Photothermal Performance of Lignin-Based Nanospheres and Their Applications in Water Surface Actuators.

In this study, the photothermal performance of lignin-based nanospheres was investigated. Subsequently, a photothermal actuator was prepared using lignin-based carbon nanospheres (LCNSs). The results demonstrated that LCNSs exhibited an impressive photothermal conversion efficiency of up to 83.8%. This extreme efficiency significantly surpasses that of lignin nanospheres (LNSs) and covalently stabilized LNSs (HT-LNSs). As a structural material, a hydrophobic coating was effectively engineered by LCNSs on the filter paper, achieving a water contact angle of 151.9° ± 4.6°, while maintaining excellent photothermal effects (with a temperature increment from room temperature to 138 °C in 2 s). When employing hydrophobic filter paper as the substrate for the photothermaldriven actuator, under the influence of a 1.0 W/cm2 power-density NIR laser, the material exhibited outstanding photothermal actuation, achieving speeds up to 16.4 mm/s. In addition, the direction of motion of the actuator can be adjusted in accordance with the location of the NIR light irradiation. This study offers valuable perspectives on the application of LNSs for highvalue applications and the development of innovative photothermal-driven actuators.

Modulation of Electronic Synergy to Enhance the Intrinsic Activity of Fe5Ni4S8 Nanosheets in Restricted Space Carbonized Wood Frameworks for Efficient Oxygen Evolution Reaction.

Modulation of electronic structure and composition is widely recognized as an effective strategy to improve electrocatalyst performance. Herein, using a simple simultaneous carbonization and sulfidation strategy, NiFe double hydroxide-derived Fe5Ni4S8 (FNS) nanosheets immobilized on S-doped carbonized wood (SCW) framework by taking benefit of the orientation-constrained cavity and hierarchical porous structure of wood is proposed. Benefiting from the synergistic relationships between bimetal ions, the spatial confinement offered by the wood cavity, and the enhanced structural effects of the nanosheets array, the FNS/SCW exhibit enhanced intrinsic activity, increased accessibility of catalytically active sites, and convection-facilitated mass transport, resulting in an excellent oxygen evolution reaction (OER) activity and durability. Specifically, it takes a low overpotential of 230 mV at 50 mA cm-2 and potential increase is negligible (3.8%) at 50 mA cm-2 for 80 hours. Density functional theory (DFT) calculations further reveal that the synergistic effect of bimetal can optimize the electronic structure and lower the reaction energy barrier. The FNS/SCW used as the cathode of zinc-air battery shows higher power density and excellent durability relative to commercial RuO2, exhibiting a good application prospect. Overall, this research offers proposals for designing and producing effective OER electrocatalysts using sustainable resources.

An electrochemically mediated ATRP synthesis of lignin-g-PDMAPS UCST-thermoresponsive polymer.

It is a promising idea to graft zwitterionic polymers onto lignin and prepare lignin-grafted-poly [2-(methacryloyloxy) ethyl] dimethyl-(3-sulfopropyl) ammonium hydroxide (Lignin-g-PDMAPS) thermosensitive polymer with the upper critical solution temperature (UCST). In this paper, an electrochemically mediated atom transfer radical polymerization (eATRP) method was used to prepare Lignin-g-PDMAPS. The structure and property of the Lignin-g-PDMAPS polymer were characterized by the fourier transform infrared spectrum (FT-IR), nuclear magnetic resonance (NMR), X-ray electron spectroscopy (XPS), dynamic light scattering (DLS), differential scanning calorimeter (DSC). Furthermore, the effect of catalyst structure, applied potential, amount of Lignin-Br, Lignin-g-PDMAPS concentration, NaCl concentration on UCST of Lignin-g-PDMAPS were investigated. It was worth noting that polymerization was well controlled when the ligand was tris (2-aminoethyl) amine (Me6TREN), applied potential was -0.38 V and the amount of Lignin-Br was 100 mg. And the UCST of the Lignin-g-PDMAPS aqueous solution (1 mg/ml) was 51.47 °C, the molecular weight was 8987 g/mol, and the particle size was 318 nm. It was also found that the UCST increased and the particle size decreased with the Lignin-g-PDMAPS polymer concentration increased, and the UCST decreased and the particle size increased with the NaCl concentration increases. This work investigated UCST-thermoresponsive polymer which possessed lignin main chain combining the zwitterionic side chain, and provided a new way for development of lignin based UCST-thermoresponsive materials and medical carrier materials, in addition to expand the scope of eATRP.

Structure and properties of nanoparticles: DES-lignin-g-PNVCL coated aspirin by self-assembly.

