Supramolecular Studies on the Behaviour of Different Chiral
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mg/mL) 40 mgc 20 0 cis trans Stereochemistry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ormalised 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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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$O *RAFQE/O{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syn anti =;IF9 3@EBJ>QF@OBMOBPBKQ>QFLKLCQEB ;A6 >KA *6<2 @LKCFDRO>QFLK !@LKCLOJ>QFLK>IPB>O@E RPFKDJLIB@RI>OJB@E>KF@P LCQEBPFKDIBJLIB@RIBP T>P ALKB 4EBPQOR@QROBLCQEBJFKFJRJFKBKBODV T>P LMQFJFPBA TFQENR>KQRJJB@E>KF@P RPFKD- 8>P$&4 CRK@QFLK>I 4L PQRAVQEBPQOR@QROBLCQEBAFJBO CFOPQIV QEBQBQO>JBO T>PPQRAFBARPFKDQEBP>JBMOL@BAROB >KAQEB ;A6 >KA *6<2 @LKCFDRO>QFLK TBOB@LKPFABOBA 4EBK QEBPQRAFBAAFJBOT>PQEBFKQBOK>IAFJBOLCQEBLMQFJFWBAPQOR@QROB LCQEBQBQO>JBO !DDOBD>QFLKBKBODVΔ%>DDFPQEBAFCCBOBK@BFKBKBODVLCQEBAFJBO>KAQTLJLKLJBOP $FPQLOQFLK BKBODV Δ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− − *6<2 − − ;A6 − − *6<2 − − ;A6 − − *6<2 − − ;A6 − − *6<2 − − > 2BPRIQPFK M>OBKQEBPBP TBOB@>I@RI>QBATFQE QEB 'A M ?>PFPPBQ /K@BQEBOBI>QFSB@LKCFDRO>QFLKLCQEB>JFABDOLRMPFPABQBOJFKBA QEBPQOR@QROB LCQEBQBQO>JBO T>P PQRAFBARPFKDQEBABP@OF?BAJBQELALILDV !CQBOQE>Q QEBEBU>JBO >KAQEBL@Q>JBO TBOB @LKPQOR@QBA?VQ>HFKDQEBPQOR@QROBLCQEBFKQBOK>IAFJBOLCQEB QBQO>JBO 4EBK>JFKFJFW>QFLKLCQEBBKBODV T>P CLIILTBA?V>$&4PFKDIBMLFKQ@>I@RI>QFLK LCQEBBKBODV 4EBPQOR@QROBP LCQEBMOBAF@QBAL@Q>JBOP >OB PELTKFK &FDROB >KA &FDROB =;IF9 &OLKQ>ISFBTLCQEBMOBAF@QBAPQOR@QROBPLCQEBL@Q>JBOF@>DDOBD>QBPLCQEB @LJMLRKAP >KA .LK MLI>OEVAOLDBKPTBOB LJFQQBACLO@I>OFQV #E>MQBO =;IF9 ,>QBO>I SFBTLCQEBMOBAF@QBA PQOR@QROBP LCQEB L@Q>JBOF@ >DDOBD>QBP LC QEB @LJMLRKAP> ? @ >KAA .LK MLI>OEVAOLDBKPTBOBLJFQQBACLO@I>OFQV 0OBAF@QBAPQOR@QROBPLCQEBL@Q>JBOF@>DDOBD>QBPPELTQE>Q@LJMLRKAP >KA TEF@E@LKQ>FK>@V@IL?RQ>KBOFKD PBIC >PPBJ?IB CLOJFKD> WFDW>D >DDOBD>QBP QEBCLOJBO TFQE>EBIF@>I IFHBPQOR@QROB TEF@EJB>KPQE>QPLJB>PVJJBQOV@LRIA?BFKAR@BAAROFKD QEB >DDOBD>QFLK MOL@BPP /K QEB LQEBO E>KCA @LJMLRKAP >KA TEF@E @LKQ>FK > @V@ILEBU>KB OFKD PBIC >PPBJ?IB CLOJFKD > OFDEQ E>KABA >KA > IBCQ E>KABA EBIF@>I >DDOBD>QBOBPMB@QFSBIV 4EB BKBODFBPLCQEBCLOJ>QFLKLCB>@E>DDOBD>QB>KAQEB>DDOBD>QFLKBKBODFBPMBO JLKLJBO >OB PELTK FK &FDROB #LJMRQBA >DDOBD>QFLK BKBODFBP FK@IRAB QEB "33% @LOOB@QFLKFKLOABOQLJFKFJFWBQEBFKCIRBK@BLCQEBIBSBILCQEBLOV 4L@LJMRQBQEBBKBODV #E>MQBO LC >K >DDOBD>QB TFQE 6 JLKLJBOP "33% T>P @LKPFABOBA 6 QFJBP LKB CLO B>@E FKQBO>@QFLK > ? 