! e<D! 0WY(a7fk! <G><=! KUJGA! G! U>G! Z=AMG! >=!
FA=<UB@;HG! <D! KG! D>b;MG! m7c9n8! ,=E! ;>_;S;<=ADE! <D! GFK;BGB;I>! BK?>;BG! e%'&#(! D! ;>_;S;<=ADE!
DEFDB?Z;B=E! <D! 0WY(a9f! ;>@DAGBB;=>G>! B=>! 0WY(! D>! DK! E;@;=! GB@;H=! $)dk! <;EM;>UCD><=! DK!
B=>EUM=!<D!)9! E;>!GZDB@GA! KG!GB@;H;<G<!0)d! m7L`n8!#K!&)9%%!<;EM;>UCI!DK! B=>EUM=!<D!)9!
EDKDB@;HGMD>@D!D>!0WY(a7k!BUG><=!DHGKUGM=E!KG!GB@;H;<G<!$)d!F=A!=:;MD@A?G!e[;JUAG!7^1f8!
#E@=! ZUD! <;Z?B;K! <D! B=MFAD><DA! <G<=! TUD! KG! GB@;H;<G<! 0)d! DE! BA?@;BG! FGAG! <GA! ;>;B;=! G! KG!
GB@;H;<G<!$)d!C!FGADB?G!F=B=!FA=SGSKD!TUD!GZDB@GA!G!KG!FA;MDAG!>=!@UH;DAG!DZDB@=E!E=SAD!KG!
! A
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!C
2$O/+,%Sd>%6J")*(%&"%3,%&(#$#%&"%P<T::%#(A+"%3,%,)*$F$&,&%"-I$1_*$),%&"%5Z?Y%S%E%T%a:b!'>_;S;B;I>!<=E;Ea
<DFD><;D>@D!<D!KG!GB@;H;<G<!0)d!<D@DAM;>G<G!F=A!DK!D>EGC=!<DK!."0/8!0WY(a9!ED!MUDE@AG!D>!DK! ;>EDA@=8!
a9b!'>_;S;B;I>!<=E;E!<DFD><;D>@D!<D!KG!GB@;H;<G<!$)d!<D@DAM;>G<G!F=A!=:;MD@A?G8!0WY(a9!ED!MUDE@AG!D>!DK!
;>EDA@=8!a7b!'>_;S;B;I>!<D!KG!GB@;H;<G<!$)d!<D!0WY(a9!F=A!&)9%%!e7`!�"f!<D@DAM;>G<G!F=A!,$!"(X"(8%,=E!
ADEUK@G<=E!B=AADEF=><D>!G!K=E!FA=MD<;=E!!!(8#8k!"sPk!<D!D:FDA;MD>@=E!F=A!@A;FK;BG<=8%
47
EDJU><G8!,=E!<;ZDAD>@DE!ADTUDA;M;D>@=E!<D!EUE@AG@=!FDA=:;<NE;B=!e9`!>"!FGAG!0WY(a7!HE8!9!
>"!FGAG!0WY(a9!FGAG!Y9)9f!_GBD>!G!0WY(a7!MNE!EUEBDF@;SKD!G!K=E!;>_;S;<=ADE!FDA=:;<NE;B=E!
m7cPnk! F=A! K=! BUGK! DE! F=E;SKD! TUD! KG! GB@;H;<G<! $)d! <D! 0WY(a9! EIK=! ZUDAG! ED>E;SKD! G!
B=>BD>@AGB;=>DE!MGC=ADE!<D!;>_;S;<=A!0)d8!%K@DA>G@;HGMD>@Dk!DE!F=E;SKD!TUD!DK!&)9%%!>=!
GZDB@D! <;ADB@GMD>@D! KG! =:;JD>GB;I>! <D! %%k! E;>=! TUD! KG! ;>_;S;B;I>! <D! KG! GB@;H;<G<! $)d!
=SEDAHG<G! FGAG! KG! ;E=Z=AMG! B=>E@;@U@;HG! ADEF=><G! D:BKUE;HGMD>@D! G! KG! ;>_;S;B;I>! <D! KG!
GB@;H;<G<!0)d8!#>!DE@D!BGE=!U>!MDBG>;EM=!<D!;>_;S;B;I>!<;ZDAD>@D!=!U>G!F=@D>B;G!<DE;JUGK!
<DK!&)9%%!_GB;G!KGE!;E=Z=AMGE!7!C!9!<D!0WY(!F=<A?G!D:FK;BGA!TUD!DK!>;@A=GKTUD>=!>=!@D>JG!