This work was carried out in order to broaden the application field of lignin and improve its additional value. The degraded deep eutectic solvent lignin-grafted poly(N-vinyl caprolactam) (DES-lignin-g-PNVCL) was synthesized by using modified DES-lignin and NVCL via activators regenerated by electron transfer-atom transfer radical polymerization (ARGET-ATRP). Aspirin was coated with DES-lignin-g-PNVCL through self-assembly by an ethanol/water anti-solvent method to obtain lignin thermosensitive polymer nanoparticle coated aspirin (aspirin@LTNP). X-ray electron spectroscopy (XPS), elemental analysis, scanning electron microscopy (SEM), transmission electron microscopy (TEM), Fourier transform infrared spectroscopy (FT-IR), dynamic light scattering (DLS), and ultraviolet visible spectroscopy (UV) were used to characterize the composition, structure and morphology of DES-lignin-g-PNVCL and aspirin@LTNP. The releasing behavior of aspirin@LTNP at different temperatures and pH values was investigated. The safety was evaluated by cytotoxicity tests. The results indicated that aspirin@LTNP was mainly accumulated by the hydrophobic effect and π-π interaction in the process of self-assembly, and its morphology was an ellipsoid stacked layer by layer. The aspirin@LTNP hydrophilic chains were increased and had externally hydrophilic and internally hydrophobic structures. The particle size decreased slightly during the self-assembly process. The red-shift occurred at the π-π interaction wavelength of the lignin aromatic ring, which indicated a physical coating process. The coating rate of aspirin@LTNP was 88.87%. Aspirin@LTNP showed an obvious temperature response; the 96 h cumulative release rate at the LCST was 73.75 ± 1.16%, while the 96 h cumulative release rate above the LCST was 28.10 ± 0.92%. The 96 h cumulative release rate was 63.21 ± 0.57% at pH = 1.5 and 49.56 ± 0.48% at pH = 7.4. The dosage of aspirin@LTNP used in the experiment was safe. This study provided a strategy for drug coating and controlled release.

Preparation of LCST regulable DES-lignin-g-PNVCL thermo-responsive polymer by ARGET-ATRP.

To expand the field of high-value utilization of lignin. The degraded deep eutectic solvent lignin-grafted poly (N-Vinyl caprolactam) (DES-lignin-g-PNVCL) was synthesized by modified DES-lignin and NVCL via the combination of activators regenerated by electron transfer-atom transfer radical polymerization (ARGET-ATRP). Fourier transform infrared spectroscopy (FT-IR), 1H NMR, X-ray electron spectroscopy (XPS), dynamic light scattering (DLS), differential scanning calorimeter (DSC) were used to characterize the structure and performance of DES-lignin-g-PNVCL. The results indicated that the PNVCL and DES-lignin-g-PNVCL were successfully prepared by ARGET-ATRP. The lowest critical solution temperature (LCST) of PNVCL was 35.75 °C. Due to different strength of hydrogen bond, different energies were required, so the LCST of the polymer can be regulated. When the molar ratio of phenolic hydroxyl group in degraded DES-lignin to 2-bromoisobutyryl bromide (BiBB) was increased from 1:1 to 1:7, the grafting rate of DES-lignin-Br was increased from 32.87% to 60.84%, and the LCST of DES-lignin-g-PNVCL was decreased from 47.98 °C to 27.88 °C. The LCST of DES-lignin-g-PNVCL was increased from 30.98 °C to 44.64 °C when the addition amount of DES-lignin-Br was increased from 20 mg to 200 mg. The LCST of DES-lignin-g-PNVCL was increased from 27.20 °C to 39.86 °C when the ratio of DMF/water was increased from 1:4 to 4:1. The LCST of DES-lignin-g-PNVCL was decreased from 52.10 °C to 31.02 °C when the concentration of DES-lignin-g-PNVCL was increased from 0.5 mg/mL to 2.5 mg/mL. The equation represented the relationship between LCST and influencing factors was obtained, the good predictability provided a tactics for preparing desired LCST thermo-responsible polymer.

Lignin-based fluorescence hollow nanoparticles: Their preparation, characterization, and encapsulation properties for doxorubicin.

Lignin shows strong adsorption, biodegradability and non-toxicity, and has opened a research hotspot in the design and manufacture of controllable nanomaterials for drug delivery. However, lignin-based materials, with both diagnostic and therapeutic functions, have yet to be developed. In this work, enzymatically hydrolysable lignin (EHL) was used to prepare blue fluorescent lignin copolymer by grafting 1-Pyrenebutyric acid onto lignin via amidation reaction and then formed self-assembled nanoparticles. The results show that such lignin-based hollow nanoparticles exhibit characteristics of fluorescent functions, size controlled and stable structure within 15 days. For anticancer drug Doxorubicin, the encapsulation efficiency and drug loading reached, respectively, 50% and 10%. This encapsulation had no cytotoxicity, and sustained-release effect on the drug. The aim of this study was to develop the multifunctional bio-nanomaterials for medical applications, through simple, environmentally friendly, low-cost methods.

Preparation of Targeted Lignin⁻Based Hollow Nanoparticles for the Delivery of Doxorubicin.

Due to their exceptional absorption capacity, biodegradability, and non-toxicity, nanoparticles (NPs) from lignin have emerged as vehicles for inorganic particles and drug molecules. However, the method for preparing targeted lignin particles is still complex and lacks sufficient research. Herein, a succinct strategy was proposed for the preparation of targeted lignin-based drug delivery NPs to load Doxorubicin Hydrochloride (DOX). The lignin hollow NPs (LHNPs) were used as a platform for the preparation of targeted delivery material by incorporating magnetic NPs and folic acid (FA) via layer-by-layer self-assembling. The results showed that the surface of LHNPs was covered uniformly by Fe3O4 NPs and grafted with folic acid. The folic-magnetic-functionalized lignin hollow NPs (FA-MLHNPs) could respond to magnetic field and folic acid receptors. In addition, the targeting performance of the FA-MLHNPs increased the cellular uptake of NPs in the case of HeLa cells. This research not only supported the modified NPs platform as a highly efficient nano-delivery method but also provided a facile approach to utilize renewable lignin biomaterials.