Stereocomplex Nanocomposite Switch Based on Dynamic Helical Polymer-Gold and Silver Nanoparticle Hybrid Materials

S e eocomplex Nanocomposi e Swi ch Based on Dynamic Helical
Polyme -Gold and Sil e Nanopa icle Hyb id Ma e ials
Manuel Nunez-Ma ínez, Emilio Quinoá, and Félix F ei e*
Ci e This: Chem. Ma e . 2023, 35, 4865−4872
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ABSTRACT: Con olled ON/OFF s e eocomplexa ion o dynamic helical
polyme -me al nanopa icle nanocomposi es�poly(phenylace ylene)-MNP
nanocomposi es (M = Au o Ag)�is p esen ed. These no el hyb id ma e ials
can be ound ei he as well-dispe sed me al nanopa icles (MNPs)
(s e eocomplex OFF) o as ibe -like agg ega es (s e eocomplex ON) wi h
he me al nanopa icles dis ibu ed along he ma e ial. A s e eocomplex-MNP
nanocomposi e is o med by he in e ac ion o wo complemen a y and
enan iome ic helical polyme -MNP nanocomposi es [Poly-(R)-1-M1NPs/
poly(S)-1-M2NPs (M1= M2o M1≠M2; M = Au, Ag)]. In e es ingly, by
using dynamic helical polyme s, i.e., poly(phenylace ylene)s (PPAs), as
coa ing agen s o he me al nanopa icles, i is possible o une he seconda y
s uc u e o he polyme �elonga ion and/o comp ession�a ac ha can
igge he o ma ion/dis up ion o he s e eocomplex. Mo eo e , he s e eocomplexa ion o hese nanocomposi es can be con olled
in a e e sible way (ON/OFF) by playing wi h he sup amolecula in e ac ions ha keep he wo enan iome ic and complemen a y
helices oge he , such as hyd ogen bonds.
1. INTRODUCTION
Me al nanopa icles (MNPs) ha e been exploi ed du ing he
las decades by he scien i ic communi y due o hei
applica ions in ields such as he anos ic,
1,2
sensing,
3
o
ca alysis.
4,5
To apply hese ma e ials in di e en ields, and
wo k unde di e en condi ions�sol en , empe a u e, e c.�
i is necessa y o deco a e he NMP su ace wi h an
app op ia e coa ing, usually an o ganic molecule. Thus, in
he li e a u e, i is possible o ind esea ch a icles dealing wi h
he unc ionaliza ion and pos unc ionaliza ion o he MNP
su ace,
6
which include helical na u al (DNA o pep ides) and
nonna u al mac omolecules (helical polyme s).
7−10
The use o nonna u al mac omolecules such as dynamic
helical polyme s
11−37
as coa ing agen s in oduces in e es ing
p ope ies in o he nanocomposi e, such as he abili y o
modi y he mac omolecula chi ali y o he coa ing�sc ew
sense�o he s e ching deg ee�helical pi ch�by changing
he en i onmen al condi ions, e.g., empe a u e, sol en , pH o
by adding ex e nal agen s, e.g., me al ions, anions, and chi al
addi i es, among o he s.
38−42
F om p e ious s udies, i is known ha he dynamic
beha io o he helical polyme in a dynamic helical polyme -
MNP nanocomposi e can be al e ed by he binding s eng h
be ween he polyme and he MNP.
9
Thus, in he case o using
PPAs bea ing a hiol o hioe he g oup as linking g oups o
he MNPs, i is necessa y o p epa e a copolyme due o he
poo solubili y o he homopolyme s con aining hiol o
hioe he g oups in he monome epea ing uni s.
7,10
In he
case o p epa ing a copolyme , i is necessa y o conside all he
chi al communica ion mechanisms ha can eme ge be ween
he wo componen s. Thus, when he copolyme is made up o
wo chi al monome s, a “Chi al Acco d” o “Chi al Coali ion”
e ec should occu be ween monome s o p ese e he
dynamic beha io and he sc ew sense excess in he copolyme ,
whe eas i one o he monome s is chi al and he o he
nonchi al a “Se gean s and Soldie s” e ec should be igge ed
wi hin he copolyme se ies.
