The lack of renewable resources and their inefficient use is a major challenge facing the society. Lignin is a natural biopolymer obtained mainly as a by-product from pulp-and paper-making industry, and is primarily burned to produce energy. However, the interest for using lignin in more advanced applications has increased rapidly. In particular, lignin based nanoparticles could find potential use in functional surface coatings, nanoglues, drug delivery, and microfluidic devices. In this work, a straightforward method to produce lignin nanoparticles from waste lignin obtained from kraft pulping is introduced.Spherical lignin nanoparticles were obtained by dissolving soft wood kraft lignin in tetrahydrofuran (THF) and subsequently introducing water into the system through dialysis. No chemical modification of the lignin was needed. Water acts as a nonsolvent reducing lignin's degrees of freedom causing the segregation of hydrophobic regions to compartments within the forming nanoparticles. The final size of the nanoparticles depended on the pre-dialysis concentration of dissolved lignin. The stability of the nanoparticle dispersion as a function of time, salt concentration and pH was studied. In pure water and room temperature the lignin nanoparticle dispersion was stable for over two months, but very low pH or high salt concentration induced aggregation. It was further demonstrated that the surface charge of the particles could be reversed and stable cationic lignin nanoparticles were produced by adsorption of poly(diallyldimethylammonium chloride) (PDADMAC).

Biorenewable polymers have emerged as an attractive alternative to conventional metallic and organic materials for a variety of different applications. This is mainly because of their biocompatibility, biodegradability and low cost of production. Lignocellulosic biomass is the most promising renewable carbon-containing source on Earth. Depending on the origin and species of the biomass, lignin consists of 20-35% of the lignocellulosic biomass. After it has been extracted, lignin can be modified through diverse chemical reactions. There are different categories of chemical modifications, such as lignin depolymerization or fragmentation, modification by synthesizing new chemically active sites, chemical modification of the hydroxyl groups, and the production of lignin graft copolymers. Lignin can be used for different industrial and biomedical applications, including biofuels, chemicals and polymers, and the development of nanomaterials for drug delivery but these uses depend on the source, chemical modifications and physicochemical properties. We provide an overview on the composition and properties, extraction methods and chemical modifications of lignin in this review. Furthermore, we describe different preparation methods for lignin-based nanomaterials with antioxidant UV-absorbing and antimicrobial properties that can be used as reinforcing agents in nanocomposites, in drug delivery and gene delivery vehicles for biomedical applications. Response to Reviewers: RESPONSE TO THE REVIEWERS' COMMENTS REVIEWER #1In this review, the authors summarized the current state of art for the preparation of lignin-based nanomaterials. Recent advances in the application of lignin-based nanomaterials in drug delivery and gene delivery vehicles were also discussed in the manuscript. However, this review is premature for publication in Progress in Materials Science. Some specific comments are listed as follows.2. "4.1 Lignin Depolymerization": There are too many descriptive statements. In order to im-prove the understanding of different lignin depolymerization processes, main reaction equa-tions (similar to fig. 4) should be added in this section. R.: As each depolymerization process can originate different products, with different chemical structures, we decided to added a figure (Fig. 4) that summarize the different conditions used for each lignin depolymerization process, with the different products that can obtained from each pro-cess. "4.4 Production of Lignin GraftCopolymers": This section is too long to read. The authors should divide it into several parts and provide some subtitles here. In this way, the readers can easily follow. R.: In order to facilitate the reading, the following subsections were created in the "4.4. Production of Lignin Graft Copolymers" section, according to the processes described in the Figures 7 and 8: 4.4.1. "Grafting from" Technique 4.4.1.1. Ring Opening Polymerization 4.4.1.2. Radical Polymerization 4.4.1.3. Atom Transfer Radical Polymerization 4.4.2. "Grafting to" Technique R. : We thank the...

Binary nanoparticle superlattices are periodic nanostructures with lattice constants much shorter than the wavelength of light and could be used to prepare multifunctional metamaterials. Such superlattices are typically made from synthetic nanoparticles, and although biohybrid structures have been developed, incorporating biological building blocks into binary nanoparticle superlattices remains challenging. Protein-based nanocages provide a complex yet monodisperse and geometrically well-defined hollow cage that can be used to encapsulate different materials. Such protein cages have been used to program the self-assembly of encapsulated materials to form free-standing crystals and superlattices at interfaces or in solution. Here, we show that electrostatically patchy protein cages--cowpea chlorotic mottle virus and ferritin cages--can be used to direct the self-assembly of three-dimensional binary superlattices. The negatively charged cages can encapsulate RNA or superparamagnetic iron oxide nanoparticles, and the superlattices are formed through tunable electrostatic interactions with positively charged gold nanoparticles. Gold nanoparticles and viruses form an AB(8)(fcc) crystal structure that is not isostructural with any known atomic or molecular crystal structure and has previously been observed only with large colloidal polymer particles. Gold nanoparticles and empty or nanoparticle-loaded ferritin cages form an interpenetrating simple cubic AB structure (isostructural with CsCl). We also show that these magnetic assemblies provide contrast enhancement in magnetic resonance imaging.

DNA origami structures can be programmed into arbitrary shapes with nanometer scale precision, which opens up numerous attractive opportunities to engineer novel functional materials. One intriguing possibility is to use DNA origamis for fully tunable, targeted, and triggered drug delivery. In this work, we demonstrate the coating of DNA origami nanostructures with virus capsid proteins for enhancing cellular delivery. Our approach utilizes purified cowpea chlorotic mottle virus capsid proteins that can bind and self-assemble on the origami surface through electrostatic interactions and further pack the origami nanostructures inside the viral capsid. Confocal microscopy imaging and transfection studies with a human HEK293 cell line indicate that protein coating improves cellular attachment and delivery of origamis into the cells by 13-fold compared to bare DNA origamis. The presented method could readily find applications not only in sophisticated drug delivery applications but also in organizing intracellular reactions by origami-based templates.

DNA origami structures have great potential as functional platforms in various biomedical applications. Many applications, however, are incompatible with the high Mg concentrations commonly believed to be a prerequisite for maintaining DNA origami integrity. Herein, we investigate DNA origami stability in low-Mg buffers. DNA origami stability is found to crucially depend on the availability of residual Mg ions for screening electrostatic repulsion. The presence of EDTA and phosphate ions may thus facilitate DNA origami denaturation by displacing Mg ions from the DNA backbone and reducing the strength of the Mg -DNA interaction, respectively. Most remarkably, these buffer dependencies are affected by DNA origami superstructure. However, by rationally selecting buffer components and considering superstructure-dependent effects, the structural integrity of a given DNA origami nanostructure can be maintained in conventional buffers even at Mg concentrations in the low-micromolar range.

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In this communication, we present a nanoscale reactor assembled from tuneable and spatially addressable tubular DNA origami units. We can controllably combine separate origami units equipped with glucose oxidase (GOx) and horseradish peroxidase (HRP), and demonstrate efficient GOx/HRP enzyme cascade reaction inside the tube. The reactor could be utilized as a nanoscale diagnostic tool, and modularity of the proposed system would further enable more complex reactions.

DALI combines DNA origami with conventional top-down fabrication for creating designer high-resolution plasmonic nanostructures.