Recent advances in biobased and biodegradable polymer nanocomposites, nanoparticles, and natural antioxidants for antibacterial and antioxidant food packaging applications.

Inorganic nanoparticles (NPs) and natural antioxidant compounds are an emerging trend in the food industry. Incorporating these substances in biobased and biodegradable matrices as polysaccharides (e.g., starch, cellulose, and chitosan) and proteins has highlighted the potential in active food packaging applications due to more significant antimicrobial, antioxidant, UV blocking, oxygen scavenging, water vapor permeability effects, and low environmental impact. In recent years, the migration of metal NPs and metal oxides in food contact packaging and their toxicological potential have raised concerns about the safety of the nanomaterials. In this review, we provide a comprehensive overview of the main biobased and biodegradable polymer nanocomposites, inorganic NPs, natural antioxidants, and their potential use in active food packaging. The intrinsic properties of NPs and natural antioxidant actives in packaging materials are evaluated to extend shelf-life, safety, and food quality. Toxicological and safety aspects of inorganic NPs are highlighted to understand the current controversy on applying some nanomaterials in food packaging. The synergism of inorganic NPs and plant-derived natural antioxidant actives (e.g., vitamins, polyphenols, and carotenoids) and essential oils (EOs) potentiated the antibacterial and antioxidant properties of biodegradable nanocomposite films. Biodegradable packaging films based on green NPs-this is biosynthesized from plant extracts-showed suitable mechanical and barrier properties and had a lower environmental impact and offered efficient food protection. Furthermore, AgNPs and TiO2 NPs released metal ions from packaging into contents insufficiently to cause harm to human cells, which could be helpful to understanding critical gaps and provide progress in the packaging field.

Biodegradable Nanocomposite with Dual Cell-Tissue Penetration for Deep Tumor Chemo-Phototherapy.

Chemo-phototherapy, as a promising cancer combination therapy strategy, has attracted widespread attention. However, the complex tumor microenvironment restricts the penetration depth of chemo-phototherapy agents in the tumor region. Here, biodegradable amphiphilic gelatin (AG) wrapped nanocomposite (PRDCuS@AG) composed of doxorubicin and copper sulfide (CuS)-loaded dendrimer is designed for deep tumor chemo-phototherapy. PR in PRDCuS@AG represents arginine-conjugated polyamidoamine dendrimer. PRDCuS@AG can rapidly biodegrade into PRDCuS by matrix metalloproteinases under near-infrared light irradiation. The resulted PRDCuS harbors dual cell-tissue penetration ability, which can effectively penetrate deep into the tumor tissue. In particular, PRDCuS@AG achieves photoacoustic imaging-guided synergistic chemo-phototherapy with 97% of tumor inhibition rate. Moreover, PRDCuS@AG can further degrade into 3 nm ultrasmall CuS, which can be eliminated from the body after treatment to avoid side effects. This strategy provides an insight that the development of chemo-phototherapy agents with high penetration ability to overcome the limitation of current deep tumor therapy.

Antineoplastic drug-loaded polymer-modified magnetite nanoparticles: Comparative analysis of EPR-mediated drug delivery.

This study aimed to design and evaluate enhanced permeation and retention (EPR)-mediated anticancer effect of polymer-modified and drug-loaded magnetite nanocomposites. The preformulated bare (10 nm), chitosan-superparamagnetic iron oxide (SPIO; 69 nm), heparin-SPIO (42 nm), and (3-aminopropyl)triethoxysilane-polyethylene glycol-SPIO (17 nm) nanocomposites were utilized to evaluate the EPR-mediated localized cancer targeting and retention of doxorubicin (DOX) and paclitaxel (PTX) in human ovarian cancer cell lines, A2780 and OVCAR-3 in vitro and in the tumor-baring Balb/c mice in vivo. Fluorescence microscopy showed that DOX- and PTX-loaded SPIO nanoparticles caused long-term accumulation and cytoplasmic retention in A2780 and OVCAR-3 cells, as compared to free drugs in vitro. In vivo antiproliferative effect of present formulations on immunodeficient female Balb/c mice showed a tremendous amount of ovarian tumor shrinkage within 6 weeks. The present nanocomposite systems of targeted drug delivery proved to be efficient drug carrier with sustained drug release and long-term retention with enhanced cytotoxic properties in vitro and in vivo.

Improved Process to Obtain Nanofibrillated Cellulose (CNF) Reinforced Starch Films with Upgraded Mechanical Properties and Barrier Character.

Nowadays, the interest on nanofibrillated cellulose (CNF) has increased owing to its sustainability and its capacity to improve mechanical and barrier properties of polymeric films. Moreover, this filler shows some drawbacks related with its high capacity to form aggregates, hindering its dispersion in the matrix. In this work, an improved procedure to optimize the dispersability of CNF in a thermoplastic starch was put forward. On the one hand, CNF needs a hydrophilic dispersant to be included in the matrix, and on the other, starch needs a hydrophilic plasticizer to obtain a thermoformable material. Glycerol was used to fulfil both targets at once. CNF was predispersed in the plasticizer before nanofibrillation and later on was included into starch, obtaining thin films. The tensile strength of these CNF-starch composite films was 60% higher than the plain thermoplastic starch at a very low 0.36% w/w percentage of CNF. The films showed a noticeable correlation between water uptake, and temperature and humidity. Regarding permeability, a ca. 55% oxygen and water vapor permeability drop was found by nanofiller loading. The hydrolytic susceptibility of the composite was confirmed, being similar to that of the thermoplastic starch.