On he o he hand, i a sup amolecula in e ac ion wi h an
amide� he MNP ype�is used o link he wo componen s
o he nanocomposi e, homopolyme s can be used, al hough
he p esence o ce ain unc ional g oups in he monome
epea ing uni o he use o pola sol en s may a ec he
co ec o ma ion o he desi ed hyb id ma e ials.
8
Hence, o
design co ec ly a dynamic chi al nanocomposi e, i is
necessa y o conside he unc ional g oups p esen in he
homopolyme /copolyme and he en i onmen al condi ions
whe e he nanocomposi e will be used.
In his wo k, we aim o demons a e ha dynamic helical
polyme -MNP nanocomposi es can be used no only o
p epa e nanoma e ials wi h a dynamic chi al coa ing, bu also
Recei ed: Ap il 17, 2023
Re ised: May 28, 2023
Published: June 9, 2023
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o in oduce addi ional p ope ies in o he ma e ial associa ed
wi h he helical s uc u e o he coa ing agen , such as he
o ma ion o s e eocomplexes. S e eocomplexes a e sup a-
molecula agg ega es o med by he in e ac ion o comple-
men a y s e eo egula polyme s wi h di e en p ope ies o he
pa en homopolyme s.
43
A ending o he composi ion o he
polyme s, wo di e en ypes o s e eocomplexes can be
o med: homos e eocomplexes, o med om enan iome ic
homopolyme s and he e os e eocomplexes, gene a ed by he
in e ac ion be ween polyme s wi h s uc u ally di e en and
opposi e absolu e con igu a ion, e.g., Poly-(D)- and Poly-(L)-
(Lac ic acid) (PLA), o di e en ac ici ies, e.g., syndio ac ic
and iso ac ic Poly(me hylme ac yla e)s [s - and i -
PMMA].
44−49
These s e eocomplexes ha e also been used o
p epa e nanocomposi es wi h g aphene oxide (GO), clay,
ca bon nano ubes, cellulose nanoc ys als, silica, o me al
nanopa icles.
46−50
Likewise, in hese s e eocomplexes�Poly-(D)-PLA/Poly-
(L)-PLA; s -PMMA/i -PMMA� he helical s uc u e adop ed
by he polyme s canno be amed by using ex e nal s imuli.
Mo eo e , he in e ac ion be ween enan iome ic o comple-
men a y helices is a ibu ed o he p esence o weak
sup amolecula in e ac ions such as Van de Waals o ces o
hyd ogen bond in e ac ions, al hough he mechanism o
o ma ion is s ill unclea .
45
He e, ou goal is o p epa e s e eocomplexes om dynamic
helical polyme -MNP (M = Ag o Au) nanocomposi es. Thus,
by playing wi h di e en ex e nal s imuli i is possible o une
he helical s uc u e o he helical polyme -MNP nano-
composi e and, he e o e, o selec i ely ac i a e he o ma-
ion/dis up ion o he s e eocomplex-nanocomposi e.
Ou g oup has expe ience in he p epa a ion o s imuli-
esponsi e s e eocomplexes by in e ac ion o helically comple-
men a y poly(phenylace ylene)s (PPAs) ob ained om poly-
me iza ion o he 4-e hynylanilides o (R)- and (S)-α-me hoxy-
α- i luo ome hylphenylace ic (i.e., (R)-1and (R)-2) yielding
poly-(R)-1and poly-(S)-1, espec i ely (Figu e 1a).
45
In his
case, he s e eocomplex is o med by sup amolecula
in e ac ions be ween complemen a y helices ha bea cis
amide bonds a hei pe iphe ies, leading o he o ma ion o
sup amolecula ibe -like agg ega es ha a highe concen-
a ions esul in gels (Figu e 1b,c). Modi ica ion o he cis−
ans amide con o ma ion a he pendan s by sol en pola i y
o dis up ing he hyd ogen bond in e ac ions by inc easing
empe a u e o addi ion o dono sol en s (e.g., MeOH) allows
he con olled o ma ion and clea age o he s e eocom-
plexes.
