Properties, vapour-phase antimicrobial and antioxidant activities of active poly(vinyl alcohol) packaging films incorporated with clove oil

Accepted Manuscript Properties, vapour-phase antimicrobial and antioxidant activities of active poly (vinyl alcohol) packaging films incorporated with clove oil

Chenwei Chen, Zhewei Xu, Yarui Ma, Jinliang Liu, Qinjun Zhang, Zhipeng Tang, Kaijia Fu, Fuxin Yang, Jing Xie PII:

S0956-7135(17)30626-6

DOI:

10.1016/j.foodcont.2017.12.039

Reference:

JFCO 5931

To appear in:

Food Control

Received Date:

21 September 2017

Revised Date:

27 December 2017

Accepted Date:

31 December 2017

Please cite this article as: Chenwei Chen, Zhewei Xu, Yarui Ma, Jinliang Liu, Qinjun Zhang, Zhipeng Tang, Kaijia Fu, Fuxin Yang, Jing Xie, Properties, vapour-phase antimicrobial and antioxidant activities of active poly(vinyl alcohol) packaging films incorporated with clove oil, Food Control (2017), doi: 10.1016/j.foodcont.2017.12.039

This is a PDF file of an unedited manuscript that has been accepted for publication. As a service to our customers we are providing this early version of the manuscript. The manuscript will undergo copyediting, typesetting, and review of the resulting proof before it is published in its final form. Please note that during the production process errors may be discovered which could affect the content, and all legal disclaimers that apply to the journal pertain.

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Properties, vapour-phase antimicrobial and antioxidant activities of active poly(vinyl alcohol) packaging films incorporated with clove oil Chenwei Chena,b,c,d, Zhewei Xua, Yarui Maa, Jinliang Liua, Qinjun Zhanga, Zhipeng Tanga, Kaijia Fub, Fuxin Yanga,b,c,d, Jing Xiea,b,c,d* aCollege

of Food Science and Technology, Shanghai Ocean University, Shanghai, 201306, China Engineering Research Center of Aquatic-Product Processing & Preservation, Shanghai, 201306, China cLaboratory of Quality and Safety Risk Assessment for Aquatic Products on Storage and Preservation (Shanghai), Ministry of Agriculture, Shanghai, 201306, China dNational Experimental Teaching Demonstration Center for Food Science and Engineering (Shanghai Ocean University), Shanghai, 201306, China bShanghai

Correspondence to: Jing Xie ([email protected]) and Chenwei Chen ([email protected]) ABSTRACT The active poly(vinyl alcohol) (PVA) films incorporated with clove oil (CO) at level of 1%, 3%, 5%, 7% and 9% (w/w) was prepared. The effects of CO content on the structural, mechanical, gas barrier and thermal stability properties of the films were investigated. The antimicrobial and antioxidant activities in vapour phase of the films were evaluated by investigating the microbiological analyses and lipid oxidation of the packed trichiurus haumela without contacting the PVA films. The oil droplets were observed on the surface and cross-section of the films as CO increased from 3% to 9% via scanning electron microscope (SEM). It resulted in the heterogeneous film structure featuring discontinuities. Some negative impacts on the properties of the films were observed with increasing CO. Compared with pure PVA film, the tensile strength (TS) of film added with 9% CO decreased 14.13%, the elongation at break increased 26.64%, water vapor transmission rate (WVTR) reduced 54.31%, oxygen transmission rate (OTR) increased 90.77% and thermal stability was worsened slightly. The bacterial growth and lipid oxidation of the packed trichiurus haumela were inhibited by the packaging with CO-containing films. The PVA film containing 9% CO showed the best quality protective effectiveness. Its microbiological shelf-life could be extended for 2 days and 28.07% reduction of malonaldehyde was obtained on day 7 comparing with control sample, indicating the antimicrobial and antioxidant activities were effective in vapour phase. It could be a promising active packaging for potential application in the non direct contact packaging-food system to create a protective atmosphere around the packaged foodstuffs. KEYWORDS: poly(vinyl alcohol), clove oil, vapour phase, antimicrobial, antioxidant, active packaging film

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1. Introduction

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Active food packaging is a promising and rapidly emerging technology in which the antimicrobial or antioxidant agents are incorporated into the packaging materials. It can provide the packed food high quality, safety and long shelf life, usually by reducing or retarding the growth of microorganisms and inhibiting the lipid oxidation (Muriel-galet, Cran, Bigger, Hernández-muñoz, & Gavara, 2015). Recently, there is a considerable interest in active food packaging films made from biodegradable polymers due to the serious environmental problems caused by conventional plastic food packaging material (Siracusa & Dalla, 2008). Poly-(vinyl alcohol) (PVA) is a biodegradable synthetic polymer 1

