polyme s
Re iew
The E ec o Nano ille s on he Func ional P ope ies
o Biopolyme -Based Films: A Re iew
Ewelina Jam óz1, Pio Kulawik 2and Pa el Kopel 3,4,*
1Ins i u e o Chemis y, Uni e si y o Ag icul u e in C acow, Balicka S ee 122, PL-30-149 K aków, Poland;
[email p o ec ed]
2Depa men o Animal P oduc s P ocessing, Uni e si y o Ag icul u e, Balicka S ee 122,
PL-30-149 K aków, Poland; [email p o ec ed]
3Depa men o Chemis y and Biochemis y, Facul y o Ag iSciences, Mendel Uni e si y in B no,
Zemedelska 1, CZ-613 00 B no, Czech Republic
4Cen al Eu opean Ins i u e o Technology, B no Uni e si y o Technology, Pu kyno a 123,
CZ-612 00 B no, Czech Republic
*Co espondence: [email p o ec ed]; Tel.: +420-545-133-350
Recei ed: 21 Ma ch 2019; Accep ed: 9 Ap il 2019; Published: 12 Ap il 2019
Abs ac :
Was e om non-deg adable plas ics is becoming an inc easingly se ious p oblem. The e o e,
mo e and mo e esea ch ocuses on he de elopmen o ma e ials wi h biodeg adable p ope ies.
Bio-polyme s a e excellen aw ma e ials o he p oduc ion o such ma e ials. Bio-based biopolyme
ilms ein o ced wi h nanos uc u es ha e become an in e es ing a ea o esea ch. Nanocomposi e ilms
a e a g oup o ma e ials ha mainly consis o bio-based na u al (e.g., chi osan, s a ch) and syn he ic
(e.g., poly(lac ic acid)) polyme s and nano ille s (clay, o ganic, ino ganic, o ca bon nanos uc u es),
wi h di e en p ope ies. The in e ac ion be ween en i onmen ally iendly biopolyme s and
nano ille s leads o he imp o ed unc ionali y o nanocomposi e ma e ials. Depending on he
p ope ies o nano ille s, new o imp o ed p ope ies o nanocomposi es can be ob ained such as:
ba ie p ope ies, imp o ed mechanical s eng h, an imic obial, and an ioxidan p ope ies o he mal
s abili y. This e iew compiles in o ma ion abou biopolyme s used as he ma ix o he ilms wi h
nano ille s as he ac i e agen s. Pa icula emphasis has been placed on he in luence o nano ille s
on unc ional p ope ies o biopolyme ilms and hei possible use wi hin he ood indus y and ood
packaging sys ems. The possible applica ions o hose nanocomposi e ilms wi hin o he indus ies
(medicine, d ug and chemical indus y, issue enginee ing) is also b ie ly summa ized.
Keywo ds:
biopolyme ilms; nano ille s; unc ional p ope ies; ilm mechanical p ope ies; ilm
pe meabili y; an imic obial ac i i y; nanocomposi e ma e ials; ood packaging sys ems
1. In oduc ion
Nanocomposi e ilms a e a new gene a ion o packaging ma e ials wi h combina ion o bio-based
polyme and ille s ha ha e a leas one nanome e scale dimension. In nanocomposi e ilms,
he biopolyme ac s as a ma ix, while he nano ille s a e dispe sed he ein o imp o e he unc ional
p ope ies. Nanocomposi es ha e a se o imp o ed p ope ies, such as mechanical, an imic obial,
o physical p ope ies. These p ope ies do no occu na u ally in he biopolyme s hemsel es, he e o e
hey a e gained due o addi ion o nanocomposi es [
1
]. The componen s o biopolyme ilms a e
cha ac e ized by high a ailabili y and good biodeg adabili y. Howe e , one-componen ilms ha e
ela i ely poo mechanical p ope ies and high wa e apo pe meabili y, which may cause hem
no o be o su icien quali y o be used as packaging ma e ials. This can be educed by mixing wo
biopolyme s wi h one ano he [
2
]. Cu en ly, a no el me hod o imp o e he p ope ies o biopolyme
Polyme s 2019,11, 675; doi:10.3390/polym11040675 www.mdpi.com/jou nal/polyme s
Polyme s 2019,11, 675 2 o 43
ilms is he use o nano ille s, which can ul ill no only he ein o cing unc ion bu also could ac as
an ac i e ing edien . In ecen yea s, he concep o ac i e agen s o biopolyme ilms has ecei ed
much mo e a en ion. Such ac i e ing edien s in biopolyme ilms can ex end he shel -li e o ood
p oduc s, h ough exhibi ing an imic obial and/o an ioxidan ac i i ies [
3
,
4
]. The p ese a i e e ec
o biopolyme ilms wi h nano ille s ha e been epo ed o he whole spec um o ood p oduc s
including ege ables and ui s, mush ooms, dai y p oduc s, mea and mea p oduc s, and ish and
o he sea ood [
5
–
15
]. The de elopmen o nano echnology has led o he design o nanocomposi e
ilm ma e ials in which nano ille s play an ac i e ole. The aim o his e iew is o summa ize ecen
ad ances and achie emen s ega ding he addi ion o nano ille s—such as clay, me als, me al oxides,
polyme nanopa icles, nanocellulose, e c.—in o biopolyme ilms wi h a ocus on hei unc ional
p ope ies and a possible use in ood packaging sys ems. Addi ionally, his e iew shows ecen
applica ions o biopolyme ilms wi h nano ille s on wound d essing, d ug, and enzyme deli e y
sys ems and issue enginee ing.
2. Types o Biopolyme s and Nano ille s
New ends and pe spec i es in nano echnology, ha e acili a ed he pa h o use nano ille s as
ac i e agen s in he packaging indus y. This solu ion applies o he p oduc ion o biodeg adable
packaging ma e ial, which is based on biopolyme s and nano ille s. This ype o nanocomposi e
ma e ial is no capable o eplacing syn he ic packaging ma e ials, because i has many disad an ages,
i.e., weak mechanical p ope ies, oo high hyd ophilici y, and suscep ibili y o decomposi ion. Howe e ,
hey a e in e es ing al e na i es o plas ic ma e ials and can be used o example in a eas whe e plas ic
eco e y is no economically easible [16].
Cu en ly, he e is a g owing in e es in he combina ion o biopolyme and nano ille -based
ma e ials. Nano ille s can ha e di e en shapes and sizes, bu hei indi idual pa icles size is,
by de ini ion o he nanoma e ials, below 100 nm [
1
]. The size o nano ille s is e y bene icial o
nanocomposi e ma e ials because hey a e based on a la ge su ace a ea which leads o a la ge
in e phase o bounda y a ea be ween he biopolyme ma ix and nano ille . Due o such in e ac ion,
he biopolyme ma ix is modi ied, which could con ibu e o he imp o emen o mechanical, he mal,
and ba ie p ope ies o bionanocomposi e ma e ials [17].
2.1. Types o Biopolyme s Ma ix
Bio-based polyme s, which a e conside ed he ma ix base du ing p epa a ion o nanocomposi e ilms,
ha e many ad an ages. They a e enewable, biodeg adable, mul i- unc ional, and biocompa ible [18].
Bio-based polyme s can be classi ied in o wo majo ca ego ies:
1. Na u al bio-based polyme s, including:
- polyme s ex ac ed om ag icul u al esou ces:
polysaccha ides:
•neu al: e.g., cellulose, hemicellulose, s a ch
•ca ionic: e.g., chi in, chi osan
•anionic: alginic acid, hyalu onic acid
•o bac e ial o igin: e.g., pullulan, ca ageenan;
p o eins: e.g., gela in and whey p o ein;
2.
O he bio-based polyme s: e.g., lipid, lignin, na u al ubbe , u ushiol, DNA, e c. polyme s
p oduced di ec ly om mic oo ganisms bac e ial cellulose; polyhyd oxyalkanoa es, poly-
ε-cap olac ones.
3. Syn he ic bio-based polyme s, including:
Polyme s 2019,11, 675 3 o 43
na u al-based o bio-based syn he ic polyme s, he monome s o which a e de i ed om
enewable esou ces (e.g., poly(lac ic acid)-PLA);
pa ially bio-based polyme s such as polye hylene (PE), poly(e hylene e eph ala e) (PET)
and polyamide (PA), e c. [19–22].