DZDB@=E!E=SAD!KG!GB@;H;<G<!$)d!<D!0WY(a98!N(!(',+8+.(.!0$M+)D,+'(!,#,(%!=.0,0-)+$(.(!1#-!
N"!OPQOP?C!)#&,-B! R/0! 0%! 34566! +$@+*0! %(! A#-)('+B$! .0! KSJ5! 0$! ()*(&! +&#A#-)(&! .0!
KSTP!=U+</-(!F7"?>!!
!
! .=<=E! K=E! D>EGC=E! D>! DE@D! @AGSG\=! ZUDA=>! ADGK;bG<=E! U@;K;bG><=!MUDE@AGE! FUAGE! <D!
&)9%%!B=MFUDE@GE!F=A!U>G!MDbBKG!<D!;EIMDA=E!F=E;B;=>GKDE8!$UG><=!DHGKUGM=E!DK!DZDB@=!
<D!;EIMDA=E!FUA=E!<D!&)9%%!E=SAD!KG!GB@;H;<G<!0)d!=SEDAHGM=E!U>G!;>_;S;B;I>!<DK!P`!GK!^`!
zk!B=MFGAGSKD!G! KG! ;>_;S;B;I>!<G<G!F=A! KG!MDbBKG! ;E=MVA;BG! e[;JUAG!7Ofk!M=E@AG><=!TUD! KG!
;>_;S;B;I>! <D! 0WY(! DE! ;><DFD><;D>@D! <D! KG! F=E;B;I>! TUD! =BUFG! DK! a&)9! D>! KG! BG<D>G!
_;<A=BGAS=>G<G! <DK! ;>_;S;<=A8! 4,-#&! $+,-#(%R/0$#&! =345N6! 9! 34546?! A/0-#$! 08(%/(.#&C!
10-#!$#!,/8+0-#$!$+$<V$!0A0',#!&#*-0!%(!(',+8+.(.!K4L!.0!KSTPGF!#!5C!)#&,-($.#!R/0!%(!
+$@+*+'+B$!.0!%(!0$M+)(!$#!0&!<0$W-+'(!(!%#&!$+,-#(%R/0$#&!&+$#!0&10'2A+'(!1(-(!0%!34566>!
2$O/+,%Se>%6J")*(%&"%3(#%$#G1"+(#%K(#$)$(-,3"#%&"%P<T::%#(A+"%3,%,)*$F$&,&%5<g>%,G!MDbBKG!<D!&)9%%!TUD!
U@;K;bGM=E! D>! DE@D! @AGSG\=! DE@N! B=MFUDE@G! F=A! U>G!MDbBKG! <D! ;EIMDA=E! F=E;B;=>GKDE8! %TU?! FUA;Z;BGM=E! K=E!
;EIMDA=E!<D! KG!MDbBKG!F=A!Y0,$!C!DHGKUGM=E!EU!DZDB@=!E=SAD! KG!GB@;H;<G<!0)d!<D!0WY(8!#K!DZDB@=!E=SAD! KG!
GB@;H;<G<! D>b;MN@;BG! no mostró diferencias significativas entre los distintos isómeros. ,=E! ADEUK@G<=E!
B=AADEF=><D>!G!K=E!FA=MD<;=E!!!(8/8k!B=>!"sPk!<D!D:FDA;MD>@=E!F=A!@A;FK;BG<=8!
48
d>T>S>V%%N(&"3(%)$-B*$)(%&"%$-C$A$)$G-%
!
"UB_=E! <D! K=E! ;>_;S;<=ADE! ADF=A@G<=E! ;>_;SD>! G! 0WY(! eGB@;H;<G<! $)df! <D! MG>DAG!
@;DMF=a<DFD><;D>@D!mRRk!7L`n8!0WY(!FAD;>BUSG<G!B=>!&)9%%!FADH;=!GK!;>;B;=!<D!KG!ADGBB;I>!
M=E@AI!U>G!GB@;H;<G<!0)d!e[;JUAG!7Q%f!C!$)d!e[;JUAG!7Q1f!AD<UB;<G!;><;BG><=!TUD!DK!@;DMF=!
DE! U>! ZGB@=A! BKGHD! D>! KG! ;>_;S;B;I>! <D! 0WY(! MD<;G<G! F=A! &)9%%8! ,G! <;EM;>UB;I>! D>! KG!
HDK=B;<G<! ;>;B;GK! <D! KG! ADGBB;I>! B=>B=M;@G>@D! GK! GUMD>@=! D>! DK! @;DMF=! <D! FAD;>BUSGB;I>!
