S1
Polyp opylene modi ied wi h Ag-based
semiconduc o s as po en ial ma e ial agains
SARS-CoV-2 and o he pa hogens
Ma celo Assisa*, La a K. Ribei oa,b , Ma iana O. Gonçal esc, Lucas H. S a ad,e , Robe S.
Pai ad, Lais R. Limad, Dyo ani Coelhob, Lauana F. Almeida ,g , Leona do N. Mo aes ,g ,
Ieda L. V. Rosab, Lucia H. Masca ob, Rejane M. T. G o o ,g , C is ina P. Sousac, Juan
And ésa, Elson Longob, Sand a A. C uzd
aDepa men o Physical and Analy ical Chemis y, Uni e si y Jaume I (UJI), Cas elló
12071.
bCDMF, LIEC, Fede al Uni e si y o São Ca los - (UFSCa ), São Ca los, SP, 13565-905
B azil.
cBiomolecules and Mic obiology Labo a o y (LaMiB), Bio echnology G adua ion
P og am (PPGBio ec), Fede al Uni e si y o São Ca los (UFSCa ), São Ca los, SP,
13565-905, B azil.
dChemis y Depa men , Fede al Uni e si y o São Ca los (UFSCa ), São Ca los, SP,
13565-905, B azil.
eDepa men o Ma e ials Enginee ing, Fede al Uni e si y o São Ca los - (UFSCa ), São
Ca los, SP, 13565-905 B azil.
School o Ag icul u e, São Paulo S a e Uni e si y (Unesp), Bo uca u, SP, 18610-034,
B azil.
gMolecula Labo a o y o Clinical Hospi al o Bo uca u, Medical School, São Paulo S a e
Uni e si y (Unesp), Bo uca u, SP, 18618-687, B azil.
S2
*Co esponding au ho : [email p o ec ed]
SUPPORTING INFORMATION
Syn hesis o Ag-based Semiconduc o s
Sil e Tungs a e (α-Ag2WO4), Sil e Molybdi e (β-Ag2MoO4) and Sil e
Ch omi e (Ag2C O4) we e syn hesized by he cop ecipi a ion (CP) me hod (CP) in an
aqueous medium a oom empe a u e. Two solu ions we e made, adding 1x10-3 mol o
he la ice o me sal (Na2WO4.2H2O (Sigma-Ald ich, 99.8%), Na2MoO4.2H2O (Al a-
Aesa , 99%) and K2C O4 (Al a-Aesa , 99.9%)) o 50.0 ml o dis illed wa e and 2x10-3
mol o AgNO3 (Cenab as, 99.8%) o 50.0 ml o dis illed wa e . Bo h solu ions we e kep
a 70°C unde cons an s i ing. The AgNO3 solu ion was added o la ice o me sal
solu ion, hen a p ecipi a e appea ed. The p ecipi a e ob ained was washed se e al imes
wi h dis illed wa e and d ied in an o en a 60 ° C o 12h.
Cha ac e iza ions o Semiconduc o s/PP Composi e Ma e ials
These composi e ma e ials we e cha ac e ized by using X-Ray Di ac ion (XRD),
Fou ie T ans o m In a ed Spec oscopy (FTIR), abso p ion spec oscopy in he egions
o Ul a iole and Visible (UV-Vis) and con ac angle. To XRD analysis a Rigaku X- ay
di ac ome e , model DMax2500PC. The equipmen will be ope a ed in he condi ions
o 40 kV and 150 mA, he adia ion used o he measu emen s will be ha o Cu-Kα (λ
= 1.5406 Å). A scan a e o 2°/min we e used in he ange o 10° o 80°. Raman
spec oscopy was ca ied ou using an iHR550 spec ome e (Ho iba Jobin-Y on, Japan)
wi h a cha ge-coupled de ice (CCD) de ec o and an a gon-ion lase (MellesG io , USA)
ope a ing a 633 nm wi h a powe o 200 mW. The di ac og ams we e compa ed wi h
he di ac ion pa e ns acco ding o he JCPDS (Join Commi ee on Powde Di ac ion
S anda ds) and ICSD (Ino ganic C ys al S uc u e Da abase) c ys allog aphic shee s.