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that showed exceptional properties of film forming, adhesive, biocompatibility, mechanical, gas barrier, chemical resistance and nontoxic. It has been extensively used in various applications such as adhesives, paper coating, drug delivery devices and packaging materials (DeMerlis & Schoneker, 2003; Liu et al., 2014). In recent years, several studies on developing antimicrobial or antioxidant packaging films have been reported by incorporating lysozyme (Buonocore, Conte, Corbo, Sinigaglia, & Del Nobile, 2005; Buonocore, Nobile, Panizza, Corbo, & Nicolais, 2003; Conte, Buonocore, Bevilacqua, Sinigaglia, & Del Nobile, 2006), vanillin (Stroescu, Stoica-Guzun, & Jipa, 2013), grapefruit seed extract (Musetti et al., 2014), sorbic acid (Jipa, Stoica-Guzun, & Stroescu, 2012), natamycin (Lantano et al., 2014), rhubarb ethanol extract and cinnamon essential oil (Han, Wang, Li, Lu, & Cui, 2014; Kim et al., 2013) into the PVA. Essential oils (EOs) derived from plants have been shown to exhibit antimicrobial, antifungal and antioxidant properties (Atarés & Chiralt, 2016; Sow, Tirtawinata, Yang, Shao, & Wang, 2017). They are categorized as Generally Recognized as Safe (GRAS) by Food and Drug Administration of the USA (Kumar, Malik, & Elisabetta, 2012). EOs have been incorporated into the packaging material to develop the active packaging films or edible films, including polyethylene (PE) (Mulla et al., 2017), EVOH (Muriel-galet et al., 2015), poly(lactic acid) (PLA) (Javidi, Hosseini, & Rezaei, 2016), chitosan (Chiralt & Vargas, 2016), hydroxypropyl methylcellulose (HPMC) (Choi, Singh, & Lee, 2016) and fish protein (Teixeira et al., 2014). These active films used in the food packaging are proved to extend the shelf life of beef, fish, cheese and fruit successfully (Han et al., 2014; Kavas, Kavas, & Saygili, 2015; Lacey & Montero, 2010; Song, Lee, Mijan, & Song, 2014; Yang et al., 2016). However, their application in the food industry is limited for the strong flavor of EOs, especially incorporating them into the food as preservatives or the active film used in the direct contact packaging-food system. Consequently, further study is worth to minimize EOs concentrations and reduce the influence on the food sensory. One of the alternative approaches is using EOs in the vapour phase. They could act for large areas/products in non direct contacts with surfaces. Several studies have been reported to reveal that EOs showed antimicrobial activity in vapour phase (Goñi et al., 2009; Khumalo et al., 2017; Nedorostova, Kloucek, Kokoska, Stolcova, & Pulkrabek, 2009; Songsamoe, Matan, & Matan, 2017). But few studies on the antimicrobial or antioxidant activities of the active packaging films incorporated with EOs in the vapour phase were reported. The antimicrobial activity of the PVA film containing microencapsulated oregano essential oil in vapour phase was demonstrated by preserving the quality of cherry tomatoes via the atmosphere surrounding the food rather than direct contact (Kwon, Chang, & Han, 2017). Hence, it would be valuable to develop active packaging for extending the shelf life of food by means of the antimicrobial or antioxidant properties of EOs’ volatile compounds in the atmosphere around the food in non direct contact packaging-food system. Clove oil is one of natural essential oils, the active ingredient of which is eugenol. It has been widely studied and demonstrated to possess antimicrobial and antioxidant activities in liquid phase, and antimicrobial activity in vapour phase (Goñi et al., 2009; Kumar et al., 2012; Song et al., 2014; Zengin & Baysal, 2015). The aim of the present study was to develop active packaging films by incorporating CO into PVA polymer and investigated their structural, mechanical and physicochemical properties. The antimicrobial and antioxidant activities of the films in vapour phase were evaluated by investigating the microbiological analyses and lipid oxidation of the packed trichiurus haumela in non direct contact packaging-food system. 2

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2. Materials and methods

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2.1. Materials

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PVA (degree of polymerization: 1799 and alcoholysis degree: 99%) was purchased from SINPEC Shanghai Petrochemical Co.Ltd (China). Clove oil was obtained from Francine chicard (SH) F&F Co., Ltd (France). Glycerol, tween-80, absolute ethanol, Plate Count Agar (PCA), trichloroacetic acid (TCA), and thio-barbituric acid (TBA) were supplied by Sinopharm Chemical Reagent Co., Ltd (China). Trichiurus haumela (410 ± 50 g) were obtained from a local aquatic market in Shanghai (China). The fish placed in a foam incubator with ice water were transferred to the laboratory of Shanghai Ocean University within 30 min and kept at 0℃ before using.

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2.2. Film preparation

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The PVA films incorporated with CO were prepared by solution-casting method following the previous study (Chen, Chen, et al., 2017). The PVA solutions were prepared by dissolving 22 g resin pellets in 200 mL distilled water at 95℃ with stirring. The glycerol (1.26 g) used as plasticizer and tween-80 employed as emulsifier (0.53 g) were added into the solutions. The PVA solutions were cooled down to 45℃ after uniformly mixed. The CO solutions were prepared by dissolving 0, 0.22, 0.66, 1.1, 1.54 and 1.98 g of CO (0%, 1%, 3%, 5%, 7%, 9% w/w relative to PVA on a dry basis) respectively into 5 mL absolute ethanol. Then the CO solutions were added into the PVA solutions under stirring for 10 min and the mixed solutions were homogenized at 5000 rpm for 3 min using a FLUKO FM200A homogenizer (Shanghai FLUKO Fluid Machinery Manufacturing Co. Ltd, China). Then the film forming solutions were degassed in the vacuum drying oven (Shanghai Yiheng Instruments Co., Ltd. China). The films were prepared by casting the mixed solutions onto a glass plate using a film steel spreader (Shanghai Xiandai Environmental Engineering Technology Co., Ltd. China). The films were dried onto flat heating stage (Shenzhen Anzhuoyuan Technology Electronic Co., Ltd. China) at 60℃ for 40 min and then were peeled from the casting surface. Each prepared film was marked as PVA-0CO, PVA-1CO, PVA-3CO, PVA-5CO, PVA-7CO and PVA-9CO for the films incorporated with 0%, 1%, 3%, 5%, 7%, 9% CO respectively. All film samples were placed into the chamber (Temperature: 25℃, RH: 50%) to perform the condition of samples for a week before measuring the properties of the films.

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2.3. Film characterization

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2.3.1. Film thickness Thickness of the films was measured at five random points of each film sample using a digital micrometer (Guilin Guanglu Measuring Instrument, Co., Ltd, China) with an accuracy of 0.001 mm. The average thickness was calculated.

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2.3.2. Scanning electron microscope (SEM)

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The surface and cross-section morphologies of the film samples were observed by using a S-3400N scanning electron microscope SEM (Hitachi Ltd, Japan) operating at 5 kV acceleration under moderate vacuum. The film samples were fractured in liquid nitrogen for cross-section morphology observation. Then all film samples were fixed manually on the bronze stub by conductive adhesive and sputtered with gold layer prior to visualization. 3

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2.3.3. Film color and opacity

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The color of films was measured by using a CR-400 Chroma Meter (Minolta Co., Tokyo, Japan). It was expressed as the Hunter L*, a*, and b* value. The white standard plate (L*= 94.20, a*= -0.61, and b*= 4.64) was used as a background for measurement and five measurements were taken. The total color difference ( E * ) was calculated as shown in following equation:

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E*  L *  a *  b *

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Where L * is the lightness, 0 for black and 100 for white; a * is redness, from green (-) to red (+); b * is yellowness, from blue (-) to yellow (+). The opacity of films was performed by the method reported by Park and Zhao(Park & Zhao, 2004). The film sample was cut into rectangle strip (10×40 mm) and placed into cuvette. The absorbance was measured at 600 nm using a spectrophotometer (UV 2100, Unico Instruments Co., Ltd., Shanghai, China). An empty cuvette without film was used as the reference. Three repetitions were performed for each film. The opacity was calculated by the following equation:

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

2

2



2 0.5

Opacity  Abs600 t

141

Where Abs600 is the value of absorbance at 600 nm and t is the thickness of film (mm).