0 -5 A A -10 -50 B B ) ) C -1 C -1 D -15 D -100 -20 (kcal mol -150 /n (kcal mol agg agg E E Δ -25 Δ -200 -30 -250 -35 2468 2468 Number of monomers Number of monomers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Δ%(" LCQEB>JFABJLFBQFBP>KAQEB S>KABO7>>IP FKQBO>@QFLKLCQEB @E>FKP Δ%SA7 )KLOABOQLABQBOJFKBQEBKBQ@LKQOF?RQFLKLCB>@ECLO@BLKQEB PBIC >PPBJ?IV QEBFKQBO>@QFLKBKBODV Δ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− − − − − − − − − − − −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s #E>MQBO #LQQLKAROFKDEFP0E$ TEBKEBCLRKAQE>Q PLJBLMQF@>IIV>@QFSBPR?PQ>K@BPMOBPBKQBA >KLJ>ILRPOLQ>QLOVAFPMBOPFLKABMBKAFKDLKQEBT>SBIBKDQE >QQEBOBDFLKLC>?LOMQFLKLC QEB@LJMLRKA )KQEFP QEBPFP QEFPQB@EKFNRB T>P CL@RPBALKQEB56 OBDFLK #$E>P KRJBOLRP >AS>KQ>DBP OBPMB@Q QL LQEBO @LKSBKQFLK>I QB@EKFNRBP PR@E >P O>MFA A>Q> @LIIB@QFLKLOB>PBLCRPB #EOLJLMELOB DOLRMP TFII >?PLO? AFCCBOBKQIV QEBAFCCBOBKQ@FO@RI>OIVMLI>OFPBAIFDEQ FC QEBV >OB @EFO>I LO FC QEBV >OB KB>O?V > @EFO>I DOLRM TEF@E FKAR@B >PVJJBQOV QL QEB @EOLJLMELOB .LK @EFO>I LO KLK FKAR@BA @EOLJLMELOB TFII >?PLO? ?LQE @FO@RI>OIV MLI>OFPBAIFDEQP>QQEBP>JBFKQBKPFQV>KAQERP QEBAFCCBOBK@BTFII?BWBOL>KAKLPFDK>ILK QEB#$PMB@QORJTFII?BL?PBOSBA #$@>K?BPQRAFBAFKPLIRQFLK>KAFKPLIFAPQ>QB )KLRO@>PB QEBPLIFAPQ>QBOBCBOP QLQEBUBOLDBIME>PB 4EBPE>MBLCQEB#$PMB@QORJFPABQBOJFKBA?VQEBOBI>QFSBMLPFQFLK LCQEBBIB@QOF@>KAJ>DKBQF@QO>KPFQFLKAFMLIBPLCQEB@EFO>I @EOLJLMELOB DOLRMP >KAQERP FQDFSBPFKCLOJ>QFLK>?LRQQEBPQOR@QROB )K PLIRQFLK QEB @EFO>IFQV LC PFKDIB JLIB@RIBP FP L?PBOSBA >KA QEB PFDK>I DFSBP FKCLOJ>QFLK>?LRQQEB @LKCLOJ>QFLKLCQEB@EOLJLMELOBP>KA FKLRO@>PBP >?LRQQEB FKQO>JLIB@RI>O >JFAB ?LKAP )KUBOLDBIME>PB LKIV@EFO>I>DDOBD>QBP TFIIDFSB>PFDK>ILK QEB#$ 4EBPFDK>IDFSBPFKCLOJ>QFLK>?LRQQEBOBI>QFSBMLPFQFLKLCQEB@EOLJLMELOBDOLRMP >KA FKLRO@>PBP >?LRQQEB FKQBOJLIB@RI>O >JFAB ?LKAP $BMBKAFKDLKQEBPQOR@QROBLC QEB>DDOBD>QB QEB OBI>QFSBMLPFQFLKLCQEB>JFABDOLRMPTFIIS>OV>KAQERP QEB PE>MBLC QEB#$PMB@QORJTFII >IPL S>OV !JFABP >?PLO? >Q KJ ARBQLQEB π π >KAQEB