Among biopolyme s, s a ch and chi osan a e he mos o en used polysaccha ides in he
p oduc ion o biopolyme ilms. Chi osan is a highly in e es ing ilm o ming base due o i s biological
(an imic obial and an ioxidan ac i i y) and physical ( he mal o mechanical) p ope ies [
23
]. The use
o s a ch as ilm o ming coa ings elimina es he p oblem o en i onmen al pollu ion because i is an
economical, non- oxic, and en i onmen ally iendly biopolyme . Howe e , s a ch’s poo mechanical
p ope ies, mois u e sensi i i y, and weak ba ie p ope ies es ic s i s use as a comme cial packaging
ma e ials [
24
]. Pullulan is a neu al polysaccha ide ob ained om he e men a ion medium o he
ungus-like yeas Au eobasidium pullulans [
25
]. I has supe b op ical p ope ies, and applica ions o his
ype o non- oxic, biodeg adable polyme o use in no el op ical ma e ials may be encou aging [26].
P o eins such as gela in a e also used in he p epa a ion o ilms. Howe e , p o eins ha e poo
mechanical p ope ies and e y high sensi i i y o mois u e which a e p oblems in he comme cializa ion
o his ype o ilm [
27
]. Beeswax is a good ba ie agains mois u e mig a ion, because i is hyd ophobic
and has a i mly packed c ys alline s uc u e, which is why i is o en added o a polysaccha ide and
p o ein ma ix o educe he pa ame e s o wa e apo pe meabili y o biopolyme ilms [28,29].
Poly(lac ic acid) o polylac ide is de i ed om enewable biomass p oduc s and was es such as
co n s a ch. This polyme is compos able, non- oxic, biocompa ible, he moplas ic, and has desi able
mechanical p ope ies [
30
]. Howe e , PLA has some limi a ions o packaging applica ions such as
weak wa e apo pe meabili y, low he mal s abili y, and high igidi y [31]. Poly inyl alcohol (PVA)
is a non- oxic polyme , which has excellen chemical esis ance and physical p ope ies [
32
]. The majo
d awback o his syn he ic polyme is i s low mechanical s eng h [
33
]. Polyhyd oxyalkanoa es (PHAs)
a e a amily o biopolyes e s p oduced by a wide a ie y o bac e ia, which a e o en used as a ilm
componen [
34
]. Due o i s biodeg adabili y and compa ibili y wi h a ious polyme s and nano ille s,
poly(
ε
-cap olac one) (PCL) has ecen ly gained in e es [
35
]. Howe e , due o he hyd ophobici y and
c ys allini y o his polyme , PCL unde goes e y slow biodeg ada ion as a esul mic oo ganisms in
he en i onmen [36].
As no ed, he e a e many ypes o biopolyme ilms wi h each ha ing hei own ad an ages and
disad an ages (Table 1). Some d awbacks o he polysaccha ide o p o ein ilms can be o e come.
Blending he di e en biopolyme s oge he is one o he p omising me hods o imp o ing he unc ional
p ope ies o biopolyme -based ilms [
37
,
38
]. The second is o use c oss-linking o biopolyme ilms
wi h a ious nano ille s.
Polyme s 2019,11, 675 4 o 43
Table 1. Ad an ages and disad an ages o biopolyme ilms.
Type o Biopolyme
Film Ad an ages Disad an ages
cellulose-based ilms
as eless, odo less, esis an o oil and
a , hyd ophilic na u e [
27
]; he mal and
chemical s abili y [39]
ha dly dissol es o mel s due o high
c ys allini y [40]; non an imic obial
ac i i y [41]
chi in and
chi osan-based ilms
good CO2ba ie p ope ies,
an imic obial ac i i y [42]
non an ioxidan and an i ungal
ac i i y [43]; limi ed oxygen and wa e
impedimen abili y [44]
s a ch-based ilms odo less, as eless, good O2and CO2
ba ie p ope ies [45]
poo wa e apo ba ie [46] and
ensile p ope ies [47]
pec in-based ilms excellen oxygen ba ing capaci y [48]high wa e apo pe meabili y [49];
poo mechanical pe o mance [48]
pullulan-based ilms
hea -sealable [50]; highly impe meable
o bo h oil and oxygen [51]; excellen
mechanical p ope ies and a low
pe meabili y o oil and oxygen [52]
low solubili y [50]; hyd ophilic
na u e [52]
algina e-based ilms good wa e solubili y, gel abili y, and
ilm- o ming p ope ies [53]
insu icien mechanical p ope ies and
poo wa e esis ance [54]
gela in-based ilms good mechanical and ba ie
p ope ies [55]low wa e apo pe meabili y [56]
whey p o ein-based
ilms
excellen ba ie p ope ies o a oma
compounds and oils [27]
hyd ophilic na u e so i has limi a ion o
mois u e [27]
lipids-based ilms excellen ba ie s agains mois u e
mig a ion [27]
damage he appea ance and gloss o he
coa ed ood p oduc s [57]
bac e ial
cellulose-based ilms
lexibili y and excellen mechanical
p ope ies [58]insoluble in wa e [59]
PCL- based ilms
high mechanical s eng h,
biocompa ibili y, p ocessabili y, and
pe meabili y [60]
highly hyd ophobic and c ys alline [61]
PLA-based ilms
en i onmen al iendliness, good
anspa ency, and biological
compa ibili y [62]
high ha dness, and b i leness, low
s eng h, and poo he mal s abili y [
63
]
PGA-based ilms high mechanical s eng h [64]
high deg ee o c ys allini y, a high
mel ing poin , and i is insoluble in
common o ganic sol en s [65]
PU-based ilms
a o able p ocessabili y, e sa ile
s uc u e–p ope y ela ionships, and
excellen elas ici y [66]
low wa e esis ance and ha dness [66]
2.2. Types o Nano ille s
The e a e ou ypes o nano ille s: clays, o ganic, ino ganic, and ca bon nanos uc u e. The o ganic
nano ille s include na u al biopolyme s (e.g. chi osan, cellulose), whe eas ino ganic agen s a e ei he a
me al (e.g. sil e ) o me al oxide (e.g. ZnO and TiO
2
) [
4
,
67
]. Ca bon nanos uc u es can be classi ied
in o ulle enes, g aphene, ca bon nano ubes, and nano ibe s [
68
]. A lis o examples o p ope ies o
a ious nano ille s is shown in Table 2.
Polyme s 2019,11, 675 5 o 43
Table 2. Recen examples o nano ille s p ope ies.
Type o Nano ille s P ope ies Added o he Film Re e ence
Clay Nano ille s
MMT, Hal e c.
UV shielding p ope ies [69]
Good mechanical s abili y
The mal s abili y [70]
O ganic Nano ille s
Nanocellulose
Blood compa ibili y
An ibac e ial e ec [71]
The mal s abili y [72]
Good mechanical s abili y
Low cy o oxici y [73]
Chi osan nanopa icles
Biocompa ibili y
Biodeg adabili y [74]
Low oxici y [75]
An imic obial ac i i y [76]
Ino ganic Nano ille s
AgNPs
An imic obial e ec [77]
UV shielding p ope ies [78]
An ioxidan ac i i y [79]
Pho oca aly ic e ec [80]
SeNPs An imic obial e ec [81]
An ioxidan ac i i y [82]
CuNPs An imic obial e ec [83]
UV shielding p ope ies [84]
SNPs An imic obial e ec [85]
TiO2NPs
An i ouling e ec [86]
An imic obial ac i i y [87]
Pho oca aly ic ac i i y [88]
UV shielding p ope ies [69]
ZnO NPs
An i ungal e ec
UV shielding p ope ies [89]
An imic obial e ec [90]
Dielec ic p ope ies
Elec omagne ic shielding
The mal conduc i i y [91]
CeO2
An imic obial e ec
UV shielding p ope ies
Flame e a dancy
W inkle esis ance [92]
Ca bon Nano ille s
G aphene, g aphene
oxide, e c. Ligh weigh
P ocessing bene i s, lexibili y, esis ance o co osion
Ex ao dina y elec ical, mechanical, and he mal p ope ies [93]
The hyb id ma e ials, which a e ma e ials made om hyb id o o ganic and ino ganic ma e ials,
a ac s mo e and mo e a en ion in a ious ields o esea ch. In compa ison o con en ional
ma e ials, o ganic–ino ganic hyb id ma e ials ha e ea u es de i ed om he ino ganic pa
( igidi y, dimensional s abili y and he mal s abili y) as well as he p ope ies o o ganic ma e ials
( enaci y and wo kabili y) [94].