51
The e o e, Poly-1is a g ea candida e o c ea e a
s imuli- esponsi e s e eocomplex PPA-MNP (M = Au, Ag)
nanocomposi e. Howe e , in p e ious wo k, we ound ha
poly-1does no o m s able poly-1-MNPs (M = Au, Ag)
h ough sup amolecula anilide-MNP in e ac ions.
8
The
p esence o a CF3g oup in he pendan deac i a es he
dono beha io o he anilides and hus hei abili y o in e ac
wi h he MNPs.
8
To o e come his p oblem and p epa e s e eocomplexes
based on Poly-1nanocomposi es [Poly-(R)-1-MNPs/poly(S)-
1-MNPs (M = Au o Ag)], a hiola ed comonome mus be
in oduced in o he Poly-1chain, o connec he dynamic
helical polyme o he MNPs. The esul ing copolyme mus
main ain he helical p ope ies and, he e o e, he s e eo-
complexa ion abili y o poly-1unal e ed (Figu e 1).
2. RESULTS AND DISCUSSION
Monome 2, consis ing o 11-me cap oundecanoic acid 4-
e hynylanilide, was designed and syn he ized as an achi al
hiola ed monome (see SI o syn he ic de ails). Nex ,
monome 2was copolyme ized wi h (R)- and (S)-1(see SI
o syn he ic de ails) using an Rh(I) ca alys o o m poly-
[(R)-11− -co-2 ] and poly-[(S)-11− -co-2 ] wi h in he ange o
0.01−0.03 (Figu e 2 and SI o syn he ic de ails). Thus, h ee
di e en copolyme s we e gene a ed o each enan iome ic
se ies�poly-[(Ro S)-10.99-co-20.01] (Mw= 308,708), poly-[(R
o S)-10.98-co-20.02] (Mw= 277,477), and poly-[(Ro S)-10.97-
co-20.03] (Mw= 296,729)�(Figu e 2a).
Chi op ical s udies show ha he ECD aces ob ained o
he di e en copolyme s a e qui e like hose ob ained o hei
Figu e 1. Chemical s uc u e o (a) monome s (R)- and (S)-1; polyme s poly-(R)- and (S)-1. (b) 3D-model o poly-(S)-1showing a cis-
con igu a ion o he amide g oups. Pic u e o a THF solu ion o poly-(S)-1. (c) 3D model o he poly-1s e eocomplex, highligh ing he cis-amide/
cis-amide sup amolecula in e ac ions be ween complemen a y helices. Pic u e o a poly-(R)-1/poly-(S)-1s e eocomplex gel in THF.
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co esponding pa en homopolyme s�poly-(R)-1and poly-
(S)-1�indica ing ha he seconda y s uc u es adop ed by he
copolyme s esemble he s uc u es adop ed by he homopol-
yme s (Figu e 2b).
Nex , s e eocomplexa ion s udies we e ca ied ou by mixing
solu ions o he copolyme s wi h he complemen a y
enan iome ic pa en homopolyme . Fo ins ance, a mix u e
o poly-[(R)-10.99-co-20.01] (0.1 mg mL−1in THF) wi h poly-
(S)-1(0.1 mg mL−1in THF) in a 50/50 ( / ) a io. Thus, six
di e en s e eocomplexes we e p epa ed�poly-[(R)-10.99-co-
20.01]/poly-(S)-1; poly-[(R)-10.98-co-20.02]/poly-(S)-1; poly-
[(R)-10.97-co-20.03]/poly-(S)-1(Figu e 2c) and poly-[(S)-
10.99-co-20.01]/poly-(R)-1; poly-[(S)-10.98-co-20.02]/poly-(R)-1;
poly-[(S)-10.97-co-20.03]/poly-(R)-1(see SI).
In all cases, DLS s udies show he p esence o la ge
agg ega es (Figu e 2c and SI), which co espond o ibe -like
agg ega es as in e ed om SEM s udies (Figu es 2d and SI).