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2.3.4. Mechanical properties

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The tensile strength (TS) and percentage of elongation at break (E) of film samples were determined using a XWL Auto Tensile Tester (Labthink mechanical and electrical technology Co. Ltd., China) according to the ASTM D638-08. The films were cut into rectangular strips (15×100 mm) and clamped in the self-aligning grips of the device. The initial distance of grip was 50 mm and the stretching speed was 50 mm/min. It was performed for three replicate film samples.

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2.3.5. Gas permeability

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2.3.5.1. Water vapor permeability The water vapor permeability of the films was carried out by using a PERMANTRAN-W® Model 1/50 water vapor transmission rate (WVTR) testing instrument (MOCON Inc., Minneapolis, MN, USA) according to ASTM E398. The films were cut into hexagon sheet using a steel mould. Then the sample was placed into the chamber of instrument. Before testing, the parameters were set as follow: the mode was continuous, effective testing area was 50 cm2, temperature was 37.8℃, permeant RH was 100% and dry side RH was 10%. The results were expressed as WVTR (g·(m·s·Pa)-1) and three replicates of each film were performed. 2.3.5.2. Oxygen permeability The oxygen transmission rate (OTR) of films was determined by using DIAMON G2/132 Gas permeability tester (Labthink mechanical and electrical technology Co. Ltd., Jinan, China). It was the same with previously reported method (Chen, Xie, Yang, Zhang, & Chen, 2017). Briefly, the films were cut into discs (95 mm in diameter) and were mounted in the gas diffusion cell for testing. The results were expressed as OTR (cm3·cm·(cm2·s·Pa)-1) and the measurements were performed in triplicate.

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2.3.6. Thermogravimetric analysis (TGA)

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The thermal property of the films was carried out using a NETZSCH TG 209 F1 thermal analyzer (NETZSCH Scientific Instruments Trading (Shanghai) Co., Ltd, Germany). The film samples were 4

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cut into pieces and about 6 mg samples were inserted into a crucible. It was heated from ambient temperature to 700℃ at a heating rate of 10℃/min under a nitrogen atmosphere with the flow rate of 20 mL/min. 2.3.7. Vapour-Phase antioxidant and antimicrobial activities The experimental procedure consisted of the minced trichiurus haumela packed in the plastic tray with sealed cover films on the top was shown in Fig. 1. The PVA film samples incorporated with 0%, 1%, 5% and 9% CO were pre-pasted onto the top films by double faced adhesive tape with the upside surface (during film drying) of the film facing the trichiurus haumela, avoiding direct contact film-food. The trichiurus haumela were got rid of viscera, heads, tails and bone. They were cleaned and minced by shredder (Beijing KINGSLH technology Co., Ltd, China). The minced fish meat samples were placed in the plastic trays and the trays were sealed with commercial polypropylene films. Then these packaging were stored at 2℃ in the refrigerator. The microbiological analyses and lipid oxidation of the packed trichiurus haumela were investigated during storage to validate the antioxidant and antimicrobial activities of the films in vapour phase, using Total Viable Counts (TVC) and Thiobarbituric acid reactive substances (TBARS) value. TVC and TBA were determined according to reported methods (Li et al., 2012) at 0, 1, 2, 3, 4, 5, 6 and 7 days. TVC were measured by counting the number of colony-forming units after incubation and the result of TVC was expressed as log CFU/g. For measuring TBA, the minced fish samples (200 mg) were added into a volumetric flask (25 mL) with 1-butanol (1 mL) for dissolving the samples. The mixture was made to volume and mixed. The mixture (5 mL) was taken out to be mixed with TBA reagent (5 mL) in the test tube. They were covered, vortexed and put into a water bath at 95℃ for 2 h and then cooled. The absorbance of the mixed solution (As) and reagent blank (Ab) were measured at 530 nm by using a UV-2100 ultraviolet spectrophotometer (Unico Shanghai Instrument Co., Ltd, China). The TBA value (mg malonaldehyde (MDA)/kg fish) can be expressed as follow: 50 × (𝐴𝑠 - 𝐴𝑏)

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TBA =

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2.3.8. Statistical analysis

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The statistical analysis of the data was performed through ANOVA using SPSS software (Version 15.0, Inc., Chicago, IL, USA). The differences among mean values were evaluated by Duncan’s multiple range tests. Significance level was defined at 5%. The data were represented as means ± standard deviation.

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3. Results and discussion

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3.1. Film color and opacity

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The color and opacity of all films were listed in Table 1. Compared with the pure PVA film, the L* value of the films added with CO decreased slightly. While the a* value decreased significantly, the b* and △E values rose markedly with the increasing CO in the films (p < 0.05). It showed that the PVA films became a little yellow for the CO incorporation, owing to the light yellow of the CO. The opacity of the films increased significantly as CO content in the films increased. It indicated that the transparency of the films was reduced for the CO incorporation into the films. Similar observations were obtained by incorporating the CO into the EVOH, chitosan and protein films (Fern, Royo, &

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Mat, 2012; Hosseini, Razavi, & Mousavi, 2009; Teixeira et al., 2014; Yang et al., 2016). The color parameters of the film were affected by the EOs incorporation depending on the amount and type of EOs used (Atarés, Bonilla, & Chiralt, 2010). The incorporation of CO caused the films became yellowish, higher chroma, lower hue and less whiteness (Teixeira et al., 2014). Table1 Color and opacity of the PVA films Film sample PVA-0CO PVA-1CO PVA-3CO PVA-5CO PVA-7CO PVA-9CO

L*

a*

b*

△E

93.61±0.07a

-0.66±0.02a

4.71±0.02f

0.59±0.06f

93.52±0.04ab 93.49±0.05b 93.47±0.08bc 93.43±0.04bc 93.37±0.01c

-0.98±0.01b -1.36±0.03c -1.67±0.02d -2.23±0.06e -2.98±0.02f

5.43±0.02e 6.24±0.03d 7.02±0.03c 8.30±0.02b 9.55±0.08a

1.11±0.03e 1.91±0.05d 2.71±0.04c 4.07±0.03b 5.52±0.09a

Opacity(Abs600/mm) 0.78±0.01f 0.90±0.02e 1.06±0.01d 1.13±0.01c 1.33±0.02b 1.66±0.01a