Polyme s 2019,11, 675 6 o 43
2.2.1. Clay and O ganic Nano ille s
Na u al clays a e inexpensi e ma e ials and exis as aluminum silica e, which consis s o
ine-g ained mine als. Cu en ly, nanoclays a e he mos commonly used nanopa icles, and hey exis
in he o m o shee s/pla ele s, which ha e a leas one dimension in he nanoscale ange. The mos o en
used nanoclay is mon mo illoni e (MMT), which consis s o wo e ahed al silica shee s connec ed o
an edge-di ided, eigh -sided aluminum oxide shee [
16
]. Ano he ype o nanoclay is halloysi e (Hal),
which is a na u al aluminosilica e clay mine al wi h hollow, cylind ical-shaped nano ubes [
95
]. The
s ong mechanical p ope ies o Hal ha e been in eg a ed wi h he an imic obial and pho oca aly ic
p ope ies o me al oxides and me al nanopa icles by g a ing hem on Hal [95–97].
Na u al biopolyme nano ib ils, which a e composed o a ious biopolyme molecules—
i.e., cellulose, collagen, and chi in—a e o en used due o hei biocompa ibili y, biodeg adabili y,
du abili y, a ailabili y, and unique mechanical p ope ies [
98
]. Nanocellulose, which is ex ac ed
om cellulose, is cha ac e ized by he eac i e su ace o hyd oxyl g oups and hus can be adap ed
o di e en su ace p ope ies [
99
,
100
]. The e a e h ee ypes o cellulose used on he nanoscale as
an addi i e o biopolyme ilms: nanoc ys alline cellulose, nano ib illa ed cellulose, and bac e ial
nanocellulose [
100
]. These ypes o nanocellulose di e in hei mo phology, deg ee o c ys allini y,
pa icle size, and some o he p ope ies. These di e ences esul om hei sou ces and a ious
ex ac ion me hods used [
100
]. Nanoc ys alline cellulose wi h i s high c ys allini y and sho - od
shape is also known as cellulose nanoc ys als o cellulose nanowhiske s and is usually ex ac ed om
cellulose ib ils by acid hyd olysis [
101
]. The sou ce o cellulose nanoc ys als may also a ec he
unc ionali y o he nano ille [102].
Nano ib illa ed cellulose is ex ac ed om cellulose ibe s using mechanical me hods. This long,
lexible, and angled nanocellulose is also known as cellulose mic o ib il, mic o ib illa ed cellulose,
cellulose nano ibe , cellulose nano ib il, and nano ib illa cellulose [100].
Bac e ial nanocellulose (BNC), which is mainly ex ac ed om cul u es o he G am-nega i e
bac e ia, Gluconace obac e xylinus, has a highe molecula weigh and c ys allini y han cellulose om
plan sou ces [
103
]. The di e en ypes o nanocellulose ha e been inco po a ed o many biopolyme
ilms [104–107].
Chi osan and chi in nanopa icles ob ained espec i ely om chi osan o chi in ha e gained
a en ion as nano ille s, due o hei a ac i e su ace a ea, biocompa ibili y, non- oxici y and ilm
o ming abili y [
108
–
112
]. An impo an limi a ion in he use o chi osan nanopa icles is hei poo
s abili y. I can be imp o ed by con olling he condi ions e.g., by changing he s uc u e wi h chemical
agen s. Poo solubili y o chi osan nanopa icles is he nex limi a ion, which is a majo p oblem in he
encapsula ion o hyd ophobic d ugs [113].
2.2.2. Ino ganic Nano ille s
Due o hei be e mechanical, he mal, physical, biological, and chemical p ope ies han bulk
ma e ials, nanopa icles (NPs) a e an in e es ing solu ion as unc ional agen s o biopolyme s ilms.
Coppe nanopa icles (CuNPs) a e known o possess an imic obial ac i i y on wide spec um o
mic obes. Released coppe ions ha e a high edox po en ial and he abili y o des oy and cause
apop osis o mic obial cell componen s [
114
]. Owing o hei excellen physicochemical and biological
p ope ies, sil e nanopa icles (AgNPs) ha e gained inc easingly mo e a en ion o use in wound
healing [
115
], ood packaging [
116
], and in medical applica ions [
117
]. Selenium nanopa icles (SeNPs)
show signi ican ly educed oxici y compa ed o selenium. In addi ion, SeNPs can be used as a pla o m
o anspo ing di e en d ugs o a ge des ina ions [118].
Me al oxide nanopa icles such as zinc oxide (ZnO NPs), i anium oxide (TiO
2
NPs), silica
(SiO
2
NPs), aluminum oxide (Al
2
O
3
NPs), ce ium oxide (CeO
2
NPs), i on oxide (Fe
2
O
3
NPs), and
coppe oxide (CuO NPs) ha e been added o biopolyme ilms as ac i e nano ille s. TiO
2
NPs and ZnO
NPs ha e pho oca aly ic an ibac e ial p ope ies, caused by eac i e oxygen species (ROS) o ma ion
a e exposu e o UV-ligh [
119
]. Addi ionally, ZnO NPs can elease zinc ions ha damage bac e ial
Polyme s 2019,11, 675 7 o 43
cells, showing ha an imic obial p ope ies do no ha e o be dependen on UV exposu e [
120
].
The low hyd ophilici y o TiO
2
p e en s he pene a ion o mois u e in o he biopolyme ma ix.
Mo eo e , he ba ie e ec o TiO
2
leads o educ ion in wa e apo pe meabili y [
121
]. CuO NPs
ha e an imic obial, an ibac e ial, and an ioxidan ac i i y and exhibi a UV-blocking e ec [
122
,
123
].
Tin oxide (SnO
2
) nanopa icles ha e elec ical, he mal, mechanical and gas ba ie p ope ies [
124
,
125
].
The addi ion o non- oxic and neu al Al
2
O
3
NPs o he biopolyme ma ix p o ides a wide ange o
p omising p ope ies due o i s small pa icles, signi ican su ace a ea, and good ac i i y [126,127].
2.2.3. Ca bon Nano ille s
G aphene-based ma e ials ha e gained a en ion due o hei p ope ies which include excellen
mechanical p ope ies and subs an ial elec on mobili y. G aphene, in compa ison o o he ca bon-based
nanoma e ials ( o example ca bon nano ubes), is cha ac e ized by a la ge su ace a ea ha could
acili a e in e ac ions wi h he polyme ma ix [
128
,
129
]. G aphene oxide (GO) is he mos p omising
nano ille , among he g aphene- amily nanoma e ials, because i has a lowe endency o agglome a e
han p is ine g aphene [
130
]. The bigges limi a ions, o he use o GO, a e i s in insic ze o band-gap
ene gy and low solubili y in o ganic and aqueous sol en s [
131
]. The chemical unc ionaliza ion o
g aphene oxide leads o i s modi ica ion and hus inc eases he possibili ies o i s po en ial applica ion.
Reduced GO (RGO) has e y good mechanical, physical, elec ical, and he mal p ope ies, which makes
i a ac i e nano ille in biopolyme ilms [132].
2.2.4. O he Nano ille s
Semiconduc o quan um do s (QDs) a e a ac ing inc easing a en ion due o hei op ical
p ope ies and high pho os abili y [
133
]. Due o hei s ong endency o oxida ion and agglome a ion,
i is desi able o imp o e he compa ibili y and s abili y o his ype o nano ille s in biopolyme s [
134
].
G aphene quan um do s (GQDs) inco po a ed in biopolyme ilms ha e ad an ages such as a ailabili y,
biodeg adabili y, low p ice, and low p oduc ion cos , making he nanocomposi e ilms a p e e ed
candida e o use in op oelec onics applica ions [135].
3. E ec s o Nano ille s on he Func ional P ope ies o Biopolyme -Based Films
The g aphical illus a ion o nano ille s use wi hin he biopolyme ma ix along wi h hei
unc ional p ope ies is p esen ed in Figu e 1.
3.1. E ec s o Nano ille s on he Physical P ope ies o Polyme -Based Films
Wa e esis ance is an impo an unc ional pa ame e o biopolyme ilms. In many s udies, wa e
esis ance o he ilms is e alua ed by hei wa e solubili y, swelling deg ee, wa e con en , and wa e
apo pe meabili y [87,136].