Analogous s e ecomplexa ion s udies we e ca ied ou
be ween he complemen a y hiola ed copolyme s, poly-[(R)-
10.99-co-20.01]/poly-[(S)-10.99-co-20.01]; poly-[(R)-10.98-co-20.02]/
poly-[(S)-10.98-co-20.02], which p oduced la ge agg ega es as
in e ed om DLS and SEM s udies (Figu e 2c). These
s e eocomplexes display s imuli- esponsi e p ope ies, which
makes i possible o swi ch ON/OFF he s e eocomplex by
playing wi h he dono cha ac e o he sol en and wi h
empe a u e. Thus, while he dono cha ac e o he sol en
a ec s he cis/ ans con en o he anilide g oup and he e o e
he o ma ion o he s e eocomplex�ON (dono sol en s, cis
anilide), OFF (non-dono sol en s, ans anilide)�(Figu e 3),
an inc ease in he empe a u e o he solu ion�wa ming up o
60 °C�o he dispe sed s e eocomplex p omo es dis up ion o
he ne wo k o H-bonds ha hold he enan iome ic and
complemen a y cis-anilide Mhelix and cis-anilide Phelix linked
oge he (Figu e 3).
Once he abili y o designed copolyme s o o m s e eo-
complexes was demons a ed, we p oceeded o he p epa a ion
o nanocomposi es by hyb idiza ion wi h MNPs (M = Au o
Ag).
2.1. Poly-[(R)-11− -co-2 ]-MNPs and Poly-[(S)-11− -co-
2 ]-MNPs Nanocomposi es: Dynamic Beha io S udies.
Six di e en poly-[(R)-11− -co-2 ]-MNPs and poly-[(S)-11− -
co-2 ]-MNPs nanocomposi es ( = 0.01−0.03; M = Au and
Ag) we e p epa ed ollowing a a ia ion o he classical B us -
Schi in p ocedu e (see SI o syn he ic de ails). ECD s udies
o THF solu ions o poly-[(R)-11− -co-2 ]-MNPs and poly-
[(S)-11− -co-2 ]-MNPs (0.3 mg mL−1) showed an ac i e
Co on E ec in he inylic egion (ca. 380 nm) indica ing
ha he nanocomposi es e ain he helical s uc u e o Poly-1
when he MNPs a e hyb idized (Figu e 4 and SI). Mo eo e ,
UV− is s udies o he nanocomposi es con i med he
o ma ion o MNPs whe e AgNPs showed he ypical LSPR
band a 420 nm, associa ed wi h he yellowish colo o he
poly-[(R)-11− -co-2 ]-AgNPs and poly-[(S)-11− -co-2 ]-AgNPs
solu ions. Mo eo e , AuNPs showed he LSPR band a 530 nm
associa ed wi h he eddish colo o he poly-[(R)-11− -co-2 ]-
AuNPs and poly-[(S)-11− -co-2 ]-AuNPs solu ions (Figu e 4
and SI).
TEM s udies we e ca ied ou o s udy he mo phology o
he MNPs wi hin he nanocomposi es which e ealed he
o ma ion o low polydispe se sphe ical AuNPs (7.1 ±3.3 nm)
and AgNPs (4.4 ±1.5 nm) (Figu e 4d,h). These nano-
composi es a e s able o se e al weeks dispe sed in solu ion
and he solid s a e, a ac ha indica es he key ole o poly-
Figu e 2. (a) Chemical s uc u e o monome s 1and 2, copolyme s
poly-[(R)-1 -co-21− ] and poly-[(S)-11− -co-2 ] ( = 0.01−0.03). (b)
ECD s udies o poly-[(R)-1 -co-21− ] and poly-[(S)-1 -co-21− ] ( =
0.01−0.03) in CHCl3. (c) DLS s udies o poly-(R)-1/poly-(S)-1and
poly-[(R)-1 -co-21− ]/poly-[(S)-1 -co-21− ] mix u es (50/50 in THF).
