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Supramolecular Studies on the Behaviour of Different Chiral

Supramolecular Studies on the Behaviour of Different Chiral

ADVERTIMENT. Lʼaccés als continguts dʼaquesta tesi queda condicionat a lʼacceptació de les condicions dʼús establertes per la següent llicència Creative Commons: http://cat.creativecommons.org/?page_id=184

ADVERTENCIA. El acceso a los contenidos de esta tesis queda condicionado a la aceptación de las condiciones de uso establecidas por la siguiente licencia Creative Commons: http://es.creativecommons.org/blog/licencias/

WARNING. The access to the contents of this doctoral thesis it is limited to the acceptance of the use conditions set by the following Creative Commons license: https://creativecommons.org/licenses/?lang=en ,IDF5AC@97I@5FGHI8=9G CBH<9 69<5J=CIF C:8=::9F9BH7<=F5@ 7M7@C5@?5B9 65G987CADCIB8G5G F979DHCFG ;9@5HCFG5B8GIF:57H5BHG

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a) b)

1.819 1.867 1.951 2.456 1.835 1.861 2.068

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3BIC >PPBJ?IV LC @>O?L@V@IF@ AF>JFAB ?>PBA DBI>QLOP FP QEOLRDE EVAOLDBK ?LKA CLOJ>QFLK TEF@E>OBAFOB@QFLK>ICLO@BPOBPMLKPF?IBQLQEBJLOMELILDVLCQEB>DDOBD>QBP >KA QEOLRDE S>K ABO7>>IP FKQBO>@QFLKP TEF@E TFII@LKQOF?RQBQLQEBPQ>?FIFW>QFLKLCQEB >DDOBD>QB >PPELTKFK &FDROB 

=;IF9  3@EBJ>QF@OBMOBPBKQ>QFLKLCQEBJ>FKCLO@BPFKSLISBAFKQEBPBIC >PPBJ?IVLC @>O?L@V@IF@AF>JFAB ?>PBADBI>QLOP

 #E>MQBO

 (6>97H=J9G

)KQEFP M>OQLC QEBQEBPFP QEBPRMO>JLIB@RI>OPQRAVLCPBSBO>I@>O?L@V@IF@AF>JFAB ?>PBA ,-7'P T>P ALKB FK LOABO QL ABQBOJFKB QEB FKCIRBK@B LC QEB OFKD PFWB  QEB PR?PQFQRQFLKP LC QEB OFKD >KA QEB PQBOBL@EBJFPQOV LC > PFKDIB JLIB@RIB LK QEB CFK>I MOLMBOQFBPLCQEB>DDOBD>QB 'BKBO>IPQOR@QROBLCQEBPQRAFBADBI>QLOPFPPELTKFK &FDROB 

=;IF9  'BKBO>IPQOR@QROBLCQEB,-7'P PQRAFBAFKQEFP@E>MQBO

4>HFKDFKQL>@@LRKQQEB>@NRFOBABUMBOFBK@BFKLROOBPB>O@EDOLRMFKQEB CFBIALCDBIP QEBL?GB@QFSBPLCQEFP M>OQLCQEBQEBPFP >OB

 3QRAV LC QEB@>M>@FQVLCQEBJBKQFLKBA@LJMLRKAPQLDBI>QBAFCCBOBKQPLISBKQP  3QOR@QRO>I PQRAV ?V .-2 BUMBOFJBKQP  3%-  @FO@RI>O AF@EOLFPJ >KA QEBLOBQF@>I @>I@RI>QFLKP  !K>IVPFPLC QEBL?Q>FKBAOBPRIQPFKLOABOQLQOVQLCFKAPLJBOBI>QFLKPEFM?BQTBBK QEBPQOR@QROB >KAQEBPQBOBL@EBJFPQOV LCQEBDBI>QLO>KAQEBCFK>IDBI>QFLK>?FIFQFBP

 #E>MQBO

  +9GI@HG5B8=G7IGG=CB

)KQEFP@E>MQBO LCQEBQEBPFP QEBPQRAVLCQEBMOLMBOQFBPLCAFCCBOBKQC>JFIFBPLC @>O?L@V@IF@AF>JFAB ?>PBAILTJLIB@RI>OTBFDEQDBI>QLOP FPABP@OF?BA !PP>FA>?LSB QEBPB HFKALCPQRAFBPDFSB ?>PF@ FKCLOJ>QFLK QE>Q @>K?BRPBAFKQEBCRQROBQLABPFDKKBT,-7'P TFQE@BOQ>FK PMB@FCF@ MOLMBOQFBP 4EBFKCIRBK@BLCQEBOFKDPFWB QEBPQBOBL@EBJFPQOV>KAQEB PR?PQFQRQFLKPLCQEBOFKDFK AF>JFAB ?>PBADBI>QLOPTFII?BAFP@RPPBA

4EBPVKQEBPBPLC>IIQEBPB,-7'P TBOB @>OOFBALRQ CLOQEBCFOPQQFJB ?V$O ->OQ> 3>KP @V@IL?RQ>KB ?>PBA  >KA  COLJ LRO OBPB>O@E DOLRM >KA ?V ->Ot> #>JMLP @LJMLRKAP COLJ  QL %COLJ .6<:7-.6>.;<20*,276.;"=I52,*;"&$ FK 3>KQF>DLAB #LJMLPQBI> '>IFW> -LOBLSBO  $O  ->OQ> 3>KP @>OOFBA LRQ PLJB MOBIFJFK>O DBI>QFLK PQRAFBPLC @LJMLRKAP   TFQEPLJBPLISBKQP>KA>IPL(2 .-2>KA3%-PQRAFBP TEF@E >OBFK@IRABAFKQEFP@E>MQBOFKLOABOQL L?Q>FK>@LJMIBQBSFBTLC>IIQEBOBPRIQP>KAQL ?BQQBOAFP@RPPQEBJ

4EOBBAFCCBOBKQC>JFIFBPLC,-7'P TBOB PQRAFBA>KA@LJM>OBAFKLOABOQLCFKALRQ AFCCBOBK@BP>KAQL?B>?IB QL?BQQBORKABOPQ>KA QEBDBI>QFLK>?FIFQFBPLCQEBPBHFKAPLC JLIB@RIBP 2BPRIQPLCQEFP@E>MQBOTFII?BMOBPBKQBA>PQEOBBPBM>O>QBAPQRAFBP 4EBPQRAFBA C>JFIFBP>OBMOBPBKQBA?BILT

&>JFIVKLK PR?PQFQRQBAAF>JFAB ?>PBA@>O?L@V@IBP

 

 

3QRAVFKDQEBPBCLROJLIB@RIBP TB@LRIAABQBOJFKBQEBFKCIRBK@BLC QEB GH9F9C7<9A=GHFM >KAQEBF=B;G=N9 LKQEB>DDOBD>QFLK>KALKQEBDBI>QFLKMOLMBOQFBP

 #E>MQBO

&>JFIV PR?PQFQRQBAAF>JFAB ?>PBA@>O?L@V@IBP



!