The addi ion o nano ille s dec eases he solubili y o biopolyme ilms due o he a io o
dimensions and c ys alline a eas o he ille s [
87
,
137
]. Noshi ani and co-wo ke s (2018) con i med
ha he lowe solubili y o he nanocomposi e ilms is caused by he hyd ogen bond be ween he
hyd oxyl g oups o s a ch, PVA, and cellulose nanoc ys als. The h ee-dimensional ne wo k gene a ed
leads o he s eng hening o he ne wo k and educes i s solubili y [
138
]. The same end was obse ed
in ke i an-caboxyme hyl cellulose ilms wi h CuO NPs [
139
] and in ke i an ilms wi h Al
2
O
3
NPs [
127
].
Mo eo e , he ype o nanopa icles also plays an impo an ole in he solubili y o he ilm. A dec ease
in he solubili y o he ilm can be a ibu ed o he e y low solubili y o he nanopa icles compa ed
o he polyme chains, which leads o a educ ion in he hyd ophilici y o he biopolyme ma ix [
121
].
The in e ac ions be ween halloysi e nanoclay and soluble soybean polysaccha ide caused a dec ease in
wa e solubili y due o educ ion in he a ailabili y o hyd oxyl g oups o in e ac wi h wa e [140].
Polyme s 2019,11, 675 8 o 43
Polyme s 2019, 11, 675 7 o 42
nanopa icles ha e elec ical, he mal, mechanical and gas ba ie p ope ies [124,125]. The addi ion o
non- oxic and neu al Al
2
O
3
NPs o he biopolyme ma ix p o ides a wide ange o p omising
p ope ies due o i s small pa icles, signi ican su ace a ea, and good ac i i y [126,127].
2.2.3. Ca bon Nano ille s
G aphene-based ma e ials ha e gained a en ion due o hei p ope ies which include excellen
mechanical p ope ies and subs an ial elec on mobili y. G aphene, in compa ison o o he ca bon-
based nanoma e ials ( o example ca bon nano ubes), is cha ac e ized by a la ge su ace a ea ha could
acili a e in e ac ions wi h he polyme ma ix [128,129]. G aphene oxide (GO) is he mos p omising
nano ille , among he g aphene- amily nanoma e ials, because i has a lowe endency o agglome a e
han p is ine g aphene [130]. The bigges limi a ions, o he use o GO, a e i s in insic ze o band-gap
ene gy and low solubili y in o ganic and aqueous sol en s [131]. The chemical unc ionaliza ion o
g aphene oxide leads o i s modi ica ion and hus inc eases he possibili ies o i s po en ial applica ion.
Reduced GO (RGO) has e y good mechanical, physical, elec ical, and he mal p ope ies, which
makes i a ac i e nano ille in biopolyme ilms [132].
2.2.4. O he Nano ille s
Semiconduc o quan um do s (QDs) a e a ac ing inc easing a en ion due o hei op ical
p ope ies and high pho os abili y [133]. Due o hei s ong endency o oxida ion and agglome a ion,
i is desi able o imp o e he compa ibili y and s abili y o his ype o nano ille s in biopolyme s [134].
G aphene quan um do s (GQDs) inco po a ed in biopolyme ilms ha e ad an ages such as a ailabili y,
biodeg adabili y, low p ice, and low p oduc ion cos , making he nanocomposi e ilms a p e e ed
candida e o use in op oelec onics applica ions [135].
3. E ec s o Nano ille s on he Func ional P ope ies o Biopolyme -Based Films
The g aphical illus a ion o nano ille s use wi hin he biopolyme ma ix along wi h hei
unc ional p ope ies is p esen ed in Figu e 1.
Figu e 1. Schema ic p epa a ion o nanocomposi e ilms and hei unc ional p ope ies.
3.1. E ec s o Nano ille s on he Physical P ope ies o Polyme -Based Films
Figu e 1. Schema ic p epa a ion o nanocomposi e ilms and hei unc ional p ope ies.
The emp y spaces in he s uc u al ne wo k o nanocomposi es can be occupied by wa e molecules.
This phenomenon is conside ed he wa e con en o he ilm [
87
,
141
]. The addi ion o nano ille s in o
he ilms can cause a dec ease in wa e con en . This beha io could be ela ed o he in e ac ion be ween
nano ille s and unc ional g oups o he biopolyme chain, which can lead o a educ ion in he a ailable
spaces in he biopolyme ma ix [
87
]. Noshi ani and co-wo ke s (2018) de eloped s a ch-PVA ilms
wi h cellulose nanoc ys als (CNC). They no iced ha he addi ion o he nano ille caused a dec ease
in he mois u e con en o he ilm. Such beha io was demons a ed by he c ys al s uc u e o he
CNC, which causes lowe wa e up ake han he polyme ma ix and he o ma ion o s ong hyd ogen
in e ac ions be ween he CNC and he s a ch-PVA ma ix [
138
]. The addi ion o nano-SiO
2
in o
whey p o ein isola e–pullulan ma ix dec eased mois u e con en o nanocomposi e ilms. The s ong
in e ac ions be ween componen s caused he di usion o wa e molecules o nanocomposi es [142].
An impo an p ope y o biopolyme ilms, and in pa icula polysaccha ide ilms, is he swelling
deg ee, which de e mines he amoun o abso bed wa e . As he alue o he swelling deg ee inc eases,
he ole ance o ilm o wa e inc eases [
143
]. In gene al, he addi ion o nano ille s imp o es he
swelling deg ee and inc eases he wa e esis ance o he ilms. This is a ibu ed o he s ong
hyd ogen in e ac ions be ween he nano ille /nano ille and he nano ille s/biopolyme ma ix [
143
].
Howe e , he e e se end can also be no iced. The addi ion o chi in nano ibe (CHNF) caused an
inc emen al swelling deg ee o chi osan ilms, which was due o inc eased amoun o OH
-
g oups om
CHNF and esul ed in inc eased wa e abso p ion [
144
]. The same phenomenon was obse ed in he
chi osan/s a ch ilms wi h halloysi e nano ubes, which was a ibu ed o he inc eased po osi y and
hyd ophilici y o he nanocomposi e ilms [145].
The wa e apo pe meabili y (WVP) is e y impo an o esh ood p oduc s and o p oduc s
whe e dehyd a ion and abso p ion o mois u e should be a oided. The alues o WVP o packaging
sys ems should be a he lowes possible le el [
28
,
87
,
146
]. The wa e apo pe meabili y in biopolyme
ilms is in luenced by he chemical na u e o mac omolecules, po osi y and c ys allini y, deg ee o
c oss-linking, ela i e humidi y, and addi ion o a plas icize [
147
,
148
]. The addi ion o nano ille s o
biopolyme ilms has an impac on he wa e apo ba ie p ope ies. The low WVP o ilms is an
impo an ea u e in he packaging o ood p oduc s as hey can educe he mois u e ans e be ween
he inne and ou e packaging en i onmen [
149
]. The p esence o impe meable nanopa icles in he
biopolyme ma ix p e en s he mobili y o he biopolyme chain, and consequen ly can lead o a
educ ion in he wa e apo pe meabili y o he nanocomposi e ilms [
28
]. In addi ion, he hyd ophobic
Polyme s 2019,11, 675 9 o 43
cha ac e o nanopa icles (e.g., TiO
2
) a ec s he educ ion o he WVP o he ilm, due o he low aspec
a io o his nanopa icle and he i egula s eng hening o he chains [
87
]. Shanka e al. concluded
ha he p esence o halloysi e nano ubes and AgNPs c ea es an inc eased o uous pa h o he passage
o wa e apo molecules h ough he algina e ma ix. On he o he hand, exceeding he c i ical
concen a ion o nano ille s inc eases he wa e apo pe meabili y o nanocomposi e ilms [
150
].
Simila pa e ns o changes in WVP p ope ies ha e been obse ed in many s udies [
87
,
95
,
143
,
151
–
153
].
The ype o nano ille used also has an e ec on he WVP o ilms. Zahedi and co-au ho s (2018)
es ablished ha sodium MMT nanoclay is mo e e ec i e in he educ ion o he WVP o ca boxylme hyl
cellulose ilms han ZnONPs. These di e ences may esul om a ious s uc u al and a angemen
ea u es. ZnONPs ha e a hexagonal close packaged s uc u e, while MMT is a laye ed silica e
s uc u e [
154
]. Nanoclays impede he di usion o he wa e apo due o impe meable laye s o his
ype o nano ille [
155
,
156
]. Howe e , he addi ion o ano he ype o nanoclay, laponi e—syn he ic
hec o i e-like clay— o ka i in ilm, does no signi ican ly a ec he WVP o he es ed ilms. The
hyd ophilic clay, due o he p esence o Si-OH g oups, can a ec he hyd ophilici y o he su ace [
157
].