(d) SEM images o s e eocomplexes o med by poly-[(R)-1 -co-21− ]/
poly-[(S)-1 -co-21− ] mix u es (50/50 in THF) (scale ba : 1000 nm).
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[(R)-11− -co-2 ] and poly-[(S)-11− -co-2 ] ( = 0.01−0.03) in
he s abiliza ion o he MNPs.
Mo eo e , ECD and UV− is s udies o poly-[(R)-11− -co-
2 ]-MNPs and poly-[(S)-11− -co-2 ]-MNPs nanocomposi es
(M = Au o Ag) in di e en sol en s�CHCl3, DCM, DMF,
and DMSO�showed he o ma ion o dynamic helical
copolyme s-MNPs nanocomposi es wi h beha io like ha o
he pa en homopolyme Poly-1(see SI). Hence, i is possible
o ob ain nanocomposi es wi h a chi al dynamic P/Mcoa ing
by uning he pola /dono p ope ies o he solu ions o poly-
[(R)-11− -co-2 ]-MNPs and poly-[(S)-11− -co-2 ]-MNPs nano-
composi es (see SI).
2.2. S e eocomplexa ion o PPA-Nanocomposi es:
S imuli-Responsi e P ope ies. Once he o ma ion o
he nanocomposi es was demons a ed, he nex s ep consis ed
in he p epa a ion o he di e en s e eocomplexes. The
p epa a ion o a dynamic s e eocomplex nanocomposi e is no
s aigh o wa d. I is necessa y o design a copolyme ha
mee s h ee equi emen s: (1) he s abiliza ion o he me allic
nanopa icle, (2) he abili y o o m enan iome ic and
complemen a y helices o induce he s e eocomplex, and (3)
he possibili y o uning he helical s uc u e by ex e nal s imuli
o c ea e a s e eocomplex swi ch (ON/OFF) o he nano-
composi es.
To de e mine i ou sys em comp ises hese equi emen s
and is able o c ea e a dynamic s e eocomplex nanocomposi e,
we i s explo e he s e eocomplexa ion be ween a nano-
composi e and he complemen a y homopolyme s. Fo his
pu pose, mix u es o he hyb id ma e ial (0.3 mg mL−1, THF)
wi h he enan iome ic homopolyme (0.3 mg mL−1, THF) in a
50/50 ( / ) mix u e we e p epa ed. As a esul , he ollowing
mix u es we e made: poly-[(R)-11− -co-2 ]-AgNPs/poly-(S)-1;
poly-[(R)-11− -co-2 ]-AuNPs/poly-(S)-1; poly-[(S)-11− -co-2 ]-
AgNPs/poly-(R)-1; poly-[(R)-11− -co-2 ]-AgNPs/poly-(R)-1
( = 0.01−0.03). In addi ion, ano he amily o s e eo-
complexes we e p epa ed by mixing wo nanocomposi es
con aining complemen a y enan iome ic helical s uc u es
hyb idized o he same o di e en me al nanopa icle, i.e.,
poly-[(R)-10.98-co-20.02]-AuNPs/poly-[(S)-10.98-co-20.02]-
AgNPs; poly-[(R)-10.99-co-20.1]-AuNPs/poly-[(S)-10.99-co-
20.01]-AgNPs; poly-[(R)-10.98-co-20.02]-AuNPs/poly-[(S)-10.97-
co-20.03]-AgNPs; poly-[(R)-1/poly-[(S)-10.98-co-20.02]-AuNPs
(see SI o mo e de ails.).
DLS s udies showed in all cases he p esence o la ge
agg ega es, which was co obo a ed by elec on mic oscopy
s udies�SEM, TEM�(Figu e 5a,b and SI) ha indica ed he
p esence o ibe -like agg ega es whe e he MNPs a e
dis ibu ed in he en i e ib illa s uc u e. F om hese s udies,
i was ound ha he MNP a ached o a dynamic PPA
copolyme does no a ec i s s uc u e o i s s e eo-
complexa ion abili y.