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a, b, c, d, e,fDifferent

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3.2. Film structure

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SEM micrographs of the surface and cross-section of the PVA films incorporated with CO at different concentrations were presented in Fig.2. The surface and cross-section of the pure PVA film was smooth, homogeneous and continuous, which was comparable with other report (Priya, Gupta, Pathania, & Singha, 2014). Compared with the pure PVA film, the surface of the PVA film added with 1% CO was just slightly uneven. The cross-section of this film was rough. But there were no oil droplets on the surface and cross-section of the film. The reason could be that the CO was well embedded into the PVA matrix due to the small size of the CO. It led to the enhanced interaction between the PVA matrix and CO, causing hardly identifiable oil droplets. It was in agreement with that the flocculation rate was restricted in lower lipid concentration (Sánchez-González, Vargas, González-Martínez, Chiralt, & Cháfer, 2009). The similar results were found by incorporating EOs into gelatin and chitosan film (Bonilla, Atarés, Vargas, & Chiralt, 2012; Fakhreddin, Rezaei, Zandi, & Farahmandghavi, 2015; Martucci, Gende, Neira, & Ruseckaite, 2015). As the concentration of CO in the film increased from 3% to 9%, the oil droplets were observed on the surface and cross-section of the film. With increasing CO in the films, the quantity of the oil droplets increased and they became a little larger. It probably ascribed to the deformation force that caused by the PVA chain aggregation during film drying. It resulted in the discontinuities structure in the film matrix, which was attributed to the weaker PVA-CO interactions in the film network. Some pores were observed in the cross-section of the PVA films containing CO from 3% to 9%. It was attributed to the evaporation of CO during drying process or the volatilization of CO (Acevedo-fani, Salvia-trujillo, Rojas-graü, & Martín-belloso, 2015; Klangmuang & Sothornvit, 2016). Encapsulation technique is helpful in improving the stability and solubility of EOs and masking their undesirable flavor as well (Wen et al., 2016). It is worth applying this to CO added in the films in the successive research to ameliorate these issues. In addition, the change of the film microstructure for the CO incorporation would affect the properties of the films.

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3.3. Mechanical properties

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The mechanical properties of all films were summarized in Table 2. For the incorporation of CO into

superscript letters between lines indicate significant difference between the results (p < 0.05) (ANOVA).

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the PVA films, the TS of the films reduced significantly (p < 0.05) with the increasing content of CO, while the elongation at break increased evidently (p < 0.05). Compared with pure PVA film, the TS of film containing 9% CO decreased 14.13% and the elongation at break increased 26.64%. It could be primarily ascribed to the reason that stronger interactions of PVA intermolecular were partially replaced by weaker PVA-CO interactions in the film matrix (Atarés & Chiralt, 2016). The heterogeneous film structure with discontinuities was formed for the CO incorporation into the film. These discontinuities caused the reduction of the resistibility that the films resisted to breakage (Sánchez-González et al., 2009). It was consistent with the findings by adding EOs into other films, such as carboxymethyl cellulose (CMC)-PVA, PLA and protein films (Javidi et al., 2016; Muppalla, Kanatt, Chawla, & Sharma, 2014; Teixeira et al., 2014). However, the opposite effects have also been reported by some studies. The increase of TS was observed in soy protein isolate films and chitosan films incorporated with cinnamon EO (Atarés, Jesús, Talens, & Chiralt, 2010; Mahdi, Rezaei, Hadi, Mohamad, & Hosseini, 2010). It was attributed to the strong interactions between cinnamon EO and soy protein isolate and between cinnamon EO and chitosan, producing crosslinker effects that reduced the free volume and the molecular mobility of the polymer. These interactions greatly relied on the type of EOs and were determined by the different components of EOs. The main component of cinnamon EO was cinnamaldehyde and the eugenol was a predominant compoment of CO, which determined their capacity to interact with the polymer matrix. Therefore, the effect of EOs incorporation on the mechanical properties of polymer films was variable and depended on the interactions between the EOs and the polymer matrix. Typically, some weakened effects were mainly ascribed to heterogeneous film structure with discontinuities caused by EOs incorporation (Atarés & Chiralt, 2016). Table2 Thickness, mechanical properties and gas permeability properties of the PVA films Film sample

Thickness(μm)

TS(MPa)

E(%)

OTR(×10-13) (cm3·cm·(cm2·s·Pa)-1)

WVTR(×10-14) (g·(m·s·Pa)-1)

PVA-0CO PVA-1CO PVA-3CO PVA-5CO PVA-7CO PVA-9CO

58.33±0.58c 59.00±1.00bc 61.33±0.58a 59.67±1.53abc 59.67±0.58abc 60.67±0.58ab

29.08±0.18a 28.57±0.17b 27.93±0.12c 26.80±0.21d 25.44±0.34e 24.97±0.11f

208.22±4.36f 221.05±2.37e 230.44±3.62d 239.46±3.57c 255.87±2.63b 263.68±5.06a

1.95±0.15d 2.12±0.14d 2.68±0.13c 3.02±0.16b 3.26±0.14b 3.72±0.16a

3.13±0.16a 2.87±0.14b 2.53±0.11c 2.20±0.16d 1.83±0.18d 1.43±0.17e

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a, b, c, d, e,fDifferent

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3.4. Gas permeability

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The WVTR and OTR of the PVA films were listed in Table 2. The WVTR of the films decreased significantly (p < 0.05) with increasing CO, suggesting their water vapor barrier properties were improved. Compared with pure PVA, the WVTR of PVA film containing 9% CO reduced 54.31%. It is may be due to the improvement of the film’s hydrophobic property, caused by incorporating hydrophobic CO into hydrophilic PVA film. The hydrophobic-hydrophilic ratio of the film constituents is an important factor that affects the water vapor molecules transfer processes in the film (Atarés & Chiralt, 2016). So the addition of hydrophobic EO into the hydrophilic polymer matrix may bring about the improvement of the water vapor barrier properties of the films. Similar conclusions were observed in sodium caseinate films incorporated with cinnamon and ginger

superscript letters between lines indicate significant difference between the results (p < 0.05) (ANOVA).