K π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θ D 0.0 Normalised [ -0.5 -1.0 195 200 205 210 215 220 225 Wavelength (nm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Δε 0 -5 -10 -15 -20 200 210 220 230 Wavelength (nm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FP>?IB QLDBI>KAFKOBA>OBOBMOBPBKQBAQEBPLISBKQPFKTEF@EFQFPPLIR?IB )KLOABO QL?BQQBO PBB QEBQTL>OB>P QEBMI>KB δ0 δ$ T>P OBMOBPBKQBA 18 16 H2O 14 12 MeOH 10 acetone CH3CN EtOH p 8 δ CH2Cl2 6 i-PrOH THF AcOEt 4 Et2O CHCl3 2 1,4-dioxane toluene 0 pentane -2 6 8 10 12 14 16 18 20 δ d =;IF9 (30POBMOBPBKQ>QFLK>KA$OBMOBPBKQ>QFLKLCQEB(30PLCQEBDBI>QFLKPQRAVLC LOD>KLDBI>QLO ! 4TLAFCCBOBKQ>OB>PLCPLISBKQPLKQEB(30PPM>@BJB>KPQTLAFCCBOBKQ ?BE>SFLROP LC QEFP LOD>KLDBI>QLO TEF@E @>K ?B OBI>QBA QL QTL AFCCBOBKQ >DDOBD>QFLK M>QQBOKP ,LLHFKD>QQEBPQOR@QROB>KA@LJM>OFKDFQQLLQEBOPQRAFBP FKQEB IFQBO>QROB TB @LRIA EVMLQEBPFPBQE>Q ! 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c >KA !cc &FDROB PELTP QEB MOBAF@QBAPQOR@QROB !c LC>K>DDOBD>QBLC@LJMLRKA ! !PFQFPPELTK FQCLOJP> KLK EBIF@>I >DDOBD>QBTEBOBQEBJLIB@RIBP>OBMI>@BAFK> WFDW>D AFPMLPFQFLK 4EBCOBB/(DOLRMP>OB CLOJFKDFKQBOJLIB@RI>OEVAOLDBK?LKAPC>SLROFKDQEB>DDOBD>QFLK )K>AAFQFLK TBQOFBA QLMOBAF@Q>PQOR@QROBTEBOBQEBPBCOBB/(DOLRMPCLOJEVAOLDBK?LKAPTFQE>KLQEBO JLIB@RIBMI>@BA FKCOLKQLC QEBLQEBO #E>MQBO =;IF9 &OLKQ>I >KA PFAB SFBT LC QEB MOBAF@QBA PQOR@QROB !c LC QEB L@Q>JBOF@ >DDOBD>QBLC@LJMLRKA ! .LK MLI>OEVAOLDBK>QLJPTBOBLJFQQBACLO@I>OFQV =;IF9 4LM>KAPFABSFBTLC QEBMOBAF@QBAPQOR@QROB !cc LCQEBL@Q>JBOF@>DDOBD>QBLC @LJMLRKA ! .LK MLI>OEVAOLDBK>QLJPTBOBLJFQQBACLO@I>OFQV #E>MQBO 0OBAF@QBA PQOR@QROB !cc PELTP QE>Q @LJMLRKA ! @>K PBIC >PPBJ?IB CLOJFKD EVAOLDBK?LKAPQEOLRDEQEBCOBB/(DOLRMP CLOJFKD>K >DDOBD>QBTEF@EPELTP>QLOPFLK QE>QTFIIMOLAR@BPLJBEBIF@FQVQLQEB>DDOBD>QBOFDEQ E>KABAEBIFU 4ERP ! @>K>ALMQ QTL AFCCBOBKQ >DDOBD>QFLK M>QQBOKP #LJM>OFKD MOBAF@QBA PQOR@QROB !c >KA MOBAF@QBA PQOR@QROB !cc FQFPPELTKQE>QTEFIB !c CLOJP> WFDW>D LOFBKQ>QFLKLCQEBEVAOLDBK?LKAP !cc E>P>M>O>IIBILOFBKQ>QFLKCLOJFKD>EBIF@>I>DDOBD>QB 3QRAVFKDQEB@FO@RI>OAF@EOLFPJ LC UBOLDBIPLC ! COLJ QTLAFCCBOBKQ PLISBKQP LKBLCB>@E>OB>COLJQEB(30PPM>@B TB @LRIA?B>?IBQLABQBOJFKBTEF@EPQOR@QROB@LOOBPMLKAPQLB>@ELKB =;IF9 0OBAF@QBA PQOR@QROB "c LC QEB L@Q>JBOF@ >DDOBD>QB