uortig Iormtio: Pti moiitio oirmtio vi 1 MR: j 5 FEFEFKFK 8.6.. 8.6 1 13 1 11 1 9 8 7 6 5 3 1 FEFEFKFK moii 1 13 1 11 1 9 8 7 6 5 3 1 m - - 3 3 g i o i o g m l g m l - - h k 3 h k 3 Figur 1: 1 -MR or th umoii moii tis 1 Grou ty Pk [m] Assigmt 1 1.3 (ko rst 8.63 oly i umoii ti) 3 Aromti rigs 7.,, (ko).-.6 5 (xt to romti rigs) 3.3 g 6 (xt to si his).85-3.15 h 7 (xt to si his).85-.5 i 8 DM-6.5 9 (xt to rst oly i moii ti).35 j 1 (si his).-. k 11 (si his) 1.-. l, m,, o 1 (ko) 7.5-8.5 Tl 1: 1 MR ks ssig to grous 15 All ks rst i th 1 MR str ( Mz Brukr) or oth th ur moii tis r ssig i Tl 1. Th most rlvt o ths r 8.63 m.35 m. Th k t 8.63 m orrsos to th r grou i th ur, umoii ti. As xt, this grou is rst oly i th origil ti ot i th moii ti. Th grou o th moii ti is th k t.35 m i th moii ti is ttriut to its ighourig grou. Ths rsults suggst th sussul moiitio o th ti. This jourl is Th Royl oity o hmistry [jourl], [yr], [vol], 1
Pti utiolistio oirmtio y MALDI-To: FEFEFKFK %It. 8 6 111.6 {r3} 113.83{r388} 111.6 {r3} 113.8 {r388} 11.9 {r3669} 5 11.9 {r3669} Figur : MALDI-To o th umoii ti (FEFEFKFK) 1115 11 115 113 1 13 15 Mss/hrg FEFEFKFK moii %It. 8 6 137.3 {r88} 137.3 {r51} 137.3{r88} 137.3{r51} 1373.8{r357} 137.8{r79} 1373.8 {r357} 1176.6 {r85} 137.8 {r79} 1365 137 1375 138 1385 1 13 15 16 17 18 19 Mss/hrg 3 Figur 3: MALDI-To o th moii ti (mo FEFEFKFK) 35 Th rsults giv i igurs 3 show sigiit ir i th molulr wight o th two tis (th moii ti is ~9 g mol -1 hvir tht th umoii ti) oirmig utiolistio. Ths rsults wr oti rom Krtos P Axim FR V...1 ort i rltio mo. [jourl], [yr], [vol], This jourl is Th Royl oity o hmistry [yr]
Ptis urity vlutio y PL: mau65 3 %D:. % %:. % Flow: 1. ml/mi 3 FEFEFKFK 8. UV_VI_ WVL:65 m 1 %B:. %. -5 5 1 15 5 3 35 6 Tim / mi Figur : PL o th umoii ti (FEFEFKFK) 5 o. Rt.Tim Ar ight Rl.Ar mi mau*mi mau % 1 3.89.17 1.55. 15.83 16.191 6.66 15.35 3 18.191 86.58 39.9 81.57 31.97 1.1 5.717 1.7 Totl 15.69 8. Tl : PL rsults or th origil ti th urity rtg This jourl is Th Royl oity o hmistry [jourl], [yr], [vol], 3
mau65 3 %D:. % %:. % Flow: 1. ml/mi FEFEFKFK moii 8. UV_VI_ WVL:65 m 5-5 1 %B:. % 5 1 15 5 3 35 6 Tim / mi Figur 5: PL o th moii ti (mo FEFEFKFK) 3 5 6 7 8 9 1. 55 o. Rt.Tim Ar ight Rl.Ar mi mau*mi mau % 1 3.93.1686 11.33 1.93 1.56 1. 3.719.93 3 17.37.37.86 3.9 18.7 85.175 36.88 75.7 5.6 11.7165 39.817 1.1 6.98.5 1.81 7.37.66 13.666.3 8.76 1.377 7.8 1.1 9 31.989 1.1651 6.86 1. 1 37.73.6698 1.575.6 Totl: 11.515 353.7 Tl 3: PL rsults or th moii ti th urity rtg 6 Th PL rsults show high urity i oth th umoii moii tis; 81 % 76 % rstivly, oirmig th MALDI rsults. Ths rsults wr otiig usig rvrs hs PL whr ur A ws PL gr wtr with.1% triluoroti i (TFA) ur B ws PL gr toitril with.1% TFA. A grit o -8% o B ws us with sml ijtio o μl. Th ollowig st u ws mloy: Diox P68 PL um, with Diox AI utomt sml ijtor, Diox UVD17U ttor. Th olum is Mhry-gl E5/.6 ulosil -5 18 olum. [jourl], [yr], [vol], This jourl is Th Royl oity o hmistry [yr]
