Preparation and properties of chitosan/polyvinyl alcohol/snail mucus composite films

doi:10.19491/j.issn.1001-9278.2022.05.010

Abstract

Abstract:

Chitosan （CS）/poly（vinyl alcohol）（PVA）/snail mucus （SM） composite films were prepared through crosslin?king with vanillin using a casting method. The effect of CS/SM mass ratio on the optical properties， water vapor permeability， water vapor， oxygen barrier capability， and mechanical and biodegradable properties of the composite films were investigated using a thermogravimetric analyzer， a scanning electron microscope， and a universal material testing machine. The results indicated that the composite films were biodegradable and hydrophilic， and their properties were optimal when the volume ratio of CS solution to SM solution was set to 5/3， presenting an antioxidant activity of 87.51%. Comparing to pure CS film， the composite films showed a decrease not only in water vapor transmission rate by 75.16 % but also in opacity by 87.74 %. However， they showed an increase in tensile strength by16.03 % and in elongation at break by a factor of 28.26. The thermal stability of the composite films decreased with an increase in the proportion of SM. In addition， the composite films exhibited good compatibility at CS/SM volume ratios of 5/1， 5/2， and 5/3. The addition of SM endowed the composite films with good ductility and flexibility， whereas the addition of vanillin improved their tensile strength and antioxidant activity. The CS/PVA/SM composite films exhibit potential prospects in the application for food packaging.

Key words: chitosan, poly（vinyl alcohol）, snail mucus, vanillin, food packaging

CLC Number:

TQ325.9

LI Fujie, QI Bin, XU Huating, WANG Limei. Preparation and properties of chitosan/polyvinyl alcohol/snail mucus composite films[J]. China Plastics, 2022, 36(5): 53-61.

