E ec o S e eoisome ism on he S uc u e and Linea
Rheology o Poly(Lac ic Acid)
Pe a Baˇ
co á, Mi ko Ma u i, Vagelis Ha manda is, Se gio I.
Molina
Depa amen o de Ciencia de los Ma e iales e Ingenie ía Me alú gica y Química
Ino gánica, Facul ad de Ciencias, IMEYMAT, Campus Uni e si a io Río San Ped o
s/n., Pue o Real, Cádiz 11510, Spain
PITS3D
PITS3D S a egy:
[1,2]
*
[1] h ps://adico k.es/index.php/sec o es/; [2] C ea ed wi h BioRende .com
PITS3D
S a e o he a : expe imen , homopolyme s
Ïc ys alline
ÏPLLA mos ly wi h some
% o D, pu e PDLA no
much known
Ïsimila LVE spec a [1]
Ïcompa able Tg[1]
101
102
103
104
105
106
10-1 100101102
dynamic moduli (G’,G’’)bT (Pa)
angula equency ωαΤ ( ad/s)
G’, D120
G’’, D120
G’, L130
G’’, L130
[1] O hman, No hayani, PhD hesis, 2012
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S a e o he a : expe imen , copolyme s
ÏPDLLA-amo phous
Ïe ec o he inc easing D-con en (XD) and ac ici y
Ï
Tg=Tg,∞−52+791XD
Mn
101
102
103
104
105
106
107
108
100101102103104105106107
%D
dynamic moduli (G’,G’’)bT (Pa)
angula equency ωαΤ ( ad/s)
G’, D100
G’’, D100
G’, L50D50
G’’, L50D50
G’, L75D25
G’’, L75D25
G’, L90D10
G’’, L90D10
[1] O hman, No hayani, PhD hesis, 2012, L.-E. Chile, P. Meh khoda andi, S. G. Ha ziki iakos, Mac omolecules
(2016) 49 (3), 909-919
[2] P. A. Klonos e al., Polyme (2024), 305, 127177
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S a e o he a : simula ion
ÏPLLA and PDLA should ha e he same o ce ield, PDLLA
no much da a
Ïsimila o p o eins: slow s uc u al ea angemen s (slow
equilib a ion and p ope ies such as Tgsensi i e o he
dihed al unc ions)
ÏH-bonds: a omis ic de ail
PLLA100
PDLA100
D-
(R)
L-
(S)
ɸijkl
i
jk
l
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Simula ions: sys ems
Label Mw Mic os uc u e
[g/mol] L D
PLLA10 0.7 k 100%0%
PLLA30 2.2 k 100%0%
PLLA100 7.2 k 100%0%
PLLA125 9.0 k 100%0%
PLLA150 10.8 k 100%0%
PLLA175 12.6 k 100%0%
PDLA30 2.2 k 0%100%
PDLA100 7.2 k 0%100%
Copo55D 7.2 k 45%55%
Copo16D 7.2 k 84%16%
PITS3D
Simula ions: s uc u al p ope ies
H-bond shapen-π*
3 o m ac o
3packing leng h
3domain analysis
3cha ac e is ic a io
ÏPDLA slighly mo e lexible han PLLA
Ïclea di e ences in n-π* pa ame e s be ween
homopolyme s
ÏPDLLA: mo e sphe ical, mo e lexible, mo e compac ,
mo e in amolecula H-bonds
Ïmo e D con en =mo e lexibili y
ÏGaussian cha ac e o chain longe han 100 monome s
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Simula ions: dynamical p ope ies
1
Ï he segmen al and e minal dynamics o PDLA slighly
as e han ha o PLLA,Tgo PDLA lowe han ha o
PLLA
ÏPDLLA: combina ion o slowe and as e segmen s,
en i onmen al e ec s
Ï e minal dynamics: be ween Rouse and en anglemen
scaling
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Expe imen s: samples
Label Mw Mic os uc u e
[g/mol] L D
PLLA10K 10 k 100%0%
PDLLA10K 10 k 50%50%
PLLA25K 25 k 100%0%
PDLA25K 25 k 0%100%
PDLLA25K 25 k 50%50%
PLLA50K 50 k 100%0%
PDLA50K 50 k 0%100%
PDLLA50K 50 k 50%50%
wo comme cial samples o 3D p in ing: PLA3D850, and
ecycled PLA (Sma il, Sma Ma e ials 3D)
PITS3D
Expe imen : linea iscoelas ic spec a homopolyme s
10-2
10-1
100
101
102
103
104
105
106
100101102103
dynamic moduli (G’,G’’) (Pa)
angula equency ωαΤ ( ad/s)
PLLA, T=190°
PLLA25K G’
PLLA25K G’’
PLLA50K G’
PLLA50K G’’
PDLA25K G’
PDLA25K G’’
PDLA50K G’
PDLA50K G’’
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Summa y
úcombina ion o compu a ional and expe imen al me hods
o unde s and s uc u e-p ope y ela ion in PLA
úlinea iscoelas ic spec a complemen he esul s om
NMR and con i m GPC
úlow Mw homopolyme s: PDLA slowe dynamics han
PLLA, indica ions o di e en in e nal packing a
monome ic le el (CG po en ials)
úcopolyme s mo e compac and sphe ical wi h in e nal
H-bonds, dynamics in e co ela ed
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To do
úquan i a i e Mw dis ibu ions (THF s. DMF)
úmodula ed DSC o PDLA
úanalysis wi h he Rep a e so wa e
úconnec ing Mw dis ibu ions wi h LVE spec a
ú emo e cummula i e e o in G( ) da a om simula ion
Keep calm and s ay uned!
)pe a.baco [email p o ec ed]
+h ps://polysim.eu/
+PITS3D p ojec (G an ag eemen ID: 101105208):
h ps://co dis.eu opa.eu/p ojec /id/101105208
/Pe a Baˇ
co á, Vagelis A. Ha manda is, Se gio I. Molina,
Compu a ional in es iga ion o s uc u al p ope ies o
poly(lac ic acid) and i s s e eoisome s: shape, size and
lexibili y, Mac omolecules, in e ision