The same end was obse ed in collagen ilms wi h laponi e [158].
In ela ed li e a u e, he opposi e e ec on he wa e ba ie p ope ies o biopolyme ilms is
also epo ed. The addi ion o MMT/alkylammonium (hexa- and e a-decyl ime hylammonium)
and MMT/chi osan o cellulose ace a e coa ings inc eased he WVP alue o he ilm [
159
]. Also he
capping agen used in he p epa a ion o he nanopa icles is c i ical o he WVP o he ilm. CMC was
used as a capping agen in p epa a ion o ZnO NPs. The nanopa icles caused an inc ease in he WVP
o he gela in ilms, which is a ibu ed o he hyd ophilic na u e o CMC used as capping agen [
160
].
Sil a and co-wo ke s (2019) p epa ed new nanocomposi es based on laponi e and cellulose nano ibe s.
They concluded ha he inc ease in WVP is ela ed o he hyd ophilic na u e o laponi e [161].
Oxygen pe meabili y (OP) is one o he c ucial pa ame e s o ilms used in ood packaging.
Low OP alues a e p e e ed, because oxygen can cause de e io a ion in he quali y o packed ood
p oduc s [
162
]. The addi ion o nano ille s in o biopolyme ilms may cause a dec ease in he OP alues.
Wu e al. (2019) s a ed ha he AgNPs addi ion in o nanocellulose ilms wi h g ape seed ex ac s
caused he imp o emen in ba ie p ope ies o he es ed ilms. AgNPs illed he in e spaces o ma ix
and hinde ed he ans e o O
2
molecules h ough he ilm [
163
]. The p esence o nanocellulose also
causes he educ ion o OP o he ilm, which can be a ibu ed o he o ma ion o a dense ne wo k
s uc u e o he ilm ma ix [
152
]. A simila phenomenon was obse ed wi h he addi ion o halloysi e
nanoclay in o po a o s a ch ilms. The educ ion in he pe meabili y alues may esul om he ac
ha gases ha e an ex ended di usion pa h [164].
3.2. E ec s o Nano ille s on he Mechanical P ope ies o Polyme -Based Films
Two main pa ame e s which a e o en used o de e mine he mechanical p ope ies o biopolyme
ilms a e ensile s eng h (TS, MPa), which is used o measu e s eng h, and he pe cen age o elonga ion
a b eak (EAB, %) which is used o de e mine he elas ici y o he ilm. These pa ame e s mus mee
ce ain s anda ds o main ain in eg i y du ing packaging [
149
]. The addi ion o nanopa icles o
biopolyme ilms signi ican ly a ec s hei mechanical p ope ies. This may be due o he ac ha
nanopa icles ha e a e y la ge speci ic su ace a ea ha can a ec in e acial s eng h and deg ee
o dispe sion. E en dis ibu ion o nanopa icles wi hin he biopolyme ma ix esul s in a speci ic
ans e o s ess h ough he shea mechanism om he biopolyme ma ix o he nanopa icles and
could esul in e ec i e load ans e and inc eased s eng h o he ilm [31,165].
The phenomenon o s eng hening he ensile s eng h may also esul om he in e ac ion be ween
he nano ille and he biopolyme ma ix, whe e hyd ogen and co alen bonds be ween nanopa icles
and, o example, hyd oxyl g oups o biopolyme a e o med, which leads o he s eng hening o
molecula o ces be ween nanopa icles and he biopolyme [143,166].
Nano ille s can ill he ee space be ween biopolyme chains, which inc eases he in e molecula
a ac ion o ce, making he biopolyme ma ix e y dense and less pe meable [
143
]. Imp o emen in TS
Polyme s 2019,11, 675 16 o 43
Table 3. Con .
Nano ille Polyme The E ec o Nano ille Addi ion Re e ence
Magne ic
nanopa icles chi osan •Imp o emen o TS (by up o ~37%) and EAB (by up o ~18%) [208]
TiO2NPs gela in
•Enhancemen o TS (by up o ~60%) and EAB (by up o ~48%)
•Imp o emen o ba ie p ope ies agains UVC ligh
•I adia ion o he ilm wi h UV-A ligh (365 nm) esul ed in he mos e ec i e an ibac e ial ac i i y
agains E. coli
[209]
TiO2NPs gela in–aga
•Imp o emen o TS (by up o ~29%) and educ ion in EAB (by up o ~22%)
•Inc emen o WS (by up o ~4%) and MC (by up o ~10%)
•Reduc ion o WVP (by up o ~32%)
•UV blocking e ec
[146]
TiO2NPs chi osan
•Imp o emen o an imic obial ac i i y agains bac e ia (S. au eus, E. coli, S. yphimu ium, and
P. ae uginosa) and ungi (Aspe gillus spp. and Penicillium spp.)
•Enhancemen o TS (by up o ~56%), WVP (by up o ~22%) and e hylene pho oca aly ic deg ada ion
p ope ies
•Reduc ion o EAB (by up o ~10%)
[210]
TiO2NPs po a o s a ch
•Reduc ion o WS (by up o ~9%), MC (by up o ~11%) and WVP (by up o ~35%)
•Imp o emen o TS (by up o ~45%) and educ ion o EAB (by up o ~28%)
•Imp o emen o UV-blocking e ec
[121]
CuO NPs PVA–gela in •Imp o emen o UV sc eening e ec [123]
ZnO NPs gela in
•Imp o emen o UV sc eening e ec and he mal s abili y
•Reduc ion o EM (by up o ~82%) and TS (by up o ~72%)
•Inc emen o WVP (by up o ~99%), MC (by up o ~29%), WCA (by up o ~20%)
•Imp o emen o an imic obial ac i i y agains E. coli ( om 9 o 5 log) and L. monocy ogenes
( om 9 o 1 log)
[160]
ZnO NPs chi osan/CMC
•Imp o emen o shel li e o whi e so cheese on which he ilm was applied
•Imp o emen o an ibac e ial ac i i y agains bac e ia S. au eus ( om 5 o 11 mm o inhibi ion zone)
P. ae uginosa ( om 3 o 11 mm), E. coli ( om 3 o 9 mm), and ungi C. albicans ( om 3 o 15 mm)
•Imp o emen o TS (by up o ~85%)
[211]
ZnO NPs chi osan
•Imp o emen o TS bu educ ion o EAB
•Imp o emen o an imic obial ac i i y agains E. coli (3.4 log educ ion a e 0.5 h) and S. au eus
(4 log educ ion a e 0.5 h)
•Biocompa ibili y and non oxici y
[212]
Polyme s 2019,11, 675 17 o 43
Table 3. Con .