"

)KQEFP@>PB TBE>SBPQRAFBAQEBFKCIRBK@BLCQEB GH9F9C7<9A=GHFM >KAQEBAFCCBOBKQ GI6GH=HIH=CBC:H<9F=B; >PTBII>P@LJM>OFKDQEBJTFQEQEBKLK PR?PQFQRQBALKBP

&>JFIVPR?PQFQRQBAAF>JFAB ?>PBA@>O?L@V@IBPTFQE>PM>@BO

# $

% &FK>IIV TFQEQEFPC>JFIVTBE>SBPQRAFBAQEBFKCIRBK@BLCQEBAFCCBOBKQ GI6GH=HIH=CBG

C:H<9F=B; >KA QEB FKCIRBK@B LC QEB ! GD579F TEF@E >CCLOA > @E>KDB FK QEB OBDFL@EBJFPQOVLCQEB>JFAB

 #E>MQBO

   9@5H=CBGHI8MC: 5A=@M

4EBDBI>QFLK>?FIFQV T>P PQRAFBAFK@LJJLKPLISBKQPCLIILTFKD >TBII HKLTK MOL@BAROBABP@OF?BAFK PB@QFLK  4LABQBOJFKBQEBMOBPBK@BLC>DBI QEBQR?BFKSBOPFLK QBPQT>PRPBA

4>?IB  PRJJ>OFWBP QEB PQRAV PELTFKD QEB ?BE>SFLRO LC B>@E ,-7' FK B>@E PLISBKQ 4EB>PMB@QLCQEBDBIT>P@I>PPFCFBA>P@IB>O QO>KPIR@FALOLM>@ !PBU>JMIB QEOBB FJ>DBPLCAFCCBOBKQDBIP>OBPELTKFK &FDROB 

=;IF9  %U>JMIBPLC@IB>OIBCQ QO>KPIR@FAJFAAIB>KALM>@OFDEQDBIP

-56@9  'BI>QFLK?BE>SFLROLC@LJMLRKAP    >KA  FK@LJJLKPLISBKQP   @ '   ( (   CADCIB8 )9BH5B9  8=CL5B9 -C@I9B9 H 7(H -! ! = )F(! 79HCB9 H(! &9(! ! !@ !

 ) )  ) 3 ) ) ) ) ) ) ) ) ) 4

 ) )  ) 3 ) ) ) ) ) ) ) ) ) 4

    ) 3 ) ) ) ) ) ) ) ) ) / / /

 )   )  ) ) ) ) ) ) ) ) ) 4 4 4

$FBIB@QOF@@LKPQ>KQFK@OB>PBPCOLJIBCQQLOFDEQ # #IB>O 44O>KPIR@FA / /M>@ -FKFJRJDBI>QFLK@LK@BKQO>QFLKFKJDJ, ))KPLIR?IB 33LIR?IB

 #E>MQBO

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

#LJMLRKAP  >KA  >OBAFCCBOBKQ?BQTBBKQEBJ?B@>RPBQEBV@>KDBI>QB AFCCBOBKQ PLISBKQP>KATFQEAFCCBOBKQ 50, S>IRBP 4EBOBCLOB QEBOBFP>KBCCB@QLCQEBPQBOBL@EBJFPQOV LKQEBFO>?FIFQVQLDBI>QB PLISBKQP #LJMLRKA  @>KDBI>QB MBKQ>KB>KA  AFLU>KB>Q >KAJDJ,OBPMB@QFSBIV )Q @>KDBI>QBQLIRBKB?RQFK>EFDE@LK@BKQO>QFLK  &FK>IIV @LJMLRKA  @>KDBI>QB   AFLU>KB QLIRBKB>KA@EILOLCLOJ>QSBOVILT@LK@BKQO>QFLKP !DLLA,-7'@>KDBI>QB >PLISBKQTFQE>K 50, S>IRBILTBOQE>KJDJ, 4EBOBCLOB FK QEFP@>PB TB@LRIA @LK@IRAB QE>Q@LJMLRKA  FP>SBOVDLLALOD>KLDBI>QLOFKQEBPBQEOBB PLISBKQP )K QEFP@>PBPQBOBL@EBJFPQOVMI>VP>SBOVFJMLOQ>KQOLIB

#LJM>OFKDQEBOFKDPFWB FQFPPELTKQE>Q@V@IL?RQ>KB ?>PBA@LJMLRKAP@>KLKIV DBI>QB QLIRBKBTEFIBQEB@V@ILEBU>KB ?>PBALKBP@>KDBI>QB LQEBOPLISBKQP )QFP@IB>OQE>Q QEBOB FP >K FKQBO>@QFLK ?BQTBBK OFKD PFWB C>@QLO >KA PQBOBL@EBJFPQOV C>@QLO  >P FQ FP OBMOBPBKQBA FK &FDROB 

100

80

60 (mg/mL) 40 mgc

20

0

cis trans

=;IF9  2BMOBPBKQ>QFLKLCQEBS>OF>QFLKLCQEB 50, ABMBKAFKDLKQEBPQBOBL@EBJFPQOV

 #E>MQBO

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

)KLOABO QL?BQQBORKABOPQ>KA QEBFKCIRBK@BLCQEBOFKDPFWB>KAQEBPQBOBL@EBJFPQOV AFCCBOBKQPRMO>JLIB@RI>OPQRAFBP TBOB @>OOFBALRQ

  !=;< F9GC@IH=CB'&+GD97HFCG7CDM

(FDE OBPLIRQFLK .-2 PMB@QOLP@LMV FP > QB@EKFNRB QE>Q FP TFABIV RPBA QL MOLSFAB BSFABK@BCLODBICLOJ>QFLK>KAQLDFSBFKCLOJ>QFLK>?LRQQEBPB@LKA>OVPQOR@QROBPQE>Q >OB >ALMQBA  )K IFNRFA PQ>QB .-2 PQRAFBP LKIV QEB IFNRFA IFHB CO>@QFLK LC > DBI @>K ?B L?PBOSBA >KAQEBPLIFA IFHBM>OQ LCQEBDBIOBJ>FKPRKABQB@QBA $ROFKDQEB@LLIFKDALTK

MOL@BPP QEB FKQBDO>ILCQEB PFDK>IPFK@OB>PB?BILTQEBQBJMBO>QROBLCDBI>QFLK 4DBI /K@B

QEB 4DBI FP OB>@EBA QEB FKQBDO>I LC QEB PFDK>IP PQ>OQP QL AB@OB>PB  3FDK>IP COLJ MOLQLKP FKSLISBAFKFKQBOJLIB@RI>OFKQBO>@QFLKP PR@E>PMOLQLKPCOLJ>K.( DOLRM @>K?B KF@BIV JLKFQLOBA

4EBPB MOLMBOQFBP >IILTBA RP QL MOLSB QEB BUFPQBK@B LC FKQBOJLIB@RI>O EVAOLDBK ?LKAP>KAQLABQBOJFKBQEBDBI>QFLKQBJMBO>QROBCLO@LJMLRKAP    >KA  4EFPPQRAV T>PALKB FK@LII>?LO>QFLKTFQE$O 0>R.LIFP COLJQEB $.:>.2-.#.;;76E6,2**06H<2,* =,4.*: $.#  COLJ QEB &62>.:;2<*< =OOFBALRQ

4EBDBI>QFLKMOL@BPPLC>PLISBKQ  FK TEF@E QEB FKQBOJLIB@RI>O FKQBO>@QFLKP >OB BKE>K@BA?VPLJBBUQBOK>IPQFJRIF OBAR@BPQEBJL?FIFQVLCQEBJLIB@RIBP 4EBOB>OBJ>KV DBI>QFLKFKAR@QLOP?RQ@E>KDBFKQEBQBJMBO>QROBFPLKBLCQEBJLPQ>MMIFBA>KA>A>MQ>?IB QL.-2 4EBOBCLOB FCDBI>QFLKFPPILT@LJM>OBAQL.-2QFJBP@>IBJB>PROBJBKQ QEFP AVK>JF@ MOL@BPP @>K ?B JLKFQLOBA ?V S>OF>?IB QBJMBO>QROB ( .-2 BUMBOFJBKQP  "V AB@OB>PFKDQEBQBJMBO>QROB >@LKQFKRLRPPFDK>IIFKB?OL>ABKFKDFPL?PBOSBA>KACFK>IIV>

 #E>MQBO

@LJMIBQBPFDK>IILPPFPMOLAR@BAARBQLQEBFK@OB>PFKDPLIFA IFHBžM>OQLCQEBDBI TEF@EFP .-2FKSFPF?IB

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

   