LC @LJMLRKA " .LK MLI>O EVAOLDBK>QLJPTBOBLJFQQBACLO@I>OFQV &FK>IIV MOBAF@QBAPQOR@QROB "c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cc LC QEB LOD>KLDBI>QLO)FPPELTKFK &FDROB =;IF9 4LM>KAPFABSFBTPLCQEBMOBAF@QBAPQOR@QROB "cc LCQEBL@Q>JBOF@>DDOBD>QBLC @LJMLRKA " .LK MLI>OEVAOLDBK>QLJPTBOBLJFQQBACLO@I>OFQV $FPQ>K@BP>OBPELTKFK c !PFQFPPELTK QEBCOBB/(DOLRMPCLOJ>HFKALCKBQTLOHLCFKQBOJLIB@RI>O>KA FKQO>JLIB@RI>O EVAOLDBK ?LKAP 4EB MOBAF@QBA >DDOBD>QB PELTP QE>Q JLIB@RIBP @>K #E>MQBO FKQBO>@QTFQE>KLQEBOJLIB@RIBFKQEBP>JBMI>KB>KAQEBK QEFPAFJBOFP>?IBQLDOLTRM QLCLOJ QEB KLK EBIF@>I >DDOBD>QB )KLOABOQLABQBOJFKBQEBPQ>?FIFQVLCQEFPMOBAF@QBAPQOR@QROBP QEB>DDOBD>QFLK BKBODVLCQEBCLOJ>QFLKLCQEBAFJBO QEBQBQO>JBO QEBEBU>JBO>KAQEBL@Q>JBO T>P @>I@RI>QBA )K>AAFQFLK QEB>DDOBD>QFLKBKBODVMBOJLIB@RIB T>P @>I@RI>QBATFQE>- 8 'AIBSBILCQEBLOV>KAFK@IRAFKDQEB"33%@LOOB@QFLK !DDOBD>QFLKBKBODVΔ%>DD >KA>DDOBD>QFLKBKBODVMBOJLIB@RIBΔ%>DDK>OBPELTK FK &FDROB E 50 F G 0 H’ H’’ I’ -50 I’’ (kcal/mol) agg -100 E Δ -150 -200 2468 Number of monomers 25 E 20 F G 15 H’ 10 H’’ 5 I’ I’’ 0 -5 /n (kcal/mol) agg -10 E Δ -15 -20 -25 -30 2468 Number of monomers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cc >KA "cc FPJLOBKBD>QFSBJLOBC>SLRO>?IBQE>K QEBCLOJ>QFLKLCQEBL@Q>JBOTFQEQEBMOBAF@QBAPQOR@QROB !c >KA "c >IQELRDEFQFP>IPL C>SLRO>?IB DFSFKDQEBMLPPF?FIFQVLCQEB@LBUFPQBK@BLC?LQEPQOR@QROBP 4EB >DDOBD>QFLK BKBODV MBO JLKLJBO PELT QE>Q FK QEBPB @>PBP > @LLMBO>QFSB BCCB@Q@>KLKIV?BL?PBOSBARKQFIQEBCLOJ>QFLKLCQEBQBQO>JBO?B@>RPBQEBKQEB Δ%K OBJ>FKPKB>OIV@LKPQ>KQ (LTBSBO PQOR@QROBP !cc >KA "cc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cc 7B @LRIA PRDDBPQ QE>Q !cc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cm -1 -5 1000 -10 -15 500 -20 ] (mdeg mmol ] (mdeg mM θ [ θ -25 [ 0 -30 -35 -500 -40 -45 -1000 205 210 215 220 225 230 235 240 245 250 255 200 205 210 215 220 225 230 235 240 245 250 255 Wavelength (nm) Wavelength (nm) @ 1.0 E (MeOH solution) E (MeOH xerogel) 0.5 F (MeOH solution) ] θ F (MeOH xerogel) 0.0 Normalised [ -0.5 -1.0 200 210 220 230 240 250 260 270 280 Wavelength (nm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xerogel G solution ] 0.5 θ 0.0 Normalised [ -0.5 -1.0 200 210 220 230 240 250 260 Wavelength (nm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c