Nano ille Polyme The E ec o Nano ille Addi ion Re e ence
ZnO NPs mahua oil-based
polyu e hane/chi osan
•Imp o emen o TS (by up o ~56%) bu educ ion o EAB (by up o ~20%)
•Reduc ion o OP (by up o ~3%) and WVP (by up o ~37%)
•Imp o emen o an imic obial ac i i y agains E. coli (~25 mm) and S. au eus (~20 mm)
•UV-sc eening abili y and biodeg ada ion
•Non-cy o oxic
[213]
ZnO NPs PLA
•Imp o emen o TS (by up o ~37%), WVP (by up o ~31%) and UV-ligh ba ie p ope ies
•Reduc ion o EAB (by up o ~10%)
•Imp o emen o an ibac e ial ac i i y agains E. coli ( om 10 o 3.5 log a e 12 h) and L. monocy ogenes
( om 12 o 8 log a e 12 h)
[31]
ZnO NPs chi osan/PVA •Imp o emen in pho oluminescen p ope ies and he mal s abili y [214]
SnO2NPs CMC
•The choice o nanocomposi e p epa a ion p ocedu e caused ou di e en mo phologies o SnO2NPs
(mic ocube, nanosphe e, oli e-like and nano- lowe ) which had di e en e ec s on he mal
s abili y o CMC
[125]
ZnO NPs
CuO NPs ca ageenan
•ZnONPs s ongly imp o ed an imic obial ac i i y agains E. coli and L. monocy ogenes, UV-blocking
e ec and he mal s abili y
•Reduc ion o TS (by up o ~55%) and EM (by up o ~26%) depending on he CuO NPs and ZnO NPs
concen a ion and he a io o nanopa icles
•Imp o emen o EAB
[215]
Fe2O3NPs cellulose •Imp o emen o TS (by up o ~10%) and YM (by up o ~15%) and he mal s abili y [216]
MgO NPs PLA/polye hylene
glycol
•Imp o emen o EAB (by up o ~86%) bu educ ion o TS (by up o ~64%)
•Enhancemen o op ical p ope ies [217]
α- Fe2O3NPs
FeNPs chi osan/PVA
•Imp o emen o magne ic p ope ies
•FeNPs dec eased TS and EM depending on he composi ion o chi osan and PVA
•Fe2O3NPs inc eased TS and EM depending on he composi ion o chi osan and PVA
•FeNPs and Fe2O3NPs caused educ ion in EAB
[33]
ZnO nano od
nano-kaolin semolina
•
Reduc ion o OP (by up o ~34%), MC (by up o ~64%) and WS (by up o ~56%), depending on he a io
ZnO nano ods/nano-koalin
•Imp o emen o UV ba ie p ope ies and an imic obial ac i i y agains E. coli ( om 0 o ~3 mm)
[218]
ZnO nano ods s a ch/gela in
•Reduc ion o OP (by up o ~61%)
•Imp o emen o TS (by up o ~30%) bu dec emen o EAB (by up o ~44%)
•Enhancemen o UV ba ie p ope ies
[174]
Polyme s 2019,11, 675 18 o 43
Table 3. Con .
Nano ille Polyme The E ec o Nano ille Addi ion Re e ence
ZnO nano ods gela in/clo e essen ial
oil
•Reduc ion o TS (by up o ~61%) and inc emen o EAB (by up o ~155%) and OP (by up o 98%)
•Inc emen o oxygen and UV ba ie p ope y
•Imp o emen o an imic obial ac i i y agains L. monocy ogenes ( om 10 o 0 log a e 7 days) and
S. yphimu ium ( om 10 o 0 log a e 7 days)
•Imp o emen o shel -li e o peeled sh imps
[219]
ZnO nano ods gela in
•Dec emen o hyd ophobici y and mois u e con en s
•Reduc ion o WVP (by up o ~80%)
•Imp o emen o UV-blocking e ec and an imic obial ac i i y agains S. au eus ( om 0 o 80 mm2o
inhibi ion zone)
[185]
ZnO nano ods soybean polysaccha ide
•Reduc ion o WVP (by up o ~36%) and OP (by up o ~43%)
•Dec emen o TS (by up o ~18%) and inc emen o EAB (by up o ~41%) and hea seal s eng h
(by up o ~29%)
•Imp o emen o an imic obial ac i i y agains E. coli ( om 7 o 5 log a e 12 h) and S. au eus
( om 6 o 1 log a e 12 h) and UV-blocking e ec
[220]
ZnO nano ods PVA/CMC •Imp o emen o dielec ic p ope ies [221]
Cellulose Nanos uc u es
cellulose nanoc ys als ca ageenan
•Imp o emen o TS (by up o ~70%) and oughness (by up o ~10%) pa ame e s
•Reduc ion o EAB (by up o ~25%)
•Enhancemen o he mal s abili y
[179]
ice cellulose
nanoc ys als chi osan/PVA
•Imp o emen o TS (by up o ~75%) and EM (by up o ~98%)
•Reduc ion o EAB (by up o ~43%)
•Enhancemen o he mal s abili y
•
No changes in an i ungal agains C. gloeospo ioides and L. heob omae and an imic obial agains S. mu ans,
S. au eus, E. coli, and P. ae uginosa ac i i ies
[222]
cellulose nanoc ys als chi osan •Imp o emen o mechanical p ope ies (by up o ~44%) and he mal s abili y [106]
lax cellulose
nanoc ys als chi osan
•Imp o emen o TS (by up o ~24%), EAB (by up o ~22%) and YM (by up o ~140%)
•Reduc ion o WVTR (by up o ~11%) and inc emen o WVP (by up o ~85%)
•Enhancemen o an imic obial ac i i y agains P. ae uginosa, E. aecalis, L. monocy ogenes, E. coli, and
S. au eus ( om 6.31 o 16.05 mm o inhibi ion zone)
[223]
bac e ial cellulose
nanoc ys al PVA •Imp o emen o TS, YM, and oughness depending on he p esence o glyce ol, bo ic acid, and BCNC
•No changes in EAB [105]
Polyme s 2019,11, 675 19 o 43
Table 3. Con .
Nano ille Polyme The E ec o Nano ille Addi ion Re e ence
cellulose
nanowhiske s chi osan •Inc emen o YM bu educ ion o TS and EAB
•Enhancemen o he mal s abili y [224]
nanoc ys alline
cellulose chi osan/gua gum
•Imp o emen o he shea iscosi y o he suspensions
•Reduc ion o ai pe meabili y (by up o ~53%) and EAB (by up o ~53%)
•Imp o emen o YM (by up o ~86%) and TS (by up o ~75%)
[225]
suga palm
nanoc ys alline
cellulose
suga palm ib e •Reduc ion o MC (by up o ~19%), WS (by up o ~56%)
•Imp o emen o WVP (by up o ~18%) and he mal s abili y [153]
bac e ial cellulose
nanoc ys als and
AgNPs
chi osan
•Imp o emen o UV ba ie p ope ies
•Enhancemen o physical, mechanical p ope ies and in he mal s abili y, depending on he
concen a ion and a io o AgNPs and BCNC
•Imp o emen o an imic obial and an i ungal ac i i y ( om 0 o 96 mm2o inhibi ion zone depending
on he concen a ion and a io o AgNPs and BCNC)
[184]
cellulose nanoc ys als
chi osan
algina e
κ-ca ageenan
•Imp o emen o YM, TS, and oughness in e e y ype o ilm
•Reduc ion in pa ame e o EAB [178]
co on lin e cellulose
nano ib il CMC
•Imp o emen o TS (by up o ~23%) and EM (by up o ~28%) bu educ ion o EAB (by up o ~26%)
•Enhancemen o he mal s abili y
•Reduc ion o WCA (by up o ~39%)
•No changes in WVP
[226]
celullose nanoc ys als CMC •Enhancemen o he mal s abili y
•Imp o emen o TS (by up o ~74%) and EM (by up o ~129%) and educ ion o EAB (by up o ~47%) [227]
cellulose nano ibe s soy p o ein
•Imp o emen o TS (by up o ~400%) and YM (by up o ~767%)
•Reduc ion o EAB (by up o ~56%)
•No e ec s o WVP
[228]
cellulose nanoc ys als cassa a s a ch
•Reduc ion o WVP (by up o ~43%), oil pe meabili y (by up o ~42%) and MC
•Imp o emen o TS (5.6 imes highe han cassa a s a ch ilms)
•Inc emen o WS
[229]
cellulose nanoc ys als PVA/CMC •Enhancemen o TS (by up o ~83%) and EM (by up o ~147%)
•Reduc ion o WVP (by up o ~82%) [2]
Polyme s 2019,11, 675 20 o 43
Table 3. Con .