=;IF9  'BI>QFLK MOL@BPP JLKFQLOBA ?V S>OF>?IB QBJMBO>QROB ( .-2 PMB@QOLP@LMV BUMBOFJBKQP FK  J- PLIRQFLKP DBI>QLOP    >KA  !  -(W "ORHBO !S>K@B ))) PMB@QOLJBQBOBNRFMMBATFQE>@LLIFKDRKFQ"#5 8QOBJBT>PRPBA

! @LKQFKRLRPFK@OB>PBLCQEB.( MOLQLKPFDK>I>OB>T>PL?PBOSBATEBK@LLIFKDQEB P>JMIB  4EB FK@OB>PB FK QEB PFDK>I >OB> AROFKD QEB @LLIFKD MOL@BPP PRDDBPQBA QE>Q QEB EVAOLDBK?LKAPTBOB?BFKDCFUBAFK@OB>PFKDIVFK>TBII ABCFKBAMLPFQFLK 4EBA>Q>L?Q>FKBA  #E>MQBO

CLO@V@IL?RQ>KBABOFS>QFSBP  >KA  OBSB>IQE>QQEB.(PFDK>ICLO?LQEFPLJBOPAB@>VP>Q  +>KAQEBFO@EBJF@>IPEFCQAROFKDQEBDBI>QFLKMOL@BPPFP>IJLPQQEBP>JB PLFQPBBJP QE>QQEBAFCCBOBK@BFKOBI>QFSB@LKCFDRO>QFLKALBPKLQIB>AQL AFCCBOBKQDBI>QFLKMOL@BPPBP /KQEBLQEBO E>KA QEBOBFP>PFDKFCF@>KQAFCCBOBK@B?BQTBBK@V@ILEBU>KBABOFS>QFSBP  >KA  4EB.(PFDK>ILC  AB@>VP>Q +TEBOB>PQEBP>JBPFDK>ICLO  AB@>VP>Q + #IB>OIV FKQEBPBJLIB@RIBPQEB ,2;<:*6; PQBOBL@EBJFPQOVMI>VP>@OR@F>IOLIBLKQEBFOPLI

DBIQO>KPFQFLKQBJMBO>QROB4DBI>KAPELTPQE>Q?LQEEVAOLDBK?LKAFKDARBQLQEBMLI>O >JFALDOLRMP>KAS>KABO7>>IPFKQBO>@QFLKP?BQTBBK >IHVI@E>FKPJ>HB <:*6; FPLJBO  JLOBMOLKBQL DBI>QB .LOJ>IFW>QFLKLCQEB.(PFDK>IPQLQEBEFDEBPQFKQBDO>IFKQEBPMB@QO> PBOFBP>IILTPSFPR>IFWFKDQEBPLIRQFLKQLDBIQO>KPQFQFLKDO>MEF@>IIV &FDROB 

A 1.0 B C 0.8 D 0.6

0.4

0.2 Normalised Integral

330 320 310 300 290 280 270 260

Tgel (K)

=;IF9  'O>MEF@>I OBMOBPBKQ>QFLK LC QEBKLOJ>IFPBA .( MOLQLK FKQBDO>IP AROFKD QEB DBI>QFLKMOL@BPPQO>KPFK?IRB>KA@FPFKOBACLOJ-PLIRQFLKP LC  >KA  RM >KA 

>KA  ALTKFKQLIRBKB -

-LOBLSBO >KLQEBOCB>QROBLC?LQEPBOFBPFPQEB@E>KDBFKQEBPBKPBLCQEB@EBJF@>I PEFCQ AFPMI>@BJBKQ LC QEB .( MOLQLK KB>O QL QEB DBI>QFLK MLFKQ 4EFPBCCB@QT>PJLOB J>OHBACLO@V@ILEBU>KBABOFS>QFSBP  >KA  QE>KCLO@V@IL?RQ>KB@LJMLRKAP  >KA  7B L?PBOSBAQEFPQOBKAFKQEBDBI>QFLKLCPLJBAFMBMQFABPJ>ABTFQE@V@IL?RQ>KB β >JFKL >@FAP >KAFQT>P>IPLOBMLOQBAFKMOBSFLRPTLOHP  ?BFKD >QQOF?RQBA QL IFMLMEFIF@ FKQBO>@QFLKP?BQTBBK>IHVI DOLRMPFKQEB>DDOBD>QBP )KQEB>@QR>I@>PB >PFJFI>OBCCB@Q

 #E>MQBO

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

4EBP>JBPQRAFBPTBOBOBMB>QBACLOIBPP@LK@BKQO>QBAPLIRQFLKPLC QEB CLRO @LJMLRKAP J->KA J- 4ERP QEBQBJMBO>QROBBCCB@QP@LRIA?BPBM>O>QBA

COLJ QEB >DDOBD>QFLK MEBKLJBK>  !P BUMB@QBA  QEB 4DBI CLO >II @LJMLRKAP T>P @LK@BKQO>QFLK ABMBKABKQ ?BFKDQEBDBICLOJ>QFLKB>PFBOTEBKFK@OB>PFKD QEB

@LK@BKQO>QFLK )K 4>?IB  QEB4DBI CLO>IIQEB@LJMLRKAP>QAFCCBOBKQ@LK@BKQO>QFLKP>OB PRJJ>OFPBA>KAQEBV>OBOBMOBPBKQBAFK &FDROB 

4EBLOABOLCQEBDBI>QFLKQBJMBO>QROBPL?Q>FKBACOLJ(2 .-2PQRAFBPFPFKDLLA >DOBBJBKQTFQEQEBLOABOLC 50, S>IRBPFKQLIRBKBL?Q>FKBACOLJQEBDBI>QFLKPQRAFBP

-56@9  #LK@BKQO>QFLKABMBKABK@BLC4DBI LC    >KA  FKQLIRBKB

-;9@ $

CADCIB8  J-  J- J-

   

   

   

   

 #E>MQBO

325

320

315 A B 310 C 305 D

(K) 300 gel T 295

290

285

280

275 4 6 8 1012141618 Concentration (mM)

=;IF9   2BMOBPBKQ>QFLK LC QEB ABMBKA>K@B LC QEB DBI>QFLK QBJMBO>QROB TFQE QEB @LK@BKQO>QFLKLCQEBLOD>KLDBI>QLO

   ,75BB=B;@97HFCB&=7FCG7CDM ,&

)K@LII>?LO>QFLKTFQE$O *RAFQE/O{COLJQEB 6;<2<=<-.2H6,2*-.*<.:2*4;-. *:,.476* )#-!" 3%-BUMBOFJBKQPTBOB@>OOFBALRQQLFKSBPQFD>QBQEBJLOMELILDVLC QEBDBIP L?Q>FKBACOLJPLIRQFLKPFKQLIRBKB 7BQDBIPTBOBAFPMLPBALK>@>O?LK CFIJ @L>QBA@LMMBODOFA>KAAOFBA?VPQ>KAFKDCLOJFKRQBPLKQEBDOFA 4EBOBPRIQFKDUBOLDBIP AOVDBIPTBOB QEBKFKQOLAR@BAFKQLQEBJF@OLP@LMB@E>J?BOTLOHFKD>Q0>>KAH6

4EBJF@OLDO>MEPTBOBQBPQBA>QQEBJFKFJRJDBI>QFLK@LK@BKQO>QFLK 50, CLO B>@ELOD>KLDBIFKQLIRBKB 4ERP DBILC  >QJDJ, DBILC  >QJDJ, DBILC  >Q JDJ,>KADBILC  >QJDJ,TBOBRPBAQLMBOCLOJ3%-BUMBOFJBKQP 4EBP>JB JBQELALILDVT>PCLIILTBACLO>II@LJMLRKAPFKLOABOQL>SLFABUQBOK>IFKCIRBK@BLKQEB JLOMELILDVLCQEB>DDOBD>QBP  4EB FJ>DBP L?Q>FKBA>OB PELTKFK &FDROB  >KA &FDROB 

 #E>MQBO

> 

U U

? 

