1. Introduction
In recent years, biobased packaging materials have obtained widespread interest due to the environmental problems caused by the use of petrochemical-based plastics. Among the biobased materials, carbohydrates, pectin, fibers, chitosan and valuable bioactive molecules, such as phenolic acids, carotenoids, flavonoids, vitamins and aromatic compounds have shown potential applications [
1,
2,
3,
4]. Yellow-flesh peaches are rich in antioxidants, dietary fiber, and trace elements, recent studies of the antioxidant composition of peaches revealed that phenolic compounds serve as major sources of potential antioxidants [
5,
6]. In addition, epidemiological studies have demonstrated that the consumption of yellow-fleshed peaches has many benefits for humans, such as supplementing vitamins and carotene, and also resisting free radicals in the human body to have the effect of anti-oxidation and beauty raising [
7]. Yellow peaches are usually processed into cans after being peeled; however, it has been found that peels contain 2–2.5 times the concentration of total phenolic compounds as compared to flesh and whole extracts [
8,
9]. Usually, yellow peach peel (YPP) is directly discarded into the environment, which caused serious pollution and waste. Based on this, the utilization of agricultural by-products, such as YPP to prepare edible films seems much more profitable from the perspective of resource recycling and environmental protection [
9,
10,
11,
12].
As one of the most versatile biodegradable polymers, Sodium alginate (SA) is a linear polysaccharide derived from brown seaweed and possesses highly negative charge densities, is water-soluble, nontoxic, biodegradable and biocompatible [
13,
14,
15,
16]. However, the researchers found that alginate films generally have disadvantages, such as low mechanical strength compared to synthetic polymers [
17]. In order to cover the drawbacks of single-component film, two or more components are usually expected to be combined via physical or chemical cross-linking [
18,
19]. Plasticizers are commonly used to improve plasticity in composite film substrates. Glycerol, due to its small molecular weight, increased the chance of chemical interactions with other substances; it is one of the most popular plasticizers used in films, in addition, it also has great stability and compatibility with hydrophilic biopolymer packaging chains [
20], such as in Riku A. Talja’s study on the effects of three plasticizers (glycerol, xylitol and sorbitol) on the physical and mechanical properties of potato starch-based edible films, glycerol is more suitable for preparing film than other two alcohols [
21].
Oxidation is one of the most common mechanisms of degradation in foodstuffs and limits the shelf of food [
22]. Various fruit extracts from fruit peels have been tested as antioxidants in oil packaging including plum, grape seed, cranberry and pomegranate [
23,
24,
25,
26]. According to MARIÄA I. GIL’s quantitative research on the antioxidant components of different varieties of yellow peach peels, the results show that the content of polyphenols in peels is higher than that of vitamin C and carotenoids. Fruit polyphenols include a variety of antioxidants compounds, namely hydroxycinnamate, flavan-3-ols (condensed tannins), gallic acid derivatives (hydrolyzable tannins), flavonols and anthocyanins, vary widely in the phenolic composition of different fruit varieties [
5]. Polyphenols have benzene rings and substituted hydroxyl groups, which can act as antioxidants, provide electrons or gas atoms, and directly participate in the removal of free radicals. The research of Lijun Sun suggested that the incorporation of apple polyphenols contributed to the antioxidant ability of the chitosan film [
27].
Studies have shown that peach peel flour has a certain antioxidant capacity, which can delay lipid oxidation of cooked turkey during 12 days of refrigeration [
28]. However, there are currently no studies on antioxidant films for YPP and SA. Thus, the objective of this study was to prepare antioxidant films based on YPP, SA and G, the best formula was optimized by RSM and the YPP, YPP-SA and YPP-SA-G films were characterized with respect to their mechanical, thermal, barrier properties and antioxidant capacity. Finally, the YPP-SA-G antioxidant film was used for the packaging of soybean oil to delay its oxidation to add value to different agro-industrial chains.
2. Materials and Methods
2.1. Materials
Yellow peaches were obtained from Baoding Industry Group Co., Ltd. (Baoding, Hebei, China). Sodium alginate and glycerol were all purchased from Wanke Chemical Reagent Co., Ltd. (Baoding, Hebei, China). Folinphenol, gallic acid and 2,2-diphenyl-1-picrylhydrazyl (DPPH) were purchased from Shanghai Yuanye Bio-Technology Co., Ltd. (Shanghai China). Soybean oil was purchased from a supermarket in Baoding. The main reagents were listed.
2.2. Films Preparation
The yellow peach peel was dried in an oven at 50 °C for 12 h, ground into flour by a high-speed mill (Shanghai, China) and then passed through a 200-mesh sieve.