Nano ille Polyme The E ec o Nano ille Addi ion Re e ence
c ys alline
nanocellulose CMC/chi osan
•Enhancemen o ba ie agains g ease and oil
•Imp o emen o TS (52% highe han CMC/chi osan ilms), YM, and WVP (by up o ~38%)
•Reduc ion o s ain a b eak
[230]
Cellulose nano ibe s
TiO2NPs whey p o ein
•TiO2inc eased he wa e esis ance
•TiO2and CNFs imp o e mechanical p ope ies and he alues depended on he concen a ion o
nano ille s
•TiO2enhances an imic obial ac i i y agains L. monocy ogenes and S. au eus and an ioxidan p ope ies
[87]
lico ice esidue
nanocellulose soy p o ein isola e
•Imp o emen o TS bu educ ion o EAB
•Reduc ion in WVP (by up o ~27%) and OP (by up o ~55%)
•UV-blocking e ec
[152]
Nanoclays
be onine nanoclays chi osan/PVA
•Reduc ion o WVP (by up o ~69%) and TS (by up o ~30%)
•Imp o emen o he mal s abili y
•
Enhancemen o an ibac e ial p ope ies agains E. coli (e iciency 48.50 %), P. ae uginosa (e iciency 40%),
S. au eus (e iciency 8%)
[231]
cloisi e Na+nanoclays
aga •Imp o emen o TS (by up o ~31%)
•Reduc ion in WVP (by up o ~50%), WCA (by up o ~10%), and WS (by up o ~23%) [155]
halloysi e nano ubes chi osan/s a ch
•Reduc ion o WS
•Imp o emen o wa e abso p ion capaci y, po osi y, olding s eng h, and WVTR
•Imp o emen o impe meabili y o bac e ia ( he mic obial pene a ion es )
[145]
hallosi e nano ubes
wi h me al ions
(Ag, Zn, Cu)
CMC
•Imp o emen o WVP and he mal s abili y
•Enhancemen o an imic obial ac i i y agains L. monocy ogenes and E. coli
•
Imp o emen in TS and EM bu educ ion o EAB (all esul s we e depending on he ype o me al ions
in hallosi e nanu ubes)
[232]
nanoclays:
Na+mon mo illoni e
halloysi e
Nanome ®I.44 P
enug eek seed gum
•Enhancemen o he mal s abili y
•No in luence on an imic obial ac i i y agains E. coli,S. au eus,B. ce eus
•An imic obial ac i i y agains L. monocy ogenes (all esul s we e depending on he ype o nanoclays)
[168]
halloysi e nano ubes
loaded wi h he
essen ial oil
pec in •Reduc ion in he mal s abili y and EAB
•Imp o emen in TS and EM and su ace hyd ophobici y [233]
Polyme s 2019,11, 675 21 o 43
Table 3. Con .
Nano ille Polyme The E ec o Nano ille Addi ion Re e ence
halloysi e nano ubes
ZnO NPs algina e
•Imp o emen o TS (by up o ~12%), WVP (by up o ~27%), and WCA (by up o ~28%)
•No changes in EAB (by up o ~6%) and EM (by up o ~7%)
•Imp o emen in UV-blocking e ec and an imic obial ac i i y agains E. coli ( om 7 o 0 log a e 3 h)
and L. monocy ogenes ( om 6 o 0 a e 9 h)
[95]
Cloisi e 30B
AgNPs gela in
•Imp o emen o op ical p ope ies
•AgNPs imp o ed TS while nanoclay inc eased EAB
•Enhancemen o an imic obial ac i i y agains E. coli and L. monocy ogenes
[234]
bismu h ungs a e/
TiO2NPs
(Bi2WO6-TiO2)
s a ch •Imp o emen o TS (by up o ~233%) and pho oca aly ic ac i i y
•Reduc ion o EAB (by up o ~15%) [235]
halloysi e
nisin s a ch
•HTN imp o ed TS and YM
•
Nisin educed TS and YM bu inc eased an imic obial p ope ies agains L. monocy ogenes, C. pe ingens,
and S. au eus
•No changes in WS
[236]
calcium
mon mo illoni e ca boxyme hyl s a ch •Imp o emen o TS (by up o ~500%), YM (by up o ~1733%), and WCA (by up o ~53%)
•Reduc ion o EAB (by up o ~49%), WS (by up o ~4%) [237]
mon mo illoni e
cellulose NPs algina e •Reduc ion o WVP
•CNC inc eased he TS and EAB, while MMT in high concen a ion educed he TS [238]
mon mo illoni e −
CuO nanocomposi es chi osan
•Enhancemen o TS, EAB, WVP, and OP
•Reduc ion o WS and UV ansi ion
•Imp o emen o an imic obial ac i i y agains E. coli, P. ae uginosa, S. au eus, B. ce eus (all esul s we e
depending on he concen a ion and a io o MMT and CuONPs
[169]
mon mo illoni e ZnO
nanopowde s ca ionic s a ch
•MMT educed o WVP and UV ligh ansmi ance
•ZnO imp o ed o WVP and UV ligh ansmi ance
•Imp o emen o TS and op ical p ope ies, bu educ ion o EAB
[166]
sodium
mon mo illoni e
nanoclay
ZnO
CMC
•Reduc ion in WVP
•Addi ion o ZnO NPs inc ease UV-blocking e ec
•Addi ion o ZnO NPs enhance an imic obial ac i i y agains E. coli and S. au eus
[154]
Polyme s 2019,11, 675 22 o 43
Table 3. Con .
Nano ille Polyme The E ec o Nano ille Addi ion Re e ence
Ca bon Nanos uc u es
mul i-walled ca bon
nano ube-Valine chi osan/PVA •Imp o emen o he mal s abili y [239]
ca bon nano ubes
AgNPs chi osan •Enhancemen o TS (by up o ~131%), EAB (by up o ~18%) and oughness (by up o 125%)
•Reduc ion o dielec ic p ope ies [240]
g aphene oxide cellulose ca bama e •Imp o emen o he mal s abili y
•Imp o emen o TS (by up o ~100%) and educ ion o EAB (by up o ~64%) [129]
g aphene
nanopla ele s CMC
•
Reduc ion o ul ima e ensile s eng h (by up o ~50%) bu inc emen o s ain o b eak (by up o ~66%)
•Enhancemen o UV-blocking e ec
•Imp o emen o wa e epelling na u e
[241]
educed g aphene
oxide sodium CMC •Imp o emen o TS (by up o ~73%) and YM (by up o ~132%) [177]
g aphene oxide amylose
•Enhancemen o s abili y in acidic and alkaline solu ions
•Imp o emen o TS (16.5 imes highe han amylose ilms)
•Reduc ion o he MC and UV ansmi ance
[242]
g aphene oxide
educed g aphene
oxide
sodium CMC/silk
ib oin •Imp o emen o he mal s abili y [131]
O he Nanos uc u es
melanin nanopa icles ca ageenan
•
Inc emen o TS (by up o ~27%), EAB (by up o ~25%), WVP (by up o ~25%) and WCA (by up o ~25%)
•Reduc ion o YM (by up o ~38%)
•
Enhancemen o an ioxidan ac i i y (by up o ~962%-DPPH me hod and by up o ~559%-ABTS me hod)
and he mal s abili y
•Imp o emen o an imic obial ac i i y agains L. monocy ogenes and E. coli
[243]
ZnS NPs chi osan/PVA
•Reduc ion o WS and SR
•
Imp o emen o TS and he mal s abili y and educ ion o EAB (all esul s we e co ela ing wi h he ype
o plas icize )
[244]
gua gum benzoa e
NPs gela in
•Imp o emen o an imic obial ac i i y agains E. coli and S. au eus
•Enhancemen o he mal s abili y
•Imp o emen o TS (by up o 67%) and YM (by up o ~550%)
•Reduc ion in EAB (by up o ~63%)
[245]
Polyme s 2019,11, 675 23 o 43
Table 3. Con .