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essential oil (Atarés, Bonilla, et al., 2010), HPMC films with tea tree essential oil (Sánchez-González et al., 2009), chitosan film with cinnamon essential oil (Mahdi et al., 2010) and gelatin film with citrus essential oils (Tongnuanchan, Benjakul, & Prodpran, 2012). The OTR of the films increased with increasing CO. It could be attributed to the heterogeneous film structure featuring discontinuities for CO incorporation. The CO droplets in the films broke the PVA matrix and the interaction between polymer chains was diminished. It might create void spaces at the PVA-CO interface. It promoted the oxygen pass through the film, so the oxygen barrier property of the films was weakened. This was consistent with other observations for chitosan films containing thyme oil (Altiok, Altiok, & Tihminlioglu, 2010) and HPMC films containing ginger essential oil or oregano essential oil or bergamot essential oil (Atarés & Chiralt, 2011; Choi et al., 2016).

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3.5. Thermal stability

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The thermogravimetric analysis (TGA) and derivative thermogravimetric (DTG) curves of all films were illustrated in Fig.3. All PVA films incorporated with different loading levels of CO decomposed in a similar three-step degradation process, corresponding to three temperature ranges: 30-180°C, 180–350°C and 350–520°C. The first degradation step with about 8% weight loss was mainly because of the loss of water in the films. It also included the degradation of CO for the films added with CO. The weight loss (about 60%) during the second degradation step was due to degradation of PVA for side chain decomposition. The third degradation step was mainly caused by the degradation of PVA for main chain decomposition, producing small molecular carbon and hydrocarbon-related products and carbon char (Chen, Chen, et al., 2017; Soo-Tueen Bee,Lee Tin Sin,Su-Luang Khor,Kien-Sin Lim, 2015). As shown in the Fig.3 (b), structural decomposition of pure PVA film started at 260°C. As the content of CO increased from 0% to 9%, the initial decomposition temperature only slowly decreased from 260°C to 258°C. This indicated that the thermal stability of the PVA films was worsened slightly with increasing CO. It might be due to the heterogeneous film structure featuring discontinuities, leading to the occurrence of gap at the PVA-CO interface (Atarés & Chiralt, 2016). 3.7 Vapour-phase antimicrobial and antioxidant activities TVC values of the trichiurus haumela affected by the different packaging system over storage were shown in Fig.4 (a). The TVC of bacteria is a key indicator of the quality of fish products (Feng, Bansal, & Yang, 2016). The initial TVC value was 2.89 log cfu/g that suggested the quality of fish meat was good (Cai et al., 2014; Feng, Ng, Mikš-Krajnik, & Yang, 2017). The TVC value of all fish samples increased significantly during storage. The TVC value of the control sample (PVA-0CO) and the sample packed with PVA-1CO film was 6.83 and 6.68 log CFU/g respectively on day 5, which was close to the maximum microbiological acceptability limit of 7 log CFU/g for raw fish (Li et al., 2012). It suggested their microbiological shelf-life was about 5-6 days. In comparison, the TVC value of the fish samples packed with PVA-5CO and PVA-9CO films was 6.92 log CFU/g on day 6 and 6.93 log CFU/g on day 7 respectively, indicating their microbiological shelf-life were extended for 1 and 2 days respectively comparing with that of the control sample. The TVC value of fish samples packed with PVA films incorporated with CO were lower than that of the control sample at the same day. These results showed that the bacterial growth of the fish samples was inhibited for the packaging system containing PVA films incorporated with CO and the degree of the inhibition increased with the increase of CO in the films. And there were no significantly differences 8

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between the control sample and the sample packed with PVA-1CO film on the TVC value at the same day. It indicated the effectiveness of the microbial growth inhibition was poor owing to the low concentration of CO in the films. However, for the fish samples packed with PVA-5CO and PVA9CO films, the TVC value was significantly lower than that of the control sample, suggesting the microbial growth were delayed effectively as the content of CO increased. These results were ascribed to the antimicrobial activity of the CO in vapour phase that released from the PVA film into the headspace of the packaging. And the vapour-phase antimicrobial activities of the films increased with increasing CO content. The released volatile antimicrobial compounds of CO adhered to or dissolved in the surface of the trichiurus haumela meat, then further migrated into the meat. Eugenol, the major antimicrobial molecules in vapour phase (Goñi et al., 2009), caused a greater affinity towards the hydrophobic microbial cell membrane for its greater hydrophobicity (Kumar et al., 2012). It resulted in the increased fluidity and permeability of cell membrane, disturbance of membrane embedded proteins, cytoplasm leakage, respiration inhibition and change of ion transport processes (Abdo & Özlem Emir, 2017; Rivera, Crandall, Bryan, & Ricke, 2015). Whereas the poor effectiveness of the microbial growth inhibition for the PVA-1CO films could be attributed to the fact that the concentration of CO in vapour phase didn’t reached the minimum inhibitory concentration (MIC) values (Kumar et al., 2012). The trichiurus haumela is high in fat, most of which are unsaturated fatty acids that are easy to oxidated. The quality loss for lipid oxidation was characterized by the rancid odours and flavours, the destruction of nutrients and the formation of probable toxic compounds (Atarés & Chiralt, 2016; Li, Li, & Hu, 2013). TBA values of the trichiurus haumela affected by the different packaging system over storage were shown in Fig. 4(b). The TBARS assay provided the information on the progress of lipid oxidation in the trichiurus haumela by measuring the amount of secondary products (malonaldehyde) of lipid oxidation. The initial TBA values of fish samples were 0.54 mg MDA/kg. The TBA of all samples increased significantly during storage. The TBA of the control sample was higher than that packed with PVA films incorporated with CO. During the first 2 days of storage, the TBA value of all samples were relatively low ranged from 0.54 mg MDA/kg to 0.77 mg MDA/kg and it showed little differences between the four groups. This might be explained that the degree of degradation of primary lipid oxidation products into secondary oxidation products was low, which peroxides were oxidized to aldehyde and ketone (Li et al., 2012). With the prolongation of storage time, the rate of malonaldehyde production of the control sample was significantly higher in trichiurus haumela packed with PVA films incorporated with CO, indicating a remarkable delay in peroxides degradation exerted by the CO. On the final day of storage, the TBA values of four groups increased to 1.71, 1.63, 1.41 and 1.23 mg MDA/kg for the samples packed with PVA-0CO (control), PVA-1CO, PVA-5CO and PVA-9CO films respectively. The results suggested that the lipid oxidation was inhibited for the packaging with PVA films incorporated with CO. The packaging with PVA films incorporated with 9% CO showed the best effect on the protection of fish meat from oxidation in vapour phase, which showed 28.07% reduction of malonaldehyde compared with control sample on day 7. A study showed a significant reduction of malonaldehyde in the smoked salmon packed with the chicken feather protein film containing CO compared with the control (Song et al., 2014). Salgado et al also reported that the lipid oxidation of refrigerated sardine patties packed with CO-containing sunflower protein film was retarded (Salgado, López-Caballero, Gómez-Guillén, Mauri, & Montero, 2013). These results were related to the antioxidant activity of CO-containing PVA films that exerted by the released volatile 9