Figure 1 showed a schematic diagram of the film-forming process. Firstly, the YPP flour was dispersed in 100 mL of water and stirred at 60 °C for 30 min to ensure thorough mixing. Then, the film-forming solution was further processed using a high-pressure homogenizer (GJJ-0.03/100, Shanghai Noni Light Industry Machinery Co., Ltd., China) at a pressure of 40 MPa. Next, SA and G were added to the dispersion, stirred using a thermomagnetic mixer (Beijing, China) for 30 min and then degassed using a vacuum pump for 10 min. Finally, 100 mL of film-forming solution was poured into a 15 cm × 15 cm Teflon plate, the film was removed from the plate after drying at 50 °C for 5 h and incubated at 25 °C and relative humidity (56% RH) for 24 h to further evaluate the physical properties of the film.
Later, pure YPP film was prepared only with YPP flour (2.50% (W/V)), YPP-SA film was prepared using the optimized formulation without adding glycerol (YPP 2.50% and SA 0.60%), YPP-SA-G film was prepared using the optimized formulation (2.50% of YPP, 0.60% SA and 0.80% of G). These film samples were used for subsequent characterization tests.
2.3. Chemical Composition of Yellow Peach Peel
Protein content was measured following the GB/T 5009.5-2016 using 6.25 as a conversion factor, and the content of lipid was evaluated according to GB/T 5009.6-2016. Total dietary fiber was determined according to the methods described in GB/T 5009.10-1985. Pectin content was calculated by the method of GB/T 10742-2008. Antioxidant activity is reflected by total phenolic content and DPPH free radical scavenging rate, all determinations were performed at least in duplicate.
2.4. Physical Properties of the Films
2.4.1. Film Thickness
A digital micrometer (Changchun, China) was used to determine the thickness of films nearest 0.001 mm. The average thickness was determined at five random positions on the films.
2.4.2. Mechanical Properties
Tensile strength (TS) and elongation at break (E) values of the films were tested with an auto tensile tester (DRK101A, Derek Instrument Co., Ltd., Shandong, China) according to the method described on GB/T13022-1991. The test samples, 80 mm × 15 mm, were cut from each film and fixed on the grips of the device with a gap of 50 mm. The crosshead speed was set at 50 mm min−1. For each sample, at least three replicates were tested.
2.4.3. Light Transmission (T)
The light transmission of the films was recorded by ultraviolet spectrophotometer (WFJ2-2000, Unocal Instrument Co., Ltd., Shanghai, China), the film was cut into 9 mm × 30 mm put directly into the cuvette to be measured. T
1 is the transmittance of the film at 600 nm, T
0 is the control, and the transmittance of the light without the film (its transmittance is 100%). The light transmission was calculated to Equation (1):
2.4.4. Water Solubility (WS)
The WS of the films was determined according to the method of Wu [
29] with slight modification. Briefly, a film (5 cm × 5 cm) was weighed (W
1) prior to dissolution in water for 24 h at room temperature, and then removed and dried at 105 °C to a constant weight (W
2). The WS was calculated by the following Equation (2):
2.4.5. Evaluation of the Comprehensive Performance of the Film
The films were evaluated by the Membership degree. In accordance with importance, the indexes of the films were normalized to optimize the production process. Four indices with high membership were calculated using Equation (3):
where X(u) is the index membership degree; X
i is the actual value; X
min is the minimum of the same index; X
max is the maximum of the same index.
According to the evaluated method by Hongyan [
10]. The weight of TS is 40%, E is 30%, T is 10%, WS is 20%. The comprehensive score (Y) was calculated with the following Equation (4):
where X
1, X
2, X
3, X
4 are membership degrees of TS, E%, WS, and T%, respectively.
2.5. RSM Design for Optimizing the Film Properties Factors
RSM is a statistical experimental method for optimizing the preparation process, which can be used for model development, evaluation of factor effects and optimal condition factors [
11]. In our study, RSM was used to study the influence factors of the content of film-forming components (including the weight of YPP, SA and G) on the comprehensive score of the film. The primary interaction and secondary effects of independent variables were optimized and evaluated using RSM. The experimental design was mainly performed at three levels (−1, 0, 1): YPP (2.0–3.0 g/100 mL), SA (0.3–0.7 g/100 mL) and G (0.6–1.0 g/100 mL) at concentrations, such as those shown in
Table 1.
To analyze the experimental data, Design Expert 8.0.6 software was used to design according to the Box-behnken design (BBC), which required 17 experiments including five replicates formed at the center point. To predict the optimal point, a second-order polynomial function was established to evaluate the relationship between the yellow peach peel, sodium alginate, and glycerol concentrations and the composite score of the film.
2.6. Verification Test
The optimal conditions of the composite film were determined by the verification experiments, and the actual experimental data were compared with the experimental values predicted by the model to verify the validity and sufficiency of the RSM model.
2.7. Characterization of Films
2.7.1. Scanning Electron Microscope (SEM)
The micromorphology of the films was observed by scanning electron microscope (SEM) using EDAX 4863-P (USA). The samples were covered with a thin layer of gold before observation, and all samples were photographed at 20 kV.
