Syn hesis and Sel -Assembly o
No el ABC Mik oa m S a
Te polyme s
DISSERTATION
zu E langung des akademisches G ades eines
Dok o s de Na u wissenscha en (D . e . na .)
im Fach Chemie
an de Bay eu he G aduie enschule
ü Ma hema ik und Na u wissenscha en
de Uni e si ä Bay eu h
o geleg on
And eas Hanisch
Gebo en in Kulmbach
Bay eu h, 2013
Die o liegende A bei wu de in de Zei on Juli 2008 bis Janua 2013 in Bay eu h am
Leh s uhl Mak omolekula e Chemie II un e Be euung on He n P o . D . Axel H. E.
Mülle ange e ig .
Volls ändige Abd uck de on de Bay eu he G aduie enschule ü Ma hema ik und
Na u wissenscha en de Uni e si ä Bay eu h genehmig en Disse a ion zu E langung
des akademischen G ades eines Dok o s de Na u wissenscha en (D . e . na .).
Disse a ion einge eich am: 25.01.2013
Zulassung du ch die P omo ionskomission: 13.02.2013
Wissenscha liches Kolloquium: 26.04.2013
Am ie ende Dekan: P o . D . Bea e Lohne
P ü ungsausschuss:
P o . D . Axel H. E. Mülle (E s gu ach e )
P o . D . S ephan Fö s e (Zwei gu ach e )
P o . D . Ma hias Ka g (Vo si z)
P o . D . Ka lheinz Sei e
“
Li e is like iding a bicycle.
To keep you balance you mus keep mo ing.
”
Albe Eins ein

Meine Familie
G e a und Oska
Table o Con en s
I
Table o Con en s
Summa y 1
Zusammen assung 3
Glossa y 7
1 – In oduc ion 9
1.1 Solu ion Based Sel -Assembly in Polyme Sys ems 9
1.1.1 Gene al Aspec s o Sel -Assembly 9
1.1.2 Mul icompa men S uc u es om Te na y Sys ems 10
1.1.2.1 Linea T iblock Te polyme s and Di ec ed Sel -Assembly 12
1.1.2.2 Mik oa m S a Te polyme s 16
1.2 Mik oa m S a Polyme s 19
1.2.1 Syn hesis 19
1.2.1.1 ABC Mik oa m S a Te polyme s as Model Sys ems 19
1.2.1.2 O he Mik oa m S a Polyme Sys ems 26
1.2.2 Sel -Assembly in Bulk 27
1.2.3 Applica ion o ABC Mik oa m S a Te polyme s o Func ional
Ma e ials 29
1.3 Syn he ic S a egies in Polyme Science 31
1.3.1 DPE Chemis y in Anionic Polyme iza ion 31
1.3.2 Click Chemis y 32
1.4 Aim o his Thesis 34
1.5 Re e ences 35
2 – O e iew o he hesis 41
2.1 Modula Syn hesis o Mik oa m S a Te polyme s 42
2.2 Coun e ion-Media ed Hie a chical Sel -Assembly o an ABC Mik oa m
S a Te polyme Con aining a Poly(N-me hyl-2- inylpy idinium
iodide) Segmen 45
2.3 Applica ion o he T iiodide-Di ec ed Sel -Assembly o o he ABC
and ABA’ Mik oa m S a Polyme s wi h a Poly(N-me hyl-2- inyl-
py idinium iodide) Segmen 47
2.4 Indi idual Con ibu ions o Join Publica ions 51
3 – A Modula Rou e o he Syn hesis o ABC Mik oa m S a
Te polyme s ia a New Alkyne-Subs i u ed Diphenyle hylene
De i a i e 53
3.1 In oduc ion 54
3.2 Expe imen al Sec ion 57
3.3 Resul s and Discussion 60
3.3.1 Syn hesis o 1-[(4-( e -Bu yldime hylsilyl)e hynyl)-phenyl]-1-phenyl-
e hylene (click-DPE) 60
3.3.2 Syn hesis o Alkyne Mid-Func ionalized Diblock Copolyme s 61
3.3.3 Hyd olysis o he Alkyne Mid-Func ionalized Diblock Copolyme s 64
3.3.4 Syn hesis o ω-Azido Homopolyme s 66
Zusammen assung
4
g ega en umlage n. Au g und ih e E scheinung in elek onenmik ospopischen Au nah-
men wu de ü diese de Beg i „woodlouse“ („Kelle assel“) einge üh . Die Agg ega e
sind nich hohl und bes ehen aus PB/P BMA Lamellen, die übe eine eilweise gequolle-
ne P2VPq Phase mi einande e bunden und dadu ch s abilisie we den. Die PB/P BMA
Lamellen besi zen dabei eine eilweise en misch e inne e S uk u .
Dieses Konzep wu de e olg eich au zwei wei e e Mik oa ms e n-Sys eme ange-
wand . Fü eine Se ie on ABC-Mik oa ms e n-Te polyme en aus PS, PB und P2VPq
(µ-BVqS) wu de eine Abhängigkei de Mizell o m om hyd ophilen An eil beobach e ;
analog zu Diblock-Copolyme en. Eine sei s wu den ü lange P2VPq-Blöcke Agg ega e
aus ges apel en Lamellen/Scheiben e hal en, die aus Kugelmizellen als G undbaus einen
en s anden sind; ande e sei s wu de ü ku ze P2VPq Blöcke die Ausbildung mul ilamel-
la e Vesikel du ch Fusion unilamella e Vesikel beobach e . Ande s als du ch die
Polyme a chi ek u e wa e , konn e ü die Vesikelwand keine Kompa men alisie ung
beobach e we den, sonde n es wi d eine lamella e Zusammense zung mi einem PB
Ke n angenommen, die du ch eine dünne PS-Schich o de P2VPq-Ko ona geschü z
wi d. Fü einen de µ-BVqS-Mik oa ms e ne wu de e olg eich eine Nanohyb ids uk u
mi Goldnanopa ikeln gebilde .
Fü ein zwei es Polyme sys em wu de das elas ische PB-Segmen du ch einen wei e-
en glasa igen PS-Block mi un e schiedliche Länge e se z (µ-SVqS‘). Obwohl mi Iodid
als Gegenion Vesikel e hal en wu den, bilde en sich bei de T iiodid-induzie en Übe -
s uk u bildung aniso ope Agg ega e aus de o mie en Vesikeln. Die Abwesenhei on
mul ilamella en Vesikeln wi d dabei au die eduzie e Dynamik de ke nbildenden, glas-
a igen PS-Blöcke zu ückge üh . Ähnlich zu den „woodlouse“ Pa ikeln on µ-BVqT,
wu den somi ü µ-SVqS‘ längliche Agg ega e mi eine lamella en S uk u e hal en,
jedoch übe Vesikel als G undbaus eine. Somi is dieses übe das T iiodid-Ion beein-
lussba e Konzep de ges eue en Selbs agg ega ion nich nu au Mik oa ms e n Sys-
eme mi einem elas ischen Block besch änk , da die Umo dnungsp ozesse wäh end des
Dialyse s a inden, wo das an angs o handene o ganische Lösungsmi el eine aus ei-
chende Mobili ä de den Mizellke n bildenden Blöcke zu Folge ha .

Zusammen assung
5
Neben eine neuen Syn heses a egie ü Mik oa ms e n-Te polyme e, basie end au
einem ielsei igen Alkin-subs i uie en DPE De i a , konn e somi die du ch das T iiodid-
Ion induzie e Übe s uk u bildung als neua iges Konzep ü ges eue e Selbs ano d-
nungsp ozesse in wäss igen Lösungen au gezeig we den.
6
Glossa y
7
Glossa y
2VP 2- inylpy idine
AAO anodic aluminium oxide
ATRP a om ans e adical polyme iza ion
CoQ10 coenzyme Q10
CRP con olled adical polyme iza ion
c yo-TEM c yogenic ansmission elec on mic oscopy
CuAAC coppe -assis ed azide-alkyne cycloaddi ion
DNA deoxy ibonucleic acid
DPE 1,1-diphenyle hylene
DVB di inylbenzene
w
olume ac ion o wa e
IPEC in e polyelec oly e complex
MCM mul icompa men micelles
NRC ni oxide adical coupling
SET-LRP single elec on ans e li ing adical polyme iza ion
PAA poly(ac ylic acid)
PB polybu adiene
PBLL poly(ε- e -bu yloxyca bonyl-L-lysine)
PCEMA poly(2-cinnamoyloxye hyl me hac yla e)
PDMAEA poly(N,N-dime hylaminoe hyl ac yla e)
PDMAEMA poly(N,N-dime hylaminoe hyl me hac yla e)
PEO poly(e hylene oxide)
PEE polye hyle hylene
PI polyisop ene
PISC poly((sul ama e-ca boxyla e)isop ene)
PMA poly(me hyl ac yla e)
PMAA poly(me hac ylic acid)
PMCL poly(γ-me hyl-ε-cap olac one)
PnBu poly(n-bu yl ac yla e)
PNiPAAm poly(N-isop opylac ylamide)
PS polys y ene
PSGA poly(sucinna ed glyce yl monome hac yla e)
P BA poly( e -bu yl ac yla e)
P BMA poly( e -bu yl me hac yla e)
PVBFP poly(pen a lu o phenyl 4- inylbenzyl e he )
P2VP poly(2- inylpy idine)
P2VPq poly(N-me hyl-2- inylpy idinium)
ROP ing-opening polyme iza ion
TEM ansmission elec on mic oscopy
THF e ahyd o u an
TPPB iphenylphosphonium b omide
ΔG
agg.
Gibbs ee ene gy o micelle o ma ion
ΔH
agg.
en halpy o micelle o ma ion
ΔS
agg.
en opy o micelle o ma ion
8
1 – In oduc ion
9
1 – In oduc ion
1.1 Solu ion Based Sel -Assembly in Polyme Sys ems
1.1.1 Gene al Aspec s o Sel -Assembly
Sel -assembly desc ibes he well-de ined o ganiza ion o one species o a se o iden ical
molecula building uni s in o highly o de ed agg ega es by non co alen in e ac ions.
He e, he complexi y and di e si y achie ed in na u e displays an imp essi e p o o ype
o such s uc u es a di e se leng h scales.
1-3
Examples o biological s uc u es o di e -
en dimensions, buil up wi h he concep o sel -assembly include e.g. DNA,
4
i uses
5
o
spide silk.
6
The enginee ing o na u al building uni s esembles a ema kable pa hway
o he p og ammed cons uc ion o nanoscale objec s in a bo om-up app oach.
7
An
ou s anding example is DNA-o igami, which is based on he combina ion o a long sca -
old s and o i us-DNA wi h small, designed s aple s ands o adequa e base-sequence
o ob ain di ec ed olding in o di e se wo-dimensional
8
o h ee-dimensional s uc-
u es.
9
Despi e he syn he ic ad ances in polyme chemis y, achie ing such a dis inc com-
plexi y wi h polyme sys ems has no been eached. Ne e heless, i ep esen s a desi -
able pa adigm o he cons uc ion o complex unc ional s uc u es o di e en dimen-
sion in analogy o sys ems in na u e (Figu e 1-1A).
10
In he case o block copolyme s as
mos simpli ied polyme ic sys em wo chemically di e en blocks a e co alen ly linked
oge he . I he polyme now is exposed o a sol en selec i e o only one block, he
indi idual molecules ha e o sel -o ganize o shield he sol ophobic block. The gain in
ee ene gy (ΔH
agg.
< 0)
o minimizing he un a o able in e ac ion be ween he sol en
and he insoluble block o e comes he loss o en opy (ΔS
agg.
> 0), leading o an o e all
nega i e Gibbs ee ene gy ΔG
agg.
.
ΔG
agg.
= ΔH
agg.
- TΔS
agg.
< 0
Depending on he ac ion o he s abilizing block he polyme s assemble in o sphe i-
cal micelles, cylind ical micelles o esicles (Figu e 1-1-B).
11-14
Despi e he s uc u al sim-
plici y o hese agg ega es he ailo ed syn hesis o block copolyme s enables cons uc -
ing unc ional ma e ial. These micella s uc u es can se e as nanoca ie s
15,16
o

1 - In oduc ion
10
nano eac o s,
17-19
o as sca old o e.g. hyb id ma e ials.
20-22
Vesicles (o also called
polyme somes) esemble he syn he ic analogues o liposomes and a e he e o e o in-
e es o biological applica ions.
23-25
E en hough his hesis deals wi h he sel -
assembly in solu ion i should be men ioned ha he same p inciples also apply o he
bulk s a e, p o ided ha he he modynamic incompa ibili y o he wo blocks is su i-
cien ly high. The co alen linkage p e en s phase sepa a ion on he mac oscale and
he e o e o ces he polyme o align in nanoscopic s uc u es, i.e. sphe ical, cylind ical,
gy oid o (pe o a ed) lamella mo phologies.
26,27
Figu e 1-1. (A) Leng h scales o molecula sel -assembled s uc u es in syn he ic and biological sys ems
wi h inc easing complexi y.
10
(B) Schema ic ep esen a ion o he s uc u es o AB diblock copolyme s in a
sol en selec i e o he B block. Depending on he olume ac ion o he soluble block,
B
, he polyme
sel assembles in o sphe ical micelles, cylind ical micelles o esicles.
11
1.1.2 Mul icompa men S uc u es om Te na y Sys ems
Ex ending he unc ionali y o block copolyme sys ems wi h a hi d chemically di e ing
block can be accomplished in wo manne s. The linea a achmen leads o iblock
e polyme s, whe eas by nonlinea conjunc ion o he hi d block mik oa m s a
e polyme s ( om he g eek wo d ικτός o mixed) a e achie ed.
28
The syn hesis o he
la e will be discussed in chap e 1.2. In con as o diblock copolyme s di e en block-
selec i e sol en s a e possible o hese e na y sys ems, which induce ei he a com-
pa men aliza ion o he co e o he co ona.
29
In he ollowing a sho o e iew o possi-
ble s uc u es a he example o sphe ical micelles is gi en. I linea e polyme s a e ex-
posed o a sol en selec i e o he end-blocks micelles wi h an ei he mixed, pa chy o
Janus- ype co ona a e ob ained (Figu e 1-2A).
30
Howe e , accessing he egion o exclu-
si ely Janus- ype micelles om ABC iblock e polyme s in endblock-selec i e sol en s
1 – In oduc ion
11
is challenging and mos ly leads o mix u es wi h pa chy micelles.
30,31
Addi ionally, in sol-
en s selec i e o he middle and one end-block co e-shell-co ona s uc u es will be
ob ained (Figu e 1-2B).
32
In con as o hei linea analogues he in luence o block se-
quence is elimina ed o mik oa m s a e polyme s as a consequence o he polyme
a chi ec u e. Hence co e-shell-co ona s uc u es a e no possible and o he co ona-
compa men alized s uc u es Janus- ype micelles a e a he un a o ed due o he
s e ical us a ion o he wo soluble blocks.
Figu e 1-2. O e iew o co ona- (A, B) and co e-compa men alized s uc u es (C) ob ained om ABC
mik oa m s a e polyme s and linea ABC e polyme s. The s uc u es depic ed a e micelles wi h a mixed,
pa chy o Janus- ype co ona (A, om le o igh ), co e-shell-co ona micelles (B) o sol en s selec i e o
he end-blocks o linea e polyme s and mul icompa men o “onion”-like micelles (C, om le o igh ).
(D) shows a schema ic illus a ion o he chain packing o ABC mik oa m s a and linea e polyme s o
ob ain mul icompa men micelles.
On he o he hand, sol en s selec i e o only one block lead o a compa men aliza ion
o he micella co e (Figu e 1-2C). Inspi ed by biological sys ems, in 1999 Ringsdo in-
oduced he concep o mul icompa men micelles (MCM’s) o syn he ic polyme sys-
ems.
33
Sepa a ed compa men s wi hin he co e would allow o s o age o wo di e -
en payloads wi hin one micelle, while simul aneously main aining access o he su -
ounding medium. When iblock e polyme s sel -assemble in sol en s selec i e o one
end block, he in e acial ene gies be ween each o he indi idual co e- o ming blocks
and he co ona- o ming block de e mine whe he micelles wi h simple concen ic com-
pa men s (“onion”-like s uc u es, igh -hand s uc u e in Figu e 1-2C)
34
o micelles
1 - In oduc ion
12
wi h non-concen ic nano-s uc u ed co es (mul icompa men micelles, le -hand s uc-
u e in Figu e 1-2C) a e ob ained.
35
Howe e , a ibu ed o hei us a ed a chi ec u e,
mik oa m s a e polyme s a e inhe en ly o ced o sel -assemble in s uc u es wi h
compa men alized co es upon dissolu ion in a sol en selec i e o one block, dis e-
ga ding di e en pai s o in e acial ene gies (Figu e 1-2D). The i s example o isuali-
za ion o he indi idual co e-segmen s o mul icompa men micelles and wo ms was
gi en by Hillmye , Lodge and co-wo ke s in 2004 o a mik oa m s a e polyme wi h
highly incompa ible segmen s, poly(e hyle hylene)-a m-poly(e hylene oxide)-a m-
poly(pe luo op opylene oxide), µ-EOF.
36,37
In c yo-TEM he pe luo ina ed segmen s
we e in-si u de ec able owing o hei inc eased elec on densi y. In con as o his
mik oa m sys em, o linea e polyme s, besides special chemical composi ion,
in e polyelec oly e complexa ion, he use o addi i es, sol en mix u es o adequa e
assembly pa hways ha e o be applied o guide he sequen ially connec ed blocks o-
wa ds mul i-compa men alized s uc u es. In he ollowing wo sec ions I will i s gi e
an o e iew o he di ec ed sel -assembly o linea iblock e polyme s in o
mul icompa men s uc u es (1.1.2.1) and hen highligh he well-de ined mo phologies
ob ained by di e en mik oa m s a e polyme sys ems (1.1.2.2).
1.1.2.1 Linea T iblock Te polyme s and Di ec ed Sel -Assembly
In he ield o linea iblock e polyme s Laschewsky e al. p esen ed he i s success ul
in-si u isualiza ion o he mul icompa men cha ac e in 2005 o a poly(4-me hyl-4-(4-
inylbenzyl)mo pholin-4-ium chlo ide)-block-polys y ene-block-poly(pen a luo ophenyl
4- inylbenzyl e he ) (PVBM-b-PS-b-PVBFP) sys em by c yo-TEM.
38
A e dialysis o wa e
he e polyme assembled in o micelles wi h a co e consis ing o sphe ical domains
(~3 nm in diame e ) o he pen a luo ophenyl g oup wi hin a hyd oca bon ma ix
o med by bo h he polys y ene block and he a oma ic moie y o he luo ina ed block
(Figu e 1-3A). The e o e seg ega ion wi hin he PVBFP block ook place. They ex ended
his polyme design o o he e polyme s based on ac yla e- ype monome s o ob ain
sphe ical compa men alized s uc u es.
39-41
Besides sys ems wi h a sol ophilic
endblock, also sys ems wi h a sol ophilic midblock we e shown o sel -assemble in o
mul icompa men s uc u es.
40-42
E en hough simula ions o iblock sys ems in mid-
1 – In oduc ion
13
block selec i e sol en s p edic mul ico e micelles, whe e he wo chemically di e en
co es a e sepa a ed by he sol ophilic block,
43
he p esence o mul icompa men mi-
celles he e migh be a ibu ed o he sho leng hs o he sol ophobic blocks and hei
chemical na u e. In e es ingly, ins ead o using iblock e polyme s, mos ecen ly,
Langlois and co-wo ke s ollowed ano he app oach u ilizing a s a is ical e polyme
based on biocompa ible poly(3-hyd oxyalkanoa es).
44
Again, he seg ega ion is induced
by he hyd ophilic, lipophilic and luo ophilic cha ac e o he a ached sidechains.
Nanop ecipi a ion in wa e o ced o polyme o o m micelles (18 and 79 nm in diame-
e o wo di e en sys ems) wi h dis inc luo ina ed subdomains in he co e.
Ano he possibili y o induce phase seg ega ion wi hin he co e is based on segmen s
ca ying cha ged unc ions. As a consequence o he cha ge neu ali y o
poly((sul ama e-ca boxyla e)isop ene) a low pH, poly((sul ama e-ca boxyla e)isop ene)-
block-polys y ene-block-poly(e hylene oxide) (PISC-b-PS-b-PEO) was epo ed o yield
micelles wi h a “ aspbe y”-like PISC co e wi h sphe ical PS domains unde acidic condi-
ions.
45
The emaining isop ene uni s wi hin he PISC domain and he o ma ion o hy-
d ogen-bonds wi h PEO a e supposed o u he educe i s wa e solubili y and addi ion-
ally he ansi ion in o micelles wi h a mixed PISC/PEO co ona was demons a ed a in-
c eased pH. Schache e al. showed o zwi e ionic polybu adiene-block-poly(N-me hyl-
2- inylpy idinium)-block-poly(me hac ylic acid) (PB-b-P2VPq-b-PMAA) ha in aqueous
media pa chy in e micella IPEC domains o P2VPq/PMAA a e o med on he PB co e.
46
Su p insingly, he non-qua e nized and non-hyd olyzed p ecu so polyme also o med
mul icompa men micelles wi h a “sphe e on sphe e” mo phology in ace one as selec-
i e sol en o he poly( e -bu yl me hac yla e) block.
47
Due o he s ong incompa ibil-
i y be ween PB and P2VP, he sys em is assumed o aim su ace minimiza ion o he
PB/P2VP in e ace.
Apa om he sphe ical mul icompa men micelles discussed so a , Fang e al.
demons a ed he hie a chical sel -assembly o p e- o med co ona-compa men alized
micelles in o one-dimensional co e-compa men alized s uc u es upon educing he
sol en quali y.
48
Depending on he co ona s uc u e (pa chy o Janus- ype) o he mi-
celles om poly(4- e -bu oxys y ene)-block-polybu adiene-block-poly( e -bu yl me h-
ac yla e) wi h a pe luo o-modi ied midblock insoluble in dioxane, he dialysis in o e ha-
1 - In oduc ion
20
o end- unc ionaliza ion o homopolyme s (1), wi h he s oichome y o adequa e linking
eac ions wi h p e- o med polyme ic building blocks o ini ia o molecules (2). E en
hough in li e a u e di e en classi ica ions ha e been used, he syn hesis o ABC
mik oa m s a e polyme s can be di ided in o ou app oaches o undamen ally di e -
ing chemis ies. Fo he i s h ee ypes anionic polyme iza ion is u ilized o he in o-
duc ion o special unc ionali ies in de ined posi ions and/o selec i e eac i i y o li ing
anionic chain ends (A-C), whe eas he ou h is based on mul i unc ional co e molecules
(D).
(A) Chlo osilane Me hod
Simila o he syn hesis o egula s a s by eac ion o li ing anionic polyme chains wi h
chlo osilanes,
85,86
hese compounds can be used as linking agen s o he cons uc ion o
ABC mik oa m s a e polyme s. The e o e, li ing anionic chain ends o di e en eac i i-
y owa d chlo ine-silicon bonds ha e o be used o allow o s ep-wise subs i u ion.
Ia ou e al. syn hesized a mik oa m s a wi h polyisop ene, polys y ene and
polybu adiene segmen s wi h ichlo ome hylsilane as i unc ional linking agen .
87
Howe e , he syn hesis can only be conduc ed in he speci ic sequence PS > PI > PB, due
o he eac i i y o he li ing anion owa d he chlo osilane unc ionali y. The less eac-
i e and mos s e ically hinde ed polyme anion has o be added i s , whe eas he less
s e ically hinde ed and mos eac i e polyme anion has o be added a he end o gua -
an ee ull con e sion. E en wi h his sequence (Scheme 1-2) he las s ep is ime-
consuming wi h eac ion imes o up o 4 weeks and o each s ep he s oichome y is o
ou e mos impo ance. Simila ly, an ABCD mik oa m s a qua e polyme was syn he-
sized by expanding he sys em wi h poly(4-me hyl s y ene) and using e achlo osilane.
88
The applica ion o his app oach o o he less eac i e polyme anions like poly(me hyl
me hac yla e) o poly(2- inylpy idine) equi es a pos - o p e-modi ica ion o he
chlo osilane compound, espec i ely.
89,90

