Smart Biopolymer-Based Nanocomposite Materials Containing pH-Sensing Colorimetric Indicators for Food Freshness Monitoring.

Nanocomposite biopolymer materials containing colorimetric pH-responsive indicators were prepared from gelatin and chitosan nanofibers. Plant-based extracts from barberry and saffron, which both contained anthocyanins, were used as pH indicators. Incorporation of the anthocyanins into the biopolymer films increased their mechanical, water-barrier, and light-screening properties. Infrared spectroscopy and scanning electron microscopy analysis indicated that a uniform biopolymer matrix was formed, with the anthocyanins distributed evenly throughout them. The anthocyanins in the composite films changed color in response to alterations in pH or ammonia gas levels, which was used to monitor changes in the freshness of packaged fish during storage. The anthocyanins also exhibited antioxidant and antimicrobial activity, which meant that they could also be used to slow down the degradation of the fish. Thus, natural anthocyanins could be used as both freshness indicators and preservatives in biopolymer-based nanocomposite packaging materials. These novel materials may therefore be useful alternatives to synthetic plastics for some food packaging applications, thereby improving the environmental friendliness and sustainability of the food supply.

A Biocompatible Multilayer Film from an Asymmetric Picolinium-Containing Polycation with Fast Visible-Light/NIR-Degradability.

Finely tuning the photodegradation behavior of the layer-by-layer (LbL) film from the view of controlling the chemical structure of the film-building polymer is still a challenge in related fields. To meet this requirement, a photodegradable polymer (P1) is rationally designed for assembling a visible-light-degradable multilayer film with polystyrene sulfonate (PSS). Compared with similar photopolymers (P2 and P3), this asymmetric picolinium-containing polymer can significantly enhance the degradation rate of as-prepared LbL films; under the same degradation condition, the degradation rate of (P1/PSS)10 is 3 and 6.6 times that of (P2/PSS)10 and (P3/PSS)10, respectively. Moreover, near-infrared light (NIR) is available for triggering the degradation of this film with the assistance of upconversion nanoparticles of YbTm@Lu. The cell cytotoxicity and cell proliferation experiments reveal that P1 is nontoxic and favorable for cell proliferation at concentrations of up to 500 µg mL-1 . As for (PSS/P1)10 films, the ratio of cell number of these two samples ((PSS/P1)10 modified: photodegraded) increases dramatically and reaches about 1.67:1 after 72 h incubation. On the basis of these results, it is anticipated that P1 and this LbL film is an exceptional candidate for visible-light/NIR degradable materials in materials and biological science, medicine, and optics.

Deep-eutectic-solvent modulation of self-assembled multi-responsive films based on polyvinyl alcohol/cellulose nanocrystal and grape skin red for highly sensitive food monitoring.

To enhance the mechanics performance, sensitivity and response range of multi-responsive photonic films, herein, a facile method for fabricating multi-responsive films is demonstrated using the evaporative self-assembly of a mixture of grape skin red (GSR), cellulose nanocrystal (CNC), polyvinyl alcohol (PVA) and deep eutectic solvent (DES). The prepared materials exhibited excellent thermal stability, strain properties, solvent resistance, ultraviolet (UV) resistance and antioxidant activity. Compared to a pure PVA film, the presence of GSR strengthened the antioxidant property of the film by 240.1 % and provided excellent UV barrier capability. The additional cross-linking of DES and CNC promoted more efficient phase fusion, yielding a film strain of 41.5 %. The addition of hydrophilic compound GSR, wetting and swelling due to the DES and the surface inhomogeneity of the films rendered the multi-responsive films high sensitivity, wide response range and multi-cyclic stability in environments with varying pH and humidity. A sample application showed that a PVA/CNC/DES film has the potential to differentiate between fresh, sub-fresh and fully spoiled shrimps. The above results help in designing intelligent thin film materials that integrate antioxidant properties, which help in monitoring the changes in food freshness and food packaging.

Rapid-Response Water-Shrink Films with High Output Work Density Based on Polyethylene Oxide and α-Cyclodextrin for Autonomous Wound Closure.

