Fabrication of PVA polymer films with improved antibacterial activity

by fine‑tuning via organic acids for food packaging applications

Sanjeevamuthu Suganthi · Shanmugam Vignesh · Jeyaperumal Kalyana Sundar · Vairamuthu Raj
Introduction
Biodegradable food packaging systems are in increasing demand in response to the environmental issues of modern society.
The long-term environmental impact of plastic packaging waste is an increasing global concern with regard to the safety of marine environments, since limited disposal methods pose a serious challenge
in food safety .
When these materials are used for food contact, they must preserve the food quality and ensure that they do not impart any quality to food that could alter its sensory properties or present a risk to
consumer health

Materials and methods UV spectral analyses Antimicrobial activity

Commercial (99.7%) hydrolyzed polyvinyl alcohol (PVA) powder Analysis of the UV spectra of pristine polymer solutions The antibacterial effects of pristine PVA and cross-linked
(99.7)% hydrolyzed. Tartaric acid (TA), lactic acid (LA), and malic results are shown in Fig. 6. A peak is observed in the PVA/OA membranes against two types of bacteria, G+
acid (MA) Sulfuric acid (98%) and Deionized (DI) water. ultraviolet region of the electromagnetic spectrum for all (S.aureus) and G−(E.coli), were investigated and the zone of
Microbiological media the investigated samples since the films are transparent. inhibition for both bacterial species relative to the control are
The maximum absorption is associated with the increase
shown in Fig. 9. Antimicrobial activity, as determined by the
Film preparation due to carboxylic acid. The shift of maximum absorption
diameter of the zone of inhibition, is dependent on the film
toward the lower-wavelength region indicates the
Pure PVA film was prepared for comparison using a solution- characteristics. Of note, the pristine PVA film showed no clear
presence of intermolecular hydrogen bonding between
casting technique (Pereira et al. 2015). microbial inhibitory zone, whereas the OA crosslinked films
PVA and the different cross-linkers. Also, the degree of
showed specific microbial inhibitory zones against both bacteria
Physicochemical characterization interaction seems to be higher for the PVA/LA system
using the well diffusion technique, demonstrating that fine-
compared with PVA/MA and PVA/TA films.
PVA/OA solutions were characterized using a PerkinElmer tuning of the polymer microstructure could have a significant
Lambda 19 UV-Vis spectrophotometer, FTIR spectra were used in effect on its antibacterial properties. Because there was no clear
a range of 400–4000 cm−1,XRD [λ(Cu-Kα) = 1.54 Å] and surrounding zone, there was no zone of inhibition. In addition, the
Thermogravimetric analysis TG/DTA. The surface morphology of value of the diameter was zero and the PVA solution showed no
the pristine PVA and PVA/OA-crosslinked films was investigated inhibitory effects against either bacteria.
by scanning electron microscopy (SEM; JEOL JSM-35CF) and
atomic force microscopy (AFM; Dualscope/Raster scope C26,
DME, Denmark). Fig. 3 UV–visible absorption spectra for pristine PVA
and crosslinked PVA films

