Lignin‐based nanomaterials fabricated by solution self‐assembly in organic–aqueous solvent mixtures are among the most attractive biomass‐derived products. To accurately control the structure, size, and properties of lignin‐based nanomaterials, it is important to achieve fundamental understanding of its dissolution and aggregation mechanisms. In this work, atomic force microscopy (AFM) and molecular dynamics (MD) simulations are employed to explore the dissolution and aggregation behavior of enzymatic hydrolysis lignin (EHL) in different organic–aqueous solvent mixtures at molecular scale. EHL was found to dissolve well in appropriate organic–aqueous solvent mixtures, such as acetone–water mixture with a volume ratio of 7:3, whereas it aggregated in pure water, ethanol, acetone, and tetrahydrofuran. The interactions between the EHL‐coated AFM probe and the substrate were 1.21±0.18 and 0.75±0.35 mN m−1 in water and acetone, respectively. In comparison, the interaction decreased to 0.15±0.08 mN m−1 in acetone–water mixture (7:3 v/v). MD simulations further indicate that the hydrophobic skeleton and hydrophilic groups of lignin could be solvated by acetone and water molecules, respectively, which significantly promoted its dissolution. Conversely, only the hydrophobic skeleton or the hydrophilic groups were solvated in organic solvent or water, respectively, inducing serious aggregation of lignin.
UV filters that contain one or two aromatic rings in conventional sunscreens generally have a poor photo-and thermal stability and can easily penetrate through stratum corneum and dermis into the blood vessel, thus causing potential health-threatening issues. Herein, a series of bioinspired photostable and biocompatible polydopamine-grafted lignin (AL-PDA) with strong bioadhesion have been synthesized through free radical addition of dopamine (DA) and alkali lignin (AL). AL-PDA was used to emulsify organic UV filters and further cross-linked to form nanocapsules through ultrasonic cavitation. The retention rate of optimal AL-PDA nanocapsules on the skin surface reached 87% after a thorough rinse with water and negligible penetration was observed, which demonstrates their excellent bioadhesion property. Force measurements using atomic force microscopy (AFM) quantitatively revealed the adhesion between the nanocapsules and skin. An average DA grafting number of 4 would be required to endow the AL-PDA nanocapsules with suitable water-penetration resistance. The nanocapsules were used as the sole active ingredient for formulating sunscreen, whose sun protection factor (SPF) value could reach 195.33 with a dosage ∼10 wt % lasting for over 8 h under UV radiation. The as-prepared nanocapsules possess excellent antioxidant capacity and biocompatibility, ensuring their superior performance and safe use in the sunscreen. This work provides new insights into the development of biomass lignin for advanced function materials and high-end products.
Due
to the growing sustainability and health requirements,
structural
color materials fabricated with functional natural polymers have attracted
increasing attention in advanced optical and biomedical fields. Lignin
has many attractive features such as great biocompatibility, ultraviolet
resistance, antioxidant property, and thermostability, making it a
promising natural resource to be fabricated as functional structural
color materials. However, to date, the utilization of lignin as the
building block for structural color materials is still a challenge
due to its disordered structure. Herein, we present a strategy to
transform disordered lignin into ordered “photonic lignin”,
in which monodisperse lignin colloidal spheres are prepared via solvent/antisolvent
self-assembly, and then the periodic structure is constructed by centrifugal
effect. The photonic lignin exhibits structural colors that are tunable
by modulating the diameter of lignin colloidal spheres. We further
demonstrate the application of photonic lignin as a natural polymer-based
coating that shows bright, angle-independent, and stimuli-responsive
structural colors. Moreover, the cytotoxicity assay indicates the
excellent biocompatibility of photonic lignin with human skin, blood
vessels, digestive systems, and other tissues, which demonstrates
the great potential of photonic lignin in the applications such as
implanted/wearable optical devices, advanced cosmetics, and smart
food packaging.
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