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LC >K >DDOBD>QB TFQE 6 JLKLJBOP  "33% T>P @LKPFABOBA 6  QFJBP  LKB CLO B>@E FKQBO>@QFLK

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Δ -25 Δ -200 -30 -250 -35 2468 2468 Number of monomers Number of monomers

=;IF9  !DDOBD>QFLKBKBODFBP>>KA>DDOBD>QFLKBKBODFBPMBOJLKLJBO?LCQEB @LJMLRKAP    >KA 

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4EB J>FK CLO@BP FKSLISBA LK QEB PBIC >PPBJ?IV MOL@BPP LC 6 JLKLJBOP >OB QEB

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0.0 Normalised [ -0.5

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0.0 Normalised [ -0.5

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200 210 220 230 240 250 260 Wavelength (nm)

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1.0 I xerogel I solution

] 0.5 θ

0.0 Normalised [ -0.5

-1.0

195 200 205 210 215 220 225 230 235 240 245 250 255 Wavelength (nm)

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1.0 J (MeOH solution) J (MeOH xerogel) 0.5 K (MeOH solution) ] θ K (CH3CN xerogel)

0.0 Normalised [ -0.5

-1.0

200 210 220 230 240 250 260 270 280 Wavelength (nm)

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0.1 0.4

0.2 0.0 0.0 190 200 210 220 230 240 250 260 190 200 210 220 230 240 250 260 Wavelength (nm) Wavelnegth (nm)

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,D97HFCG7CD=785H55B8D

20 3^4 D   ,   #(#I

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C@55AD<=D<=@9 - F

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PLIFA TEF@ET>P@OVPQ>IIFPBACOLJ-B/(%Q/>CCLOAFKD?LI>>JMEFMEFIB - F  JD  VFBIA

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20 3^4 D   ,   -B/(

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D  JJLIFK>KEVAOLRP#(#I J, 4EBJFUQROBT>PPQFOOBA>QOLLJQBJMBO>QROB LSBOKFDEQ 4EBPLISBKQT>POBJLSBARKABOOBAR@BAMOBPPROBQLMOLSFAB   JD NR>KQFQ>QFSBVFBIA>P >KLFI

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J,T>P>AABA>KAQEBPLIRQFLKT>PT>PEBATFQEP>QRO>QBA>NRBLRP.>(#/ PLIRQFLK UJ,>KAP>QRO>QBA>NRBLRP.>#IPLIRQFLKUJ, 4EBLOD>KF@I>VBOT>PAOFBALSBO

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,D97HFCG7CD=785H55B8D

L & D   #%Q/ MBKQ>KB

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    79HM@  8=A9H

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4L > PQFOOBA PLIRQFLK LC − SBO?BKLKB   J,  JJLIFK

AF@EILOLJBQE>KB >@BQLKFQOFIB T>QBOJ,TBOB>AABA@>Q>IVQF@2R#I EVAO>QB D

  BN >KA .>)/   D    JJLI    BN  4EB JFUQROB T>P PQFOOBA >Q OLLJ QBJMBO>QROBCLOE 4EB@ORABL?Q>FKBAT>PCFIQBOBAQEOLRDE#BIFQBY>KAQEBLOD>KF@ I>VBO T>P BUQO>@QBA TFQE AF@EILOLJBQE>KB  U  J,  4EBK  QEB @LJ?FKBA LOD>KF@

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,D97HFCG7CD=785H5 :CF7CADCIB8

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"RODBPP +  ,F 3 2B?BKPMFBP * %.<:*1.-:76.<<    

 +,  N=8C75F6CBM@  8=A9H

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šEBU>KB QL >CCLOA @>O?>J>QB  JD  VFBIA

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,D97HFCG7CD=785H55B8 D

!'&+ -(W #$#I   P ( <:*6; #(  P ( ,2; #(  P (

(   J ( (  AA   (W   (W ( (  J ( (  @

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3MB@QOLP@LMF@A>Q>>OB@LKPFPQBKQTFQEQELPBOBMLOQBAFKOBCBOBK@B

!DRFIBO> * -LDIFLKF ! ' -LIQO>PFL ' 9 /OQRxL 2 - %.<:*1.-:76 ;A55.<:A     

9BNM@  ,+  A9H

!KF@B @LLIBAPLIRQFLKLCPLAFRJEVML?OLJFQB;MOBM>OBA COLJ ?OLJFKBJ,   JJLI>KAPLAFRJEVAOLUFAB  D JJLI<FKJ,LCT>QBOT>P>AABAQL>PLIRQFLK LCHBQLKB   D   JJLIFKAFLU>KBšT>QBO MOBSFLRPIV@LLIBA>Q# 4EBJFUQROB T>PAFIRQBATFQE CROQEBOAFLU>KBJ,>KAPQFOOBA>Q #CLOE 4EBK QEBOB>@QFLK JFUQROBT>PT>PEBATFQEAF@EILOLJBQE>KB U J, QOB>QBATFQEPLAFRJPRICFQB>KA CFK>IIV   (#IT>P>AABAQLOB>@EM(š 4EB>@FAPLIRQFLKT>P BUQO>@QBATFQEBQEVI >@BQ>QBU J,>KAQEBLOD>KF@ BUQO>@QPTBOB AOFBALSBOJ>DKBPFRJ PRIC>QB  4EB PLISBKQ T>POBJLSBAQL>CCLOA>@FA   JD  VFBIA TEF@E T>P RPBA FKQEBKBUQ PQBMPTFQELRQCROQEBOMROFCF@>QFLK

,D97HFCG7CD=785H55B8 D

!'&+ -(W #$#I   P ( <:*6; #(  P ( ,2; #(  J (  J (  J (  J (  @ > (  @ > (  ?OP (

3MB@QOLP@LMF@A>Q>>OB@LKPFPQBKQTFQEQELPBOBMLOQBAFKOBCBOBK@B

!DRFIBO> * -LDIFLKF ! ' -LIQO>PFL ' 9 /OQRxL 2 - %.<:*1.-:76 ;A55.<:A     

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LSBOKFDEQ #()BU@BPPT>POBJLSBA 26>*,=7 >KA%Q/!@J,T>P>AABA 4EBPLIRQFLK T>PT>PEBATFQEP>QRO>QBA>NRBLRP.>(#/ PLIRQFLKUJ, P>QRO>QBA>NRBLRP.>#I

PLIRQFLKUJ,>KATFQE(/UJ, 4EBOBPRIQFKDLOD>KF@I>VBOT>PQEBKAOFBA

LSBO>KEVAOLRP-D3/ CFIQBOBA>KAPLISBKQPOBJLSBARKABOOBAR@BAMOBPPROB 4EBPLIFA T>PMROFCFBA?VPFIF@>DBI@EOLJ>QLDO>MEVRPFKD%Q/!@EBU>KBQL>CCLOA    D  

,D97HFCG7CD=785H55B8 D

!'&+ -(W #$#I   P ( <:*6; #(  P ( ,2; #(  J (  J (  AA  (W   (W (  P (  AA  (W    (W (  A   (W (  A  (W (  A   (W (   @LJMIBU>?PLOMQFLK (

3MB@QOLP@LMF@A>Q>>OB@LKPFPQBKQTFQEQELPBOBMLOQBAFKOBCBOBK@B

!DRFIBO> * -LDIFLKF ! ' -LIQO>PFL ' 9 /OQRxL 2 - %.<:*1.-:76 ;A55.<:A     

'!( _6I (&9 

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LCKFQOFILQOF>@BQF@>@FA  JD  JJLIFK>KEVAOLRP#(#I J, &BTAOLMPLC >KEVAOLRP$-&TBOB>AABA>KAQEBJFUQROBT>PPQFOOBARKABOOBCIRUCLOE !JFKL>@FA   D  JJLI>KA $)0%! J, JJLITBOB>AABA>KAQEBJFUQROBT>P PQFOOBARKABOOBCIRUCLOE 4EBPLISBKQT>POBJLSBARKABOOBAR@BAMOBPPROB %Q/!@