Nex , s imuli- esponsi e s udies we e ca ied ou wi h he
di e en s e eocomplex-nanocomposi es o de e mine i i is
possible o con ol he o ma ion/dis up ion (ON/OFF) o
he s e eocomplex by al e ing he seconda y s uc u e o he
polyme , o by ac i a ing/deac i a ing he ne wo k o H-bonds
ha keep he s e eocomplex nanocomposi e linked oge he .
As expec ed, i was ound ha by playing wi h he dono
cha ac e o he sol en i is possible o swi ch ON (THF)/
OFF (chlo o o m) he s e eocomplex-nanocomposi e (Figu e
5a,b and SI). The same swi ch was ob ained in a s e eo-
complex-nanocomposi e dispe sed in THF by playing wi h he
empe a u e�ON (<60 °C)/OFF (>60 °C)�(Figu e 5c,d
and SI).
3. CONCLUSIONS
In his wo k, i was demons a ed ha i is possible o p epa e
s imuli- esponsi e s e eocomplex-nanocomposi es based on
dynamic-helical polyme -MNP (M = Au o Ag) hyb id
ma e ials. Thus, wo complemen a y and enan iome ic helical
polyme s unc ionalized wi h Au o Ag nanopa icles in e ac
Figu e 3. (a) G aphic illus a ion and elec on mic oscopy s udies o he ON/OFF s e eocomplexa ion o a 50/50 / mix u e o poly-[(R)-10.98-
co-20.02]/poly-[(S)-10.98-co-20.02] in CHCl3(OFF), THF (ON) and THF a 60 °C (OFF). (b) DLS s udies o he ON/OFF s e eocomplexa ion o
a 50/50 ( / ) mix u e o poly-[(R)-10.98-co-20.02]/ poly-[(S)-10.98-co-20.02] in THF (ON), THF a 60 °C (OFF) and cooling again o 25 °C (scale
ba s e eocomplex: 1000 nm).
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be ween hem o o m ibe -like agg ega es s abilized by a
hyd ogen bonding ne wo k o med by cis-amide g oups loca ed
a he c es o he helical polyme s. The possibili y o uning
he helical s uc u e o he polyme by ex e nal s imuli in
combina ion wi h he possibili y o ac ing on he hyd ogen
bonding ne wo k makes i possible o c ea e a s imulus-
esponsi e s e eocomplex nanocomposi e, and whe e di e en
ibe -like nanos uc u es can be ob ained o he mix u e o
enan iome ic hyb id ma e ials.
This wo k is pionee ing in his opic, and we belie e ha
impo an applica ions can eme ge bo h in he ield o helical
polyme s and in he ield o me al nanopa icles by a co ec
design o he hyb id ma e ials used o p epa e he s e eo-
complexes.
4. EXPERIMENTAL SECTION
4.1. Chemicals. Comme cially a ailable chemicals ha e been used
as deli e ed. Sol en s we e pu chased as eagen g ade and dis illed i
necessa y. Anhyd ous sol en s we e ei he pu chased as ul a-d y
sol en s om Ac os O ganics o ecei ed om a sol en pu i ica ion
sys em. Fo he coupling and polyme iza ion eac ions, d y THF was
ob ained om he MBRAUN SPS 800 sol en pu i ica ion sys em.
Wa e was pu i ied by he Millipo e wa e pu i ica ion sys em.
Coupling eagen s (2-(7-Aza-1H-benzo iazole-1-yl)-1,1,3,3- e ame-
hylu onium hexa luo ophospha e) (HATU), 4-e hynylbenzoic acid,
and 4-e hynylaniline we e pu chased om AnaSpec Inc. (R)-(S)-α-
me hoxy-α- i luo ome hylphenylace ic acid, 11-me cap oundecanoic
acid, oxalyl chlo ide, hodium no bo nadiene chlo ide dime {[Rh-
(nbd)Cl]2}, diisop opyl ie hylamine (DIEA), ie hylamine (TEA,
99%), 1-dodecane hiol, sodium bo ohyd ide (NaBH4), gold(III)
chlo ide ihyd a e (HAuCl4) and sil e pe chlo a e (AgClO4) we e
pu chased om Ald ich.