Figures/Tables 12

References 32

1	EL⁃MEKAWY R E， ELHADY H A， AL⁃SHAREEF H F， et al. Highly stretchable， smooth， and biodegradable hydrogel films based on chitosan as safety food packaging［J］. Polymers and Polymer Composites， 2021， 29 （6）： 563⁃573.
2	KHALID M N， AGNELY F， YAGOUBI N， et al. Water state characterization， swelling behavior， thermal and mechanical properties of chitosan based networks［J］. European Journal of Pharmaceutical Sciences， 2002， 15（5）：425⁃432.
3	EDIYILYAM S， GEORGE B， SHANKAR S S， et al. Chitosan/gelatin/silver nanoparticles composites films for biodegradable food packaging applications［J］. Polymers， 2021， 13（11）：1680.
4	ZHANG Z D， LIU Y， LIN S D， et al. Preparation and properties of glutaraldehyde crosslinked poly（vinyl alcohol） membrane with gradient structure［J］. Journal of Polymer Research， 2020， 27：228.
5	AMMARA R， KHALID M Z， MOHAMMAD Z， et al. Chitosan functionalized poly（vinyl alcohol） for prospects biomedical and industrial applications： a review［J］. International Journal of Biological Macromolecules， 2016， 87：141⁃154.
6	BAHRAMI S B， KORDESTANI S S， MIRZADEH H， et al. Poly （vinyl alcohol）⁃chitosan blends： preparation， mechanical and physical properties［J］. Iranian Polymer Journal， 2003， 12（2）：139⁃146.
7	BEPPU M M， VIEIRA R S， AIMOLI C G， et al. Crosslinking of chitosan membranes using glutaraldehyde： effect on ion permeability and water absorption［J］. Journal of Membrane Science， 2007， 301（1/2）：126⁃130.
8	KOWALCZYK D， KORDOWSKA⁃WIATER M， NOWAK J， et al. Characterization of films based on chitosan lactate and its blends with oxidized starch and gelatin［J］. International Journal of Biological Macromolecules， 2015， 77：350⁃359.
9	ZHANG Z H， HAN Z， ZENG X A， et al. Enhancing mechanical properties of chitosan films via modification with vanillin［J］. International Journal of Biological Macromolecules， 2015， 81：638⁃643.
10	SOUZA V G L， FERNANDO A L， PIRES J R A， et al. Physical properties of chitosan films incorporated with natural antioxidants［J］. Industrial Crops & Products， 2017， 107：565⁃572.
11	DOMINGUEZ⁃MARTINEZ B M， MARTÍNEZ⁃FLORES H E， BERRIOS J D J， et al. Physical characterization of biodegradable films based on chitosan， polyvinyl alcohol and opuntia mucilage［J］. Journal of Polymers and the Environment， 2017， 25（3）：683⁃691.
12	DI FILIPPO M F， PANZAVOLTA S， ALBERTINI B， et al. Functional properties of chitosan films modified by snail mucus extract［J］. International Journal of Biological Macromolecules， 2019， 143：126⁃135.
13	CLAUDIO T， ROBERTA R， STEFANIA G， et al. Helix complex snail mucus exhibits pro⁃survival， proliferative and pro⁃migration effects on mammalian fibroblasts［J］. Scientific Reports，2018，8（1）：1834.
14	ABDULLAH K， TALIP K. Characterization of a new biodegradable edible film made from salep glucomannan［J］. Carbohydrate Polymers， 2014， 104：50⁃58.
15	UBONRAT S， BRUCE R H. Physical properties and antioxidant activity of an active film from chitosan incorpora⁃ted with green tea extract［J］. Food Hydrocolloids， 2010， 24（8）：770⁃775.
16	VERNON L S， RUDOLF O， LAMUELA⁃RAVENTÓS R M. Analysis of total phenols and other oxidation substrates and antioxidants by means of folin⁃ciocalteu reagent［J］. Methods in Enzymology， 1999， 299：152⁃178.
17	CONSIDINE G D. American Society for Testing and Materials （ASTM）［M］. New York： American Cancer Socie⁃ty， 2005：142⁃147.
18	FIRESTONE D， SOCIETY A. Official methods and recommended practices of the AOCS［J/OL］. AOCS， 2009. .
19	KUMAR D P， MAHADEVAN R， SIVARAMAN G K， et al. Biomodulation of poly（vinyl alcohol）/starch polymers into composite⁃based hybridised films： physico⁃chemical， structural and biocompatibility characterization［J］. Journal of Polymer Research， 2021， 28（7）：1⁃12.
20	US Department of Defense. Standard test method for tensile properties of thin plastic sheeting：［S］. West Conshohoken： ASTM International， 2012.
21	MENG W， SHI J， ZHANG X， et al. Effects of peanut shell and skin extracts on the antioxidant ability， physical and structure properties of starch⁃chitosan active packaging films［J］. International Journal of Biological Macromolecules， 2020， 152：137⁃146.
22	SOPHIE G， WALTRAUD K， NORBERT C， et al. Snail mucus⁃glandular origin and composition in helix pomatia［J］. Zoology， 2017， 122：126⁃138.
23	刘敏. 蜗牛粘液/丝素蛋白复合材料的制备与性能研究［D］.苏州：苏州大学，2018.
24	ZHANG Z H， HAN Z， LIU Y J， et al. Enhancing mechanical properties of chitosan films via modification with vanillin［J］. International Journal of Biological Macromolecules， 2015， 81：638⁃643.
25	WU Y， YE Y， LIU Y， et al. Preparation of chitosan/poly vinyl alcohol films and their inhibition of biofilm formation against pseudomonas aeruginosa PAO1［J］. International Journal of Biological Macromolecules， 2018， 118： 2 131⁃2 137.
26	ABDELGHANY A M， MENAZEA A A， ISMAIL A M. Synthesis characterization and antimicrobial activity of chitosan/polyvinyl alcohol blend doped with hibiscus sabdariffa L. extract［J］. Journal of Molecular Structure，2019，1 197： 603⁃609.
27	LIU Y W， WANG S Y， LAN W T. Fabrication of antibacterial chitosan⁃PVA blended film using electrospray technique for food packaging applications［J］. Internatio⁃nal Journal of Biological Macromolecules， 2017：848⁃854.
28	FU F N， SINGH B R， DEOLIVEIRA D B， et al. Secondary structure estimation of proteins using the amide III region of fourier transform infrared spectroscopy： application to analyze calcium⁃binding⁃induced structural changes in calsequestrin［J］. Applied Spectroscopy， 1994， 48（11）：1 432⁃1 441.
29	XIE M X， LIU Y. Studies on amide Ⅳ infrared bands for the secondary structure determination of proteins［J］. Chemi⁃cal Research in Chinese Universities， 2003，2：226⁃231.
30	WANG X， YONG H， GAO L， et al. Preparation and characterization of antioxidant and pH⁃sensitive films based on chitosan and black soybean seed coat extract［J］. Food Hydrocolloids， 2019， 89：56⁃66.
31	ZHEN Y， LI B， CHU J， et al. Silica in situ enhanced PVA/chitosan biodegradable films for food packages［J］. Carbohydrate Polymers， 2018， 184：214.
32	DI FILIPPO M F， SILVIA P， BEATRICE A， et al. Functional properties of chitosan films modified by snail mucus extract［J］. International Journal of Biological Macromolecules， 2020， 143：126⁃135.