PELTP> WFDW>D @LKCLOJ>QFLKLCQEBEVAOLDBK?LKAP>KACLOJP > KLK EBIF@>I >DDOBD>QB 4>HFKD FKQL >@@LRKQ QEB >@NRFOBA HKLTIBADB LC QEFP HFKA LC @LJMLRKAP QEFPPQOR@QROBPELRIADFSB> ?FPFDK>QB #LQQLKBCCB@QLKQEB#$PMB@QORJ 4ERP TB@LRIA PRDDBPQ QE>Q@LJMLRKA ! PBIC >PPBJ?IBP FKQL>K>DDOBD>QBTFQEQEBMOBAF@QBA PQOR@QROB !c FKMLI>OPLISBKQPPR@E>P>@BQLKB &ROQEBOJLOB MOBAF@QBAPQOR@QROB !cc PELTP >K>DDOBD>QB TFQE>QLOPFLKQE>QDBKBO>QBP>EBIF@>IPQOR@QROB TEF@E @LRIA ?BOBI>QBAQL> ?>KAFKQEB#$PMB@QORJ 4ERP TB@LRIAP>VQE>Q@LJMLRKA ! PBIC >PPBJ?IBP CLOJFKD>K >DDOBD>QBTFQE>MOBAF@QBAPQOR@QROB !cc FK>MLI>OPLISBKQPPR@E>PMBKQ>KB 4EBOBCLOB TB @LRIA?B >?IB QLABQBOJFKBTEF@EPQOR@QROBE>PB>@EOBDFLKLCPLISBKQPCOLJQEB(30P PM>@B 1.0 H xerogel pentane H solution methanol H xerogel acetone ] 0.5 θ 0.0 Normalised [ -0.5 -1.0 200 210 220 230 240 250 260 270 Wavelength (nm) =;IF9 .LOJ>IFPBA#$PMB@QO>LCLOD>KLDBI>QLO ! FKJBQE>KLIPLIRQFLK>Q J->KA FKUBOLDBIPME>PBCOLJMBKQ>KB>KA>@BQLKB>Q >KA JJLIDLC+"O>Q Z# OBPMB@QFSBIV $RBQLQEBILTPLIR?FIFQV LC " FKJBQE>KLI QEBFKQBKPFQVLCQEBPFDK>IFPSBOVILT>KA QEBOBPRIQ FKPLIRQFLK @>KKLQ?B@LKPFABOBA>PDLLA>PFKQEBLQEBO@>PBP ?RQFQ@>K?BRPBA GRPQQL@LJM>OBFQTFQEQEB#$PMB@QO>OBDFPQBOBAFKUBOLDBIME>PB 4EB UBOLDBI T>P L?Q>FKBA?VAOVFKDQEBL?Q>FKBADBI>QQEB 50, FK QLIRBKB &FDROB PELTPQE>QTEFIB @LJMLRKA " PELTP>?>KAFKPLIRQFLK FKUBOLDBIFQMOBPBKQP> @IB>O ?FPFDK>QB#LQQLKBCCB@Q TFQE>WBOL@OLPPFKD >QKJ !CQBOAFCCBOBKQ@LFK@FABK@BP TB@LRIAP>VQE>Q> ?FPFDK>QB PFDK>I PELRIA@LOOBPMLKAQL> KLK EBIF@>I >DDOBD>QB (LTBSBO ?LQEMOBAF@QBAPQOR@QROBP #E>MQBO LCQEB>DDOBD>QBPLC " MOBPBKQ KLK EBIF@>I >DDOBD>QBP TEF@EFPFK>DOBBJBKQTFQEQEBLQEBO @>PBP?RQALBPKLQ>IILTRPQLAFPQFKDRFPE?BQTBBKQEB>DDOBD>QFLK M>QQBOKP !QQEFPMLFKQ TB@LRIAPRDDBPQ QE>QFKMLI>OPLISBKQP@LJMLRKA " PBIC >PPBJ?IBP CLOJFKD>K>DDOBD>QB IFHB QEB MOBAF@QBA PQOR@QROB "cc ?RQ TB @>KKLQ EVMLQEBPFPB FC FK >MLI>O PLISBKQP QEB PQOR@QROBFP "c LO "cc LOBSBKTEBQEBOFQPBIC >PPBJ?IBP LOKLQ 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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kcal/mol) -80 /n (kcal/mol) -15 agg agg E Δ -100 E Δ -20 -120 -25 -140 -160 -30 2468 2468 Number of monomers Number of monomers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eOH 