J,T>P>AABA>KAQEBPLIRQFLKT>PT>PEBATFQEP>QRO>QBA.>(#/ PLIRQFLKUJ,

  %UMBOFJBKQ>I$BQ>FIP

>KA P>QRO>QBA .>#I PLIRQFLK  U  J,  4EB LOD>KF@ I>VBO T>P AOFBA LSBO >KEVAOLRP

-D3/ CFIQBOBA>KABS>MLO>QBA QLMOLSFABJDLCA>OH?OLTKPLIFA 4EB@ORABT>PCFOPQ

MROFCFBA?VPFIF@>DBI@EOLJ>QLDO>MEVRPFKD%Q/!@>KA#(#I-B/(>PBIRBKQP>KA I>QBO?VMOB@FMFQ>QFLKRPFKDBQEBO>KAMBKQ>KBQL>CCLOAQOF>JFAB  JD  >PM>IB VBIILTPLIFA

,D97HFCG7CD=785H55B8 D

20 − 3^4 D   ,   #(#I

& D   Z#%Q/MBKQ>KB

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#  #  #  #  #

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 IHM@    8C897M@75F65ACM@7M7@C6IHM@75F65A5H9 

4L>PLIRQFLK LCJD JJLILC>@FA  FKJ,LC>KEVAOLRP#(#I  J, LC$)0%! JJLI BN>KAJDLC0V"/0 JJLI  BN>OB>AABA !CQBO JFKRQBPPQFOOFKD>QOLLJQBJMBO>QROB JDLCALAB@VI>JFKB  JJLI  BNFKJ,

LC>KEVAOLRP #(#I >OB>AABA 4EBPLIRQFLKFPPQFOOBALSBOKFDEQ>QOLLJQBJMBO>QROB

4EBK J,LC #(#I >OB>AABA>KAQEBPLIRQFLKFPT>PEBATFQE.>(#/ 4EBLOD>KF@

I>VBOFPAOFBATFQE-D3/ >KAQEBPLISBKQFPOBJLSBA 4EB@ORABFPMROFCFBA?V@LIRJK @OLJ>QLDO>MEVRPFKDEBU>KB %Q/!@ JDLC@LJMLRKA  >OBL?Q>FKBA>P>TEFQB PLIFAFK>LCVFBIA

,D97HFCG7CD=785H55B8 D

20 3^4 D    ,   #(#I

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 IHM@    8C897M@75F65ACM@7M7@C6IHM@75F65A5H9 

4L>PLIRQFLK LCJD JJLILC>@FA  FKJ,LC>KEVAOLRP#(#I  J, LC $)0%! JJLI BN>KAJDLC0V"/0 JJLI  BN>OB>AABA !CQBO JFKRQBPPQFOOFKD>QOLLJQBJMBO>QROB JDLCALAB@VI>JFKB  JJLI  BNFKJ,

LC>KEVAOLRP#(#I >OB>AABA 4EBPLIRQFLKFPPQFOOBALSBOKFDEQ>QOLLJQBJMBO>QROB

4EBK J,LC#(#I >OB>AABA>KAQEBPLIRQFLKFPT>PEBATFQE.>(#/ 4EBLOD>KF@

I>VBOFPAOFBATFQE-D3/ >KAQEBPLISBKQFPOBJLSBA 4EB@ORABFPMROFCFBA?V@LIRJK @OLJ>QLDO>MEV RPFKDEBU>KB %Q/!@  JDLC@LJMLRKA  >OBL?Q>FKBA>P>TEFQB PLIFAFK>  LCVFBIA

,D97HFCG7CD=785H55B8 D

20 3^4 D    ,   #(#I

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 IHM@     <9L5897M@75F65ACM@7M7@C6IHM@75F65A5H9

O 12 26 COOH 11 H2N(CH2)15CH3 13 27 10 N 89 H DIPEA, PyBOP 7 6 4 O 2 NHBoc HN 1 CH2Cl2, o/n, r.t. 5 3 71 O 88

4L>PLIRQFLKLC JD JJLILC>@FA  FKJ,LC>KEVAOLRP#(#I   J,LC$)0%!  JJLI BN>KA JDLC0V"/0  JJLI  BN>OB>AABA !CQBO JFKRQBPPQFOOFKD>QOLLJQBJMBO>QROB JDLC EBU>AB@VI>JFKB  JJLI  BN

FKJ,LC>KEVAOLRP#(#I >OB >AABA  4EB PLIRQFLK FP PQFOOBA LSBOKFDEQ >Q OLLJ

QBJMBO>QROB 4EBK J,LC#(#I >OB>AABA>KAQEBPLIRQFLKFPT>PEBATFQE.>(#/

4EBLOD>KF@I>VBOFPAOFBATFQE-D3/ >KAQEBPLISBKQFPOBJLSBA 4EB@ORABFPMROFCFBA?V @LIRJK@OLJ>QLDO>MEV RPFKDEBU>KB %Q/!@ JDLC@LJMLRKA  >OBL?Q>FKBA>P >TEFQBPLIFAFK> LCVFBIA

,D97HFCG7CD=785H55B8 D

20 − 3^4 D    ,   #(#I

& D   Z##(#I

"+ !42 >      @J 

!'&+ -(W #$#I N  Q   (W ( (  P ( (   P

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  %UMBOFJBKQ>I$BQ>FIP

 IHM@    <9L5897M@75F65ACM@7M7@C6IHM@75F65A5H9 

4L> PLIRQFLK LCJD JJLILC>@FA  FK J,LC>KEVAOLRP#(#I  J, LC$)0%! JJLI BN>KA JDLC0V"/0  JJLI  BN>OB>AABA !CQBO JFKRQBPPQFOOFKD>QOLLJQBJMBO>QROB JDLCEBU>AB@VI>JFKB   JJLI  BNFK

J,LC>KEVAOLRP#(#I >OB>AABA 4EBPLIRQFLKFPPQFOOBALSBOKFDEQ>QOLLJQBJMBO>QROB

4EBK J,LC#(#I >OB>AABA>KAQEBPLIRQFLKFPT>PEBATFQE.>(#/ 4EBLOD>KF@

I>VBOFPAOFBATFQE-D3/ >KAQEBPLISBKQFPOBJLSBA 4EB@ORAB FPMROFCFBA?V@LIRJK @OLJ>QLDO>MEV RPFKDEBU>KB %Q/!@  JDLC@LJMLRKA  >OBL?Q>FKBA>P>TEFQB PLIFAFK> LCVFBIA

,D97HFCG7CD=785H55B8 D

20 − 3^4 D    ,   #(#I

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    C897M@75F65ACM@7M7@C6IH5B 5AACB=IA7<@CF=89  

4L> PLIRQFLKLCJDLC   JJLIFKJ,LC>KEVAOLRP#(#I J,LC

- (#I FK %Q/ >OB >AABA  4EB PLIRQFLK FP PQFOOBA LSBOKFDEQ >Q OLLJ QBJMBO>QROB  4EB PLISBKQ FP OBJLSBA RKABO S>@RRJ  4EB MOLAR@Q FP MROFCFBA ?V MOB@FMFQ>QFLK FK >@BQLKB L?Q>FKFKD  JDLCPROC>@Q>KQ   FK> NR>KQFQ>QFSB VFBIA