65 oirmtio o ojugtio y soli stt MR: PiPAAm * * = romti FEFEFKFK 3 3-3 -φ ) = ) * * * 18 9 m rom TM ojugtdmf 18 9 m rom TM 1 1 ) 5 15 5 m rom TM 7 Figur 6: oli stt MR: ) ur olymr, ) ur ti ) th ojugt. 75 Atr sythsis uriitio th ojugt ws lys y soli stt MR usig th oojugt olymr th ti s strs. tr r show i Figur 6 whr ks hv itii. For th ojugt (Figur 6), sulmtry ks wr ou i th rg o 11-15 m, tht orrsos to th hyl rigs rst i th ti. Ths rsults oirm th rs o th ti i th ojugt strutur. MR str wr ror t 9. T usig Brukr DX- stromtr, i 1 to 13 ross-olristio mgi gl siig mo. This jourl is Th Royl oity o hmistry [jourl], [yr], [vol], 5
6 [jourl], [yr], [vol], This jourl is Th Royl oity o hmistry [yr] Qutiitio ti/ipaam rtio i ojugt y 1 MR UV: 8 Figur 7: 1 MR str or ur olymr or th ojugt 85 Figur 8: Mgii 1 MR str or ur olymr or th ojugt PIPAAm 5g/L PFEFEFKFEFK 5g/L...1..3.6.5.7.9.8 5. m PIPAAm 5g/L PFEFEFKFEFK 5g/L...1..3.6.5.7.9.8 5. m PFEFEFKFK 5g/L - 3 3 3 3-3 3 3 3-3 3 3 3-3 3 3 3-3 3 3 3-3 3 3 3-3 3 3 3-3 3 3 3-3 3 3 3-3 3 3 3-3 3 3 3-3 3 3 3-3 3 3 3-3 3 3 3-3 3 3 3-3 3 3 3
9 As. Itsity /.u. 1.9.8.7.6.5..3..1 ti 1g L -1 ti.9g L -1 ti.7g L -1 ti.5g L -1 ti.3g L -1 As. / u...8.7.6.5..3..1 lirtio ourv or ti...6.8 1 otrtio / g L -1 ti.1g L -1 ojugt 1g L -1 5 7 9 31 33 35 wvlgth / m Figur 9: UV str or umoii ti solutios with vryig otrtios (ott lis) or ojugt solutio t 1 g L 1. Isrt: lirtio urv (los imos) oti or 95 th umoii ti ojugt sor (o imo). 15 I orr to qutiy th mout o ti tth t th o th olymri hi, two mthos wr us: roto MR UV. Pk ssigmt i th 1 MR str is show i Figur 7 th rgio o itrst or qutiitio is mgii i Figur 8. Th ks t.1,.55.8 m orrso to th rom th ko o th ti r vry istitiv. Ths ks wr us or qutiitio tkig th 3 grous o olymri hi s rr oit. Th 1 MR str wr ror o Brukr, Mz stromtr, usig 16 ss or tim vrgig. Th sor t 58 m ws us to oirm th qutiitio o mout o ti y UV. A lirtio urv ws uil usig th moii ti ws th susqutly us to qutiy th mout o ti rst i th ojugt. tr wr ror o himzu 51 oul m stromtr. This jourl is Th Royl oity o hmistry [jourl], [yr], [vol], 7
Grhil ott Etry 3 3 olymr-ti ioojugt 3 3 Tm ~ 75 º Tim, RT Tm. < ~ 3 º < 8 [jourl], [yr], [vol], This jourl is Th Royl oity o hmistry [yr]