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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ππ QO>KPFQFLKP FP>PPL@F>QBAQL( QVMB>DDOBD>QBP FKTEF@EQEB>?PLOMQFLKFPJLOBBKBODBQF@QE>KQEB >?PLOMQFLKLCQEBJLKLJBOPRDDBPQFKD>PQOLKDFKQBO>@QFLK?BQTBBKQEB>JFAB DOLRMPLC QEBJLKLJBOP>KA QERP QEBT>SBIBKDQELCQEBJ>UFJRJFPPEFCQBAQLILTBO T>SBIBKDQEP 3QOR@QROB LC QEB MOBAF@QBA >DDOBD>QBP @>K ?B OBI>QBA TFQE ( QVMB >DDOBD>QBP TEF@EPELTQE>QQEBAFOB@QFLKLC>DDOBD>QFLKLCQEBJLKLJBOPFPOLRDEIV MBOMBKAF@RI>OQLQEBMI>KBLCQEBJLKLJBO !IPLFQFP@LKPFPQBKQTFQELQEBOPQRAFBPTFQE PFJFI>OLOD>KLDBI>QLOP 3QBOBL@EBJFPQOV>KAOFKDPFWBE>SB>KFKCIRBK@BLKQEB>DDOBD>QFLKM>QQBOK !JFAB DOLRMPCLOJQEB ?>@H?LKB LCQEB>DDOBD>QB>KAQERP >DDOBD>QFLKPQOR@QROBABMBKAPLK QEBOBI>QFSBMLPFQFLKLCQEB>JFABDOLRMP (LTBSBO FKQEBPR?PQFQRQBA@>O?L@V@IBP LQEBO EVAOLDBK ?LKAP ?BQTBBK JLKLJBOP >OB CLOJBA >KA QEBK PQBOBL@EBJFPQOV E>P IBPP FKCIRBK@BLKQEBCFK>I>DDOBD>QFLK 4EB@LKQOF?RQFLKLC>IIQEBEVAOLDBK?LKAPE>PQL?B @LKPFABOBA )Q FP L?PBOSBA QE>Q TEFIB QEBLOBQF@>I @>I@RI>QFLKP >OB FK >DOBBJBKQ TFQE QEB BUMBOFJBKQ>I @FO@RI>O AF@EOLFPJ LC QEB UBOLDBIP >KV PQOLKD OBI>QFLKPEFM ?BQTBBK QEB #E>MQBO PQOR@QROBLCQEB>DDOBD>QB>KAQEBDBI>QFLK?BE>SFLRO T>P KLQ L?PBSBA )CQEBOBT>P@IB>O OBI>QFLKPEFMQEBKTB@LRIA?B>?IBQL@>OOVLRQ * 8:27:2 MOBAF@QFLKP LC QEB DBI>QFLK ?BE>SFLROLC>DBILKIVRPFKDQEBLOBQF@>I@>I@RI>QFLKP (LTBSBO >PFQFPHKLTK QEBT>VQL CFKAQEB (LIV'O>FI FPKLQPLB>PV 4EB BCCB@Q LC E>SFKD > #( PM>@BO PBBJP KLQ QL C>SLRO QEB DBI>QFLK >?FIFQFBP #LJM>OFKD @LJMLRKAP LC &>JFIV TFQE QEBFO ELJLILDRBP COLJ &>JFIV QEB DBI>QFLK >?FIFQV FP OBAR@BA FK >II @>PBP BU@BMQ TFQE @LJMLRKA $ TEF@E E>SB >K RKBUMB@QBA ?BE>SFLRODBI>QFKDPBIB@QFSBIV>@BQLKFQOFIBFK>OBI>QFSBIVILT 50, &FK>IIV TE>QMI>VP>KFJMLOQ>KQOLIBQLQEBDBI>QFLK?BE>SFLRO>OBQEBAFCCBOBKQ PR?PQFQRQFLKP LC QEB OFKD #LJMLRKAP E>SFKD > 4"$-3 MOLQB@QFLK >OB >?IB QL DBI>QB >I@LELIP TEFIB@LJMLRKAPTFQELOCOBB/(DOLRMP>OB>?IBQLDBI>QB>MLI>OPLISBKQP !PFQFPL?PBOSBA FQPBBJPQL?BBSFABKQQE>QQEBLOD>KLDBI>QLOALBPKLQFKQBO>@QTFQEQEB PLISBKQRPFKDFQPPR?PQFQRQFLKP 4EBDBI>QFLK>?FIFQVE>PQL?BOBI>QBAQLQEBBCCB@QQE>QQEBPB JLIB@RIBPTFQEQEBPBPR?PQFQRQFLKPMI>VFKPFABQEBPLISBKQ @E>KDFKDQEBPROC>@BQBKPFLK >KAFK@OB>PFKDQEBBKBODVLCQEB PVPQBJ #E>MQBO #E>MQBO 5H=CB=76C@55AD<=D<=@9GK=H<5 7M7@C6IH5B9G75::C@869<5J=CIF5G GIF:57H5BHG #E>MQBO #E>MQBO 5H=CB=7 