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20 − 3^4 D    ,   -B/(

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  %UMBOFJBKQ>I$BQ>FIP

    C897M@75F65ACM@7M7@C6IH5B 5AACB=IA7<@CF=89 - 

4L> PLIRQFLKLCJDLC   JJLIFKJ,LC>KEVAOLRP#(#I J,LC

- (#I FK %Q/ >OB >AABA  4EB PLIRQFLK FP PQFOOBA LSBOKFDEQ >Q OLLJ QBJMBO>QROB  4EB PLISBKQ FP OBJLSBA RKABO S>@RRJ  4EB MOLAR@Q FP MROFCFBA ?V MOB@FMFQ>QFLK FK >@BQLKB L?Q>FKFKD  JDLCPROC>@Q>KQ -  FK>NR>KQFQ>QFSBVFBIA

,D97HFCG7CD=785H55B8 D

20 3^4 D    ,   -B/(

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  %UMBOFJBKQ>I$BQ>FIP

    !9L5897M@75F65ACM@7M7@C6IH5B 5AACB=IA7<@CF=89  

4L> PLIRQFLKLC JDLC   JJLIFKJ,LC>KEVAOLRP#(#I J,LC

- (#I FK %Q/ >OB >AABA  4EB PLIRQFLK FP PQFOOBA LSBOKFDEQ >Q OLLJ QBJMBO>QROB  4EB PLISBKQ FP OBJLSBA RKABO S>@RRJ  4EB MOLAR@Q FP MROFCFBA ?V MOB@FMFQ>QFLK FK >@BQLKB L?Q>FKFKD  JDLCPROC>@Q>KQ   FK>NR>KQFQ>QFSBVFBIA

,D97HFCG7CD=785H55B8 D

20 − 3^4 D    ,   -B/(

& D    Z#!@BQLKB

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!'&+ -(W -B/$ -  N  Q   (W ( (  P ( (    š

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 '&+ -(W -B/$ -  N                                

!+&, #>I@RI>QBACLO;- − #I<    &LRKA  

  %UMBOFJBKQ>I$BQ>FIP

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296 12. Annex

 BB9L

297 12. Annex

298 12. Annex

 BB9L

 FMC-&=A5;9GC:D! 89D9B89BHGIF:57H5BHG

25000X 25000X

50000X 50000X

20000X 15000X

=;IF9 . CryoTEM images of   at three different pH’s: 2 (top), natural (middle) and 12 (bottom).

299 12. Annex

20000X 20000X

5000X 12000X

15000X 12000X

=;IF9 . CryoTEM images of -  at three different pH’s: 2 (top), natural (middle) and 12 (bottom).

300 12. Annex

15000X 5000X

3000X 15000X

25000X 20000X

=;IF9 . CryoTEM images of   at three different pH’s: 2 (top), natural (middle) and 12 (bottom).

301 12. Annex

12000X 12000X

15000X 3000X

30000X 5000X

=;IF9 . CryoTEM images of -  at three different pH’s: 2 (top), natural (middle) and 12 (bottom).

302 12. Annex

 CFF9@5H=CB7IFJ9GC:%,

a) b)

1.0 1.0

0.8 0.8 C12 1 T12 1 C12 2 T12 2 0.6 C12 3 0.6 T12 3

0.4 0.4 Correlation Coefficient 0.2 Correlation Coefficient 0.2

0.0 0.0

10-1 100 101 102 103 104 105 106 107 108 10-1 100 101 102 103 104 105 106 107 108 c)Time (μs) d) Time (μs)

1.0 1.0 T16 1 C16 1 T16 2 0.8 C16 2 0.8 T16 3 C16 3

0.6 0.6

0.4 0.4

Correlation Coefficient 0.2 Correlation Coefficient 0.2

0.0 0.0

10-1 100 101 102 103 104 105 106 107 108 10-1 100 101 102 103 104 105 106 107 108 Time (μs) Time (μs)

=;IF9 . Correlation function of the DLS measurements of surfactant a)  , b) - , c)   and d) - .

303 12. Annex

  A=GG=CB ,D97HF5 C: ' 9@,H5FO 7CAD@9L9G 5H 8=::9F9BH GIF:57H5BH7CB79BHF5H=CBG

1.2 1.2

1.0 C12 1.0 T12 0.8 0.8

0.6 0.6

0.4

Normalized Intensity 0.4 Normalized Intensity

0.2 0.2

0.0 0.0 540 560 580 600 620 640 660 680 700 540 560 580 600 620 640 660 680 700 1.2 Wavelength (nm) 1.2 Wavelength (nm)

1.0 1.0 C16 T16

0.8 0.8

0.6 0.6

0.4 0.4 Normalized Intensity Normalized Intensity

0.2 0.2

0.0 0.0 540 560 580 600 620 640 660 680 700 540 560 580 600 620 640 660 680 700 Wavelength (nm) Wavelength (nm)

1.4 1.4

1.2 1.2 CTAB DTAB 1.0 1.0

0.8 0.8

0.6 0.6 Normalized Intensity

Normalized Intensity 0.4 0.4

0.2 0.2

0.0 0.0 540 560 580 600 620 640 660 680 700 540 560 580 600 620 640 660 680 700 Wavelength (nm) Wavelength (nm)

=;IF9 . Emission Spectra of DNA-GelStar complexes at different surfactant concentrations.

304 12. Annex

  CAD5F=GCB 69HK99B H<9 F9GI@HG C6H5=B98 :FCA  5B8 &,

To compare the obtained results, the superposition of the DEA and the EMSA results were represented. These two techniques give us different information about the formed complexes, but the behaviour of these surfactants with DNA can be compared.

Superposed graphics are shown in Figure 148. Blue line represents the Zhp-3 and purple line show the CMC of the surfactant.

1.2 1.0 C12 1.0 T12 0.8 DEA DEA EMSA 0.8 EMSA 0.6 0.6

0.4 0.4 Normalized data Normalized data 0.2 0.2

0.0 0.0

0.1 1 10 100 1000 10000 0.1 1 10 100 1000 10000 Concentration (μM) Concentration (μM) 1.0 1.0 C16 T16 0.8 DEA 0.8 DEA EMSA EMSA

0.6 0.6

0.4 0.4 Normalized Intensity 0.2 Normalized Intensity 0.2

0.0 0.0

0.1 1 10 100 1000 0.1 1 10 100 1000 Concentration (μM) Concentration (μM)

1.0 1.4

CTAB 1.2 DTAB 0.8 DEA 1.0 EMSA DEA EMSA 0.6 0.8

0.6 0.4 0.4 Normalized Intensity 0.2 Normalized Intensity 0.2

0.0 0.0 -0.2 0.1 1 10 100 1000 1 10 100 1000 10000 Concentration (μM) Concentration (μM) =;IF9 . Superposed results of DEA and EMSA experiments. Blue line represents the

3 Z

Results of both techniques are in very good agreement with each other and they verify that all the obtained results are reproducible and correct.

As it is shown, some information about the mechanism of the formation of the complexes can be find out. Difference between the 12-carbon and 16-carbon chain length can be observed. On the one hand, in both   and - , the concentration of the critical intensity (from DEA) corresponds to the starting point of the decrease of the free DNA concentration (from EMSA), while in   and - , the concentration of the critical intensity (from DEA) corresponds to the final point of the decrease of the free DNA concentration (from EMSA). It clearly means that the mechanism of the complex formation is different depending on the chain length and it seems to be independent on the stereochemistry.

Once the concentration of surfactant is above the CAC, surfactant aggregates start to form a complex with free DNA. In the case of   and - , the binding avoids GelStar® to bind DNA, reducing the intensity in DEA but they do not decrease the negative charges of the DNA. Once the CCI is reached, concentration of free DNA starts to decrease. After the Zhp-2 (in DEA), they show a broad peak where the intensity is increased and then it is decreased again. Comparing the results of DEA and EMSA, it is observed that the maximum of this broad peak corresponds to the Zhp-3 (blue line). After this point, the formation of the positively charged complex or the precipitation starts.

On the other hand,   and -  not only avoid GelStar® to bind DNA but also reduce the negative charges of the DNA until the Zhp-2 is reached. Then, the non-charged complex is obtained (Zhp-3, blue line) and the formation of the positively charged complex or the precipitation starts.