FTIR was pe o med using a Jasco FT/IR-6200 (Japan) spec opho ome e ope a ed in
S3
abso bance mode a oom empe a u e in he ange o 470-4000 cm-1. A e , analysis by
UV-Vis we e pe o med on a Ca y equipmen , model 5G by he me hod o o al di use
e lec ance using an in eg a ing sphe e. Sho ly he ea e , he composi es we e
cha ac e ized by he AFM images. The cha ac e iza ion was ob ained using a Flex-AFM
con olled by Easyscan 2 so wa e (Nanosu , Swi ze land) in Cons as Phase mode on
ac i e ib a ion isola ion able (model TS-150, Table S able LTD®). The can ile e used
o image acquisi ion was silicon Tap190G (Resonan equency 190 kHz, o ce cons an
48 N/m, Budge Senso s) in se poin o 50%. To inalize he s uc u al su ace
cha ac e iza ions, con ac angle analyses we e ca ied ou using he me hod o sessile d op
in s a ic mode in a goniome e (Model 260 F4 Se ies Ramé-ha ). On he su ace o each
sample, a 5µL d op o dis illed wa e was deposi ed, and he angle o med be ween he
d op and he polyme su ace was de e mined by DROPimage Ad anced so wa e. The
analyses we e pe o med in iplica e and da a we e ea ed using ha monic media. The
heological beha io o composi es, as well as he deg ee o dispe sion and he in e ac ion
be ween PP and semiconduc o oxides, we e e alua ed by measu es o complex iscosi y
(*) as a unc ion o equency (). in a pa allel pla e heome e (An on Paa MCR 305),
The measu emen s we e ca ied ou a 190 °C, in oscilla o y mode, using a 25 mm
diame e pla es, 1 mm gap and a equency ange o 0.1 o 500 ad/s. The de o ma ion
used was 1%, as i is in he linea iscoelas ic ange, de ined acco ding o a p e ious
ampli ude sweep es . S ess-s ain cu es we e ob ained in he EMIC DL3000 equipmen
wi h a load cell o 20N and a s ain a e o 2.5×10−4 mm/min. The es was based on
ASTM D 638: 2014 and ec angula samples, in ilm o m, wi h app oxima e dimensions
o 30x5 mm and app oxima e hickness o 0.13 mm we e used. Di e en ial scanning
calo ime y (DSC) was pe o med in a DSC 203 F3-Maia (Ne zsch) on samples o 5–10
mg unde he ollowing he mal p og amming: hea ing om -70°C o 200°C a a a e o
10°C/min. The deg ee o c ys allini y o PP was calcula ed om mel ing en halpy (ΔHm),
using Equa ion 1, whe e φ is he mass ac ion o he Ag-based semiconduc o (0, 0.5, 1,
o 3 w %) and is he mel ing en halpy o hypo he ically 100% c ys alline PP, equal
𝛥𝐻
0
𝑚
o 207 J/g.
(Eq. 1)
%
𝐶
=
𝛥
𝐻
𝑚
(100
―
𝜑
)
𝛥𝐻
0
𝑚
𝑥
100
Op ical Analyses o Semiconduc o s/PP Composi e Ma e ials
S4
The UV-Vis-NIR di use e lec ance o he p is ine PP, sil e -based e na y
oxides, and PP modi ied wi h Ag-based e na y oxide a e shown in Figu e S1. In he
Figu e S1A and S1B, he samples con aining he ille s o wide band gap do no exhibi
clea ly abso p ions due o he p esence o he addi i es α-Ag2WO4 and β-Ag2MoO4,
espec i ely, bu he e a e signi ican changes in he o al di use e lec ance o inciden
adia ion and in he colo o he samples (Table S1). On he o he hand, he inco po a ion
o he Ag2C O4 is e iden o PP modi ica ion, which show abso p ions nea o band gap
o he p is ine me al oxide. Fu he mo e, he band abso p ions a 1200, 1400, and 1730
nm a e cha ac e is ic o he 2nd o e one, 1s o e one combina ion, and 1s o e one due
o he C-H single bond ib a ion abso p ion,1 which is in ag eemen wi h he li e a u e.2
The highes dec ease in he o al di use e lec ance is obse ed in he samples con aining
3% o ille s, whe e he obse ed changes in he abso p ion a ibu ed o he 2nd o e one
and 1s o e one combina ion o C-H single bond ib a ion.1 I is belie ed ha is due o
he change in he chain s uc u e o he polyme . Only he PP samples modi ied wi h β-
Ag2MoO4 keep hei s uc u e.
S5
Figu e S1 - Di use e lec ance spec um o he sil e based e na y oxides,
p is ine PP and PP modi ied wi h (A) α-Ag2WO4, (B) β-Ag2MoO4, and (C) Ag2C O4.
300 600 900 1200 1500 1800 2100
0
20
40
60
80
100
Ag2 C O4
PP
PPAC05
PPAC1
PPAC3
Rd / %
Wa eleng h / nm
300 600 900 1200 1500 1800 2100
0
20
40
60
80
100
Ag2MoO4
PP
PPAM05
PPAM1
PPAM3
Rd / %
Wa eleng h / nm
300 600 900 1200 1500 1800 2100
0
20
40
60
80
100
Ag2WO4
PP
PPAW05
PPAW1
PPAW3
Rd / %
Wa eleng h / nm
AB
C

S6
Table S1 – Digi al images o he PP, PPAW, PPAM and PPAC samples.
% added o he polyme (in weigh )
Composi e
P is ine
0.5%
1.0%
3.0%
PP
α-Ag2WO4
β-Ag2MoO4
Ag2C O4
The adia ion abso p ions obse ed in he ul a iole - isible spec um can be
asc ibed o he ansi ions om HOMO o LUMO o polyme and om he alence o he
conduc ion bands o he sil e -based e na y oxides. In he Figu e S1 i is obse ed ha
he polyme ma ix shows a dec ease in he o al di use e lec ance spec um a ound 350
nm, which is associa ed wi h -∗ ansi ions om he ca bonyl g oups o igina ed by
oxida ion o PP.3,4 Fu he , he p is ine sil e -based e na y oxides display abso p ions
a ound 410, 380, and 740 o α-Ag2WO4, β-Ag2MoO4, and Ag2C O4, espec i ely.
