A pH-sensitive film based on chitosan/gelatin and anthocyanin from Zingiber striolatum Diels for monitoring fish freshness.

As a new type of packaging method, the anthocyanin-based pH-sensitive indicator film has gained much attention owing to low cost, small size, and visually informative property. In this study, an intelligent film based on chitosan/gelatin (CG) matrix with Zingiber striolatum Diels (ZSD) anthocyanin for fish freshness monitoring was developed. The film properties, including thickness, moisture content, color, mechanical properties, UV-vis light barrier property, as well as pH and ammonia sensitivity, were evaluated. The CG-ZSD films exhibited a more compact structure when compared with the CG film. The CG-ZSD20 film showed the highest elongation at break (6.33 ± 0.62%) and lowest tensile strength (20.0 ± 0.58 MPa). FTIR spectra revealed the strong hydrogen bond interactions between ZSD and polymer matrix. Film incorporated with 15% anthocyanin extract has increased melting temperature at 118.9 °C, and a lower weight loss (13.8%) at melting temperature. In pH 1-14 buffer, the color of CG-ZSD films underwent a significant change from red to yellow-green. The CG-ZSD15 film was utilized for monitoring fish freshness and showed visible color changes from deep purple to brown. The total volatile basic nitrogen content and pH value changes of fish were closely related to the visual color changes in film. This demonstrated that the film was a highly pH-sensitive film for quantifying fish freshness in real-time.

A versatile bilayer smart packaging based on konjac glucomannan/alginate for maintaining and monitoring seafood freshness.

This study introduces a novel multi-functional double-layer intelligent packaging. It focuses on developing a dual-function system capable of real-time monitoring and freshness preservation. Specifically, cellulose nanocrystalline (CNC) was obtained through acid hydrolysis, and then CNC/soybean protein isolate (CNC/SPI) complex colloid particles were prepared via antisolvent method. These particles served as stabilizers to prepare oil-in-water (O/W) cinnamon essential oil Pickering emulsion (CSCEO). The CSCEO was then integrated into the emulsified hydrophobic layer of a konjac glucomannan (Kgm) matrix through intermolecular hydrogen bonding. Finally, alginate (Alg) matrix containing alizarin (Al) as an indicator was added to construct the bilayer structure using a layer-by-layer casting strategy. The inner layer Alg/Al was the pH/NH3-responsive indicator layer, while the outer layer Kgm/CSCEO acted as the high-barrier bacteriostatic layer. The obtained dual-function, double-layer film (Alg/Al-Kgm/CSCEO), which possesses a sensitive, reversible and rapid response towards pH/NH3, shows exceptional antibacterial and antioxidant properties, as well as excellent mechanical property, light-blocking capability and hydrophobicity. For monitoring and maintaining the actual freshness of shrimp, such a bilayer packaging displays smallest change of ∆E and TVB-N (18.65 mg/100 g) even after 72 h, which further highlighting its potential in enhancing food safety and extending shelf life.

Enzymatically green-produced bacterial cellulose nanoparticle-stabilized Pickering emulsion for enhancing anthocyanin colorimetric performance of versatile films.

To enhance the colorimetric performance of anthocyanin (Ant), a konjac glucomannan (KGM)-based multifunctional pH-responsive indicator film was fabricated by introducing enzymatically prepared bacterial nanocellulose (EBNC) stabilized camellia oil/camellia essential oil Pickering emulsion (BCCE). Specifically, optimized enzymatic hydrolysis time (36 h) was determined based on the particle size and microstructure. Then BCCE (containing 0.4% EBNC) was incorporated into Ant-containing KGM, and the novel active indicator film (KGM-Ant-BCCE) was constructed. Films with varying BCCE concentrations (3%-11%) exhibited enhanced UV shielding, thermal stability, mechanical strength, water vapor and oxygen permeability, hydrophobicity, and antioxidant performance. The pronounced color change of KGM-Ant-BCCE indicated its potential for visually detecting shrimp freshness. Moreover, the biodegradability (25 days) confirmed the environmentally benign property of the film. In summary, incorporating green-produced EBNC nanoparticle-stabilized BCCE offers an innovative pathway to improve the color indication capability of polysaccharide-based smart packaging.