1 – In oduc ion
21
Scheme 1-2. Syn hesis o an ABC mik oa m s a e polyme by he successi e eac ion o li ing polyme
anions wi h ichlo osilane as linking agen .
(B) Mac omonome Me hod
Apa om he special chemis y o chlo osilanes, diphenyle hylene (DPE) and i s dou-
ble-diphenyle hylene de i a i es ep esen a powe ul class o compounds, as hei ina-
bili y o homopolyme ize pe mi s selec i e unc ionaliza ion o diblock copolyme s.
91
P e o med mac omonome s wi h a e minal DPE unc ionali y can be applied o he
sequen ial li ing anionic polyme iza ion o diblock copolyme s. By sequen ial addi ion o
he mac omonome a e polyme iza ion o he i s block, ABC mik oa m s a
e polyme s a e accessible unde con ol o he s oichome y (Scheme 1-3A). Fo his
pu pose Qui k e al. used 1,4-bis(1-phenyl-e henyl)benzene (Scheme 1-3B) o syn hesize
A
2
B and ABC mik oa m s a polyme s.
92
When he DPE de i a i e was used in wo- old
excess o he linking eac ion wi h polys y yl-li hium p ima ily monoaddi ion ook place
o gene a e he polys y ene mac omonome . Simila ly, Hücks äd e al. demons a ed 1-
(4-b omome hylphenyl)-1-phenyle hylene (Scheme 1-3B) o be a sui able e mina ion
agen o li ing anions o polybu adiene
93
and polys y ene
94
. These se ed as
mac omonome s o he syn hesis o a polybu adiene-a m-polys y ene-a m-poly(me hyl
me hac yla e) mik oa m s a e polyme and se ies o polys y ene-a m-polybua diene-
a m-poly(2- inylpy idine) mik oa m s a e polyme s, espec i ely. Howe e , also in he
case o he b omo- unc ionalized DPE, o ma ion o dime ic mac omonome s can occu
unde inadequa e eac ion condi ions as a esul o Wu z-analogous side eac ions. Be-
sides he use o DPE de i a i es as e mina ion agen s o he mac omonome syn hesis,
Qui k and co-wo ke s p o ed 1-(4-hyd oxyp opylphenyl)-1-phenyle hylene o be a sui -
able ini a o o he syn hesis o poly(e hylene oxide) mac omonome s a e
dep o ona ion wi h iphenylme hylpo assium (Scheme 1-3B).
95
In his way a polys y-
ene-a m-poly(e hylene oxide)-a m-poly( e -bu yl me hac yla e) mik oa m s a
e polyme was success ully syn hesized. In a simila s a egy a polys y ene-a m-
poly(dime hylsiloxane)-a m-poly( e -bu yl me hac yla e) mik oa m s a e polyme was
1 - In oduc ion
22
accessible by ing opening polyme iza ion o hexame hylcyclo isiloxane wi h li hia ed
pa a-(dime hylhyd oxy)silyl-α-phenyls y ene as ini ia io .
96
Fo he syn hesis in ol ing
mac omonome s he s oichome y o he endcapping eac ion has o be conside ed o
allow o simple pu i ica ion o possible side p oduc s. Fu he mo e, he choice o mon-
ome sequence is limi ed o he di e en eac i i ies o li ing anionic polyme chains.
Scheme 1-3. (A) Schema ic ep esen a ion o he syn hesis o ABC mik oa m s a e polyme s ia sequen-
ial anionic polyme iza ion u ilizing mac omonome s. (B) DPE-de i a i es used o he syn hesis o
mac omonome s: 1,4-bis(1-phenyl-e henyl)benzene,
92
1-(4-b omome hylphenyl)-1-phenyle hylene,
93,94
1-
(4-hyd oxyp opylphenyl)-1-phenyle hylene dep o ona ed wi h ime hylphenylpo assium
95
( om le o
igh )
(C) Mid-Func ionalized Diblock Copolyme s
Ano he possibili y o cons uc ing ABC mik oa m s a e polyme s is he syn hesis o
mid- unc ional diblock copolyme s. The hi d a m hen is a ached by adequa e eac-
ions wi h he unc ional g oup (Scheme 1-4). Again, DPE chemis y is ad an ageous
wi hin his con ex , as homopolyme iza ion is excluded and he e o e
mono unc ionaliza ion is gua an eed unde app op ia e eac ion condi ions and
polyme iza ions sequences. Exclusi ely hyd oxyl- unc ionalized DPE’s in hei p o ec ed
o m ha e been used so a .
97,98
Lambe e al. syn hesized mid- unc ional polys y ene-
block-poly(e hylene oxide) and polys y ene-block-poly(me hyl me hac yla e) by sequen-
ial anionic polyme iza ion wi h 1-[4-(2- e -bu yldime hylsiloxy)e hyl]phenyl-1-
phenyle hylene (Scheme 1-4A). A e dep o ec ion and dep o ona ion he hyd oxyl-
unc ion se ed as ini ia o o he anionic ing opening polyme iza ion o ɛ-
cap olac one
97
o L-lac ide
98
in he case o polys y ene-block-poly(e hylene oxide) as
diblock copolyme , o o e hylene oxide
98
in he case o polys y ene-block-poly(me hyl
1 – In oduc ion
23
me hac yla e). Using a simila DPE de i a i e, Hi ao and co-wo ke s syn hesized hyd oxy
mid- unc ionalized polys y ene-block-poly(2-(pe luo ooc yl)-e hyl me hac yla e) diblock
copolyme s (Scheme 1-4B).
99
Howe e , a e ans o ma ion o he silyl-p o ec ed hy-
d oxyl unc ion in o benzyl b omide, li ing anionic polyme s o 2- inylpy idine and me-
hyl me hac yla e we e g a ed o he diblock copolyme s by anionic coupling eac ions.
Modi ica ion o he syn he ic s a egy and using a dual hyd oxy- unc ionalized DPE u -
he yielded A
3
B, ABC
2
and ABCD mik oa m s a polyme s. Ano he elegan way o in-
oduc ion o a hyd oxyl unc ion a he bo de o wo blocks is he use o 2-
me hoxyme hoxyme hyloxi ane o he endcapping o li ing polyme anions (Scheme 1-
4C).
62,64,100
The hyd oxy unc ion inhe en ly gene a ed du ing he coupling eac ion wi h
he endcappe is used o he ing opening polyme iza ion o e hylene oxide as second
block. A e dep o ec ion he second hyd oxy unc ion was used o a ach a ca boxyl-
e mina ed poly(pe luo op opylene oxide) ia es e i ica ion
100
o “g a ing- om” o γ-
me hyl-ɛ-cap olac one
62
o N,N-dime hylaminoe hyl ac yla e
64
a e pos -modi ica ion o
he alcohol o ob ain amphiphilic ABC mik oa m s a e polyme s. In a simila manne
polys y ene-block-poly(e hylene oxide) diblock copolyme s bea ing an p ima y amino-
101
o allyl- unc ion
102
a he block bo de we e syn hesized by F ey and co-wo ke s om
he co esponding unc ionalized glycidyl e he s. Due o hei de ined mid- unc ionali y,
hese a e o possible u u e in e es o he cons uc ion o mik oa m s a polyme s.
Howe e , o such glycidyl compounds as endcapping agen s, he polyme iza ion me-
hod o he second block is es ic ed o anionic ing-opening polyme iza ion. Also o
he app oaches u ilizing DPE o gene a e he mid- unc ionali y he choice o monome
sequence is dependen on he eac i i y o he monome s.
91
1 - In oduc ion
24
Scheme 1-4. O e iew o mid- unc ional diblock copolyme s o he cons uc ion o ABC mik oa m s a
e polyme s. U ilizing DPE chemis y (A,B)
97-99
o a glycidyl e he (C)
62,64,100
hyd oxyl mid- unc ionalized
diblock copolyme s we e syn hesized which se e as p ecu so o he a achmen o he hi d block ia
“g a ing- om” o “g a ing- o” app oaches.
(D) He e o unc ional Co e Molecules
All he examples discussed up o now ake ad an age o anionic polyme iza ions s eps o
gene a e well-de ined and unc ionalized polyme s as building blocks o he mik oa m
s a e polyme syn hesis. Howe e , in he pas decade, an inc easing numbe o eac-
ions ul illing he c i e ia o click chemis y we e u ilized in polyme chemis y o he
cons uc ion o a ious polyme a chi ec u es in combina ion wi h con olled adical
polyme iza ion me hods.
103
He ein, he e o unc ional co e molecules can se e as com-
mon junc ion poin o he “g a ing- om” and “g a ing- o” o di e en polyme seg-
men s by a combina ion o such click eac ions wi h s anda d polyme iza ion me hods o
cons uc mik oa m s a e polyme s. Fo example Zhang e al. syn hesized a
i unc ional co e molecule bea ing an alkyne-, hyd oxyl- and b omine- unc ion.
104
Due
o he compa ibili y and ole ance o he eac ion condi ions simul aneous azide-alkyne
click chemis y, ing-opening polyme iza ion and ATRP was possible o syn hesize poly-
s y ene-a m-poly(ɛ-cap olac one)-a m-poly(N,N-dime ylaminoe hyl me hac yla e) o
poly(e hylene oxide)-a m-poly(ɛ-cap olac one)-a m-poly(N,N-dime ylaminoe hyl me h-
ac yla e) in a one-po eac ion (Scheme 1-5A). Based on he same p inciples, di e se
o he s a egies a e epo ed in li e a u e whe e consecu i e ATRP, ing-opening
polyme iza ion, click eac ions like azide-alkyne o hiol-ene click chemis y, es e i ica-
ion and ans o ma ion eac ions we e combined o cons uc ABC mik oa m s a
e polyme s.
66-68,77,105-110
Fu he mo e, Tunca and co-wo ke s p esen ed an app oach
u ilizing h ee o hogonal click eac ions o he cons uc ion o a poly(e hylene oxide)-
a m-poly(ɛ-cap olac one)-a m-poly(N-bu yl oxano boneneimide) mik oa m s a
1 – In oduc ion
25
(Scheme 1-5B).
111
Fi s he poly(e hylene oxide) segmen was a ached o he co e mole-
cule by a Diels-Alde click eac ion, ollowed by he simul aneous liga ion o he o he
wo blocks by azide-alkyne cycloaddi ion and ni oxide adical coupling click eac ion.
Huan e . al epo ed a acile s a egy o he cons uc ion o sup amolecula ABC
mik oa m s a e polyme s using β-cyclodex in as co e molecule.
112
Recen ly, he g oup
o Li demons a ed he Passe ini h ee-componen eac ion o be a powe ul me hod o
simul aneously in oduce an ATRP ini a o and an alkyne- unc ion o aldehyde end-
unc ionalized poly(e hylene oxide).
113
S a ing wi h his dual- unc ionalized PEO di e se
ABC mik oa m s a e polyme s we e accessible ei he by consecu i e ATRP and azide-
alkyne cycloaddi ion o simul aneous SET-LRP and click eac ion (Scheme 1-5C). Addi-
ionally, in li e a u e di e en o he mik oa m s a a chi ec u es like ABCD,
114
s a -
115
and H-shaped ABCDE mik oa m s a s
116
and he i s ABC mik oa m s a e polyme wi h
cyclic a ms
117
a e epo ed by modi ica ions o hese s a egies wi h he e o unc ional
co e molecules.
Scheme 1-5. Syn he ic s a egies o he cons uc ion o ABC mik oa m s a e polyme s wi h
he e o unc ional co e molecules ia simul aneous ATRP, ROP and CuAAC (A),
104
consecu i e iple click
eac ions (B)
111
o h ee-componen Passe ini eac ion (C).
113

1 - In oduc ion
26
1.2.1.2 O he Mik oa m S a Polyme Sys ems
Hi ao and co-wo ke s designed special eac ion sequences which enable he i e a i e
syn hesis o asymme ic s a b anched polyme s by epea ing he sequence.
76
These
indi idual s eps in ol e he linking eac ion o a li ing polyme anion wi h a polyme
con aining a sui able unc ional g oup (1), which is ollowed by he egene a ion o he
unc ional g oup a he eac ion si e (2). Based on he silyl-p o ec ed hyd oxyl-
unc ionalized DPE shown in Scheme 1-4B such an i e a i e me hodology is possible,
s a ing wi h a li ing polyme anion endcapped wi h his DPE de i a i e. A e ans o -
ma ion o he p o ec ed hyd oxy g oup in o a benzyl b omide unc ion a second li ing
anion endcapped wi h his DPE is eac ed wi h he b omide, which esembles s ep 1.
Regene a ion o he b omide unc ion a he co e om he newly in oduced silyl-
p o ec ed hyd oxyl- unc ion esembles s ep 2, which allows o epea ing he cycle
(Scheme 1-6). In his manne an ABCD mik oa m s a polyme was syn hesized.
118
How-
e e , as a p e equisi e o he e-in oduc ion o he unc ional g oup he li ing polyme
anion used in he las s ep has o be nucleophilic enough o copolyme ize wi h DPE.
The e o e, o less nucleophilic li ing anions o polyme s like poly(me hyl me hac yla e),
a ein oduc ion o he unc ional g oup is no possible and hey ha e o be a ached in
he las s ep. This me hodology was also applied o b omide- unc ionalized DPE
119
o
b omide- unc ionalized 1,3-bu adiene,
120
which a e used o e-in oduce a non-
homopolyme izable DPE o bu adiene end- unc ionali y. Repea ing hese s eps, s a s
con aining up o se en di e en a ms could be achie ed. Ano he unc ionali y capable
o such linking eac ions wi hou unde going homopolyme iza ion is he α-phenyl ac y-
la e, which can also copolyme ize wi h less eac i e monome s like e -bu yl me hac y-
la e. Using a dual hyd oxy- unc ionalized DPE de i a i e, which p o ec ing g oups can be
selec i ely clea ed o es e i y hem wi h he α-phenylac ylic acid in sepa a e s eps,
ABCDE mik oa m s a s we e syn hesized wi h an i e a i e me hodology in he g oup o
Hi ao.
121
Fo all hese s a egies addi ional ac iona ion is necessa y o ob ain he pu e
mik oa m s a polyme s as he linking eac ions a e conduc ed wi h excess o he li ing
anionic polyme chain o gua an ee 100% con e sion.
1 – In oduc ion
27
Scheme 1-6. I e a i e me hodology o he syn hesis o s a b anched polyme s ia eac ion o li ing pol-
yme anions wi h a benzyl b omide unc ion.
118
Ano he widely used me hod is he di inylbenzene (DVB) me hod, based on he abili y o
p e o med polys y ene a ms o anionically copolyme ize wi h di inylbenzene o o m a
co e wi h ac i e eac ion si es.
122
Addi ion o a second monome leads o polyme chains
g owing om his co e. The e o e, wi h his “in-ou ” me hod, s a sys ems o he ype
A
n
B
n
wi h symme ical composi ion and di e en second blocks we e easily accessible as
shown by Tsi silianis and co-wo ke s.
123-126
By he addi ion o a hi d monome u he -
mo e A
n
(B-block-C)
n
mik oa m s a sys ems wi h a polys y ene and poly(2- inylpy idine)-
block-poly( e -bu yl ac yla e) segmen s we e syn hesized.
127
Howe e he numbe o
a ms ep esen s an a e age alue, which is only oughly adjus able by he amoun o
DVB and molecula weigh o he s a ing polyme .
1.2.2 Sel -Assembly in Bulk
In addi ion o he sel -assembled s uc u es o mik oa m s a e polyme s in solu ion
(see 1.1.2.2), hei mo phology in he bulk s a e ep esen s an unique p ope y. Al eady
linea iblock e polyme s we e shown o p oduce a wide a ie y o in e es ing mo -
phologies due o he linea connec ion o h ee immiscible blocks wi h h ee di e en
se s o in e ac ion pa ame e s.
27,71,128-131
Howe e , o mik oa m s a e polyme s o
su icien incompa ibili y he cons i u ion o he h ee polyme segmen s a a common
1 - In oduc ion
28
poin o ces hese o align in a one-dimensional ashion. In con as o ha he wo di -
e en junc ion poin s in linea ABC iblock e polyme s a e loca ed a wo-dimensional
polyme in e aces. Consequen ly, comple ely seg ega ing mik oa m s a e polyme s
a e supposed o assemble in o columna bulk mo phologies (Figu e 1-6A).
132
The wo-
dimensional c oss-sec ions o he spa ial a angemen o hese cylinde s can be de-
sc ibed by A chimedian iling pa e ns.
132-134
Due o he challenging syn hesis o mik oa m s a e polyme s sys ema ic in es iga-
ions o he composi ional in luence on he mo phology a e qui e a e. Besides ea lie
mo phological s udies,
135,136
Thomas and co-wo ke s p o ed he alignmen o he junc-
ion poin s in a one-dimensional ashion o a sys em consis ing o polys y ene, polyiso-
p ene and poly(me hyl me hac yla e).
137
Hücks äd e al. ga e he i s de ailed mo pho-
logical s udy on a polys y ene-a m-polybu adiene-a m-poly(2- inylpy idine) sys em o
a ious composi ions.
94
Fo ano he sys em con aining polys y ene, polyisop ene and
poly(2- inylpy idine) a ms he a ia ion o he olume ac ions yielded mani old s uc-
u es o complex iling pa e ns as exempla ily depic ed in Figu e 1-6B.
138-141
When
mik oa m s a s o mo e asymme ic composi ions we e in es iga ed, ansi ions o high-
ly pe iodic, subs uc u ed lamella mo phologies could be obse ed.
142
Simila ly, Ikkala
and co-wo ke s epo ed he hie a chical smec ic sel -assembly o a mik oa m s a
e polyme con aining a α-helical poly(ε- e -bu yloxyca bonyl-L-lysine) (PBLL) seg-
men .
143
The mo phology composed o an o e all lamella s uc u e wi h one ype o
lamella o packed helices o PBLL and a second ype o med om al e na ing ec angula
cylinde s o polys y ene and polyisop ene (Figu e 1-6C). In addi ion Abe z e al. demon-
s a ed ha blending o polys y ene-a m-polybu adiene-a m-poly(2- inylpy idine)
mik oa m s a s wi h diblock copolyme s can be u ilized o une he ob ained mo pholo-
gy wi hin ce ain limi s.
144
1 – In oduc ion
29
Figu e 1-6. (A) Schema ic illus a ion o he one-dimensional alignmen o junc ion poin s and he esul ing
columna a angemen o he indi idual blocks o ABC mik oa m s a e polyme s.
132
(B) TEM mic og aphs
o ou polyisop ene-a m-polys y ene-a m-poly(2 inylpy idine) (µ-ISV) mik oa m s a e polyme s ( op
ow) and he co esponding schema ic iling pa e ns (bo om ow): (a) µ-I
1.0
S
1.8
I
1.0
, (b) µ-I
1.0
S
1.8
I
1.6
, (c) µ-
I
1.0
S
1.8
I
2.0
, (d) µ-I
1.0
S
1.8
I
2.9
( he subsc ip s deno e he co esponding olume a ios). The da k, ligh and g ay
domains co espond o PI, PS, and P2VP phases.
141
(C) TEM mic og aph and schema ic illus a ion o he
bulk mo phology o a µ-(PS)(PI)(PBLL) mik oa m s a . The sample is s ained wi h OsO
4
(PI da k, PS and
PBLL ligh ).
143
1.2.3 Applica ion o ABC Mik oa m S a Te polyme s o Func ional Ma e-
ials
Due o he b oad a ie y o hie a chies ob ained bo h in solu ion and bulk (see 1.1.2.2
and 1.2.2), mik oa m s a e polyme s a e o special in e es o he design o no el ma-
e ials wi h compa men alized s uc u es. Up o now only a limi ed numbe o publica-
ions has been dealing wi h he applica ion o mik oa m s a e polyme s in ma e ials
esea ch, mos p obably due o he complica ed syn hesis and accessibili y o la ge
amoun s o ma e ial. Howe e , his si ua ion will change wi h he ad ances ob ained in
mik oa m s a syn hesis du ing he las decade.
Al eady o linea diblock copolyme s he in il a ion in anodized aluminium oxide
was demons a ed o be a powe ul me hod o he ab ica ion o one-dimensional
nanoscopic s uc u es.
145-148
The phase beha io o symme ic ABC mik oa m s a
e polyme s in cylind ical nanopo es was sys ema ically in es iga ed by Mon e Ca lo
1 - In oduc ion
36
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40
2 – O e iew o he Thesis
41
2 – O e iew o he Thesis
This disse a ion con ains h ee publica ions, p esen ed om chap e 3 o 5.
No el mik oa m s a e polyme s a e he common issue connec ing he h ee
publica ions wi hin his hesis. The main ocus o he in es iga ions is based on he
syn hesis o such ma e ials on he one side and on he cha ac e iza ion o he micella
s uc u es ob ained by sel -assembly o he polyme s in solu ion on he o he side.
The e o e, a new app oach o he syn hesis o a ious ABC mik oa m s a e polyme s
was de eloped. Mid-alkyne unc ionalized diblock copolyme s, which we e syn hesized
by anionic polyme iza ion u ilizing 1,1-diphenyle hylene (DPE) chemis y, o m he key
building blocks. These allowed modula liga ion wi h azido- unc ionalized homopolyme s
ia azide-alkyne Huisgen cycloaddi ion, which is p esen ed in Chap e 3.
Fo a mik oa m s a e polyme con aining a poly(2- inylpy idine block) (P2VP) he
mechanism o hie a chical supe s uc u e o ma ion was in es iga ed. The polyme
a chi ec u e, qua e niza ion o P2VP and iiodide as coun e ion we e ound o be
p e equisi es o he di ec ed sel -assembly in o complex “woodlouse”-shaped
agg ega es. The o ma ion o cylind ical s uc u es om sphe ical micelles, he meande -
like a angemen o hese cylinde s and, inally, he usion in o lamella agg ega es o
ba el-like shape was shown o be he unde lying mechanism. Chap e 4 includes he
esul s o his coun e ion-media ed hie a chical supe s uc u e o ma ion.
Wi h he knowledge o he necessa y pa ame e s o such a di ec ed sel -assembly,
his s udy was u he expanded o o he ABC mik oa m s a e polyme s and an ABA’
mik oa m s a copolyme . Enabled by ou modula app oach he in luence o molecula
and chemical composi ion on he ob ained supe s uc u e was e alua ed (Chap e 5).
He ein, s uc u es simila o he “woodlouse” agg ega es we e obse ed, howe e om
a di e en mechanism s a ing wi h esicles as p ima y building uni s ins ead o
micelles.
Below, an o e iew o e he mos impo an esul s o each o he h ee ollowing
chap e s is gi en. The eade is e e ed o he co esponding chap e o an ex ensi e

