Correction to "Ductile, High-Lignin-Content Thermoset Films and Coatings".

[This corrects the article DOI: 10.1021/acssuschemeng.3c03030.].

Ductile, High-Lignin-Content Thermoset Films and Coatings.

In the context of transitioning toward a more sustainable use of natural resources, the application of lignin to substitute commonly utilized petroleum-based plastics can play a key role. Although lignin is highly available at low cost and presents interesting properties, such as antioxidant and UV barrier activities, its application is limited by its low reactivity, which is a consequence of harsh conditions normally used to extract lignin from biomass. In this work, the use of glyoxylic acid lignin (GA lignin), rich in carboxylic acid groups and hence highly reactive toward epoxy cross-linkers, is presented. GA lignin, which is directly extracted from biomass via a one-step aldehyde-assisted fractionation process, allowed the preparation of thermoset films and coatings via a simple reaction with sustainable poly(ethylene glycol) diglycidyl ether and glycerol diglycidyl ether cross-linkers. This allows one to prepare freestanding films containing up to 70 wt % lignin with tunable mechanical properties and covalently surface-attached coatings containing up to 90 wt % lignin with high solvent resistance. Both films and coatings display antioxidant properties and combine excellent UV barrier activity with high visible transparency, which is attractive for applications in sustainable food packaging.

Opportunities and Challenges for Lignin Valorization in Food Packaging, Antimicrobial, and Agricultural Applications.

The exploration of renewable resources is essential to help transition toward a more sustainable materials economy. The valorization of lignin can be a key component of this transition. Lignin is an aromatic polymer that constitutes approximately one-third of the total lignocellulosic biomass and is isolated in huge quantities as a waste material of biofuel and paper production. About 98% of the 100 million tons of lignin produced each year is simply burned as low-value fuel, so this renewable polymer is widely available at very low cost. Lignin has valuable properties that make it a promising material for numerous applications, but it is far from being fully exploited. The aim of this Perspective is to highlight opportunities and challenges for the use of lignin-based materials in food packaging, antimicrobial, and agricultural applications. In the first part, the ongoing research and the possible future developments for the use of lignin as an additive to improve mechanical, gas and UV barrier, and antioxidant properties of food packaging items will be treated. Second, the application of lignin as an antimicrobial agent will be discussed to elaborate on the activity of lignin against bacteria, fungi, and viruses. Finally, the use of lignin in agriculture will be presented by focusing on the application of lignin as fertilizer.

Lignin: A Sustainable Antiviral Coating Material.

Transmission of viruses through contact with contaminated surfaces is an important pathway for the spread of infections. Antiviral surface coatings are useful to minimize such risks. Current state-of-the-art approaches toward antiviral surface coatings either involve metal-based materials or complex synthetic polymers. These approaches, however, even if successful, will have to face great challenges when it comes to large-scale applications and their environmental sustainability. Here, an antiviral surface coating was prepared by spin-coating lignin, a natural biomass residue of the paper production industry. We show effective inactivation of herpes simplex virus type 2 (>99% after 30 min) on a surface coating that is low-cost and environmentally sustainable. The antiviral mechanism of the lignin surface was investigated and is attributed to reactive oxygen species generated upon oxidation of lignin phenols. This mechanism does not consume the surface coating (as opposed to the release of a specific antiviral agent) and does not require regeneration. The coating is stable in ambient conditions, as demonstrated in a 6 month aging study that did not reveal any decrease in antiviral activity. This research suggests that natural compounds may be used for the development of affordable and sustainable antiviral coatings.

Uniformly Dispersed Poly(lactic acid)-Grafted Lignin Nanoparticles Enhance Antioxidant Activity and UV-Barrier Properties of Poly(lactic acid) Packaging Films.

Poly(lactic acid) (PLA) represents one of the most widely used biodegradable polymers for food packaging applications. While this material provides many advantages, it is characterized by limited antioxidant and UV-barrier properties. Blending PLA with lignin is an attractive strategy to address these limitations. Lignin possesses antioxidant properties and absorbs UV-light and is a widely available low value byproduct of the paper and pulp industry. This study has explored the use of lignin nanoparticles to augment the properties of PLA-based films. A central challenge in the preparation of PLA-lignin nanoparticle blend films is to avoid nanoparticle aggregation, which could compromise optical properties as well as antioxidant activity, among others. To avoid nanoparticle aggregation in the PLA matrix, PLA-grafted lignin nanoparticles were prepared via organocatalyzed lactide ring-opening polymerization. In contrast to lignin and unmodified lignin nanoparticles, these PLA-grafted lignin nanoparticles could be uniformly dispersed in PLA for lignin contents up to 10 wt %. The addition of as little as the equivalent of 1 wt % of lignin of these nanoparticles effectively blocked transmission of 280 nm UV-light. At the same time, these blend films retained reasonable visible light transmittance. The optical properties of the PLA lignin blend films also benefited from the well-dispersed nature of the PLA-grafted nanoparticles, as evidenced by significantly higher visible light transmittance of blends of PLA and PLA-grafted nanoparticles, as compared to blends prepared from PLA with lignin or unmodified lignin nanoparticles. Finally, blending PLA with PLA-grafted lignin nanoparticles greatly augments the antioxidant activity of these films.