Nano ille Polyme The E ec o Nano ille Addi ion Re e ence
chi osan NPs ice s aw
nano ib illa ed cellulose
•Imp o emen o TS (by up o ~40%) and YM (by up o ~42%) bu educ ion o EAB (by up o ~94%)
•Enhancemen o an imic obial ac i i y agains bac e ia (S. au eus, E. coli), and yeas (S. ce isiae)
•Reduc ion in po osi y
•No changes in WVP
[110]
chi osan NPs a a gum
•Imp o emen o TS and educ ion o EAB
•Reduc ion o WS (by up o ~74%), WVP (by up o ~23%) and MC (by up o ~24%)
•An imic obial ac i i y agains E. coli ( om 0 o 87.32 mm2o inhibi on zone) and S. au eus ( om 0 o
111.71 mm2)
[246]
chi osan NPs PVA/mulbe y ex ac •Imp o emen o TS bu educ ion o EAB [111]
lignin NPs
chi osan
PVA
chi osan/PVA
•Imp o emen o TS and YM o PVA ilms
•Enhancemen o he mal s abili y o chi osan, PVA, and chi osan/PVA ilms
•Imp o emen o UV ba ie p ope ies o es ed ilms
•Enhancemen o an ioxidan ac i i y o chi osan ilms wi h LNP
•Imp o emen o an imic obial ac i i y agains E winia ca o o o a subsp. ca o o o a and Xan homonas
a bo icola p . P uni
[247]
chi osan/gallic acid
NPs konjac glucomannan
•Imp o emen o UV ba ie p ope ies
•Enhancemen o TS (by up o ~43%) bu educ ion o EAB (by up o ~16%) and WVP (by up o ~33%)
•
Imp o emen o an imic obial ac i i y agains S. au eus ( om 0 o 20 mm o inhibi ion zone) and E. coli
( om 0 o 12 mm)
[167]
chi in nano ibe gela in/CMC •Reduc ion o WS, SR and WVP
•Imp o emen o TS [109]
chi in nanowhiske s maize s a ch
•Imp o emen o TS (by up o ~125%) and he mal s abili y bu educ ion o EAB (by up o ~37%) and
WVP (by up o ~58%)
•Enhancemen o an imic obial ac i i y agains E. coli and L. monocy ogenes
[143]
oxidized chi in
nanoc ys als CMC •Imp o emen o TS (by up o ~88%) and EM (by up o ~244%)
•Reduc ion o WVP (by up o ~10%), WCA (by up o ~14%) and EAB (by up o ~65%) [248]
chi in nanowhiske s
/hyb id ZnO-Ag NPs CMC
•Enhancemen o he mal s abili y and UV-ba ie p ope y
•Imp o emen o TS (by up o ~32%) and YM (by up o ~101%) bu educ ion o EAB (by up o ~34%)
•Enhancemen o an imic obial ac i i y agains E.coli ( om 6 o 0 log a e 6h) and L, monocy ogenes
( om 7 o 4 log a e 9 h)
•Reduc ion o WVP (by up o ~23%)
[249]
Polyme s 2019,11, 675 24 o 43
Table 3. Con .
Nano ille Polyme The E ec o Nano ille Addi ion Re e ence
pullulan lysozyme nano ibe s
•Imp o emen o YM (by up o ~48%), TS (by up o ~7%) bu educ ion o EAB (by up o ~80%)
•
Enhancemen o an ioxidan ac i i y ( om 0 o ~80% DPPH me hod) and an imic obial ac i i y agains
S. au eus
[250]
chi osan nanoc ys alline e bium
doped hyd oxyapa i e •Imp o emen in an imic obial ac i i y agains E. coli and S. au eus [251]
po a o s a ch
apioca s a ch
chi osan
u me ic nano ibe
•Imp o emen o TS, YM, and he mal s abili y
•Reduc ion o EAB
•
An imic obial ac i i y agains B. ce eus, E. coli, S. au eus, and S. yphimu ium ( he alues we e depending
in he ype o biopolyme )
[252]
mal odex in poly inyl ace a e NPs •Imp o emen o TS (by up o ~106%) [165]
Abb e ia ions: NPs—nanopa icles; CMC—ca boxyme hyl cellulose; PVA—poly( inyl) alcohol; PLA—poly(lac ic acid); TS— ensile s eng h; EAB—elonga ion a b eak; YM—Young’s
modulus; EM—elas ic modulus; WVP—wa e apo pe meabili y; OP—oxygen pe meabili y; WS—wa e solubili y; SR—swelling a io; MC—mois u e con en ; WCA—wa e con ac angle.
Polyme s 2019,11, 675 25 o 43
4. Func ional Applica ion o Biopolyme -Based Films wi h Nano ille s
Al hough many coun ies ha e made legal egula ions ega ding he con ac o nanoma e ials wi h
ood o wi h human skin, hose egula ions a y om coun y o coun y. Mo eo e , he de ini ion o
’nanoma e ial’ is no e en uni ied be ween coun ies. The de ailed e iew o he legal s a us egula ions
o nanoma e ials in EU has been ecen ly pe o med by Rausche e al. [
253
]. Nanoma e ials ha a e
allowed o use in con ac wi h humans a e equi ed o ha e a de ailed isk assessmen [
254
]. This
chap e is de o ed o nanocomposi e ma e ials and hei use in a ious a eas o li e.
4.1. Food P ese a ion Applica ion
Packaging ma e ials made om na u al biopolyme s a e cha ac e ized by poo mechanical
p ope ies and high WVP pa ame e s. The u iliza ion o nano echnology in his ield may help o
imp o e hese pa ame e s as well as gi e hem comple ely new ac i e p ope ies. The main ask o he
nanocomposi e packaging is o inc ease he shel -li e o ood du ing s o age and dis ibu ion [67].
Chi osan–gela in ilms wi h he addi ion o AgNPs ha e been used o p o ec ed g apes.
P elimina y s udies con i med he ac i e na u e o such coa ings, ex ending he s o age ime o g apes.
The addi ion o 0.05% AgNPs in he chi osan–gela in ilms esul ed in he ex ension o he ed g apes
shel -li e wi h no signs o molds o 14 days, whe eas he concen a ion o 0.1% AgNPs p olonged he
shel -li e o 18 days [
200
]. In ano he case, AgNPs we e inco po a ed in o chi osan ilms and p olonged
he s o age ime o li chi om 4 o 7 days [
5
]. The inco po a ion o MMT in o s a ch–cashew ee gum
inc eased p o ec ion agains mois u e loss o cashew nu ke nels. Howe e , he MMT addi i e did no
achie e he c i ical alue o pe oxides o accep ance (10 o 20–30 mEq O2kg−1) [6].
So whi e cheese was packed in o chi osan-PVA ilms wi h TiO
2
NPs and s o ed a 7
◦
C o
30 days. A e 15 days o s o age, he numbe o coli o ms signi ican ly dec eased in he samples coa ed
wi h ilms wi h 2%, 4%, and 8% TiO
2
(by 1.47, 1.47, 1.30 log c u/g cheese, espec i ely, compa ed o he
con ol (1.90 log c u/g). The esul s showed ha bionanocomposi e ilms wi h s ong an imic obial
ac i i y agains g am posi i e (S. au eus), g am nega i e (P. ae uginosa, E. coli) bac e ia and ungi
(C. albicans) could be used as an en i onmen ally iendly ma e ial o ood packaging. Addi ionally,
he lack o mig a ion o TiO
2
om he ilm o cheese was con i med, which p o es he high sa e y o his
ype o ma e ial [
7
]. Nanos uc u ed chi osan–manolau in ilms caused a educ ion o L. monocy ogenes
popula ion (by 2.3–2.4 log) on ul a il e ed cheese a e 14 days [8].
The addi ion o ZnO nanopa icles in o mahua oil-based polyu e hane/chi osan ilm signi ican ly
in luenced an ibac e ial p ope ies when hese ilms we e used o packing ca o slices. A e 9 days
o s o age, ca o slices packed in mahua oil-based polyu e hane/chi osan+ZnO NPs ilms had a
lowe deg ee o bac e ia g ow h (by app ox. 0.3–0.6 log c u/g) han pieces o ca o slices wi hou
ilm and wi h PE ilm [
213
]. An imic obial ac i i y agains E. coli and L. monocy ogenes was eco ded
o cooked minced ish pas e packaged in PLA ilms wi h ZnO NPs and a e 10 days o s o age,
he numbe o colonies o bo h bac e ia was educed o ze o. The an imic obial ac i i y migh ha e
esul ed om di ec con ac o mic oo ganisms wi h ZnO NPs o Zn
2+
ions emi ed om he ilm [
31
].
The addi ion o ZnO NPs in o chi osan/CMC also posi i e in luenced packaged Egyp ian whi e so
cheese ( heological p ope ies, colo measu emen s, mois u e, pH, and i a able acidi y) du ing
s o age [
211
]. The s a ch–halloysi e–nisin nanocomposi e ilms e ec i ely p o ec ed Minas F escal
cheese agains pos -p ocess con amina ion wi h L. monocy ogenes [
236
]. Eche e ia and co-wo ke s
(2018) in es iga ed he e ec o MMT and clo e essen ial oil in s a ch ilms on s o age o muscle ille s o
blue in una (Thunnus hynnus). They no iced ha he p esence o clay p olonged he an imic obial and
an ioxidan e ec s o clo e essen ial oil, while no mig a ion o clay’s me al (Si and Al) in o he muscle
o he ish we e obse ed [
9
]. Ma hew and co-wo ke s (2019) de eloped PVA/MMT K10 clay/AgNPs
ilms and used hem o imp o e he shel -li e o chicken sausages. The esul s showed ha his ype
o nanocomposi e packaging sys em is sui able o sausages, inhibi ing he g ow h o o al ae obic
bac e ia [10].
Polyme s 2019,11, 675 32 o 43
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