2 – O e iew o he Thesis
42
discussion on he pa icula opic o syn hesis and sel -assembly o he mik oa m s a
e polyme s.
2.1 Modula Syn hesis o Mik oa m S a Te polyme s
Besides ou es elying exclusi ely on anionic polyme iza ion, he syn hesis o mik oa m
s a e polyme s is ypically accomplished by a combina ion o di e en polyme iza ion
me hods. The e o e, specially designed linking eac ions in combina ion wi h p ecisely
unc ionalized diblock copolyme s and pos unc ionaliza ion/ ans o ma ion eac ions
ha e o be conduc ed. In his chap e we p esen a mo e gene alized me hod, which can
be applied o a b oad a ie y o ( unc ional) monome s. The syn he ic s eps in ol e
sequen ial anionic polyme iza ion o alkyne mid- unc ionalized diblock copolyme s and
subsequen liga ion wi h azido- unc ionalized diblock copolyme s (Scheme 2-1).
Scheme 2-1. Syn he ic ou e o ABC mik oa m s a e polyme s by he combina ion o anionic
polyme iza ion in THF wi h DPE chemis y and click chemis y.
Fo he p epa a ion o he alkyne mid- unc ionalized diblock copolyme we u ilized DPE
chemis y, as i allows exac inco po a ion o exac ly one DPE uni a he block bo de
unde app op ia e choice o monome sequence. Fo his pu pose, we syn hesized a
no el DPE de i a i e ca ying a p o ec ed alkyne- unc ion (click-DPE, 1-[(4-( e -
bu yldime hylsilyl)-e hynyl)phenyl]-1-phenyle hylene). Due o he conjuga ion o he π-
sys em wi h he alkyne- unc ion in pa a-posi ion he co esponding li ing anion exhibi s
a ba hoc omic shi in he UV-spec um as compa ed o unsubs i u ed DPE (Figu e 2-1A).
2 – O e iew o he Thesis
43
As a consequence o his al e ed elec onic con igu a ion click-DPE was shown o
copolyme ize wi h li ing anions o poly(2- inylpy idine) (P2VP) by MALDI-ToF MS
in es iga ion o an app op ia e es eac ion (Figu e 2-1B), in con as o o he DPE
de i a i es epo ed in li e a u e. Hence, he li ing anion o click-DPE can p incipally
bo h be used o s a he anionic polyme iza ion 2- inylpy idine (2VP) and o
end unc ionaliza ion o li ing anions o P2VP.
Figu e 2-1. (A) UV- is abso p ion spec um o he adduc o 1,1-diphenyle hylene (do ed line) and 1-[(4-
( e -bu yldime hylsilyl)e hynyl)phenyl]-1-phenyle hylene (solid line) wi h sec-BuLi in THF. The inse shows
he pic u e o he cu e e con aining he li ing anion o he unsubs i u ed DPE ( op) and he click-DPE
(bo om). (B) MALDI-ToF MS spec a o poly(2- inylpy idine) be o e (black line) and a e addi ion o click-
DPE (cDPE, ed line), eco ded in e lec on mode (B) wi h AgTFA as ioniza ion agen . 
He e, we p epa ed di e en alkyne mid- unc ionalized diblock copolyme s wi h
polybu adiene as i s block and poly(2- inylpy idine), poly( e -bu yl me hac yla e)
(P BMA), o poly(N,N-dime hylaminoe hyl me hac yla e)
(PDMAEMA) as second block.
Excep hyd olysis no u he ans o ma ion eac ions a e necessa y o gene a e he
alkyne- unc ion. We de e mined he deg ee o alkyne- unc ionaliza ion by a es click
eac ion wi h an azido- unc ional pe ylene bisimide as ch omopho e in combina ion
wi h UV measu emen s. Fo he diblock copolyme s wi h P2VP as second block only a
sligh o e -inco po a ion o he click-DPE could be achie ed unde app op ia e eac ion
condi ions (~120% alkyne- unc ionaliza ion). This is due o he addi ion o a second DPE
uni o some chains. In con as , o P BMA as second block nea -quan i a i e
unc ionaliza ion was p o en (~93% alkyne unc ionaliza ion).
λ
max
= 549 nm
λ
max
= 500 nm
4750 4800 4850 4900 4950
VP45
VP42cDPE1
VP41cDPE1
VP44
m/z
4780 4800 4820
VP
44 VP41cDPE1
~ 4.5 g/mol
A
B
400 450 500 550 600 650 700
abso bance
λ
[nm]
2 – O e iew o he Thesis
44
By a modula combina ion o hese mid- unc ional diblock copolyme s wi h azido-
unc ionalized homopolyme s we syn hesized di e en no el ABC mik oa m s a
e polyme s ia coppe -ca alyzed azide-alkyne Huisgen cycloaddi ion. Fo he example
o a PB-b-P BMA diblock copolyme (cBT2) he mik oa m s a e polyme s ob ained a e
click eac ion wi h azido- unc ional polys y ene (PS), poly(e hylene oxide) (PEO) and
PDMAEMA homopolyme s a e lis ed in Table 2-1. The co esponding SEC eluog ams a e
depic ed in Figu e 2-2. In all cases na owly dis ibu ed mik oa m s a e polyme s we e
ob ained. We u he showed o click- eac ions wi h PEO and PDMAEMA
homolopolyme s ha a eac ion pa hway wi h an excess o he homopolyme was
possible and monomodal mik oa m s a e polyme s we e achie ed a e app op ia e
pu i ica ion p ocedu es, like e.g. dialysis (Figu e 2-2B).
Table 2-1. Molecula Cha ac e iza ion o ABC Mik oa m S a Te polyme s Ob ained
om Click Reac ions wi h Alkyne Mid-Func ionalized PB
111
-b-P BMA
42
Diblock
Copolyme cBT2 (Subsc ip s Deno e he Co esponding Deg ees o Polyme iza ion)
sample ID
a
DP(3
d
block)
b
M
n, h.
c
[kg/mol] M
n,app
d
[kg/mol]
Ɖ
d
µ-BT2S1,
(µ-B
38
T
38
S
23
15.9
) 36 15.9 20.5 1.03
µ-BT2S2,
(µ-B
33
T
33
S
3318.1
) 57 18.1 22.4 1.03
µ-BT2E,
(µ-B
32
T
32
E
3518.8
) 150 18.8 25.4 1.03
µ-BT2D,
(µ-B
34
T
34
D
3117.6
) 34 17.6 20.8 1.11
a
The supe sc ip deno es he heo e ical numbe a e age molecula weigh o he ABC mik oa m s a
e polyme , as calcula ed om he espec i e alues o he diblock copolyme and homopolyme and he
indices he heo e ical weigh ac ion o he espec i e blocks.
b
Calcula ed om he molecula weigh o
he 3
d
block.
c
Theo e ical molecula weigh .
d
Appa en molecula weigh and dispe si y de e mined by
SEC wi h polys y ene calib a ion. Fo he mik oa m s a e polyme s con aining PDMAEMA THF-SEC wi h
addi ional 0.25 w % e abu ylammonium b omide (TBAB) was used.
2 – O e iew o he Thesis
45
Figu e 2-2. SEC aces o mik oa m s a e polyme s om click eac ions o a polybu adiene-block-
poly( e -bu yl me hac yla e) diblock copolyme (cBT2) wi h (A) wo polys y ene homopolyme s (PS1-N
3
,
PS2-N
3
) and a poly(e hylene oxide) homopolyme (PEO-N
3
) and (B) a poly(N,N-dime hylaminoe hyl
me hac yla e) homopolyme (PDMAEMA-N
3
). Fo (B) THF-SEC wi h addi ional sal was used and as he
click eac ion was conduc ed wi h 2 equi o he PDMAEMA-N
3
, excess homopolyme was emo ed ia
dialysis.
Wi h his modula app oach a a ie y o unc ional mik oa m s a e polyme s a e
accessible. Fu he mo e, click-DPE o e s no el syn he ic ad an ages in he cons uc ion
o polyme ic a chi ec u es ia a combina ion o anionic polyme iza ion and click-
chemis y. The mik oa m s a e polyme s syn hesized he ein all ca y a polybu adiene
block, which can be used o u he modi ica ion and unc ionaliza ion ia hiol-ene
chemis y. Mo eo e new amphiphilic mik oa m s a e polyme s we e syn hesized,
which ca y hyd ophilic (PEO, PDMAEMA) and s imuli- esponsi e a ms (PDMAEMA,
P BMA a e hyd olysis).
2.2 Coun e ion-Media ed Hie a chichal Sel -Assembly o an ABC Mik oa m
S a Te polyme Con aining a Poly(N-me hyl-2- inylpy idinium iodide)
Segmen
Fo a mik oa m s a e polyme con aining a polybu adiene, poly( e -bu yl
me hac yla e) and poly(2- inylpy idine) segmen (µ-BVT), qua e niza ion wi h me hyl
iodide and ans e in o aqueous solu ion was obse ed o yield wo s uc u ally
comple ely di e ing limi ing cases o agg ega ion o ms: sphe ical micelles (d
micelle
= 24.5
± 2.0 nm) and pa icles wi h a complex lamella in e io (200-500 nm in longi udinal
axis). The concen a ion o iiodide as pola izable coun e ion o he qua e nized P2VP
26 28 30 32 34 36 38
0.0
0.2
0.4
0.6
0.8
1.0
cBT2
PS1$N
3
PS2$N
3
PEO$N
3

$BT2S1

$BT2S2

$BT2E
no malized RI signal
V
e
[mL]
14 15 16 17 18 19
0.0
0.2
0.4
0.6
0.8
1.0
V
e
[mL]
cBT2
PDMAEMA$N
3
.
$BT2D, undial.
.
$BT2D, dial.
A
B
2 – O e iew o he Thesis
52
Felix H. Schache , Hi oshi Jinnai and Axel H. E. Mülle we e in ol ed in scien i ic
discussions and co ec ion o he manusc ip .
Chap e 5
This wo k is published in Polyme 2013, 54, 4528-4537 unde he i le:
“Hie a chical Sel -Assembly o Mik oa m S a Polyme s Con aining a
Polyca ionic Segmen : A Gene al Concep ”
by And eas Hanisch, And é H. G öschel, Melanie Fö sch, Tina I. Löbling, Felix H.
Schache ,* and Axel H. E. Mülle *
I w o e he publica ion and conduc ed mos o he expe imen s.
Excep ions a e s a ed below:
And é H. G öschel was in ol ed in scien i ic discussions.
Melanie Fö sch pe o med almos all TEM and c yo-TEM measu emen s.
Tina I. Löbling eco ded some o he TEM mic og aphs.
Felix H. Schache and Axel H. E. Mülle we e in ol ed in scien i ic discussions and
co ec ion o he manusc ip .

3 – A Modula Rou e o he Syn hesis o ABC Mik oa m S a Te polyme s
53
3 – A Modula Rou e o he Syn hesis o ABC Mik oa m
S a Te polyme s ia a New Alkyne-Subs i u ed
Diphenyle hylene De i a i e
And eas Hanisch, Holge Schmalz, and Axel H. E. Mülle
ABSTRACT: We in oduce a modula ou e o he syn hesis o well-de ined ABC
mik oa m s a e polyme s. To his aim, he syn hesis o a 1,1-diphenyle hylene de i a-
i e bea ing a p o ec ed alkyne unc ion (1-[(4-( e -bu yldime hylsilyl)e hynyl)phenyl]-
1-phenyle hylene) was de eloped. This compound was o he i s ime employed in
sequen ial anionic polyme iza ion o eadily p epa e alkyne mid- unc ionalized diblock
copolyme s wi h polybu adiene as i s and a poly(alkyl me hac yla e) (poly( e -bu yl
me hac yla e), poly(N,N-dime hylaminoe hyl me hac yla e)) as second block. Fo he
hi d a m con olled adical polyme iza ion me hods (polys y ene, poly( e -bu yl me h-
ac yla e), poly(N,N-dime hylaminoe hyl me hac yla e)) and anionic ing-opening
polyme iza ion (poly(e hylene oxide)) we e used o sepa a ely p epa e homopolyme s
wi h an azido unc ion. A e wa d, azide-alkyne Huisgen cycloaddi ion was success ully
employed o syn hesize a lib a y o ABC mik oa m s a e polyme s wi h di e en mo-
lecula weigh s and chemical composi ions ia modula combina ion o he unc ional-
ized diblock copolyme s and homopolyme s. The esul ing new ABC mik oa m s a
e polyme s showed na ow, monomodal molecula weigh dis ibu ions wi h
dispe si ies ypically below 1.10, as de e mined by size exclusion ch oma og aphy.
3 – A Modula Rou e o he Syn hesis o ABC Mik oa m S a Te polyme s
54
3.1 In oduc ion
Polyme a chi ec u e and composi ion is a decisi e ac o o con olling s uc u e o -
ma ion bo h in bulk and in solu ion. Besides he choice o monome and he numbe and
sequence o polyme ic building blocks he way o molecula conjunc ion o hese blocks
is o ou e mos impo ance. Compa ed o hei linea analogues, mik oa m s a
e polyme s, whe e he polyme chains a e connec ed a one common junc ion poin ,1
p esen a much mo e complex sys em. A a ie y o unique bulk mo phologies we e
ound,2-4 which a e inaccessible by linea iblock e polyme s. This is a di ec conse-
quence o he con ined geome y o he polyme chains, which o ces he common junc-
ion poin s o he h ee di e en blocks o be aligned in a 1-dimensional ashion. These
mik oa m s a e polyme mo phologies we e also u ilized o gene a ing cylind ical,
compa men alized pa icles by selec i e c osslinking o one block.5 In addi ion, heo e -
ical s udies sugges ha e en mo e complex mo phologies a e expec ed unde cylind i-
cal con inemen o ABC mik oa m s a e polyme s.6 Depending on he leng h a io o
he espec i e a ms, Hillmye , Lodge and co-wo ke s7,8 ob ained di e en
mul icompa men s uc u es in aqueous solu ion om ABC mik oa m s a e polyme s
wi h a luo ina ed segmen . These anged om hambu ge micelles o segmen ed
wo mlike micelles and nanos uc u ed esicles.
The conjunc ion o h ee chains a one common linking poin leads o special e-
qui emen s conce ning he syn he ic s a egy. The main di icul ies a e (1) he exac
unc ionaliza ion o a diblock copolyme wi h a unc ional g oup o polyme block a he
junc ion o he wo blocks and (2) he s oichome y o he linking eac ion. Fou di e -
en syn he ic s a egies ha e been epo ed so a o mik oa m s a e polyme s.
One app oach uses he di e en eac i i y o li ing anionic polyme chains owa d he
chlo ine-silicon g oups o ichlo osilanes. Using me hyl ichlo osilane as linking agen ,
Hadjich is idis and cowo ke s syn hesized a mik oa m s a e polyme consis ing o poly-
isop ene, polys y ene, and polybu adiene.9 Howe e , he sequence o in oduc ion o
a ms is s ongly limi ed o he eac i i y and s e ic demand o he polyme ic anions, and
adap ion o o he monome s equi es a modi ica ion o he me hod.10,11 The second
anionic app oach u ilizes mac omonome s wi h nonhomopolyme izable endg oups
3 – A Modula Rou e o he Syn hesis o ABC Mik oa m S a Te polyme s
55
which we e di ec ly sequen ially copolyme ized wi h wo so s o monome s.2,12-14 In
ano he app oach, i s diblock copolyme s we e syn hesized ca ying unc ional g oups
a he junc ion poin o he wo blocks. Again, nonhomopolyme izable compounds o
special polyme iza ion s a egies ha e o be employed o assu e ha only one unc ional
g oup is loca ed exac ly in be ween he wo polyme ic building blocks. Up o now, main-
ly hyd oxyl- unc ions we e used o conjuga e he hi d block, which we e in oduced ia
a 1,1-diphenyle hylene (DPE) de i a i e15,16 o 2-me hoxyme hyloxyme hyloxi ane17-19 as
end-capping molecule. This hyd oxyl unc ion se es as ancho ing poin o he hi d
block, which can be “g a ed om” by anionic ing opening polyme iza ion (AROP)15-17 o
con olled adical polyme iza ion (CRP) a e app op ia e modi ica ion19 o “g a ed o”
ia di ec es e i ica ion.18 Hi ao and co-wo ke s ecen ly used in-chain-benzyl b omide-
unc ionalized diblock copolyme s o he mik oa m s a e polyme syn hesis in ol ing
specially designed anionic linking eac ions.20
The possibili y o cons uc ing complex polyme ic a chi ec u es wi h con olled adi-
cal polyme iza ion me hods inc eased wi hin he las decade.21,22 This suppo ed he
de elopmen o new s a egies o he syn hesis o ABC mik oa m s a e polyme s
whe e anionic polyme iza ion is no in ol ed. In addi ion, click eac ions in gene al, o
coppe (I)-ca alyzed azide-alkyne cycloaddi ion (CuAAC) in pa icula ha e become pow-
e ul ools o highly e icien linking o polyme ic building blocks.23-25 These no el syn-
he ic ou es ake ad an age o he o hogonali y o he di e en polyme iza-
ion/liga ion me hods, which is a p e equisi e o he syn hesis o well-de ined ABC
mik oa m s a e polyme s. By designing special co e molecules wi h h ee di e en
unc ionali ies, he a ms can be “g a ed on o” o “g a ed om” in di e en s eps.26-31
He ein, we p esen a mo e gene al me hod by combining anionic polyme iza ion,
employed o he syn hesis o eadily alkyne mid- unc ionalized diblock copolyme s,
wi h o he polyme iza ion echniques ia azide-alkyne Huisgen cycloaddi ion (Scheme 3-
1). Ba ne -Kowollik and co-wo ke s al eady epo ed he liga ion o alkyne mid-
unc ionalized homopolyme s wi h azide-bea ing homopolyme s.32 Howe e , only A2B
mik oa m s a e polyme s we e accessible. The syn hesis o an alkyne mid-
unc ionalized diblock copolyme consis ing o polys y ene and poly( e -bu yl ac yla e)
was also epo ed.33,34 Ne e heless, mul iple polyme analogous eac ions had o be
3 – A Modula Rou e o he Syn hesis o ABC Mik oa m S a Te polyme s
56
conduc ed and/o swi ching he polyme iza ion sys em was necessa y. Thus, we syn he-
sized 1-[(4-( e -bu yldime hylsilyl)e hynyl)phenyl]-1-phenyle hylene o di ec ly p epa e
mid-chain alkyne-subs i u ed diblock copolyme s ia sequen ial anionic polyme iza ion.
Because o he di ec in oduc ion o he alkyne-g oup in o he diblock copolyme by he
use o DPE chemis y, a wide a ie y o unc ional diblock copolyme s a e accessible, and
excep hyd olysis no edious ans o ma ion eac ions ha e o be conduc ed. The ob-
ained diblock copolyme s we e a e wa d liga ed wi h di e en azide-bea ing
homopolyme s p epa ed by a om ans e adical polyme iza ion (ATRP), e e sible ad-
di ion- agmen a ion chain ans e (RAFT) polyme iza ion, and anionic ing opening
polyme iza ion ia azide-alkyne click chemis y. Di e en no el ABC mik oa m s a
e polyme s we e syn hesized u ilizing his modula combina ion.
Scheme 3-1. Syn he ic ou e o he syn hesis o ABC mik oa m s a e polyme s o he example o a s a
consis ing o a ms o polybu adiene, poly( e -bu yl me hac yla e), and polys y ene
3 – A Modula Rou e o he Syn hesis o ABC Mik oa m S a Te polyme s
57
3.2 Expe imen al Sec ion
Ma e ials. Fo he pu i ica ion o monome s, eagen s and sol en and he syn hesis o
used compounds see he Suppo ing In o ma ion.
Syn hesis o 1-[(4-( e -Bu yldime hylsilyl)e hynyl)phenyl]-1-phenyle hylene (Click-
DPE). The s a ing molecule 1-(4-b omophenyl)-1-phenyle hylene was syn hesized as
desc ibed elsewhe e.35 The syn he ic p o ocol o he coupling eac ion wi h he p o-
ec ed alkyne de i a i e was adop ed om he li e a u e.36 Fi s , 1-(4-b omophenyl)-1-
phenyle hylene was dissol ed in pipe idine (~50 mg/mL) and
bis( iphenylphosphine)palladium(II) dichlo ide (0.03 equi ) and CuI (0.004 equi ) we e
added unde a ni ogen a mosphe e. A e degassing wi h ni ogen o 30 minu es, e -
bu yldime hylsilylace ylene (1.2 equi ) was added d opwise a 50 °C, and he solu ion
was s i ed o e nigh . The eac ion mix u e was il e ed, he sol en e apo a ed, and he
c ude p oduc was dissol ed in THF. A e addi ion o wa e , he p oduc was ex ac ed
wi h hexane o h ee imes. The o ganic ac ions we e d ied o e sodium sul a e, and
he sol en was e apo a ed o ob ain a b own oil. This was u he pu i ied by column
ch oma og aphy wi h hexane as sol en o ob ain a clea oil. Dis illa ion o he p oduc
was no possible e en unde high acuum condi ions. Be o e he use in anionic polyme -
iza ion, he compound was eeze-d ied om benzene solu ion on a high acuum line
and subsequen ly dissol ed in d y THF o ob ain a s ock solu ion o low iscosi y. sec-
BuLi was added d opwise ( ypically 1-2 d ops) unde ni ogen low un il a deeply iole
colo was ob ained. Besides p o ing he absence o impu i ies, he pe sis en colo also
se ed as indica ion o he pu i y o he s ock solu ion. 1H NMR (300 MHz, CDCl3): δ =
7.50-7.27 (m, 9H, A ), 5.50 (s, 2H, -C=CH2), 1.03 (s, 9H, SiC(CH3)3), 0.22 (s, 6H, SiCH3)
Polyme iza ions. Sequen ial Li ing Anionic Polyme iza ion in THF. All polyme iza ions
we e ca ied ou a low empe a u es in a he mos a ed labo a o y au ocla e (Büchi)
unde d y ni ogen a mosphe e using THF as sol en . The day be o e polyme iza ion,
eshly dis illed THF (~250 mL o 15 g o polyme ) was ea ed wi h 1 mL o sec-BuLi pe
100 mL o sol en a -20 °C, ollowed by s i ing o e nigh o o m li hium alkoxides.
These exhibi s abilizing e ec s on he li ing chain end o polybu adiene and u he -
mo e in he case o me hac yla e- ype monome s no addi ion o LiCl is necessa y o ob-