Poly (d/l) lactide/polycaprolactone/bioactive glasss nanocomposites materials for anterior cruciate ligament reconstruction screws: The effect of glass surface functionalization on mechanical properties and cell behaviors.

In this paper, different nanocomposites made of a polymer blend (80% of PDLLA and 20% of PCL in w/w) and various amounts of a sol-gel derived bioactive glass nanoparticles (0, 1, 3 and 6wt%) were prepared using a solvent-evaporation technique. The morphology, mechanical properties and osteoblastic cell behaviors of the nanocomposites were evaluated. According to the early results, addition of bioactive glass nanoparticles to the polymer matrix reduced the tensile and flexural strength because of a non-uniform distribution of the nanoparticles. Thus, a homogeneous dispersion was obtained by surface modification of the glass nanoparticles using (3-aminopropyl)triethoxysilane as a coupling agent. The results showed that the tensile and flexural strength of the nanocomposite were improved by the nanoparticle functionalization, however the glass content was a crucial factor. The maximum tensile and flexural strength values of 38MPa and 94MPa were obtained for the polymer matrix loaded with 3wt% of the modified nanofiller and further increase of filler content led to sever agglomeration and hence a reduction of the mechanical properties. The obtained mechanical properties are favorable for anterior cruciate ligament reconstruction screws. Besides, the results of cell culture using human osteoblastic cells illustrated better cell attachment and cell growth of the nanocomposites compared to the neat polymer blend.

Effect of Cellulose Nanocrystals and Bacterial Cellulose on Disintegrability in Composting Conditions of Plasticized PHB Nanocomposites.

Poly(hydroxybutyrate) (PHB)-based films, reinforced with bacterial cellulose (BC) or cellulose nanocrystals (CNC) and plasticized using a molecular (tributyrin) or a polymeric plasticizer (poly(adipate diethylene)), were produced by solvent casting. Their morphological, thermal, wettability, and chemical properties were investigated. Furthermore, the effect of adding both plasticizers (20 wt % respect to the PHB content) and biobased selected nanofillers added at different contents (2 and 4 wt %) on disintegrability in composting conditions was studied. Results of contact angle measurements and calorimetric analysis validated the observed behavior during composting experiments, indicating how CNC aggregation, due to the hydrophilic nature of the filler, slows down the degradation rate but accelerates it in case of increasing content. In contrast, nanocomposites with BC presented an evolution in composting similar to neat PHB, possibly due to the lower hydrophilic character of this material. The addition of the two plasticizers contributed to a better dispersion of the nanoparticles by increasing the interaction between the cellulosic reinforcements and the matrix, whereas the increased crystallinity of the incubated samples in a second stage in composting provoked a reduction in the disintegration rate.

Enhancing the Mechanical Properties of Biodegradable Polymer Blends Using Tubular Nanoparticle Stitching of the Interfaces.

"Green" polymer nanocomposites were made by melt blending biodegradable poly(lactic acid) (PLA) and poly(butylene adipate-co-butylene terephthalate) (PBAT) with either montmorillonite clays (Cloisite Na(+)), halloysite nanotubes (HNTs), the resorcinol diphenyl phosphate (RDP)-coated Cloisite Na(+), and coated HNTs. A technique for measuring the work of adhesion (Wa) between nanoparticles and their matrixes was used to determine the dispersion preference of the nanoparticles in the PLA/PBAT blend system. Transmission electron microscopy (TEM) images of thin sections indicated that even though both RDP-coated nanotubes and clay platelets segregated to the interfacial regions between the two immiscible polymers, only the platelets, having the larger specific surface area, were able to reduce the PBAT domain sizes. The ability of clay platelets to partially compatibilize the blend was further confirmed by the dynamic mechanical analysis (DMA) which showed that the glass transition temperatures of two polymers tended to shift closer. No shift was observed with either coated or uncoated HNTs samples. Izod impact testing demonstrated that the rubbery PBAT phase greatly increased the impact strength of the unfilled blend, but addition of only 5% of treated clay decreased the impact strength by nearly 50%. On the other hand, an increase of 9% relative to the unfilled blend sample was observed with the addition of 5% treated nanotubes. TEM cross-section analysis confirmed that the RDP-coated clay platelets covered most of the interfacial area. On one hand, this enabled them to reduce the interfacial tension effectively; on the other hand, it prevented chain entanglements across the phase boundary and increased the overall brittleness, which was confirmed by rheology measurements. In contrast, the RDP-coated HNTs were observed to lie perpendicular to the interface, which made them less effective in reducing interfacial tension but encouraged interfacial entanglements across the interface, resulting in "stitching" of the interface and an increase in the Izod impact of the blend.

Preparation of cellulose composites with in situ generated copper nanoparticles using leaf extract and their properties.

In the present work, copper nanoparticles (CuNPs) were in situ generated in cellulose matrix using Ocimum sanctum leaf extract as a reducing agent and aq. CuSO4 solution by diffusion process. Some CuNPs were also formed outside the film in the solution which were separated and viewed by Transmission electron microscope and Scanning electron microscope (SEM). The composite films showed good antibacterial activity against Escherichia coli bacteria when the CuNPs were generated using higher concentrated aq. CuSO4 solutions. The cellulose, matrix and the composite films were characterized by Fourier transform infrared spectroscopic, X-ray diffraction, thermogravimetric analysis and SEM techniques. The tensile strength of the composite films was lower than that of the matrix but still higher than the conventional polymers like polyethylene and polypropylene used for packaging applications. These biodegradable composite films can be considered for packaging and medical applications.