Conventional wound closure methods, including sutures and tissue adhesives, present significant challenges for self-care treatment, particularly in the context of bleeding wounds. Existing stimuli-responsive contractile materials designed for autonomous wound closure frequently lack sufficient output work density to generate the force needed to bring the wound edges into proximity or necessitate stimuli that are not compatible with the human body. Here, semi-transparent, flexible, and water-responsive shrinkable films, composed of poly(ethylene oxide) and α-cyclodextrin, are reported. These films exhibit remarkable stability under ambient conditions and demonstrate significant contraction (≈50%) within 6 s upon exposure to water, generating substantial contractile stress (up to 6 MPa) and output work density (≈1028 kJ m-3), which is 100 times larger than that of conventional hydrogel and 25 times larger than that of skeletal muscles. Remarkably, upon hydration, these films are capable of lifting objects 10 000 times their own weight. Leveraging this technology, water-shrink tapes, which, upon contact with water, effectively constrict human skin and autonomously close bleeding wounds in animal models within 10 seconds, are developed further. This work offers a novel approach to skin wound management, showing significant potential for emergency and self-care scenarios.

Triple-function chitosan-based film for pork and shrimp packaging.

A film simultaneously with colorimetric, fluorescent and active functions was engineered using chitosan (CS) and polyvinyl alcohol (PVA) as the film matrix and curcumin-ß-cyclodextrin complex (Cur-ß-CD) as the indicator for freshness monitoring and maintaining of pork and shrimp. In addition to the efficacy of prolonging shelf life, the film's color could change from yellow to orange with ΔE > 5 and its fluorescence intensity could decrease during storage. The incorporation of PVA significantly enhanced the mechanical properties of CS film with tensile strength of 31.80 MPa and elongation at break of 127.22 %. The Cur-ß-CD improved the antioxidant and antibacterial properties, water contact angle (from 86.3° to 111.2°), water vapor permeability (from 3.28 × 10-10 g (m s Pa)-1 to 0.42 × 10-10 g (m s Pa)-1) and mechanical properties of CS/PVA film. These results show the potential of the film as promising alternatives for intelligent and active food packaging.

Preparation of pH-Responsive Films from Polyvinyl Alcohol/Agar Containing Cochineal for Monitoring the Freshness of Pork.

This study reported the production of pH-responsive films based on 8 wt% polyvinyl alcohol solution/0.2 wt% agar solution incorporated with cochineal-loaded starch particles (CSN) (2, 4, 6 and 8 wt% on agar basis) by a casting process. Results revealed that CSN presented obvious color changes over the pH range of 2-12. FTIR, XRD spectra and SEM micrographs presented that the incorporation of CSN formed new hydrogen bonds with a matrix and a tighter network structure. A certain improvement was observed in the color stability, swelling index and functional properties (antimicrobial and antioxidant activities) but water solubility, water vapor permeability and water contact angle of the pH-responsive films were decreased by the addition of CSN. The release of cochineal was a rate-limiting step following the Korsmeyer-Peppas model. The agar/polyvinyl alcohol film containing 6% CSN (PVA/GG-6) exhibited the best sensitivity for ammonia detection and its limit of detection was 35.4 ppm (part per million) for ammonia. The application trials showed that the PVA/GG-6 film presented different color changes for pork freshness. Hence, these pH-responsive films can be used as potential packaging materials for tracking the freshness of protein-rich fresh food in a non-destructive way.

pH-responsive and antibacterial properties of self-assembled multilayer films based on chitosan and tannic acid.

Polyelectrolyte layer-by-layer (LbL) films that disintegrate under physiological conditions are intensively studied as coatings to enable the release of bioactive components. Herein, we report on the interactions and pH-stability of LbL films composed of chitosan (CH) or N-(2-hydroxypropyl)-3-trimethylammonium chitosan chloride (CMCH) and tannic acid (TA), employed to guarantee the film disintegration. The self-assembly of TA with CH and CMCH at pH 5 and with CMCH at pH 7.4 were proven by turbidimetric, surface plasmon resonance and UV-Vis analyses. The LbL films exhibited pH-dependent properties; CMCH/TA films prepared at pH 7.4 showed exponential growth as well as a higher layer thickness and surface roughness, whereas films prepared at pH 5 grew linearly and were smoother. The film stability varied with the pH used for film assembly; CH/TA films assembled at pH 5 were unstable at pH 8.5, whereas CMCH/TA films assembled at pH 7.4 disintegrated at pH 4. All films exhibited a similar disassembly at pH 7.4. The coatings reduced the adhesion of E. coli and S. aureus by approximately 80%. CMCH-terminated CMCH/TA films were more resistant to bacterial adhesion, whereas CH-terminated CH/TA films demonstrated stronger killing activity. The prepared pH-triggered decomposable LbL films could be used as degradable coatings that allow the release of therapeutics for biomedical applications and also prevent bacterial adhesion.