3 – A Modula Rou e o he Syn hesis o ABC Mik oa m S a Te polyme s
58
ain well-de ined polyme s.37 Fo he diblock copolyme s, i s bu adiene was ini ia ed
wi h sec-BuLi a -70 °C and hen polyme ized a -50 o -15 °C depending on he block
leng h o he di e en polyme iza ions. To ensu e comple e consump ion o he bu adi-
ene he polyme iza ion was ollowed by in-line NIR ibe -op ic spec oscopy. The li ing
polybu adienyl anion was end-capped wi h 1-[(4-( e -
bu yldime hylsilyl)e hynyl)phenyl]-1-phenyle hylene (1.1-1.5 equi ) a -50 °C o 2 h.
Be o e and a e he addi ion o he click-DPE samples o SEC and MALDI-ToF MS we e
wi hd awn. In he case o poly(2- inylpy idine) (P2VP) as second block he monome was
added a -70 °C and polyme ized o 5 minu es. A e e mina ion wi h degassed me ha-
nol he polyme (cBV) was isola ed by p ecipi a ion in wa e . Fo he diblock copolyme s
wi h e -bu yl me hac yla e ( BMA) he monome addi ion was conduc ed a -70 °C and
he polyme iza ion ook place a -45 °C o 1 h be o e i was e mina ed wi h degassed
me hanol. A e he addi ion o he BMA he iole colo o he DPE end-capped li ing
anion slowly aded away. The inal polyme (cBT) was p ecipi a ed in a mix u e o iso-
p opanol/wa e 3/1 ( / ). Fo he hi d ype o diblock he N,N-dime hylaminoe hyl
me hac yla e (DMAEMA) was injec ed in o he eac o a -70 °C and polyme ized o 1 h.
Immedia ely a e addi ion o he monome he colo o he DPE end-capped
polybu adienyl anion anished comple ely. A e e mina ion wi h degassed me hanol,
he esul ing polyme (cBD) was dialyzed agains THF and inally eeze-d ied om
dioxane. The molecula weigh s o he diblock copolyme s wi h P2VP o PDMAEMA as
second block we e calcula ed by a combina ion o MALD-ToF MS and 1H NMR. The e-
o e, he Mn o he polybu adiene (PB) p ecu so polyme was de e mined by mass spec-
ome y. By he ela i e mola a ios o he cha ac e is ic signals o PB (5.10-5.60 ppm,
2H 1,2-PB; 5.70-5.15 ppm, 1H 1,2-PB and 2H 1,4-PB) and P2VP (8.50-8.00 ppm, 1H) o
PDMAEMA (4.30-3.90 ppm, 2H) he o e all molecula weigh was calcula ed using he
PB p ecu so molecula weigh as e e ence. The Mn o he PB-b-P BMA diblock copoly-
me s was di ec ly measu ed by MALDI-ToF MS. All he da a o he diblock cha ac e iza-
ion a e summa ized in Table 3-1.
Alkyne Dep o ec ion. Fo he dep o ec ion p ocedu e, he espec i e polyme was dis-
sol ed in THF (~0.1 g/mL) and degassed o 30 min. Then, 10 equi o
e abu ylammonium luo ide (1 M solu ion in THF) ela i e o alkyne unc ions we e
3 – A Modula Rou e o he Syn hesis o ABC Mik oa m S a Te polyme s
59
added a 0 °C and s i ed a his empe a u e o 2 h. A e wa ming up o oom empe -
a u e he solu ion was s i ed o e nigh . The polyme was p ecipi a ed in pu e wa e o
isop opanol/wa e 3/1 ( / ) o PB-b-P2VP and PB-b-P BMA, espec i ely. A e wa d, he
polyme was dissol ed in THF and dialyzed agains THF (MWCO 1 000 g/mol) o emo e
impu i ies. Finally, he polyme s we e eeze-d ied om dioxane. In he case o he
diblock copolyme wi h DMAEMA he eac ion mix u e was di ec ly dialyzed agains THF
p io o eeze-d ying.
Click Reac ions. Fo he de e mina ion o he deg ee o unc ionaliza ion wi h alkyne-
subs i u ed DPE, es click eac ions wi h N-(1-hep yloc yl)-N′-(hexyl-6′-azido)-pe ylene-
3,4,9,10- e acaboxylic acid bisimide we e conduc ed. In a ypical un, 100 mg o he
dep o ec ed diblock copolyme we e dissol ed in 5 mL THF in a sc ew-cap glass. Then, 2
equi o he azido- unc ionalized pe ylene bisimide ela i e o he alkyne unc ion was
added. A e pu ging wi h ni ogen o 10 min, 1 equi o CuB was added, ollowed by
u he degassing o 10 min. By addi ion o 1 equi o N,N,N′,N′,N′′-
pen ame hyldie hylene iamine (PMDETA) as ligand, he click eac ion was s a ed and
s i ed a oom empe a u e o 3 days. A e e mina ion by exposu e o ai , he e-
maining coppe was emo ed by il a ion o e a sho silica gel column. P epa a i e SEC
wi h THF as eluen was employed o emo e excess pe ylene. An in ense ed-colo ed
polyme was ob ained a e eeze-d ying om dioxane.
The click eac ions o he cons uc ion o he mik oa m s a e polyme s we e con-
duc ed in a simila manne . Typically, he mola a ios o alkyne unc ion:azido unc-
ion:CuB :PMDETA was se o 1:1:1:1 (i no s a ed elsewhe e), and he polyme concen-
a ion was ~20 mg/mL in THF. The eac ions we e conduc ed a oom empe a u e and
ollowed by wi hd awing samples o SEC measu emen s. Finally, when no u he
changes in he SEC eluog amms we e obse ed, he esul ing mik oa m s a e polyme
was pu i ied by passing h ough a small silica gel column o emo e coppe . The poly-
me s we e ob ained as whi e powde s a e eeze-d ying om dioxane.
3 – A Modula Rou e o he Syn hesis o ABC Mik oa m S a Te polyme s
60
3.3 Resul s and Discussion
3.3.1 Syn hesis o 1-[(4-( e -Bu yldime hylsilyl)e hynyl)phenyl]-1-
phenyle hylene (Click-DPE)
The key compound o his modula ou e owa d ABC mik oa m s a e polyme s
(Scheme 3-1) was di ec ly syn hesized by he palladium-ca alyzed Sonogashi a coupling
eac ion be ween 1-(4-b omophenyl)-1-phenyle hylene and e -bu yldime hylsilyl p o-
ec ed ace ylene. Simila compounds, like 4-( ime hylsilyl)e hynyls y ene36 and me hac-
yla e de i a i es as 3- ime hylsilyl-2-p opynyl me hac yla e,38 ha e al eady been syn-
hesized and used in anionic polyme iza ion o ob ain polyme s wi h p edic able mo-
lecula weigh s and na ow dis ibu ions. As known o DPE and i s de i a i es
homopolyme iza ion o such compounds is no possible due o s e ic hind ance.39 In
con as o me hods epo ed in li e a u e,33,34 his syn he ic ad an age enables us o
use one sequen ial polyme iza ion p ocess o selec i ely inco po a e exac ly one alkyne
unc ion be ween he wo polyme ic blocks unde adequa e choice o monome s. The
click-DPE was pu i ied ia column ch oma og aphy o gi e a clea iscous oil. The chemi-
cal s uc u e and he pu i y we e con i med by 1H NMR spec oscopy (Figu e 3-1a).
Figu e 3-1. 1H NMR spec a o (a) 1-[(4-( e -bu yldime hylsilyl)e hynyl)phenyl]-1-phenyle hylene (click-
DPE), (b) he p o ec ed alkyne- unc ionalized diblock cBT2, and (c) he co esponding diblock a e hyd o-
lysis o he silyl-p o ec ing g oup (sol en signals a e s iked ou ).
3 – A Modula Rou e o he Syn hesis o ABC Mik oa m S a Te polyme s
61
The UV- is spec um o he deeply iole solu ion o he li ing anion (Figu e 3-2) gene -
a ed by eac ion o 1-[(4-( e -bu yldime hylsilyl)e hynyl)phenyl]-1-phenyle hylene wi h
sec-BuLi shows a maximum a 549 nm. In con as , he li ing anion o unsubs i u ed 1,1-
diphenyle hylene has a deep ed colo , and we de e mined he abso p ion maximum a
a ound 500 nm unde he same condi ions.40 This clea ba hoc omic shi o igina es
om he conjuga ion o he π-sys em wi h he p o ec ed alkyne g oup. Simila ly, Tsuda
e al. epo ed a b ownish- ed colo in he anionic polyme iza ion o 4-
( im hylsilyl)e hylens y ene,36 in con as o he o ange colo o polys y yl anions.41
Figu e 3-2. UV- is abso p ion spec um o he adduc o 1,1-diphenyle hylene (do ed line) and 1-[(4-( e -
bu yldime hylsilyl)e hynyl)phenyl]-1-phenyle hylene (solid line) wi h sec-BuLi in THF. The inse shows he
pic u e o he cu e e con aining he li ing anion o he unsubs i u ed DPE ( op) and he click-DPE (bo -
om).
3.3.2 Syn hesis o Alkyne Mid-Func ionalized Diblock Copolyme s
Bu adiene was chosen o he i s block and o he second block 2- inylpy idine (2VP)
o me hac yla e ype monome s as e -bu yl me hac yla e ( BMA) and N,N-
dime hylaminoe hyl me hac yla e (DMAEMA). The anionic polyme iza ion o bu adiene
was conduc ed in THF a -50 o -15 °C (depending on he espec i e block leng h) using
sec-BuLi as ini ia o . A e comple e con e sion – as ollowed in si u wi h ibe -op ics NIR
spec oscopy – 1.1 o 1.5 equi o he click-DPE s ock solu ion was added ia sy inge a
-50 °C. The addi ion o he diphenyle hylene de i a i e was clea ly isible by he imme-
3 – A Modula Rou e o he Syn hesis o ABC Mik oa m S a Te polyme s
68
weigh s close o 100 000 g/mol we e p oduced ia CuAAC,49,50 we suppose ha in ou
case he alkyne unc ion a he block junc ion is s e ically less amenable han an alkyne
unc ion in α- o ω-posi ion. Ou i s ials wi h highe molecula weigh polyme s (ex-
ceeding 40 000-50 000 g/mol o he indi idual compounds) we e no success ul. The e-
o e, we chose mode a e molecula weigh s o he indi idual compounds, so ha he
o e all molecula weigh did no exceed 25 000 g/mol and he unc ional g oups we e
no oo dilu ed. The cou se o he click eac ions wi h cBT diblock copolyme s was ol-
lowed by SEC. The eac ions we e conduc ed unde equimola condi ions. A e 24 h he
molecula weigh dis ibu ion o he diblock copolyme s cBT1 and cBT2 shi ed com-
ple ely (see Figu e 3-3 and Figu e 3-S4), esembling he success ul gene a ion o he de-
si ed mik oa m s a e polyme . Howe e , despi e equimola eac ion condi ions in bo h
cases he e was s ill a mino amoun o un eac ed homopolyme le . Fu he SEC meas-
u emen s showed ha he peak o he PS1-N3 al eady disappea ed nea ly comple ely
a e 11.5 h (Figu e 3-S5) o he click eac ion wi h cBT2. Inc easing he eac ion ime
did no lead o any change in he eluog amm. The e o e, we addi ionally ca ied ou a
eac ion be ween cBT1 and only 0.8 equi o PS1-N3. Unde he same eac ion condi-
ions, again, a compa able amoun o homopolyme was le ( esul s no shown). We
assume ha du ing polyme iza ion and wo k-up o he homopolyme , a mino pa o
he b omine g oup is elimina ed, as al eady epo ed in li e a u e.51 This leads o a small
amoun o non-azido- unc ionalized homopolyme which canno ake pa in he click
eac ion (see discussion o MALDI-TOF spec um in he Suppo ing In o ma ion). This
was also con i med by he click eac ion o cBT2 wi h PS3-N3 (Figu e 3-S6). Unde
equimola eac ion condi ions no u he liga ion ook place a e 15 h, leading o a non-
negligible amoun o un eac ed diblock and homopolyme . In con as o he click eac-
ions wi h lowe molecula weigh polys y enes he con e sion o he click eac ion wi h
PS3-N3 was much lowe a e 3.25 h (whe e he eac ion was mo e o less inished in he
o he cases). Fu he addi ion o 0.5 equi o homopolyme esul ed in a comple e shi
o he diblock due o comple e click e iciency as depic ed in Figu e 3-S6. Thus, he de-
g ee o un unc ionalized polys y ene inc eased wi h inc easing molecula weigh .

3 – A Modula Rou e o he Syn hesis o ABC Mik oa m S a Te polyme s
69
26 28 30 32 34 36
0.0
0.2
0.4
0.6
0.8
1.0
no malized RI signal
V
e
[mL]
cBT1
PS1-N3
PS2-N3
µ
-BT1S1
µ
-BT1S2
Figu e 3-3. THF-SEC (RI signal) o alkyne- unc ionalized diblock cBT1, azido- unc ionalized PS (PS1-N3, PS2-
N3) and he co esponding ABC mik oa m s a e polyme s (µ-BT1S1 and µ-BT1S2) ob ained a e
equimola click eac ion o 24 h.
Ne e heless, comple e shi s o he molecula weigh dis ibu ions o he mik oa m s a
e polyme s owa d lowe elu ion olumes compa ed o he p is ine diblock copolyme s
we e de ec ed in all cases. This demons a es he success ul o ma ion o ABC mik oa m
s a e polyme s. Addi ionally, he o e all shi s o he esul ing ABC mik oa m s a
e polyme s we e no oo dis inc . This is in acco dance wi h heo y, whe e he hyd o-
dynamic adius o s a polyme s is expec ed o be smalle han he hyd odynamic adius
o a linea polyme wi h he same composi ion and molecula weigh due o he highe
segmen al densi y o s a polyme s.52 All syn hesized µ-BTS s a e polyme s exhibi ed
symme ical peaks wi h a na ow molecula weigh dis ibu ion. The heo e ical molecu-
la weigh s we e calcula ed om he known molecula weigh s o he liga ed diblock
copolyme s. These a e shown oge he wi h he appa en molecula weigh s and he
espec i e dispe si ies in Table 3-3. Fu he mo e an exempla ily 1H NMR o µ-BT1S1 is
shown in Figu e 3-S7. All cha ac e is ic signals o he polyme ic building blocks a e p e-
sen in he ob ained mik oa m s a e polyme .
3 – A Modula Rou e o he Syn hesis o ABC Mik oa m S a Te polyme s
70
Table 3-3. Molecula Cha ac e iza ion o ABC Mik oa m S a Te polyme s Ob ained
om Click Reac ions wi h Alkyne Mid-Func ionalized Diblock Copolyme s
sample IDa DP(PB)b DP(2nd
block)c
DP(3 d
block)d
Mn, h.
e
[kg/mol]
Mn,app
[kg/mol] Ɖ
µ-
BT1S1
(µ-B
63
T
18
S
18
20.7) 242 27 36 20.7 28.0 1.03
µ-
BT1S2
(µ-B
57
T
17
S
26
22.9) 242 27 57 22.9 30.0 1.03
µ-
BT1E
(µ-B
55
T
16
E
28
23.6) 242 27 150 23.6 32.7 1.04
µ-
BT1D
(µ-B
58
T
17
D
24
22.4)
242 27 34 22.4 31.5 1.10
µ-
BT2S1
(µ-B
38
T
38
S
23
15.9) 111 42 36 15.9 20.5 1.03
µ-
BT2S2
(µ-B
33
T
33
S
33
18.1) 111 42 57 18.1 22.4 1.03
µ-BT2S3
g
(µ-B
29
T
29
S
40
20.5) 111 42 80 20.5 25.0 1.03
µ-
BT2E
(µ-B
32
T
32
E
35
18.8) 111 42 150 18.8 25.4 1.03
µ-
BT2D
(µ-B
3
4
T
34
D
31
17.6)
111 42 34 17.6 20.8 1.11
µ-BDT
g
(µ-B
40
D
28
T
31
24.5)
181 44 53 24.5 26.3 1.08
μ-BDE
g
(µ-B
42
D
29
E
28
23.5)
181 44 150 23.5 32.5 1.06
aThe numbe -a e age molecula weigh o he ABC mik oa m s a e polyme was calcula ed om he
espec i e alues o diblock copolyme s and he homopolyme s. The e o e, he supe sc ip deno es he
heo e ical numbe -a e age molecula weigh o he ABC mik oa m s a e polyme and he indices he
heo e ical weigh ac ion o he espec i e blocks. bDeg ee o polyme iza ion (DP) de e mined om
MALDI-ToF MS o he PB-p ecu so . cCalcula ed by he di e ence in Mn de e mined by he MALDI-ToF MS
spec a o diblock and p ecu so . dCalcula ed om he molecula weigh o he 3 d block. eTheo e ical mo-
lecula weigh . Appa en molecula weigh and dispe si y de e mined by SEC wi h polys y ene calib a ion.
Fo he mik oa m s a e polyme s con aining PDMAEMA THF-SEC wi h addi ional 0.25 w %
e abu ylammonium b omide (TBAB) was used. gIn hese cases he appa en molecula weigh and
dispe is y we e de e mined excluding he sepa a ed homopolyme peak.
Click Reac ions wi h ω-Azido-Func ionalized Poly(e hylene oxide). These i s success ul
es eac ions wi h azido- unc ionalized polys y ene p o e he easibili y o ou ap-
p oach. To p epa e amphiphilic mik oa m s a e polyme s we conduc ed click eac ions
wi h PEO-N3. Fi s a emp s unde equimola eac ion condi ions led o a non-negligible
amoun o un eac ed diblock copolyme . The e o e, he click eac ions we e ca ied ou
wi h an excess o he unc ionalized PEO-N3. By s epwise addi ion o PEO-N3 o he eac-
ion mix u e, he equi alen s necessa y o a comple e click eac ion we e de e mined
3 – A Modula Rou e o he Syn hesis o ABC Mik oa m S a Te polyme s
71
(Figu e 3-S8). The e o e, in a i s s ep, he eac ion wi h 1 equi o PEO-N3 was ollowed
by SEC. As a e 24 h no u he change in he eluog am was de ec ed, and s ill a signi i-
can amoun o un eac ed diblock copolyme was le o e , 0.5 equi o PEO-N3 was
added subsequen ly. Finally, a e 3.5 h eac ion ime, u he 0.2 equi o PEO-N3 was
added o he click eac ion con aining al eady 1.5 equi . As his did no esul in a
change compa ed o he eluog am a e eac ion wi h 1.5 equi o PEO-N3, he equi a-
len s necessa y o comple e liga ion we e de e mined o be 1.5 equi .
The eason o he use o such a huge excess o PEO-N3 s ill emains unclea . F om he
amoun o coupled p oduc (~6 w % om SEC) only a sligh excess o he azido-
unc ionalized compound would be easonable. Howe e , maybe pa ial elimina ion o
he azido g oup o PEO o uncomple e unc ionaliza ion due o side eac ion du ing he
end-capping eac ion could be a easible explana ion (see discussion o MALDI-ToF spec-
um in he Suppo ing In o ma ion). The espec i e SEC aces o he click eac ions
wi h cBT1, cBT2, and cBD (whe e he a io o cBX:PEO-N3 was minimum 1:1.5) a e shown
in Figu e 3-4. In case o he diblock copolyme s wi h P BMA as second block he excess
PEO-N3 was easily emo ed du ing pu i ica ion om coppe wi h a sho column o silica
due o in e ac ions wi h he column. Using PEO-N3 in excess and subsequen emo al o
un eac ed homopolyme gua an eed he comple e con e sion o he alkyne unc ion.
Howe e , in he case o he diblock cBD con aining DMAEMA a highe amoun o PEO
homopolyme was le o e a e wo k-up. Fu he pu i ica ion wi h a column, c ys alli-
za ion om cold THF, o dialysis in aqueous media did no educe he amoun o he
undesi ed PEO homopolyme . A possible explana ion could be ha PEO o ms hyd ogen
bonds wi h PDMAEMA, which he e o e p e en he comple e emo al o excess PEO
homopolyme . He e, one has o no ice ha o u he applica ions, whe e he PEO
se es as co ona in aqueous solu ions, his mino amoun o PEO homopolyme is no
p oblema ic.
In con as o he p e ious click eac ions, dis inc shi s o he molecula weigh dis-
ibu ions o he ABC mik oa m s a e polyme s compa ed o he co esponding diblock
p ecu so s we e de ec ed. The absence o a peak om esidual diblock also gi es e i-
dence ha all diblock copolyme chains ca y an alkyne unc ion. Like o he click eac-
3 – A Modula Rou e o he Syn hesis o ABC Mik oa m S a Te polyme s
72
A
B
14 15 16 17 18
0.0
0.2
0.4
0.6
0.8
1.0 cBD
PEO-N3
µ
-BDE, dial.
V
e
[mL]
26 28 30 32 34
0.0
0.2
0.4
0.6
0.8
1.0
no malized RI signal
V
e
[mL]
cBT1
cBT2
PEO-N3

BT1E

BT2E
ions wi h PS-N3 low dispe si ies o he esul ing ABC mik oa m s a e polyme s we e
de ec ed (Table 3-3).
Figu e 3-4. THF-SEC (A) o alkyne- unc ionalized diblock copolyme s cBT1, cBT2, he azido- unc ionalized
PEO-N3, and he co esponding ABC mik oa m s a e polyme s (µ-BT1E and µ-BT2E) ob ained a e azide-
alkyne click coupling and sal -THF-SEC aces (B) o cBD, PEO-N3, and he esul ing ABC mik oa m s a
e polyme (µ-BDE) a e dialysis. In all cases he RI-signals a e shown.
Click Reac ions wi h ω-Azido-Func ionalized Poly(N,N-dime hylaminoe hyl me hac yla e).
To ob ain PDMAEMA as a wa e -soluble polyme , which esponds bo h o pH and em-
pe a u e,53 we used an azido-subs i u ed CTA.44 As he gene al applicabili y o ou ap-
p oach unde equimola condi ions was p o en we conduc ed he click eac ions wi h a
2- old excess o PDMAEMA-N3 o 5 days, wi hou op imizing he eac ion ime. Wi h
his eac ion pa hway we we e also able o gua an ee 100% con e sion o he alkyne-
compound. The SEC aces o he aw p oduc o he click eac ions o he azido-
unc ionalized PDMAEMA-N3 wi h he wo cBT diblock copolyme s a e shown in Figu e
3-5A and 3-5B, espec i ely. In bo h cases he molecula weigh dis ibu ions o he
mik oa m s a e polyme s shi ed comple ely in he co esponding SEC- aces com-
pa ed o hei diblock copolyme p ecu so s. The excess PDMAEMA-N3 was emo ed by
dialysis in a mix u e o me hanol/isop opanol (2/1 / ), whe e he mik oa m s a
e polyme o ms micelles wi h a polybu adiene co e. The e o e, a dialysis memb ane
wi h a cu -o (50 000 g/mol) much highe han he molecula weigh o he
homopolyme was used. The SEC aces o he ob ained mik oa m s a e polyme s a e
plo ed in Figu e 3-5A and B. In he case o µ-BT1D he iny coupling shoulde a lowe
elu ion olume became mo e p onounced a e dialysis. The e o e, we assume ha his
3 – A Modula Rou e o he Syn hesis o ABC Mik oa m S a Te polyme s
73
A
B
14 15 16 17 18 19
0.0
0.2
0.4
0.6
0.8
1.0
V
e
[mL]
cBT2
PDMAEMA-N3
µ
-BT2D, undial.
µ
-BT2D, dial.
14 15 16 17 18 19
0.0
0.2
0.4
0.6
0.8
1.0
no malized RI signal
V
e
[mL]
cBT1
PDMAEMA-N3
µ
-BT1D, undial.
µ
-BT1D, dial.
shoulde migh be he esul o some agg ega ion e ec s, which occu ed o his eac-
ion. Ano he explana ion could be he oxida ion o he amine, which leads o he o -
ma ion o amine oxide. Fo he dialysis o µ-BT2D e en unde ex ensi e exchange o he
sol en , he small esidual peak om un eac ed PDMAEMA-N3 could no be emo ed
comple ely. Howe e , compa ed o he p oduc peak his peak is negligible. The molecu-
la cha ac e iza ion o he µ-BTD mik oa m s a e polyme s is lis ed in Table 3-3. In a
simila way a µ-BDT mik oa m s a e polyme consis ing o he same monome uni s
was syn hesized by liga ion o cBD wi h P BMA-N3 (see Suppo ing In o ma ion and Ta-
ble 3-3).
Figu e 3-5. Sal -THF-SEC (RI signal) o µ-BTD mik oa m s a e polyme s ob ained by click coupling o he
alkyne- unc ionalized diblock copolyme s (A) cBT1 and (B) cBT2 wi h he azido- unc ionalized PDMAEMA-
N3. As in bo h cases 2 equi o PDMAEMA we e used wi hin he click eac ion, SEC aces o he aw p o-
duc and he mik oa m s a e polyme a e dialysis a e shown.