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compounds of CO. The eugenol made the main contribution to the strong antioxidant activity of clove essential oil (Teixeira et al., 2013). It was attributed to the redox properties of the phenolic compounds, acting as singlet oxygen quenchers, reducing agents, hydrogen donors as well as metal chelators (Abdo & Özlem Emir, 2017). In summary, the above results indicated that the PVA films incorporated with CO showed effective antimicrobial and antioxidant activities in vapour phase, which increased with increasing CO. In the meanwhile, the CO odour of the fish meat became stronger as the content of CO increased. So if the negative impacts on properties of PVA films due to the increasing addition of CO could be improved, it might be a promising active packaging for potential application in the non direct contact packaging-food system to create a protective atmosphere around the packaged foodstuffs.

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The active PVA films containing different concentrations of CO with antioxidant and antimicrobial activities in vapour phase were developed. The results showed that the discontinuous structure was formed in the films with oil droplets embedded in the network for higher concentrations of CO incorporation. These caused some negative impacts on physicochemical, mechanical and morphological properties of the films, like reducing tensile strength, oxygen barrier property and thermal stability. These were attributed to the weak interaction between PVA and CO, which greatly depended on the type of EOs and their main components. So how to minimize these negative impacts as low as possible or completely improve the properties of the films is worth studying in the successive research. The PVA films incorporated with CO showed effective antimicrobial and antioxidant activities in vapour phase and they increased with increasing content of CO, by inhibiting the bacterial growth and lipid oxidation of the trichiurus haumela. Thus, the developed PVA films containing CO could potentially be applied to the food packaging industry as active packaging materials in the non direct contact with food. In spite of this, it is also worthwhile to investigate the effect of films incorporated with CO on the overall quality of the packed food in future, especially the influence on the food sensory.

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Acknowledgments

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This study has been financed by the National Key Research and Development Program (2016YFD0400106), the project Shanghai Science and Technology Committee Engineering Research Center Construction: Shanghai Engineering Research Center of Aquatic-Product Processing & Preservation (16DZ2280300) and the special foundation for science and technology development of Shanghai Ocean University (A2-0203-00-100218).

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References

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Abdo, H., & Özlem Emir, Ç. (2017). Essential oils for antimicrobial and antioxidant applications in fish and other seafood products. Trends in Food Science & Technology, 68, 26–36. Acevedo-fani, A., Salvia-trujillo, L., Rojas-graü, M. A., & Martín-belloso, O. (2015). Edible films from essential-oilloaded nanoemulsions : Physicochemical characterization and antimicrobial properties. Food Hydrocolloids, 47, 10

ACCEPTED MANUSCRIPT 400 401 402 403 404 405 406 407 408 409 410 411 412 413 414 415 416 417 418 419 420 421 422 423 424 425 426 427 428 429 430 431 432 433 434 435 436 437 438 439 440 441 442 443

168–177. Altiok, D., Altiok, E., & Tihminlioglu, F. (2010). Physical , antibacterial and antioxidant properties of chitosan films incorporated with thyme oil for potential wound healing applications. Journal of Materials Science: Materials in Medicine, 21, 2227–2236. Atarés, L., Bonilla, J., & Chiralt, A. (2010). Characterization of sodium caseinate-based edible films incorporated with cinnamon or ginger essential oils. Journal of Food Engineering, 100, 678–687. Atarés, L., & Chiralt, A. (2011). The role of some antioxidants in the HPMC film properties and lipid protection in coated toasted almonds. Journal of Food Engineering, 104, 649–656. Atarés, L., & Chiralt, A. (2016). Essential oils as additives in biodegradable films and coatings for active food packaging. Trends in Food Science & Technology, 48, 51–62. Atarés, L., Jesús, C. De, Talens, P., & Chiralt, A. (2010). Characterization of SPI-based edible films incorporated with cinnamon or ginger essential oils. Journal of Food Engineering, 99(3), 384–391. Bonilla, J., Atarés, L., Vargas, M., & Chiralt, A. (2012). Effect of essential oils and homogenization conditions on properties of chitosan-based films. Food Hydrocolloids, 26(1), 9–16. Buonocore, G. G., Conte, A., Corbo, M. R., Sinigaglia, M., & Del Nobile, M. A. (2005). Mono- and multilayer active films containing lysozyme as antimicrobial agent. Innovative Food Science and Emerging Technologies, 6(4), 459– 464. Buonocore, G. G., Nobile, M. A. Del, Panizza, A., Corbo, M. R., & Nicolais, L. (2003). A general approach to describe the antimicrobial agent release from highly swellable films intended for food packaging applications. Journal of Controlled Release, 90, 97–107. Cai, L., Wu, X., Li, X., Zhong, K., Li, Y., & Li, J. (2014). Effects of different freezing treatments on physicochemical responses and microbial characteristics of Japanese sea bass ( Lateolabrax japonicas ) fillets during refrigerated storage. LWT - Food Science and Technology, 59(1), 122–129. Chen, C., Chen, Y., Xie, J., Xu, Z., Tang, Z., & Yang, F. (2017). Effects of montmorillonite on the properties of crosslinked poly (vinyl alcohol)/boric acid films. Progress in Organic Coatings, 112, 66–74. Chen, C., Xie, J., Yang, F., Zhang, H., Xu, Z., Liu, J., & Chen, Y. (2017). Development of moisture-absorbing and antioxidant active packaging film based on poly ( vinyl alcohol ) incorporated with green tea extract and its effect on the quality of dried eel. Journal of Food Processing and Preservation. . https://doi.org/10.1111/ jfpp.13374 Chiralt, A., & Vargas, M. (2016). Properties of film-forming dispersions and films based on chitosan containing basil or thyme essential oil. Food Hydrocolloids, 57, 271–279. Choi, W. S., Singh, S., & Lee, Y. S. (2016). Characterization of edible film containing essential oils in hydroxypropyl methylcellulose and its effect on quality attributes of “ Formosa ” plum ( Prunus salicina L .). LWT - Food Science and Technology, 70, 213–222. Conte, A., Buonocore, G. G., Bevilacqua, A., Sinigaglia, M., & Del Nobile, M. A. (2006). Immobilization of lysozyme on polyvinylalcohol films for active packaging applications. Journal of Food Protection, 69(4), 866–870. DeMerlis, C. C., & Schoneker, D. R. (2003). Review of the oral toxicity of polyvinyl alcohol (PVA). Food and Chemical Toxicology, 41(3), 319–326. Fakhreddin, S., Rezaei, M., Zandi, M., & Farahmandghavi, F. (2015). Bio-based composite edible films containing Origanum vulgare L . essential oil. Industrial Crops & Products, 67, 403–413. Feng, X., Bansal, N., & Yang, H. (2016). Fish gelatin combined with chitosan coating inhibits myofibril degradation of golden pomfret (Trachinotus blochii) fillet during cold storage. Food Chemistry, 200, 283–292. Feng, X., Ng, V. K., Mikš-Krajnik, M., & Yang, H. (2017). Effects of fish gelatin and tea polyphenol coating on the spoilage and degradation of myofibril in fish fillet during cold storage. Food and Bioprocess Technology, 10(1), 89–102. 11