Influence of cross-linking in loading/release applications of polyelectrolyte multilayer assemblies. A review.

Design of polymeric matrices for loading/release purposes is of great interest in various applications, such as drug delivery systems, antimicrobial surfaces, biosensors, water purification. Compared with other strategies to fabricate materials for such applications, the Layer-by-Layer (LbL) assembly remarked itself by the countless possibilities to tailor the organic architectures at nanoscale owing to the structural diversity of "nano-bricks" suitable for assembly and easiness to control the deposition features. LbL assembled systems have been extensively used as matrices to load/release low molecular compounds such as drugs and dyes, proteins and enzymes, or DNA (RNA). In many studies, cross-linking the layers was investigated as a mean to stabilize and to induce new functionalities in the obtained architectures, as well as to tune their loading/release properties. In this review we discuss recent progress in the use of LbL constructions in loading/release of bioactive species, with a main focus on the role of cross-linking on such features. Overviews of the LbL assembly strategy describing the parameters which influence the build-up process and of the main synthetic routes used to cross-link the obtained architectures are briefly presented. The use of LbL systems (either as thin films deposited on solid surfaces or as hollow capsules) to load/release low molecular compounds and proteins/enzymes, highlighting the role of cross-linking in such processes (construction of porous architectures capable to load high molecular compounds or decreasing the assemblies permeability to delay the release of encapsulated compounds) was thoroughly discussed.

Mimosa Origami: A nanostructure-enabled directional self-organization regime of materials.

One of the innate fundamentals of living systems is their ability to respond toward distinct stimuli by various self-organization behaviors. Despite extensive progress, the engineering of spontaneous motion in man-made inorganic materials still lacks the directionality and scale observed in nature. We report the directional self-organization of soft materials into three-dimensional geometries by the rapid propagation of a folding stimulus along a predetermined path. We engineer a unique Janus bilayer architecture with superior chemical and mechanical properties that enables the efficient transformation of surface energy into directional kinetic and elastic energies. This Janus bilayer can respond to pinpoint water stimuli by a rapid, several-centimeters-long self-assembly that is reminiscent of the Mimosa pudica's leaflet folding. The Janus bilayers also shuttle water at flow rates up to two orders of magnitude higher than traditional wicking-based devices, reaching velocities of 8 cm/s and flow rates of 4.7 µl/s. This self-organization regime enables the ease of fabricating curved, bent, and split flexible channels with lengths greater than 10 cm, demonstrating immense potential for microfluidics, biosensors, and water purification applications.

Surface Stiffness--a Parameter for Sensing the Chirality of Saccharides.

Surface stiffness is considered a key parameter for designing high-performance implantable materials and artificial extracellular matrices because of its substantial effects on cell behavior. How to transform biomolecule recognition events, particularly chiral recognition, into stiffness change on material surfaces is biologically essential but very challenging for chemists. Here, we report a chirality-triggered stiffness transition on a smart polymer film, which consists of flexible polyethylenimine (PEI) main chains grafted with dipeptide units capable of discriminating chiral monosaccharides. The polymer film became substantially softer after interacting with L-ribose and became more rigid after interacting with D-ribose (the basic building block of DNA and RNA). This chiral effect provides a new method for determining the enantiomeric purity of an L/D-ribose mixture and facilitates the chiral separation of deoxyribose racemates as well as the separation of diverse mono-, di-, and oligosaccharides. These are three puzzle problems in carbohydrate chemistry. Furthermore, taking advantage of the significant differences in the surface stiffness, the proliferation of fibroblast cells on the polymeric surfaces can also be regulated by chiral biomolecules.