Polymer Nanoparticle-Mediated Delivery of Oxidized Tumor Lysate-Based Cancer Vaccines.

Cancer vaccination is a powerful strategy to combat cancer. A very attractive approach to prime the immune system against cancer cells involves the use of tumor lysate as antigen source. The immunogenicity of tumor lysate can be further enhanced by treatment with hypochlorous acid. This study explores poly(lactic-co-glycolic acid) (PLGA) nanoparticles to enhance the delivery of oxidized tumor lysate to dendritic cells. Using human donor-derived dendritic cells, it is found that the use of PLGA nanoparticles enhances antigen uptake and dendritic cell maturation, as compared to the use of the free tumor lysate. The ability of the activated dendritic cells to stimulate autologous peripheral blood mononuclear cells (PBMCs) is assessed in vitro by coculturing PBMCs with A375 melanoma cells. Live cell imaging analysis of this experiment highlights the potential of nanoparticle-mediated dendritic-cell-based vaccination approaches. Finally, the efficacy of the PLGA nanoparticle formulation is evaluated in vivo in a therapeutic vaccination study using B16F10 tumor-bearing C57BL/6J mice. Animals that are challenged with the polymer nanoparticle-based oxidized tumor lysate formulation survive for up to 50 days, in contrast to a maximum of 41 days for the group that receives the corresponding free oxidized tumor lysate-based vaccine.

Reduction-Sensitive Protein Nanogels Enhance Uptake of Model and Tumor Lysate Antigens In Vitro by Mouse- and Human-Derived Dendritic Cells.

Peptides and proteins represent an emerging class of powerful therapeutics. Peptide and protein nanogels are attractive carriers for the transport and delivery of biologically active peptides and proteins because they allow essentially quantitative encapsulation of these biologics. One interesting field of use of peptide and protein nanogels is the transport of antigens and adjuvants in cancer immunotherapy. This study demonstrates the use of reduction-sensitive protein nanogels for the delivery of ovalbumin and oxidized tumor lysate-based antigens to mouse and human-donor-derived dendritic cells. Challenging mouse-derived and human dendritic cells with reduction-sensitive ovalbumin nanogels was found to significantly enhance antigen uptake as compared to the use of the corresponding free protein antigen. The experiments with mouse-derived dendritic cells further showed that the administration of ovalbumin in the form of reduction-sensitive nanogels enhanced dendritic cell maturation as well as the presentation of the SIINFEKL epitope as compared to experiments that use free ovalbumin. In addition to ovalbumin as a model antigen, the feasibility of reduction-sensitive nanogels was also demonstrated for the delivery of oxidized, whole tumor lysate-based cancer antigens. In experiments with dendritic cells harvested from human donors, dendritic cell uptake of the oxidized tumor lysate antigen was significantly enhanced in experiments that used oxidized tumor lysate nanogels as compared to the free antigen.

Supramolecular functionalization of carbon nano-onions with hyaluronic acid-phospholipid conjugates for selective targeting of cancer cells.

Carbon nano-onions (CNOs) are promising materials for biomedical applications due to their low cytotoxicity and excellent biocompatibility. Supramolecular functionalization with biocompatible polymers is an effective strategy to develop engineered drug carriers for targeted delivery applications. In this study, we report the use of a hyaluronic acid-phospholipid (HA-DMPE) conjugate to target CD44 overexpressing cancer cells, while enhancing solubility of the nanoconstruct. Non-covalently functionalized CNOs with HA-DMPE show excellent in vitro cell viability in human breast carcinoma cells overexpressing CD44 and are uptaken to a greater extent compared to human ovarian carcinoma cells with an undetectable amount of CD44. In addition, they possess high in vivo biocompatibility in zebrafish (Danio Rerio) during the different stages of development and they prevalently localize in the digestive tract of the zebrafish larvae.

Thermally Induced Silane Dehydrocoupling on Silicon Nanostructures.

Organic trihydridosilanes can be grafted to hydrogen-terminated porous Si nanostructures with no catalyst. The reaction proceeds efficiently at 80 °C, and it shows little sensitivity to air or water impurities. The modified surfaces are stable to corrosive aqueous solutions and common organic solvents. Octadecylsilane H3 Si(CH2 )17 CH3 , and functional silanes H3 Si(CH2 )11 Br, H3 Si(CH2 )9 CH=CH2 , and H3 Si(CH2 )2 (CF2 )5 CF3 are readily grafted. When performed on a mesoporous Si wafer, the perfluoro reagent yields a superhydrophobic surface (contact angle 151°). The bromo-derivative is converted to azide, amine, or alkyne functional surfaces via standard transformations, and the utility of the method is demonstrated by loading of the antibiotic ciprofloxaxin (35 % by mass). When intrinsically photoluminescent porous Si films or nanoparticles are used, photoluminescence is retained in the grafted products, indicating that the chemistry does not introduce substantial nonradiative surface traps.