Figu e 4. (a) G aphic illus a ion o he p epa a ion o poly-[(R)-
11− -co-2 ]-AuNPs. (b) CD spec um o poly-[(R)-10.99-co-20.01]-
AuNPs. (c) UV− is spec um o poly-[(R)-10.99-co-20.01]-AuNPs.
(d) TEM image o poly-[(R)-10.99-co-20.01]-AuNPs (scale ba : 50 nm).
(e) G aphic illus a ion o he p epa a ion o poly-[(S)-10.99-co-20.01]-
AgNPs. ( ) CD spec um o poly-[(S)-10.99-co-20.01]-AgNPs. (g) UV−
is spec um o poly-[(S)-10.99-co-20.01]-AgNPs. (h) TEM image o
poly-[(S)-10.99-co-20.1]-AgNPs (scale ba : 50 nm).
Figu e 5. (a) G aphic illus a ion and elec on mic oscopy s udies o
he ON/OFF s e eocomplexa ion-nanocomposi e o a 50/50 /
mix u e o poly-[(R)-10.98-co-20.02]-AgNP/poly-[(S)-10.98-co-20.02]-
AuNP nanocomposi es in CHCl3(OFF) and THF (ON). (b) DLS
s udies o he ON/OFF s e eocomplexa ion o a 50/50 ( / ) mix u e
o poly-[(R)-10.98-co-20.02]-AgNP/ poly-[(S)-10.98-co-20.02]-AuNP
nanocomposi es in THF (ON) and CHCl3(OFF). (c) Re e sible
s e eocomplex-nanocomposi e o ma ion o a 50/50 ( / ) mix u e o
poly-[(R)-10.98-co-20.02]-AgNP/ poly-[(S)-10.98-co-20.02]-AuNP nano-
composi es in THF media ed by empe a u e changes. (d) G aphic
illus a ion and elec on mic oscopy s udies o he ON/OFF
s e eocomplexa ion-nanocomposi e o a 50/50 / mix u e o poly-
[(R)-11− -co-2 ]-AgNP/poly-[(S)-11− -co-2 ]-AuNP nanocomposi es
in THF media ed by empe a u e changes.
Chemis y o Ma e ials pubs.acs.o g/cm A icle
h ps://doi.o g/10.1021/acs.chemma e .3c00912
Chem. Ma e . 2023, 35, 4865−4872
4869

4.2. Ins umen a ions and Cha ac e iza ions. NMR expe i-
men s we e ca ied ou in a Va ian Ino a 300 (300 MHz esonance
1H). Size exclusion ch oma og aphy s udies we e pe o med on he
Alliance 2695 HPLC Sys em (Wa e s) liquid ch oma og aphy sys em
equipped wi h a UV 2489 de ec o (Wa e s). The samples we e
elu ed by h ee Phenogel columns connec ed o each o he wi h
s a iona y phases o 103, 104, and 105Ams ong and packed wi h a
solid suppo o a c oss-linked s y ene and p-di inylbenzene
copolyme . CD and UV measu emen s we e egis e ed in a Jasco-
720 spec opola ime e and a Jasco-730 spec opho ome e espec-
i ely a a nanocomposi e concen a ion o 0.3 mg mL−1. FT-IR
measu emen s we e ca ied ou on a B uke IFS-66 . DLS s udies
we e pe o med on a Nano-ZS 90 (Mal e n) equipped wi h a He-Ne
lase (l= 633 nm) unde a sca e ing angle o 173°. The samples we e
main ained a he designed empe a u e o 5 min be o e es ing. DLS
measu emen s we e ca ied ou in all cases a 0.1 mg·mL−1. SEM
measu emen s we e pe o med on an LEO-435VP elec on mic o-
scope equipped wi h an ene gy-dispe si e X- ay (EDX) spec ome e .