3 – A Modula Rou e o he Syn hesis o ABC Mik oa m S a Te polyme s
74
3.4 Conclusions
This gene al modula ou e o he syn hesis o ABC mik oa m s a e polyme s com-
bines anionic polyme iza ion echniques wi h CRP me hods and anionic ing opening
polyme iza ion using azide-alkyne Huisgen cycloaddi ion as liga ion me hod. Fo his
pu pose, we success ully employed ou alkyne-modi ied DPE de i a i e in sequen ial
anionic polyme iza ion. In he case o me hac yla e- ype monome s well-de ined alkyne
mid unc ional diblock copolyme s consis ing o a i s block o PB and a second block o
ei he P BMA o PDMAEMA we e syn hesized. Click eac ions wi h azido- unc ionalized
pe ylene bisimide e i ied he success ul inco po a ion o only one DPE uni a he block
junc ion. In con as o o he DPE de i a i es, we obse ed ha click-DPE can copoly-
me ize wi h 2VP, which o e s he ad an age o p oducing alkyne mid- unc ionalized
diblock copolyme s wi h P2VP as i s block and a me hac yla e as second block. The e-
o e, 2VP and bu adiene and s y ene and hei de i a i es can be used as i s blocks and
me hac yla e ype monome s as second block o ob ain well de ined-diblock copolyme s
bea ing an alkyne unc ion a he block junc ion. By using a oolbox o di e en azido-
unc ionalized homopolyme s, we demons a e ha a a ie y o well-de ined ABC
mik o a m s a e polyme s is accessible ia his modula app oach. These exhibi ed
monomodal molecula weigh dis ibu ions wi h small dispe is ies close o 1.10 o e en
lowe .
The ob ained mik oa m s a e polyme s a e in e es ing new polyme s ega ding
hei bulk mo phologies and solu ion-based sel -assembly. Resul s om he sel -
assembly o hese ABC mik oa m s a e polyme s will be epo ed in subsequen publi-
ca ions. A u he ad an age is ha due o he use o anionic polyme iza ion mik oa m
s a e polyme s wi h a polybu adiene block a e accessible, which can a e wa d be
unc ionalized h ough hiol-ene click chemis y54 o used o selec i e c osslinking.5,55
Fu he mo e, he ABC mik oa m s a e polyme con aining a ms o polybu adiene,
poly(N,N-dime hylaminoe hyl me hac yla e) and poly(e hylene oxide) is a p omising
candida e in he ield o bio echnological applica ions like gene deli e y.56-58 Ou ap-
p oach enables he upscaling o he syn hesis o ABC mik oa m s a e polyme s o mo e
han one g am. Bo h syn he ic s eps o diblock and homopolyme syn hesis a e well-
es ablished polyme iza ion me hods, and no u he complex syn he ic p ocedu es a e
3 – A Modula Rou e o he Syn hesis o ABC Mik oa m S a Te polyme s
75
necessa y, as compa ed o o he me hods. Because o he s ong e sa ili y o click
chemis y and he inc easing amoun o publica ions dealing wi h i , we expec ou click-
DPE o o e a a ie y o new possibili ies in he design o no el cus om polyme a chi-
ec u es and ma e ials.
Suppo ing In o ma ion. Ma e ials sec ion, polyme iza ion p ocedu es, cha ac e iza ion
sec ion, cha ac e iza ion o ω-azido homopolyme s, click eac ion wi h poly( e -bu yl
me hac yla e) and discussion o he eac i i y o click-DPE owa d li ing P2VP-Li; UV- is
spec a o pe ylene-labeled diblock copolyme s, SEC aces o polybu adiene p ecu so s,
poly(e hylene oxide) and click eac ions, MALDI-ToF mass spec a o polybu adiene p e-
cu so s and an exempla ily 1H NMR spec um o µ-BT1S1. This In o ma ion is a ailable
ee o cha ge ia he In e ne a h p://pubs.acs.o g/.
Acknowledgmen s. This wo k was suppo ed by he Deu sche Fo schungsgemeinscha
wi hin SPP 1165 (Mu896/22). We hank Ch is o B. Ts e ano and Ma kus Müllne o
ui ul discussion. Melanie Fö sch, Annika P a enbe ge , and Ch is ophe V.
Syna schke a e acknowledged o pe o ming MALDI-ToF MS measu emen s and Ma ie -
a Böhm, Ka ha ina Neumann, and Robin Pe au o conduc ing SEC measu emen s. We
u he hank And é H. G öschel o p o iding one o he polys y ene homopolyme s,
S e an Reinicke o he syn hesis o he azidoace yl chlo ide, and Julia Ewe o RAFT
polyme iza ion o he PDMAEMA homopolyme . And eas S. Lang is acknowledged o
p o iding he azido- unc ionalized pe ylene bisimide.
3 – A Modula Rou e o he Syn hesis o ABC Mik oa m S a Te polyme s
76
3.5 Re e ences
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(3) Junnila, S.; Houbeno , N.; Hanski, S.; Ia ou, H.; Hi ao, A.; Hadjich is idis, N.; Ikkala, O. Mac omol-
ecules 2010, 43, 9071-9076.
(4) Ma sushi a, Y.; Hayashida, K.; Takano, A. Mac omol. Rapid Commun. 2010, 31, 1579-1587.
(5) Wal he , A.; Yuan, J.; Abe z, V.; Mülle , A. H. E. Nano Le . 2009, 9, 2026-2030.
(6) Song, J.; Shi, T.; Chen, J.; An, L. J. Phys. Chem. B 2010, 114, 16318-16328.
(7) Li, Z.; Hillmye , M. A.; Lodge, T. P. Langmui 2006, 22, 9409-9417.
(8) Li, Z.; Hillmye , M. A.; Lodge, T. P. Nano Le . 2006, 6, 1245-1249.
(9) Ia ou, H.; Hadjich is idis, N. Mac omolecules 1992, 25, 4649-4651.
(10) Sioula, S.; Tselikas, Y.; Hadjich is idis, N. Mac omolecules 1997, 30, 1518-1520.
(11) Ma oudis, A.; Hadjich is idis, N. Mac omolecules 2005, 39, 535-540.
(12) Fujimo o, T.; Zhang, H.; Kazama, T.; Isono, Y.; Hasegawa, H.; Hashimo o, T. Polyme 1992, 33,
2208-2213.
(13) Hücks äd , H.; Abe z, V.; S adle , R. Mac omol. Rapid Commun. 1996, 17, 599-606.
(14) Qui k, R. P.; Yoo, T.; Lee, B. J. Mac omol. Sci. 1994, 31, 911-926.
(15) Lambe , O.; Dumas, P.; Hu ez, G.; Riess, G. Mac omol. Rapid Commun. 1997, 18, 343-351.
(16) Lambe , O.; Reu enaue , S.; Hu ez, G.; Riess, G.; Dumas, P. Polym. Bull. 1998, 40, 143-149.
(17) Sai o, N.; Liu, C.; Lodge, T. P.; Hillmye , M. A. Mac omolecules 2008, 41, 8815-8822.
(18) Li, Z.; Hillmye , M. A.; Lodge, T. P. Mac omolecules 2004, 37, 8933-8940.
(19) Liu, C.; Hillmye , M. A.; Lodge, T. P. Langmui 2009, 25, 13718-13725.
(20) Abouelmagd, A.; Sugiyama, K.; Hi ao, A. Mac omolecules 2011, 44, 826-834.
(21) Ma yjaszewski, K.; Tsa e sky, N. V. Na . Chem. 2009, 1, 276-288.
(22) G ego y, A.; S enzel, M. H. P og. Polym. Sci. 2012, 37, 38-105.
(23) Huisgen, R. Angew. Chem., In . Ed. 1963, 2, 633-645.
(24) Binde , W. H.; Sachsenho e , R. Mac omol. Rapid Commun. 2008, 29, 952-981.
(25) Huisgen, R. Angew. Chem., In . Ed. 1963, 2, 565-598.
(26) Liu, H.; Li, C.; Liu, H.; Liu, S. Langmui 2009, 25, 4724-4734.
(27) Zhang, Y.; Liu, H.; Dong, H.; Li, C.; Liu, S. J. Polym. Sci., Pa A: Polym. Chem. 2009, 47, 1636-1650.
(28) Khanna, K.; Va shney, S.; Kakka , A. Mac omolecules 2010, 43, 5688-5698.
(29) Iskin, B.; Yilmaz, G.; Yagci, Y. J. Polym. Sci., Pa A: Polym. Chem. 2011, 49, 2417-2422.
(30) Zhang, Y.; Li, C.; Liu, S. J. Polym. Sci., Pa A: Polym. Chem. 2009, 47, 3066-3077.
(31) Gunay, U. S.; Du maz, H.; Gungo , E.; Dag, A.; Hizal, G.; Tunca, U. J. Polym. Sci., Pa A: Polym.
Chem. 2011, 729-735.
(32) Wong, E. H. H.; S enzel, M. H.; Junke s, T.; Ba ne -Kowollik, C. Mac omolecules 2010, 43, 3785-
3793.
(33) Wang, G.; Luo, X.; Liu, C.; Huang, J. J. Polym. Sci., Pa A: Polym. Chem. 2008, 46, 2154-2166.
(34) Ye, C.; Zhao, G.; Zhang, M.; Du, J.; Zhao, Y. Mac omolecules 2012, DOI: 10.1021/ma3015118.
(35) Schlosse , M.; Schaub, B. Chimia 1982, 36, 396-397.
(36) Tsuda, K.; Ishizone, T.; Hi ao, A.; Nakahama, S.; Kakuchi, T.; Yoko a, K. Mac omolecules 1993, 26,
6985-6991.
(37) Ausch a, C.; S adle , R. Polym. Bull. 1993, 30, 257-264.
(38) Ishizone, T.; Ueha a, G.; Hi ao, A.; Nakahama, S.; Tsuda, K. Mac omol. Chem. Phys. 1998, 199,
1827-1834.
(39) Qui k, R.; Yoo, T.; Lee, Y.; Kim, J.; Lee, B. Ad . Polym. Sci. 2000, 153, 67-162.
(40) Waack, R.; Do an, M. A. J. Am. Chem. Soc. 1969, 91, 2456-2461.
(41) Giebele , E.; S adle , R. Mac omol. Chem. Phys. 1997, 198, 3815-3825.
(42) Lang, A. S.; Neubig, A.; Somme , M.; Thelakka , M. Mac omolecules 2010, 43, 7001-7010.
(43) Hsieh, H. L.; Qui k, R. P. In Anionic Polyme iza ion: P inciples and P ac ical Applica ions; Ma cel
Dekke : New Yo k, 1996.
(44) Gondi, S. R.; Vog , A. P.; Sume lin, B. S. Mac omolecules 2007, 40, 474-481.
(45) Man o ani, G.; Ladmi al, V.; Tao, L.; Haddle on, D. M. Chem. Commun. 2005, 2089-2091.
(46) Reinicke, S.; Schmalz, H. Colloid Polym. Sci. 2011, 289, 497-512.
(47) Coessens, V.; Ma yjaszewski, K. J. Mac omol. Sci. 1999, 36, 667-679.
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(48) Ba ne -Kowollik, C.; Du P ez, F. E.; Espeel, P.; Hawke , C. J.; Junke s, T.; Schlaad, H.; Van Camp, W.
Angew. Chem., In . Ed. 2011, 50, 60-62.
(49) Du , C. J.; Emme ling, S. G. J.; Lede hose, P.; Kaise , A.; B andau, S.; Klimpel, M.; Ba ne -Kowollik,
C. Polym. Chem. 2012, 3, 1048-1060.
(50) Inglis, A. J.; Pie a , P.; Mulle , T.; B ase, S.; Ba ne -Kowollik, C. So Ma e 2010, 6, 82-84.
(51) Zhong, M.; Ma yjaszewski, K. Mac omolecules 2011, 44, 2668-2677.
(52) Roo e s, J.; Hadjich is idis, N.; Fe e s, L. J. Mac omolecules 1983, 16, 214-220.
(53) Plampe , F. A.; Schmalz, A.; Peno -Chang, E.; D echsle , M.; Jusu i, A.; Ballau , M.; Mülle , A. H.
E. Mac omolecules 2007, 40, 5689-5697.
(54) Jus ynska, J.; Ho dyjewicz, Z.; Schlaad, H. Polyme 2005, 46, 12057-12064.
(55) Wal he , A.; Goldmann, A. S.; Yelamanchili, R. S.; D echsle , M.; Schmalz, H.; Eisenbe g, A.; Mülle ,
A. H. E. Mac omolecules 2008, 41, 3254-3260.
(56) an de We e ing, P.; Che ng, J.-Y.; Talsma, H.; Hennink, W. E. J. Con olled Release 1997, 49, 59-
69.
(57) Schallon, A.; Jé ôme, V.; Wal he , A.; Syna schke, C. V.; Mülle , A. H. E.; F ei ag, R. Reac . Func .
Polym. 2010, 70, 1-10.
(58) Majewski, A. P.; Schallon, A.; Jé ôme, V.; F ei ag, R.; Mülle , A. H. E.; Schmalz, H.
Biomac omolecules 2012, 13, 857-866.
3 – A Modula Rou e o he Syn hesis o ABC Mik oa m S a Te polyme s
84
26 28 30 32 34 36 38
0.0
0.2
0.4
0.6
0.8
1.0
no malied RI signal
V
e
[mL]
cBT2
PS1-N3
click: 3.25 h
click: 11.5 h
and 48 h
Figu e 3-S5. THF-SEC (RI-signal) o samples wi hd awn du ing equimola click eac ion be ween cBT2 and
PS1-N3 a e 3.25 h (-), 11.5 h and 48 h (···).
26 28 30 32 34 36
0.0
0.2
0.4
0.6
0.8
1.0 cBT2
PS3-N3
click: 1 eq./3.25 h
click: 1 eq./48 h
click: 1.5 eq./25 h
no malized RI signal
V
e
[mL]
Figu e 3-S6. THF-SEC (RI signal) o click eac ion be ween cBT2 and PS3-N3 wi h u he addi ion o 0.5
equi PS3-N3 48 h a e s a o he click eac ion. 25 h a e addi ion o he second po ion o PS3-N3 a
inal sample was aken o SEC.

3 – A Modula Rou e o he Syn hesis o ABC Mik oa m S a Te polyme s
85
Figu e 3-S7. 1H NMR spec um o µ-BT1S1 in CDCl3. The cha ac e is ic signals o he espec i e polyme
blocks a e highligh ed.
26 28 30 32 34 36
0.0
0.2
0.4
0.6
0.8
1.0
no malized RI signal
V
e
[mL]
cBT2
PEO-N3
click: 1 eq./1.75 h
click: 1. eq./24 h
click: 1.5 eq./3.5 h
and click: 1.7 eq./1.75 h
Figu e 3-S8. THF-SEC (RI signal) o click eac ion be ween cBT2 and PEO-N3 wi h s epwise addi ion o PEO-
N3. Fu he 0.5 equi PEO-N3 we e added 24 h a e s a o he click eac ion and 3.5 h la e u he 0.2
equi PEO-N3 we e added. The co esponding eac ion imes a e ela i e o he poin o addi ion o a u -
he PEO-N3 po ion. The excess o PEO-N3 is no isible as he PEO is adso bed a he silica column used
o emo ing coppe ca alys .
3 – A Modula Rou e o he Syn hesis o ABC Mik oa m S a Te polyme s
86
3.6.3 Tes Polyme iza ion wi h P2VP and Click-DPE
In con as o polybu adienyl and polys y yl li hium, he li ing anion o poly(2-
inylpy idine) is less nucleophilic and hence, he ini ial assump ion was ha i is no able
o a ack excess click-DPE. This would lead o he desi ed diblock copolyme s wi h only
one click-DPE a he block junc ion. I he 2VP would inco po a e mo e uni s o click-DPE
he diblock would ca y mo e han on alkyne unc ion, which would esul in s a
e polyme s wi h mo e han h ee a ms. Hogen-Esch e al. epo ed ha he endcapping
o P2VPLi wi h unsubs i u ed DPE is an equilib ium eac ion9 and ha e en he addi ion
o a la ge excess o 1,1-diphenyle hylene o li ing poly(2- inylpy idine) does no lead o
a signi ican endcapping o he anion.10 Hi ao e al. showed ha silyl-p o ec ed hyd oxyl-
unc ionalized DPE, 1-(3- e -bu yldime hylsilyloxyme hylphenyl)-1-phenyle hylene did
no unde go copolyme iza ion wi h li ing poly(2- inylpy idine) anions.11 Also, in p e ious
es s on he endcapping o poly(2- inylpy idine) wi h DPE unc ionalized polybu adiene
mac omonome s, we ound no signi ican coupling be ween he wo polyme ic chains.
The e o e, a es eac ion was conduc ed o e i y whe he he alkyne-subs i u ed click-
DPE can be a acked by a li ing P2VPLi as a esul o he al e ed elec onic con igu a ion
o he DPE de i a i e. Fo his pu pose, 2- inylpy idine was polyme ized in THF a -70 °C
wi h sec-BuLi as ini ia o , yielding a molecula weigh o 5 000 g/mol. Then, a 2- old ex-
cess o he alkyne- unc ionalized click-DPE was added a he same empe a u e. Di ec ly
a e injec ion, he colo o he P2VPLi anion changed om ed o iole gi ing a i s
quali a i e indica ion o he addi ion o he click-DPE. 1H NMR de e mined he deg ee
o alkyne unc ionaliza ion as a ound 98%.
MALDI-ToF MS suppo ed a quan i a i e end- unc ionaliza ion (Figu e 3-S9A). Be o e
addi ion he Mn o he P2VP was 4 750 g/mol. A e 1 h eac ion wi h click-DPE he Mn
inc eased o 5 230 g/mol. These alues indica e ha click-DPE addi ion ook place quan-
i a i ely, conside ing he accu acy o he de e mina ion me hod. Mo eo e , he mo-
lecula weigh dis ibu ion shi ed comple ely and in he case o he e lec on mode a
dis inc shi o he indi idual peaks was no iceable (Figu e 3-S9B). This p o ed he p es-
ence o only one species a e addi ion o click-DPE. The shi o he peaks wi h a di e -
ence o a ound 4.5 g/mol is in good ag eemen wi h he expec ed 3 g/mol di e ence
(M(2VP) = 105.14 g/mol, M(click-DPE) = 318.53 g/mol; Δ = 318.53 g/mol - 3 x 105.14
3 – A Modula Rou e o he Syn hesis o ABC Mik oa m S a Te polyme s
87
g/mol = 3.11 g/mol). Fo example, he peak a m/z = 4791.6 in he P2VP p ecu so , i.e.
be o e addi ion o click-DPE, co esponds o 44 epea ing uni s o 2VP wi h a sec-bu yl
esidue and Ag+ as coun e -ion. This is in acco dance wi h he heo e ical m/z alue o
4792.0. In he spec um a e click-DPE addi ion, he modi ied P2VP wi h he same num-
be o epea ing uni s and an addi ional click-DPE was de ec ed a m/z = 5111.1. Also
he e, his alue is consis en wi h he expec ed 5110.5 (= 4792.0 + 318.5). Hence, click-
DPE adds o li ing poly(2- inylpy idine) anions quan i a i ely, in con as o o he DPE
de i a i es epo ed in li e a u e.
Figu e 3-S9. MALDI-ToF MS spec a o poly(2- inylpy idine) be o e (black line) and a e addi ion o click-
DPE (cDPE, ed line), eco ded in linea (A) and e lec on mode (B) wi h AgTFA as ioniza ion agen .
In summa y, he anion o he alkyne- unc ionalized DPE has a nucleophilici y compa able
o P2VPLi, whe eas he anion o unsubs i u ed DPE is mo e nucleophilic han P2VPLi.
One eason o his migh be he elec on wi hd awing e ec o he e -
bu yldime hylsilyl g oup which leads o a educ ion o he elec on densi y in he double
bond and hus dec eases he nucleophilici y o he click-DPE as compa ed o he
unsubs i u ed DPE.12 As he li ing anion o he click-DPE is able o s a he polyme iza-
ion o P2VP and click-DPE also adds o P2VPLi, i is possible o copolyme ize P2VP and
click-DPE. The e o e, i he click-DPE is used in a sligh excess and no unde equimola
condi ions, he DPE de i a i e migh also be inco po a ed in o mos p obably a e con-
sump ion o all 2VP monome a he end o he P2VP block o he aimed PB-b-P2VP
diblock copolyme s. In con as o bu adiene and s y ene, me hac yla es a e known o
be no nucleophilic enough o a ack diphenyle hylene and i s de i a i i es.13,14 Conse-
4780 4800 4820
VP44 VP41cDPE1
~ 4.5 g/mol
4750 4800 4850 4900 4950
VP45
VP42cDPE1
VP41cDPE1
VP44
m/z
2000 4000 6000 8000
P2VP-p ec
P2VP-DPE
i P2VP-p ec
i P2VP-DPE
m/z
3 – A Modula Rou e o he Syn hesis o ABC Mik oa m S a Te polyme s
88
quen ly, monome s like BMA and DMAEMA can be polyme ized as second block o ob-
ain well-de ined diblock copolyme s wi h exac ly one alkyne unc ion a he block junc-
ion.
Due o he al e ed eac i i y o he click-DPE owa d li ing P2VP-Li compa ed o o he
DPE de i a i es bo h α- and ω-alkyne modi ied P2VP homopolyme s a e accessible. In
addi ion, alkyne mid- unc ionalized diblock copolyme s wi h poly(2- inylpy idine) as i s
and a me hac yla e- ype monome as second block can be syn hesized.
3.6.4 Cha ac e iza ion o ω-Azido Homopolyme s
Besides he quali a i e p oo o he p esence o an azido unc ion ia IR (Figu e 3-S10)
he deg ee o azide- unc ionaliza ion was addi ionally ied o be quan i ied by MALDI-
ToF MS o 1H NMR.
4000 3500 3000 2500 2000 1500 1000
P
BMA-N3
PDMAEMA-N3
PEO-N3
ela i e ansmission
wa enumbe cm-1
PS-1-N3
Figu e 3-S10. IR spec a o he co esponding homopolyme s show he cha ac e is ic s e ching ib a ion
o he azido g oup a ~ 2098 cm-1.
In case o PS1-N3 and PEO-N3 mass spec ome y in e lec on mode was possible. The
espec i e spec a a e shown in Figu e 3-S11 and 3-S12. In he case o he azido-
e mina ed PS1-N3 only a small peak esembling he desi ed unc ional species is p e-
sen . As al eady epo ed in li e a u e o ma ion o pos sou ce me as able ions om
azido- unc ionalized polyme s is possible unde high lase powe s in e lec on mode.15
3 – A Modula Rou e o he Syn hesis o ABC Mik oa m S a Te polyme s
89
The e o e, by compa ing he ela i e in ensi ies o he azido- unc ionalized species and
he co esponding me as able ion wi h he in ensi y o he un unc ionalized species, as
main popula ion he azido- e mina ed polys y ene is clea ly concluded. We ha e o
men ion he e ha he peak a he le side o he p o on- e mina ed polys y ene could
no be assigned clea ly.
3320 3360 3400 3440 3480
[PS29H+Ag]+[PS30H+Ag]+
[PS31N3-N2+Ag]+
me as able
[PS30N3-N2+Ag]+
me as able
[PS31N3+Ag]+
O
O
N3
x
m/z
= PSxN3
[PS30N3+Ag]+
 ~ 104
Figu e 3-S11. MALDI-ToF MS spec um o PS1-N3 eco ded in e lec on mode wi h AgTFA as ioniza ion
agen .
In he MALDI spec um o PEO-N3 (Figu e 3-S12) wo se ies o peaks we e p esen . He e,
he main popula ion esembles he azido- e mina ed PEO. The second popula ion could
be a ibu ed o azido- e mina ed PEO wi h a p o on as coun e ion. Ano he possible
explana ion could be deduced om SEC measu emen s, whe e a small second peak a
lowe elu ion olume was de ec ed (a ound 6 w .%, see Figu e 3-S13). This o igina es
om minimal esidual amoun s o hionyl chlo ide which was used o he syn hesis o
he azidoace yl chlo ide and is ha d o emo e comple ely despi e ho ough pu i ica-
ion.1 This popula ion canno ake pa in he click eac ion. Fo he molecula cha ac e -
iza ion, only he majo peak was aken in o conside a ion. The molecula weigh de e -
mined by MALDI-ToF MS was consis en wi h he alues om SEC. The e o e, he second
popula ion in MALDI can be in e p e ed as he lowe molecula weigh side o he cou-
pling p oduc wi h hionyl chlo ide. E en hough he main peak co esponds o he de-