ACCEPTED MANUSCRIPT 444 445 446 447 448 449 450 451 452 453 454 455 456 457 458 459 460 461 462 463 464 465 466 467 468 469 470 471 472 473 474 475 476 477 478 479 480 481 482 483 484 485 486 487

Fern, I., Royo, M., & Mat, J. I. (2012). Antimicrobial activity of whey protein isolate edible films with Eessential oils against food spoilers and foodborne pathogens. Journal of Food Science, 77, 383–390. Goñi, P., López, P., Sánchez, C., Gómez-lus, R., Becerril, R., & Nerín, C. (2009). Antimicrobial activity in the vapour phase of a combination of cinnamon and clove essential oils. Food Chemistry, 116(4), 982–989. Han, C., Wang, J., Li, Y., Lu, F., & Cui, Y. (2014). Antimicrobial-coated polypropylene films with polyvinyl alcohol in packaging of fresh beef. Meat Science, 96(1), 901–907. Hosseini, M. H., Razavi, S. H., & Mousavi, M. A. (2009). Antimicrobial,physical and mechanical properties of chitosanbased films incorporated with thyme, clove and cinnamon essential oils. Journal of Food Processing and Preservation, 33, 727–743. Javidi, Z., Hosseini, S. F., & Rezaei, M. (2016). Development of flexible bactericidal films based on poly (lactic acid) and essential oil and its effectiveness to reduce microbial growth of refrigerated rainbow trout. LWT - Food Science and Technology, 72, 251–260. Jipa, I. M., Stoica-Guzun, A., & Stroescu, M. (2012). Controlled release of sorbic acid from bacterial cellulose based mono and multilayer antimicrobial films. LWT - Food Science and Technology, 47(2), 400–406. Kavas, G., Kavas, N., & Saygili, D. (2015). The effects of thyme and clove essential oil fortified edible films on the physical, chemical and microbiological characteristics of kashar cheese. Journal of Food Quality, 38, 405–412. Khumalo, K. N., Tinyane, P., Soundy, P., Romanazzi, G., Glowacz, M., & Sivakumar, D. (2017). Effect of thyme oil vapour exposure on the brown rot infection , phenylalanine ammonia-lyase (PAL) activity , phenolic content and antioxidant activity in red and yellow skin peach cultivars. Scientia Horticulturae, 214, 195–199. Kim, I. H., Han, J., Na, J. H., Chang, P. S., Chung, M. S., Park, K. H., & Min, S. C. (2013). Insect-resistant food packaging film development using cinnamon oil and microencapsulation technologies. Journal of Food Science, 78(2). Klangmuang, P., & Sothornvit, R. (2016). Barrier properties , mechanical properties and antimicrobial activity of hydroxypropyl methylcellulose-based nanocomposite films incorporated with Thai essential oils. Food Hydrocolloids, 61, 609–616. Kumar, A., Malik, A., & Elisabetta, M. (2012). Essential oil vapour and negative air ions : A novel tool for food preservation. Trends in Food Science & Technology, 26(2), 99–113. Kwon, S.-J., Chang, Y., & Han, J. (2017). Oregano essential oil-based natural antimicrobial packaging film to inactivate Salmonella enterica and yeasts/molds in the atmosphere surrounding cherry tomatoes. Food Microbiology, 65, 114–121. Lacey, A. L. De, & Montero, P. (2010). Biodegradable gelatin e chitosan films incorporated with essential oils as antimicrobial agents for fish preservation. Food Microbiology, 27(7), 889–896. Lantano, C., Alfieri, I., Cavazza, A., Corradini, C., Lorenzi, A., Zucchetto, N., & Montenero, A. (2014). Natamycin based sol-gel antimicrobial coatings on polylactic acid films for food packaging. Food Chemistry, 165, 342–347. Li, T., Hu, W., Li, J., Zhang, X., Zhu, J., & Li, X. (2012). Coating effects of tea polyphenol and rosemary extract combined with chitosan on the storage quality of large yellow croaker ( Pseudosciaena crocea ). Food Control, 25(1), 101–106. Li, T., Li, J., & Hu, W. (2013). Changes in microbiological , physicochemical and muscle proteins of post mortem large yellow croaker ( Pseudosciaena crocea ). Food Control, 34(2), 514–520. Liu, G., Song, Y., Wang, J., Zhuang, H., Ma, L., Li, C., & Zhang, J. (2014). Effects of nanoclay type on the physical and antimicrobial properties of PVOH-based nanocomposite films. LWT - Food Science and Technology, 57(2), 562– 568. Mahdi, S., Rezaei, M., Hadi, S., Mohamad, S., & Hosseini, H. (2010). Development and evaluation of a novel biodegradable film made from chitosan and cinnamon essential oil with low affinity toward water. Food 12

ACCEPTED MANUSCRIPT 488 489 490 491 492 493 494 495 496 497 498 499 500 501 502 503 504 505 506 507 508 509 510 511 512 513 514 515 516 517 518 519 520 521 522 523 524 525 526 527 528 529 530 531