TEM measu emen s we e pe o med on a JEOL JEM 2010 and 200
KV as a ol age. To s udy he nanocomposi es o s e eocomplexes,
he same p o ocol was used. A dispe sion o he nanocomposi es o
s e eocomplexes a a concen a ion o 0.1 mg mL−1was d op-cas ed
on o o silicon wa e chip and allowed o d y a o 12 h o SEM
s udies, while in he case o TEM s udies, he dispe sed ma e ials we e
d op-cas ed on o a ca bon chip and allowed o d y a o 12 h.
■ASSOCIATED CONTENT
*
sı Suppo ing In o ma ion
The Suppo ing In o ma ion is a ailable ee o cha ge a
h ps://pubs.acs.o g/doi/10.1021/acs.chemma e .3c00912.
Ma e ials and me hods, syn hesis o monome s, syn-
hesis o copolyme s, he mal s udies o copolyme s,
TGA s udies, CD s udies o poly-(11− -co-2 ) ( = 0.01−
0.03) in di e en sol en s, agg ega ion s udies o
copolyme s poly-(11− -co-2 ) se ies, SEM mic oscopy
images o s e ocomplexes o med by copolyme s poly-
[11− -co-2 ] ( = 0.01−0.03), syn hesis o poly-(11− -co-
2 )-AuNPs and poly-(11− -co-2 )-AgNPs ( = 0.01−
0.03), s imuli- esponsi e s udies o poly-(11− -co-2 )-
MNPs (M = Au o Ag) in di e en sol en s, Raman
s udies o poly-(11− -co-2 )-MNPs (Au o Ag), Raman
s udies o poly-(11− -co-2 )-MNPs (Au o Ag), ON/OFF
s e eocomplexa ion s udies o copolyme s poly-[(R)-
11− -co-2 )]/poly-[(S)-11− -co-2 )] and poly-(11− -co-2 )/
poly-1, CD s udies o copolyme s poly-(11− -co-2 )-
MPNs (M = Au o Ag), agg ega ion s udies o
copolyme s poly-(11− -co-2 )-MPNs (M = Au o Ag),
SEM s udies o poly-[(R)-11− -co-2 )]/poly-[(S)-11− -co-
2 )]-MNPs mix u es, TEM s udies o poly-[(R)-11− -co-
2 )]-AuNPs/poly-[(S)-11− -co-2 )]-AgNPs mix u es, and
e e ences (PDF)
■AUTHOR INFORMATION
Co esponding Au ho
Félix F ei e −Cen o Singula de In es igación en Química
Biolóxica e Ma e iais Molecula es (CiQUS), Uni e sidade de
San iago de Compos ela, 15782 San iago de Compos ela,
Spain; o cid.o g/0000-0002-2672-5830;
Email: [email p o ec ed]
Au ho s
Manuel Nunez-Ma ínez −Cen o Singula de In es igación
en Química Biolóxica e Ma e iais Molecula es (CiQUS),
Uni e sidade de San iago de Compos ela, 15782 San iago de
Compos ela, Spain
Emilio Quinoá −Cen o Singula de In es igación en Química
Biolóxica e Ma e iais Molecula es (CiQUS), Uni e sidade de
San iago de Compos ela, 15782 San iago de Compos ela,
Spain; o cid.o g/0000-0003-3019-3408
Comple e con ac in o ma ion is a ailable a :
h ps://pubs.acs.o g/10.1021/acs.chemma e .3c00912
Au ho Con ibu ions
The manusc ip was w i en h ough con ibu ions o all
au ho s. All au ho s ha e gi en app o al o he inal e sion o
he manusc ip .
Funding
Financial suppo om AEI (PID2019-109733GB-I00), Xun a
de Galicia (ED431C 2022/21, Cen o Singula de In es-
igacion de Galicia ac edi acion 2019−2022, ED431G 2019/
03, and he Eu opean Regional De elopmen Fund (ERDF)
and is g a e ully acknowledged.
No es
The au ho s decla e no compe ing inancial in e es .
■ACKNOWLEDGMENTS
M. N.-M. hanks MICINN o a FPI con ac (BES-2016-
078107). We also hank Se icio de Mic oscopía Elec ónica
(RIAIDT, Uni e sidad de San iago de Compos ela) o SEM
and TEM s udies.
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