A green versatile packaging based on alginate and anthocyanin via incorporating bacterial cellulose nanocrystal-stabilized camellia oil Pickering emulsions.

This study aims to develop a versatile intelligent packaging based on alginate (Alg) and anthocyanin (Ant) by incorporating bacterial cellulose nanocrystal-stabilized camellia oil Pickering emulsions. Firstly, bacterial cellulose nanocrystals (BCNs) matrix produced from kombucha was incorporated with camellia oil into via ultrasonic triggering, forming a stable and multifunctional camellia oil-bacterial cellulose nanocrystal Pickering nanoemulsions (CBPE). The microstructure and rheology results of the emulsion confirmed the stabilized preparation of CBPE. Subsequently, the CBPE was integrated into the three-dimensional network structure composed of alginate/anthocyanin. The composite film (Alg-Ant-CBPE) was designed through Ca2+ crosslinking, intermolecular hydrogen bonding and dehydration condensation. The fabricated color indicator films with different concentrations of CBPE (0.1 %-0.4 %), showed varying degree of improvement in hydrophobicity, UV shielding, mechanical strength, thermal stability, water vapor barrier properties and antioxidant capacities. When applied to yogurt, the Alg-Ant-CBPE4 exhibited more pronounced color changes compared to Alg-Ant, enabling visual detection of food freshness. In conclusion, the incorporation of Pickering nanoemulsion provides an effective and promising approach to enhance the performance of polysaccharide-based intelligent packaging.

Preparation and Application of pH-Sensitive Film Containing Anthocyanins Extracted from Lycium ruthenicum Murr.

A new pH-sensitive film was developed using Artemisia sphaerocephala Krasch. gum (ASKG), soybean protein isolate (SPI), and natural anthocyanin extracted from Lycium ruthenicum Murr. The film was prepared by adsorbing anthocyanins dissolved in an acidified alcohol solution on a solid matrix. ASKG and SPI were used as the solid matrix for the immobilization of the Lycium ruthenicum Murr. anthocyanin extract, which was absorbed into the film as a natural dye using the facile-dip method. Regarding the mechanical properties of the pH-sensitive film, the tensile strength (TS) values increased approximately 2-5-fold, but the elongation at break (EB) values decreased significantly by about 60% to 95%. With the increase in anthocyanin concentration, the oxygen permeability (OP) values first decreased by about 85%, and then increased by about 364%. The water vapor permeability (WVP) values increased by about 63%, and then decreased by about 20%. Colorimetric analysis of the films revealed variations in color at different pH values (pH 2.0-10.0). Fourier-transform infrared (FT-IR) spectra and XRD patterns indicated compatibility among ASKG, SPI, and anthocyanin extracts. In addition, an application test was conducted to establish a correlation between film color change and carp meat spoilage. At storage temperatures of 25 °C and 4 °C, when the meat was totally spoiled, the TVB-N values reached 99.80 ± 2.53 mg/100 g and 58.75 ± 1.49 mg/100 g, and the film's color changed from red to light brown and from red to yellowish green, respectively. Therefore, this pH-sensitive film could be used as an indicator to monitor the freshness of meat during storage.

Preparation and characterization of antioxidant and pH-sensitive films based on arrowhead (Sagittaria sagittifolia) starch, κ-carrageenan and black chokeberry (Aronia melanocarpa) extract for monitoring spoilage of chicken wings.

In this study, we firstly developed an antioxidant and pH-sensitive film based on arrowhead starch (AS), κ-carrageenan (KC) and black chokeberry extract (BCE) and its physical and structural properties were investigated. We found BCE showed different colors in different pH solutions and incorporation with KC and BCE could significantly decrease light transmittance, increase thickness, elongation at break and pH-sensitive property of AS film. The results of structural property assay indicated that there were some intermolecular interactions between BCE and AS/KC in AS-KC-BCE films. Secondly, we investigated the rheological property of AS, AS-KC and AS-KC-BCE suspensions and found the suspensions showed an obvious shear-thinning behavior with high apparent viscosity. Finally, the functional properties of AS-KC-BCE films were investigated and AS-KC-BCE films showed strong scavenging activity on DPPH free radical and presented visible colour changes in response to the changes of the chicken wing qualities. The results suggest that AS-KC-BCE films can be used in active and intelligent packaging of food industry.