The band gap ene gies (Eg) we e expe imen ally es ima ed by ex apola ing he
linea po ion o he Tauc plo cu es, which a e shown in he Figu e S2. Al hough he
p is ine α-Ag2WO4 and β-Ag2MoO4 ha e Eg smalle han he ansi ion HOMO-LUMO
o he polyme , he modi ied PP samples wi h hese ma e ials’ p esen alues o Eg nea
o ansi ion obse ed o pu e PP. I can be associa ed wi h he indi ec ansi ion
beha io o he mechanism o exci a ion o hese me al oxides,5 which could b ing a
supe posi ion o he in e band ansi ion o he me al oxide wi h he HOMO-LUMO
ansi ion o he polyme . In his way, he Tauc plo cu e show jus one ansi ion.
Howe e , as he pe cen age o me al oxides inc eases in he polyme ma ix, he bandgap
dec eases ending o he alue o p is ine me al oxides. Rega ding he PP modi ied wi h
Ag2C O4, he Eg alues we e simila o he me al oxides.5 In his la e case, he na ow
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Eg o he me al oxide does no o e lap wi h he HOMU-LUMO ansi ion o he PP, which
allows he clea obse a ion o he changes in he Tauc plo (Figu e S2). I is no ewo hy
o men ion ha he alues o he Eg es ima ed o he p is ine me al oxide a e in ag eemen
wi h hose epo ed in he li e a u e.5
Figu e S2 – Tauc plo o he (A) PP, (B) PPAW, (C) PPAM, and (D) PPAC. The a ows
indica e he band gap ene gy in he ma e ials wi h indi ec band gap, while he band gap
o di ec ansi ions is he linea ex apola ion c ossing he X axis.
Figu e S3 shows he Raman spec a ob ained o he samples. In all samples i is
possible o obse e he peaks o he polyp opylene polyme ma ix. Be ween 950 and
1500 cm-1 i is possible o obse e he Raman modes ela ed o he de o ma ion and
s e ching ib a ion modes o he -CH2 and -CH3 g oups o he PP skele on.6 In he egions
be ween 2700 and 3000 cm-1, he modes ela ed o he bending ib a ions o he -CH2
g oups a e obse ed.6 On he o he hand, i is possible o di e en ia e he samples due o
he p esence o speci ic Raman modes o he α-Ag2WO4, β-Ag2MoO4 and Ag2C O4. Fo
he PPAW samples, i is possible o obse e an A2g mode a ound 875 cm-1 ela ed o he
s e ching o he [WO4] clus e s.7 In he PPAM samples, an A1g mode loca ed a 873 cm-
1 is also obse ed, ela ed o he symme ical s e ching o he [MoO4] clus e s.8 In he
case o PPAC samples, wo cha ac e is ic Ag modes a e obse ed a 770 and 805 cm-1,
1.5 2.0 2.5 3.0 3.5 4.0
[F(Rd)h] 2 / a.u.
h / eV
PP
1.5 2.0 2.5 3.0 3.5 4.0
Ag2C O4
1.85 eV
1.90 eV
PPAC05
[F(Rd)h] 2 / a.u.
1.88 eV
PPAC1
1.78 eV
PPAC3
h / eV
1.5 2.0 2.5 3.0 3.5 4.0
Ag2MoO4
3.31 eV
PPAM05
3.48 eV
[F(Rd)h] 1/2 / a.u.
PPAM1
3.48 eV
PPAM3
3.45 eV
h / eV
1.5 2.0 2.5 3.0 3.5 4.0
Ag2WO4
3.11 eV
PPAW05
[F(Rd)h] 1/2 / a.u.
3.71 eV
PPAW1
3.68 eV
PPAW3
h / eV
3.61 eV
AB
CD
S8
ela ed o he s e ching o he [C O4] clus e s.9 In his way, as in he XRD and FTIR
analyses, i can be obse ed ha he s uc u es o he polyme and he Ag-based
semiconduc o s a e main ained e en a e he o ma ion o he composi es.
Figu e S3 – Raman spec a o he (A) PPAW, (B) PPAM, and (C) PPAC samples.
500 1000 1500 2000 2500 3000 3500
Raman shi (cm-1)
No malized in ensi y (uni s a b.)
PPAW3
PPAW1
PPAW05
PP
A
B
C
500 1000 1500 2000 2500 3000 3500
PPAC3
PPAC1
PPAC05
PP
Raman shi (cm-1)
No malized in ensi y (a b. uni s)
500 1000 1500 2000 2500 3000 3500
No malized in ensi y (a b. uni s)
Raman shi (cm-1)
PPAM3
PPAM1
PPAM05
PP
S9
Figu e S4 - S o age (G′) and loss modulus (G″) o PPAW (A), PPAM (B) and PPAC (C)
samples a 190° C as a unc ion o equency.