Antibacterial studies Thermal stability

PVA and PVA/OA polymer solutions and fabricated In Fig. 7, it is clearly observed that the cross-linked
polymer films were tested against G+ (S. aureus) and G− PVA/MA, PVA/TA, and PVA/LA samples display three stage
(E. coli) bacteria using a well diffusion method to degradation with better thermal stability compared with
determine their potential antibacterial activity the pristine PVA, which exhibits only two-stage
(Suganthi et al. 2018). After incubation, the inhibitory degradation. This is due mainly to the loss of moisture Fig. 6 Antibacterial inhibitory effects of pristine PVA, PVA/ MA, PVA/TA, and PVA/LA
polymer solutions
effect was estimated based on the clear zone in the adhesion and removal of water molecules from the
polymer matrix, with the pristine PVA incurring the The zone of inhibition for the samples demonstrated the
solution. In the case that there was no clear zone
greatest loss of water molecules. The cross-linked PVA following order: PVA < PVA/ TA < PVA/LA < PVA/MA. Figure 10
around the well, it was assumed that the PVA and
structures are gradually degraded in the range of 160 °C. presents a schematic comparison of the antibacterial activity of
PVA/OA solution exerted no inhibitory effect on the
In this zone, all cross-linked PVA films are relatively the pristine PVA film and PVA/OA cross-linked film. The
bacteria.
stable, indicating that the thermal energy is not sufficient antibacterial activity can be grouped into two types,
Results and discussion to break the ester linkages resulting from the reaction characterized by bactericidal and anti-adhesion mechanisms.
between the hydroxyl groups of the PVA and the The main PVA/LA has affirmed to the higher antibacterial
carboxylic group of OA, hindering facile movement has a place with the higher surface roughness. These
degradation.Among the three cross-linked PVA networks, outcomes propose that the antimicrobial exercises of natural
PVA/LA demonstrates the highest thermal stability acids can be impacted by the qualities of pH, grid structure, and
because of the presence of functional groups that can cell thickness. The best inhibitory effects are found when LA is
actively participate in inter/intramolecular hydrogen used as cross-linker, in contrast to the other two OAs used on
bonding caused by the spatial proximity of the –COOH this look at signifying that the occurrence of LA is valuable for
Fig. 1 The visual appearance of pristine PVA and cross-linked PVA and –OH groups. antibacterial activity. The antibacterial interest of given
filmstext impetuses may be credited to the two viable mechanisms.
Similar results are observed with LA cross-linked films, which
FTIR SPECTRAL ANALYSES show good bacteriostatic properties against the pathogenic
bacterial species S. aureus and could be utilized in medical
shows the characteristic broad band located at 3300 cm−1
applications and protective packaging.
appearing in the spectrum of the pristine PVA and
crosslinked PVA is attributed to intermolecular and
intramolecular hydrogen bonding and –OH stretching
vibrations of PVA. The preservation of all peaks shows that
Fig. 4 TGA curves for a PVA, b PVA/MA, c PVA/TA, and d PVA/LA
the molecular structure is maintained. The spectral analysis tofilms
thus demonstrates both PVA and PVA/OA with few new
peaks and different peaks appearing with a shift in their
Contact angle measurements
position, confirming effective cross-linking.
The contact angles of the pristine PVA and PVA/TA, Fig. 7 Schematic representation comparing antibacterial activity of pristine PVA/ cross-linked
PVA/ MA, and PVA/LA cross-linked samples were film with different carboxylic acids

measured and are shown in Fig. 8. The maximum

Summary and conclusion
contact angles for PVA, PVA/MA, PVA/TA, and PVA/LA
Three different organic acids were used for cross-linking
are 46.4°, 75.3°, 77.4°, and 83.3°, respectively. With the
cross-linking of carboxylic acid, the film becomes with PVA.
moderately hydrophobic, as compared with the The functionality of the cross-linker significantly
highly hydrophilic nature of PVA. These results affected the physicochemical properties of PVA and
demonstrate that PVA/LA has the greatest contact improved bactericidal activity.
angle. The film's properties were significantly improved by
Fig.2 FTIR spectra for pristine PVA and cross-linked PVA films cross-linking with lactic acid.
LA acted as an antimicrobial agent, reducing the local
prepared by: Supervised by: pH of the bacteria, and the altered film permeability led
to bacterial cell death.
Abeer Almabadi-1912457 Nazeeha Alkayal The effects of cross-linking with malic acid, tartaric acid,
Ohood Hassan-1914363 and lactic acid on the antimicrobial properties of PVA,
fetoon Alsulami-1906760 without the addition of antibiotics or inorganic materials
Noha alshnbry-1817144 have major implications for the use of PVA-based
Ahood Almalawi-1906271 dynamic food packaging.
Ghaida Alahmadi-2005905 Fig. 5 Contact angles for a PVA, b PVA/MA, c PVA/TA,
and d PVA/ LA films The increased density from cross-linking, reducing the
free volume of the surface, and the electrostatic and
Reference: hydrophilic/hydrophobic bacteria–substrate
https://doi.org/10.1007/s13201-020-1162-y interactions provide deeper insight into the bacterial
adhesion process.