6C@55AD<=D<=@9G K=H< 5 7M7@C6IH5B9 G75::C@8 69<5J9CIF5GGIF:57H5BHG "BHFC8I7H=CB !JMEFMEFIF@ JLIB@RIBP >OB QELPB QE>Q E>SB ?LQE EVAOLMEFIF@ >KA EVAOLMEL?F@ MOLMBOQFBP !JMEFMEFIF@ @LJMLRKAP TEF@E >OB PROC>@B >@QFSB >DBKQP >OB @LJJLKIV OBCBOOBA>PPROC>@Q>KQP 3ROC>@B>@QFSB>DBKQPJB>K QE>QQEBPB@LJMLRKAP>OB>?IB QL ILTBO QEBPROC>@BQBKPFLKLC>@BOQ>FKIFNRFA >FOFKQBOC>@B KLOJ>IIV >FO T>QBO 3ROC>@B QBKPFLKFPQEB BKBODV KBBABAQLFK@OB>PBQEBPROC>@BLKBRKFQLC>OB> )QFP> MEBKLJBKLK MOLJLQBA ?V QEB @LEBPFSB CLO@BP ?BQTBBK IFNRFA JLIB@RIBP ,FNRFA JLIB@RIBP >Q QEB PROC>@BFKQBO>@QTFQEQEBJPBISBP>KAQEBIFNRFA >@NRFOBP QEB JFKFJRJMLPPF?IB PROC>@B >OB> 4EBVMOLAR@BCL>JARBQLQEBFO>@QFLK>QQEB>FO T>QBOFKQBOC>@B >KAQEBVJ>HBQEB DOB>PBQO>KPCBOCOLJ AFOQV E>KAPFKQLQEBPL>MVT>QBO>P>OBPRIQLCFQP>@QFSFQV>QQEBT>QBO LFIDOB>PBFKQBOC>@B $RBQLQEBFO>JMEFMEFIF@?BE>SFLRO >QILTPROC>@Q>KQ@LK@BKQO>QFLK JLIB@RIBP>OB MI>@BA >Q QEB >FO T>QBO FKQBOC>@B ?V HBBMFKD QEB EVAOLMEFIF@ M>OQ FK T>QBO >KA QEB EVAOLMEL?F@Q>FIMLFKQFKDLRQQLQEB>FO 7EBKFK@OB>PFKDQEB@LK@BKQO>QFLK JLIB@RIBP>OB >APLO?BA>QQEBFKQBOC>@B 4EBMOBPBK@BLCEVAOLMEL?F@@E>FKP>QQEB>FO T>QBOFKQBOC>@B @>RPBPQEBAB@OB>PBLCQEBPROC>@BQBKPFLKLCQEBT>QBOJLIB@RIBP 4EFPMOL@BPP@>K?B ABP@OF?BA RPFKD QEB 'F??P >APLOMQFLK FPLQEBOJ %NR>QFLK TEF@E ABP@OF?BP QEB 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7.0 7.0 6.5 6.5 C12 6.0 6.0 T12 pKa = 8.5 pKa = 8.2 5.5 5.5 pKa < 0 pH pH pKa < 0 5.0 5.0 CMC = 1.0 mM 4.5 pKa = 0 4.5 pKa = 6.9 CMC = 0.60 mM strong acid 4.0 pKa = 6.25 4.0 weak acid 3.5 3.5 0.01 0.1 1 10 0.01 0.1 1 10 Concentration (mM) Concentration (mM) @ A 7.5 6.0 5.5 7.0 pKa = 9.0 pKa = 5.4 5.0 6.5 T16 4.5 6.0 C16 4.0 pH pH 5.5 3.5 CMC = 0.32 mM 5.0 3.0 CMC = 0.16 mM 4.5 2.5 4.0 2.0 0.01 0.1 1 10 0.01 0.1 1 10 Concentration (mM) Concentration (mM) =;IF9 M(S>IRBP>Q Z#SBOPRPPROC>@Q>KQ@LK@BKQO>QFLK > ? - @ >KA A - /K@BQEBM(FPABQBOJFKBA FQFPMLPPF?IBQLOBMOBPBKQQEBS>OF>QFLKLCQEBM+> ABMBKAFKDLKQEB@LK@BKQO>QFLKLCQEBPROC>@Q>KQ >@@LOAFKDQL QEBCLIILTFKDBUMOBPPFLK %NR>QFLK /?Q>FKBAS>IRBP>OB PELTKFK &FDROB %NR>QFLK ! #E>MQBO > ? 9.5 8.5 9.0 pKa = 8.2 pKa = 8.5 C12 8.5 8.0 8.0 T12 7.5 pKa pKa 7.5 7.0 6.5 pKa=6.25 6.0 7.0 pKa = 6.9 5.5 0.01 0.1 1 10 0.01 0.1 1 10 Concentration (mM) Concentration (mM) @ A 9.5 6.0 5.5 9.0 pKa = 9.0 T16 pKa = 5.4 5.0 8.5 C16 4.5 pKa pKa 8.0 4.0 7.5 3.5 pKa = 3.8 pKa = 7.2 7.0 3.0 0.01 0.1 1 10 0.01 0.1 1 10 Concentration (mM) Concentration (mM) =;IF9 #>I@RI>QBAM+> S>IRBPSBOPRPPROC>@Q>KQ@LK@BKQO>QFLK > ? 