Chemistry, 122(1), 161–166. Martucci, J. F., Gende, L. B., Neira, L. M., & Ruseckaite, R. A. (2015). Oregano and lavender essential oils as antioxidant and antimicrobial additives of biogenic gelatin films. Industrial Crops & Products, 71, 205–213. Mulla, M., Ahmed, J., Al-attar, H., Castro-aguirre, E., Ali, Y., & Auras, R. (2017). Antimicrobial efficacy of clove essential oil infused into chemically modified LLDPE film for chicken meat packaging. Food Control, 73, 663– 671. Muppalla, S. R., Kanatt, S. R., Chawla, S. P., & Sharma, A. (2014). Carboxymethyl cellulose-polyvinyl alcohol films with clove oil for active packaging of ground chicken meat. Food Packaging and Shelf Life, 2, 51–58. Muriel-galet, V., Cran, M. J., Bigger, S. W., Hernández-muñoz, P., & Gavara, R. (2015). Antioxidant and antimicrobial properties of ethylene vinyl alcohol copolymer films based on the release of oregano essential oil and green tea extract components. Journal of Food Engineering, 149, 9–16. Musetti, A., Paderni, K., Fabbri, P., Pulvirenti, A., Al-Moghazy, M., & Fava, P. (2014). Poly(vinyl alcohol)-Based Film Potentially Suitable for Antimicrobial Packaging Applications. Journal of Food Science, 79(4). Nedorostova, L., Kloucek, P., Kokoska, L., Stolcova, M., & Pulkrabek, J. (2009). Antimicrobial properties of selected essential oils in vapour phase against foodborne bacteria. Food Control, 20, 157–160. Park, S. Il, & Zhao, Y. (2004). Incorporation of a high concentration of mineral or vitamin into chitosan-based films. Journal of Agricultural and Food Chemistry, 52(7), 1933–1939. Priya, B., Gupta, V. K., Pathania, D., & Singha, A. S. (2014). Synthesis, characterization and antibacterial activity of biodegradable starch/PVA composite films reinforced with cellulosic fibre. Carbohydrate Polymers, 109, 171–179. Rivera, J., Crandall, P. G., Bryan, C. A. O., & Ricke, S. C. (2015). Essential oils as antimicrobials in food systems-A review. Food Control, 54, 111–119. Salgado, P. R., López-Caballero, M. E., Gómez-Guillén, M. C., Mauri, A. N., & Montero, M. P. (2013). Sunflower protein films incorporated with clove essential oil have potential application for the preservation of fish patties. Food Hydrocolloids, 33(1), 74–84. Sánchez-González, L., Vargas, M., González-Martínez, C., Chiralt, A., & Cháfer, M. (2009). Characterization of edible films based on hydroxypropylmethylcellulose and tea tree essential oil. Food Hydrocolloids, 23, 2102–2109. Siracusa, V., & Dalla, M. (2008). Biodegradable polymers for food packaging : a review. Trends in Food Science & Technology, 19(12), 634–643. Song, N., Lee, J., Mijan, M. Al, & Song, K. Bin. (2014). Development of a chicken feather protein film containing clove oil and its application in smoked salmon packaging. LWT - Food Science and Technology, 57(2), 453–460. Songsamoe, S., Matan, N., & Matan, N. (2017). Antifungal activity of michelia alba oil in the vapor phase and the synergistic effect of major essential oil components against Aspergillus flavus on brown rice. Food Control, 77, 150–157. Bee, S., Sin, L., Khor, S.,Lim, K., &Rahmat, A. (2015). Enhancement of mechanical and thermal properties of (poly[vinyl alcohol])-pialdehyde starch composites via the incorporation of montmorillonite nanofillers. Journal of Vinyl & Additive Technology, 18(8), 1–14. Sow, L. C., Tirtawinata, F., Yang, H., Shao, Q., & Wang, S. (2017). Carvacrol nanoemulsion combined with acid electrolysed water to inactivate bacteria, yeast in vitro and native microflora on shredded cabbages. Food Control, 76, 88–95. Stroescu, M., Stoica-Guzun, A., & Jipa, I. M. (2013). Vanillin release from poly(vinyl alcohol)-bacterial cellulose mono and multilayer films. Journal of Food Engineering, 114(2), 153–157. Teixeira, B., Marques, A., Pires, C., Ramos, C., Batista, I., Alexandre, J., & Leonor, M. (2014). Characterization of fish protein films incorporated with essential oils of clove , garlic and origanum : Physical , antioxidant and antibacterial properties. LWT - Food Science and Technology, 59(1), 533–539. Teixeira, B., Marques, A., Ramos, C., Neng, N. R., Nogueira, J. M. F., Alexandre, J., & Leonor, M. (2013). Chemical 13

ACCEPTED MANUSCRIPT 532 533 534 535 536 537 538 539 540 541 542

composition and antibacterial and antioxidant properties of commercial essential oils. Industrial Crops & Products, 43, 587–595. Tongnuanchan, P., Benjakul, S., & Prodpran, T. (2012). Properties and antioxidant activity of fish skin gelatin film incorporated with citrus essential oils. Food Chemistry, 134(3), 1571–1579. Wen, P., Zhu, D., Wu, H., Zong, M., Jing, Y., & Han, S.. (2016). Encapsulation of cinnamon essential oil in electrospun nanofibrous film for active food packaging. Food Control, 59, 366–376. Yang, H., Wang, J., Yang, F., Chen, M., Zhou, D., & Li, L. (2016). Active packaging films from ethylene vinyl alcohol copolymer and clove essential nil as fhelf life extenders for grass carp slice. Packaging Technology and Science, 29, 383–396. Zengin, H., & Baysal, A. H. (2015). Antioxidant and antimicrobial activities of thyme and clove essential oils and application in minced beef. Journal of Food Processing and Preservation, 39, 1261–1271.

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ACCEPTED MANUSCRIPT Fig.1 A diagram of the packaging system for trichiurus haumela Fig.2 SEM micrographs of the surface (A) and cross-section (B) of PVA films Fig. 3 Thermal characterization: (a) TGA curves of PVA films; (b) DTG curves of PVA films Fig.4 TVC and TBA changes of trichiurus haumela with different packaging during storage: (a) TVC; (b) TBA

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Highlights     

The active PVA films incorporated with clove oil were developed. The films were characteristic of heterogeneous structure featuring discontinuities. Some negative impacts on properties of films were caused with increasing clove oil. The films possessed antioxidant and antimicrobial activities in vapour phase. It could be a promising active material for potential food packaging application.

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