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The Effect of Nanofillers on the Functional Properties of Biopolymer-Based Films: A Review

Abstract

Waste from non-degradable plastics is becoming an increasingly serious problem. Therefore, more and more research focuses on the development of materials with biodegradable properties. Bio-polymers are excellent raw materials for the production of such materials. Bio-based biopolymer films reinforced with nanostructures have become an interesting area of research. Nanocomposite films are a group of materials that mainly consist of bio-based natural (e.g., chitosan, starch) and synthetic (e.g., poly(lactic acid)) polymers and nanofillers (clay, organic, inorganic, or carbon nanostructures), with different properties. The interaction between environmentally friendly biopolymers and nanofillers leads to the improved functionality of nanocomposite materials. Depending on the properties of nanofillers, new or improved properties of nanocomposites can be obtained such as: barrier properties, improved mechanical strength, antimicrobial, and antioxidant properties or thermal stability. This review compiles information about biopolymers used as the matrix for the films with nanofillers as the active agents. Particular emphasis has been placed on the influence of nanofillers on functional properties of biopolymer films and their possible use within the food industry and food packaging systems. The possible applications of those nanocomposite films within other industries (medicine, drug and chemical industry, tissue engineering) is also briefly summarized.

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The Effect of Nanofillers on the Functional Properties of Biopolymer-Based Films: A Review

Author: Jamroz, Ewelina; Kulawik, Piotr; Kopel, Pavel
Publisher: MDPI
Year: 2019
DOI: 10.3390/polym11040675
Source: https://dspace.vut.cz/bitstreams/23975911-3296-4f82-828a-43529cfd6508/download
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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