3 – A Modula Rou e o he Syn hesis o ABC Mik oa m S a Te polyme s
90
si ed unc ionalized PEO, one has o no ice ha chains whe e HN3 was elimina ed (Δ ~43
g/mol) and chains which we e e mina ed wi h a p o on ins ead o he acid chlo ide (Δ
~5 g/mol) would no be dis inguishable and could possibly be p esen .
6180 6200 6220 6240 6260
[PEO126SO+Ag]+[PEO127SO+Ag]+
= PEOx+ySO
OS
O
O
x y
[PEO133N3+H]+[PEO134N3+H]+
 ~ 44
= PEOxN3
O
O
N3
x
[PEO131N3+Ag]+
m/z
[PEO132N3+Ag]+
Figu e 3-S12. MALDI-ToF MS spec um o PEO-N3 eco ded in e lec on mode wi h AgTFA as ioniza ion
agen .
27 28 29 30 31 32 33 34
0.0
0.2
0.4
0.6
0.8
1.0
no malized RI signal
V
e
[mL]
PEO-N3
Figu e 3-S13. THF-SEC (RI signal) o azido- unc ionalized poly(e hylene oxide).
Bo h in case o P BMA-N3 and PDMAEMA-N3 endg oup de e mina ion was no possible
ia MALDI-ToF MS. In con as o P BMA-N3 o he DMAEMA homopolyme calcula ion
3 – A Modula Rou e o he Syn hesis o ABC Mik oa m S a Te polyme s
91
o he deg ee o azido- unc ionaliza ion was possible om he cha ac e is ic signals in
he 1H NMR spec um (Figu e 3-S14). Acco ding o he calcula ed alue o app oxima ely
96 %, quan i a i e azido- unc ionaliza ion o he polyme was assumed.
Figu e 3-S14. 1H NMR spec um o PDMAEMA-N3 in CDCl3. The cha ac e is ic signals o he monome uni
and chain ans e agen a e highligh ed.
3.6.5 Click Reac ion wi h ω-Azido-Func ionalized Poly( e -bu yl me hac y-
la e)
Since we also syn hesized an alkyne- unc ionalized diblock wi h DMAEMA as second
block (cBD), a µ-BDT mik oa m s a e polyme was achie able by click eac ion wi h he
azido- e mina ed P BMA. Simila o he click eac ions wi h PDMAEMA-N3, he eac ion
condi ions we e no op imized. The liga ion was conduc ed o 3 days wi h 1.3 equi o
azido- unc ionalized homopolyme o gua an ee 100 % conjuga ion o he diblock. The
SEC o he click-p oduc a e dialysis in me hanol/isop opanol (2/1 / ) is shown in Fig-
u e 3-S15 and a comple e shi o he molecula weigh dis ibu ion o he mik oa m s a
e polyme compa ed o he diblock e polyme was de ec ed. This demons a es he
e iciency o ou app oach. E en hough we we e no able o emo e all excess
homopolyme , we showed ha o ma ion o a µ-BDT mik oa m s a e polyme is possi-
3 – A Modula Rou e o he Syn hesis o ABC Mik oa m S a Te polyme s
92
ble s a ing om wo di e en diblock copolyme s. The molecula pa ame e s o he
ob ained ABC mik oa m s a e polyme a e summa ized in Table 3-3.
14 15 16 17 18 19
0.0
0.2
0.4
0.6
0.8
1.0
cBD
P
BMA-N3
µ
-BDT, dial.
no malized RI signal
Ve [mL]
Figu e 3-S15. Sal -THF-SEC (RI-signal) o he µ-BDT mik oa m s a e polyme s ob ained a e click eac ion
o alkyne- unc ionalized diblock cBD wi h he azido unc ionalized P BMA-N3.
3.6.6 Re e ences
(1) Reinicke, S.; Schmalz, H. Colloid Polym. Sci. 2011, 289, 497-512.
(2) Gondi, S. R.; Vog , A. P.; Sume lin, B. S. Mac omolecules 2007, 40, 474-481.
(3) Lang, A. S.; Neubig, A.; Somme , M.; Thelakka , M. Mac omolecules 2010, 43, 7001-7010.
(4) Eßwein, B.; Mölle , M. Angew. Chem. 1996, 108, 703-705.
(5) Schmalz, H.; Lanzendö e , M. G.; Abe z, V.; Mülle , A. H. E. Mac omol. Chem. Phys. 2003, 204,
1056-1071.
(6) Schmalz, A.; Hanisch, M.; Schmalz, H.; Mülle , A. H. E. Polyme 2010, 51, 1213-1217.
(7) Man o ani, G.; Ladmi al, V.; Tao, L.; Haddle on, D. M. Chem. Commun. 2005, 2089-2091.
(8) Coessens, V.; Ma yjaszewski, K. J. Mac omol. Sci. 1999, 36, 667-679.
(9) Hela y, G.; Fon anille, M.; Khan, I. M.; Hogen-Esch, T. E. Mak omol. Chem. 1989, 190, 341-348.
(10) Yin, R.; Hogen-Esch, T. E. J. Polym. Sci., Pa A: Polym. Chem. 1994, 32, 363-368.
(11) Hi ao, A.; Mu ao, K.; Abouelmagd, A.; Uema su, M.; I o, S.; Goseki, R.; Ishizone, T. Mac omole-
cules 2011, 44, 3302-3311.
(12) Tsuda, K.; Ishizone, T.; Hi ao, A.; Nakahama, S.; Kakuchi, T.; Yoko a, K. Mac omolecules 1993, 26,
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(13) Hsieh, H. L.; Qui k, R. P. In Anionic Polyme iza ion: P inciples and P ac ical Applica ions; Ma cel
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(14) Qui k, R.; Yoo, T.; Lee, Y.; Kim, J.; Lee, B. Ad . Polym. Sci. 2000, 153, 67-162.
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4 – “Woodlouse” S uc u es om µ-BVqT
93
4 – Coun e ion-Media ed Hie a chical Sel -Assembly o an
ABC Mik oa m S a Te polyme
And eas Hanisch, And é H. G öschel, Melanie Fö sch, Ma kus D echsle , Hi oshi Jinnai,
Thomas M. Ruhland, Felix H. Schache , and Axel H. E. Mülle
ABSTRACT: Di ec ed sel -assembly p ocesses o polyme ic sys ems ep esen a powe ul
app oach o he gene a ion o s uc u al hie a chy in analogy o biological sys ems.
He ein, we u ilize iiodide as a s ongly pola izable coun e ion o induce hie a chical
sel -assembly o an ABC mik oa m s a e polyme comp ising a polybu adiene (PB), a
poly( e -bu yl me hac yla e) (P BMA), and a poly(N-me hyl-2- inylpy idinium) (P2VPq)
segmen . He eby, he mik oa m a chi ec u e in conjunc ion wi h an inc easing a io o
iiodide e sus iodide coun e ions allows o a s epwise assembly o sphe ical micelles
as ini ial building blocks in o cylind ical s uc u es and supe s uc u es he eo . Finally,
mic ome e -sized mul icompa men pa icles wi h a pe iodic lamella ine s uc u e a e
obse ed, o which we in oduce he e m “woodlouse”. The coun e ion-media ed de-
c ease in hyd ophilici y o he co ona- o ming P2VPq block is he unde lying igge o
induce his hie a chical s uc u e o ma ion. All indi idual s eps and he co esponding
in e media es owa d hese well-de ined supe s uc u es we e in ensi ely s udied by
sca e ing and elec on mic oscopic echniques, including ansmission elec on
mic o omog aphy.
Keywo ds: ABC Mik oa m S a Te polyme , Hie a chical Sel -Assembly, Polyelec oly es,
Mul icompa men Micelles, Poly(2- inylpy idine)
4 – “Woodlouse” S uc u es om µ-BVqT
100
Be o e s udying he sel -assembly mechanism in de ail, we we e in e es ed in he in lu-
ence o he polyme s uc u e i sel on he ob ained agg ega es. The e o e, ma e ials o
simila chemical composi ion bu di e en a chi ec u e we e used, mo e p ecisely a
diblock copolyme (B
109
V
81
) and a linea iblock e polyme (B
1108
V
142
T
93
). Howe e , only
ill-de ined agg ega es we e ob ained om hese linea polyme s a e qua e niza ion
and compa able p epa a ion condi ions (see ep esen a i e mic og aphs o he iblock
e polyme in Figu e 4-S4). These indings demons a e ha he mik oa m a chi ec u e
i sel is an impo an c i e ion o he hie a chical sel -assembly in o subs uc u ed pa i-
cles. Hadjich is idis and co-wo ke s al eady showed bo h expe imen ally and by heo e -
ical in es iga ions ha he micelliza ion beha iou o A
2
B mik oa m sys ems is di e en
compa ed o linea AB diblock copolyme s due o opological di e ences a he co e-
co ona in e ace.
45
4.2.2.1 Hie a chical Supe s uc u e Fo ma ion
Acco ding o c yo-TEM (Figu e 4-1D), he “woodlouse” agg ega es can be p elimina ily
desc ibed as ei he supe s uc u es om cylind ical micelles o lamellae. Howe e , as
he pe iodici y o hese pa icles is in he size ange o he diame e obse ed o he
sphe ical micelles in Figu e 4-1B, we assume hese o ac as p ima y building blocks. The
di e en s uc u es obse ed would hen simply co espond o di e en le els o supe -
s uc u e o ma ion. Rega ding he o e all mo phology, simila s uc u es, such as la e -
ally s uc u ed esicles o laye ed s uc u es, we e al eady p edic ed by simula ions o
ABC mik oa m s a e polyme s wi h wo sol ophobic blocks.
46,47
Mo e de ailed in o ma-
ion abou he supe s uc u e o ma ion was gained om in es iga ions o he in e me-
dia e s uc u es ob ained unde compa able p epa a ion condi ions (Figu e 4-2A). He e,
he agg ega es clea ly consis o se e al in e wined and pa ially w apped-up cylind ical
micelles. Again, he dimensions o he cylinde s a e in good ag eemen wi h he diame-
e o he sphe ical micelles (d
cylinde
= 27.5 ± 2.5 nm, as compa ed o d
micelle
= 24.5 ± 2.0
nm), which co obo a es he assump ion ha sphe ical micelles a e indeed he unde ly-
ing building blocks. S aining wi h OsO
4
e eals a PB (o mixed PB/P BMA) co e o he
cylinde s (Figu e 4-2B). Subsequen ly, hese cylinde s align in a pa allel, ibbon-like ash-
ion, which we ega d as ano he in e media e le el on he way owa d highly pe iodic

4 – “Woodlouse” S uc u es om µ-BVqT
101
lamella “woodlice”. Ou assump ion o a mixed PB/P BMA co e is u he suppo ed by
he calcula ed phase seg ega ion pa ame e , o PB/P BMA, χN ~1.1.
48
Acco ding o he
heo y o phase sepa a ion o diblock copolyme s, his is in he diso de ed egime due
o he small deg ees o polyme iza ion o ou sys em.
49,50
Fu he mo e, cas ilms o PB-
b-P BMA diblock copolyme s wi h compa able molecula weigh s did no show any
phase sepa a ion in he bulk ( esul s no shown).
C yo-TEM shows highly in e wined and en angled cylind ical micelles (Figu e 4-2C). A
su p isingly highly egula packing o indi idual cylinde s can be obse ed in some cases,
highligh ed in he inse s and g ay scale analysis o Figu e 4-2C. Rema kably, some o he
s uc u es show long- ange o de and dimensions o up o 1 µm in leng h.

Figu e 4-2. TEM (A,B) and c yo-TEM mic og aphs (C) o in e media e micella s uc u es om µ-BVqT in
aqueous solu ion.
The inal polyme concen a ion was 0.2 g/L o TEM and 0.4 g/L o c yo-TEM. Whe eas
o (A) no s aining was pe o med, he sample in (B) was s ained wi h OsO
4
. He e, he g ay scale analysis o
he highligh ed a ea e eals a ibbon-like a angemen o cylinde s.
Wi h he example o hese in e media e s uc u es, we u he in es iga ed he in lu-
ence o wo o he pa ame e s du ing he p ocess o s uc u e o ma ion ( o de ails see
Suppo ing In o ma ion): (i) he solu ions we e he mally annealed, and (ii) he ime in
be ween qua e niza ion in dioxane and dialysis o wa e was inc eased o up o 1
mon h. Whe eas he mal annealing did no esul in highe s uc u al pe ec ion a all,
he s uc u es we e sligh ly mo e de eloped a e 1 mon h in dioxane p io o dialysis
(Figu e 4-S5). None heless, om all he TEM in es iga ions discussed so a , di e en
4 – “Woodlouse” S uc u es om µ-BVqT
102
le els o hie a chy om app oxima ely 20 nm o 1 µm we e de ec ed o µ-BVqT, s a -
ing om sphe ical micelles (le el 1), which agg ega e in o cylinde s (le el 2), and inally
in o mul ilamella supe s uc u es (le el 3).
4.2.2.2 Impo ance o he Na u e o he Coun e ion
I is known ha me hyl iodide can unde go pho odecomposi ion o o m ee iodine.
51
Based on his ac , one hypo hesis o he obse ed s uc u al di e ences was he p es-
ence o a ying amoun s o elemen a y iodine in he espec i e dioxane solu ions. In
combina ion wi h he iodide coun e ion, his hen o ms iiodide, I
3-
, which is a s ongly
pola izable coun e ion,
52,53
al eady desc ibed o qua e nized poly(4- inylpy idine)
(P4VPq).
54
The inc eased hyd ophobici y o P2VPq wi h iiodide as coun e ion is clea ly
demons a ed by DLS measu emen s o a P2VPq homopolyme in wa e (Figu e 4-S8).
Highe amoun s o added iodine led o an inc ease o he hyd odynamic adii, which we
assign o hyd ophobic in e ac ions. In con as , chlo ide o me hyl sul a e coun e ions
did no lead o he o ma ion o any hie a chically s uc u ed agg ega es o he µ-BVqT
sys em (see Suppo ing In o ma ion).
Howe e , addi ion o supplemen a y iodine o an aqueous micella solu ion o µ-
BVqT (Figu e 4-1B) did no induce signi ican s uc u al changes. We a ibu e his o wo
di e en easons: i s , owing o he educed co e dynamics, ea angemen p ocesses
a e supp essed. Second and mos impo an , iodine i sel is no soluble in wa e bu is
solubilized by he o ma ion o iiodide. Howe e , he iodide coun e ions a e mainly
loca ed wi hin he micella co ona – app oxima ely 90% acco ding o in es iga ions o
qua e nized poly(N,N-dime hylaminoe hyl me hac yla e) s a s
55
– leading o e y slow
exchange p ocesses. Consequen ly, we added di e en amoun s o iodine o he µ-BVqT
solu ion in dioxane p io o dialysis. The samples we e allowed o equilib a e o 2 h o
gua an ee he con e sion o iiodide and hen dialyzed o wa e . Al eady he addi ion
o 0.08 equi o I
2
induced d as ic s uc u al changes (Figu e 4-3A), as wo m-like micelles
and elonga ed supe s uc u es we e obse ed in con as o sphe ical micelles in he
absence o iodine (Figu e 4-1B). Again, he diame e o hese cylind ical agg ega es e-
e s o he ini ially obse ed sphe ical micelles (d
micelle
= 24.5 ± 2.0 nm and d
cylinde
= 25.0
± 2.0 nm). The co ona- o ming P2VPq block can be clea ly dis inguished in c yo-TEM
4 – “Woodlouse” S uc u es om µ-BVqT
103
(inse in Figu e 4-3A and Figu e 4-S9A). Fo 0.25 equi , almos exclusi ely supe s uc-
u es om agg ega ed and in e wined cylind ical micelles a e ound. In addi ion, ewe
p o usions and an inc eased endency o he cylinde s o o m meande -like s uc u es
we e obse ed. The inse in Figu e 4-3B depic s an a ea whe e he cylinde s o m p e-
s ages o ibbons. When 0.42 equi o I
2
was added, “woodlouse” agg ega es wi h a pe-
iodic, mul ilaye ed s uc u e we e ound (d
lam
= 19.5 ± 1.0 nm, Figu e 4-3C). This pa e n
is also clea ly isible in c yo-TEM, accompanied by a eas whe e he lamellae a e less
densely packed (highligh ed a ea in Figu e 4-S9B) o pa icles which seem o be apped
as cylind ical supe s uc u es (inse in Figu e 4-S9B). A mino ac ion o micelles and
cylinde s was ound, as well.