2.7.2. Fourier Transform Infrared (FTIR)
The samples were detected and analyzed using an FTIR spectrometer (Shimadzu In-strument Co., Ltd., Beijing, China) in the attenuated total reflection mode, with a scanning range of 4000–1000 cm−1 and a spectral resolution of 4 cm−1.
2.7.3. X-ray Diffraction (XRD)
The composite film was cut and placed on the X-ray diffractometer (cuka radiation) (D2Phaser, broker AXS Instrument, Co., Ltd., Beijing, China). Determination parameters: room temperature, X-ray wavelength a = 0.154 nm, Cu target, graphite monochromator, tube pressure 40 kV, Current 30 Ma, scanning range 10°~70° seventy Scanning speed 2°/min.
2.7.4. Thermo Gravimetric Analysis (TGA)
TGA was carried out on a thermogravimetric analyzer (HCT-2, Hengjiu Scientific Instrument, Co. Ltd., Beijing, China) under a nitrogen gas atmosphere to evaluate the thermal stability of the specimens. Approximately 10 mg of the sample was precisely cut into small pieces and heated at a rate of 10 °C/min from room temperature to 700 °C.
2.7.5. Water Contact Angle (WCA)
The hydrophilicity of all films was evaluated by contact angle measurements using a VCA dynamic contact angle tester. The contact angles of all films were measured using deionized water (5 µL).
2.8. Antioxidant Activity
2.8.1. Total Phenolic Content (TPC)
The TPC in composite films was determined by a colorimetric reaction to the phenol method with slight modifications. Aqueous gallic acid concentrations ranging from 0 to 15 mg/mL
−1 were used to obtain calibration curves [
30]. Thin film test solutions were prepared by soaking 150 mg of thin film samples in 15 mL of distilled water for 24 h. A mix of 0.1 mL of the solution with 0.7 mL of Folinphenol reagent was added to 3 mL of 10 wt% sodium carbonate solution and then the total volume of the mixture was brought to 10 mL with distilled water, and then incubated at room temperature for 2 h in the dark. Then, the absorbance of the mixture at 765 nm was measured using an ultraviolet spectrophotometer (WFJ2-2000, Unocal Instruments Co., Ltd., Shanghai, China). The TPC in the film was expressed as mg gallic acid equivalent (GAE)/g dry weight. Each sample was tested three times and the average was taken.
2.8.2. DPPH Free Radical Scavenging Activity
DPPH free radical scavenging ability is one of the important indicators to measure antioxidant activity [
31]. Briefly, 1 g film samples were put into 100 mL water, stirred for 24 h and mixed until completely dissolved; 2 mL film solution was mixed with 2 mL DPPH methanol solution (0.06 mmol/L). Afterward, the absorbance of the supernatants was measured at 517 nm on an ultraviolet spectrophotometer. The DPPH free radical scavenging activity of the films was calculated as follows:
where A
0 and A
1 were the absorbance of DPPH of the control (without film sample) and film samples, respectively.
2.9. Application in Edible Oil
2.9.1. Anti-Permeate Ability for Oil
The YPP-SA-G film was cut into bags of 50 mm × 50 mm, and 2 g of soybean oil was added to the bags to seal with starch adhesive. The bags were then placed on filter paper in a glass dish, and all oil bags were stored in a humidity-controlled room (55 ± 2% relative humidity) at 23 °C for 10 days. The weight loss rate of the oil bag is determined by weighing it against the initial weight (W
i) at specific time intervals (W) and reported as percent weight loss.
2.9.2. Peroxide Value (POV)
Soybean oil was filled into glass test tubes, covered with YPP-SA-G film, and sealed with a string, and a sample without film was used as a control. All samples were stored at 25 °C for 30 days. According to GB/T 5009.227-2016, the peroxide value (POV) was measured every 5 days, and the triplicate results were averaged.
2.10. Statistical Analysis
Analysis of variance (ANOVA) was performed using IBM SPSS Statistics 26 software to assess differences between factors and levels. All data are presented as mean ± standard deviation.
4. Conclusions
The YPP-SA-G antioxidant films were successfully prepared by RSM and exhibited excellent mechanical properties and the ability to retard oil oxidation. The effect of SA and G on YPP film was systematically studied. The oxidation resistance of YPP-based film did not change with the addition of SA/G, but the addition of SA greatly improved the mechanical properties of YPP film, which was opposite to the effect of G. The surface of the YPP-SA-G films were smooth and fruity, and the films had excellent hydrophilicity with the addition of SA and G. Compared with the films (YPP and YPP-SA), the YPP-SA-G film has a higher thermal degradation performance and the crystallization peak of the film changed obviously. With the increase of days, compared with the control, soybean oil wrapped in YPP-SA-G film had a lower peroxide value. Therefore, the yellow peach skin film obtained in this study has potential application value in the field of oil packaging, which is in line with the development concept of today’s green packaging and is conducive to resource recovery and environmental protection.