In all cases, CMC is above the concentration at which the positively charged complex starts to be formed. The formation of micelles (or other surfactant aggregates) in solution favours that these new aggregates bind DNA forming the cationic complex.

306 12. Annex

  '5G9 CCH)F=BH=B;GG5M

NruI:

=;IF9 . Resulting images from the electrophoresis of the NruI DNAse Foot Printing Assays. Concentrations are shown in μM of surfactant/ppm of DNA.

307 12. Annex

Standard DNAse:

=;IF9  . Resulting images from the electrophoresis of the DNAse Foot Printing Assays. Concentrations are shown in μM of surfactant/ppm of DNA.

308 12. Annex

  -F5BG:97H=CBGHI8=9G

=;IF9  . Images of the cells and images of the fluorescence microscope of the transfection studies of compounds DTAB, -  and  .

309 12. Annex

=;IF9 . Images of the cells and mages of the fluorescence microscope of the transfection studies of compounds CTAB, -  and  .

310 12. Annex

  )FC;F5Ad5@7I@Ge

Calculs is a program created using Bash code using the terminal to control the status of the computational calculations and to show which calculations are finished. Additionally, it shows all the useful information of each calculation.

Example of the output of the program:

Picard:/users/bernat>calculs

*******************************************************************************************************************************************

Hola bernat! Avui es dia 10/03/16, son les 09:48:47 i aquests son els teus calculs:

*******************************************************************************************************************************************

BORG2: max 12 jobs, 96 procs

Job ID Username Queue Jobname NDS Nodes S Time Main Borg Starting time ------156059.kirk.uab bernat borg2 trans16h-monomer-optbp.gjf 1 12 R 07:13 borg2-21 Mar 10 02:35:06 156074.kirk.uab bernat borg2 trans16-monomer-spbg.xyz 1 12 R 00:47 borg2-29 Mar 10 09:00:31

# Total borg2: 2 (2 + 0) # Estas fent servir 24 procs

********************************************************************************************************************************************

ACABATS: trans16-monomer-optbp.xyz (borg1)

********************************************************************************************************************************************

COMENTARIS:

******************************************* πππππππππππππππππππππππππππ *******************************************

Code of the program:

#!/bin/bash

# AQUEST ES EL FITXER FINAL DEL PROGRAMA. # SI VOLS UTILITZAR-LO, PRIMER HAS DE CREAR UNA CARPETA QUE ES DIGUI estatcalculs DINS DE LA TEVA CARPETA bin. # CANVIA EL TEU NOM D’USUARI. ALLA ON POSA bernat, POSA-HI EL TEU NOM. POTS SUBSTITUIR EL NOM DE TOT EL FITXER. # ASSEGURA’T QUE LES CUES ON TU CORRES ESTAN ACTIVADES --> NO HAN DE TENIR EL SIMBOL # AL DAVANT. # JA POTS EXECUTAR EL PROGRAMA. LA PRIMERA VEGADA QUE L’EXECUTIS ET SORTIRA ALGUN ERROR PERQUE S’HAN D’AUTOGENERAR UNS FITXERS. # A PARTIR D’ARA JA NOMES CAL QUE FACIS SERVIR EL PROGRAMA. SI EL TENS DINS DE LA CARPETA bin, NOMES ESCRIVINT calculs PODRAS EXECUTAR-LO. # PER ELIMINAR ELS CALCULS ACABATS, HAS D’ANAR A LA CARPETA estatcalculs I OBRIR EL FITXER acabatsnomdelacua (p.ex. acabatsborg1). # ELIMINA EL NOM DEL CALCUL QUE HAGI ACABAT I SURT DEL FITXER FENT :wq, DEIXANT EL FITXER EN BLANC. # POTS EDITAR EL .bashrc PER TAL DE POSAR UN ALIAS PER OBRIR AQUESTS FITXERS. PER EXEMPLE, endb1 POT SERVIR PER VEURE ELS FITXERS QUE HAN ACABAT A BORG1. # ENDAVANT I GAUDIR DEL PROGRAMA! # NO CAL DIR QUE QUALSEVOL ERROR QUE TROBIS O QUALSEVOL MILLORA, ESTAREM ENCANTATS DE QUE ENS HO DIGUIS. #Darrera actualitzacio: 06/02/2014 16:36 clear tinccalculs=$(qstat -u bernat |grepbernat -c) if [ "$tinccalculs"==0 ];then echo "" echo -e "\e[0;31m ******************************************************************************************************************* \e[0m" echo "" echo "" echo "NO TENS CAP CALCUL CORRENT!" echo "" echo "" echo -e " \e[0;36mACABATS:\e[0m" grep . /users/bernat/bin/estatcalculs/acabats_borg1 | awk ’{print " "$0" (borg1)"}’ grep . /users/bernat/bin/estatcalculs/acabats_borg2 | awk ’{print " "$0" (borg2)"}’ grep . /users/bernat/bin/estatcalculs/acabats_borg3 | awk ’{print " "$0" (borg3)"}’

311 12. Annex

echo "" echo -e "\e[0;31m ******************************************************************************************************************* \e[0m" echo "" exit fi touch /users/bernat/bin/estatcalculs/noms_antic1 touch /users/bernat/bin/estatcalculs/noms_antic2 touch /users/bernat/bin/estatcalculs/noms_antic3 touch /users/bernat/bin/estatcalculs/date_antic touch /users/bernat/bin/estatcalculs/num_antic username=$(whoami) hora=$(date | awk ’{print $4}’) dia=$(date +"%d/%m/%y") echo "" echo -e "\e[0;31m ******************************************************************************************************************* \e[0m" echo "" echo -e "\e[0;36m Hola ${username}! Avui es dia $dia, son les $hora i aquests son els teus calculs: \e[0m" echo "" gruppropi=$(id -gn) grup=$(infocues $gruppropi |grep"Estat"|awk ’{print $6}’) for i in $grup;do cua=$(qstat -u $username $i) if test -n "$cua";then total=$(qstat -u ${username} $i |grep$username -c) #a = Job Id, Username and Queue a=$(qstat $i -u ${username} | awk ’NR>5 {print " "$1"s" " " $2 " " $3 " " }’) #b = Jobname b=$(qstat -f $(qstat -u ${username} $i | awk ’NR>5 {print $1"es"}’) | grep -e "Job_Name"|awk ’{print $3}’) #c = NDS and Nodes c=$(qstat $i -n1u ${username} | awk ’NR>5 {print " "$6 " " $7}’) #d = Status and Time d=$(qstat $i -n1u ${username} | awk ’NR>5 {print $10 " " $11}’) #e = starting date e=$(qstat -f $(qstat -u ${username} $i | awk ’NR>5 {print $1"es"}’) | grep -e "start_time"|awk ’{print $4 " " $5 " " $6}’)

#nombre de calculs run_borg=$(qstat -u $username $i |grep " R " -c) queue_borg=$(qstat -u $username $i |grep " Q " -c) maxprocs=$(infocues $i | awk ’NR>9 && NR<11 {print $3}’)

# comença el programa! echo " Job ID Username Queue">>output echo " ------">>output if test -n "${total}";then echo "${a}">>output echo "Jobname">>output echo "------">>output echo "${b}">>output echo "NDS Nodes">>output echo "------">>output echo "${c}">>output echo "S Time">>output echo "-----">>output echo "${d}">>output echo "Main Borg">>output echo "------">>output long=$(qstat $i -n1u ${username} | awk ’NR>5 {print $12 }’) for j in ${long};do short=${j:0:8} echo $short >> output done echo "Starting time">>output echo "------">>output echo "${e}">>output fi

#fila on comença cada bloc inb1=$((0 + 1)) inb2=$((0 + $total + 3)) inb3=$((0 + 2 * $total + 5)) inb3b=$((0 + 3 * $total + 7)) inb4=$((0 + 4 * $total + 9)) inb5=$((0 + 5 * $total + 11))