Figu e 4-3. TEM mic og aphs om 0.2 g/L aqueous micella solu ions o µ-BVqT a e dialysis in he p es-
ence o di e en amoun s o iodine. The solu ions we e p epa ed wi h 0.08 (A), 0.25 (B) and 0.42 (C) equi
o iodine wi h espec o P2VPq monome uni s. The inse in (A) shows he co esponding c yo-TEM mi-
c og aph. The schema ic illus a ions ep esen he dominan agg ega e mo phology. Fo he espec i e
sample wi hou addi ional iodine, see Figu e 4-1B.
To e alua e his lamella packing wi hin he pa icles in mo e de ail, addi ional SAXS
measu emen s we e conduc ed om eeze-d ied powde s o he sample depic ed in
Figu e 4-3C. The SAXS pa e n (Figu e 4-4A) shows peaks wi h a q a io o 1:2:3, ep e-
sen ing he [100], [200], and [300] e lec ions, hus con i ming he lamella s uc u e.
The long pe iod was calcula ed o d
lam
= 20.0 ± 1.5 nm and is in pe ec ag eemen wi h
he alues obse ed in TEM (d
lam
= 19.5 ± 1.0 nm). In he SAXS pa e n o he in e medi-
a e s uc u e (as shown in Figu e 4-S5), he e lec ions we e less p onounced (Figu e 4-
4B). This was al eady expec ed om he TEM images (Figu e 4-S5), which e eal a less
egula a angemen . Howe e , he assump ion o an o e all lamella mo phology and
he p esence o he [100] and [200] e lec ions allow he calcula ion o d
lam
= 22.5 ± 2.0
4 – “Woodlouse” S uc u es om µ-BVqT
104
nm. Compa able long pe iods om “woodlice” and agg ega ed cylinde s u he suppo
ou p oposed mechanism o supe s uc u e o ma ion.
Figu e 4-4. SAXS pa e n o a eeze-d ied powde om (A) he “woodlouse” s uc u e (Figu e 4-3C) and
(B) he in e media e s uc u e (Figu e 4-S5). The in ege numbe s indica e he ela i e e lex posi ions,
and he inse in A depic s he sca e ing pa e n obse ed a he 2D de ec o .
These di e en le els o hie a chical sel -assembly o µ-BVqT in o sphe ical micelles
(le el 1), ollowed by cylinde s (le el 2), supe s uc u es he eo and, inally, he s acking
and back- olding o lamellae in o compa men alized mic ome e -sized polyme pa i-
cles (le el 3) can be a ibu ed o su ace minimiza ion due o dec easing hyd ophilici y
o he P2VPq co ona igge ed by he p esence o iiodide coun e ions. He eby, he su-
pe s uc u e o ma ion o lamellae ia olding (o s acking) is suppo ed by simula ions
on he sphe e-cylinde -lamellae ansi ion in diblock copolyme sys ems.
56
As we a e
mos p obably dealing wi h non-equilib ium s uc u es o med du ing dialysis, he old-
ed cylinde s a e supposed o be ansien in e media e s uc u es on he way owa d
lamellae. Simila s uc u es we e al eady epo ed o linea ABC iblock e polyme s,
whe e ei he he addi ion o a diamine in he case o poly(ac ylic acid) as solubilizing
block
31-33
o changes in sol en quali y o he P2VP co ona
23
igge ed he o ma ion o
supe s uc u es. Howe e , in ou case, his is clea ly caused by changes in he
pola izabili y o he coun e ion, igge ed by he addi ion o iodine. The amoun o
iiodide ep esen s he essen ial igge he e. Bo h he assembly pa hway and a delica e
balance o iodide/ iiodide egula e s uc u al p ecision and he o e all colloidal s abili y
o he subs uc u ed pa icles. Fu he mo e, he e, he well-de ined compac s uc u es
4 – “Woodlouse” S uc u es om µ-BVqT
105
clea ly e ol e h ough a complex agg ega ion and usion ia cylind ical building uni s in
con as o he s acking o disk-like s uc u es as epo ed in li e a u e.
23,31-33
The sys em
p esen ed he e is ela i e simple as no sophis ica ed p epa a ion pa hways u ilizing
bi unc ional addi i es ha e o be applied, and he s uc u es a e ob ained in aqueous
solu ion a he han in sol en mix u es. Also, he di ec ed sel -assembly is induced by
he mono alen coun e ion, and he s uc u al in eg i y is a he una ec ed by he pH o
he solu ion (see agg ega es wi hin acidic media o pH 3 as depic ed in Figu e 4-S10)
4.2.3 S uc u al Cha ac e iza ion o “Woodlouse” Agg ega es
So a , we ha e desc ibed he iiodide-media ed hie a chical sel -assembly o µ-BVqT
in o compa men alized pa icles. The highly pe iodic in e nal ine s uc u e is con i med
by g ay-scale analysis o he TEM mic og aphs o indi idual pa icles (Figu e 4-5A). He e,
he da ke domains co espond o he P2VPq phase con aining iodide/ iiodide
coun e ions (d
1
= 8 nm), whe eas he con as is in e ed when s aining wi h OsO
4
was
pe o med (selec i e o he PB phase, d
2
= 11 nm Figu e 4-5B). The wide lamellae p e-
sumably consis o a mixed P BMA/PB phase as al eady discussed abo e.
In c yo-TEM, e en h ee di e en epea ing dis ances a e isible (Figu e 4-5C). He e,
he obse ed pe iodici ies can be explained in a simila way. The 8 nm o d
2
ep esen a
mixed phase o PB and P BMA, which is sligh ly b oadened in TEM (d
2
in Figu e 4-5B), as
he lamella is la ened and collapsed on o he ca bon ilm in he d ied s a e. On he
o he hand, bo h d
1A
and d
1B
ep esen P2VPq, se ing as he co ona o he mixed
PB/P BMA domains. A he in e ace (d
1A
), he densi y o P2VPq chains is highe as com-
pa ed o he pe iphe y (d
1B
), leading o an inc eased elec on densi y. The p oposed
chain packing and he co esponding dimensions a e illus a ed in Figu e 4-5D. He eby,
he indi idual lamella shee s o he supe s uc u es can ei he s ack (whi e a ow in
Figu e 4-5C) o back- old (black a ows in Figu e 4-5C), leading o “open” o “closed”
s uc u es a he edge o he pa icles.

4 – “Woodlouse” S uc u es om µ-BVqT
106
Figu e 4-5. TEM mic og aphs o “woodlouse” agg ega es o µ-BVqT
ob ained ia dialysis om dioxane in o
wa e (A,B). The concen a ion was 0.1 g/L. In (A), he con as eme ges solely om he iodide coun e ion
o he P2VPq phase, whe eas (B) was s ained wi h OsO
4
. In c yo-TEM (C), a egula pa e n o h ee dis-
ances is isible. The concen a ion was 0.6 g/L. The co esponding g ay scale analyses a e shown below
he mic og aphs. The p oposed a angemen o he mik oa m s a e polyme s is illus a ed in (D).
We addi ionally pe o med c yo-TEM a di e en il angles (Figu e 4-S11 and ideo 4-
S3). The eby, he in luence o he woodlouse o ien a ion wi hin he i i ied ilm was
examined, and om he p ojec ions a di e en il angles, a ci cula c oss sec ion o he
agg ega es can be clea ly deduced. Again, he p esence o la wo-dimensional assem-
blies can be excluded, which is addi ionally suppo ed by SEM o he d ied pa icles (Fig-
u e 4-S12). In he c yo-TEM il images, he in e nal ine s uc u e is only isible i he
pa icles a e o ien ed pe pendicula o he beam di ec ion. I he s age is il ed u he ,
he s uc u al ea u es blu and, inally, disappea comple ely. The ac ha such s uc-
u al ea u es a e only isible unde speci ic iewing angles has al eady been obse ed.
57
C oss-sec ional analysis o he “woodlice” wi hin hin ilm cu s o epoxy esin embed-
ded pa icles (Figu e 4-6A and 4-S13) clea ly showed a pe iodic ine s uc u e, u he
con i ming ou assump ion ha he pa icles a e no hollow. When he sample was
ea ed wi h OsO
4
(s aining o PB, Figu e 4-6A), undula ed lamellae a e isualized as al-
4 – “Woodlouse” S uc u es om µ-BVqT
107
eady discussed o he in e media e s uc u es. The a he undula ed shape o he
PB/P BMA lamella migh be ela ed o pa ial demixing o PB and P BMA, despi e he
a he low χN. This could be a consequence o he longe DP o he PB block (109) as
compa ed o P BMA (DP = 53), as well as di e en χ
o he PB/P2VP and he
P BMA/P2VP in e ac ions, leading o minimiza ion o he PB/P2VP in e ace.
48,58
Addi-
ionally, om DSC measu emen s o he mik oa m s a e polyme , he p esence o a T
g
a -2 °C also hin s owa d he p esence o a sepa a ed PB phase in he bulk s a e (Figu e
4-S14). This leads o a di ec P BMA/P2VPq in e ace, accompanied by an in e ace o
P2VPq wi h he adjacen mixed PB/P BMA phase and, inally, a pu e PB domain wi hou
a PB/P2VPq in e ace. The p oposed a angemen o he cons i u ing segmen s is illus-
a ed in Figu e 4-6B. S aining wi h OsO
4
enhances con as mainly in he PB phase, bu
also he mixed phase appea s da ke (Figu e 4-6A), whe eas he pu e P BMA domains
appea b igh e . Simila ly, he TEM mic og aphs o he cylind ical in e media e agg e-
ga es unde he same sample p epa a ion me hod also hin owa d an undula ed phase
bounda y (Figu e 4-S6B).
Finally, he olume mo phology o he “woodlice” was in es iga ed using TEM omo-
g aphy (TEMT). We he e o e p epa ed hicke slices (~150 nm) o he esin-embedded
sample and pe o med s aining wi h OsO
4
o p o ide maximum con as . In Figu e 4-6C,
a h ee-dimensional econs uc ion o a slice o a woodlouse pa icle wi h iew in o he
lamella bulk mo phology is shown. Addi ionally, Figu e 4-6D shows h ee di e en slices
o he same econs uc ion o a single pa icle. Bo h h ee-dimensional econs uc ions
clea ly con i m he p esence o lamellae wi h an undula ed su ace h oughou he en-
i e sample (also see ideo 4-S4). He eby, he o ma ion o well-de ined lamella s uc-
u es as compa ed o micella clus e s (obse ed o linea polyme s; see Figu e 4-S4) is
p obably a di ec consequence o he mik oa m a chi ec u e. In acco dance wi h bo h
heo y and expe imen al wo k,
59
he inc eased segmen al densi y has a dis inc i e e ec
on he su ace cu a u e and, in he case o ou sys em, acili a es he o ma ion o la-
mellae wi h low su ace cu a u e.
4 – “Woodlouse” S uc u es om µ-BVqT
108
Figu e 4-6. (A) TEM mic og aph o 50 nm hick cu s om eeze-d ied and embedded samples o µ-BVqT
agg ega es, s ained wi h OsO
4
. (B) Schema ic illus a ion o he block a angemen wi hin he “woodlouse”
s uc u e is depic ed, wi h he wo possibili ies o ben (uppe pa ) and s acked lamellae (lowe pa ). The
g ay a eas esemble he P2VPq phase; P BMA is ed, and PB is blue. The iole domains ep esen a mixed
PB/P BMA phase. TEM omog aphy 3D econs uc ions o a slice o he “woodlouse” s uc u e (C) and
c oss-sec ional analysis o a single pa icle (D). The omog aphy images we e ob ained om a 150 nm
hick cu , which was addi ionally ea ed wi h OsO
4
o selec i ely s ain he mixed PB/P BMA phase (plo -
ed in g een). The app oxima e leng h o he long ma ked edge o he econs uc ions is 280 nm in (C) and
220 nm in (D).
4 – “Woodlouse” S uc u es om µ-BVqT
109
4.3 Conclusions
We ha e demons a ed he hie a chical sel -assembly o an ABC mik oa m s a
e polyme in o subs uc u ed pa icles o up o 1µm in size, which we e m “wood-
louse” pa icles. Sphe ical micelles wi h a mixed PB/P BMA co e and a P2VPq co ona ac
as he basic building blocks (le el 1). S epwise agg ega ion o hese esul s in cylind ical
micelles (le el 2), ollowed by supe s uc u es he eo , and inally compa men alized
pa icles o up o 1 µm in size. These pa icles ea u e a highly pe iodic, lamella ine
s uc u e (le el 3). The p esence and amoun o iiodide as a highly pola izable
coun e ion o he P2VPq co ona is an essen ial igge o induce his supe s uc u e
o ma ion in o di e en le els o hie a chy (Figu e 4-7). All in e media es o inc easing
hie a chy in ol ed on he way o he inal “woodlice” a e isualized by TEM and c yo-
TEM. The iodide/ iiodide sys em is an elegan app oach o di ec ing he hie a chical
sel -assembly o such ma e ials. The na u e o he coun e ion, he mik oa m s a a chi-
ec u e, and he assembly pa hway a e essen ial pa ame e s and in luence s uc u al
pe ec ion and he inal mo phology. To ecapi ula e, a de ailed unde s anding o he
sel -assembly mechanism in o complex supe s uc u es was ob ained, which bea s uc-
u al simila i ies o biological sys ems such as mi ochond ia. Applying hese esul s o
o he mik oa m s a e polyme sys ems wi h highe segmen al incompa ibili y migh
lead o comple ely phase-sepa a ed co es and ep esen s an in e es ing app oach o
co e-compa men alized s uc u es o complex shape. Fu he unc ionaliza ion and
modi ica ion o hese s uc u es will enable he p epa a ion o a a ie y o s imuli-
esponsi e highly s uc u ed ma e ials wi h de ined in e nal pe iodici y.
The ques ion a ises whe he his app oach is applicable o o he mik oa m s a sys-
ems con aining polyca ionic segmen s in gene al o whe he he combina ion o P2VPq
and a “dynamic”, low T
g
segmen like PB is a p e equisi e. This will be he subjec o u-
u e wo k. The use o iodide/ iiodide as a se sc ew o di ec he sel -assembly o di e -
en ma e ials in o well-de ined hie a chical supe s uc u es would be ad an ageous and
desi able.
4 – “Woodlouse” S uc u es om µ-BVqT
116
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4 – “Woodlouse” S uc u es om µ-BVqT
119
4.6 Suppo ing In o ma ion
4.6.1 Addi ional Expe imen al Sec ion
Syn hesis
Qua e niza ion o 2-Vinylpy idine Homopolyme s (P2VP) and P epa a ion o Aqueous
Solu ions
The qua e niza ion p ocedu e was simila o he me hod desc ibed o he mik oa m
s a e polyme wi h sligh modi ica ions. A e h ee days o eac ion wi h me hyl iodide
10 ol% o wa e we e added o he pa ially p ecipi a ed eac ion mix u e in dioxane
and i was allowed o s i o an addi ional day. A e wa d, i was i s dialyzed o a mix-
u e o dioxane:wa e (90:10) and hen he sol en composi ion was g adually inc eased
o (80:20). The ob ained s ock solu ion in he dioxane:wa e mix u e was a e wa d dia-
lyzed o wa e . The iiodide complexes we e p epa ed in he same manne as desc ibed
in he manusc ip .
P epa a ion o µ-BVqT wi h Di e en Coun e ions
The exchange o he iodide coun e ion wi h chlo ide was achie ed by dialysis o he
dioxane s ock solu ion o 50 mM solu ion o LiCl in THF. A e wa d he solu ion was dia-
lyzed agains pu e THF o emo e excess sal . Be o e dialysis o wa e , he sol en was
again changed o dioxane h ough dialysis.
The qua e niza ions wi h dime hyl sul a e we e conduc ed ei he in THF o dioxane. A
polyme solu ion was p epa ed wi h a concen a ion o 2 g/L and hen degassed o 15
minu es. A e wa d, 10 equi o dime hyl sul a e ega ding 2VP uni s we e added and
he eac ion mix u e was allowed o s i a 40 °C o 3 days. Finally he solu ion was pu i-
ied om he excess qua e niza ion agen by dialysis wi h he espec i e eac ion me-
dium. A e dilu ion o a concen a ion o 1 g/L he solu ions we e dialyzed o wa e .
Cha ac e iza ion
Size Exclusion Ch oma og aphy (SEC)
SEC measu emen s we e pe o med on a se o 30 cm SDV-gel columns (5 µm bead size,
wi h po e sizes o 10
5
, 10
4
, 10
3
and 10
2
Å) using e ac i e index and UV (λ = 254 nm)
4 – “Woodlouse” S uc u es om µ-BVqT
120
de ec ion. THF was used as eluen a a low a e o 1 mL/min. Toluene was used as in-
e nal s anda d and he sys em was calib a ed wi h PS and 1,4-PB s anda ds.
1
H NMR Spec oscopy
1
H NMR spec a we e eco ded on a B uke Ul ashield 300 spec ome e a an ope a -
ing equency o 300 MHz. CDCl
3
was used as sol en and e ame hylsilane as in e nal
s anda d.
Ma ix-Assi ed Lase Deso p ion Ioniza ion Time-o -Fligh Mass Spec ome y (MALDI-
ToF MS)
MALDI-ToF MS analysis was pe o med on a B uke -Re lex III appa a us equipped wi h a
N
2
lase (λ = 337 nm) a an accele a ion ol age o 20 kV. ans-2-[3-(4- e -Bu ylphenyl)-
2-me hyl-2-p openyliden]maloni ile (DCTB, Fluka, 99,0 %) was used as ma ix and sil e
i luo oace a e (AgTFA, Sigma-Ald ich, 99.99%) as ioniza ion agen . Samples we e p e-
pa ed om THF solu ion by mixing ma ix, polyme and sal in a a io o 20/5/1 ( / ).
Scanning Elec on Mic oscopy (SEM)
The pa icles we e analyzed by ield emission scanning elec on mic oscopy on a Zeiss
LEO 1530 Gemini mic oscope equipped wi h a ield emission ca hode ope a ing a 0.5-5
kV. Specimen p epa a ion was accomplished as ollows: silicon wa e s we e cleaned us-
ing isop opanol and ace one in a s anda d p ocedu e. To ob ain a eas o di e en con-
cen a ion o pa icles, he wa e was i s dip-coa ed om 0.02 g/L solu ion and hen a
u he d op o he solu ion was deposi ed and allowed o d y. The specimens we e
coa ed wi h a hin pla inum laye using a spu e coa e (C essing on 208HR) o ende
he specimen conduc i e.
Dynamic Ligh Sca e ing (DLS)
DLS measu emen s we e pe o med on an ALV DLS/SLS-SP 5022F compac goniome e
sys em wi h an ALV 5000/E c oss co ela o and a He-Ne lase (λ = 632.8 nm). The meas-
u emen s we e ca ied ou in cylind ical sca e ing cells (d = 10 mm) a an angle o 90°
and a empe a u e o 20 °C. P io o he ligh sca e ing measu emen s, he sample solu-
ions we e il e ed using nylon il e s (Magna, Ro h) wi h a po e size o 5 µm. The CON-
4 – “Woodlouse” S uc u es om µ-BVqT
121
TIN algo i hm was applied o analyze he ob ained co ela ion unc ions. Appa en hy-
d odynamic adii we e calcula ed acco ding o he S okes-Eins ein equa ion.
DSC
The mal analysis and de e mina ion o he glass ansi ion empe a u es was pe o med
on a Pe kin–Elme Diamond DSC a a hea ing a e o 20 K/min.
4.6.2 Syn hesis and Cha ac e iza ion o PB-a m-P2VP-a m-P BMA Mik-
oa m S a Te polyme
The syn hesis o he PB-a m-P2VP-a m-P BMA mik oa m s a e polyme was accom-
plished by combining sequen ial anionic polyme iza ion wi h azide-alkyne Huisgen
cycloaddi ion. The e o e, an alkyne- unc ionalized polybu adiene-b-poly(2- inylpy idine)
(PB-b-P2VP) diblock copolyme was di ec ly p epa ed by anionic polyme iza ion using an
alkyne- unc ionalized DPE de i a i e (click-DPE). The molecula cha ac e iza ion o he
diblock copolyme is lis ed in Table 4-S1. As al eady epo ed, in he case o he click-
DPE, inco po a ion in, o mos p obably a he end o he poly(2- inylpy idine) (P2VP)
block akes place. This leads o diblock copolyme s which bea addi ional alkyne-
unc ions in o a he end o he P2VP block, as he DPE de i a i e is used in excess. Ne -
e heless, unde app op ia e eac ion condi ions, i.e. using only a sligh excess o click-
DPE, low empe a u es and sho eac ion imes an o e all deg ee o alkyne-
unc ionaliza ion o 116 % was achie ed.
1
Taking in o accoun he e o s o he de e mi-
na ion me hod his esembles only a sligh o e -inco po a ion o click-DPE in o he ma-
e ial.
The alkyne g oup is hen used o a ach he hi d block, poly( e -bu yl me hac yla e)
(P BMA), ia azide-alkyne Huisgen cycloaddi ion. Thus, in he ollowing click eac ion an
excess o 10% o azido- unc ionalized homopolyme chains ela i e o he diblock chains
was used o ensu e ha all diblock chains unde go conjuga ion. As a di ec consequence
he ob ained mik oa m s a e polyme con ains a mino ac ion wi h mo e han one
chain o P BMA. Figu e 4-S1 displays he SEC aces o he p ecu so homopolyme and
diblock copolyme , and he ob ained mik oa m s a e polyme . Table 4-S1 lis s he co -
esponding cha ac e iza ion da a. Due o he use o an azido- unc ionalized ATRP ini ia-

4 – “Woodlouse” S uc u es om µ-BVqT
122
o o he P BMA polyme iza ion in case o ecombina ion polyme s bea ing wo azido
end-g oups a e o med. The e o e, a small pe cen age o α,ω-azido-bi unc ionalized
homopolyme could lead o H-shaped mik oa m s a e polyme s and explain he ob-
se ed highe molecula weigh shoulde . F om es click eac ions wi h PS
homopolyme s, whe e he b omo- unc ion was ans o med in o an azide a e polyme -
iza ion, no such coupling shoulde was de ec ed, suppo ing ou assump ion.
Table 4-S1. Molecula Cha ac e is ics o Poly( e -bu yl me hac yla e) (T), Polybu adi-
ene-block-poly(2- inylpy idine) (BV), and µ-BVT
Polyme
a
M
n
b
/ kg/mol
PDI
c
T
53
7.6 1.17
B
109
V
81
14.7 1.02
µ-B
109
V
81
T
53
22.2 1.07
a
The subsc ip s deno e he deg ees o polyme iza ion o he co esponding blocks as calcula ed om he
espec i e numbe a e age molecula weigh s.
b
Fo he P BMA homopolyme he numbe a e age molec-
ula weigh was de e mined by SEC using a P BMA calib a ion. Fo he diblock copolyme he molecula
weigh was calcula ed om
1
H NMR using he molecula weigh o he PB as e e ence. This was measu ed
di ec ly ia MALDI-ToF MS. Fo he ABC mik oa m s a e polyme he o e all molecula weigh was calcu-
la ed om he co esponding p ecu so polyme s.
c
De e mined by SEC in THF calib a ed wi h PS s anda ds
o in he case o P BMA homopolyme wi h P BMA s anda ds.
Figu e 4-S1. SEC eluog ams o he PB-a m-P2VP-a m-P BMA mik oa m s a e polyme (µ-BVT), he p e-
cu so diblock copolyme (PB-b-P2VP), and he homopolyme (P BMA). In all cases he RI signal is shown.

26 28 30 32 34 36 38
0.0
0.2
0.4
0.6
0.8
1.0
no malized RI de ec ion
V
e
[mL]
PB
b
P2VP
P
BMA
"
BVT
4 – “Woodlouse” S uc u es om µ-BVqT
123
4.6.3 Sel -Assembly o µ-BVqT
Figu e 4-S2. In ensi y-weigh ed DLS CONTIN plo (A) o qua e nized µ-BVT (µ-BVqT) in 1 g/L dioxane solu-
ion, R
h,app
= 12.5 nm.