! A
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2$O/+,%Sf>%6J")*(%&"3%*$"1K(%"-%3,%$-C$A$)$G-%&"%5Z?Y>!a:b!!WANZ;B=E!FA;MGA;=E!<D!KG!GB@;H;<G<!0)d!<D!0WY(a7!
e9`!>"f!FGAG!<;ZDAD>@DE!@;DMF=E!<D!FAD;>BUSGB;I>!0WY(a&)9%%k!<D@DAM;>G<G!F=A!DK!D>EGC=!<DK!."0/8!Los
resultados que se muestran son representativos de PGHS-1 y 5 µM NO2AA! a9b!%B@;H;<G<!$)d!<D!0WY(a9!D>!
FADED>B;G! <D! <=E;E! BADB;D>@DE! <D! &)9%%k! FAD;>BUSG<=! B=>! KG! D>b;MG! <UAG>@D! 7! =! 7^! M;>U@=E! FADH;=! G! KG!
<D@DAM;>GB;I>! <D! 0W#9k! F=A! "(X"(8! ,=E! ADEUK@G<=E! B=AADEF=><D>! G! K=E! FA=MD<;=E!!! (8#8k! B=>! "sPk! <D!
D:FDA;MD>@=E!F=A!<UFK;BG<=8%
49
D>b;MGaEUE@AG@=!e[;JUAG!7Q%f!ADZKD\I!TUD!KG!;>@DAGBB;I>!D>b;MGa;>_;S;<=A!e#a'f!@;D>D!KG!M;EMG!
DEBGKG! @DMF=AGK! TUD! DK! ADBGMS;=! e=! @UA>=HDAf! <D! KG! D>b;MG! m7cLn8! #:;E@D>! GK! MD>=E! @ADE!
M=<DK=E!<D! ;>@DAGBB;I>!#a'! B=>!VE@G! B;>V@;BG!<D!U>;I>! KD>@G! BGAGB@DA?E@;BG!<D!U>! ;>_;S;<=A!
@;DMF=a<DFD><;D>@D! e#ETUDMG! 9f8! 0GAG! BGAGB@DA;bGA! B;>V@;BGMD>@D! KG! ;>_;S;B;I>k! DE! BKGHD!
B=>=BDA! KG! ADKGB;I>!D>@AD! KGE!B=>E@G>@DE!=SEDAHG<GE!<D! ;>_;S;B;I>! e'=SEf!C! KG!B=>BD>@AGB;I>!
<DK! ;>_;S;<=A8!%TU?! <D@DAM;>GM=E! BG<G!'=SE! FGAG!0WY(a7! e[;JUAG!7cf! C! 0WY(a9! e[;JUAG!7Rf!
G\UE@G><=!D:F=>D>B;GKMD>@D!D>!=A<D>!7!KG!GB@;H;<G<!0)d!ADMG>D>@D!D>!ZU>B;I>!<DK!@;DMF=!
<D! FAD;>BUSGB;I>! B=>! U>G! B=>BD>@AGB;I>! Z;\G! <D! &)9%%! e[;JUAGE! 7c! C! 7Rk! ;>EDA@=f8!
3DFADED>@GM=E! KGE! B=>E@G>@DE! =S@D>;<GE! D>! ZU>B;I>! <D! KG! B=>BD>@AGB;I>! <D! &)9%%! FGAG!
<D@DAM;>GA!BUNK!<D!K=E!M=<DK=E!;KUE@AG<=E!D>!DK!DETUDMG!9!ED!G\UE@G!G!KG!;>@DAGBB;I>!0WY(a
&)9%%! e[;JUAG! 9`f8! %>@DE! <D! ADGK;bGA! DK! G\UE@D!MG@DMN@;B=! CG! ED! FU<=! <D@DAM;>GA! TUD! KG!
;>@DAGBB;I>!>=!B=AADEF=><D!G!U>G! ADGBB;I>!S;M=KDBUKGA! E;MFKD! e#ETUDMG!9k!M=<DK=! ;;fk! CG!
TUD!>=! DE! K;>DGK! KG! ADKGB;I>! D>@AD!'=SE! C! m&)9%%n8! 0=A! DK! B=>@AGA;=k! KGE!'=SE!M=E@AGA=>!U>G!
ADKGB;I>! _;FDASIK;BG! B=>! KG! B=>BD>@AGB;I>! <D! &)9%%! D>! GMSGE! ;E=Z=AMGE! <D! KG! D>b;MG!
e[;JUAG!9`fk!ADFADED>@G@;H=!<D!U>!;>_;S;<=A!TUD!GB@iG!D>!<=E!FGE=Eo!ED!DE@GSKDBD!U>!FA;MDA!
DTU;K;SA;=!<D!U>;I>!D>@AD!D>b;MG!D! ;>_;S;<=A!eB=>!U>G!B=>E@G>@D!<D!DTUK;SA;=!<D@DAM;>G<G!