Development of a pH-sensitive film based on collagen/chitosan/ZnO nanoparticles and mulberry extract for pork freshness monitoring.

pH-sensitive films based on collagen, chitosan, ZnO-nanoparticles and mulberry extract (CC/ZnO/ME) were developed to monitor pork freshness. Fourier transform infrared analysis revealed that collagen, chitosan, ZnO-nanoparticles and ME interacted via hydrogen bonds. The UV-vis light barrier ability of CC/ZnO/ME film was gradually enhanced as increasing ME content from 0.5 to 2.0 % wt. Compared with CC film, the mechanical strength and DPPH radical free scavenging rate of the CC/ZnO/ME film had increased by 13.84 MPa and 58.74 %, respectively. CC/ZnO/ME1 and CC/ZnO/ME2 films exhibited better pH-sensitivity than CC/ZnO/ME3 film, with color visibly changing from red to blue/green in different buffer solutions (pH 3-12). When monitoring the freshness of pork stored at 4℃, the color of CC/ZnO/ME2 film changed from deep purple to blue when TVB-N content exceeded the maximum permissible limit (15 mg/100 g) on 6th day.

Gelatin-Based Film as a Color Indicator in Food-Spoilage Observation: A Review.

The color indicator can monitor the quality and safety of food products due to its sensitive nature toward various pH levels. A color indicator helps consumers monitor the freshness of food products since it is difficult for them to depend solely on their appearance. Thus, this review could provide alternative suggestions to solve the food-spoilage determination, especially for perishable food. Usually, food spoilage happens due to protein and lipid oxidation, enzymatic reaction, and microbial activity that will cause an alteration of the pH level. Due to their broad-spectrum properties, natural sources such as anthocyanin, curcumin, and betacyanin are commonly used in developing color indicators. They can also improve the gelatin-based film's morphology and significant drawbacks. Incorporating natural colorants into the gelatin-based film can improve the film's strength, gas-barrier properties, and water-vapor permeability and provide antioxidant and antimicrobial properties. Hence, the color indicator can be utilized as an effective tool to monitor and control the shelf life of packaged foods. Nevertheless, future studies should consider the determination of food-spoilage observation using natural colorants from betacyanin, chlorophyll, and carotenoids, as well as the determination of gas levels in food spoilage, especially carbon dioxide gas.

Bio-Based pH Indicator Films for Intelligent Food Packaging Applications.

The widespread concerns about the environmental problems caused by conventional plastic food packaging and food waste led to a growing effort to develop active and intelligent systems produced from renewable biodegradable polymers for food packaging applications. Among intelligent systems, the most widely used are pH indicators, which are generally based on a pH-sensitive dye incorporated into a solid support. The objective of this study was to develop new intelligent systems based on renewable biodegradable polymers and a new bio-inspired pH-sensitive dye. The structure of the dye was elucidated through FT-IR and 1D and 2D NMR spectroscopic analyses. UV-VIS measurements of the dye solutions at various pH values proved their halochromic properties. Their toxicity was evaluated through theoretical calculations, and no toxicity risks were found. The new anthocyanidin was used for the development of biodegradable intelligent systems based on chitosan blends. The obtained polymeric films were characterized through UV-VIS and FT-IR spectroscopy. Their thermal properties were assessed through a thermogravimetric analysis, which showed a better stability of chitosan-PVA-dye and chitosan-starch-dye films compared to those of chitosan-cellulose-dye films and the dye itself. The films' sensitivity to pH variations was evaluated through immersion in buffer solutions with pH values ranging from 2 to 12, and visible color changes were observed.

Preparation, physicochemical and application evaluation of raspberry anthocyanin and curcumin based on chitosan/starch/gelatin film.