Figu e 4-S3. O e iew o a ious c yo-TEM images o di e en “woodlouse” agg ega ion o ms obse ed
in ~0.6 g/L aqueous solu ions o µ-BVqT.
4 – “Woodlouse” S uc u es om µ-BVqT
124

Figu e 4-S4. (A) TEM and (B) c yo-TEM mic og aphs om aqueous solu ions o linea B
1108
Vq
142
T
93
a 0.2
and 0.65 g/L, espec i ely. A e dialysis o wa e p ecipi a ion occu ed g adually. Whe eas he image in
(A) is uns ained, he inse in (A) shows an enla ged a ea a e s aining wi h OsO
4
. In bo h cases micella
clus e s can be seen, wi hou any in e nal ine s uc u e (see s aining in he inse in (A) o he b igh e
a eas in he c yo-TEM in (B)). Please no e ha he molecula weigh o he iblock e polyme was much
highe and also he mola ac ions we e di e en o he s udied mik oa m s a e polyme µ-B
101
V
81
T
53
.
Addi ionally, he sequence was PB-b-P2VP-b-P BMA due o he es ic ions o anionic polyme iza ion and
he e o e he middle block o ms he co ona. This leads o a olding o he polyme chain o shield he
hyd ophobic end blocks.
4.6.3.1 In e media e S uc u es o “Woodlouse” Agg ega es
The dioxane solu ion o µ-BVqT, which yielded he in e media e s uc u es (Figu e 4-2),
was allowed o age o an addi ional mon h be o e dialysis o wa e . TEM analysis
showed ha he ob ained agg ega es we e o sligh ly highe s uc u al o de and he
in e nal ine s uc u e o he “woodlouse” was al eady isible o some objec s (Figu e 4-
S5A). Ne e heless, he s uc u es seem o be kine ically apped du ing he p ocess, as
u he ageing o aqueous solu ions did no lead o any inc ease in o de . As obse ed by
c yo-TEM he supe s uc u es we e mo e densely packed (Figu e 4-S5B). Less cylind ical
p o usions emana e om he cen e o he agg ega es, and he g ay-scale analysis con-
i ms h ee pe iodic dis ances (d
1
= 4.5 ± 1.0 nm, d
2
= 4.5 ± 1.0 nm, d
3
= 9.0 ± 1.0 nm. The
s uc u e was u he isualized using di e en il angles in c yo-TEM (Suppo ing ide-
os 4-S1 and 4-S2), con i ming a 3-dimensional a ay o he cylinde s.

4 – “Woodlouse” S uc u es om µ-BVqT
125

Figu e 4-S5. TEM (A) and c yo-TEM mic og aphs (B) o in e media e micella s uc u es o µ-BVqT ob-
ained by dialysis o wa e a e ageing o he dioxane solu ion o one mon h.
The inal polyme concen-
a ion was 0.2 g/L o TEM and 0.4 g/L in case o c yo-TEM. The uppe inse in (B) displays a g ay-scale
analysis o he highligh ed a ea.

We u he p epa ed hin ilm cu s o his s uc u al in e media e by eeze-d ying o he
solu ion and embedding he pa icles in o an epoxy esin. The co esponding TEM mi-
c og aphs om hin slices (wi h and wi hou addi ional OsO
4
s aining) a e shown in Fig-
u e 4-S6 and an in e nal lamella s uc u e can be obse ed (black a ows in Figu e 4-S6).
Addi ionally, OsO
4
s aining e ealed an undula ed shape o he lamellae, which can also
be in e p e ed as a dense packing o sphe es (Figu e 4-S6B). The same obse a ion was
made o some o he cylind ical s uc u es (whi e a ows in Figu e 4-S6B). As indica ed
by he whi e a ows o he non-s ained mic og aphs in Figu e 4-S6A (only P2VPq is isi-
ble), cylind ical p o usions wi h a ubula na u e we e also iden i ied. These indings
con i m ou ini ial assump ion o cylind ical micelles as in e media es. Fu he mo e, he
absence o s uc u es wi h a di use co e egion suppo s he assump ion o compac
pa icles. The p esence o bo h cylind ical p o usions and elonga ed pa icles o a he
compac shape wi h a sphe ical c oss sec ion we e u he con i med ia SEM measu e-
men s (Figu e 4-S7).
132

5 – T iiodide-Di ec ed Sel -Assembly o Di e en Mik oa m S a Polyme s
133
5 – Hie a chical Sel -Assembly o Mik oa m S a Polyme
Sys ems Con aining a Polyca ionic Segmen : A Gene al
Concep
And eas Hanisch, And é H. G öschel, Melanie Fö sch, Tina I. Löbling, Felix H. Schache ,
and Axel H. E. Mülle
ABSTRACT: We ecen ly in oduced a concep o he coun e ion-media ed hie a chical
sel -assembly o amphiphilic mik oa m s a e polyme s in aqueous media in o mic om-
e e -sized compa men alized pa icles wi h a highly pe iodic lamella ine s uc u e
(“woodlice”). He ein, we ex end his concep o di e en mik oa m s a polyme sys-
ems con aining a polyca ionic segmen . The p esence o a poly(N-me hyl-2-
inylpy idinium) (P2VPq) block and i s in e ac ion wi h iodide/ iiodide coun e ions is
c ucial. In analogy o linea diblock copolyme sys ems he hyd ophilic/hyd ophobic bal-
ance o polybu adiene-a m-poly(N-me hyl-2- inylpy idinium iodide)-a m-polys y ene
mik oa m s a e polyme s de e mines he mo phology o he p ima y building blocks
(sphe ical micelles and cylind ical micelles/ esicles) and he ob ained supe s uc u es
(s acked lamella s uc u es and mul ilamella esicles) du ing his hie a chical p ocess.
When an ABA’ mik oa m s a copolyme (polys y ene-a m-poly(N-me hyl-2-
inylpy idinium iodide)-a m-polys y ene) wi hou a dynamic co e- oming block was
in es iga ed, a di e en mechanism in o “woodlouse”-s uc u ed agg ega es ia agg e-
ga ion and de o ma ion o in e media e esicles was ound. The indi idual s eps o he
5 – T iiodide-Di ec ed Sel -Assembly o Di e en Mik oa m S a Polyme s
134
di e en sel -assembly p ocesses we e in es iga ed by ansmission elec on mic oscopy
and addi ionally suppo ed by dynamic ligh sca e ing, di e en ial scanning calo ime y,
and small-angle X- ay sca e ing.
Keywo ds: Mik oa m S a Polyme , Polyelec oly e, Hie a chical Sel -Assembly
5 – T iiodide-Di ec ed Sel -Assembly o Di e en Mik oa m S a Polyme s
135
5.1 In oduc ion
One s aigh o wa d me hod o con ol he mo phology o sel -assembled s uc u es
om block copolyme s is changing he olume ac ion o he cons i u ing segmen s.
This led o a di e si y o mo phologies in he bulk
1-4
and in solu ion.
5-10
In he la e
case, p edominan ly sphe ical micelles a e o med, bu also cylind ical o esicula s uc-
u es, as well as he co esponding in e media es ha e been epo ed.
11
Despi e he ple ho a o nanos uc u es being accessible oday, he s uc u al di e si y
and complexi y eached in biological sys ems s ill ep esen s he ul ima e benchma k.
He e, sel -o ganiza ion o di e se biomac omolecules induces hie a chy o e se e al
leng h scales h ough in a- and in e molecula in e ac ions by encoding u mos unc-
ionali y ia he indi idual building blocks. Such p ocesses can be conside ed as con e -
gen since he coope a i i y o a mul i ude o (di e en ) weak in e ac ions leads o he
o ma ion o p ima y building blocks, which u he assemble in o s uc u es o in-
c eased complexi y a a he modynamic minimum. The accumula ion o weak in e ac-
ions wi hin and be ween he building blocks compensa es o he loss in en opy.
12,13
Fo example, p o eins old in o complex h ee-dimensional s uc u es guided by he in-
o ma ion encoded wi hin he p ima y s uc u e o he amino acid sequence.
14
Com-
monly, hese s uc u es a e monodispe se, as shown o he obacco mosaic i us
(TMV), whe e 2130 iden ical p o ein subuni s a ange a ound a single s and o RNA in a
helical ashion o p oduce a igid od o 18 x 300 nm.
15
E en hough he dimensions ob ained in na u al sys ems a e di icul o each by di-
ec ed sel -assembly o syn he ic mac omolecules in gene al, his s ill p o ides a
s aigh o wa d app oach o he design o well-de ined unc ional ma e ials. Inc easing
he ansc ip ed chemical in o ma ion o he sys em by an addi ional block (AB o ABC)
al eady leads o a d as ic inc ease o he me e numbe o mo phologies being accessi-
ble.
16
This is a consequence o h ee unlike polyme -polyme in e ac ion pa ame e s and
he possibili y o sol en s being selec i e o one o wo segmen s. Depending on he
indi idual solubili y, his enables he p epa a ion o co ona- o co e-compa men alized
s uc u es.
17-19
In his con ex Hillmye , Lodge and co-wo ke s ga e a de ailed in es iga-
ion o he compa men aliza ion in micella sys ems by using mik oa m s a
5 – T iiodide-Di ec ed Sel -Assembly o Di e en Mik oa m S a Polyme s
136
e polyme s. Th ough his unique mac omolecula a chi ec u e “hambu ge ” micelles,
segmen ed wo m-like micelles, and subs uc u ed esicles could be ob ained as co e-
compa men alized analogs o sphe ical, wo m-like and esicula s uc u es.
20-22
Mo e-
o e , in he ield o iblock e polyme s i is well demons a ed ha he complexa ion
wi h single s anded DNA
23
o he use o diamines as addi i es
24,25
display addi ional
igge s o hie a chical s uc u e o ma ion. Especially “kine ic con ol” allowed o he
s epwise sel -assembly o poly(ac ylic acid)-block-poly(me hyl ac yla e)-block-
polys y ene iblock e polyme s in o o oids, s acks o disk-like micelles, and lamella
phase sepa a ed d ople s. He eby, he s uc u es we e in luenced by he polyme se-
quence, composi ion, he na u e o he di alen coun e ion, he sol en mix u e, and
he p epa a ion pa hway and he con ol o hese pa ame e s allowed o manipula ion
o he ob ained agg ega ion o ms.
25-30
Recen ly, we epo ed he coun e ion-di ec ed sel -assembly o a polybu adiene-a m-
poly(N-me hyl-2- inylpy idinium iodide)-a m-poly( e -bu yl me hac yla e) (µ-BVqT)
mik oa m s a e polyme in o mul ilaye ed “woodlouse” agg ega es, aking ad an age
o bo h he polyme a chi ec u e and he unabili y o he coun e ion.
31
The p esence o
iodide as coun e ion o he qua e nized poly(2- inylpy idine) segmen was c ucial o
achie e supe s uc u e o ma ion. Iodine as addi i e led o he o ma ion o iiodide, a
highly pola izable coun e ion, which induced hie a chical sel -o ganiza ion om sphe i-
cal micelles in o cylind ical s uc u es and well-de ined supe s uc u es he eo . Besides
he na u e o he coun e ion and he mik oa m s a a chi ec u e also he p epa a ion
pa hway was essen ial o ob ain well-de ined agg ega es. He e, we y o ob ain a mo e
de ailed insigh in o he unde lying mechanism o his p ocess by expanding i o o he
mik oa m s a polyme sys ems. We ake ad an age o ou newly de eloped modula
app oach o he s aigh o wa d syn hesis o such ma e ials.
32
Fi s , he in luence o he
molecula composi ion on he ob ained building uni s om h ee di e en
polybu adiene-a m-poly(N-me hyl-2- inylpy idinium iodide)-a m-polys y ene mik oa m
s a e polyme s (µ-BVqS) and he esul ing coun e ion-di ec ed supe s uc u es will be
elabo a ed. In his con ex , he P2VPq co ona was addi ionally u ilized o he gene a-
ion and hos ing o Au nanopa icles. Second, he iiodide-di ec ed sel -assembly o a
5 – T iiodide-Di ec ed Sel -Assembly o Di e en Mik oa m S a Polyme s
137
polys y ene-a m-poly(N-me hyl-2- inylpy idinium iodide)-a m-polys y ene mik oa m
s a copolyme (µ-SVqS’) as a model sys em wi hou a low T
g
segmen is in es iga ed.

5 – T iiodide-Di ec ed Sel -Assembly o Di e en Mik oa m S a Polyme s
138
5.2 Expe imen al Pa
Syn hesis
Ma e ials
Bu adiene (Rießne -Gase) was passed h ough columns illed wi h molecula sie es (4 Å) and
basic aluminium oxide and s o ed o e dibu ylmagnesium (1 M solu ion in hep ane, Ald ich).
2-Vinylpy idine (2-VP, Ald ich) was degassed, s i ed wi h ie hylaluminium (1 M solu ion in
hexanes, Ald ich)
and condensed on a high acuum line. S y ene (BASF) was pu i ied in a
simila manne , excep ha i was s i ed wi h dibu ylmagnesium (1 M solu ion in hep ane,
Ald ich) ins ead o ie hylaluminium. THF (Sigma-Ald ich) was dis illed om CaH
2
and Na/K
alloy. sec-Bu ylli hium (Ac os, 1.3 M in cyclohexane/hexane: 92/8) was used wi hou u he
pu ifica ion. e -Bu yl me hac yla e ( BMA, Sigma-Ald ich) and s y ene (Sigma-Ald ich) o
ATRP we e il e ed o e basic aluminium oxide be o e use. N,N,N′,N′,N′′-
Pen ame hyldie hylene iamine (PMDETA) and CuB we e pu chased om Ald ich and dis-
illed and degassed o ea ed wi h pu e ace ic acid and il e ed, espec i ely. 1-(4- e -bu yl-
dime hylsilyl)e hynylphenyl)-1-phenyle hylene (click-DPE) was syn hesized om 1-(4-
b omophenyl)-1-phenyle hylene as al eady epo ed
32
. The aqueous solu ions we e p e-
pa ed wi h dis illed desalina ed wa e . All o he chemicals we e o analy ical g ade and used
as ecei ed. The dialysis memb ane used o all s eps was pu chased om Ro h (Spec a
Po ), wi h a molecula weigh cu -o (MWCO) o 1 000 g/mol.
Syn hesis and Qua e niza ion o Mik oa m S a Te - and Copolyme s
The de ailed p ocedu es o he syn hesis o he alkyne mid- unc ional diblock copolyme s
(polybu adiene-block-poly(2- inylpy idine)) and azido- unc ionalized homopolyme s (poly-
s y ene and poly( e -bu yl me hac yla e)) ha e al eady been epo ed elsewhe e.
32
Simila -
ly, ano he alkyne mid- unc ionalized diblock copolyme , polys y ene-block-poly(2-
inylpy idine) (PS-b-P2VP), was also syn hesized ia anionic polyme iza ion in THF u ilizing
he alkyne-subs i u ed diphenyle hylene (click-DPE) de i a i e. The e o e, s y ene was ini i-
a ed wi h sec-BuLi a -70 °C and allowed o polyme ize a his empe a u e o 25 minu es
be o e he click-DPE was added (1.1 equi ela i e o li ing chains). A e s i ing a -50 °C o
2 h he empe a u e was se o -70 °C and 2VP was added and allowed o polyme ize o 5
5 – T iiodide-Di ec ed Sel -Assembly o Di e en Mik oa m S a Polyme s
139
minu es be o e e mina ion wi h degassed isop opanol. The polyme was pu i ied by p ecipi-
a ion in wa e .
Finally, he liga ions o he alkyne- unc ionalized diblock copolyme s wi h he azido-
unc ionalized homopolyme s we e conduc ed by azide-alkyne Huisgen cycloaddi ion.
33
The e o e, a mix u e o he diblock copolyme and 1.1 equi o he espec i e homopolyme
we e dissol ed in THF a a concen a ion o ~20 g/L and degassed o 10 min. A e addi ion
o 1 equi CuB , he solu ion was degassed o u he 15 min. PMDETA (1 equi ) was added
o complex he coppe and s a he eac ion, which was ollowed by SEC. A e 2 days, he
esul ing mik oa m s a e polyme s we e pu i ied by passing he solu ion h ough a small
column wi h basic alumina o emo e coppe and inally eeze-d ied om dioxane.
P epa a ion o Aqueous Micella Solu ions
The ans o ma ion o he P2VP compa men in o a s ong ca ionic polyelec oly e (P2VPq)
was conduc ed using me hyl iodide as qua e niza ion agen . The de ailed p ocedu e is gi en
in he li e a u e.
31
To simpli y ma e s, in case o all qua e nized solu ions he gi en concen-
a ions esemble he concen a ion o he p is ine mik oa m s a e polyme be o e he
modi ica ion, hus neglec ing he inc ease o mass due o qua e niza ion.
Fo he p epa a ion o he iiodide complexes an iodine s ock solu ion was p epa ed wi h
dioxane as sol en a 15 g/L. This iodine solu ion was hen added o he dioxane solu ion o
he qua e nized s a e polyme s un il he desi ed a io o iodine o amino- unc ion was
achie ed. A e wa ds, he solu ions we e s i ed o 2 h and hen ea ed wi h ul asound o
15 min. Subsequen ly, he solu ions we e dialyzed agains wa e , as desc ibed abo e and
ob ained wi h concen a ions anging om 0.3 o 0.7 g/L. Some o he solu ions we e col-
loidally s able o e mon hs, whe eas o he s sedimen ed wi h ime.
Gene a ion o Au Nanopa icles
To 1.5 mL o an aqueous solu ion o µ-BVq1S, which was ob ained om dialysis o he co e-
sponding dioxane solu ion wi h addi ional 0.25 equi I
2
( ega ding P2VPq uni s), was added a
highly concen a ed aqueous solu ion o HAuCl
4
un il an Au:N a io o 0.6 was eached. Di-
ec ly a e addi ion, p ecipi a ion occu ed, and he e o e he sample was ea ed wi h ul-
asound o 30 minu es. A e s i ing o 90 minu es he solu ion was subjec ed o cen i u-
ga ion. The supe na an liquid was decan ed and he solid con en was edispe sed in 1.5 mL
5 – T iiodide-Di ec ed Sel -Assembly o Di e en Mik oa m S a Polyme s
140
o wa e . A eshly p epa ed solu ion o NaBH
4
was added (5 M equi wi h espec o Au) and
hen he solu ion was s i ed o e nigh . A e cen i uga ion o emo e excess eagen s, he
solid con en was again edispe sed in 1.5 mL o wa e o ob ain a solu ion o cha ac e is ic
ed- iole colo .
Cha ac e iza ion
T ansmission Elec on Mic oscopy (c yo-TEM and TEM)
TEM mic og aphs we e aken wi h a Zeiss CEM 902 o 922 OMEGA elec on mic oscope op-
e a ed a 80 kV o 200 kV, espec i ely. Bo h machines we e equipped wi h an in column
ene gy il e . Fo sample p epa a ion 2 µL o he solu ion ( ypically 0.1-0.2 g/L) we e depos-
i ed on a hyd ophilized TEM g id (coppe , 200 mesh). A e wa ds, he emaining sol en was
emo ed wi h a blo ing pape . In ano he p epa a ion pa hway a d op o he solu ion was
deposi ed on a TEM g id on a piece o pa a ilm, immedia ely ozen wi h liquid ni ogen and
a e wa ds eeze-d ied. Fo in es iga ion o he pa icle ilm he eeze-d ied polyme was
embedded in o a esin (EpoTek 301). 50 nm hin cu s we e p epa ed wi h a Leica EM UC7
mic o ome equipped wi h a diamond kni e and deposi ed on o TEM g ids (coppe , 200
mesh). Fo c yo-TEM s udies, a d op (~2 mL) o he aqueous micella solu ion (c ~0.4-0.7 g/L)
was placed on a lacey ca bon-coa ed coppe TEM g id (200 mesh, Science Se ices), whe e
mos o he liquid was emo ed wi h blo ing pape , lea ing a hin film s e ched o e he
g id holes. The specimens we e shock i ified by apid imme sion in o liquid e hane in a
empe a u e-con olled eezing uni (Zeiss C yobox, Zeiss NTS GmbH) and cooled o ap-
p oxima ely 90 K. The empe a u e was moni o ed and kep cons an in he chambe du ing
all o he p epa a ion s eps. A e eezing he specimens, hey we e inse ed in o a c yo-
ans e holde (CT3500, Ga an) and ans e ed o a Zeiss EM922 OMEGA EFTEM ins u-
men . Examina ions we e ca ied ou a empe a u es a ound 90 K. The mic oscope was op-
e a ed a an accele a ion ol age o 200 kV. Ze o-loss fil e ed images (ΔE = 0 eV) we e aken
unde educed dose condi ions. All images we e egis e ed digi ally by a bo om-moun ed
CCD came a sys em (Ul ascan 1000, Ga an), combined, and p ocessed wi h a digi al imaging
p ocessing sys em (Ga an Digi al Mic og aph 3.9 o GMS 1.4). E alua ion o he espec i e
leng h scales o he s uc u es was achie ed by measu ing 50-100 di e en spo s wi hin he
sample wi h he UTHSCSA ImageTool V. 3.00.
5 – T iiodide-Di ec ed Sel -Assembly o Di e en Mik oa m S a Polyme s
141
UV-Vis Spec oscopy
UV- is spec a we e eco ded on a Hi achi 3000 spec opho ome e .
Dynamic Ligh Sca e ing (DLS)
DLS measu emen s we e pe o med on an ALV DLS/SLS-SP5022F compac goniome e sys-
em equipped wi h an ALV 5000/E c oss co ela o and a He-Ne lase (λ = 632.8 nm). The
measu emen s we e ca ied ou in cylind ical sca e ing cells (d = 10 mm) a an angle o 90 °
and a empe a u e o 20 °C. The solu ions we e measu ed wi hou il a ion. The CONTIN
algo i hm was applied o analyze he ob ained co ela ion unc ions. Appa en hyd ody-
namic adii we e calcula ed acco ding o he S okes-Eins ein equa ion.
Small-Angle X-Ray Sca e ing (SAXS)
SAXS measu emen s o he eeze-d ied powde s we e pe o med on a B uke AXS Nanos a
(B uke , Ka ls uhe, Ge many), equipped wi h a mic o ocus X- ay sou ce (Incoa ec IµS
Cu
E025,
Incoa ec Gees hach , Ge many), ope a ing a λ = 1.54 Å. A pinhole se up wi h 750, 400, and
1000 µm (in he o de om sou ce o sample) was used and he sample- o-de ec o dis ance
was 107 cm. Samples we e moun ed on a me al ack and ixed using ape. The sca e ing
pa e ns we e co ec ed o he beam s op and he backg ound (Sco ch ape) p io o
e alua ions. The measu emen ime was 12 h.
Di e en ial Scanning Calo ime y (DSC)
The mal analyses and de e mina ion o he glass ansi ion empe a u es we e pe o med
on a Pe kin-Elme Diamond DSC a a hea ing a e o 20 K/min.
The desc ip ion o he SEC, NMR and MALDI-ToF expe imen s is gi en in he Suppo ing In-
o ma ion