F=A!'7!C!'9!D>!K=E!M=<DK=E!;;;!C!;H!<DK!DETUDMG!9fk!EDJU;<=!<D!U>G!M=<;Z;BGB;I>!<D!KG!D>b;MG!
TUD!ADEUK@G!D>!U>G! ;>_;S;B;I>!ADHDAE;SKD! eM=<DK=! ;;;k!#ETUDMG!9f!=! ;AADHDAE;SKD! eM=<DK=! ;Hk!
#ETUDMG!9f!m7cLn8!,=E!JANZ;B=E!<D!'=SE!HE8!m&)9%%n!ED!G\UE@GA=>!MD\=A!G!KGE!DBUGB;=>DE!FGAG!
DK!M=<DK=!<D!;>_;S;B;I>!@;DMF=a<DFD><;D>@D!D>!<=E!FGE=E!e#ETUDMG!Pf!C!=S@UH;M=E!K=E!!
6#L/"1,%T>%N(&"3(#% )$-B*$)(#%&"% $-C$A$)$G-% *$"1K(4&"K"-&$"-*">% a+b% @DGBB;I>! D>b;MN@;BG! D>! GUED>B;G! <D!
;>_;S;<=A8! a++b! '>_;S;B;I>! E;MFKDk! ADGBB;I>! S;M=KDBUKGA! D>@AD! KG! D>b;MG! e#f! C! DK! ;>_;S;<=A! e'f8! ,G! F=@D>B;G! C!
ADHDAE;S;K;<G<! DE@N! <G<G! F=A! K=E! HGK=ADE! <D! '7! e'=>f! C! '9! e'=ZZf8! %K@DA>G@;HGMD>@Dk! ED! FUD<D! DE@GSKDBDA! U>G!
;>@DAGBB;I>!D>@AD!KG!D>b;MG!C!DK!;>_;S;<=A!Z=AMG><=!U>!B=MFKD\=!e#'f!D>!U>G!FA;MDAG!ADGBB;I>k!EDJU;<=!<D!U>G!
EDJU><G!ADGBB;I>!<=><D!KG!D>b;MG!EUZAD!U>G!M=<;Z;BGB;I>!!a+++b!ADHDAE;SKD!=!x;E=MDA;bGB;I>!D>;bMN@;BGy!=!a+8b!
;AADHDAE;SKD8!,G!BGAGB@DA;bGB;I>!B;>V@;BG!FDAM;@D!<D@DAM;>GA!DK!FGE=!K;M;@G>@D!e'=>!FUD<D!B=AADEF=><DA!G!'7!=!
'Pf!C!KG!ADHDAE;S;K;<G<!<D!KG!;>_;S;B;I>!eHGK=A!<D!'Lf8!
e%<GF@G<=!<D!$=FDKG><k!38!%8!e9```f!I"DJB(1/#KL*M)(-#Fk!9><!#<;@;=>!D<>8f!
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2$O/+,%Sh>%'"*"+1$-,)$G-%&"%X(A#%K,+,%3,%$-C$A$)$G-%&"%3,%,)*$F$&,&%5<g%"-%5Z?Y4S>!(D!MUDE@AG>!ADEUK@G<=E!
ADFADED>@G@;H=E!FGAG!KG!D>b;MG!;>_;S;<G!B=>!&)9%%!a:b!P!U"!C!a9b!c!U"8!%!FGA@;A!<D!K=E!<G@=E!FA;MGA;=E!<D!
."0/=:! FGAG! @;DMF=E! <D! FAD;>BUSGB;I>! B=>! B=>BD>@AGB;=>DE! BADB;D>@DE! <D! &)9%%! BADB;D>@DE! e;>EDA@=f!
BGKBUKGM=E! KG! GB@;H;<G<! DEFDB?Z;BG! 0)d! eHDK=B;<G<! ;>;B;GKk! P`! EDJU><=Ef! C! ADFADED>@GM=E! JANZ;BGMD>@D! KG!
GB@;H;<G<!0)d!ADMG>D>@D!FGAG!@;DMF=E!<D!FAD;>BUSGB;I>!BADB;D>@DE8!%\UE@GM=E!K=E!<G@=E!G!U>G!D:F=>D>B;GK!
<D!=A<D>!7!FGAG!=S@D>DA! K=E!HGK=ADE!<D!'=SE8! ,=E! ADEUK@G<=E!B=AADEF=><D>!G! K=E!FA=MD<;=E!!! (8/8k!"sPk!<D!
D:FDA;MD>@=E!GK!MD>=E!@A;FK;BG<=E8!