样品	厚度/mm	W_C/%	S_D/%	W_S/%
CS	0.210±0.015^a	7.48±0.30ⁱ	1680.50±36.28^a	18.77±0.74^e
CS/PVA	0.196±0.011^a	10.75±0.18^g	710.61±24.42^b	25.65±1.16^c
CPV	0.180±0.003^b	8.95±0.34^h	38.32±0.56^f	20.58±0.95^d
CSP	0.119±0.022^c，d	58.10±0.98^a	106.02±0.85^c	29.68±1.74^a
CSPV1	0.174±0.016^b	16.46±0.16^f	42.13±0.27^f	25.20±0.66^c
CSPV2	0.167±0.018^b	36.91±0.46^e	53.48±0.94^e，f	26.82±0.72^b，c
CSPV3	0.136±0.031^c	42.09±0.67^d	63.02±0.59^e，f	27.64±0.47^b，c
CSPV4	0.126±0.021^c，d	49.03±0.38^c	74.65±0.58^d，e	28.30±1.34^a，b
CSPV5	0.110±0.008^d	56.48±0.58^b	91.06±1.14^c，d	29.76±1.00^a

样品	厚度/mm	W_C/%	S_D/%	W_S/%
CS	0.210±0.015^a	7.48±0.30ⁱ	1680.50±36.28^a	18.77±0.74^e
CS/PVA	0.196±0.011^a	10.75±0.18^g	710.61±24.42^b	25.65±1.16^c
CPV	0.180±0.003^b	8.95±0.34^h	38.32±0.56^f	20.58±0.95^d
CSP	0.119±0.022^c，d	58.10±0.98^a	106.02±0.85^c	29.68±1.74^a
CSPV1	0.174±0.016^b	16.46±0.16^f	42.13±0.27^f	25.20±0.66^c
CSPV2	0.167±0.018^b	36.91±0.46^e	53.48±0.94^e，f	26.82±0.72^b，c
CSPV3	0.136±0.031^c	42.09±0.67^d	63.02±0.59^e，f	27.64±0.47^b，c
CSPV4	0.126±0.021^c，d	49.03±0.38^c	74.65±0.58^d，e	28.30±1.34^a，b
CSPV5	0.110±0.008^d	56.48±0.58^b	91.06±1.14^c，d	29.76±1.00^a

样品	拉伸强度/MPa	断裂伸长率/%
CS	24.57±1.65^f	2.25±0.59ⁱ
CS/PVA	28.29±1.82^d	24.43±2.18^g
CPV	36.44±2.22^a	15.37±1.79^h
CSP	15.53±1.09^g	85.67±2.16^a
CSPV1	34.41±1.26^b	82.40±2.67^b
CSPV2	30.14±1.42^c	78.00±1.44^c
CSPV3	28.51±1.28^c，d	65.84±2.19^d
CSPV4	26.56±1.13^e	53.27±1.18^e
CSPV5	25.19±1.05^e，f	34.13±1.95^f

样品	拉伸强度/MPa	断裂伸长率/%
CS	24.57±1.65^f	2.25±0.59ⁱ
CS/PVA	28.29±1.82^d	24.43±2.18^g
CPV	36.44±2.22^a	15.37±1.79^h
CSP	15.53±1.09^g	85.67±2.16^a
CSPV1	34.41±1.26^b	82.40±2.67^b
CSPV2	30.14±1.42^c	78.00±1.44^c
CSPV3	28.51±1.28^c，d	65.84±2.19^d
CSPV4	26.56±1.13^e	53.27±1.18^e
CSPV5	25.19±1.05^e，f	34.13±1.95^f

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[8]	XU Meng, GAO Dali, ZHANG Shijun. Progress and Upgrade of Food Packaging Polymer Materials [J]. China Plastics, 2021, 35(3): 74-82.
[9]	YIN Peng, MA Hongpeng, GUO Bin, LI Panxin. Thermoplastic starch composites reinforced synergistically with PLA fiber and PVA fiber [J]. China Plastics, 2021, 35(12): 16-20.
[10]	Lin ZONG, Chenwei CHEN, Zhijie CHEN, Jing XIE. Research Progress in Starch/Poly(vinyl alcohol) Active Packaging Film and Its Application in Food Packaging [J]. China Plastics, 2020, 34(8): 101-112.
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