#fila on acaba cada bloc fib1=$((0 + $total + 2 )) fib2=$((0 + 2 * $total + 4)) fib3=$((0 + 3 * $total + 6)) fib3b=$((0 + 4 * $total + 8)) fib4=$((0 + 5 * $total + 10)) fib5=$((0 + 5 * $total + $run_borg + 12))

#el que conte cada bloc 312 12. Annex

(sed -n ${inb1},${fib1}p output)>file1 (sed -n ${inb2},${fib2}p output)>file2 (sed -n ${inb3},${fib3}p output)>file3 (sed -n ${inb3b},${fib3b}p output)>file4 (sed -n ${inb4},${fib4}p output)>file5 (sed -n ${inb5},${fib5}p output)>file6 echo -e "\e[0;31m ******************************************************************************************************************* \e[0m" echo "" if [ "$i"=="borg1" ];then echo -e "\e[0;32m BORG1\e[0m: max 10 jobs, 32 procs" else if [ "$i"=="borg2" ];then echo -e "\e[0;32m BORG2\e[0m: max 12 jobs, 96 procs" else if [ "$i"=="borg3" ];then echo -e "\e[0;32m BORG3\e[0m: " fi fi fi

echo "" paste file1 file2 file3 file4 file5 file6 | column -s $’\t’-t echo "" echo " # Total $i: $total ($run_borg + $queue_borg)" suma=$(qstat -u $username $i |grep’R ’|awk ’{print $7}’) n=0 for k in $suma;do n=$(($k + $n)) done echo " # Estas fent servir $n procs" echo "" #elimina els fitxers temporals creats rm file{1..6} rm output fi done echo -e "\e[0;31m ******************************************************************************************************************* \e[0m" totalborg1=$(qstat -u bernat borg1) totalborg2=$(qstat -u bernat borg2) totalborg3=$(qstat -u bernat borg3) total=$(qstat -u bernat |grepbernat -c) antic1=$(cat /users/bernat/bin/estatcalculs/noms_antic1) antic2=$(cat /users/bernat/bin/estatcalculs/noms_antic2) antic3=$(cat /users/bernat/bin/estatcalculs/noms_antic3) dateantic=$(cat /users/bernat/bin/estatcalculs/date_antic | awk ’{print $2 " " $3 " " $4}’) if test -n "$totalborg1";then noms1=$(qstat -f $(qstat -u ${username} borg1 | awk ’NR>5 {print $1"es"}’) | grep -e "Job_Name"|awk ’{print $3}’) echo "$noms1">>actual1 for i in $antic1;do comproba1=$(grep "$i" actual1 |grep"$i" -c) if [ "$comproba1"==0 ];then echo $i >> /users/bernat/bin/estatcalculs/acabats_borg1 fi done rm actual1 else for i in $antic1;do echo $i >> /users/bernat/bin/estatcalculs/acabats_borg1 done fi if test -n "$totalborg2";then noms2=$(qstat -f $(qstat -u ${username} borg2 | awk ’NR>5 {print $1"es"}’) | grep -e "Job_Name"|awk ’{print $3}’) echo "$noms2">>kk2 for i in $antic2;do comproba=$(grep "$i" kk2 |grep"$i" -c) if [ "$comproba"==0 ];then echo $i >> /users/bernat/bin/estatcalculs/acabats_borg2 fi done rm kk2 else for i in $antic2;do comproba2=$(grep "$i" /users/bernat/bin/estatcalculs/acabats_borg2 |grep"$i" -c) if [ "$comproba2"==0 ];then echo $i >> /users/bernat/bin/estatcalculs/acabats_borg2 fi done fi if test -n "$totalborg3";then noms3=$(qstat -f $(qstat -u ${username} borg3 | awk ’NR>5 {print $1"es"}’) | grep -e "Job_Name"|awk ’{print $3}’) echo "$noms3">>kk3 for i in $antic3;do comproba=$(grep "$i" kk3 |grep"$i" -c) 313 12. Annex

if [ "$comproba"==0 ];then echo $i >> /users/bernat/bin/estatcalculs/acabats_borg3 fi done rm kk3 else for i in $antic3;do comproba3=$(grep "$i" /users/bernat/bin/estatcalculs/acabats_borg3 |grep"$i" -c) if [ "$comproba3"==0 ];then echo $i >> /users/bernat/bin/estatcalculs/acabats_borg3 fi done fi if test -n "$totalborg1";then antic1_bis=$(qstat -f $(qstat -u ${username} borg1 | awk ’NR>5 {print $1"es"}’) | grep -e "Job_Name"|awk ’{print $3}’) echo "$antic1_bis">/users/bernat/bin/estatcalculs/noms_antic1 else echo "" > /users/bernat/bin/estatcalculs/noms_antic1 fi if test -n "$totalborg2";then antic2_bis=$(qstat -f $(qstat -u ${username} borg2 | awk ’NR>5 {print $1"es"}’) | grep -e "Job_Name"|awk ’{print $3}’) echo "$antic2_bis">/users/bernat/bin/estatcalculs/noms_antic2 else echo "" > /users/bernat/bin/estatcalculs/noms_antic2 fi if test -n "$totalborg3";then antic3_bis=$(qstat -f $(qstat -u ${username} borg3 | awk ’NR>5 {print $1"es"}’) | grep -e "Job_Name"|awk ’{print $3}’) echo "$antic3_bis">/users/bernat/bin/estatcalculs/noms_antic3 else echo "" > /users/bernat/bin/estatcalculs/noms_antic3 fi date > /users/bernat/bin/estatcalculs/date_antic numcalcantic=$(cat /users/bernat/bin/estatcalculs/num_antic) numcalcactual=$(qstat -u bernat |grepbernat -c) resta=$(($numcalcantic - $numcalcactual)) qstat -u bernat | grep bernat -c > /users/bernat/bin/estatcalculs/num_antic echo "" echo -e " \e[0;36mACABATS:\e[0m" touch /users/bernat/bin/estatcalculs/acabats_borg1 touch /users/bernat/bin/estatcalculs/acabats_borg2 touch /users/bernat/bin/estatcalculs/acabats_borg3 grep . /users/bernat/bin/estatcalculs/acabats_borg1 | awk ’{print " "$0" (borg1)"}’ grep . /users/bernat/bin/estatcalculs/acabats_borg2 | awk ’{print " "$0" (borg2)"}’ grep . /users/bernat/bin/estatcalculs/acabats_borg3 | awk ’{print " "$0" (borg3)"}’ echo "" echo -e "\e[0;31m ******************************************************************************************************************* \e[0m" echo "" echo -e " \e[0;36mCOMENTARIS:\e[0m" grep . /users/bernat/bin/estatcalculs/comentaris_calculs | awk ’{print " "$0}’ echo "" echo -e "\e[0;31m ******************************************* \e[1;33m?~@?~@?~@\e[m\e[1;31m?~@?~@?~@\e[m\e[1;33m?~@?~@?~@\e[m\e[1;31m?~@?~@?~@\e[m\e[1;33m?~@?~@?~@\e[m\ e[1;31m?~@?~@?~@\e[m\e[1;33m?~@?~@?~@\e[m\e[1;31m?~@?~@?~@\e[m\e[1;33m?~@?~@?~@\e[m\e[0;31m ******************************************* \e[0m" echo "" # AUTORS: Pi-Boleda, B.; Navarro, J. # Amb la col·laboració de: Canales, I. End of the program.

314 12. Annex

  )CGH9FG

H<-9HF5<98FCB,MADCG=IA Berlin, June 2015

315 12. Annex

H<-9HF5<98FCB,MADCG=IA Berlin, June 2015

316 12. Annex

#CFB589GC7HCF5@G Bellaterra, June 2016

It was awarded with the First Price.

317