Raspberry anthocyanin (RA) from Rubus idaeus L. (Rosaceae) and curcumin (Cur) from Curcuma longa L. (Zingiberaceae) can effectively improve the physicochemical properties of composite films, and as bioactive pigment components, they can impart pH-responsive properties to the film. In this study, RA and Cur were added to chitosan/starch/gelatin composite film (CSG) to prepare CSG-RA, CSG-Cur, CSG-RA/Cur82 and CSG-RA/Cur73 color films by solution casting method. The color films could change color under different pH conditions and had higher antioxidant activities using ABTS (2,2'-azino-bis-(3-ethylbenzothiazoline-6-sulfonic acid)) assay. The results from fourier transform infrared spectroscopy and scanning electron microscopy showed that RA and Cur were well dispersed in the CSG matrix and improved the structure of the composite films. The hydrophobic Cur increased the tensile strength from 6 Mpa (CSG) to 14 Mpa (CSG-Cur), but reduced the elongation at break from 55 % (CSG) to 40 % (CSG-Cur). These color films had a good fresh-keeping effect and freshness monitoring, in particular, CSG-RA/Cur73, had the better opacity, water solubility, thickness, moisture content and water vapor permeability than the other films. Briefly, binary pigment films had the potential to become a pH-sensitive indicator/packing film.

pH indicator films fabricated from soy protein isolate modified with chitin nanowhisker and Clitoria ternatea flower extract.

Sensor films are finding wide range of applications. Different type of sensing films is fabricated for the identification of chemicals, ions, heavy metals, changes in the pH, etc. The present report is on the fabrication of pH sensitive films from completely natural sources-soy protein isolate, chitin nano whiskers and flower extract. The highly crystalline chitin nano whiskers (CNW) were extracted from prawn shell under neutral condition via steam explosion technique. Multifunctional Soy protein isolate (SPI) films were prepared by adding chitin nanowhisker and Clitoria ternatea flower extract and its effect on thermal, mechanical and moisture properties of SPI film was investigated. The isolated CNW presented a needle like morphology with a diameter of 10-50 nm and a crystallinity index of 99.67%. The extracted chitin nanowhisker was used to prepare biodegradable films with soy protein isolate immobilized with anthocyanin from Clitoria ternatea flower extract. The prepared Soy protein -chitin nanowhisker films was found to have a tensile strength of about 15.45 ± 0.97 MPa with 8% chitin nanowhisker addition. The addition of CTE was found to decrease the tensile strength of SPI-CNW film but was found to make the film pH sensitive. The developed indicator film showed visible color changes in acidic and basic medium and hence can be used to monitor the freshness of food materials.

Colorimetric films based on pectin/sodium alginate/xanthan gum incorporated with raspberry pomace extract for monitoring protein-rich food freshness.

Raspberry pomace extracts (RPE) with different concentrations (0.5 g/L, 1.5 g/L and 3 g/L) were incorporated into pectin/sodium alginate/xanthan gum composite film (PAX) to prepare colorimetric raspberry films (PAXR5, PAXR15 and PAXR30). Fourier Transform Infrared and Scanning Electron Microscopy analysis showed RPE had good compatibility with PAX. Compared to PAX, the raspberry films had lower water vapor permeability and water swelling ratio, higher tensile strength, opacity and antioxidant capacity. The films presented a smoother surface and denser structure than PAX. Furthermore, PAXR15 had an excellent discoloration at pH 1-13, especially at pH 5-10, the color changes of PAXR15 from pink-red-brown-blue-dark green distinguished by the naked eyes. Therefore, it has the potential to become a pH-sensitive film used in monitoring protein-rich food freshness.

Development of red apple pomace extract/chitosan-based films reinforced by TiO2 nanoparticles as a multifunctional packaging material.

A chitosan-based (CS) film was developed with nanosized TiO2 and red apple pomace extract (APE). The intermolecular interactions of CS, TiO2 and APE were evaluated by Fourier transform infrared spectroscopy, scanning electron microscopy and X-ray diffraction. TiO2 nanoparticles remarkably improved the water vapor and UV-Vis light barrier properties, mechanical strength and thermal stability of CS-APE films. The strong antioxidant abilities of CS-APE and CS-TiO2-APE films were characterized. Nano-TiO2 and APE showed a synergistic enhancement of the antimicrobial activity in CS matrix. The addition of TiO2 nano-particles into CS-APE films resulted the sensitive color variations, which applied successfully as an indicator to monitor the freshness of salmon fillets. Consequently, the development of CS-APE-TiO2 film provides a new solution to convert rad apple pomace to an active and multifunctional food packaging material with considerable mechanical, antibacterial, antioxidant and pH-responsive color-changing properties.