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12 12 C12 11 T12 10 10 NaOH 9 NaOH HCl 8 HCl 8 pKa = 7.2 pKa = 7.2 pH pKa = 7.1 pKa = 7.1 pH 7 6 6 5 4 4 3 2 5 4 3 2 1 5 4 3 2 Concentration (mM) Concentration (mM) @ A 12 11 C16 T16 10 NaOH 10 NaOH 9 HCl HCl 8 8 pKa = 6.8 7 pKa = 6.5 pKa = 6.5 pKa = 6.1 pH pH 6 6 5 4 4 3 2 2 5 4 3 2 5 4 3 2 Concentration (mM) Concentration (m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cm cm -1 -1 0 5.00 mM 3.76 mM 3.01 mM 5.00 mM 2.50 mM 3.76 mM -20 3.01 mM ] mdeg mM 1.25 mM ] mdeg mM θ θ -20 2.50 mM [ 0.94 mM [ 0.75 mM 1.25 mM 0.63 mM 0.94 mM 0.75 mM 0.63 mM -40 -40 190 200 210 220 230 240 250 260 190 200 210 220 230 240 250 260 Wavelength (nm) Wavelength (nm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mM 5.00 mM 3.76 mM 3.76 mM 3.01 mM 2.5 3.01 mM 2.5 2.50 mM 2.50 mM 1.25 mM 0.94 mM 2.0 1.25 mM 2.0 0.94 mM 0.63 mM 0.63 mM 0.41 mM 1.5 0.41 mM 1.5 1.0 1.0 T12 Absorbance (a. u.) C12 Absorbance (a. u.) 0.5 0.5 0.0 0.0 =;IF9190 200 56 SFP>?PLOMQFLKPMB@QO>LCPROC>@Q>KQP 210 220 230 240 250 260 190 200IBCQ>KA 210 220- 230OFDEQ>QAFCCBOBKQ 240 250 260 Wavelength (nm) Wavelength (nm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avelength (nm) Wavelength (nm) 205 200 CMC = 1.1 mM 200 CMC = 1.2 mM 195 0123456 012345 Concentration (mM) Concentration (m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mM 1.26 mM 60 2.50 mM -1 -1 0.63 mM 1.25 mM 15 cm cm -1 -1 40 10 T16 C16 ] mdeg mM ] mdeg mM θ θ 20 5 [ [ 0 0 -5 190 200 210 220 230 240 250 260 190 200 210 220 230 240 250 260 Wavelength (nm) Wavelength (nm) =;IF9 #FO@RI>O$F@EOLFPJPMB@QO>LCPROC>@Q>KQP IBCQ>KA - OFDEQ>QAFCCBOBKQ @LK@BKQO>QFLKPFKT>QBO 0.7 2.50 mM 2.0 1.25 mM 0.6 2.50 mM 0.63 mM 1.8 1.25 mM 0.32 mM 0.63 mM 0.5 0.16 mM 1.6 0.32 mM 0.08 mM 0.16 mM 1.4 0.04 mM 0.08 mM 0.4 0.02 mM 1.2 0.04 mM 0.02 mM 0.3 1.0 C16 0.8 0.2 Absorbance (a. u.) 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Experimental Aspects of Solid State Circular Dichroism. 12:*42 296 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